Research Article Complexation of Oxovanadium(IV) and … · 2019. 7. 31. · obtained using Jobs continuous variation and molar ratio methods ( Figure ). e monomeric nature of vanadyl

Research ArticleComplexation of Oxovanadium(IV) andDioxouranium(VI) with Synthesized12-(Diimino-41015840-antipyrinyl)-12-diphenylethane Schiff BaseA Thermodynamic Kinetic and Bioactivity Investigation

Shabnum Bashir Syed Raashid Maqsood Ghulam Mustafa PeerzadaBadruddin Khan and Masood Ahmad Rizvi

Department of Chemistry University of Kashmir Hazratbal Srinagar Jammu and Kashmir 190006 India

Correspondence should be addressed to Masood Ahmad Rizvi masoodku2gmailcom

Received 28 June 2014 Revised 22 September 2014 Accepted 7 October 2014 Published 28 December 2014

Academic Editor Radhey Srivastava

Copyright copy 2014 Shabnum Bashir et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

We report the comparative synthetic methodologies and characterization of a tetradentate Schiff base ligand 12-(diimino-41015840-antipyrinyl)-12-diphenylethane (DE) The target synthesis of oxovanadium(IV) and dioxouranium(VI) complexes (vanadyl anduranyl) with the (DE) ligand was also attempted to envisage the effect of metal ion steric factor on complexation processthrough solution phase thermodynamic and kinetic studiesThe thermodynamic stabilities of synthesized vanadyl and uranyl (DE)complexes are discussed in light of their solution phase thermodynamic stability constants obtained by electroanalytical method Acomparative kinetic profile of vanadyl and uranyl complexation with DE is also reportedThe complexation reaction proceeds withan overall 2nd order kinetics with both metal ions Temperature dependent studies of rate constants present an activation energybarrier of ca 40913 and 48661 KJmolminus1 for vanadyl and uranyl complexation respectively highlighting the metal ion steric andligand preorganization effects The synthesized Schiff base ligand and its vanadyl and uranyl complexes were screened for biocidalpotential as antibacterial antifungal and anthelmintic agents with the results compared to corresponding reference drugs

1 Introduction

Studies related to structure reactivity and applications ofnewly reported ligands and complexes form an imperativeaspect of modern day inorganic chemistry An insight intothermodynamic kinetic and biological property of com-pounds is always exciting and desirable from applicationpoint of view Schiff bases are one of the most widely usedorganic compounds and their metal complexes have a varietyof biological analytical and material applications in additionto their important roles in catalysis and organic synthesis[1ndash6] Schiff bases derived from the condensation of 4-aminoantipyrinewith diketones represent an interesting classof biologically important chelating ligands metal complexesof these ligands are of great interest owing to their phar-macological and analytical applications [7ndash11] Conventional

Schiff base synthesis makes use of high boiling toxic organicsolvent as reaction media for refluxing the amine and thealdehyde mixtures followed by lengthy chromatographicworkup of purification and recrystallization In addition tokeep the equilibrium in the direction of forward reaction thewater is usually removed either azeotropically by distillationor with a suitable drying agent [12ndash14] Environmentallybenign synthetic methods have received considerable atten-tion and some solvent-free protocols have been developed[15] Microwave assisted organic synthesis (MAOS) aremotivating for their low energy expense very little solventdemand enhanced yields and shortened reaction times ina variety of reactions [16 17] In embracing the principlesof green chemistry [18ndash20] herein we depict a comparativeaccount of the conventional and nonconventional syntheticprotocols for the synthesis of Schiff base (DE) obtained from

Hindawi Publishing CorporationJournal of Inorganic ChemistryVolume 2014 Article ID 268383 11 pageshttpdxdoiorg1011552014268383

2 Journal of Inorganic Chemistry

the condensation reaction of 4-aminoantipyrine with benzilThe target synthesis of oxovanadium(IV) and dioxoura-nium(VI) (vanadyl and uranyl) complexes with the Schiffbase ligand (DE) was also attempted to envisage the effectof metal ion steric factor on complexation process throughsolution phase thermodynamic and kinetic studiesThe ther-modynamic stabilities of vanadyl and uranyl Schiff base (DE)complexes are discussed in light of their calculated solutionphase stability constants using Calvin-Bjerrum and Irwing-Rossotti [21 22] potentiometric method The kinetic profileof theDE-uranyl andDE-vanadyl complexation throughUV-Visible studies describes the effect of metal ion concentrationand Steric effect on complexation reaction Keeping in viewthe bioactive nature of the starting compounds and reportedbioactivity of vanadium complexes [23ndash25] the synthesisedligand (DE) and its complexes were screened for biocidalpotential using the standard protocols [26] with the resultscompared to corresponding reference drugs

2 Materials and Methods

All chemicals and solvents were obtained from commercialsources as laboratory reagents and used without furtherpurification in the syntheses The metal salts used in com-plexation were analytical grade uranyl nitrate and vanadylsulphate The microwave assisted synthesis was carried outin Teflon reaction cells with SHARP 1000WR-21LCF com-mercial microwave oven fitted with a temperature relaywith circuit break at 145∘C The high performance liquidchromatography (HPLC) was carried on Schimadzu LC-20Awith a SPD-M20A variable-wavelength UV detector Themobile phase used consisted of water methanol (10 90 vv)flowing at rate of 05mLminminus1 Electronic spectra of thecomplexes were recorded on a Shimadzu 3600 UV-Visiblespectrophotometer with thermostatic control CHN analysesof all the synthesized compounds were done on Vario EL IIICHNS analyser FT-IR spectra were recorded as KBr pelletswith a Perkin Elmer FTIR Spectrum-2 in the 4000ndash400 cmminus1range The 1H NMR spectrum was recorded in CDCl

3on a

Bruker Avance DRX 500MHzNMR spectrometer The massspectra were taken on Micromass Q-Tof micro YA-105 Allinstrumental measurements were done at room temperature(around 25∘C) except in case of kinetic profile

3 Synthesis of 12-(Diimino-41015840-antipyrinyl)-12-diphenylethane (DE)

The tetradentate Schiff base ligand was synthesized by threedifferent synthetic protocols (solvent refluxing microwaveassisted and solvent free fusion method) for a comparativestudy aimed at environmentally benign procedure

31 Solvent Refluxing Method In this method an ethanolicsolution of benzil (105 g 5mmol) and 4-aminoantipyrine(203 g 10mmol) was refluxed at 60∘C for about 05 hrs Oncooling and solvent evaporation the yellow solid of Schiffbase ligand (DE) got separated which was filtered as crudeproduct and recrystallized from ethanol

32Microwave AssistedMethod In thismethod the reactantsin a molar ratio of 2 1 (203 g 10mmol of 4-aminoantipyrineand 105 g 5mmol of benzil) were thoroughly mixed withsilica gel and put inside the Teflon tube for microwaveirradiation under medium power for 05 minutes generating amaximum temperature up to 145∘C The solid product wasdissolved in ethanol to separate the compound and silicagel the Schiff base product got separated on evaporation ofsolvent

33 Solvent-Free Fusion Method In an effort to introduce anovel eco-friendly synthetic procedure solvent-free fusionmethod was attempted In the solvent-free fusion reac-tion the reactant with higher melting point that is 4-aminoantipyrine (MP = 110∘C) was melted and then theother reactant benzil (MP = 90∘C) was added to the moltenstate of the former which served both as the reagent andas solvent besides providing a high reaction temperatureThe reaction mixture was kept at 100∘C in a silicone oil bathunder constant stirring for 2 hrs over amagnetic stirrer Afterstirring time the solid product was dissolved in ethanol andfiltered the filtrate on evaporation produced the Schiff basecompound

4 Synthesis of Complexes

The complexation of DE with metal salts was carried out byrefluxing an equimolar (1 1) mixture of uranyl nitrate andvanadyl sulphate with Schiff base ligand DE respectively forabout 5-6 hrs in ethanol The progress of the reaction wasfollowed by TLC After completion of reaction time (6 hrs)the refluxed solution was concentrated to one-third of itsinitial volume on awater bathTheproducts were obtained onfiltration washed with ethanol and dried under vacuum Abright yellow compound of composition [UO

2(DE)](NO

3)2

with melting point (MP) 290ndash300∘C and a grey compoundof composition [VO(DE)]SO

4with MP 220ndash225∘C were

obtained for uranyl nitrate and vanadyl sulphate complexa-tion with DE

5 Results and Discussion

51 Comparative Synthetic Methodology The Schiff base 12-(diimino-4-antipyrinyl)-12-diphenylethane (DE) was syn-thesised by the condensation of 1-phenyl-23-dimethyl-4-aminopyrazol-5-one (4-aminoantipyrine) with 12-diphen-ylethane-12-dione (benzil) using three synthetic methodolo-gies The efficacy of these methods was compared in terms ofreaction time percent yield and energy demand (Table 1)

The conventional solvent refluxing method was the leastefficient of the three methodologies in terms of time andenergy demand besides being economically and environ-mentally less viable The proposed fusion method is impres-sive in terms of product purity and appreciable yield in asmaller timeThus relatively smaller reaction time no solventdemand and lower chemical and energy expense makethis method meet green chemistry criteria [18] Althoughmicrowave assisted synthesis required minimum reaction

Journal of Inorganic Chemistry 3

Table 1 Comparative account of synthetic procedures in terms of yield and time

Solvent refluxing Fusion method MicrowaveSolid support (silica gel) Solvent (ethanol)

Time (min) yield Time (min) yield Time (min) yield Time (min) yieldSchiff base(DE)

240 40 120 50 3 32 1 321300 45 150 70 5 60 5 781

Table 2 Characterization of Schiff base complexes

Compound (formula) Elemental analysis Melting point IR absorption (cmminus1) Λmax Λ119898

C H N (∘C) ]C=O ]C=N ]MndashN ]MndashO (nm) (Ωminus1cm2molminus1)[C36H32N6O2]

DE7286(7454)

540(551)

1277(1448) 179ndash185 1655

(vs)1635(vs) mdash mdash 410 200

[VO-(DE)]SO4527

(5307)385(393)

1008(1032) 220ndash225 1630

(s)1600(ms)

400(m)

540(m) 502 1606

[UO2(DE)](NO3)25106(5298)

498(423)

1052(1132) 290ndash300 1632

(s)1615(ms)

410(m)

570(m) 480 1728

vs very strong s strong ms medium to strong m medium

time and also generated the best yield the little needof solvent product purification workup and the need ofmicrowave oven and microwave reaction vials put it next inchoice over the fusion method

In the synthetic procedures apart from a sharp meltingpoint of 180∘C formation of condensation product wasalso evidenced from UV-Visible spectral change and HPLCretention time (Figure 1) Reaction progress and completionand product purity were monitored by TLC (Ethyl acetate n-hexane (1 1) developing solvent and iodine vapour visualiza-tion)The Schiff base ligandwas purified by chromatographicseparation over a silica column using 1 1 ethyl acetate andn-hexane mobile phase The compounds eluted from thecolumn in the following order Benzil Schiff base (DE) andfinally 4-aminoantipyrine with retention time 267 288 and397 minutes sequentially

52 Spectroscopic Characterization of Ligand and ComplexesThe structural characterization of the ligand was done by thespectral (IR NMR) mass and elemental (C H N) analysisThe Schiff base ligandwas obtained as light yellow compoundwith MP 179ndash185∘C The IR (KBr) displayed characteristicCarbonyl absorption (] cmminus1) 1650ndash1660 ](cyclicketoneC=O) 1630ndash1640 ](CH=N) In the 1H NMR 1H NMR(CDCl

3 400MHz 120575 ppm) (717ndash76m for aromatic protons

of C6H5) 33-34 (m 6H for ndashNndashCH

3protons) 23 (m for

methyl protons on double bonded ring carbon =CndashCH3)

The high resolution electron impact mass spectrometryHRESIMS depicted the molecular ion peak at (mz) 58144calcd for C

36H32N6O2[M+H]+ The absorption spectra of

10minus4M solution of DE in ethanol at 120582 ranging from 300 to700 nm against the same solvent as a blank give 2 bands at330 nm (120576 = 19 times 102Mminus1 cmminus1) and a sharp band (120582max)410 nm with (120576 = 20 times 103Mminus1 cmminus1) The absorptioncan be

assigned to the intraligand transition bands corresponding ton-120587lowast and 120587-120587lowast transitions respectively [27]

The characterization of Schiff base (DE) complexes wasdone through changes in the diagnostic IR absorption bandsUV-Visible spectra melting point and CHN analysis whichare summarized in Table 2 The 1 1 stoichiometry of vanadyland uranyl complexes of DE was spectrophotometricallyobtained using Jobs continuous variation and molar ratiomethods (Figure 2) The monomeric nature of vanadyl DEcomplex was established from the characteristic metal-oxygen ](V=O) stretching frequency in the region 965ndash960 cmminus1 [28] the absence of a band below 900 cmminus1 due tobridging vanadyl group ndashVndashOndashVndash rules out the possibilityof polymeric vanadyl complexes [29] The three IR bandscorresponding to ionic sulphate group in [VO(DE)]SO

4

complex were observed at 900 620 and 1110 cmminus1 [30] TheIR frequency of the O=U=O was observed at 908 cmminus1 andwas in accordance with the expected value for a cationicuranyl complex [31] The electronic spectra of the vanadyland uranyl complexes depict slight splitting and shifting ofthe band positions to longer wavelength compared to thatof the free ligand DE The absorption bands at 502 nm and795 nm (weak band) in case of [VO(DE)]2+ were assigned tothe 2B

2rarr2A1and 2B

2rarr2E transitions of square pyram-

idal geometry [30] The intense band at 480 nm in case[UO2(DE)]2+ was assigned to the ligand to metal charge

transfer (LMCT) transition of nonbonding electrons of ligandDE to the empty d orbitals of dioxouranium(VI) [32] Thehigh molar conductance of the DMF solution of vanadyland uranyl DE complexes (Table 2) verify electrolytic natureof [VO(DE)](NO

3)2and uranyl [UO

2(DE)]SO

4 To get an

insight of molecular geometry we used density functionaltheory for structure optimization of Schiff base ligand (DE)


600

400

200

0

0 5

Retention time

POA 454nm

(a)

400

200

0

0 5

Retention time

POA 454nm

(b)

Retention time Column temperature minus25∘C

Solvent system

Solvent pH minus3

Flow rate

Retention time

Benzil

Schiff base (DE)

400

200

0

0 5

POA 454 nm

minus05 mL minminus1

(a) 267 min

(b) 397 min

(c) 288 min

4-Aminoantipyrine

CH3OH H2O (9 1)

(c)

Figure 1 HPLC retention time of Schiff base (DE) and reagents

and its uranyl and vanadyl complexesThe optimized geome-tries of vanadyl [VO(DE)]2+ and uranyl [UO

2(DE)]2+ com-

plex ions were found to be square pyramidal and tetragonallycompressed octahedron respectively (Figure 3)

53 Thermodynamics of Complexation The synthesis of theSchiff base and its complexation with vanadyl nitrate anduranyl sulphate was carried in two steps and is depicted inScheme 1

54 Determination of Stability Constant The protonationconstant of DE was determined by adopting the methodsuggested by Irwing and Rossetti The plots of pH versus

volume of alkali added were drawn (Figure 4) and used forevaluation of nA using

nA =(1198640+ 119873) (119881

2minus 1198811)

(1198810+ 1198811) 119879L0 (1)

where 119873 stands for concentration of KOH (100mM) and(1198812minus1198811) is the displacement (mL) of the ligand curve relative

to acid curve (Figure 4) where 1198812and 119881

1are the volume of

alkali added to reach the same pH value as for free acid 1198640

and 119879L0 are the resultant concentrations of HCl and Ligand(DE) respectively119881

0is the initial volume of reactionmixture

(20mL) Proton-ligand stability constant log119870a value of


O

O

NN

O

NN

O

N

N

NN

NN

O

O N

N

NN

NN

O

OM

Ph

Ph

Ph

PhPh

PhPh

PhPh

PhPh

Ph

MeMe

Me Me Me Me Me

MeMeMeMe

Me

H2N

H2NEthanolreflux

minus2H2O

Benzil

DE

+

M = UO22+ VO2+

4-Aminoantipyrine

Scheme 1 Synthesis of Schiff base (DE) and its metal ion complexation

ligand was calculated from formation curve (nA versus pH)by half integral method pH at which nA = 05 (Figure 5(a))From the shift in equivalence point values and correspondingpH values the value of p119870a for DE was calculated to be 783Stability constants of metal-DE complexes ([VO(DE)]2+ and[UO2(DE)]2+ complex) were determined using Bjerrum pH

metric method In this regard three sets of solutions weretitrated pH metrically against standard potassium hydroxidesolution at constant temperature (298K)

(1) Free acid titration (A) HCl (100mM)(2) Free acid + ligand titration (A + DE) HCl + Schiff

base (DE)(3) Free acid + ligand+metal titration (A+DE+M)HCl

+ ligand (DE) +Metal ion solution (M) [M= (Vanadylsulphate Uranyl nitrate)]

Metal-ligand stability constants (log119870) were determinedby the half integral method by plotting nL versus pL(Figure 5(b)) The experimental nL values were determinedusing

nL =(1198640+ 119873) (119881

3minus 1198812)

(1198810+ 1198812) 119879M0

(2)

where119873 11986401198810 and119881

2have same significance as in (1)119881

3is

the volume of KOH added in the metal ion titration to attainthe same pH reading and 119879M0 (10mM) is the concentrationof metal ion in reaction mixture Plots of nL versus pLallowed calculation of the stability constants by the Bjerrummethod (Figure 5(c)) The calculated stability constant valuesof metal-DE complexes are 501times103 and 282times103 (log119870 =370 and 345) for vanadyl and uranyl complexes respectivelyThe relatively higher stability constant of the vanadyl complexthan uranyl complex can be attributed to the preorganizationenergies needed for the metal ion to get into the planar Schiffbase ligand (DE) [27 33 34]

6 Kinetics of Complexation

Kinetic investigation of complexation reaction was carriedout by absorbancemeasurements at 410 nm (120582max of DE)Theabsorbance at 410 nm showed remarkable changes (decrease)in a time dependent manner upon addition of metal ions

010

008

006

004

002

000

00 02 04 06 08 10

Abso

rban

ce

[UO2(DE)]2+

[VO(DE)]2+

[M][M] + [L]

016

014

012

010

008

006

004

0020 1 2 3 4 5 6

Abso

rban

ce

[L][M]

Figure 2 Stoichiometry of DE-vanadyl and DE-uranyl complexa-tion by Jobs method Insert mole ratio plot

which we ascribed to the slowness of the complexationreaction The decreases in absorbance were relatively slowerin case of uranyl system than vanadyl system It was thisslowness which prompted us to undertake the kinetic studiesof this complexation reactionThe reaction ofmetal ions withDE can be expressed by the following equation

M + DE [M (DE)] (3)

where M = UO2

2+ and VO2+ The rate equation for thecomplexation reaction was established as under

Rate (]) prop [M]119883 [DE]119884

] = 119896 [M]119883 [DE]119884(4)

under pseudo first order conditions

]1= 1198961015840

[M]119883

]2= 11989610158401015840

[DE]119884 where 1198961015840 = 119896 [DE] 11989610158401015840 = 119896 [M] (5)


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H

Optimized geometries

Level of theory used

DFT B3LYP (functional)

LanL2MB (basis set)

(a) Schiff base (DE)

(b) vanadyl (DE) complex

(c) uranyl (DE) complex

(c)

Figure 3 Optimized geometries of Schiff base (DE) vanadyl-DE and uranyl-DE complex

The absorbance changes at varying concentrations of onereactant and fixed (excess) concentration of other in logarith-mic scale was observed as a straight line with slopes equalto 119909 and 119910 respectively and the intercepts equal to 1198961015840 and11989610158401015840 respectively Value of actual rate constant (119896) was then

determined from the intercept values after substituting forthe concentration values used for the studies The plots ofLn (Rate) versus metal ion concentration were observed tobe a straight line with slope of 0980 indicative of first orderkinetics with respect to metal ion concentration (Figure 6)Similar studies keeping DE concentration as limiting andmetal ion concentration in excess again showed a straightline predicting first order kinetics with respect to DE aswell Thus from concentration profile kinetic study the

complexation reaction was observed to follow first orderkinetics with respect to metal ions and DE with an overall2nd order kinetics However the pseudo first order kineticswith respect to both reactants was further verified by usingthe 1st order integrated rate equation

119905 =2303

119896

log1198600

119860119905

(6)

The plot of 119905 versus log(1198600119860119905) was observed as a straight

line with slope equal to 1198962303 (Figure 7) The rate constantvalues from both the initial rate method and integrated ratelaw calculations were in close agreement with each otherconfirming 1st order kinetics for both reactants and an overall


12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)

(1) Acid(2) Acid + DE

(3) Acid + DE + UO2(II)(4) Acid + DE + VO(II)

Figure 4 Plot depicting pH titration of ligand (DE) in presence of vanadyl and uranyl metal ions

065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)

Figure 5 (a) Plot depicting variation of nH with pH (b) nL as a function of pL for vanadyl-DE (c) nL as a function of pL for uranyl-DEcomplexation reactions


080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [

Figure 6 Pseudo first order kinetic profile of uranyl-DE complexa-tion reaction

012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)

Temperature (K)(1) 278

(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)

Figure 7 Plot of integrated rate law for uranyl-DE complexationreaction

order of two The value of rate constant 119896 at 25∘C from anaverage of three sets of experiments was calculated to be 525times 10minus2 Lmolminus1sminus1 for vanadyl DE and 347 times 10minus3 Lmolminus1sminus1for uranyl DE complexation Temperature dependent kineticstudies were carried to calculate the activation energy (119864

119886) for

the said complexation reactions Rate constants determinedat the studied temperatures are tabulated in Table 3 From theplot of individual rate constant values at different tempera-tures (Lnk vs 1119879) (Figure 8) activation energy barrier (119864

119886)

of ca 40913 and 48661 KJmolminus1 was calculated for vanadyland uranyl DE complexation respectively from the slope =minus119864119886119877 (where 119877 stands for gas constant)

10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036

System R2 St line equation[VO(DE)]2+[UO2(DE)]2+

Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)

Figure 8 Arrhenius plot for the determination of activation energybarrier of vanadyl-DE and uranyl-DE complexation

From the kinetic investigations it was concluded thatcomplexation of both vanadyl and uranyl ions with Schiffbase ligand DE is a slow reaction however the complexationreaction is more slow in case of uranyl than vanadyl ionThis difference in the kinetics of two complexation reactionshighlighted the influence of metal ion steric factors andanticipated ligand preorganization on complexation process[35] The presence of two axial oxygen atoms on uranium incase of uranyl poses a double steric restriction for approachof the ligand to the metal ion in comparison to single axialoxygen on vanadium in vanadyl Accordingly the complex-ation reaction is slower in uranyl than vanadyl MoreoverDE as a tetradentate ligand has a rigid frame work due tothe presence of four phenyl rings on its outer peripherynearly perpendicular to the N

2O2plane (Figure 2) Presence

of two axial oxygens on uranyl ion causes DE to makemore adjustments so as to occupy four planar positions Thisrigidity of DE coupled with the preoccupation of two axialsites by oxygen atoms result in a very slow DE complexationwith uranyl due to ligand preorganization barriers [36]

7 Bioactivity Evaluation

The in vitro screening of biocidal potential of the Schiffbase ligand (DE) and its vanadyl and uranyl complexes asantibacterial antifungal and antihelminthic was carried outThe antibacterial activities of synthesised ligand (DE) andits metal complexes towards the Gram-positive bacteria Saureus and the Gram-negative bacteria K pneumoniae Styphi Ecoli and S flexneri were compared through theradius of zones of inhibition against Gentamycin (Control)The antibacterial study was done by Well diffusion method[37] Figure 9 The antifungal activities of Schiff base ligandDE and its vanadyl and uranyl complex were evaluated by the


Table 3 Rate constants of vanadyl and uranyl (DE) complexation at different temperatures

Temperature (∘C) 1119879 (Kminus1)VO (DE)

rate constant (1198961)119896 plusmn 005 (sminus1)

UO2 (DE)rate constant (1198962)119896 plusmn 005 (sminus1)

ln(1198961) ln(1198962)

5 0003597 019 025 minus166 minus13415 0003472 032 047 minus114 minus07625 0003356 058 087 minus054 minus01430 00033 172 119 minus032 01735 0003247 112 230 0113 083

25

20

15

10

5

020 40 20 40 20 40

S aureusK pneumoniaeE coli

S typhiS flexneri

DE [VOL]SO4 Gentamycin

IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri

Figure 9 Antibacterial activities of Schiff base (DE) vanadyl-DE and uranyl-DE complex and Gentamycin (Control) at 20 and 40 120583gmLminus1

AgarWell Diffusionmethod [37] against the two types of fungiA niger and ldquoR bataticolardquo The comparison of antifungalactivity was done in terms of zones of inhibition (in mm)measured against Amphotericin (Control) Figure 10

The Schiff base (DE) and its vanadyl and uranyl com-plexes were tested for in vitro antihelminthic activity byGhosh et al method [38] wherein the adult Pheretimaposthuma (earth worms) were exposed to different concen-trations of Schiff base (DE) and its complexes The dosedependent antihelminthic activity was compared on the basisof time taken for paralysis and death of individual earthwormagainst Albendazole as control drug Figure 11

It was observed from the inhibition zone radii and timetaken for death of earth worm that the biocidal potential ofDE increases on complexation with the studied metal ionsThis can be well explained by Overtones concept and Tweedychelation theory [39ndash41] The lipophilicity of free ligandincreases and polarity of metal ion gets reduced due to over-lap of ligand and metal orbitals on complexation Accordingto the Overtonersquos concept of cell permeability an increasein the hydrophobicity increases the antimicrobial activitydue to enhanced bioavailability Moreover due to increaseddelocalization of electrons over the whole chelate ring thelipophilicity of the complexes is boosted This increasedlipophilicity enhances the biocidal potential of bioactivecompounds by their penetration into the lipid membrane

and cytoplasm In our study the antimicrobial antifungaland antihelminthic activity were found to be in the order[VODE]SO

4gt [UO

2DE](NO

3)2gt [DE] The maximum

biocidal potential of vanadyl complex can be attributed toits maximum lipophilicity and relatively lower polarity (dueto single oxygen attached to metal) in light of Overtonersquosconcept and better ability to bind with cellular componentsdue to coordinatively unsaturated pentacoordinate nature oftrigonal bipyramidal geometry

8 Conclusion

In summary this work describes the synthesis and structureelucidation of a tetradentate Schiff base ligand (DE) and itstarget complexation with oxovanadium(IV) and dioxoura-nium(VI) metal ions The solution phase thermodynamicstability constants of log119870 = 370 and 345were calculated for[VO(DE)]SO

4and [UO

2DE](NO

3)2complexes respectively

An extensive kinetic investigation of DE complexation reac-tion with oxovanadium(IV) and dioxouranium(VI) predictsoverall 2nd order kinetics with rate constants of 525 times 10minus2for vanadyl and 347times10minus3 Lmolminus1sminus1 for uranylDE complexThe different complexation rates under identical conditionsin case of oxovanadium(IV) and dioxouranium(VI) werecorroborated with the ligand preorganization and metal ionsteric effects The presence of one and two axial oxygen


60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE [UO2L](NO3)2[VOL]SO4 Amphotericin

Rhizoctonia bataticola

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin

Aspergillus niger Aspergillus nigerRhizoctonia bataticola

Figure 10 Antifungal activities of Schiff base (DE) vanadyl-DE and uranyl-DE complex and Amphotericin (Control) at 100 200 and300 120583gmLminus1

Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)

Motion lostDeath time

Schi

ff ba

se(D

E)

Figure 11 Antihelminthic activity of Schiff base (DE) vanadyl-(DE) and uranyl-(DE) complex and Albendazole (Control) at25 120583gmLminus1

atoms in case of oxovanadium(IV) and dioxouranium(VI)respectively creates less steric restriction in case of oxovana-dium(IV) than dioxouranium(VI) The biological screening(antibacterial antifungal and antihelminthic) of the Schiffbase ligand DE its oxovanadium(IV) and dioxouranium(VI)complex were found to be in the order [VODE]SO

4gt

[UO2DE](NO

3)2gt [DE] Further studies aimed at the mode

of action of the screened compounds are underway andefforts are continued towards synthesizing compounds ofpossible therapeutic significance

Conflict of Interests

The authors declare that they have no competing financialinterest and there is no conflict of interests regarding thepublication of this paper

References

[1] A Syamal and D Kumar ldquoMolybdenum complexes of bioinor-ganic interest New dioxomolybdenum(VI) complexes of schiffbases derived from salicylaldehydes and salicylhydraziderdquoTransition Metal Chemistry vol 7 no 2 pp 118ndash121 1982

[2] Y Jin Y Zhu and W Zhang ldquoDevelopment of organic porousmaterials through Schiff-base chemistryrdquo Crystal EngineeringCommunication vol 15 no 8 pp 1484ndash1499 2013

[3] E Ispir S Toroglu and A KayraldIz ldquoSyntheses characteriza-tion antimicrobial and genotoxic activities of new Schiff basesand their complexesrdquo Transition Metal Chemistry vol 33 no 8pp 953ndash960 2008

[4] S Krishnaraj M Muthukumar P Viswanathamurthi and SSivakumar ldquoStudies on ruthenium(II) Schiff base complexes ascatalysts for transfer hydrogenation reactionsrdquo TransitionMetalChemistry vol 33 no 5 pp 643ndash648 2008

[5] A Ganguly B K Paul S Ghosh S Kar and N GuchhaitldquoSelective fluorescence sensing of Cu(II) and Zn(II) using anew Schiff base-derived model compound naked eye detectionand spectral deciphering of the mechanism of sensory actionrdquoAnalyst vol 138 no 21 pp 6532ndash6541 2013

[6] Z Chen H Morimoto S Matsunaga and M ShibasakildquoA bench-stable homodinuclear Ni

2-Schiff base complex for

catalytic asymmetric synthesis of 120572-tetrasubstituted anti-120572120573-diamino acid surrogatesrdquo Journal of the American ChemicalSociety vol 130 no 7 pp 2170ndash2171 2008

[7] R C Maurya D D Mishra M Pandey P Shukla and RRathour ldquoSynthesis and spectral studies of octacoordinateddioxouranium(VI) complexes with some Schiff Bases derivedfrom 4-acetyl-23-dimethyl-l-(4-methylphenyl)-3-pyrazoline-5-one and aromatic aminesrdquo Synthesis and Reactivity in Inor-ganic and Metal-Organic Chemistry vol 23 no 1 pp 161ndash1741993

[8] K Z Ismail A El-Dissouky and A Z Shehada ldquoSpectro-scopic and magnetic studies on some copper(II) complexes ofantipyrine Schiff base derivativesrdquo Polyhedron vol 16 no 17 pp2909ndash2916 1997

[9] R K Agarwal P Garg H Agarwal and S Chandra ldquoSyn-thesis magneto-spectral and thermal studies of cobalt(II) and


nickel(II) complexes of 4-[N-(4-dimethylaminobenzylidene)amino] antipyrinerdquo Synthesis and Reactivity in Inorganic andMetal-Organic Chemistry vol 27 no 2 pp 251ndash268 1997

[10] R K Agarwal and J Prakash ldquoSynthesis and characterizationof thorium(IV) and dioxouranium(VI) complexes of 4-[N(2-hydroxy-1-naphthalidene)amino]antipyrinerdquo Polyhedron vol10 no 20-21 pp 2399ndash2403 1991

[11] G Shankar R R Premkumar and S K Ramalingam ldquo4-Aminoantipyrine schiff-base complexes of lanthanide anduranyl ionsrdquo Polyhedron vol 5 no 4 pp 991ndash994 1986

[12] S K Sridhar M Saravanan and A Ramesh ldquoSynthesis andantibacterial screening of hydrazones Schiff andMannich basesof isatin derivativesrdquo European Journal of Medicinal Chemistryvol 36 no 7-8 pp 615ndash625 2001

[13] H Kunz W Pfrengle K Ruck and W Sager ldquoStereoselectivesynthesis of L-amino acids via Strecker and Ugi reactions oncarbohydrate templatesrdquo Synthesis no 11 pp 1039ndash1042 1991

[14] I Vazzana E Terranova FMattioli and F Sparatore ldquoAromaticSchiff bases and 23-disubstituted-13-thiazolidin-4-one deriva-tives as antiinflammatory agentsrdquo Arkivoc vol 2004 no 5 pp364ndash374 2004

[15] A Rivera J Rıos-Motta and F Leon ldquoRevisiting the reactionbetween diaminomaleonitrile and aromatic aldehydes a greenchemistry approachrdquo Molecules vol 11 no 11 pp 858ndash8662006

[16] R S Varma R Dahiya and S Kumar ldquoClay catalyzed synthesisof imines and enamines under solvent-free conditions usingmicrowave irradiationrdquo Tetrahedron Letters vol 38 no 12 pp2039ndash2042 1997

[17] A Vass J Dudas and R S Varma ldquoSolvent-free synthesisof N-sulfonylimines using microwave irradiationrdquo TetrahedronLetters vol 40 no 27 pp 4951ndash4954 1999

[18] P T Anastas and J C Warner Green Chemistry Theory andPractice Oxford University Press New York NY USA 1998

[19] DWarrenGreen Chemistry A Teaching Resource Royal Societyof Chemistry Cambridge UK 2001

[20] J Clark and D Macquarrie Handbook of Green Chemistry andTechnology Blackwell Oxfordshire UK 2002

[21] J Bjerrum ldquoOn the tendency of the metal ions toward complexformationrdquo Chemical Reviews vol 46 no 2 pp 381ndash401 1950

[22] H Irving andH S Rossotti ldquoMethods for computing successivestability constants from experimental formation curvesrdquo Jour-nal of the Chemical Society pp 3397ndash3405 1953

[23] O Taheri M Behzad A Ghaffari et al ldquoSynthesis crystalstructures and antibacterial studies of oxidovanadium(IV)complexes of salen-type Schiff base ligands derived frommeso-12-diphenyl-12-ethylenediaminerdquo Transition Metal Chemistryvol 39 no 2 pp 253ndash259 2014

[24] A Sheela and R Vijayaraghavan ldquoA study on the glucose low-ering effects of ester-based oxovanadium complexesrdquoTransitionMetal Chemistry vol 35 no 7 pp 865ndash870 2010

[25] M Rangel ldquoPyridinone oxovanadium(IV) complexes a newclass of insulin mimetic compoundsrdquo Transition Metal Chem-istry vol 26 no 1-2 pp 219ndash223 2001

[26] E Goldman Green Practical Handbook of Microbiology CRCPress Taylor amp Francis New York NY USA 2nd edition 2009

[27] G A Lawrance M Maeder and M J Robertson ldquoSynthesis ofa four-strand N

2O2-donor ligand and its transition metal com-

plexation probed by electrospray ionisationmass spectrometryrdquoTransition Metal Chemistry vol 29 no 5 pp 505ndash510 2004

[28] X R Bu E A Mintz X Z You et al ldquoSynthesis and charac-terization of vanadyl complexes with unsymmetrical bis-Schiffbase ligands containing a cis-N

2O2coordinate chromophorerdquo

Polyhedron vol 15 no 24 pp 4585ndash4591 1996[29] N R Rao P V Rao G V Reddy and M C Ganorkar ldquoMetal

chelates of a Physiologically active ONS tridentate Schiff baserdquoIndian Journal of Chemistry vol 26A pp 887ndash890 1987

[30] A P Mishra and M Soni ldquoSynthesis structural and biologicalstudies of some Schiff bases and their metal complexesrdquoMetal-Based Drugs vol 2008 Article ID 875410 7 pages 2008

[31] C C Gatto E Schulz Lang A Kupfer A Hagenbach D Willeand U Abram ldquoDioxouranium complexes with acetylpyridinebenzoylhydrazones and related ligandsrdquo Zeitschrift fur Anor-ganische und Allgemeine Chemie vol 630 no 5 pp 735ndash7412004

[32] A T Mubarak ldquoStructural model of dioxouranium(VI) withhydrazono ligandsrdquo Spectrochimica Acta Part A Molecular andBiomolecular Spectroscopy vol 61 no 6 pp 1163ndash1170 2005

[33] M A Rizvi R M Syed and B Khan ldquoComplexation effecton redox potential of Iron(III)mdashIron(II) couple a simplepotentiometric experimentrdquo Journal of Chemical Education vol88 no 2 pp 220ndash222 2011

[34] C A Chang Y-L Liu C-Y Chen and X-M Chou ldquoLigandpreorganization inmetal ion complexation molecular mechan-icsdynamics kinetics and laser-excited luminescence studiesof trivalent lanthanide complex formation with macrocyclicligands TETA and DOTArdquo Inorganic Chemistry vol 40 no 14pp 3448ndash3455 2001

[35] Y Z Yousif and F J M Al-Imarah ldquoSpectrophotometric studyof the effect of substitution on the thermodynamic stabilityof the 11 complexes of the dioxouranium(II) ion with mono-substituted salicylic acids in aqueous mediardquo Transition MetalChemistry vol 14 no 2 pp 123ndash126 1989

[36] Y Anjaneyula and R P Rao ldquoPreparation characterization andantimicrobial activity studies on some ternary complexes of Cu(II) with acetylacetone and various salicylic acidsrdquo SyntheticReaction Inorganic Metal Organic Chemistry vol 16 no 2 pp257ndash272 1986

[37] M J Pelczar E C S Chan and N R Krieg MicrobiologyBlackwell Science New York NY USA 5th edition 1998

[38] T Ghosh T K Maity A Bose and G K Dash ldquoAnthelminticactivity of Bacopa Monierrirdquo Indian Journal of Natural Productvol 21 pp 16ndash19 2005

[39] P Knopp K Weighardt B Nuber J Weiss andW S SheldrickldquoSyntheses electrochemistry and spectroscopic and magneticproperties of new mononuclear and binuclear complexesof vanadium(III) -(IV and -(V) containing the tridentatemacrocycle 147-trimethyl-147-triazacyclononane (L) Crystalstructures of [L2V2(acac)2(mu-O)]I22H2O [L2V2O4(mu-O)]14H

2O and [L2V2O2(OH)2(mu-O)](ClO4)2rdquo Inorganic

Chemistry vol 29 no 3 pp 363ndash371 2009[40] L Mishra and V K Singh ldquoSynthesis structural and antifungal

studies of Co(II Ni(II Cu(II) and Zn(II) complexes withnew Schiff bases bearing benzimidazolesrdquo Indian Journal ofChemistry vol 32 no 5 pp 446ndash457 1993

[41] N Dharmaraj P Viswanathamurthi and K Natarajan ldquoRuthe-nium(II) complexes containing bidentate Schiff bases and theirantifungal activityrdquo Transition Metal Chemistry vol 26 no 1-2pp 105ndash109 2001

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


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


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


the condensation reaction of 4-aminoantipyrine with benzilThe target synthesis of oxovanadium(IV) and dioxoura-nium(VI) (vanadyl and uranyl) complexes with the Schiffbase ligand (DE) was also attempted to envisage the effectof metal ion steric factor on complexation process throughsolution phase thermodynamic and kinetic studiesThe ther-modynamic stabilities of vanadyl and uranyl Schiff base (DE)complexes are discussed in light of their calculated solutionphase stability constants using Calvin-Bjerrum and Irwing-Rossotti [21 22] potentiometric method The kinetic profileof theDE-uranyl andDE-vanadyl complexation throughUV-Visible studies describes the effect of metal ion concentrationand Steric effect on complexation reaction Keeping in viewthe bioactive nature of the starting compounds and reportedbioactivity of vanadium complexes [23ndash25] the synthesisedligand (DE) and its complexes were screened for biocidalpotential using the standard protocols [26] with the resultscompared to corresponding reference drugs

2 Materials and Methods

All chemicals and solvents were obtained from commercialsources as laboratory reagents and used without furtherpurification in the syntheses The metal salts used in com-plexation were analytical grade uranyl nitrate and vanadylsulphate The microwave assisted synthesis was carried outin Teflon reaction cells with SHARP 1000WR-21LCF com-mercial microwave oven fitted with a temperature relaywith circuit break at 145∘C The high performance liquidchromatography (HPLC) was carried on Schimadzu LC-20Awith a SPD-M20A variable-wavelength UV detector Themobile phase used consisted of water methanol (10 90 vv)flowing at rate of 05mLminminus1 Electronic spectra of thecomplexes were recorded on a Shimadzu 3600 UV-Visiblespectrophotometer with thermostatic control CHN analysesof all the synthesized compounds were done on Vario EL IIICHNS analyser FT-IR spectra were recorded as KBr pelletswith a Perkin Elmer FTIR Spectrum-2 in the 4000ndash400 cmminus1range The 1H NMR spectrum was recorded in CDCl

3on a

Bruker Avance DRX 500MHzNMR spectrometer The massspectra were taken on Micromass Q-Tof micro YA-105 Allinstrumental measurements were done at room temperature(around 25∘C) except in case of kinetic profile

3 Synthesis of 12-(Diimino-41015840-antipyrinyl)-12-diphenylethane (DE)

The tetradentate Schiff base ligand was synthesized by threedifferent synthetic protocols (solvent refluxing microwaveassisted and solvent free fusion method) for a comparativestudy aimed at environmentally benign procedure

31 Solvent Refluxing Method In this method an ethanolicsolution of benzil (105 g 5mmol) and 4-aminoantipyrine(203 g 10mmol) was refluxed at 60∘C for about 05 hrs Oncooling and solvent evaporation the yellow solid of Schiffbase ligand (DE) got separated which was filtered as crudeproduct and recrystallized from ethanol

32Microwave AssistedMethod In thismethod the reactantsin a molar ratio of 2 1 (203 g 10mmol of 4-aminoantipyrineand 105 g 5mmol of benzil) were thoroughly mixed withsilica gel and put inside the Teflon tube for microwaveirradiation under medium power for 05 minutes generating amaximum temperature up to 145∘C The solid product wasdissolved in ethanol to separate the compound and silicagel the Schiff base product got separated on evaporation ofsolvent

33 Solvent-Free Fusion Method In an effort to introduce anovel eco-friendly synthetic procedure solvent-free fusionmethod was attempted In the solvent-free fusion reac-tion the reactant with higher melting point that is 4-aminoantipyrine (MP = 110∘C) was melted and then theother reactant benzil (MP = 90∘C) was added to the moltenstate of the former which served both as the reagent andas solvent besides providing a high reaction temperatureThe reaction mixture was kept at 100∘C in a silicone oil bathunder constant stirring for 2 hrs over amagnetic stirrer Afterstirring time the solid product was dissolved in ethanol andfiltered the filtrate on evaporation produced the Schiff basecompound

4 Synthesis of Complexes

The complexation of DE with metal salts was carried out byrefluxing an equimolar (1 1) mixture of uranyl nitrate andvanadyl sulphate with Schiff base ligand DE respectively forabout 5-6 hrs in ethanol The progress of the reaction wasfollowed by TLC After completion of reaction time (6 hrs)the refluxed solution was concentrated to one-third of itsinitial volume on awater bathTheproducts were obtained onfiltration washed with ethanol and dried under vacuum Abright yellow compound of composition [UO

2(DE)](NO

3)2

with melting point (MP) 290ndash300∘C and a grey compoundof composition [VO(DE)]SO

4with MP 220ndash225∘C were

obtained for uranyl nitrate and vanadyl sulphate complexa-tion with DE

5 Results and Discussion

51 Comparative Synthetic Methodology The Schiff base 12-(diimino-4-antipyrinyl)-12-diphenylethane (DE) was syn-thesised by the condensation of 1-phenyl-23-dimethyl-4-aminopyrazol-5-one (4-aminoantipyrine) with 12-diphen-ylethane-12-dione (benzil) using three synthetic methodolo-gies The efficacy of these methods was compared in terms ofreaction time percent yield and energy demand (Table 1)

The conventional solvent refluxing method was the leastefficient of the three methodologies in terms of time andenergy demand besides being economically and environ-mentally less viable The proposed fusion method is impres-sive in terms of product purity and appreciable yield in asmaller timeThus relatively smaller reaction time no solventdemand and lower chemical and energy expense makethis method meet green chemistry criteria [18] Althoughmicrowave assisted synthesis required minimum reaction





240 40 120 50 3 32 1 321300 45 150 70 5 60 5 781




DE7286(7454)

540(551)

1277(1448) 179ndash185 1655


[VO-(DE)]SO4527

(5307)385(393)

1008(1032) 220ndash225 1630

(s)1600(ms)

400(m)

540(m) 502 1606

[UO2(DE)](NO3)25106(5298)

498(423)

1052(1132) 290ndash300 1632

(s)1615(ms)

410(m)

570(m) 480 1728







3protons) 23 (m for







4


2rarr2A1and 2B




3)2and uranyl [UO

2(DE)]SO

4 To get an



600

400

200

0

0 5

Retention time

POA 454nm

(a)

400

200

0

0 5

Retention time

POA 454nm

(b)


Solvent system

Solvent pH minus3

Flow rate

Retention time

Benzil

Schiff base (DE)

400

200

0

0 5

POA 454 nm


(a) 267 min

(b) 397 min

(c) 288 min

4-Aminoantipyrine

CH3OH H2O (9 1)

(c)



2(DE)]2+ com-





nA =(1198640+ 119873) (119881

2minus 1198811)

(1198810+ 1198811) 119879L0 (1)



1are the volume of






O

O

NN

O

NN

O

N

N

NN

NN

O

O N

N

NN

NN

O

OM

Ph

Ph

Ph

PhPh

PhPh

PhPh

PhPh

Ph

MeMe

Me Me Me Me Me

MeMeMeMe

Me

H2N

H2NEthanolreflux

minus2H2O

Benzil

DE

+

M = UO22+ VO2+

4-Aminoantipyrine








nL =(1198640+ 119873) (119881

3minus 1198812)

(1198810+ 1198812) 119879M0

(2)

where119873 11986401198810 and119881


3is




010

008

006

004

002

000

00 02 04 06 08 10

Abso

rban

ce

[UO2(DE)]2+

[VO(DE)]2+

[M][M] + [L]

016

014

012

010

008

006

004

0020 1 2 3 4 5 6

Abso

rban

ce

[L][M]



M + DE [M (DE)] (3)

where M = UO2


Rate (]) prop [M]119883 [DE]119884

] = 119896 [M]119883 [DE]119884(4)


]1= 1198961015840

[M]119883

]2= 11989610158401015840

[DE]119884 where 1198961015840 = 119896 [DE] 11989610158401015840 = 119896 [M] (5)


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H




LanL2MB (basis set)




(c)





119905 =2303

119896

log1198600

119860119905

(6)




12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





240 40 120 50 3 32 1 321300 45 150 70 5 60 5 781




DE7286(7454)

540(551)

1277(1448) 179ndash185 1655


[VO-(DE)]SO4527

(5307)385(393)

1008(1032) 220ndash225 1630

(s)1600(ms)

400(m)

540(m) 502 1606

[UO2(DE)](NO3)25106(5298)

498(423)

1052(1132) 290ndash300 1632

(s)1615(ms)

410(m)

570(m) 480 1728







3protons) 23 (m for







4


2rarr2A1and 2B




3)2and uranyl [UO

2(DE)]SO

4 To get an



600

400

200

0

0 5

Retention time

POA 454nm

(a)

400

200

0

0 5

Retention time

POA 454nm

(b)


Solvent system

Solvent pH minus3

Flow rate

Retention time

Benzil

Schiff base (DE)

400

200

0

0 5

POA 454 nm


(a) 267 min

(b) 397 min

(c) 288 min

4-Aminoantipyrine

CH3OH H2O (9 1)

(c)



2(DE)]2+ com-





nA =(1198640+ 119873) (119881

2minus 1198811)

(1198810+ 1198811) 119879L0 (1)



1are the volume of






O

O

NN

O

NN

O

N

N

NN

NN

O

O N

N

NN

NN

O

OM

Ph

Ph

Ph

PhPh

PhPh

PhPh

PhPh

Ph

MeMe

Me Me Me Me Me

MeMeMeMe

Me

H2N

H2NEthanolreflux

minus2H2O

Benzil

DE

+

M = UO22+ VO2+

4-Aminoantipyrine








nL =(1198640+ 119873) (119881

3minus 1198812)

(1198810+ 1198812) 119879M0

(2)

where119873 11986401198810 and119881


3is




010

008

006

004

002

000

00 02 04 06 08 10

Abso

rban

ce

[UO2(DE)]2+

[VO(DE)]2+

[M][M] + [L]

016

014

012

010

008

006

004

0020 1 2 3 4 5 6

Abso

rban

ce

[L][M]



M + DE [M (DE)] (3)

where M = UO2


Rate (]) prop [M]119883 [DE]119884

] = 119896 [M]119883 [DE]119884(4)


]1= 1198961015840

[M]119883

]2= 11989610158401015840

[DE]119884 where 1198961015840 = 119896 [DE] 11989610158401015840 = 119896 [M] (5)


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H




LanL2MB (basis set)




(c)





119905 =2303

119896

log1198600

119860119905

(6)




12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


600

400

200

0

0 5

Retention time

POA 454nm

(a)

400

200

0

0 5

Retention time

POA 454nm

(b)


Solvent system

Solvent pH minus3

Flow rate

Retention time

Benzil

Schiff base (DE)

400

200

0

0 5

POA 454 nm


(a) 267 min

(b) 397 min

(c) 288 min

4-Aminoantipyrine

CH3OH H2O (9 1)

(c)



2(DE)]2+ com-





nA =(1198640+ 119873) (119881

2minus 1198811)

(1198810+ 1198811) 119879L0 (1)



1are the volume of






O

O

NN

O

NN

O

N

N

NN

NN

O

O N

N

NN

NN

O

OM

Ph

Ph

Ph

PhPh

PhPh

PhPh

PhPh

Ph

MeMe

Me Me Me Me Me

MeMeMeMe

Me

H2N

H2NEthanolreflux

minus2H2O

Benzil

DE

+

M = UO22+ VO2+

4-Aminoantipyrine








nL =(1198640+ 119873) (119881

3minus 1198812)

(1198810+ 1198812) 119879M0

(2)

where119873 11986401198810 and119881


3is




010

008

006

004

002

000

00 02 04 06 08 10

Abso

rban

ce

[UO2(DE)]2+

[VO(DE)]2+

[M][M] + [L]

016

014

012

010

008

006

004

0020 1 2 3 4 5 6

Abso

rban

ce

[L][M]



M + DE [M (DE)] (3)

where M = UO2


Rate (]) prop [M]119883 [DE]119884

] = 119896 [M]119883 [DE]119884(4)


]1= 1198961015840

[M]119883

]2= 11989610158401015840

[DE]119884 where 1198961015840 = 119896 [DE] 11989610158401015840 = 119896 [M] (5)


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H




LanL2MB (basis set)




(c)





119905 =2303

119896

log1198600

119860119905

(6)




12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


O

O

NN

O

NN

O

N

N

NN

NN

O

O N

N

NN

NN

O

OM

Ph

Ph

Ph

PhPh

PhPh

PhPh

PhPh

Ph

MeMe

Me Me Me Me Me

MeMeMeMe

Me

H2N

H2NEthanolreflux

minus2H2O

Benzil

DE

+

M = UO22+ VO2+

4-Aminoantipyrine








nL =(1198640+ 119873) (119881

3minus 1198812)

(1198810+ 1198812) 119879M0

(2)

where119873 11986401198810 and119881


3is




010

008

006

004

002

000

00 02 04 06 08 10

Abso

rban

ce

[UO2(DE)]2+

[VO(DE)]2+

[M][M] + [L]

016

014

012

010

008

006

004

0020 1 2 3 4 5 6

Abso

rban

ce

[L][M]



M + DE [M (DE)] (3)

where M = UO2


Rate (]) prop [M]119883 [DE]119884

] = 119896 [M]119883 [DE]119884(4)


]1= 1198961015840

[M]119883

]2= 11989610158401015840

[DE]119884 where 1198961015840 = 119896 [DE] 11989610158401015840 = 119896 [M] (5)


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H




LanL2MB (basis set)




(c)





119905 =2303

119896

log1198600

119860119905

(6)




12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


CC

HH

H HHH H

H

H

H

HH

HH

HH

H

H

H

H

H

H

N

NN

N

NN

O

O

HH

HH

H

H

HH

CC

C

CC

C

C

CCC C

CC

CC

CC

C

CC

C

CC

CC C

C

C

CH

C

C

C

CH

C

(a)

HH

H

C

H

H

H

C

CC H

H

C

H

H

HH

C

H

CN

H

C

C

C

C

C

C

H

C

CN

C

CC

C

H

NC

C

C

C

H

H

H

O

CN C

H

V

H

C

H

H

O

CC

H

C

C

N

O

N

H

H

H

H

C

CC

H

C

C

H

H

CH

(b)

H

H

C

C

H

H H

C

C

C

HH

C

C

H

C

C

HH

H

C

H

C

C

C

H

CC

HC

C

N

H

N C

H O

H

H

HN

C

NC

CUCC

H

CO

H

C

H

C

O

NO

H

C

NC

H

H

C

C

C

H

H

C

H

C

H

C

H

C

C

H

H




LanL2MB (basis set)




(c)





119905 =2303

119896

log1198600

119860119905

(6)




12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


12

10

8

6

4

2

pH

0 2 4 6 8 10 12 14 16 18

Volume of KOH (mL)

(1)(2) (3)(4)




065

060

055

050

045

040

nH

pH5 6 7 8 9

(a)

10

08

06

04

02

nL

pL30 32 34 36 38 40 42

(b)

nL

pL

4

3

2

1

028 30 32 34 36 38

(c)



080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


080

075

070

065

060

055

050

045

040

035

0300 500 1000 1500 2000 2500

Time (s)

Abso

rban

ce (a

u)

UO2] (mM)00

01

02

03

04

949290888684828078

Ln (r

ate)

(au

)(s

)

y = 098x minus 04716R2 = 09976

84 86 88 90 92 94 96 98 100

Ln[UO2]

1mM Schiff base + [


012

010

008

006

004

002

000

0 50 100 150 200 250 300

Time (s)


(2) 288

(3) 298

(4) 303

(5) 308

(5)

(4)

(3)

(2)

(1)

log(A

0A

t)



119886) for


119886)


10

05

00

minus05

minus10

minus15

minus2000032 00033 00034 00035 00036


Y = minus4921x + 1599

Y = minus5977x + 2003

0988

0971

ln k

1T (Kminus1)












ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






ln(1198961) ln(1198962)


25

20

15

10

5

020 40 20 40 20 40


S typhiS flexneri


IZ (m

m)

[UO2L]

25

20

15

10

5

020 40 20 40 20 40

DE Gentamycin

IZ (m

m)


S typhiS flexneri






4gt [UO

2DE](NO



8 Conclusion


4and [UO

2DE](NO




60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


60

50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300



50

40

30

20

10

0

IZ (m

m)

100 200 300 100 200 300 100 200 300

DE Amphotericin



Tim

e (m

in)

25

20

15

10

5

0

VO(I

I)-D

Eco

mpl

ex

UO

2(II

)-D

Eco

mpl

ex

Alb

enda

zole

(ref

dru

g)


Schi

ff ba

se(D

E)



4gt

[UO2DE](NO





References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Complexation of Oxovanadium(IV) and … · 2019. 7. 31. · obtained using Jobs continuous variation and molar ratio methods ( Figure ). e monomeric nature of vanadyl