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Research ArticlePreparation of AgHBPPAN Nanofiber Web andIts Antimicrobial and Filtration Property
Li-Rong Yao12 Xiao-Mo Song3 Guang-Yu Zhang2 Shan-Qing Xu2 Ye-Qun Jiang2
De-Hong Cheng1 and Yan-Hua Lu1
1Liaoning Provincial Key Laboratory of Functional Textile Materials Eastern Liaoning University Dandong 118001 China2School of Textile and Clothing Nantong University Nantong 226019 China3Department of Chemical Environment and Life Dalian University of Technology Dalian 116024 China
Correspondence should be addressed to De-Hong Cheng chengdehongldxyqqcom and Yan-Hua Lu yanhualualiyuncom
Received 27 December 2015 Revised 5 February 2016 Accepted 8 February 2016
Academic Editor Tamer Uyar
Copyright copy 2016 Li-Rong Yao et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
To widen the application of nanofibers web in the field of medical health materials a new Agamino-terminated hyperbranchedpolymer (HBP)polyacrylonitrile (PAN) nanofiber web with excellent antimicrobial activity and filtration property was producedwith AgHBP dispersion solution and PAN nanofiber AgHBP dispersion solution was prepared with HBP as reducer andstabilizer and AgHBPPANnanofiber was prepared bymodifying electrospun PANnanofiber with AgHBP aqueous solutionThecharacterization results showed that spherical Ag nanoparticles were prepared and they had a narrow distribution in HBP aqueoussolutionThe results of AgHBPPANnanofiber characterized with SEM and EDS showed that the content of silver nanoparticles onthe surface of PAN nanofiber was on the increase when the treating temperature roseThe bacterial reduction rates of HBP-treatedPAN nanofiber against S aureus and E coliwere about 89 while those of the AgHBPPAN nanofiber against S aureus and E coliwere 999 and 9996 respectively due to the cooperative effects from the amino groups inHBP andAg nanoparticles Moreoverthe small pores and high porosity in AgHBPPAN nanofiber web resulted in high filtration efficiency (999) for removing smallerparticles (01 120583msim07 120583m) which was much higher than that of the gauze mask
1 Introduction
Nanofibers which have small pores a great surface area andhigh porosity are widely used in filtration Li-ion batterieswound dressing and other fields [1ndash5] Electrospinning is auseful one-step and straightforward process for fabrication ofnanofibers one is the treatment of multiple working fluidssynchronously on one spinneret to create nanofibers withcomplicated structures such as core-shell or multiple layers[6 7] and the other is after treatment or transition of theelectrospun nanofibers for functional applications [8]
Polyacrylonitrile (PAN) is a kind of polymer materialwith good stability mechanical properties and abundantfunctional cyanogroups (ndashCN) on its macromolecular chainThe preparation of PAN nanofibers by electrospinning hasattracted wide attention including preparation conditionsof PAN nanofibers [9] PAN nanocomposite and so forth
[10ndash12] The nanofiber or nanocomposite web was the usefulselective layer for removing smaller particles Compared tothe microfiltration (MF) ultrafiltration (UF) and reverseosmosis (RO) membranes have porosities from 5 to 35the nanofiber membranes could easily be made into MFand UF membranes with porosities in range of 80 to 90[13] In addition the interconnectivity of the pores eliminatesthe inefficiency of the dead-end pores that are commonlyformed in conventional membranes These characteristicswould significantly increase flux and reduce transmembranepressure drop
Recently polymer nanofibers loaded metal nanoparticleshave attracted wide interest Compared with other metalssilver has a unique catalytic performance high conductivityand antibacterial so more attention has been receivedIn recent years electrospun PAN nanofibers loaded silvernanoparticles have been prepared using different methods
Hindawi Publishing CorporationJournal of NanomaterialsVolume 2016 Article ID 4515769 10 pageshttpdxdoiorg10115520164515769
2 Journal of Nanomaterials
For example by the silvermirror reaction (SMR)method thesilver nanoparticles were uniformly dispersed on the surfaceof PAN nanofibers [14] And some researchers preparedthe silver nanoparticles by electrospinning mixed solutionof AgNO
3and PAN using chemical reduction method to
reduce Ag+ into Ag0 [15ndash18] Using the ion exchange methodto get silver nanoparticles from Ag
2CO3 we finally got PAN
composite nanofibers [19] Atmospheric plasma treatmentand high temperature were some other methods to pre-pare electrospun PAN nanofibers loaded silver nanoparticles[20 21] These PAN nanofibers loaded silver nanoparticleshave excellent antibacterial and conductive property [22ndash25] However the silver nanoparticles prepared in the aboveresearch had lower stability because there were no protectorsoutside them and the weak combination between silvernanoparticles and PAN nanofiber was another shortcoming
Hyperbranched polymers (HBP) are a subfamily of den-dritic polymers and can be used as effective polymers dueto their unique sphere structure network low viscosity andfunctional terminal groups such as hydroxyl amine epoxideanhydride carboxylic and isocyanate groups especially foramino-terminal HBP which has shown excellent adsorptionto several organic polymers andmetal-binding behavior [26]HBP has an excellent dispersion and stabilization in aqueouswhich can be used as a reducer and stabilizer for preparingnanoparticles [27]
In our work HBP was synthesized and used to pre-pare silver nanoparticles aqueous solution and a newAgHBPPAN nanofiber web with excellent antibacterial andfiltration property was successfully prepared At first thesilver nanoparticles with a mean size of about 10 nm wereprepared bymixing AgNO
3andHBP solution under stirring
the nanosilver solution was used to treat PAN nanofiber webthe concentration of nanosilver solution and the treatingtemperature were mainly investigated which were the keyfactors affecting the content of Ag nanoparticles on PANnanofibers Then the antibacterial activity and filtrationproperties were also investigated
2 Experimental Section
21 Materials Polyacrylonitrile (PAN white powder Mw= 85000) silver nitrate (AgNO
3) NN-dimethylformamide
(DMF) ethylenediamine methyl acrylate methanol andcotton gauze were purchased from Sinopharm ChemicalReagent Co Ltd (China) and were of analytical grade Inall the experiments the chemicals were of analytical gradeand all the reagents were used as received without any furtherpurification
22 Preparation of AgHBP Solution Hyperbranched poly-mer (HBP) was synthesized and AgHBP solution wasprepared according to our previous work in patent [28]Firstly ethylenediamine (305 g 05mol) was added to a500mL three-necked round-bottomed glass flask equippedwith nitrogen gas protection and magnetic stirring andmethyl acrylate (4305 g 05mol) in methanol (100mL) wasadded dropwise to the flask with a magnetic agitator and
cooled with an ice bath Then the mixture was removedfrom the ice bath and left for stirring for further 6 h at roomtemperature The mixture was transferred into an eggplant-shaped flask for automatic rotary vacuum evaporation andthe temperature was raised to 150∘C in oil bath for 4 h underlow pressure after removing the methanol the yellow viscidHBP was obtained
Then 001molL AgNO3(20mL) solution was added
dropwise to 2 gL HBP (100mL) solution with constantstirring at 50∘C for 60min and light yellow semitransparentAgHBP hybrid was prepared
23 Characterization of AgHBP Transmission electronmicroscopy (TEM) images were obtained using an FEICompany (USA) Tecnai G220 transmission electron micro-scope operating at 300 kV accelerating voltage Samples wereprepared by evaporating the solution of nanoparticles ontoa 200-mesh copper grid which was coated with a carbonsupport film The Zetasizer Nano ZS system (90Plus Zeta)from Brookhaven Company (USA) was used to test the sizedistribution of AgHBP UV-vis spectra from 200 to 900 nmwere obtained using a UVVisible Absorption Spectropho-tometry
24 Preparation ofAgHBPPANAntibacterialNanofiberWebThe concentration of 12 wt PAN solution was prepared insolvent DMF and the electrospinning was carried out byapplying high voltage between the polymer solution con-tained in the syringe and the metallic collector the syringein this experiment can move from right to left For all ofthe electrospinning experiments in this study aluminum foilacceptor was placed on the collector for the deposition offibersThe voltage used was 15 kV the feed rate was 04mLhand the needle collector distance was 15 cm The thickness ofnanofiber web was controlled by changing the spinning time
The PAN nanofiber web prepared as mentioned abovewas immersed in the AgHBP solution at 30∘C 60∘C and90∘C in a water bath for 120min respectively the liquor-to-fabric ratio was 50 1 Another sample was immersed in HBPsolution at the same liquor-to-fabric ratio as a control sampleThe treated samples were air-dried at room temperature forsubsequent characterization
25 Characterization of AgHBPPAN Nanofiber Web AHitachi scanning electron microscope (model S-4800 LaB6gun Kevex X-ray EDS) was used to observe the morphologyof the Ag nanoparticles on the surface of the samplesThe diameter of PAN nanofiber was measured by imageprocessing software (Image-Pro Plus 50) the Brunauer-Emmett-Teller (BET) surface areawasmeasured at 77Kusinga nitrogen adsorption-desorption Micromeritics ASAP-2020analyzer (Micromeritics Co USA) The porosity of PANnanofiber web was calculated by the following equation
120576 = (1 minus119898
119885 times 119860 times 120588) times 100 (1)
where 120576 is the porosity of the relevant fibrous membrane 119898119885 and 119860 are the mass mean thickness and area of per unit
Journal of Nanomaterials 3
H2N
H2NH2N
H2N
H2N
H2N
H2N
H2N NH2
NH2
NH2
NH2
NH2NH2
NH2
NH2
NH2
NH2
NH2
NH2AgO
O
O
O
O
OO O
O O
OO
O
O
O
O
O
O
O
O
OO
HN
HN
N
H
H
N
HN
NN
N
N
N
N
N
N
NN
HN HNHN
HN
NH
NH
NH
NH
CH2
CH2
Heatingvacuum
+
Terminal unit
Linear unit
AgNO3stirring
Figure 1 Scheme process of preparing AgHBP nanoparticle
measuredmembrane respectively 120588 is the density of polymerraw material and the density of PAN is 1184 gcm3 Thenanofiber web was immersed in liquid nitrogen for severalminutes and then cut off under liquid nitrogenThe thicknessof nanofiber web was measured under optical microscope(Olympus CX31 Japan) the mean thickness was calculatedafter measurements for 5 times at different cross section
26 Antimicrobial Activity of AgHBPPAN Nanofiber WebThe antimicrobial activity of AgHBPPAN nanofiber webwas tested against E coli and S aureus by using a shake-flaskmethod according to the literature [29] The antimicrobialactivity of AgHBPPAN nanofiber web was tested against Ecoli and S aureus by using a shake-flask method according toFZT 73023-2006 (China)Thismethod is especially designedfor specimens treated with nonreleasing antibacterial agentsunder dynamic contact conditions A sample of fabric (05 g)cut into small pieces with size of around 05 times 05 cm2 wasdipped into a flask containing 70mL 03mM phosphate-buffered saline (PBS monopotassium phosphate pH 72)culture solution with cell concentration of 1 times 105ndash4 times 105colony-forming units (CFU)mL The flask was then shakenat 150 rpm on a rotary shaker at 24∘C for 18 h From eachincubated sample 1mL solution was taken diluted anddistributed onto an agar plate All plates were incubated at37∘C for 24 h and the colonies formed were counted Thepercentage reduction was determined as follows
Reduction in CFU () = 119862 minus 1198621015840
119862times 100 (2)
where 119862 and 1198621015840 are the bacterial colonies of the PANnanofiber web and the Ag-treated PAN nanofiber webrespectively
27 Filtration Property of AgHBPPAN Nanofiber Web TheAgHBPPAN nanofiber web was placed between two layersof cotton gauze to form a sandwich structure then thefiltration of them and cotton gauze with 14 layers were testedThe aerosol filtration efficiency and airflow resistance weremeasured with a Filter Media Test System (AFC-131 TOPASCorp Germany) NaCl aerosol particles were prepared by
an aerosol particle generator (SAG-410 TOPAS Corp Ger-many) The neutralized NaCl aerosol particles were fed intoa filter holder and down through the filter with an effectivearea of 100 cm2 The diameter of sample is 115 cm the testwas conducted at room temperature with the continuous airflow rate at the surface of sample fixed at 534 cms
3 Results and Discussion
31 Preparation of AgHBP The schematic illustration forfabrication of AgHBP aqueous solution was given inFigure 1 Hyperbranched polymer (HBP) was synthesizedfrom ethylenediamine and methyl acrylate by melt poly-condensation under vacuum The AgHBP aqueous solutionwas synthesized by mixing AgNO
3aqueous solution and
HBP aqueous solution under vigorous stirring at 50∘CAbundant amino groups (primary amine secondary amineand quaternary amine) inside or at the terminal of HBPmacromolecule have reduction performance to reduce Ag+to silver nanoparticles and NH
2groups outside the silver
nanoparticles play roles of both reductant and stabilizerwhich can protect nanosilver particles from oxidation andprovide higher security during use [30]
32 Characterization of AgHBP Themicromorphology andsize distribution of the Ag nanoparticles are showed inFigure 2 The image of TEM shows that the diameter ofAg nanoparticles is about 10 nm and the nanosilvers showa standardized spherical particle and are well dispersed(Figure 2(a)) and the dates from Figure 2(b) further confirmthat theAg nanoparticles prepared have a narrow particle sizedistribution and the size is about 7 nmsim13 nm Results of UV-vis adsorption spectra in Figure 2(c) prove the characteristicadsorption peak of AgHBP at 40709 nm confirming thenanocrystalline character of Ag nanoparticles
33 Preparation of AgHBPPAN Nanofiber The process ofpreparing AgHBPPANnanofiber web is present in Figure 3As shown in Figure 3 three steps are needed for preparingAgHBPPAN nanofiber Firstly the concentration of 12 wtPAN solution was used for electrospinning and uniform PAN
4 Journal of Nanomaterials
(a) TEM image of AgHBP
7 8 9 10 11 12 136
Size (nm)
0
20
40
60
80
100
Cum
ulat
e dist
ribut
ion
()
0
20
40
60
80
100
Calc
ulus
dist
ribut
ion
()
(b) Size distribution of AgHBP aqueous
00
02
04
06
08
10
12
Abso
rban
ce
100 200 300 400 500 600 700 800 900 1000
Wavelength (nm)
40709
(c) UV-vis adsorption spectra of AgHBP aqueous
Figure 2 Morphology and size distribution of AgHBP
PANsolution
HBP-NH2solution
PAN nanofiber web
Nanosilversolution
Immersion
heating
PANAg nanofiber web
Nanofiber
Silver particle
Stirring
AgNO3
Electrospinning
Figure 3 Scheme process of preparing AgHBPPAN nanofiber
Journal of Nanomaterials 5
(a) PAN nanofiber (b) AgHBPPAN nanofiber 002wt
(c) AgHBPPAN nanofiber 005 wt (d) AgHBPPAN nanofiber 008wt
Figure 4 The morphology of AgHBPPAN nanofiber (temperature of water bath is 30∘C)
nanofiber with mean diameter of 200 nmndash300 nm was pre-pared The second step is to synthesize AgHBP solution bymixing HBP and AgNO
3under 50∘C water bath Then PAN
nanofiber web prepared as mentioned above is immersed inthe AgHBP solution the concentration of AgHBP solutionand treating temperature are investigated as the main factorsaffecting the fabrication of AgHBPPAN nanofiber web
34 Characterization of AgHBPPAN Nanofiber Figure 4shows the morphology of PAN and Ag-treated PANnanofibers As shown in Figure 4 the low treating temper-ature (30∘C) is used and no significant increase of silvernanoparticles on the surface of PAN nanofibers is observedin SEM images [Figures 4(b) 4(c) and 4(d)] when theconcentration of AgHBP solution increased from 002wtto 008wt which indicated that treating temperature playsa much more important role to fix the silver nanoparticlesonto the surface of PAN nanofiber
The SEM pictures of PAN nanofibers loaded silver nano-particles are shown in Figure 5 From images of Figure 5 noobvious changes are observed onmorphology fiber diameterand pore size of PAN nanofiber web before and after treat-ment with AgHBP solution However the silver nanopar-ticles on the surface of PAN nanofiber have a significantincrease when the processing temperature rose from 30∘C to90∘CThis indicates that the assembly procedure was temper-ature dependent It is believed that the increased electrostaticinteractionwas responsible for the improved assembly ability
Specifically with increasing the temperature the aminogroups (ndashNH
2) capped on surface of the silver nanoparticles
are highly cationized endowing the nanoparticle surfacewithmuch higher positive charges Thus the electrostatic inter-action between negatively charged PAN nanofiber and pos-itively charged Ag nanoparticles was strengthened Besidesby the increase of temperature the functional cyanogroup (ndashCN) on PAN nanofiber and the amino group (ndashNH
2) outside
the silver nanoparticles have higher activity to combine witheach other and the silver nanoparticleswill permeate throughthe pores inside nanofiber web which have more opportunityto contact with the cyanogroups on PAN nanofiber
The schematic diagram of hydrogen bonds formationbetween cyanogroup (ndashCN) and amino group (ndashNH
2) is
shown in Scheme 1 Compared to the silver nanoparticles insitu reduced on the surface of fiber this kind of hydrogenbonding provides stronger combining power between silvernanoparticles and PAN nanofibers In general there are twoways to prepare Ag-containing antibacterial materials thismeans that the Ag particles are placed inside of the fiberor fixed on the surface of fiber For the disposable hygieneproducts or breathing mask the Ag particles on surface offiber show rapid and efficient antimicrobial activity
35 EDS Analysis EDS test is used to characterize elementchange on the surface of PAN nanofiber and prove thereaction between AgHBP solution and PAN nanofibersindirectly as shown in Figure 6The results show that carbon
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Nano
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Journal ofNanomaterials
2 Journal of Nanomaterials
For example by the silvermirror reaction (SMR)method thesilver nanoparticles were uniformly dispersed on the surfaceof PAN nanofibers [14] And some researchers preparedthe silver nanoparticles by electrospinning mixed solutionof AgNO
3and PAN using chemical reduction method to
reduce Ag+ into Ag0 [15ndash18] Using the ion exchange methodto get silver nanoparticles from Ag
2CO3 we finally got PAN
composite nanofibers [19] Atmospheric plasma treatmentand high temperature were some other methods to pre-pare electrospun PAN nanofibers loaded silver nanoparticles[20 21] These PAN nanofibers loaded silver nanoparticleshave excellent antibacterial and conductive property [22ndash25] However the silver nanoparticles prepared in the aboveresearch had lower stability because there were no protectorsoutside them and the weak combination between silvernanoparticles and PAN nanofiber was another shortcoming
Hyperbranched polymers (HBP) are a subfamily of den-dritic polymers and can be used as effective polymers dueto their unique sphere structure network low viscosity andfunctional terminal groups such as hydroxyl amine epoxideanhydride carboxylic and isocyanate groups especially foramino-terminal HBP which has shown excellent adsorptionto several organic polymers andmetal-binding behavior [26]HBP has an excellent dispersion and stabilization in aqueouswhich can be used as a reducer and stabilizer for preparingnanoparticles [27]
In our work HBP was synthesized and used to pre-pare silver nanoparticles aqueous solution and a newAgHBPPAN nanofiber web with excellent antibacterial andfiltration property was successfully prepared At first thesilver nanoparticles with a mean size of about 10 nm wereprepared bymixing AgNO
3andHBP solution under stirring
the nanosilver solution was used to treat PAN nanofiber webthe concentration of nanosilver solution and the treatingtemperature were mainly investigated which were the keyfactors affecting the content of Ag nanoparticles on PANnanofibers Then the antibacterial activity and filtrationproperties were also investigated
2 Experimental Section
21 Materials Polyacrylonitrile (PAN white powder Mw= 85000) silver nitrate (AgNO
3) NN-dimethylformamide
(DMF) ethylenediamine methyl acrylate methanol andcotton gauze were purchased from Sinopharm ChemicalReagent Co Ltd (China) and were of analytical grade Inall the experiments the chemicals were of analytical gradeand all the reagents were used as received without any furtherpurification
22 Preparation of AgHBP Solution Hyperbranched poly-mer (HBP) was synthesized and AgHBP solution wasprepared according to our previous work in patent [28]Firstly ethylenediamine (305 g 05mol) was added to a500mL three-necked round-bottomed glass flask equippedwith nitrogen gas protection and magnetic stirring andmethyl acrylate (4305 g 05mol) in methanol (100mL) wasadded dropwise to the flask with a magnetic agitator and
cooled with an ice bath Then the mixture was removedfrom the ice bath and left for stirring for further 6 h at roomtemperature The mixture was transferred into an eggplant-shaped flask for automatic rotary vacuum evaporation andthe temperature was raised to 150∘C in oil bath for 4 h underlow pressure after removing the methanol the yellow viscidHBP was obtained
Then 001molL AgNO3(20mL) solution was added
dropwise to 2 gL HBP (100mL) solution with constantstirring at 50∘C for 60min and light yellow semitransparentAgHBP hybrid was prepared
23 Characterization of AgHBP Transmission electronmicroscopy (TEM) images were obtained using an FEICompany (USA) Tecnai G220 transmission electron micro-scope operating at 300 kV accelerating voltage Samples wereprepared by evaporating the solution of nanoparticles ontoa 200-mesh copper grid which was coated with a carbonsupport film The Zetasizer Nano ZS system (90Plus Zeta)from Brookhaven Company (USA) was used to test the sizedistribution of AgHBP UV-vis spectra from 200 to 900 nmwere obtained using a UVVisible Absorption Spectropho-tometry
24 Preparation ofAgHBPPANAntibacterialNanofiberWebThe concentration of 12 wt PAN solution was prepared insolvent DMF and the electrospinning was carried out byapplying high voltage between the polymer solution con-tained in the syringe and the metallic collector the syringein this experiment can move from right to left For all ofthe electrospinning experiments in this study aluminum foilacceptor was placed on the collector for the deposition offibersThe voltage used was 15 kV the feed rate was 04mLhand the needle collector distance was 15 cm The thickness ofnanofiber web was controlled by changing the spinning time
The PAN nanofiber web prepared as mentioned abovewas immersed in the AgHBP solution at 30∘C 60∘C and90∘C in a water bath for 120min respectively the liquor-to-fabric ratio was 50 1 Another sample was immersed in HBPsolution at the same liquor-to-fabric ratio as a control sampleThe treated samples were air-dried at room temperature forsubsequent characterization
25 Characterization of AgHBPPAN Nanofiber Web AHitachi scanning electron microscope (model S-4800 LaB6gun Kevex X-ray EDS) was used to observe the morphologyof the Ag nanoparticles on the surface of the samplesThe diameter of PAN nanofiber was measured by imageprocessing software (Image-Pro Plus 50) the Brunauer-Emmett-Teller (BET) surface areawasmeasured at 77Kusinga nitrogen adsorption-desorption Micromeritics ASAP-2020analyzer (Micromeritics Co USA) The porosity of PANnanofiber web was calculated by the following equation
120576 = (1 minus119898
119885 times 119860 times 120588) times 100 (1)
where 120576 is the porosity of the relevant fibrous membrane 119898119885 and 119860 are the mass mean thickness and area of per unit
Journal of Nanomaterials 3
H2N
H2NH2N
H2N
H2N
H2N
H2N
H2N NH2
NH2
NH2
NH2
NH2NH2
NH2
NH2
NH2
NH2
NH2
NH2AgO
O
O
O
O
OO O
O O
OO
O
O
O
O
O
O
O
O
OO
HN
HN
N
H
H
N
HN
NN
N
N
N
N
N
N
NN
HN HNHN
HN
NH
NH
NH
NH
CH2
CH2
Heatingvacuum
+
Terminal unit
Linear unit
AgNO3stirring
Figure 1 Scheme process of preparing AgHBP nanoparticle
measuredmembrane respectively 120588 is the density of polymerraw material and the density of PAN is 1184 gcm3 Thenanofiber web was immersed in liquid nitrogen for severalminutes and then cut off under liquid nitrogenThe thicknessof nanofiber web was measured under optical microscope(Olympus CX31 Japan) the mean thickness was calculatedafter measurements for 5 times at different cross section
26 Antimicrobial Activity of AgHBPPAN Nanofiber WebThe antimicrobial activity of AgHBPPAN nanofiber webwas tested against E coli and S aureus by using a shake-flaskmethod according to the literature [29] The antimicrobialactivity of AgHBPPAN nanofiber web was tested against Ecoli and S aureus by using a shake-flask method according toFZT 73023-2006 (China)Thismethod is especially designedfor specimens treated with nonreleasing antibacterial agentsunder dynamic contact conditions A sample of fabric (05 g)cut into small pieces with size of around 05 times 05 cm2 wasdipped into a flask containing 70mL 03mM phosphate-buffered saline (PBS monopotassium phosphate pH 72)culture solution with cell concentration of 1 times 105ndash4 times 105colony-forming units (CFU)mL The flask was then shakenat 150 rpm on a rotary shaker at 24∘C for 18 h From eachincubated sample 1mL solution was taken diluted anddistributed onto an agar plate All plates were incubated at37∘C for 24 h and the colonies formed were counted Thepercentage reduction was determined as follows
Reduction in CFU () = 119862 minus 1198621015840
119862times 100 (2)
where 119862 and 1198621015840 are the bacterial colonies of the PANnanofiber web and the Ag-treated PAN nanofiber webrespectively
27 Filtration Property of AgHBPPAN Nanofiber Web TheAgHBPPAN nanofiber web was placed between two layersof cotton gauze to form a sandwich structure then thefiltration of them and cotton gauze with 14 layers were testedThe aerosol filtration efficiency and airflow resistance weremeasured with a Filter Media Test System (AFC-131 TOPASCorp Germany) NaCl aerosol particles were prepared by
an aerosol particle generator (SAG-410 TOPAS Corp Ger-many) The neutralized NaCl aerosol particles were fed intoa filter holder and down through the filter with an effectivearea of 100 cm2 The diameter of sample is 115 cm the testwas conducted at room temperature with the continuous airflow rate at the surface of sample fixed at 534 cms
3 Results and Discussion
31 Preparation of AgHBP The schematic illustration forfabrication of AgHBP aqueous solution was given inFigure 1 Hyperbranched polymer (HBP) was synthesizedfrom ethylenediamine and methyl acrylate by melt poly-condensation under vacuum The AgHBP aqueous solutionwas synthesized by mixing AgNO
3aqueous solution and
HBP aqueous solution under vigorous stirring at 50∘CAbundant amino groups (primary amine secondary amineand quaternary amine) inside or at the terminal of HBPmacromolecule have reduction performance to reduce Ag+to silver nanoparticles and NH
2groups outside the silver
nanoparticles play roles of both reductant and stabilizerwhich can protect nanosilver particles from oxidation andprovide higher security during use [30]
32 Characterization of AgHBP Themicromorphology andsize distribution of the Ag nanoparticles are showed inFigure 2 The image of TEM shows that the diameter ofAg nanoparticles is about 10 nm and the nanosilvers showa standardized spherical particle and are well dispersed(Figure 2(a)) and the dates from Figure 2(b) further confirmthat theAg nanoparticles prepared have a narrow particle sizedistribution and the size is about 7 nmsim13 nm Results of UV-vis adsorption spectra in Figure 2(c) prove the characteristicadsorption peak of AgHBP at 40709 nm confirming thenanocrystalline character of Ag nanoparticles
33 Preparation of AgHBPPAN Nanofiber The process ofpreparing AgHBPPANnanofiber web is present in Figure 3As shown in Figure 3 three steps are needed for preparingAgHBPPAN nanofiber Firstly the concentration of 12 wtPAN solution was used for electrospinning and uniform PAN
4 Journal of Nanomaterials
(a) TEM image of AgHBP
7 8 9 10 11 12 136
Size (nm)
0
20
40
60
80
100
Cum
ulat
e dist
ribut
ion
()
0
20
40
60
80
100
Calc
ulus
dist
ribut
ion
()
(b) Size distribution of AgHBP aqueous
00
02
04
06
08
10
12
Abso
rban
ce
100 200 300 400 500 600 700 800 900 1000
Wavelength (nm)
40709
(c) UV-vis adsorption spectra of AgHBP aqueous
Figure 2 Morphology and size distribution of AgHBP
PANsolution
HBP-NH2solution
PAN nanofiber web
Nanosilversolution
Immersion
heating
PANAg nanofiber web
Nanofiber
Silver particle
Stirring
AgNO3
Electrospinning
Figure 3 Scheme process of preparing AgHBPPAN nanofiber
Journal of Nanomaterials 5
(a) PAN nanofiber (b) AgHBPPAN nanofiber 002wt
(c) AgHBPPAN nanofiber 005 wt (d) AgHBPPAN nanofiber 008wt
Figure 4 The morphology of AgHBPPAN nanofiber (temperature of water bath is 30∘C)
nanofiber with mean diameter of 200 nmndash300 nm was pre-pared The second step is to synthesize AgHBP solution bymixing HBP and AgNO
3under 50∘C water bath Then PAN
nanofiber web prepared as mentioned above is immersed inthe AgHBP solution the concentration of AgHBP solutionand treating temperature are investigated as the main factorsaffecting the fabrication of AgHBPPAN nanofiber web
34 Characterization of AgHBPPAN Nanofiber Figure 4shows the morphology of PAN and Ag-treated PANnanofibers As shown in Figure 4 the low treating temper-ature (30∘C) is used and no significant increase of silvernanoparticles on the surface of PAN nanofibers is observedin SEM images [Figures 4(b) 4(c) and 4(d)] when theconcentration of AgHBP solution increased from 002wtto 008wt which indicated that treating temperature playsa much more important role to fix the silver nanoparticlesonto the surface of PAN nanofiber
The SEM pictures of PAN nanofibers loaded silver nano-particles are shown in Figure 5 From images of Figure 5 noobvious changes are observed onmorphology fiber diameterand pore size of PAN nanofiber web before and after treat-ment with AgHBP solution However the silver nanopar-ticles on the surface of PAN nanofiber have a significantincrease when the processing temperature rose from 30∘C to90∘CThis indicates that the assembly procedure was temper-ature dependent It is believed that the increased electrostaticinteractionwas responsible for the improved assembly ability
Specifically with increasing the temperature the aminogroups (ndashNH
2) capped on surface of the silver nanoparticles
are highly cationized endowing the nanoparticle surfacewithmuch higher positive charges Thus the electrostatic inter-action between negatively charged PAN nanofiber and pos-itively charged Ag nanoparticles was strengthened Besidesby the increase of temperature the functional cyanogroup (ndashCN) on PAN nanofiber and the amino group (ndashNH
2) outside
the silver nanoparticles have higher activity to combine witheach other and the silver nanoparticleswill permeate throughthe pores inside nanofiber web which have more opportunityto contact with the cyanogroups on PAN nanofiber
The schematic diagram of hydrogen bonds formationbetween cyanogroup (ndashCN) and amino group (ndashNH
2) is
shown in Scheme 1 Compared to the silver nanoparticles insitu reduced on the surface of fiber this kind of hydrogenbonding provides stronger combining power between silvernanoparticles and PAN nanofibers In general there are twoways to prepare Ag-containing antibacterial materials thismeans that the Ag particles are placed inside of the fiberor fixed on the surface of fiber For the disposable hygieneproducts or breathing mask the Ag particles on surface offiber show rapid and efficient antimicrobial activity
35 EDS Analysis EDS test is used to characterize elementchange on the surface of PAN nanofiber and prove thereaction between AgHBP solution and PAN nanofibersindirectly as shown in Figure 6The results show that carbon
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 3
H2N
H2NH2N
H2N
H2N
H2N
H2N
H2N NH2
NH2
NH2
NH2
NH2NH2
NH2
NH2
NH2
NH2
NH2
NH2AgO
O
O
O
O
OO O
O O
OO
O
O
O
O
O
O
O
O
OO
HN
HN
N
H
H
N
HN
NN
N
N
N
N
N
N
NN
HN HNHN
HN
NH
NH
NH
NH
CH2
CH2
Heatingvacuum
+
Terminal unit
Linear unit
AgNO3stirring
Figure 1 Scheme process of preparing AgHBP nanoparticle
measuredmembrane respectively 120588 is the density of polymerraw material and the density of PAN is 1184 gcm3 Thenanofiber web was immersed in liquid nitrogen for severalminutes and then cut off under liquid nitrogenThe thicknessof nanofiber web was measured under optical microscope(Olympus CX31 Japan) the mean thickness was calculatedafter measurements for 5 times at different cross section
26 Antimicrobial Activity of AgHBPPAN Nanofiber WebThe antimicrobial activity of AgHBPPAN nanofiber webwas tested against E coli and S aureus by using a shake-flaskmethod according to the literature [29] The antimicrobialactivity of AgHBPPAN nanofiber web was tested against Ecoli and S aureus by using a shake-flask method according toFZT 73023-2006 (China)Thismethod is especially designedfor specimens treated with nonreleasing antibacterial agentsunder dynamic contact conditions A sample of fabric (05 g)cut into small pieces with size of around 05 times 05 cm2 wasdipped into a flask containing 70mL 03mM phosphate-buffered saline (PBS monopotassium phosphate pH 72)culture solution with cell concentration of 1 times 105ndash4 times 105colony-forming units (CFU)mL The flask was then shakenat 150 rpm on a rotary shaker at 24∘C for 18 h From eachincubated sample 1mL solution was taken diluted anddistributed onto an agar plate All plates were incubated at37∘C for 24 h and the colonies formed were counted Thepercentage reduction was determined as follows
Reduction in CFU () = 119862 minus 1198621015840
119862times 100 (2)
where 119862 and 1198621015840 are the bacterial colonies of the PANnanofiber web and the Ag-treated PAN nanofiber webrespectively
27 Filtration Property of AgHBPPAN Nanofiber Web TheAgHBPPAN nanofiber web was placed between two layersof cotton gauze to form a sandwich structure then thefiltration of them and cotton gauze with 14 layers were testedThe aerosol filtration efficiency and airflow resistance weremeasured with a Filter Media Test System (AFC-131 TOPASCorp Germany) NaCl aerosol particles were prepared by
an aerosol particle generator (SAG-410 TOPAS Corp Ger-many) The neutralized NaCl aerosol particles were fed intoa filter holder and down through the filter with an effectivearea of 100 cm2 The diameter of sample is 115 cm the testwas conducted at room temperature with the continuous airflow rate at the surface of sample fixed at 534 cms
3 Results and Discussion
31 Preparation of AgHBP The schematic illustration forfabrication of AgHBP aqueous solution was given inFigure 1 Hyperbranched polymer (HBP) was synthesizedfrom ethylenediamine and methyl acrylate by melt poly-condensation under vacuum The AgHBP aqueous solutionwas synthesized by mixing AgNO
3aqueous solution and
HBP aqueous solution under vigorous stirring at 50∘CAbundant amino groups (primary amine secondary amineand quaternary amine) inside or at the terminal of HBPmacromolecule have reduction performance to reduce Ag+to silver nanoparticles and NH
2groups outside the silver
nanoparticles play roles of both reductant and stabilizerwhich can protect nanosilver particles from oxidation andprovide higher security during use [30]
32 Characterization of AgHBP Themicromorphology andsize distribution of the Ag nanoparticles are showed inFigure 2 The image of TEM shows that the diameter ofAg nanoparticles is about 10 nm and the nanosilvers showa standardized spherical particle and are well dispersed(Figure 2(a)) and the dates from Figure 2(b) further confirmthat theAg nanoparticles prepared have a narrow particle sizedistribution and the size is about 7 nmsim13 nm Results of UV-vis adsorption spectra in Figure 2(c) prove the characteristicadsorption peak of AgHBP at 40709 nm confirming thenanocrystalline character of Ag nanoparticles
33 Preparation of AgHBPPAN Nanofiber The process ofpreparing AgHBPPANnanofiber web is present in Figure 3As shown in Figure 3 three steps are needed for preparingAgHBPPAN nanofiber Firstly the concentration of 12 wtPAN solution was used for electrospinning and uniform PAN
4 Journal of Nanomaterials
(a) TEM image of AgHBP
7 8 9 10 11 12 136
Size (nm)
0
20
40
60
80
100
Cum
ulat
e dist
ribut
ion
()
0
20
40
60
80
100
Calc
ulus
dist
ribut
ion
()
(b) Size distribution of AgHBP aqueous
00
02
04
06
08
10
12
Abso
rban
ce
100 200 300 400 500 600 700 800 900 1000
Wavelength (nm)
40709
(c) UV-vis adsorption spectra of AgHBP aqueous
Figure 2 Morphology and size distribution of AgHBP
PANsolution
HBP-NH2solution
PAN nanofiber web
Nanosilversolution
Immersion
heating
PANAg nanofiber web
Nanofiber
Silver particle
Stirring
AgNO3
Electrospinning
Figure 3 Scheme process of preparing AgHBPPAN nanofiber
Journal of Nanomaterials 5
(a) PAN nanofiber (b) AgHBPPAN nanofiber 002wt
(c) AgHBPPAN nanofiber 005 wt (d) AgHBPPAN nanofiber 008wt
Figure 4 The morphology of AgHBPPAN nanofiber (temperature of water bath is 30∘C)
nanofiber with mean diameter of 200 nmndash300 nm was pre-pared The second step is to synthesize AgHBP solution bymixing HBP and AgNO
3under 50∘C water bath Then PAN
nanofiber web prepared as mentioned above is immersed inthe AgHBP solution the concentration of AgHBP solutionand treating temperature are investigated as the main factorsaffecting the fabrication of AgHBPPAN nanofiber web
34 Characterization of AgHBPPAN Nanofiber Figure 4shows the morphology of PAN and Ag-treated PANnanofibers As shown in Figure 4 the low treating temper-ature (30∘C) is used and no significant increase of silvernanoparticles on the surface of PAN nanofibers is observedin SEM images [Figures 4(b) 4(c) and 4(d)] when theconcentration of AgHBP solution increased from 002wtto 008wt which indicated that treating temperature playsa much more important role to fix the silver nanoparticlesonto the surface of PAN nanofiber
The SEM pictures of PAN nanofibers loaded silver nano-particles are shown in Figure 5 From images of Figure 5 noobvious changes are observed onmorphology fiber diameterand pore size of PAN nanofiber web before and after treat-ment with AgHBP solution However the silver nanopar-ticles on the surface of PAN nanofiber have a significantincrease when the processing temperature rose from 30∘C to90∘CThis indicates that the assembly procedure was temper-ature dependent It is believed that the increased electrostaticinteractionwas responsible for the improved assembly ability
Specifically with increasing the temperature the aminogroups (ndashNH
2) capped on surface of the silver nanoparticles
are highly cationized endowing the nanoparticle surfacewithmuch higher positive charges Thus the electrostatic inter-action between negatively charged PAN nanofiber and pos-itively charged Ag nanoparticles was strengthened Besidesby the increase of temperature the functional cyanogroup (ndashCN) on PAN nanofiber and the amino group (ndashNH
2) outside
the silver nanoparticles have higher activity to combine witheach other and the silver nanoparticleswill permeate throughthe pores inside nanofiber web which have more opportunityto contact with the cyanogroups on PAN nanofiber
The schematic diagram of hydrogen bonds formationbetween cyanogroup (ndashCN) and amino group (ndashNH
2) is
shown in Scheme 1 Compared to the silver nanoparticles insitu reduced on the surface of fiber this kind of hydrogenbonding provides stronger combining power between silvernanoparticles and PAN nanofibers In general there are twoways to prepare Ag-containing antibacterial materials thismeans that the Ag particles are placed inside of the fiberor fixed on the surface of fiber For the disposable hygieneproducts or breathing mask the Ag particles on surface offiber show rapid and efficient antimicrobial activity
35 EDS Analysis EDS test is used to characterize elementchange on the surface of PAN nanofiber and prove thereaction between AgHBP solution and PAN nanofibersindirectly as shown in Figure 6The results show that carbon
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
4 Journal of Nanomaterials
(a) TEM image of AgHBP
7 8 9 10 11 12 136
Size (nm)
0
20
40
60
80
100
Cum
ulat
e dist
ribut
ion
()
0
20
40
60
80
100
Calc
ulus
dist
ribut
ion
()
(b) Size distribution of AgHBP aqueous
00
02
04
06
08
10
12
Abso
rban
ce
100 200 300 400 500 600 700 800 900 1000
Wavelength (nm)
40709
(c) UV-vis adsorption spectra of AgHBP aqueous
Figure 2 Morphology and size distribution of AgHBP
PANsolution
HBP-NH2solution
PAN nanofiber web
Nanosilversolution
Immersion
heating
PANAg nanofiber web
Nanofiber
Silver particle
Stirring
AgNO3
Electrospinning
Figure 3 Scheme process of preparing AgHBPPAN nanofiber
Journal of Nanomaterials 5
(a) PAN nanofiber (b) AgHBPPAN nanofiber 002wt
(c) AgHBPPAN nanofiber 005 wt (d) AgHBPPAN nanofiber 008wt
Figure 4 The morphology of AgHBPPAN nanofiber (temperature of water bath is 30∘C)
nanofiber with mean diameter of 200 nmndash300 nm was pre-pared The second step is to synthesize AgHBP solution bymixing HBP and AgNO
3under 50∘C water bath Then PAN
nanofiber web prepared as mentioned above is immersed inthe AgHBP solution the concentration of AgHBP solutionand treating temperature are investigated as the main factorsaffecting the fabrication of AgHBPPAN nanofiber web
34 Characterization of AgHBPPAN Nanofiber Figure 4shows the morphology of PAN and Ag-treated PANnanofibers As shown in Figure 4 the low treating temper-ature (30∘C) is used and no significant increase of silvernanoparticles on the surface of PAN nanofibers is observedin SEM images [Figures 4(b) 4(c) and 4(d)] when theconcentration of AgHBP solution increased from 002wtto 008wt which indicated that treating temperature playsa much more important role to fix the silver nanoparticlesonto the surface of PAN nanofiber
The SEM pictures of PAN nanofibers loaded silver nano-particles are shown in Figure 5 From images of Figure 5 noobvious changes are observed onmorphology fiber diameterand pore size of PAN nanofiber web before and after treat-ment with AgHBP solution However the silver nanopar-ticles on the surface of PAN nanofiber have a significantincrease when the processing temperature rose from 30∘C to90∘CThis indicates that the assembly procedure was temper-ature dependent It is believed that the increased electrostaticinteractionwas responsible for the improved assembly ability
Specifically with increasing the temperature the aminogroups (ndashNH
2) capped on surface of the silver nanoparticles
are highly cationized endowing the nanoparticle surfacewithmuch higher positive charges Thus the electrostatic inter-action between negatively charged PAN nanofiber and pos-itively charged Ag nanoparticles was strengthened Besidesby the increase of temperature the functional cyanogroup (ndashCN) on PAN nanofiber and the amino group (ndashNH
2) outside
the silver nanoparticles have higher activity to combine witheach other and the silver nanoparticleswill permeate throughthe pores inside nanofiber web which have more opportunityto contact with the cyanogroups on PAN nanofiber
The schematic diagram of hydrogen bonds formationbetween cyanogroup (ndashCN) and amino group (ndashNH
2) is
shown in Scheme 1 Compared to the silver nanoparticles insitu reduced on the surface of fiber this kind of hydrogenbonding provides stronger combining power between silvernanoparticles and PAN nanofibers In general there are twoways to prepare Ag-containing antibacterial materials thismeans that the Ag particles are placed inside of the fiberor fixed on the surface of fiber For the disposable hygieneproducts or breathing mask the Ag particles on surface offiber show rapid and efficient antimicrobial activity
35 EDS Analysis EDS test is used to characterize elementchange on the surface of PAN nanofiber and prove thereaction between AgHBP solution and PAN nanofibersindirectly as shown in Figure 6The results show that carbon
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 5
(a) PAN nanofiber (b) AgHBPPAN nanofiber 002wt
(c) AgHBPPAN nanofiber 005 wt (d) AgHBPPAN nanofiber 008wt
Figure 4 The morphology of AgHBPPAN nanofiber (temperature of water bath is 30∘C)
nanofiber with mean diameter of 200 nmndash300 nm was pre-pared The second step is to synthesize AgHBP solution bymixing HBP and AgNO
3under 50∘C water bath Then PAN
nanofiber web prepared as mentioned above is immersed inthe AgHBP solution the concentration of AgHBP solutionand treating temperature are investigated as the main factorsaffecting the fabrication of AgHBPPAN nanofiber web
34 Characterization of AgHBPPAN Nanofiber Figure 4shows the morphology of PAN and Ag-treated PANnanofibers As shown in Figure 4 the low treating temper-ature (30∘C) is used and no significant increase of silvernanoparticles on the surface of PAN nanofibers is observedin SEM images [Figures 4(b) 4(c) and 4(d)] when theconcentration of AgHBP solution increased from 002wtto 008wt which indicated that treating temperature playsa much more important role to fix the silver nanoparticlesonto the surface of PAN nanofiber
The SEM pictures of PAN nanofibers loaded silver nano-particles are shown in Figure 5 From images of Figure 5 noobvious changes are observed onmorphology fiber diameterand pore size of PAN nanofiber web before and after treat-ment with AgHBP solution However the silver nanopar-ticles on the surface of PAN nanofiber have a significantincrease when the processing temperature rose from 30∘C to90∘CThis indicates that the assembly procedure was temper-ature dependent It is believed that the increased electrostaticinteractionwas responsible for the improved assembly ability
Specifically with increasing the temperature the aminogroups (ndashNH
2) capped on surface of the silver nanoparticles
are highly cationized endowing the nanoparticle surfacewithmuch higher positive charges Thus the electrostatic inter-action between negatively charged PAN nanofiber and pos-itively charged Ag nanoparticles was strengthened Besidesby the increase of temperature the functional cyanogroup (ndashCN) on PAN nanofiber and the amino group (ndashNH
2) outside
the silver nanoparticles have higher activity to combine witheach other and the silver nanoparticleswill permeate throughthe pores inside nanofiber web which have more opportunityto contact with the cyanogroups on PAN nanofiber
The schematic diagram of hydrogen bonds formationbetween cyanogroup (ndashCN) and amino group (ndashNH
2) is
shown in Scheme 1 Compared to the silver nanoparticles insitu reduced on the surface of fiber this kind of hydrogenbonding provides stronger combining power between silvernanoparticles and PAN nanofibers In general there are twoways to prepare Ag-containing antibacterial materials thismeans that the Ag particles are placed inside of the fiberor fixed on the surface of fiber For the disposable hygieneproducts or breathing mask the Ag particles on surface offiber show rapid and efficient antimicrobial activity
35 EDS Analysis EDS test is used to characterize elementchange on the surface of PAN nanofiber and prove thereaction between AgHBP solution and PAN nanofibersindirectly as shown in Figure 6The results show that carbon
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
6 Journal of Nanomaterials
CH2 CH2 CH2CH2 CH2 CH2 CH2CH2
CN CN CNCNn n
H2N H2N
H2N
H2N
H2N
H2N
Heating
Hydrogen bonds
NH2
NH2
NH2 NH2
NH2
NH2
+ +
AgAg
Scheme 1 Schematic diagram of bonding formation
(a) Untreated (b) Treated under 30∘C
(c) Treated under 60∘C (d) Treated under 90∘C
Figure 5 The morphology of AgHBPPAN nanofiber (concentration of silver solution is 005wt)
nitrogen oxygen and silver are the principle elements inAgHBPPAN nanofiber web The EDS analysis providesdirect evidence that the silver nanoparticles are fixed on PANnanofiber surface which is also identified by SEM images inFigure 5 As shown in Figure 6 the silver content on PANnanofiber was 245wt 841 wt and 1049wt respec-tively when the treating temperature increased from 30∘C to90∘C The increase of Ag content on PAN nanofiber plays animportant role in improving its antimicrobial activity
36 Antimicrobial Activity The antimicrobial activity of theAgHBPPAN nanofiber web is evaluated using S aureus andE coli and with cotton gauze as control sample The antimi-crobial activity of PANnanofiber HBP-treated nanofiber and
AgHBP-treated nanofiber (005wt 90∘C) is presented inTable 1
Almost the same surviving cells shown in Table 1 indicatethat PAN nanofiber shows few actions against S aureus or Ecoli The PAN nanofiber web treated with HBP aqueous solu-tion shows antibacterial activity and the bacterial reductionrates against S aureus and E coli are about 89 The reasonmay be ascribed to the abundant amino groups on the PANnanofiber which tend to deteriorate the cell membranes ofbacteria and induce leakage of intracellular components frombacterial cells thereby inhibiting their effective growth [29]After treatment with silver nanoparticles the AgHBPPANnanofiber web exhibits excellent antibacterial activity andthe bacterial reduction rates against S aureus and E coliboth reached 999 which may be due to the cooperative
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 7
00
11
22
32
43
54KC
nt
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
Element wt atCKNKOKPtMMatrix
6943
2481
0136
0440
Correction
7203
2642
0121
0034
ZAF
PtON
C
(a) Untreated
Element wt atCKNKOKPtMAgLMatrix Correction ZAF
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
6870
1724
0464
0245
0397
7924
1756
0247
0035
0038
00
09
18
28
37
46
KCnt
PtO
N
C
Ag
(b) Treated under 30∘C
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
KCnt
00
12
25
37
49
61 Element wt atCKNKOKPtM
Matrix
6592
1801
0322
0444
Correction
7756
1817
0285
0032
AgL 0841 0110
ZAF
PtO
N
C
Ag
(c) Treated under 60∘C
Element wt atCKNKOKPtM
Matrix
6338
1857
0379
0377
Correction
7586
1906
0340
0028
AgL 1049 0140
ZAF100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
Energy (keV)
00
11
23
34
46
57
KCnt
PtO
C
N Ag
(d) Treated under 90∘C
Figure 6 EDS of AgHBPPAN nanofibers (concentration of silver solution is 005wt)
Table 1 Antimicrobial activity of AgHBPPAN nanofiber web
Antimicrobial activitySamples S aureus E coli
Surviving cells (CFUmL) reduction Surviving cells (CFUmL) reductionCotton gauze 161 times 106 656 times 106
PAN nanofiber 154 times 106 0 632 times 106 0HBP-treated nanofiber 176 times 105 8857 671 times 105 8938AgHBP-treated nanofiber 148 times 103 9990 233 times 103 9996
antimicrobial activity from the amino groups in HBP and Agnanoparticles on PAN nanofibers
37 Filtration Property Figure 7 shows the filtration effi-ciency of different filters A lower face velocity was chosenin this paper because the filter we prepared may be usedas a mask (534 cms) The dates in Figure 7 show that thefiltration efficiency of cotton gauze differs enormously fromnanofiber web for removing smaller particles (particle sizelower than 07 120583m) a clear U glyph filtration efficiency curve
of cotton gauze is observed the filtration efficiency of cottongauze is lower than 80 when the particle size is smallerthan 07 120583m and the particles about 04 120583m are the mostdifficult to filter out for common filter such as gauze mask(filtration efficiency 361) however the filtration efficiencyof AgHBPPAN nanofiber web easily reached 999 Theexcellent filtration efficiency of nanofiber web is mainly dueto the ultrafine fiber (about 180 nm) small pore diameter(less than 1 120583m) high porosity (864) and BET (253m2g)(shown in Table 2) The thickness of nanofiber web was
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
8 Journal of Nanomaterials
Table 2 Characterization of nanofiber web
Samples Spinning time (min) Thickness (120583m) Fiber diameter (nm) BET (m2g) Porosity ()PAN 20 885 1764 plusmn 425 267 859AgHBPPAN-1 20 812 1881 plusmn 316 253 864AgHBPPAN-2 40 1539 1817 plusmn 269 244 848AgHBPPAN-3 60 2306 1844 plusmn 303 257 855
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauze
0
10
20
30
40
50
60
70
80
90
100
110
Effici
ency
()
Cotton gauze + PANCotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 7 Filtration efficiency of filters
controlled by spinning time in our experiment which almosthas no effects on its filtration efficiency
The pressure drop of the filters is shown in Figure 8Clearly higher pressure drop is observed for AgHBPPANnanofiber web We know that small pore diameter highporosity and thickness will improve the filtration efficiency offilters However the factors mentioned above are also the keyreasons for increasing the pressure drop Therefore smallerthickness of nanofiber web is necessary for decreasing thepressure dropwhen itsmechanical property is enough duringuse The pressure drop of AgHBPPAN nanofiber web isa little higher than the PAN nanofiber web which may beattributed to the pore change in nanofiber web during theprocess of Ag-containing treatment
4 Conclusions
The amino-terminated hyperbranched polymer (HBP) wassynthesized in this paper at first then the HBP was usedas reductant and stabilizer to prepare AgHBP aqueoussolutionThe silver nanoparticles were prepared with a meandiameter of about 10 nm and they have an outstandingdisperse ability and stability in aqueous solutionTheuniformPAN nanofiber web was prepared by electrospinning andtreated with AgHBP solution under water bath The SEM
Pres
sure
dro
p (P
a)
01 02 03 04 05 06 07 08
Size (120583m)
Cotton gauzeCotton gauze + PAN
800
700
600
500
400
300
200
100
0
Cotton gauze +Cotton gauze +Cotton gauze +
AgHBPPAN-1AgHBPPAN-2AgHBPPAN-3
Figure 8 Pressure drop of filters
and EDS showed that it was difficult for silver nanoparticlesto be fixed on the surface of PAN nanofiber under lowtemperature (30∘C) and the content of silver nanoparticleson PAN nanofiber increased from 245wt to 1084wtwhen temperature rose to 90∘C The antibacterial activityand the bacterial reduction rates of S aureus and E coliof HBP-treated PAN nanofiber are about 89 however theAgHBPPANnanofiber showed better antibacterial propertyand it had 999 bacterial reduction of Staphylococcus aureusand 9996 bacterial reduction of Escherichia coli respec-tively which may be due to the cooperative effects from theamino groups in HBP and Ag nanoparticles The filtrationefficiency of cotton gauze differs enormously from nanofiberweb for removing smaller particles (particle size lower than07 120583m) a clear U glyph filtration efficiency curve of cottongauze was observed and the filtration efficiency of gauzemask (14 layers) was lower than 80 and as low as 361 forthe particles of 04 120583m however the filtration efficiency ofPAN nanofiber web easily reached 999 Compared to lowerpressure drop of gauze mask (about 20 Pa) a further cut inpressure drop of Ag-containing nanofiber web is the primarymission in our future work
Competing Interests
The authors declare that there are no competing interests
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 9
Acknowledgments
This work was supported by Liaoning Provincial Key Labora-tory of Functional TextileMaterials National Natural ScienceFund (51503105 and 51343002) College Students Innovationand Entrepreneurship Training Program in Jiangsu Province(201410304028Z) and Liaoning BaiQianWan Talents Pro-gram
References
[1] S M S Shahabadi A Kheradmand V Montazeri and HZiaee ldquoEffects of process and ambient parameters on diameterand morphology of electrospun polyacrylonitrile nanofibersrdquoPolymer Science Series A vol 57 no 2 pp 155ndash167 2015
[2] M Yanilmaz and X-W Zhang ldquoPolymethylmethacrylatepoly-acrylonitrile membranes via centrifugal spinning as separatorin Li-ion batteriesrdquo Polymers vol 7 no 4 pp 629ndash643 2015
[3] M A Al-Omair ldquoSynthesis of antibacterial silver-poly(120576-capro-lactone)-methacrylic acid graft copolymer nanofibers and theirevaluation as potential wound dressingrdquo Polymers vol 7 no 8pp 1464ndash1475 2015
[4] J-J Xu B-H Xu D Shou X-J Xia and Y Hu ldquoPreparationand evaluation of vancomycin-loaded N-trimethyl chitosannanoparticlesrdquo Polymers vol 7 no 9 pp 1850ndash1870 2015
[5] V Mottaghitalab and A K Haghi ldquoA study on electrospinningof polyacrylonitrile nanofibersrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 114ndash118 2011
[6] D-G Yu X-Y Li X Wang J-H Yang S W Annie Blighand G R Williams ldquoNanofibers fabricated using triaxial elec-trospinning as zero order drug delivery systemsrdquo ACS AppliedMaterials amp Interfaces vol 7 no 33 pp 18891ndash18897 2015
[7] D-G Yu C Yang M Jin et al ldquoMedicated Janus fibers fab-ricated using a Teflon-coated side-by-side spinneretrdquo Colloidsand Surfaces B Biointerfaces vol 138 pp 110ndash116 2016
[8] D-G Yu K White N Chatterton Y Li L Li and X WangldquoStructural lipid nanoparticles self-assembled from electrospuncore-shell polymeric nanocompositesrdquoRSCAdvances vol 5 no13 pp 9462ndash9466 2015
[9] I Heidari M M Mashhadi and G Faraji ldquoA novel approachfor preparation of aligned electrospun polyacrylonitrile nano-fibersrdquo Chemical Physics Letters vol 590 pp 231ndash234 2013
[10] L W Ji A J Medford and X-W Zhang ldquoEffects of processand ambient parameters on diameter and morphology ofelectrospun polyacrylonitrile nanofibersrdquo Polymer vol 50 no2 pp 605ndash612 2009
[11] R Nirmala K Jeon R Navamathavan B-S Kim M-S Khiland H Y Kim ldquoFabrication and characterization of II-VI semi-conductor nanoparticles decorated electrospun polyacryloni-trile nanofibersrdquo Journal of Colloid and Interface Science vol397 pp 65ndash72 2013
[12] Y Tong X-F Lu W-N Sun G Nie L Yang and C WangldquoElectrospun polyacrylonitrile nanofibers supported AgPdnanoparticles for hydrogen generation from the hydrolysis ofammonia boranerdquo Journal of Power Sources vol 261 pp 221ndash226 2014
[13] K Yoon K Kim X Wang D Fang B S Hsiao and B ChuldquoHigh flux ultrafiltration membranes based on electrospunnanofibrous PAN scaffolds and chitosan coatingrdquo Polymer vol47 no 7 pp 2434ndash2441 2006
[14] Y-Z Shi Y-J Li J-F Zhang Z Yu and D Yang ldquoElectrospunpolyacrylonitrile nanofibers loaded with silver nanoparticles bysilvermirror reactionrdquoMaterials Science and Engineering C vol51 pp 346ndash355 2015
[15] C Q Zhang Q B Yang N Q Zhan et al ldquoSilver nanoparticlesgrown on the surface of PAN nanofiber preparation charac-terization and catalytic performancerdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 362 no 1ndash3 pp58ndash64 2010
[16] D-Y Lee K-H Lee B-Y Kim and N-I Cho ldquoSilver nanopar-ticles dispersed in electrospun polyacrylonitrile nanofibers viachemical reductionrdquo Journal of Sol-Gel Science and Technologyvol 54 no 1 pp 63ndash68 2010
[17] J Bai Q B Yang S Wang and Y Li ldquoPreparation andcharacterization of electrospun Agpolyacrylonitrile compositenanofibersrdquoKorean Journal of Chemical Engineering vol 28 no8 pp 1761ndash1763 2011
[18] M A Kudryashov A I Mashin A S Tyurin A E FedosovG Chidichimo and G de Filpo ldquoMorphology of a silverpoly-acrylonitrile nanocompositerdquo Technical Physics vol 56 no 1pp 92ndash96 2011
[19] G Panthi S-J Park T W Kim et al ldquoElectrospun compositenanofibers of polyacrylonitrile and Ag
2CO3nanoparticles for
visible light photocatalysis and antibacterial applicationsrdquo Jour-nal of Materials Science vol 50 no 13 pp 4477ndash4485 2015
[20] Q Shi N Vitchuli J Nowak et al ldquoDurable antibacterialAgpolyacrylonitrile (AgPAN) hybrid nanofibers prepared byatmospheric plasma treatment and electrospinningrdquo EuropeanPolymer Journal vol 47 no 7 pp 1402ndash1409 2011
[21] A Mahapatra N Garg B P Nayak B G Mishra and G HotaldquoStudies on the synthesis of electrospun PAN-Ag compositenanofibers for antibacterial applicationrdquo Journal of AppliedPolymer Science vol 124 no 2 pp 1178ndash1185 2012
[22] D-G Yu C J Branford-White N P Chatterton et al ldquoElectro-spinning of concentrated polymer solutionsrdquo Macromoleculesvol 43 no 24 pp 10743ndash10746 2010
[23] A Tyurin G de Filpo D Cupelli F P Nicoletta AMashin andG Chidichimo ldquoParticle size tuning in silver-polyacrylonitrilenanocompositesrdquo Express Polymer Letters vol 4 no 2 pp 71ndash78 2010
[24] I Karbownik O Rac M Fiedot P Suchorska-Wozniak and HTeterycz ldquoIn situ preparation of silverndashpolyacrylonitrile nano-composite fibresrdquo European Polymer Journal vol 69 pp 385ndash395 2015
[25] M A Kudryashov A I Mashin A S Tyurin G Chidichimoand G De Filpo ldquoMetal-polymer composite films basedon polyacrylonitrile and silver nanoparticles preparation andpropertiesrdquo Journal of Surface Investigation vol 4 no 3 pp 437ndash441 2010
[26] H Dodiuk-Kenig K Lizenboim S Roth et al ldquoPerfor-mance enhancement of dental composites using electrospunnanofibersrdquo Journal of Nanomaterials vol 2008 Article ID840254 6 pages 2008
[27] W-W Zhang D-S Zhang Y-Y Chen and H Lin ldquoHyper-branched polymer functional TiO
2nanoparticles synthesis and
its application for the anti-UVfinishing of silk fabricrdquoFibers andPolymers vol 16 no 3 pp 503ndash509 2015
[28] F Zhang and L R Yao ldquoPreparation of nano-silver solutionrdquoChina Patent ZL 2010101663583 2011
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
10 Journal of Nanomaterials
[29] G Zhang Y Liu H Morikawa and Y Chen ldquoApplicationof ZnO nanoparticles to enhance the antimicrobial activityand ultraviolet protective property of bamboo pulp fabricrdquoCellulose vol 20 no 4 pp 1877ndash1884 2013
[30] E S Abdel-Halim and S S Al-Deyab ldquoUtilization of hydrox-ypropyl cellulose for green and efficient synthesis of silvernanoparticlesrdquo Carbohydrate Polymers vol 86 no 4 pp 1615ndash1622 2011
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials