Vol 78, No 4 - Abstracts

JSCS Vol 78, No. 4

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Whole issue - PDF 3,036 KB

J. Serb. Chem. Soc. 78 (4) 463–468 (2013)

UDC 547.753/.756+542.913+546.74:544.412.3; JSCS–4429; doi: 10.2298/JSC120506076O Original scientific paper

A novel approach to bis(indolyl)methanes using nickel nanoparticles as a reusable catalyst under solvent-free conditions

ABOLFAZL OLYAEI, MOHSEN VAZIRI, REZA RAZEGHI, BAHAREH SHAMS and HASAN BAGHERI*

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

*Department of Chemistry, Takestan Branch, IslAMic Azad University, Takestan, Iran

(Received 6 May, revised 10 July 2012)

Nano-sized nickel as a catalyst has been developed for the electrophilic substitution reactions of indole with various aromatic aldehydes under solvent-free conditions to afford the corresponding bis(indolyl)methanes in high to excellent yields. The described method has promising features, such as no hazardous organic solvents or catalysts, short reaction time, high product yields, simple work-up procedure, reusable catalyst and easy product separation without further purification with column chromatography.

Keywords: indole; aldehyde; electrophilic substitution; Nickel.

Full Article - PDF 164 KB Supplementary Material PDF 140 KB Available OnLine: 14. 07. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 469–476 (2013)

UDC 546.185–323+547.269.3+547.387’592+544.478; JSCS–4430; doi: 10.2298/JSC120508088K Original scientific paper

Phospho sulfonic acid: a novel and efficient solid acid catalyst for the one-pot preparation of indazolo[1,2-b]-phthalazinetriones

ALI REZA KIASAT, ARASH MOURADZADEGU and SEYYED JAFAR SAGHANEZHAD

Chemistry Department, College of Science, Shahid ChAMran University, Ahvaz 61357-4-3169, Iran

(Received 8 May, revised 27 August 2012)

An efficient one-pot condensation of aldehyde, dimedone and phthalhydrazide has been achieved in the presence of a catalytic AMount of phospho sulfonic acid as a novel environmentally benign heterogeneous solid acid under solvent-free conditions. Diverse indazolo[1,2-b]phthalazinetrione derivatives were prepared in good to excellent yields in short times. The economical factors (time, cost, waste, etc.) for this three-component reaction hold promise for the future of organic synthesis.

Keywords: indazolo[1,2-b]phthalazinetrione; multicomponent reaction; phthalhydrazide; dimedone; solvent-free; phospho sulfonic acid.

Full Article - PDF 247 KB Supplementary Material PDF 150 KB Available OnLine: 03. 09. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 477–482 (2013)

UDC 542.9+547.571+547.551:542.913:547.673; JSCS–4431; doi: 10.2298/JSC120409092F Short communication

SHORT COMMUNICATION

An efficient synthesis and spectroscopic characterization of Schiff bases containing the 9,10-anthracenedione moiety

GHULAM FAREED*,**, MUHAMMAD ALI VERSIANI**, NIGHAT AFZA*, NAZIA FAREED**, MUHAMMAD IRFAN ALI* and MAHBOOB ALI KALHORO*

*Pharmaceutical Research Center, PCSIR Laboratories Complex Karachi, Shahrah-e-Dr. Salim-uz-ZAMan Siddiqui, Karachi-75280, Sindh, Pakistan

**Department of Chemistry, Federal Urdu University of Arts, Science and Technology, Ghulshan-e-Iqbal, Karachi-75300, Sindh, Pakistan

(Received 9 April, revised 28 August 2012)

A new method was developed for the synthesis of novel Schiff bases containing the anthraquinone moiety using dodecatungstosilicic acid/P2O5 under solvent-free conditions at room temperature. The reaction was completed in 1–3 minutes with excellent yields. This method was found to be very efficient, easy and hazardous-free for the synthesis of azomethines. The development of these types of methodologies in synthetic chemistry may contribute to green chemistry. The structures of synthesized novel Schiff bases were elucidated using 1H-NMR, 13C-NMR, LC–MS, FTIR and CHN analysis.

Keywords: azomethine; dodecatungstosilicic acid; P2O5; anthraquinone.

Full Article - PDF 174 KB Supplementary Material PDF 177 KB Available OnLine: 12. 09. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 483–494 (2013)

UDC 66.095.253+546.16+547.313.3–31; JSCS–4432; doi: 10.2298/JSC120831097H Original scientific paper

Theoretical study on the nucleophilic fluoroalkylation of propylene oxide with fluorinated sulfones

LING-LI HAN* and TAO LIU*^,**

*Department of Chemistry and Chemical Engineering, Key Laboratory of Inorganic Chemistry in Universities of Shandong, Jining University, Qufu 273155, Shandong, China
*School of Chemistry and Chemical Engineering, Shandong University, Jinan 250010, Shandong, China

(Received 31 August, revised 18 September 2012)

The paths of nucleophilic fluoroalkylation reaction of propylene oxide with PhSO2CYF- (Y = F, H, and PhSO2, respectively) in the gas phase and in Et2O solvent were studied theoretically. The nucleophilic fluoroalkylation of propylene oxide with fluorinated carbanions was probed by comparison of the reactivities (phenylsulfonyl)monofluoromethyl anion (PhSO2CHF-), the (phenylsulfonyl)difluoromethyl anion (PhSO2CF2-), and the bis(phenylsulfonyl)monofluoromethyl anion ((PhSO2)2CF-). The nucleophilicity reactivity order of PhSO2CYF- (Y = F, H, and PhSO2) is (PhSO2)2CF- > PhSO2CHF- > PhSO2CF2-, which indicates that the introduction of another electron-withdrawing phenylsulfonyl group is an effective way to significantly increase the nucleophilicity of fluorinated carbanions. For comparison, the nucleophilic addition reaction of propylene oxide with the chlorine-substituted carbanion PhSO2CHCl- was investigated. The calculated results show that the nucleophilicity of PhSO2CYF- is better than that of PhSO2CHCl- in the ring opening reaction with propylene oxide. The calculated results are in good agreement with the available experimental ones.

Keywords: nucleophilic fluoroalkylation; propylene oxide; PhSO2CYF- (Y = F, H and PhSO2).

Full Article - PDF 369 KB Available OnLine: 25. 09. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 495–506 (2013)

UDC 616.98:578.828:547.568–36+547.854.4:615.37; JSCS–4433; doi: 10.2298/JSC120713085I; Original scientific paper

A quantitative structure–activity relationships study for the anti-HIV-1 activities of 1-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine derivatives using the multiple linear regression and partial least squares methodologies

DANIELA IVAN, LUMINITA CRISAN, SIMONA FUNAR-TIMOFEI and MIRCEA MRACEC

Institute of Chemistry of Romanian Academy, Department of Computational Chemistry, 24 Mihai Viteazul Bvd., 300223, Timisoara, Romania

(Received 13 July 2012)

A quantitative structure–activity relationships (QSAR) study using Multiple Linear Regression (MLR) and Partial Least Squares (PLS) methodologies was performed for a series of 127 derivatives of 1-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine (HEPT), a potent inhibitor of the of the human immunodeficiency virus type 1, HIV-1 reverse transcriptase (RT). The MLR and PLS methods were employed to explore the relationship between the descriptors (as independent variables) of a pool of HEPT derivative and anti-HIV-1 activity, expressed as log (1/EC50) (as dependent variables). Using Dragon descriptors, the present study was aimed at developing a predictive and robust QSAR model for predicting anti-HIV activity of HEPT derivatives for a better understanding of the molecular features of these compounds important for their biological activity. According to the squared correlation coefficients, which had values between 0.826 and 0.809 for the MLR and PLS methods, the results demonstrated almost identical qualities and good predictive ability for both the MLR and PLS models. After dividing the dataset into training and test sets, the model predictability was tested by several parAMeters, including the Golbraikh–Tropsha external criteria and the goodness of fit, tested using the Y- randomization test.

Keywords: Golbraikh–Tropsha criteria; Dragon descriptors; Y-randomization.

Full Article - PDF 195 KB Supplementary Material PDF 177 KB Available OnLine: 30. 08. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 507–521 (2013)

UDC 678.01+537.311.1:544.174.5:535.37+547.21.024+547.733; JSCS–4434; doi: 10.2298/JSC120327111R; Original scientific paper

Spectroscopic analysis of the structure and stability of two electrochemically synthesized poly(3-alkylthiophene)s

ELAINE CRISTINA RODRIGUES MAIA, DANIELLY CRISTINA BENTO, EDSON LAURETO*, DIMAS AUGUSTO MOROZIN ZAIA, ERALCI MOREIRA THERÉZIO**, GREGORY J. MOORE*** and HENRIQUE DE SANTANA

DepartAMento de Química, Universidade Estadual de Londrina, 86051-990, Londrina, PR, Brazil

*DepartAMento de Física, Universidade Estadual de Londrina, 86051-990, Londrina, PR, Brazil

**Instituto de Física, Universidade Federal de Uberlândia, 38400-902, Uberlândia, MG, Brazil

***Yardney Technical Products, Inc. Pawcatuck, Stonington, CT, USA

(Received 27 March, revised 3 September 2012)

In this work, poly (3-methylthiophene) (P3MT) and poly (3-octylthiophene) (P3OT) films were electrochemically synthesized in non-aqueous media through the oxidation of the monomers, (3-methylthiophene and 3-octylthiophene) using a standard three-electrode cell in acetonitrile with 0.100 mol L-1 LiClO4. The polymeric thin films were deposited on platinum plates for optimal quality control of the process. It was observed that the material as-prepared by anodic electropolymerization undergoes a natural process of de-protonation as a function of time. Moreover, the partial de-doped form obtained in NH4OH solution presents a good chemically stable form but becomes unstable again when radiated with blue light. Films obtained by these methods were characterized by cyclic voltAMmetry, RAMan and photoluminescence spectroscopy. Both RAMan and photoluminescence (PL) spectra led to the characterization of two structures (pristine and non-pristine forms of the thiophene rings), which formed the P3MT and P3OT polymer chains. These results were associated with the stabilization of pristine chains and mixed chains (non-pristine structures), radical cation and dication forms, in the polymeric film. Their bands in the RAMan and PL spectra were broad and asymmetric and their adjustments by Gaussian functions indicated that there were three distinct contributions to the vibration and two to the emission spectra in the formed polymeric material.

Keywords: conducting polymers; RAMan; photoluminescence; poly(alkylthiophenes).

Full Article - PDF 647 KB Available OnLine: 22. 10. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 523–536 (2013)

UDC 66.017+547.461.2:543.57:544.421.032.4; JSCS–4435; doi: 10.2298/JSC120519145B; Original scientific paper

Thermal decomposition of a molecular material {N(n-C₄H₉)₄[Fe^IIFe^III(C₂O₄)₃]}_¥ leading to ferrite: A reaction kinetics study

ASHIS BHATTACHARJEE, DEBASIS ROY, MADHUSUDAN ROY* and ARUNABHA ADHIKARI**

Department of Physics, Visva-Bharati University, Santiniketan, India

*Applied Material Science Division, Saha Institute of Nuclear Physics, Kolkata, India

***Department of Physics, West Bengal State University, Barasat, India

(Received 19 May 2012)

A multi-step thermal decomposition of a molecular precursor, {N(n-C4H9)4[FeIIFeIII(C2O4)3}∞ was studied using non-isothermal thermogravimetric (TG) measurements in the temperature range 300 to ≈800 K at multiple heating rates (5, 10 and 20 K min-1). The thermal decomposition of the oxalate-based complex proceeded stepwise through a series of intermediate reactions. Two different isoconversional methods, nAMely, an improved iterative method and a model-free method were employed to evaluate the kinetic parAMeters: activation energy and rate of reaction. The most probable reaction mechanism of thermal decomposition was also determined. The different reaction pathways leading to different steps in the TG profile were also explored, which are supplemented by earlier experimental observations.

Keywords: molecular materials; oxalates; non-isothermal thermogravimetry; decomposition kinetics; model free methods.

Full Article - PDF 755 KB Available OnLine: 17. 12. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 537–548 (2013)

UDC 547.978+666.122.3:543.552+544.6.076.32–039.26; JSCS–4436; doi: 10.2298/JSC120527093C; Original scientific paper abstract

Differential pulse anodic stripping voltAMmetric determination of berberine using a nano-Na-montmorillonite clay-modified carbon paste electrode

WEN CHEN, MING-XIAO ZHANG, CONG LI and YONG-LING LI

School of Chemistry and Chemical Engineering, Southwest University, 2 Rd Tiansheng, Beibei District, Chongqing, P. R. China

(Received 27 May, revised 16 July 2012)

A simple and sensitive method is presented for the electrochemical determination of berberine based on a nano-Na-montmorillonite (nano-Na-MMT) clay-modified carbon paste electrode. The electrochemical oxidation and adsorption behavior of berberine was studied at the proposed electrode by linear sweep voltAMmetry in acetate buffer (0.2 M, pH 5.6). A differential pulse anodic stripping voltAMmetric procedure was developed for the determination of the drug. A good linear relationship between the oxidation peak current magnitude and the concentration of berberine was observed in the range from 1.0 to 18.0 µg mL-1 with a detection limit of 0.07 µg mL-1 and a quantification limit of 0.24 µg mL-1. The proposed method was successfully applied to the determination of berberine in pharmaceutical tablets.

Keywords: berberine; nano-Na-montmorillonite clay; carbon paste electrode; modified electrode; electrochemical determination.

Full Article - PDF 309 KB Available OnLine: 12. 09. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 549–554 (2013)

UDC 546.714+544.478.1+544.654.2:544.351–145.82; JSCS–4437; doi: 10.2298/JSC121215160L; Extended abstract

EXTENDED ABSTRACT

Electrodeposition and characterization of Ni–MoO₂ composite coatings as cathodes for the hydrogen evolution reaction in alkaline solution

UROŠ Č. LAČNJEVAC

Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade, Serbia

(Received 15 December 2012)

Composite Ni–MoO2 coatings were prepared and characterized with respect to their possible application as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. The composites were electrodeposited onto Ni meshes from an AMmonium chloride Ni solution with suspended MoO2 particles under simulated industrial conditions for the production of commercial cathodes. The influence of the concentration of MoO2 particles in the solution and deposition current density on the morphology, and chemical and phase composition of the obtained coatings were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Catalytic activity of the coatings for the HER was exAMined by polarization measurements in a 32 wt. % NaOH solution at 90 °C and compared to the activity of the commercial De Nora’s cathode (DN). It was shown that the most active Ni–MoO2 coating exhibited better polarization characteristics for the HER than the DN cathode. The mechanism of the HER on the specified Ni–MoO2 coating was investigated in 8 mol dm-3 NaOH at 30 °C by means of steady-state polarization measurements and an electrochemical impedance spectroscopy (EIS). Based on the theoretical interpretation of the experimental data, the rate constants of the three individual steps of the HER were determined and the source of catalytic activity of the coating was elucidated.

Keywords: hydrogen evolution; electrocatalysis; Ni–MoO₂ coating; morphology; electrochemical impedance spectroscopy.

Full Article - PDF 175 KB Available OnLine: 29. 12. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 555–564 (2013)

UDC 637.12+520.8.07+546.226+547.867.2:543.4/.5; JSCS–4438; doi: 10.2298/JSC120303080G; Original scientific paper

Genetic algorithm-based wavelength selection in multicomponent spectrophotometric determinations by partial least square regression: application to a sulfAMethoxazole and trimethoprim mixture in bovine milk

MOHAMMAD HADI GIVIANRAD, MOHAMMAD SABER-TEHRANI and SABER ZARIN

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

(Received 3 March, revised 26 May 2012)

The simultaneous determination of sulfAMethoxazole (SMX) and trimethoprim (TMP) mixtures in bovine milk by spectrophotometric method is, due to spectral interferences, a difficult problem in analytical chemistry. By means of multivariate calibration methods, such as partial least square (PLS) regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. A genetic algorithm (GA) is a suitable method for selecting the wavelengths for PLS calibration of mixtures with almost identical spectra without the loss of prediction capacity using a spectrophotometric method. In this study, a calibration model based on the absorption spectra in the 200–400 nm range for 25 different mixtures of SMX and TMP. Calibration matrices were formed from sAMples containing 0.25–20 and 0.3–21 µg mL-1 for SMX and TMP, at pH 10, respectively. The root mean squared error of deviation (RMSED) for SMX and TMP with PLS and genetic algorithm partial least square (GAPLS) were 0.242 and 0.066 µg mL-1, and 0.074 and 0.027 µg mL-1, respectively. This procedure allowed the simultaneous determination of SMX and TMP in synthetic and real sAMples and good reliability of the determination was proved.

Keywords: sulfAMethoxazole; trimethoprim; partial least square; simultaneous determination; bovine milk.

Full Article - PDF 632 KB Available OnLine: 26. 07. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 565–577 (2013)

UDC 669.214:54.064:543.4:669.015.5; JSCS–4439; doi: 10.2298/JSC120505135S; Original scientific paper

Determination of trace elements in refined gold sAMples by inductively coupled plasma atomic emission spectrometry

MIRJANA STEHARNIK, MARIJA TODOROVIĆ*, DRAGAN MANOJLOVIĆ*, DALIBOR STANKOVIĆ*, JELENA MUTIĆ* and VLASTIMIR TRUJIĆ

Mining and Metallurgy Institute Bor, Department of Chemical Investigations, 19210 Bor, Serbia

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

(Received 5 May, revised 24 September 2012)

This paper presents a method for the determination of trace contents of silver, copper, iron, palladium, zinc and platinum in refined gold sAMples. A simultaneous inductively coupled plasma atomic emission spectrometer in the radial torch position and with a cross flow nebulizer was used for the determinations. In order to compare the different calibration strategies, two sets of calibration standards were prepared. The first set was based on matrix matched calibration standards and the second was prepared without the addition of matrix material. The detection limits for the matrix-matched calibrations were higher for some elements than those without matrix matching. In addition, the internal standardization method was applied and experiments indicated that indium was the best option as the internal standard. The obtained results for gold sAMples with matrix matched and matrix free calibrations were compared with the results obtained by the standard addition method. The accuracy of the methods was tested by performing a recovery test. The recoveries for the spiked sAMple were in the range of 90–115 %. The accuracy of the methods was also tested by analysis of a certified reference material of high purity gold AuGHP1. The best results were achieved by matrix free calibration and standard addition method using indium as the internal standard at a wavelength of 230 nm.

Keywords: refined gold sAMples; trace elements; ICP-AES; certified reference material of high purity gold AuGHP1.

Full Article - PDF 201 KB Available OnLine: 08. 12. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 579–590 (2012)

UDC 549.623.9–033.62+621.927+541.12–116:66.017; JSCS–4440; doi: 10.2298/JSC120829107M; Original scientific paper

Mechanochemical treatment of Serbian kaolin clay to obtain a highly reactive pozzolana

ALEKSANDRA MITROVIĆ and MIODRAG ZDUJIĆ

Institute for Testing of Materials, Bulevar vojvode Mišića 43, 11000 Belgrade, Serbia

*Institute of Technical Sciences of the Serbian Academy of Sciences and Arts, Knez Mihailova 35, 11000 Belgrade, Serbia

(Received 29 August, revised 11 October 2012)

Mechanochemical treatment of Serbian kaolin clay was performed in a planetary ball mill using two different milling media, hardened steel or zirconia vials and balls. The sAMples obtained after various milling times were characterized by particle size laser diffraction (PSLD), X-ray diffraction (XRD), differential scanning calorimetry/thermogravimetry (DTA/TGA) and Fourier-transform infrared (FTIR) analyses. The mechanochemical treatment induced AMorphization of the kaolinite phase accompanied by dehydroxylation. It was found that for given milling parAMeters, AMorphization mainly occurred in the milling period up to 15 min, and was completed after about 30 min of milling for both employed milling media. The pozzolanic activities were determined by the Chapelle method. Milling in the hardened steel milling medium had no significant influence on pozzolanic activity, even though there was accumulated iron contAMination. For both milling media, a pozzolanic activity of 0.79 was obtained for the sAMples milled for 15 min and it remained almost unchanged with prolonged milling. The determined pozzolanic activity values were similar to those of commercial metakaolinite or metakaolinite obtained by calcination of the sAMe clay, thereby, indicating that highly reactive pozzolana could be obtained by mechanochemical treatment of Serbian kaoline clay.

Keywords: kaolin clay; kaolinite; metakaolinite; mechanochemical treatment; pozzolana.

Full Article - PDF 390 KB Available OnLine: 11. 10. 2012. Cited by

J. Serb. Chem. Soc. 78 (4) 591–602 (2013)

UDC 628.3+546.171.6:628.161.2:546.47/.49’56’815; JSCS–4441; doi: 10.2298/JSC120228050E; Original scientific paper

Polyaza macroligands as potential agents for heavy metal removal from wastewater

PERLA ELIZONDO MARTÍNEZ, BLANCA NÁJERA MARTÍNEZ, NANCY PÉREZ RODRÍGUEZ, LAURA HINOJOSA REYES and ISABEL GÓMEZ del RÍO*

Universidad Autonoma de Nuevo Leon, UANL, Chemistry School of Sciences, Avenida Universidad S/N, Cd. Universitaria, 66451 San Nicolas de los Garza, NL, Mexico

*Universidad Nacional de Educación a Distancia, Madrid, España, Paseo Senda del Rey # 9, 28040 Madrid, Spain

(Received 28 February, revised 9 April 2012)

Two polyaza macroligands N,N´-bis(2-AMinobenzyl)-1,2-ethanediAMine (L1) and 3,6,9,12-tetraaza-4(1,2),11(1,2)-dibenzo-1(1,3)-pyridinacyclotridecaphane (L2) were characterized and investigated for their metal ion extraction capabilities. The nature of all complexes was established by spectroscopic techniques. The equilibrium constants were determined by spectrophotometric and potentiometric techniques and the residual concentration of metals in the solutions by atomic absorption spectrometry (AAS). The capacity of the ligands to remove heavy metals such as Cu(II), Ni(II), Cd(II), Zn(II) and Pb(II) as insoluble complexes was evaluated in wastewater from industrial effluents. These agents showed high affinity for the studied metals. The values of the equilibrium constants of the isolated complexes (between 1×104 and 2×107) demonstrated the feasibility of applying these chelating agents as alternatives for the removal of heavy metals from industrial effluents.

Keywords: polyaza macroligands; pollutant removal; wastewater; heavy metals.

Full Article - PDF 328 KB Available OnLine: 08. 05. 2012. Cited by