6
Research Article Synthesis of Silver Abietate as an Antibacterial Agent for Textile Applications A. YJldJz and M. DeLirmencioLlu Namık Kemal University, Corlu Engineering Faculty, 59860 Tekirda˘ g, Turkey Correspondence should be addressed to A. Yıldız; aylinfi[email protected] Received 17 December 2014; Revised 13 February 2015; Accepted 17 February 2015 Academic Editor: Viktor Brabec Copyright © 2015 A. Yıldız and M. De˘ girmencio˘ glu. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. is study explored the potential use of new silver abietate obtained from abietic acid as an antibacterial agent for textile applications. Synthesis, structure, and antibacterial studies of silver abietate compound are reported. Silver complex was obtained reacting abietic acid with silver. e new compounds were characterized by 1 H NMR, 13 C NMR, DEPT, IR, UV, and ESI-MS techniques which support the proposed structures. e new Ag abietate complex has no environmental hazard, its antibacterial activities were evaluated aſter being applied to cotton fabric by padding process according to the JIS L 1902-2008 agar diffusion test method and against three Gram-negative and three Gram-positive bacteria, respectively. Stability of antibacterial effect aſter repeated washings (3, 5, 10, and 20) was also tested which indicated that the synthesized silver abietate compound could be used as a new antibacterial agent in textile industry. In this way, the compound has been synthesized the first time in the literature and the applications have been investigated. 1. Introduction Abietic acid, one of the most important natural naphthenic acids, is a tricyclic diterpene. Among resin acids obtained from resins and diterpenes, the most useful acids, abietic acid (also called sylvic acid) is naturally obtained from pine resins and does not dissolve in water [1]. Several chemical sub- stances are used for antimicrobial finishing on textiles, and finishing with metal and metal salt has an important weight among these substances. Since even low concentrations of many heavy metals are toxic for microorganisms, various metals such as copper, zinc, and cobalt have been used as an antimicrobial agent in textile industry. However, the metal most widely used for this purpose has been silver, especially in wound dresses as it has a strong antimicrobial impact, low toxicity, and little risk against bacterial resistance [28]. Silver ion is known to have been used since ancient times, and its impact on more than 650 pathogen microorganisms was proved in clinical experiments [9]. Silver is used in many fields of textile industry including production processes and several finished products, owing to its electrical and heat conductivity and optical reflection and antimicrobial properties [10]. Different forms of silver products used in previous studies include metallic silver [11], silver chloride [12, 13], silver zeolite [14], silver dendrimer and composites [15], polymer-silver nanoparticles [16, 17], silver nanoparticles [1820], PU coated silver nanoparticles [21], and Ag/TiO 2 composite nanopowders [22]. Antimicrobial fabrics are not visually different from common textile prod- ucts and are produced by adding some hygienic properties. Antimicrobial fabrics are widely used in daily life for different needs and in different places ranging from hospitals, hotels, and restaurants to baby clothes and sports clothes. Microorganisms living in textile products may damage both the product and the user. Antimicrobial textile products help to minimize or eliminate negative impacts of microorganisms by preventing the growth of infecting microorganisms as well as microorganism-induced bad smell, staining, color change, and quality loss [23]. Recently, numerous studies have been conducted to seek antibacterial agents [2426]. is study aimed at producing, with high yield, synthesized silver abietate (abietic acid Hindawi Publishing Corporation Bioinorganic Chemistry and Applications Volume 2015, Article ID 215354, 5 pages http://dx.doi.org/10.1155/2015/215354

Research Article Synthesis of Silver Abietate as an ...downloads.hindawi.com/journals/bca/2015/215354.pdfreacted with silver) so as to be used as an antibacterial agent for textile

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Research ArticleSynthesis of Silver Abietate as an Antibacterial Agent forTextile Applications

A YJldJz and M DeLirmencioLlu

Namık Kemal University Corlu Engineering Faculty 59860 Tekirdag Turkey

Correspondence should be addressed to A Yıldız aylinfirincihotmailcom

Received 17 December 2014 Revised 13 February 2015 Accepted 17 February 2015

Academic Editor Viktor Brabec

Copyright copy 2015 A Yıldız and M Degirmencioglu This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

This study explored the potential use of new silver abietate obtained fromabietic acid as an antibacterial agent for textile applicationsSynthesis structure and antibacterial studies of silver abietate compound are reported Silver complex was obtained reactingabietic acid with silver The new compounds were characterized by 1H NMR 13C NMR DEPT IR UV and ESI-MS techniqueswhich support the proposed structures The new Ag abietate complex has no environmental hazard its antibacterial activities wereevaluated after being applied to cotton fabric by padding process according to the JIS L 1902-2008 agar diffusion test method andagainst three Gram-negative and three Gram-positive bacteria respectively Stability of antibacterial effect after repeated washings(3 5 10 and 20) was also tested which indicated that the synthesized silver abietate compound could be used as a new antibacterialagent in textile industry In this way the compound has been synthesized the first time in the literature and the applications havebeen investigated

1 Introduction

Abietic acid one of the most important natural naphthenicacids is a tricyclic diterpene Among resin acids obtainedfrom resins and diterpenes themost useful acids abietic acid(also called sylvic acid) is naturally obtained from pine resinsand does not dissolve in water [1] Several chemical sub-stances are used for antimicrobial finishing on textiles andfinishing with metal and metal salt has an important weightamong these substances Since even low concentrations ofmany heavy metals are toxic for microorganisms variousmetals such as copper zinc and cobalt have been used asan antimicrobial agent in textile industry However the metalmost widely used for this purpose has been silver especiallyin wound dresses as it has a strong antimicrobial impactlow toxicity and little risk against bacterial resistance [2ndash8]Silver ion is known to have been used since ancient timesand its impact on more than 650 pathogen microorganismswas proved in clinical experiments [9]

Silver is used in many fields of textile industry includingproduction processes and several finished products owing

to its electrical and heat conductivity and optical reflectionand antimicrobial properties [10] Different forms of silverproducts used in previous studies include metallic silver [11]silver chloride [12 13] silver zeolite [14] silver dendrimer andcomposites [15] polymer-silver nanoparticles [16 17] silvernanoparticles [18ndash20] PU coated silver nanoparticles [21]and AgTiO

2composite nanopowders [22] Antimicrobial

fabrics are not visually different from common textile prod-ucts and are produced by adding some hygienic properties

Antimicrobial fabrics are widely used in daily life fordifferent needs and in different places ranging from hospitalshotels and restaurants to baby clothes and sports clothesMicroorganisms living in textile products may damage boththe product and the user Antimicrobial textile products helptominimize or eliminate negative impacts ofmicroorganismsby preventing the growth of infectingmicroorganisms as wellas microorganism-induced bad smell staining color changeand quality loss [23]

Recently numerous studies have been conducted to seekantibacterial agents [24ndash26] This study aimed at producingwith high yield synthesized silver abietate (abietic acid

Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2015 Article ID 215354 5 pageshttpdxdoiorg1011552015215354

2 Bioinorganic Chemistry and Applications

R (CH3)2CH

CH3 CH3

2RCOOH + 2NaOH + Ag(NO3)2 Ag(RCOO)2 + 2NaNO3 + 2H2O

R abietate

997888rarr

Scheme 1

reacted with silver) so as to be used as an antibacterialagent for textile applications Antibacterial activities of thiscompoundwere evaluated after being applied to cotton fabricby padding process [27]

2 Experimental

Cotton woven fabric was supplied from Denge Chem-istry Co Ltd (Turkey) For synthesis reactions silvernitrate (Tekkim) abietic acid (Sigma Aldrich) diethyl ether(Tekkim) and NaOH (Merck) were used

IR spectra were taken by using a KBr table with ShimatsuIR-470 Infrared Spectrophotometer NMR spectra were donein DMSO on a Varian Unity Inova (Varian Palo Alto CAUSA) 500MHz for 1H NMR 13C NMR and DEPT ESI-MS was measured onThermo Finnigan LCQAdvantageMaxLCMSMS apparatus (Basel Switzerland) UV-Vis spectra ofthe complexes were recorded at 25∘C in aqueous solution onan Agilant 4583 diode array spectrometer

21 Synthesis of Agent In this study the potential use ofabietate known as saturated hydrocarbons was explored asan antibacterial agent in the textile industry by followingthe two main steps of (1) synthesis and characterization ofantibacterial agent and (2) use of synthesized antibacterialagent in textile applications Silver abietate compound (thenaphthenate silver complex)withwhite colorwas synthesizedfrom the reaction of abietic acid with silver saltThe synthesisreaction of silver abietate compound is shown in Scheme 1

To carry out the reaction abietic acid was first dissolvedin the organic solvent acids and sodium salts were composedby adding caustic soda Then silver abietate was obtained byadding silver nitrateThe synthesis of the agent was describedbelow

Thermometer condenser and dropping funnel wereplaced at the necks of a three-necked flask Abietic acidsolution in 10 (v) diethyl ether calculated stoichiometricallywas put into the flask and 10 (v) NaOH solution was putinto the dropping funnel The temperature was raised to40ndash45∘C by running a magnetic stirrer and the solutionwas stirred while dropping NaOH from dropping funnel for60min Medium pH was adjusted between 7 and 8 Thecalculated amount of 10 (v) Ag(NO

3)2solution was added

to themixtureThe heater was turned on the dropping funnelwas opened and the mixture was stirred by running anelectromagnetic stirrer (Hot-Plate 300∘C 15 cm circular M15type) at room temperature for 1 h and then this solutionwas held for 24 h The solution obtained was put into

Table 1 Inhibition zone diameters (mm) of synthesized silver abi-etate against Gram-positive and Gram negative bacteria measuredon cotton fabric before washing and after 3 5 10 and 20 washings

Bacteria mdash 3rd 5th 10th 20thB subtilis 4 4 4 4 3S aureus 3 3 3 2 2E faecalis 2 2 2 1 05K pneumoniae 4 4 4 4 3E coli 3 3 3 2 1P aeruginosa 4 4 4 4 3

the extraction flask and liquid phase was separated from theorganic phase After the removal of solvent from the organicphase silver abietate compound was obtained

After the agent was synthesized the chemical structurewas analyzed with by spectroscopic techniques such as 1HNMR 13C NMR DEPT IR UV and ESI-MS

22 Use of Synthesized Antibacterial Agent in Textile Appli-cations After the synthesis of silver abietate was completedthe compound containing 40 gL silver abietate 1 gL dis-persing agent (Denpol HT-DengeKimya) 1 gL wetting agent(Denwet PB 100-Denge Kimya) and acetic acid (for adjustingpH to 5) was prepared by stirring at 40ndash45∘C for 10ndash15minin an ultrasonic bath (Baysonic) Application recipe wasdetermined by taking the pretest results into considerationCotton fabrics were impregnated with these liquors and driedwith a tenter frame dryer at 85∘C for 4min

Antibacterial tests were applied to the fabrics beforewashing and after 3 5 10 and 20 washings according tothe JIS L 1902-2008 protocol Test and control specimens(nonsterile) were cut into the recommended dimensionsof 25 times 50mm and sterilized by autoclaving (at 120∘C for15min) Inoculumwas prepared as followsThe bacteria wereincubated for 24 h at 37 plusmn 2∘C in nutrient broth (NB) 10 plusmn01mL from the inoculum with 1 times 107 cellsmL was addedto 15mL of nutrient agar (NA) warmed at 45-46∘C Thissolution was disposed in a sterilized Petri dish After agarsolidification the sterilized textile samples were placed overthe agar and incubated for 24 h at 37 plusmn 2∘C

Escherichia coli (ATCC25922) Klebsiella pneumoniae(ATCC13883) and Pseudomonas aeruginosa (ATCC27853)as Gram-negative bacteria and Staphylococcus aureus(ATCC29213) Bacillus subtilis (NRRL NRS744) and Ente-rococcus faecalis (ATCC29212) as Gram-positive bacteriawere used The stability of antibacterial effect after repeatedwashings (3 5 10 and 20) was also tested according to BS ENISO 26330 standard at 30∘C where ECE Standard Detergentof SDC Enterprises Ltd was applied

The structure of the synthesized compound was eluci-dated by spectroscopic techniques such as 1H NMR 13CNMR DEPT IR UV and ESI-MS

The silver abietate obtainedwith78 yield as a crystallineobtained light gray powderThe IR spectrum of silver abietateshowed absorptions at 3485 (ndashOH) 1710 (gtC=O) 1399 1573(carboxylic acid salt) 1630 (ndashC=Cndash) 2876 and 2941 (ndashCH

Bioinorganic Chemistry and Applications 3

Table 2 Antibacterial activity of silver abietate applied cotton fabrics after 3ndash20 washings against six different bacteria

Bacteriatypes mdash 3st 5th 10th 20th

B subtilis

S aureus

E faecalis

Kpneumoniae

E coli

Paeruginosa

ndashCH2 and ndashCH

3) cmminus1 In the UV spectrum compound

maximum absorptions were observed at the 267 nm The1H NMR spectrum of the synthesized compound showedcharacteristic signals for a silver abietate with the signals096 (119889 119869 = 72Hz ndashCH(CH

3)) indicating the presence of

two isopropyl groups and broadened singlet with singlet at 120575531 (2H brs Hb) and 568 (2H s Ha) showing unsaturatedconjugated protons The presence of two methyl groups wasobserved at 120575H 070 with a singlet signal corresponding to sixprotons However in the 1H NMR spectrum of compound

4 Bioinorganic Chemistry and Applications

(H3C)2HC

H3C CH3

C OO Ag

OO

C

H3C C

CH(CH3)2

H3

Figure 1 Molecular structure of silver abietate antimicrobial agent

the singlet at 120575 104 was attributed to methyl protons adjacentto C=O In addition in the 1H NMR spectrum of compoundshowed a multiple centered 107ndash211 (12 ndashCH

2 10 ndashCH

protons)A detailed study on the 13C NMR and DEPT spectra

revealed 4 carbon signals due to four sp2 quaternary carbonsfour sp2 methines and two carbonyl carbons The signal at120575C 1784 for the two carbonyl carbons eight other signals ofsp2 carbons at 120575C 11431 1212 1338 and 1195 and aliphaticndashCHndashCH

2ndashCH

3carbons at 208 332 233 217 489 159

427 326 287 408 347 326 and 298 were characteristic ofa silver abietate structure

The silver abietate gave a molecular ion peak [M]+ at11989811991171031 (15) in positive ESI-MS which was consistent with amolecular formula of C

40H58O4Ag

Based on the above evidence the structure of compoundwas identified as silver abietate (Figure 1)

Antibacterial test results according to the JIS L 1902-2008 protocol standards of silver abietate compound-appliedcotton fabrics before washing and after 3 5 10 and 20washings are presented in Table 1

Results of the antibacterial test for silver abietatecompound-applied cotton woven fabrics before and afterwashings according to the JIS L 1902-2008 protocol standardsare presented in Table 2

Antibacterial activity against B subtilis K pneumoniaeand P aeruginosa was not different and was stronger sig-nificantly than the other bacteria The lowest antibacterialactivity was observed in E faecalisThe antibacterial activitiesof silver abietate (silver naphthenate) applied to the cottonfabrics in successive washings were still permanent after 20washings

3 Conclusion

After silver abietate (silver naphthenate) was synthesizedwiththe abietic acid its use as an antibacterial agent in finishingof cotton fabrics against the three Gram-negative and threeGram-positive bacteria was found to be promising Further-more the antibacterial impact was permanent even after20 successive washings After the washings silver abietatewas observed to exhibit a better antibacterial activity againstBacillus subtilis Klebsiella pneumoniae and Pseudomonasaeruginosa than the other bacteria The antibacterial activitywas strong for the three bacteria even after 20 successivewashingsThe lowest antibacterial activitywas againstEntero-coccus faecalis Although antibacterial activitywas low againstthis bacterium permanency wasmore important Test resultsconfirmed that the complex was active against the six differ-ent bacteria and was permanent after 20 successive washingsAnother advantage of the obtained antibacterial agent is that

the synthesized silver abietate as a complex compound cannotget onto the skin [28] All the above considerations togetherpoint to silver abietate as a new antibacterial agent in textileindustry Since it has been determined in this study that silverabietate is a potential antibacterial agent synthesis of low costandmore effective silver abietate has been planned for furtherwork

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was financially supported by the Research Com-mission ofNamikKemalUniversity (NKUBAP0017YL1207)

References

[1] A Yildiz T Sabudak F Mikailzade S Kazan and A FeyizogluldquoSynthesis and structural investigations of copper abietat com-plexesrdquo Asian Journal of Chemistry vol 24 no 4 pp 1719ndash17232012

[2] A Yadav V Prasad A A Kathe et al ldquoFunctional finishing incotton fabrics using zinc oxide nanoparticlesrdquo Bulletin of Mate-rials Science vol 29 no 6 pp 641ndash645 2006

[3] T Charbonneaux and S Rochat ldquoArticles with antibacterial andantifungal activityrdquo US Patent Application no 0208390 2006

[4] M S Antelman ldquoHigh performance cobalt (II III) oxide anti-microbial textile articlesrdquo US Patent no 6228491 2001

[5] T Ramachandran K Rajendrakumar and R RajendranldquoAntimicrobial textilesmdashan overviewrdquo Journal of the Institutionof Engineers (India) Part TX Textile Engineering Division vol84 no 2 pp 42ndash47 2004

[6] G Supuren A Cay E Kanat and I Tarakcioglu ldquoAntimicrobialfibresrdquo in Textile and Apparel Research pp 171 15ndash17ndash172 83ndash89 2007 (Turkish)

[7] S Palamutcu R Keskin N Devrent et al ldquoFunctional textilesII antimicrobial textilesrdquo Electronic Journal of Textile Technol-ogy vol 3 pp 95ndash108 2009

[8] M Yusuf A Ahmad M Shahid et al ldquoAssessment of colori-metric antibacterial and antifungal properties of woollen yarndyedwith the extract of the leaves of henna (Lawsonia inermis)rdquoJournal of Cleaner Production vol 27 pp 42ndash50 2012

[9] S Palamutcu M Sengul N Devrent and R Keskin ldquoThe iden-tification tests of antimicrobial activity in textile productsrdquo inProceedings of the 7thNationalMeasurement Science Conference2007

[10] L Windler M Height and B Nowack ldquoComparative evalu-ation of antimicrobials for textile applicationsrdquo EnvironmentInternational vol 53 pp 62ndash73 2013

Bioinorganic Chemistry and Applications 5

[11] S Arora J Jain JM Rajwade andKM Paknikar ldquoInteractionsof silver nanoparticles with primary mouse fibroblasts and livercellsrdquo Toxicology and Applied Pharmacology vol 236 no 3 pp310ndash318 2009

[12] O Choi K K Deng N-J Kim L Ross Jr R Y Surampalli andZ Hu ldquoThe inhibitory effects of silver nanoparticles silver ionsand silver chloride colloids on microbial growthrdquo WaterResearch vol 42 no 12 pp 3066ndash3074 2008

[13] E Matyjas-Zgondek A Bacciarelli E Rybicki M I Szynk-owska and M Kołodziejczyk ldquoAntibacterial properties ofsilver-finished textilesrdquo Fibres amp Textiles in Eastern Europe vol16 no 5 pp 101ndash107 2008

[14] MM Cowan K Z Abshire S L Houk and SM Evans ldquoAnti-microbial efficacy of a silver-zeolite matrix coating on stainlesssteelrdquo Journal of Industrial Microbiology and Biotechnology vol30 no 2 pp 102ndash106 2003

[15] L Balogh D R Swanson D A Tomalia G L Hagnauer andA T McManus ldquoDendrimer-silver complexes and nanocom-posites as antimicrobial agentsrdquo Nano Letters vol 1 no 1 pp18ndash21 2001

[16] S K Bajpai Y M Mohan M Bajpai R Tankhiwale andV Thomas ldquoSynthesis of polymer stabilized silver and goldnanostructuresrdquo Journal of Nanoscience and Nanotechnologyvol 7 no 9 pp 2994ndash3010 2007

[17] A Burkitbay B R Taussarova A Z Kutzhanova and S MRakhimova ldquoDevelopment of a polymeric composition forantimicrobial finish of cotton fabricsrdquo Fibres and Textiles inEastern Europe vol 104 no 2 pp 96ndash101 2014

[18] A IWasif and S K Laga ldquoUse of nano silver as an antimicrobialagent for cottonrdquo Autex Research Journal vol 9 no 1 pp 5ndash132009

[19] N Duran P D Marcato G I H de Souza O L Alves and EEsposito ldquoAntibacterial effect of silver nanoparticles producedby fungal process on textile fabrics and their effluent treatmentrdquoJournal of Biomedical Nanotechnology vol 3 no 2 pp 203ndash2082007

[20] Z Foltynowicz D Gwiazdowska D Rodewald A Nowaczykand M Filipiak ldquoAntimicrobial properties of socks protectedwith silver nanoparticlesrdquo Fibres and Textiles in Eastern Europevol 21 no 5 pp 91ndash96 2013

[21] P Jain and T Pradeep ldquoPotential of silver nanoparticle-coatedpolyurethane foam as an antibacterial water filterrdquo Biotechnol-ogy and Bioengineering vol 90 no 1 pp 59ndash63 2005

[22] M-K Yeo and M Kang ldquoEffects of nanometer sized silvermaterials on biological toxicity during zebrafish embryogene-sisrdquo Bulletin of the Korean Chemical Society vol 29 no 6 pp1179ndash1184 2008

[23] A Yildiz M Oztas A O Agirgan and D GulenThe Synthesisof Silver Carboxylate and the Investigations of AntibacterialActivity in Textiles NKUBAP0017YL1207 2013 (Turkish)

[24] M I Khan A Ahmad S A Khan et al ldquoAssessment of anti-microbial activity of Catechu and its dyed substraterdquo Journal ofCleaner Production vol 19 no 12 pp 1385ndash1394 2011

[25] H E Emam A P Manian B Siroka et al ldquoTreatments toimpart antimicrobial activity to clothing and household cellu-losic-textilesmdashwhy lsquonanorsquo-silverrdquo Journal of Cleaner Produc-tion vol 39 pp 17ndash23 2013

[26] A Yildiz R AtavM Oztas et al ldquoInvestigating the usage possi-bility of metal mono carboxylates (metal naphthenates) as anti-bacterial agent in textile applicationsrdquo Industria Textila vol 65no 3 pp 140ndash144 2014

[27] M Degirmencioglu Waste recycling textıle fınıshıng obtaınedby the use of metal naphthenates [MS thesis] Namik KemalUniversity Institute of Natural and Applied Sciences 2013(Turkish)

[28] A Yildiz R Atav A O Agırgan and Z Kanat Evrim ldquoInves-tigation of the usage possibility of copper cyclohexane mono-carboxylate (copper naphthenate) as a textile dyerdquo IndustriaTextila vol 63 no 3 pp 144ndash150 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

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Carbohydrate Chemistry

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

2 Bioinorganic Chemistry and Applications

R (CH3)2CH

CH3 CH3

2RCOOH + 2NaOH + Ag(NO3)2 Ag(RCOO)2 + 2NaNO3 + 2H2O

R abietate

997888rarr

Scheme 1

reacted with silver) so as to be used as an antibacterialagent for textile applications Antibacterial activities of thiscompoundwere evaluated after being applied to cotton fabricby padding process [27]

2 Experimental

Cotton woven fabric was supplied from Denge Chem-istry Co Ltd (Turkey) For synthesis reactions silvernitrate (Tekkim) abietic acid (Sigma Aldrich) diethyl ether(Tekkim) and NaOH (Merck) were used

IR spectra were taken by using a KBr table with ShimatsuIR-470 Infrared Spectrophotometer NMR spectra were donein DMSO on a Varian Unity Inova (Varian Palo Alto CAUSA) 500MHz for 1H NMR 13C NMR and DEPT ESI-MS was measured onThermo Finnigan LCQAdvantageMaxLCMSMS apparatus (Basel Switzerland) UV-Vis spectra ofthe complexes were recorded at 25∘C in aqueous solution onan Agilant 4583 diode array spectrometer

21 Synthesis of Agent In this study the potential use ofabietate known as saturated hydrocarbons was explored asan antibacterial agent in the textile industry by followingthe two main steps of (1) synthesis and characterization ofantibacterial agent and (2) use of synthesized antibacterialagent in textile applications Silver abietate compound (thenaphthenate silver complex)withwhite colorwas synthesizedfrom the reaction of abietic acid with silver saltThe synthesisreaction of silver abietate compound is shown in Scheme 1

To carry out the reaction abietic acid was first dissolvedin the organic solvent acids and sodium salts were composedby adding caustic soda Then silver abietate was obtained byadding silver nitrateThe synthesis of the agent was describedbelow

Thermometer condenser and dropping funnel wereplaced at the necks of a three-necked flask Abietic acidsolution in 10 (v) diethyl ether calculated stoichiometricallywas put into the flask and 10 (v) NaOH solution was putinto the dropping funnel The temperature was raised to40ndash45∘C by running a magnetic stirrer and the solutionwas stirred while dropping NaOH from dropping funnel for60min Medium pH was adjusted between 7 and 8 Thecalculated amount of 10 (v) Ag(NO

3)2solution was added

to themixtureThe heater was turned on the dropping funnelwas opened and the mixture was stirred by running anelectromagnetic stirrer (Hot-Plate 300∘C 15 cm circular M15type) at room temperature for 1 h and then this solutionwas held for 24 h The solution obtained was put into

Table 1 Inhibition zone diameters (mm) of synthesized silver abi-etate against Gram-positive and Gram negative bacteria measuredon cotton fabric before washing and after 3 5 10 and 20 washings

Bacteria mdash 3rd 5th 10th 20thB subtilis 4 4 4 4 3S aureus 3 3 3 2 2E faecalis 2 2 2 1 05K pneumoniae 4 4 4 4 3E coli 3 3 3 2 1P aeruginosa 4 4 4 4 3

the extraction flask and liquid phase was separated from theorganic phase After the removal of solvent from the organicphase silver abietate compound was obtained

After the agent was synthesized the chemical structurewas analyzed with by spectroscopic techniques such as 1HNMR 13C NMR DEPT IR UV and ESI-MS

22 Use of Synthesized Antibacterial Agent in Textile Appli-cations After the synthesis of silver abietate was completedthe compound containing 40 gL silver abietate 1 gL dis-persing agent (Denpol HT-DengeKimya) 1 gL wetting agent(Denwet PB 100-Denge Kimya) and acetic acid (for adjustingpH to 5) was prepared by stirring at 40ndash45∘C for 10ndash15minin an ultrasonic bath (Baysonic) Application recipe wasdetermined by taking the pretest results into considerationCotton fabrics were impregnated with these liquors and driedwith a tenter frame dryer at 85∘C for 4min

Antibacterial tests were applied to the fabrics beforewashing and after 3 5 10 and 20 washings according tothe JIS L 1902-2008 protocol Test and control specimens(nonsterile) were cut into the recommended dimensionsof 25 times 50mm and sterilized by autoclaving (at 120∘C for15min) Inoculumwas prepared as followsThe bacteria wereincubated for 24 h at 37 plusmn 2∘C in nutrient broth (NB) 10 plusmn01mL from the inoculum with 1 times 107 cellsmL was addedto 15mL of nutrient agar (NA) warmed at 45-46∘C Thissolution was disposed in a sterilized Petri dish After agarsolidification the sterilized textile samples were placed overthe agar and incubated for 24 h at 37 plusmn 2∘C

Escherichia coli (ATCC25922) Klebsiella pneumoniae(ATCC13883) and Pseudomonas aeruginosa (ATCC27853)as Gram-negative bacteria and Staphylococcus aureus(ATCC29213) Bacillus subtilis (NRRL NRS744) and Ente-rococcus faecalis (ATCC29212) as Gram-positive bacteriawere used The stability of antibacterial effect after repeatedwashings (3 5 10 and 20) was also tested according to BS ENISO 26330 standard at 30∘C where ECE Standard Detergentof SDC Enterprises Ltd was applied

The structure of the synthesized compound was eluci-dated by spectroscopic techniques such as 1H NMR 13CNMR DEPT IR UV and ESI-MS

The silver abietate obtainedwith78 yield as a crystallineobtained light gray powderThe IR spectrum of silver abietateshowed absorptions at 3485 (ndashOH) 1710 (gtC=O) 1399 1573(carboxylic acid salt) 1630 (ndashC=Cndash) 2876 and 2941 (ndashCH

Bioinorganic Chemistry and Applications 3

Table 2 Antibacterial activity of silver abietate applied cotton fabrics after 3ndash20 washings against six different bacteria

Bacteriatypes mdash 3st 5th 10th 20th

B subtilis

S aureus

E faecalis

Kpneumoniae

E coli

Paeruginosa

ndashCH2 and ndashCH

3) cmminus1 In the UV spectrum compound

maximum absorptions were observed at the 267 nm The1H NMR spectrum of the synthesized compound showedcharacteristic signals for a silver abietate with the signals096 (119889 119869 = 72Hz ndashCH(CH

3)) indicating the presence of

two isopropyl groups and broadened singlet with singlet at 120575531 (2H brs Hb) and 568 (2H s Ha) showing unsaturatedconjugated protons The presence of two methyl groups wasobserved at 120575H 070 with a singlet signal corresponding to sixprotons However in the 1H NMR spectrum of compound

4 Bioinorganic Chemistry and Applications

(H3C)2HC

H3C CH3

C OO Ag

OO

C

H3C C

CH(CH3)2

H3

Figure 1 Molecular structure of silver abietate antimicrobial agent

the singlet at 120575 104 was attributed to methyl protons adjacentto C=O In addition in the 1H NMR spectrum of compoundshowed a multiple centered 107ndash211 (12 ndashCH

2 10 ndashCH

protons)A detailed study on the 13C NMR and DEPT spectra

revealed 4 carbon signals due to four sp2 quaternary carbonsfour sp2 methines and two carbonyl carbons The signal at120575C 1784 for the two carbonyl carbons eight other signals ofsp2 carbons at 120575C 11431 1212 1338 and 1195 and aliphaticndashCHndashCH

2ndashCH

3carbons at 208 332 233 217 489 159

427 326 287 408 347 326 and 298 were characteristic ofa silver abietate structure

The silver abietate gave a molecular ion peak [M]+ at11989811991171031 (15) in positive ESI-MS which was consistent with amolecular formula of C

40H58O4Ag

Based on the above evidence the structure of compoundwas identified as silver abietate (Figure 1)

Antibacterial test results according to the JIS L 1902-2008 protocol standards of silver abietate compound-appliedcotton fabrics before washing and after 3 5 10 and 20washings are presented in Table 1

Results of the antibacterial test for silver abietatecompound-applied cotton woven fabrics before and afterwashings according to the JIS L 1902-2008 protocol standardsare presented in Table 2

Antibacterial activity against B subtilis K pneumoniaeand P aeruginosa was not different and was stronger sig-nificantly than the other bacteria The lowest antibacterialactivity was observed in E faecalisThe antibacterial activitiesof silver abietate (silver naphthenate) applied to the cottonfabrics in successive washings were still permanent after 20washings

3 Conclusion

After silver abietate (silver naphthenate) was synthesizedwiththe abietic acid its use as an antibacterial agent in finishingof cotton fabrics against the three Gram-negative and threeGram-positive bacteria was found to be promising Further-more the antibacterial impact was permanent even after20 successive washings After the washings silver abietatewas observed to exhibit a better antibacterial activity againstBacillus subtilis Klebsiella pneumoniae and Pseudomonasaeruginosa than the other bacteria The antibacterial activitywas strong for the three bacteria even after 20 successivewashingsThe lowest antibacterial activitywas againstEntero-coccus faecalis Although antibacterial activitywas low againstthis bacterium permanency wasmore important Test resultsconfirmed that the complex was active against the six differ-ent bacteria and was permanent after 20 successive washingsAnother advantage of the obtained antibacterial agent is that

the synthesized silver abietate as a complex compound cannotget onto the skin [28] All the above considerations togetherpoint to silver abietate as a new antibacterial agent in textileindustry Since it has been determined in this study that silverabietate is a potential antibacterial agent synthesis of low costandmore effective silver abietate has been planned for furtherwork

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was financially supported by the Research Com-mission ofNamikKemalUniversity (NKUBAP0017YL1207)

References

[1] A Yildiz T Sabudak F Mikailzade S Kazan and A FeyizogluldquoSynthesis and structural investigations of copper abietat com-plexesrdquo Asian Journal of Chemistry vol 24 no 4 pp 1719ndash17232012

[2] A Yadav V Prasad A A Kathe et al ldquoFunctional finishing incotton fabrics using zinc oxide nanoparticlesrdquo Bulletin of Mate-rials Science vol 29 no 6 pp 641ndash645 2006

[3] T Charbonneaux and S Rochat ldquoArticles with antibacterial andantifungal activityrdquo US Patent Application no 0208390 2006

[4] M S Antelman ldquoHigh performance cobalt (II III) oxide anti-microbial textile articlesrdquo US Patent no 6228491 2001

[5] T Ramachandran K Rajendrakumar and R RajendranldquoAntimicrobial textilesmdashan overviewrdquo Journal of the Institutionof Engineers (India) Part TX Textile Engineering Division vol84 no 2 pp 42ndash47 2004

[6] G Supuren A Cay E Kanat and I Tarakcioglu ldquoAntimicrobialfibresrdquo in Textile and Apparel Research pp 171 15ndash17ndash172 83ndash89 2007 (Turkish)

[7] S Palamutcu R Keskin N Devrent et al ldquoFunctional textilesII antimicrobial textilesrdquo Electronic Journal of Textile Technol-ogy vol 3 pp 95ndash108 2009

[8] M Yusuf A Ahmad M Shahid et al ldquoAssessment of colori-metric antibacterial and antifungal properties of woollen yarndyedwith the extract of the leaves of henna (Lawsonia inermis)rdquoJournal of Cleaner Production vol 27 pp 42ndash50 2012

[9] S Palamutcu M Sengul N Devrent and R Keskin ldquoThe iden-tification tests of antimicrobial activity in textile productsrdquo inProceedings of the 7thNationalMeasurement Science Conference2007

[10] L Windler M Height and B Nowack ldquoComparative evalu-ation of antimicrobials for textile applicationsrdquo EnvironmentInternational vol 53 pp 62ndash73 2013

Bioinorganic Chemistry and Applications 5

[11] S Arora J Jain JM Rajwade andKM Paknikar ldquoInteractionsof silver nanoparticles with primary mouse fibroblasts and livercellsrdquo Toxicology and Applied Pharmacology vol 236 no 3 pp310ndash318 2009

[12] O Choi K K Deng N-J Kim L Ross Jr R Y Surampalli andZ Hu ldquoThe inhibitory effects of silver nanoparticles silver ionsand silver chloride colloids on microbial growthrdquo WaterResearch vol 42 no 12 pp 3066ndash3074 2008

[13] E Matyjas-Zgondek A Bacciarelli E Rybicki M I Szynk-owska and M Kołodziejczyk ldquoAntibacterial properties ofsilver-finished textilesrdquo Fibres amp Textiles in Eastern Europe vol16 no 5 pp 101ndash107 2008

[14] MM Cowan K Z Abshire S L Houk and SM Evans ldquoAnti-microbial efficacy of a silver-zeolite matrix coating on stainlesssteelrdquo Journal of Industrial Microbiology and Biotechnology vol30 no 2 pp 102ndash106 2003

[15] L Balogh D R Swanson D A Tomalia G L Hagnauer andA T McManus ldquoDendrimer-silver complexes and nanocom-posites as antimicrobial agentsrdquo Nano Letters vol 1 no 1 pp18ndash21 2001

[16] S K Bajpai Y M Mohan M Bajpai R Tankhiwale andV Thomas ldquoSynthesis of polymer stabilized silver and goldnanostructuresrdquo Journal of Nanoscience and Nanotechnologyvol 7 no 9 pp 2994ndash3010 2007

[17] A Burkitbay B R Taussarova A Z Kutzhanova and S MRakhimova ldquoDevelopment of a polymeric composition forantimicrobial finish of cotton fabricsrdquo Fibres and Textiles inEastern Europe vol 104 no 2 pp 96ndash101 2014

[18] A IWasif and S K Laga ldquoUse of nano silver as an antimicrobialagent for cottonrdquo Autex Research Journal vol 9 no 1 pp 5ndash132009

[19] N Duran P D Marcato G I H de Souza O L Alves and EEsposito ldquoAntibacterial effect of silver nanoparticles producedby fungal process on textile fabrics and their effluent treatmentrdquoJournal of Biomedical Nanotechnology vol 3 no 2 pp 203ndash2082007

[20] Z Foltynowicz D Gwiazdowska D Rodewald A Nowaczykand M Filipiak ldquoAntimicrobial properties of socks protectedwith silver nanoparticlesrdquo Fibres and Textiles in Eastern Europevol 21 no 5 pp 91ndash96 2013

[21] P Jain and T Pradeep ldquoPotential of silver nanoparticle-coatedpolyurethane foam as an antibacterial water filterrdquo Biotechnol-ogy and Bioengineering vol 90 no 1 pp 59ndash63 2005

[22] M-K Yeo and M Kang ldquoEffects of nanometer sized silvermaterials on biological toxicity during zebrafish embryogene-sisrdquo Bulletin of the Korean Chemical Society vol 29 no 6 pp1179ndash1184 2008

[23] A Yildiz M Oztas A O Agirgan and D GulenThe Synthesisof Silver Carboxylate and the Investigations of AntibacterialActivity in Textiles NKUBAP0017YL1207 2013 (Turkish)

[24] M I Khan A Ahmad S A Khan et al ldquoAssessment of anti-microbial activity of Catechu and its dyed substraterdquo Journal ofCleaner Production vol 19 no 12 pp 1385ndash1394 2011

[25] H E Emam A P Manian B Siroka et al ldquoTreatments toimpart antimicrobial activity to clothing and household cellu-losic-textilesmdashwhy lsquonanorsquo-silverrdquo Journal of Cleaner Produc-tion vol 39 pp 17ndash23 2013

[26] A Yildiz R AtavM Oztas et al ldquoInvestigating the usage possi-bility of metal mono carboxylates (metal naphthenates) as anti-bacterial agent in textile applicationsrdquo Industria Textila vol 65no 3 pp 140ndash144 2014

[27] M Degirmencioglu Waste recycling textıle fınıshıng obtaınedby the use of metal naphthenates [MS thesis] Namik KemalUniversity Institute of Natural and Applied Sciences 2013(Turkish)

[28] A Yildiz R Atav A O Agırgan and Z Kanat Evrim ldquoInves-tigation of the usage possibility of copper cyclohexane mono-carboxylate (copper naphthenate) as a textile dyerdquo IndustriaTextila vol 63 no 3 pp 144ndash150 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Bioinorganic Chemistry and Applications 3

Table 2 Antibacterial activity of silver abietate applied cotton fabrics after 3ndash20 washings against six different bacteria

Bacteriatypes mdash 3st 5th 10th 20th

B subtilis

S aureus

E faecalis

Kpneumoniae

E coli

Paeruginosa

ndashCH2 and ndashCH

3) cmminus1 In the UV spectrum compound

maximum absorptions were observed at the 267 nm The1H NMR spectrum of the synthesized compound showedcharacteristic signals for a silver abietate with the signals096 (119889 119869 = 72Hz ndashCH(CH

3)) indicating the presence of

two isopropyl groups and broadened singlet with singlet at 120575531 (2H brs Hb) and 568 (2H s Ha) showing unsaturatedconjugated protons The presence of two methyl groups wasobserved at 120575H 070 with a singlet signal corresponding to sixprotons However in the 1H NMR spectrum of compound

4 Bioinorganic Chemistry and Applications

(H3C)2HC

H3C CH3

C OO Ag

OO

C

H3C C

CH(CH3)2

H3

Figure 1 Molecular structure of silver abietate antimicrobial agent

the singlet at 120575 104 was attributed to methyl protons adjacentto C=O In addition in the 1H NMR spectrum of compoundshowed a multiple centered 107ndash211 (12 ndashCH

2 10 ndashCH

protons)A detailed study on the 13C NMR and DEPT spectra

revealed 4 carbon signals due to four sp2 quaternary carbonsfour sp2 methines and two carbonyl carbons The signal at120575C 1784 for the two carbonyl carbons eight other signals ofsp2 carbons at 120575C 11431 1212 1338 and 1195 and aliphaticndashCHndashCH

2ndashCH

3carbons at 208 332 233 217 489 159

427 326 287 408 347 326 and 298 were characteristic ofa silver abietate structure

The silver abietate gave a molecular ion peak [M]+ at11989811991171031 (15) in positive ESI-MS which was consistent with amolecular formula of C

40H58O4Ag

Based on the above evidence the structure of compoundwas identified as silver abietate (Figure 1)

Antibacterial test results according to the JIS L 1902-2008 protocol standards of silver abietate compound-appliedcotton fabrics before washing and after 3 5 10 and 20washings are presented in Table 1

Results of the antibacterial test for silver abietatecompound-applied cotton woven fabrics before and afterwashings according to the JIS L 1902-2008 protocol standardsare presented in Table 2

Antibacterial activity against B subtilis K pneumoniaeand P aeruginosa was not different and was stronger sig-nificantly than the other bacteria The lowest antibacterialactivity was observed in E faecalisThe antibacterial activitiesof silver abietate (silver naphthenate) applied to the cottonfabrics in successive washings were still permanent after 20washings

3 Conclusion

After silver abietate (silver naphthenate) was synthesizedwiththe abietic acid its use as an antibacterial agent in finishingof cotton fabrics against the three Gram-negative and threeGram-positive bacteria was found to be promising Further-more the antibacterial impact was permanent even after20 successive washings After the washings silver abietatewas observed to exhibit a better antibacterial activity againstBacillus subtilis Klebsiella pneumoniae and Pseudomonasaeruginosa than the other bacteria The antibacterial activitywas strong for the three bacteria even after 20 successivewashingsThe lowest antibacterial activitywas againstEntero-coccus faecalis Although antibacterial activitywas low againstthis bacterium permanency wasmore important Test resultsconfirmed that the complex was active against the six differ-ent bacteria and was permanent after 20 successive washingsAnother advantage of the obtained antibacterial agent is that

the synthesized silver abietate as a complex compound cannotget onto the skin [28] All the above considerations togetherpoint to silver abietate as a new antibacterial agent in textileindustry Since it has been determined in this study that silverabietate is a potential antibacterial agent synthesis of low costandmore effective silver abietate has been planned for furtherwork

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was financially supported by the Research Com-mission ofNamikKemalUniversity (NKUBAP0017YL1207)

References

[1] A Yildiz T Sabudak F Mikailzade S Kazan and A FeyizogluldquoSynthesis and structural investigations of copper abietat com-plexesrdquo Asian Journal of Chemistry vol 24 no 4 pp 1719ndash17232012

[2] A Yadav V Prasad A A Kathe et al ldquoFunctional finishing incotton fabrics using zinc oxide nanoparticlesrdquo Bulletin of Mate-rials Science vol 29 no 6 pp 641ndash645 2006

[3] T Charbonneaux and S Rochat ldquoArticles with antibacterial andantifungal activityrdquo US Patent Application no 0208390 2006

[4] M S Antelman ldquoHigh performance cobalt (II III) oxide anti-microbial textile articlesrdquo US Patent no 6228491 2001

[5] T Ramachandran K Rajendrakumar and R RajendranldquoAntimicrobial textilesmdashan overviewrdquo Journal of the Institutionof Engineers (India) Part TX Textile Engineering Division vol84 no 2 pp 42ndash47 2004

[6] G Supuren A Cay E Kanat and I Tarakcioglu ldquoAntimicrobialfibresrdquo in Textile and Apparel Research pp 171 15ndash17ndash172 83ndash89 2007 (Turkish)

[7] S Palamutcu R Keskin N Devrent et al ldquoFunctional textilesII antimicrobial textilesrdquo Electronic Journal of Textile Technol-ogy vol 3 pp 95ndash108 2009

[8] M Yusuf A Ahmad M Shahid et al ldquoAssessment of colori-metric antibacterial and antifungal properties of woollen yarndyedwith the extract of the leaves of henna (Lawsonia inermis)rdquoJournal of Cleaner Production vol 27 pp 42ndash50 2012

[9] S Palamutcu M Sengul N Devrent and R Keskin ldquoThe iden-tification tests of antimicrobial activity in textile productsrdquo inProceedings of the 7thNationalMeasurement Science Conference2007

[10] L Windler M Height and B Nowack ldquoComparative evalu-ation of antimicrobials for textile applicationsrdquo EnvironmentInternational vol 53 pp 62ndash73 2013

Bioinorganic Chemistry and Applications 5

[11] S Arora J Jain JM Rajwade andKM Paknikar ldquoInteractionsof silver nanoparticles with primary mouse fibroblasts and livercellsrdquo Toxicology and Applied Pharmacology vol 236 no 3 pp310ndash318 2009

[12] O Choi K K Deng N-J Kim L Ross Jr R Y Surampalli andZ Hu ldquoThe inhibitory effects of silver nanoparticles silver ionsand silver chloride colloids on microbial growthrdquo WaterResearch vol 42 no 12 pp 3066ndash3074 2008

[13] E Matyjas-Zgondek A Bacciarelli E Rybicki M I Szynk-owska and M Kołodziejczyk ldquoAntibacterial properties ofsilver-finished textilesrdquo Fibres amp Textiles in Eastern Europe vol16 no 5 pp 101ndash107 2008

[14] MM Cowan K Z Abshire S L Houk and SM Evans ldquoAnti-microbial efficacy of a silver-zeolite matrix coating on stainlesssteelrdquo Journal of Industrial Microbiology and Biotechnology vol30 no 2 pp 102ndash106 2003

[15] L Balogh D R Swanson D A Tomalia G L Hagnauer andA T McManus ldquoDendrimer-silver complexes and nanocom-posites as antimicrobial agentsrdquo Nano Letters vol 1 no 1 pp18ndash21 2001

[16] S K Bajpai Y M Mohan M Bajpai R Tankhiwale andV Thomas ldquoSynthesis of polymer stabilized silver and goldnanostructuresrdquo Journal of Nanoscience and Nanotechnologyvol 7 no 9 pp 2994ndash3010 2007

[17] A Burkitbay B R Taussarova A Z Kutzhanova and S MRakhimova ldquoDevelopment of a polymeric composition forantimicrobial finish of cotton fabricsrdquo Fibres and Textiles inEastern Europe vol 104 no 2 pp 96ndash101 2014

[18] A IWasif and S K Laga ldquoUse of nano silver as an antimicrobialagent for cottonrdquo Autex Research Journal vol 9 no 1 pp 5ndash132009

[19] N Duran P D Marcato G I H de Souza O L Alves and EEsposito ldquoAntibacterial effect of silver nanoparticles producedby fungal process on textile fabrics and their effluent treatmentrdquoJournal of Biomedical Nanotechnology vol 3 no 2 pp 203ndash2082007

[20] Z Foltynowicz D Gwiazdowska D Rodewald A Nowaczykand M Filipiak ldquoAntimicrobial properties of socks protectedwith silver nanoparticlesrdquo Fibres and Textiles in Eastern Europevol 21 no 5 pp 91ndash96 2013

[21] P Jain and T Pradeep ldquoPotential of silver nanoparticle-coatedpolyurethane foam as an antibacterial water filterrdquo Biotechnol-ogy and Bioengineering vol 90 no 1 pp 59ndash63 2005

[22] M-K Yeo and M Kang ldquoEffects of nanometer sized silvermaterials on biological toxicity during zebrafish embryogene-sisrdquo Bulletin of the Korean Chemical Society vol 29 no 6 pp1179ndash1184 2008

[23] A Yildiz M Oztas A O Agirgan and D GulenThe Synthesisof Silver Carboxylate and the Investigations of AntibacterialActivity in Textiles NKUBAP0017YL1207 2013 (Turkish)

[24] M I Khan A Ahmad S A Khan et al ldquoAssessment of anti-microbial activity of Catechu and its dyed substraterdquo Journal ofCleaner Production vol 19 no 12 pp 1385ndash1394 2011

[25] H E Emam A P Manian B Siroka et al ldquoTreatments toimpart antimicrobial activity to clothing and household cellu-losic-textilesmdashwhy lsquonanorsquo-silverrdquo Journal of Cleaner Produc-tion vol 39 pp 17ndash23 2013

[26] A Yildiz R AtavM Oztas et al ldquoInvestigating the usage possi-bility of metal mono carboxylates (metal naphthenates) as anti-bacterial agent in textile applicationsrdquo Industria Textila vol 65no 3 pp 140ndash144 2014

[27] M Degirmencioglu Waste recycling textıle fınıshıng obtaınedby the use of metal naphthenates [MS thesis] Namik KemalUniversity Institute of Natural and Applied Sciences 2013(Turkish)

[28] A Yildiz R Atav A O Agırgan and Z Kanat Evrim ldquoInves-tigation of the usage possibility of copper cyclohexane mono-carboxylate (copper naphthenate) as a textile dyerdquo IndustriaTextila vol 63 no 3 pp 144ndash150 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

4 Bioinorganic Chemistry and Applications

(H3C)2HC

H3C CH3

C OO Ag

OO

C

H3C C

CH(CH3)2

H3

Figure 1 Molecular structure of silver abietate antimicrobial agent

the singlet at 120575 104 was attributed to methyl protons adjacentto C=O In addition in the 1H NMR spectrum of compoundshowed a multiple centered 107ndash211 (12 ndashCH

2 10 ndashCH

protons)A detailed study on the 13C NMR and DEPT spectra

revealed 4 carbon signals due to four sp2 quaternary carbonsfour sp2 methines and two carbonyl carbons The signal at120575C 1784 for the two carbonyl carbons eight other signals ofsp2 carbons at 120575C 11431 1212 1338 and 1195 and aliphaticndashCHndashCH

2ndashCH

3carbons at 208 332 233 217 489 159

427 326 287 408 347 326 and 298 were characteristic ofa silver abietate structure

The silver abietate gave a molecular ion peak [M]+ at11989811991171031 (15) in positive ESI-MS which was consistent with amolecular formula of C

40H58O4Ag

Based on the above evidence the structure of compoundwas identified as silver abietate (Figure 1)

Antibacterial test results according to the JIS L 1902-2008 protocol standards of silver abietate compound-appliedcotton fabrics before washing and after 3 5 10 and 20washings are presented in Table 1

Results of the antibacterial test for silver abietatecompound-applied cotton woven fabrics before and afterwashings according to the JIS L 1902-2008 protocol standardsare presented in Table 2

Antibacterial activity against B subtilis K pneumoniaeand P aeruginosa was not different and was stronger sig-nificantly than the other bacteria The lowest antibacterialactivity was observed in E faecalisThe antibacterial activitiesof silver abietate (silver naphthenate) applied to the cottonfabrics in successive washings were still permanent after 20washings

3 Conclusion

After silver abietate (silver naphthenate) was synthesizedwiththe abietic acid its use as an antibacterial agent in finishingof cotton fabrics against the three Gram-negative and threeGram-positive bacteria was found to be promising Further-more the antibacterial impact was permanent even after20 successive washings After the washings silver abietatewas observed to exhibit a better antibacterial activity againstBacillus subtilis Klebsiella pneumoniae and Pseudomonasaeruginosa than the other bacteria The antibacterial activitywas strong for the three bacteria even after 20 successivewashingsThe lowest antibacterial activitywas againstEntero-coccus faecalis Although antibacterial activitywas low againstthis bacterium permanency wasmore important Test resultsconfirmed that the complex was active against the six differ-ent bacteria and was permanent after 20 successive washingsAnother advantage of the obtained antibacterial agent is that

the synthesized silver abietate as a complex compound cannotget onto the skin [28] All the above considerations togetherpoint to silver abietate as a new antibacterial agent in textileindustry Since it has been determined in this study that silverabietate is a potential antibacterial agent synthesis of low costandmore effective silver abietate has been planned for furtherwork

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This work was financially supported by the Research Com-mission ofNamikKemalUniversity (NKUBAP0017YL1207)

References

[1] A Yildiz T Sabudak F Mikailzade S Kazan and A FeyizogluldquoSynthesis and structural investigations of copper abietat com-plexesrdquo Asian Journal of Chemistry vol 24 no 4 pp 1719ndash17232012

[2] A Yadav V Prasad A A Kathe et al ldquoFunctional finishing incotton fabrics using zinc oxide nanoparticlesrdquo Bulletin of Mate-rials Science vol 29 no 6 pp 641ndash645 2006

[3] T Charbonneaux and S Rochat ldquoArticles with antibacterial andantifungal activityrdquo US Patent Application no 0208390 2006

[4] M S Antelman ldquoHigh performance cobalt (II III) oxide anti-microbial textile articlesrdquo US Patent no 6228491 2001

[5] T Ramachandran K Rajendrakumar and R RajendranldquoAntimicrobial textilesmdashan overviewrdquo Journal of the Institutionof Engineers (India) Part TX Textile Engineering Division vol84 no 2 pp 42ndash47 2004

[6] G Supuren A Cay E Kanat and I Tarakcioglu ldquoAntimicrobialfibresrdquo in Textile and Apparel Research pp 171 15ndash17ndash172 83ndash89 2007 (Turkish)

[7] S Palamutcu R Keskin N Devrent et al ldquoFunctional textilesII antimicrobial textilesrdquo Electronic Journal of Textile Technol-ogy vol 3 pp 95ndash108 2009

[8] M Yusuf A Ahmad M Shahid et al ldquoAssessment of colori-metric antibacterial and antifungal properties of woollen yarndyedwith the extract of the leaves of henna (Lawsonia inermis)rdquoJournal of Cleaner Production vol 27 pp 42ndash50 2012

[9] S Palamutcu M Sengul N Devrent and R Keskin ldquoThe iden-tification tests of antimicrobial activity in textile productsrdquo inProceedings of the 7thNationalMeasurement Science Conference2007

[10] L Windler M Height and B Nowack ldquoComparative evalu-ation of antimicrobials for textile applicationsrdquo EnvironmentInternational vol 53 pp 62ndash73 2013

Bioinorganic Chemistry and Applications 5

[11] S Arora J Jain JM Rajwade andKM Paknikar ldquoInteractionsof silver nanoparticles with primary mouse fibroblasts and livercellsrdquo Toxicology and Applied Pharmacology vol 236 no 3 pp310ndash318 2009

[12] O Choi K K Deng N-J Kim L Ross Jr R Y Surampalli andZ Hu ldquoThe inhibitory effects of silver nanoparticles silver ionsand silver chloride colloids on microbial growthrdquo WaterResearch vol 42 no 12 pp 3066ndash3074 2008

[13] E Matyjas-Zgondek A Bacciarelli E Rybicki M I Szynk-owska and M Kołodziejczyk ldquoAntibacterial properties ofsilver-finished textilesrdquo Fibres amp Textiles in Eastern Europe vol16 no 5 pp 101ndash107 2008

[14] MM Cowan K Z Abshire S L Houk and SM Evans ldquoAnti-microbial efficacy of a silver-zeolite matrix coating on stainlesssteelrdquo Journal of Industrial Microbiology and Biotechnology vol30 no 2 pp 102ndash106 2003

[15] L Balogh D R Swanson D A Tomalia G L Hagnauer andA T McManus ldquoDendrimer-silver complexes and nanocom-posites as antimicrobial agentsrdquo Nano Letters vol 1 no 1 pp18ndash21 2001

[16] S K Bajpai Y M Mohan M Bajpai R Tankhiwale andV Thomas ldquoSynthesis of polymer stabilized silver and goldnanostructuresrdquo Journal of Nanoscience and Nanotechnologyvol 7 no 9 pp 2994ndash3010 2007

[17] A Burkitbay B R Taussarova A Z Kutzhanova and S MRakhimova ldquoDevelopment of a polymeric composition forantimicrobial finish of cotton fabricsrdquo Fibres and Textiles inEastern Europe vol 104 no 2 pp 96ndash101 2014

[18] A IWasif and S K Laga ldquoUse of nano silver as an antimicrobialagent for cottonrdquo Autex Research Journal vol 9 no 1 pp 5ndash132009

[19] N Duran P D Marcato G I H de Souza O L Alves and EEsposito ldquoAntibacterial effect of silver nanoparticles producedby fungal process on textile fabrics and their effluent treatmentrdquoJournal of Biomedical Nanotechnology vol 3 no 2 pp 203ndash2082007

[20] Z Foltynowicz D Gwiazdowska D Rodewald A Nowaczykand M Filipiak ldquoAntimicrobial properties of socks protectedwith silver nanoparticlesrdquo Fibres and Textiles in Eastern Europevol 21 no 5 pp 91ndash96 2013

[21] P Jain and T Pradeep ldquoPotential of silver nanoparticle-coatedpolyurethane foam as an antibacterial water filterrdquo Biotechnol-ogy and Bioengineering vol 90 no 1 pp 59ndash63 2005

[22] M-K Yeo and M Kang ldquoEffects of nanometer sized silvermaterials on biological toxicity during zebrafish embryogene-sisrdquo Bulletin of the Korean Chemical Society vol 29 no 6 pp1179ndash1184 2008

[23] A Yildiz M Oztas A O Agirgan and D GulenThe Synthesisof Silver Carboxylate and the Investigations of AntibacterialActivity in Textiles NKUBAP0017YL1207 2013 (Turkish)

[24] M I Khan A Ahmad S A Khan et al ldquoAssessment of anti-microbial activity of Catechu and its dyed substraterdquo Journal ofCleaner Production vol 19 no 12 pp 1385ndash1394 2011

[25] H E Emam A P Manian B Siroka et al ldquoTreatments toimpart antimicrobial activity to clothing and household cellu-losic-textilesmdashwhy lsquonanorsquo-silverrdquo Journal of Cleaner Produc-tion vol 39 pp 17ndash23 2013

[26] A Yildiz R AtavM Oztas et al ldquoInvestigating the usage possi-bility of metal mono carboxylates (metal naphthenates) as anti-bacterial agent in textile applicationsrdquo Industria Textila vol 65no 3 pp 140ndash144 2014

[27] M Degirmencioglu Waste recycling textıle fınıshıng obtaınedby the use of metal naphthenates [MS thesis] Namik KemalUniversity Institute of Natural and Applied Sciences 2013(Turkish)

[28] A Yildiz R Atav A O Agırgan and Z Kanat Evrim ldquoInves-tigation of the usage possibility of copper cyclohexane mono-carboxylate (copper naphthenate) as a textile dyerdquo IndustriaTextila vol 63 no 3 pp 144ndash150 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Bioinorganic Chemistry and Applications 5

[11] S Arora J Jain JM Rajwade andKM Paknikar ldquoInteractionsof silver nanoparticles with primary mouse fibroblasts and livercellsrdquo Toxicology and Applied Pharmacology vol 236 no 3 pp310ndash318 2009

[12] O Choi K K Deng N-J Kim L Ross Jr R Y Surampalli andZ Hu ldquoThe inhibitory effects of silver nanoparticles silver ionsand silver chloride colloids on microbial growthrdquo WaterResearch vol 42 no 12 pp 3066ndash3074 2008

[13] E Matyjas-Zgondek A Bacciarelli E Rybicki M I Szynk-owska and M Kołodziejczyk ldquoAntibacterial properties ofsilver-finished textilesrdquo Fibres amp Textiles in Eastern Europe vol16 no 5 pp 101ndash107 2008

[14] MM Cowan K Z Abshire S L Houk and SM Evans ldquoAnti-microbial efficacy of a silver-zeolite matrix coating on stainlesssteelrdquo Journal of Industrial Microbiology and Biotechnology vol30 no 2 pp 102ndash106 2003

[15] L Balogh D R Swanson D A Tomalia G L Hagnauer andA T McManus ldquoDendrimer-silver complexes and nanocom-posites as antimicrobial agentsrdquo Nano Letters vol 1 no 1 pp18ndash21 2001

[16] S K Bajpai Y M Mohan M Bajpai R Tankhiwale andV Thomas ldquoSynthesis of polymer stabilized silver and goldnanostructuresrdquo Journal of Nanoscience and Nanotechnologyvol 7 no 9 pp 2994ndash3010 2007

[17] A Burkitbay B R Taussarova A Z Kutzhanova and S MRakhimova ldquoDevelopment of a polymeric composition forantimicrobial finish of cotton fabricsrdquo Fibres and Textiles inEastern Europe vol 104 no 2 pp 96ndash101 2014

[18] A IWasif and S K Laga ldquoUse of nano silver as an antimicrobialagent for cottonrdquo Autex Research Journal vol 9 no 1 pp 5ndash132009

[19] N Duran P D Marcato G I H de Souza O L Alves and EEsposito ldquoAntibacterial effect of silver nanoparticles producedby fungal process on textile fabrics and their effluent treatmentrdquoJournal of Biomedical Nanotechnology vol 3 no 2 pp 203ndash2082007

[20] Z Foltynowicz D Gwiazdowska D Rodewald A Nowaczykand M Filipiak ldquoAntimicrobial properties of socks protectedwith silver nanoparticlesrdquo Fibres and Textiles in Eastern Europevol 21 no 5 pp 91ndash96 2013

[21] P Jain and T Pradeep ldquoPotential of silver nanoparticle-coatedpolyurethane foam as an antibacterial water filterrdquo Biotechnol-ogy and Bioengineering vol 90 no 1 pp 59ndash63 2005

[22] M-K Yeo and M Kang ldquoEffects of nanometer sized silvermaterials on biological toxicity during zebrafish embryogene-sisrdquo Bulletin of the Korean Chemical Society vol 29 no 6 pp1179ndash1184 2008

[23] A Yildiz M Oztas A O Agirgan and D GulenThe Synthesisof Silver Carboxylate and the Investigations of AntibacterialActivity in Textiles NKUBAP0017YL1207 2013 (Turkish)

[24] M I Khan A Ahmad S A Khan et al ldquoAssessment of anti-microbial activity of Catechu and its dyed substraterdquo Journal ofCleaner Production vol 19 no 12 pp 1385ndash1394 2011

[25] H E Emam A P Manian B Siroka et al ldquoTreatments toimpart antimicrobial activity to clothing and household cellu-losic-textilesmdashwhy lsquonanorsquo-silverrdquo Journal of Cleaner Produc-tion vol 39 pp 17ndash23 2013

[26] A Yildiz R AtavM Oztas et al ldquoInvestigating the usage possi-bility of metal mono carboxylates (metal naphthenates) as anti-bacterial agent in textile applicationsrdquo Industria Textila vol 65no 3 pp 140ndash144 2014

[27] M Degirmencioglu Waste recycling textıle fınıshıng obtaınedby the use of metal naphthenates [MS thesis] Namik KemalUniversity Institute of Natural and Applied Sciences 2013(Turkish)

[28] A Yildiz R Atav A O Agırgan and Z Kanat Evrim ldquoInves-tigation of the usage possibility of copper cyclohexane mono-carboxylate (copper naphthenate) as a textile dyerdquo IndustriaTextila vol 63 no 3 pp 144ndash150 2012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of