Vol 78, No 10 - Abstracts

JSCS Vol 78, No. 10

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J. Serb. Chem. Soc. 78 (10) 1461–1479 (2013)

UDC 543.632.472:628:504.53; JSCS–4510; doi:10.2298/JSC130315064R Review

REVIEW

Analytical methods for arsenic speciation analysis

LJUBINKA V. RAJAKOVIĆ, ŽAKLINA N. TODOROVIĆ*, VLADANA N. RAJAKOVIĆ-OGNJANOVIĆ**, ANTONIJE E. ONJIA*

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia

*Vinča Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia

**Faculty of Civil Engineering, University of Belgrade,Bulevar kralja Aleksandra 73, Belgrade, Serbia

(Received 15 March, revised 29 May 2013)

Arsenic exists in the form of various chemical species differing in their physicochemical behaviour, toxicity, bioavailability and biotransformation. The determination of arsenic species is an important issue for environmental, clinical and food chemistry. However, differentiation of these species is a quite complex analytical task. Numerous speciation procedures have been studied that include electrochemical, chromatographic, spectrometric and hyphenated techniques. This review presents the relevant research in the field of arsenic speciation analysis with novel applications and significant advances. Stability of arsenic species and each of the analytical steps (sAMple collection, storage, preservation, extraction) of the arsenic speciation methods is particularly evaluated. Analytical validation and performance of these methods are also reviewed. 7

Keywords: arsenic speciation; adsorption; extractions; water, soil; biological sAMple.

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J. Serb. Chem. Soc. 78 (10) 1481–1489 (2013)

UDC 547.368+546.27:547.831+542.9; JSCS–4511; doi: 10.2298/JSC121017061S Original scientific paper

B(HSO₄)₃: An efficient and recyclable catalyst for the Friedländer synthesis of substituted quinolines

SEYYED JAFAR SAGHANEZHAD, HAMID REZA SAFAEI*

Young Researchers Club, Shiraz Branch, IslAMic Azad University, Shiraz, Iran

*Department of Applied Chemistry, College of Science, Shiraz Branch, IslAMic Azad University, P. O. Box 71993-5, Shiraz, Iran

(Received 17 October 2012, revised 26 May 2013)

Substituted quinolines have been synthesized in the presence of catalytic AMounts of boron hydrogen sulfate (BHS) under solvent-free conditions. This methodology offers some advantages, including high yield, short reaction time, low cost of the catalyst, green conditions by avoiding toxic solvents and recoverable catalyst.

Keywords: boron hydrogen sulfate; substituted quinolines; solvent-free conditions; Friedländer reaction.

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J. Serb. Chem. Soc. 78 (10) 1491–1501 (2013)

UDC 577.164.1+577.213.3:577.15+544.4; JSCS–4512; doi: 10.2298/JSC130322050P Original scientific paper

Enzymatic synthesis of a vitAMin B₆ precursor

NEVENA Ž. PRLAINOVIĆ, DEJAN I. BEZBRADICA*, ZORICA D. KNEŽEVIĆ—JUGOVIĆ*, DUŠAN V. VELIČKOVIĆ**, DUŠAN Ž. MIJIN*

Innovation Center of Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia
*Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia

**Faculty of Chemistry, University of Belgrade, Studentski trg 12, 11000 Belgrade, Serbia

(Received 22 March, revised 10 May 2013)

3-Cyano-4-(ethoxymethyl)-6-methyl-2-pyridone, an important precursor in the synthesis of vitAMin B6, is obtained in the addition reaction between 2-cyanoacetAMide and 1-ethoxy-2,4-pentanedione catalyzed by lipase from Candida rugosa (triacylglycerol acylhydrolases, EC 3.1.1.3). This work shows new experimental data and mathematical modeling of the lipase-catalyzed synthesis of 3-cyano-4-(ethoxymethyl)-6-methyl-2-pyridone. Kinetic measurements were performed at 50 °C with an enzyme concentration of 1.2 % w/v. The experimental results were fitted with two kinetic models: the ordered bi–ter and ping–pong bi–ter model, and the initial rates of the reaction were found to correlate best with the ping–pong bi–ter mechanism with inhibition by 2-cyanoacetAMide. The obtained specificity constants indicated that lipase from C. rugosa had a higher affinity towards 1-ethoxy-2,4-pentanedione compared to 2-cyanoacetAMide.

Keywords: Candida rugosa lipase; ping–pong kinetics; pyridone; 1-ethoxy-2,4-pentanedione.

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J. Serb. Chem. Soc. 78 (10) 1503–1512 (2013)

UDC 546.742’482’472:541.69:546.23+547.288.3:615.27; JSCS–4513; doi: 10.2298/JSC130315035D Original scientific paper

High antioxidative potential and low toxic effects of selenosemicarbazone metal complexes

DRAGANA DEKANSKI, TAMARA TODOROVIĆ*, DRAGANA MITIĆ*, NENAD FILIPOVIĆ**, NATALIJA POLOVIĆ*, KATARINA ANĐELKOVIĆ*

Biomedical Research, R&AMp;D Institute, Galenika a.d., Pasterova 2, 11000 Belgrade, Serbia

*Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11000 Belgrade, Serbia

**Faculty of Agriculture, University of Belgrade, Nemanjina 6, 11080 Belgrade, Serbia

(Received 15 March, revised 27 March 2013)

Novel metal-based compounds with therapeutic potential have become the subject of intense investigations in inorganic chemistry and biomedical science. Recently, strong dose-dependent cytotoxic activities of selenosemicarbazone metal complexes against several human cancer cell lines were demonstrated. The aim of the present study was to investigate in vitro antioxidative potential of Ni(II), Cd(II) and Zn(II) selenosemicarbazone complexes. All three investigated complexes exhibited high 2,2'-azinobis(3-ethylbenzothiazoline-6-sulphonic acid) radical cation (ABTS·+) scavenging capacity, comparable with ascorbic acid. In an acute toxicity study, administration of the compounds was performed orally to mice at single doses. The mice were observed for clinical signs, body weight effects and mortality for 14 days, after which they were sacrificed for gross organ necropsy. The body weight did not vary after administration, and the autoptic analysis failed to show appreciable macroscopic alterations of internal organs. Generally, the compounds exhibited low toxic effects as required for further in vivo therapeutic studies.

Keywords: Ni(II), Cd(II) and Zn(II) complexes; selenosemicarbazones; antioxidative activity; in vivo toxicity.

Full Article - PDF 422 KB Available OnLine: 28. 03. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1513–1530 (2013)

UDC 546.268.1–034.1+547.584:66.094.2:539.2; JSCS–4514; doi: 10.2298/JSC130119019D; Original scientific paper

Comparative study of reactions between m-nitrido- or m-oxo-bridged iron tetrasulfophthalocyanines and sulfur-containing reductants

ILIA A. DEREVEN’KOV, SVETLANA S. IVANOVA, EVGENY V. KUDRIK, SERGEI V. MAKAROV, ANNA S. MAKAROVA*, PAVEL A. STUZHIN

1State University of Chemistry and Technology, Engels Str. 7, 153000 Ivanovo, Russia

*G. A. Krestov Institute of Solution Chemistry of the RAS, Academicheskaya Str. 1, 153045 Ivanovo, Russia

(Received 19 January, revised 11 February 2013)

A comparative study of reactivity of μ-nitrido- and μ-oxo-dimers of iron tetrasulfophthalocyanine has been performed in aqueous solutions of various acidity. The substantially higher stability of the nitrido-bridged structure under both strongly acidic and strongly alkaline environments was demonstrated. The reactions of the complexes with sulfur-containing reductants (sodium dithionite, thiourea dioxide, sodium hydroxymethanesulfinate, L-cysteine) were studied. Differences in reduction processes were explained.

Keywords: m-nitrido dimer, m-oxo dimer, iron phthalocyanine, reduction.

Full Article - PDF 1,380 KB Supplementary Material PDF 446 KB Available OnLine: 13.02. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1531–1537 (2013)

UDC 547.313.4+546.13+547.466.23+549.464+542.913:541.57:548.7; JSCS–4515; doi: 10.2298/JSC130214054D; Short communication

SHORT COMMUNICATION

Synthesis, characterization and crystal structure of butyl N-(3-chloropropyl)-(2S)-alaninate hydrochloride

DEJANA P. DIMITRIJEVIĆ, SLAĐANA B. NOVAKOVIĆ*, GORDANA R. RADIĆ**, VERICA V. JEVTIĆ, LAURA MENÉNDEZ-TABOADA***, SANTIAGO GARCÍA-GRANDA***, SREĆKO R. TRIFUNOVIĆ

Department of Chemistry, Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000 Kragujevac, Serbia

*Vinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia

**Faculty of Medical Sciences, University of Kragujevac, Svetozara Markovića 69, 34000 Kragujevac, Serbia

***Physical and Analytical Chemistry Department, University Oviedo, Faculty of Chemistry, C/ Julian Claveria, 8, 33006 Oviedo, Asturias, Spain

(Received 14 February, revised 9 May 2013)

The synthesis of butyl N-(3-chloropropyl)-(2S)-alaninate hydrochloride is reported here. The compound was characterized by elemental analysis, infrared, and 1H- and 13C-NMR spectroscopy. The structure of butyl N-(3-chloropropyl)-(2S)-alaninate hydrochloride was confirmed by single-crystal X-ray analysis.

Keywords: asymmetric ligand; infrared; 1H- and 13C-NMR spectroscopy; X-ray analysis.

Full Article - PDF 474 KB Available OnLine: 19. 05. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1539–1546 (2013)

UDC 541:547.52+547.53+549.746; JSCS–4516; doi: 10.2298/JSC130520057G; Original scientific paper

A test of Clar aromatic sextet theory

IVAN GUTMAN, SLAVKO RADENKOVIĆ, MARIJA ANTIĆ, JELENA ĐURĐEVIĆ

Faculty of Science, University of Kragujevac, P. O. Box 60, 34000 Kragujevac, Serbia

(Received 20 May, revised 28 May 2013)

The Clar aromatic sextet theory predicts that the intensity of cyclic conjugation in chevron-type benzenoid hydrocarbons monotonically decreases along the central chain. This regularity has been tested by means of several independent theoretical methods (by the energy effects of the respective six-membered rings, as well as by their HOMA, NICS, and SCI values, calculated at the B3LYP/6-311G(d,p) level of DFT theory). Our results show that the predictions of Clar theory are correct only for the first few members of the chevron homologous series, and are violated at the higher members. This indicates that Clar theory is not universally applicable, even in the case of fully conjugated benzenoid molecules.

Keywords: Clar theory, aromatic sextet, cyclic conjugation, benzenoid hydrocarbons, chevron homologous series.

Full Article - PDF 389 KB Available OnLine: 10. 06. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1547–1559 (2013)

UDC 546.881–31+547.261:544.351.3; JSCS–4517; doi: 10.2298/JSC130317072M; Original scientific paper

Calculation of the stability constants for complex formation of dioxovanadium(V) with methyliminodiacetic acid in various H₂O + CH₃OH solutions using the KAMlet–Abboud–Taft equation

KAVOSH MAJLESI, SAGHAR REZAIENEJAD, NAZILA DOUSTMAND SARABI, MEHRDOKHT FAHMI and FERESHTEH TAHAMTAN

Department of Chemistry, Science and Research Branch, IslAMic Azad University, Tehran, Iran

(Received 17 March, revised 21 June 2013)

The stability constants for the complex formation of VO2+ with methyliminodiacetic acid (MIDA) were determined in this study for various volume fractions of methanol (0–45 %, v/v) at T = 298 K, I = 0.1 mol dm-3 (sodium perchlorate). Potentiometric and UV spectrophotometric methods were utilized for the collection of experimental data. Different species were investigated but the best model contained VO2HL and VO2L- for the employed data treatment. One-, two- and three-parAMeter KAMlet–Abboud–Taft (KAT) equations were applied for the determination and calculation of the solvatochromic regression coefficients for the KAT models.

Keywords: vanadium(V); linear solvation energy relationships; solvent effects; methanol; methyliminodiacetic acid.

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J. Serb. Chem. Soc. 78 (10) 1561–1567 (2013)

UDC 541.138+543.554:54–145.2+547.261+546.33’131; JSCS–4518; doi:10.2298/JSC130104039F; Original scientific paper

Autoprotolysis in water/methanol/NaCl ternary systems

ALI FARAJTABAR, FERESHTEH NADERI*, FARROKH GHARIB**

Young Researchers Club, Jouybar Branch, IslAMic Azad University, Jouybar, Iran,

*Department of Chemistry, Shahr-e-Qods branch, IslAMic Azad University, Tehran, Iran

**Chemistry Department, Faculty of Sciences, Shahid Beheshti University, Tehran, Evin, Iran

(Received 4 January, revised 10 March 2013)

A potentiometric method was used to determine the autoprotolysis constant for aqueous solutions containing 0, 20 and 40 mass % of methanol over a wide range of NaCl concentrations at 25 °C. The ionic strength ranged between 0.25 and 2.00 mol L-1 at intervals of 0.25 units. The osmotic and activity coefficients of the mixed solvents were calculated as a function of ionic strength. The dependence on ionic strength was analyzed using the ori.ginal specific ion interaction theory. The specific ion interaction parAMeters associated with the thermodynAMic autoprotolysis constant were extracted. Results indicate that interaction between ions increases with increasing methanol content in the mixture.

Keywords: autoprotolysis; water–methanol; sodium chloride; specific ion interaction theory.

Full Article - PDF 342 KB Available OnLine: 15. 04. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1569–1581 (2013)

UDC 546.47’711+66.022.3+547.571:44.654.2; JSCS–4519; doi: 10.2298/JSC130118025B; Original scientific paper

The influence of substituted aromatic aldehydes on the electrodeposition of Zn–Mn alloy

MIHAEL BUČKO, UROŠ LAČNJEVAC*, JELENA BAJAT

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia

*Institute for Multidisciplinary Research, University of Belgrade, P. O. Box 33, 11030 Belgrade, Serbia

(Received 18 January, revised 20 February 2013)

Additives are necessary in the electrodeposition of Zn–Mn alloys at high current densities, in order to reduce the hydrogen evolution reaction and prevent dendrite formation. The influences of two aromatic aldehydes, 4-hydroxy-benzaldehyde and 3,4-dimethoxy-benzaldehyde, as additives in the Zn–Mn plating electrolyte, were exAMined in this study. The characterization of the coatings by scanning electron microscopy and X-ray energy dispersive spectroscopy, as well as an exAMination of the effect of the additives by electrochemical methods, indicated a complex involvement of additive molecules in hydrogen evolution, as well as in Zn2+ and Mn2+ reduction. Consequently, a levelling action could be achieved and the chemical composition of the Zn–Mn alloy tailored by the addition of the proper type and concentration of additive in the plating electrolyte.

Keywords: Zn–Mn alloy; plating additive; hydrogen inhibitor; leveller; surface morphology.

Full Article - PDF 1,921 KB Available OnLine: 27. 02. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1583–1594 (2013)

UDC 546.56’57+539.377+66.094.3:66.065.53; JSCS–4520; doi: 10.2298/JSC121224049R; Original scientific paper

Comparison of the electrochemical behavior of cast and sintered CuAg 4 at. % alloy during thermomechanical treatment

MIRJANA M. RAJČIĆ-VUJASINOVIĆ, VESNA J. GREKULOVIĆ, ZORAN M. STEVIĆ, SVETLANA D. NESTOROVIĆ, IVANA I. MARKOVIĆ, SLAVKO B. SIMOV

University of Belgrade, Technical faculty in Bor, V. J. 12, 19210 Bor, Serbia

(Received 24 December 2012, revised 13 March 2013)

The paper presents a comparison of the electrochemical behavior of sAMples of CuAg 4 at. % alloy obtained by the powder metallurgy method and the sAMe alloy obtained by melting and casting during oxidation in an alkaline medium. The investigated alloys exhibited the anneal hardening effect. Hence, they were exAMined in each stage of thermomechanical treatment resulting in this effect. Cyclic voltAMmetry investigations showed that both the sintered and cast sAMples after cold rolling to a final reduction of 60 % behaved as completely homogenous phases. In this stage of thermomechanical treatment, peaks corresponding to reactions on silver did not appear and the currents on the cyclic voltAMmogrAMs were the lowest. After annealing below the recrystallization temperature, both sAMples exhibited anneal hardening; in this stage, the sintered alloy retained its corrosion stability, whereas the current densities for the cast alloy increased and peaks characteristic for silver appeared again. Further annealing above the recrystallization temperature led increasing current density on voltAMmogrAMs for sAMples obtained by both methods and all characteristic current peaks for silver reappeared.

Keywords: copper; silver; anodic oxidation; anneal hardening; recrystallization.

Full Article - PDF 2,135 KB Available OnLine: 13. 05. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1595–1607 (2013)

UDC 577.112.386+544.6.076.32–039.6:544.4:543.552;JSCS–4521; doi: 10.2298/JSC121019022M; Original scientific paper

Electrocatalytic oxidation and determination of homocysteine at nanotubes-modified carbon paste electrode using dopAMine as a mediator

SAFOORA MOHAMMADZADEH*, MASOUD FOULADGAR*

Department of Chemistry, PayAMe Noor University, P. O. Box 19395-3697 Tehran, Iran

*Department of Biochemistry, Falavarjan Branch, IslAMic Azad University, Falavarjan, Iran

(Received 29 October 2012, revised 11 January 2013)

A carbon paste electrode modified with multiwall carbon nanotubes (MWCNTPE) was prepared to study the electrocatalytic activity of dopAMine (DP) in the presence of homocysteine (HCy) and it was used for the determination of HCy. The diffusion coefficient of HCy (D = 6.79×10-6 cm2 s-1), and the kinetic parAMeters of its oxidation, such as electron transfer coefficient (α = 0.46), and rate constant (kh = 7.44×102 dm3 mol-1 s-1) were also determined using electrochemical approaches. Under the optimum pH of 5.0, the peak current of oxidation of HCy at MWCNTPE in the presence of DP occurred at a potential of about 530 mV and the results showed that the oxidation peak current of HCy at the modified carbon nanotubes electrode was higher than on the unmodified electrode. The peak current of differential pulse voltAMmogrAMs of HCy solutions increased linearly in the range 3.0–600 μM HCy with a detection limit of 2.08 µM HCy. This method was also exAMined for determination of HCy in physiological serum and urine sAMples.

Keywords: homocysteine; dopAMine; electrocatalytic effect; carbon nanotubes, carbon paste electrode; voltAMmetry.

Full Article - PDF 734 KB Available OnLine: 22. 02. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1609–1616 (2013)

UDC *Doxorubicin+547.391.1+546.723’722:615.277; JSCS–4522; doi: 10.2298/JSC121225041O; Original scientific paper

Preparation and in vitro drug delivery response of doxorubicin-loaded poly(acrylic acid)-coated magnetite nanoparticles

REYHAN OMIDIRAD, FARZANEH HOSSEINPOUR RAJABI, BAHMAN VASHEGHANI FARAHANI

Department of Chemistry, Faculty of Science, ImAM Khomeini International University, Qazvin, Iran

(Received 25 December 2012, revised 12 March 2013)

In this study, spherical superparAMagnetic iron oxide nanoparticles (SPION) with mean diAMeter of 6 nm were prepared by a reduction–precipitation method. The surface of SPION were coated with poly(acrylic acid) 5000 (PAA-5000) and followed by loading with the anticancer drug doxorubicin (DOX). The drug loading efficiency was (14.64±0.29). In vitro drug release studies were realized for 8 h at two different pH values 4.2 and 7.4. The drug release rate at pH 4.2 (100 % DOX released in 2 h) was much faster than that at pH 7.4 (≈78 % DOX released in 8 h). These results indicate that these DOX-carrier nanoparticles have a high drug loading capacity and favourable release property for magnetic drug targeting. The drug release kinetics followed the Korsmeyer–Peppas model at pH 4.2, while at pH 7.4 the zero order model was fitted the best. The drug release mechanism followed super-case II transport in acidic and basic medium. The sAMples were characterized by XRD, SEM, TEM, FTIR, and UV–Vis.

Keywords: magnetite drug targeting; functionalization; poly(acrylic acid); anticancer drug; controlled delivery; release kinetic studies.

Full Article - PDF 879 KB Available OnLine: 23. 04. 2013. Cited by

J. Serb. Chem. Soc. 78 (10) 1617–1632 (2013)

UDC 632.95+541.183+54–145.2+549.74; JSCS–4523; doi: 10.2298/JSC131227006V; Original scientific paper

Influence of different carbon monolith preparation parAMeters on pesticide adsorption

MARIJA VUKČEVIĆ, ANA KALIJADIS*, BILJANA BABIĆ**, ZORAN LAUŠEVIĆ*, MILA LAUŠEVIĆ

Faculty of Technology and Metallurgy, University of Belgrade, P. O. Box 494, 11001 Belgrade, Serbia

*Laboratory of Physics, Vinča Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia

**Laboratory of Material Science, Vinča Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia

(Received 27 December 2012, revised 14 January 2013)

The capacity of carbon monolith for pesticide removal from water, and the mechanism of pesticide interaction with the carbon surface were exAMined. Different carbon monolith sAMples were obtained by varying the carbonization and activation parAMeters. In order to exAMine the role of surface oxygen groups on pesticide adsorption, the carbon monolith surface was functionalized by chemical treatment in HNO3, H2O2 and KOH. The surface properties of the obtained sAMples were investigated by determination of the Brunauer, Emmett and Teller (BET) surface area, pore size distribution and temperature-progrAMmed desorption. Adsorption of pesticides from aqueous solution onto the activated carbon monolith sAMples was studied using five pesticides belonging to different chemical groups (acetAMiprid, dimethoate, nicosulfuron, carbofuran and atrazine). The presented results show that higher temperature of carbonization and AMount of activating agent enable microporous carbon monolith with higher numbers of surface functional groups to be obtained. The adsorption properties of the activated carbon monolith were more readily affected by the number of surface functional groups than by the specific surface area. Results obtained after carbon monolith functionalization showed that π–π interactions were the driving main force for adsorption of pesticides with an aromatic structure, while acidic groups played an important role in adsorption of pesticides with no aromatic ring in their chemical structure.

Keywords: carbon monolith; activation; surface properties; adsorption; pesticides.

Full Article - PDF 1,087 KB Available OnLine: 21. 01. 2013. Cited by

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