Vol 78, No 11 - Abstracts

JSCS Vol 78, No. 11

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Publication of this issue is financially co-supported by the Faculty of Physical Chemistry, University of Belgrade

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EDITORIAL

This issue of the Journal of the Serbian Chemical Society is dedicated to the celebration of the 110th anniversary of Physical Chemistry teaching at the University of Belgrade. Dean of the Faculty of Physical Chemistry, University of Belgrade and Guest Editor of the issue, together with the Editor in Chief of the Journal, invited some of their distinguished colleagues from different institutions, most of which are located outside of Serbia, to contribute to the issue in their respective scientific areas. The invited authors, including several young scientists from the Faculty of Physical Chemistry, are former students of the University of Belgrade. Through the papers contributed to this special issue, the influence of Physical Chemistry on the development of the University of Belgrade could be recognized.

The selected papers by invited authors cover a variety of contemporary research topics. The issue includes a Preface, 3 review papers, 8 research papers and 1 short communication.

The Guest Editor of this special issue of the Journal would sincerely like to thank all authors who accepted the invitation to submit their valuable contributions for this issue and to the expert reviewers for their efforts and valuable and important contributions to the evaluation process. The Guest Editor also wishes to express his profound gratitude to the Editor in Chief Branislav Nikolić and to the Technical Editors of the Journal of the Serbian Chemical Society for their support in the process of compiling this special issue devoted to the celebration of the of the 110 th anniversary of Physical Chemistry teaching at the University of Belgrade.

Slobodan K. Milonjić

Guest Editor.

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J. Serb. Chem. Soc. 78 (11) 1635–1639 (2013)

UDC 544.2”1903–2013”+378.4(497.1–25)

PREFACE

110 Years of Physical Chemistry at the University of Belgrade

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J. Serb. Chem. Soc. 78 (11) 1641–1654 (2013)

UDC 616–008.854+54.351–039.7:543.422.25+543.456; JSCS–4524; doi: 10.2298/JSC131108108M Original scientific paper

NMR microscopy of tissue in organic and mixed solvents

SLOBODAN MACURA, PRASANNA K. MISHRA, JEFFREY D. GAMEZ* and ISTVAN PIRKO*

Department of Biochemistry and Molecular Biology, Mayo Clinic, Rochester, Minnesota, 55905, USA

*Department of Neurology, Mayo Clinic, Rochester, Minnesota, 55905, USA

(Received 8 October 2013)

The use organic and mixed solvents for nuclear magnetic resonance microscopy of fixed tissue is proposed as a means for improving image information content. NMR properties of some standard solvents (methanol, acetone or DMSO) and solvents in use for tissue processing in pathology (xylenes, paraffin, “Clearify”) have been measured, reviewed and analyzed. It was found that DMSO and paraffin are very useful solvents that provide images of better quality than those obtained in water (neutralized formalin buffer). This is illustrated on formalin-fixed mouse brain sections imaged at 16.4 T (700 MHz).

Keywords: NMR, MRI, MRM, nuclear magnetic resonance, NMR imaging, NMR microscopy, magnetization transfer, cross-relaxation.

Full Article - PDF 395 KB Available OnLine: 19. 10. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1655–1670 (2013)

UDC 615.211:546.41:577.112.02:543.422.25:577.1:544; JSCS–4525; doi: 10.2298/JSC130523090J Original scientific paper

Halothane binds to druggable sites in the [Ca²⁺]₄-calmodulin (CaM) complex, but does not inhibit [Ca²⁺]₄-CaM activation of kinase

NENAD O. JURANIĆ, KEITH A. JONES*, ALAN R. PENHEITER, THOMAS J. HOCK* and JOHN H. STREIFF*

Mayo College of Medicine at Rochester, U.S.A.

*University of AlabAMa at BirminghAM, U.S.A.

(Received 23 May 2013)

The mechanism(s) of volatile anesthetics (VAs) are poorly understood. High-resolution NMR spectroscopy was used to determine the structure of the halothane–[Ca2+]4-calmodulin ([Ca2+]4-CaM) complex, and it was found that halothane molecules bind in the druggable sites. Then it was exAMined whether VAs binding to druggable sites in calmodulin would affect the [Ca2+]4-CaM dependent activity of myosin light chain kinase. Fluorescence assays were used to determine that VA mediate [Ca2+]4-CaM activation of smooth-muscle-myosin-light-chain-kinase (smMLCK), but do not alter significantly the Kd of [Ca2+]4-CaM binding to skeletal-myosin-light-chain-kinase-peptide recognition sequence (skMLCKp). The results suggested that VAs do not alter [Ca2+]4-CaM dependent MLCK activity via direct interactions with [Ca2+]4-CaM.

Keywords: volatile anesthetic, calmodulin, halothane, drugs, protein structure.

Full Article - PDF 693 KB Supplementary Material PDF 361 KB Available OnLine: 15. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1671–1688 (2013)

UDC 577.112+543.426.1+543.456:539.24:539.219.3; JSCS–4526; doi: 10.2298/JSC130815102J; Review

REVIEW

Super-resolution fluorescence imaging and correlation spectroscopy: principles and exAMples of application

TIJANA JOVANOVIĆ-TALISMAN and VLADANA VUKOJEVIĆ*

Department of Molecular Medicine, Beckman Research Institute of the City of Hope Comprehensive Cancer Center, Duarte, CA 91010, USA and Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii 96822, USA

*Department of Clinical Neuroscience, Karolinska Institutet, CMM L8:01, Stockholm, Sweden

(Received 15 August, revised 30 September 2013)

Self-organization of cell-surface receptors in structurally distinct domains in the plasma membrane is of vital importance for correct cellular signaling. However, this dynAMic process is difficult to study in cells with sufficiently high temporal and spatial resolution. Herein, two quantitative high-resolution methods with single-molecule sensitivity are presented, i.e., fluorescence correlation spectroscopy (FCS) and pair-correlation photo-activated localization microscopy (pcPALM), which enable the non-destructive study of receptor diffusion and lateral organization at the nanoscale level. The methods are introduced and their application in studies of lateral organization of G protein-coupled receptors (GPCRs) is reviewed. ExAMples from studies on the lateral organization of opioid receptors are presented in order to illustrate the most recent advances in the field.

Keywords: fluorescence correlation spectroscopy, super-resolution fluorescence imaging, sub-diffraction limit, photo-activated localization microscopy, G protein-coupled receptors, lipid rafts.

Full Article - PDF 420 KB Available OnLine: 30. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1689–1702 (2013)

UDC 539.216+546.92–3+544.478:66.094.1; JSCS–4527; doi: 10.2298/JSC130916119S; Original scientific paper

Single crystalline thin films as a novel class of electrocatalysts

JOSHUA SNYDER, NENAD M. MARKOVIC AND VOJISLAV R. STAMENKOVIC

Materials Science Division, Argonne National Laboratory, Argonne, IL 60439, USA

(Received 16 September, revised 30 October 2013)

The ubiquitous use of single crystal metal electrodes has garnered invaluable insight into the relationship between surface atomic structure and functional electrochemical properties. However, the sensitivity of their electrochemical response to surface orientation and the AMount of precious metal required can limit their use. Herein, a generally applicable procedure for the production of thin metal films with a large proportion of atomically flat (111) terraces without the use of an epitaxial template is presented. Thermal annealing in a controlled atmosphere induces long-range ordering of magnetron sputtered thin metal films deposited on an AMorphous substrate. The ordering transition in these thin metal films yields characteristic (111) electrochemical signatures using a minimal AMount of material and provides an adequate replacement for oriented bulk single crystals. This procedure could be generalized towards a novel class of practical multimetallic thin film-based electrocatalysts with tunable near-surface compositional profiles and morphologies. Annealing of atomically corrugated sputtered thin film Pt-alloy catalysts yields an atomically smooth structure with highly crystalline, (111)-like ordered and Pt segregated surface that displays superior functional properties, bridging the gap between extended/bulk surfaces and nanoscale systems.

Keywords: thin films; magnetron sputtering; Pt-alloys; oxygen reduction reaction.

Full Article - PDF 502 KB Available OnLine: 31.10. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1703–1716 (2013)

UDC 547.261+66.094.3+546.92:544.4+621.352; JSCS–4528; doi: 10.2298/JSC130718091K; Original scientific paper

Electrochemical oxidation of methanol on Pt/(RuxSn1–x)O2 nanocatalyst

MILA N. KRSTAJIĆ, MAJA D. OBRADOVIĆ*, BILJANA M. BABIĆ**, VELIMIR R. RADMILOVIĆ, UROŠ Č. LAČNJEVAC***, NEDELJKO V. KRSTAJIĆ and SNEŽANA Lj. GOJKOVIĆ

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

*Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11000 Belgrade, Serbia

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

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

(Received 18 July, revised 4 September 2013)

Abstract: Ru-doped SnO2 powder, (RuxSn1-x)O2, with a Sn:Ru atomic ratio of 9:1 was synthesized and used as a support for Pt nanoparticles (30 mass % loading). The (RuxSn1-x)O2 support and the Pt/(RuxSn1-x)O2 catalyst were characterized by X-ray diffraction measurements, energy dispersive X-ray spectroscopy and transmission electron microscopy (TEM). The (RuxSn1-x)O2 was found to be a two-phase material consisting of probably a solid solution of RuO2 in SnO2 and pure RuO2. The average Pt particle size determined by TEM was 5.3 nm. Cyclic voltAMmetry of Pt/(RuxSn1-x)O2 indicated good conductivity of the support and displayed the usual features of Pt. The results of the electrochemical oxidation of COads and methanol on Pt/(RuxSn1-x)O2 were compared with those on commercial Pt/C and PtRu/C catalysts. Oxidation of COads on Pt/(RuxSn1-x)O2 starts at lower positive potentials than on PtRu/C and Pt/C. PotentiodynAMic polarization curves and chronoAMperometric curves of methanol oxidation indicated higher initial activity of the Pt/(RuxSn1-x)O2 catalyst compared to PtRu/C, but also a greater loss in current density over time. A potentiodynAMic stability test of the catalysts revealed that deactivation of Pt/(RuxSn1-x)O2 and Pt/C was primarily caused by poisoning of the Pt surface by residues of methanol oxidation, which mostly occurred during the first potential cycle. In the case of PtRu/C, the poisoning of the surface was minor and deactivation was caused by surface area loss of the PtRu.

Keywords: methanol oxidation, CO oxidation, platinum, Ru-doped SnO2, electrocatalysis, fuel cell.

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J. Serb. Chem. Soc. 78 (11) 1717–1727 (2013)

UDC 547.551+66.095.253.095.64+544.6.076.32:546.817–71+546.482–71:544.6; JSCS–4529; doi: 10.2298/JSC130731101S; Original scientific paper

Nanostructured materials for sensing Pb(II) and Cd(II) ions: manganese oxohydroxide versus carbonized polyanilines

BILJANA ŠLJUKIĆ, DARKO MICIĆ, NIKOLA CVJETIĆANIN, GORDANA ĆIRIĆ-MARJANOVIĆ

Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12–16, 11158 Belgrade, Serbia

(Received 31 July, revised 29 September 2013)

Nanostructured materials including three different carbonized polyanilines and manganese oxyhydroxide were prepared and evaluated as electrode materials for sensing of lead and cadmium ions in aqueous media. Anodic stripping voltAMmetry results indicated that all prepared materials could be successfully used for determination of these two heavy metal ions. Carbonized polyaniline-based electrodes have higher signal and lower limits of detection (10-7 М) compared to manganese oxyhydroxide-based electrode. Among the three studied carbonized polyanilines, the one that was derived from polyaniline precursor produced in the presence of 3,5-dinitrosalicyclic acid showed the highest electrocatalytic activity towards the lead and cadmium oxidation.

Keywords: lead ions; cadmium ions; carbonized nanostructured polyaniline; manganese oxyhydroxide; electrochemical sensors.

Full Article - PDF 291 KB Available OnLine: 30. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1729–1761 (2013)

UDC 544.6.076.32+543.257.2:681.586:543.554; JSCS–4530; doi: 10.2298/JSC130829098R; Authors’ review

AUTHORS’ REVIEW

Ion selective electrodes in environmental analysis

ALEKSANDAR RADU, TANJA RADU*, CHRISTINA MCGRAW**, PETER DILLINGHAM***, SALZITSA ANASTASOVA-IVANOVA**** AND DERMOT DIAMOND*****

Keele University, Birchall Centre and Environment, Physical Sciences and Mathematics (EPSAM) Research Institute, Lennard-Jones Labs, Stoke-on-Trent , ST5 2BG, United Kingdom

*Loughborough University, School of Civil and Building Engineering, Loughborough, LE11 3TU, United Kingdom

**Institute for Marine and Antarctic Studies (IMAS), University of Tasmania, Private Bag 129, Hobart 7005, Tasmania, Australia

***University of New England, School of Science and Technology, Armidale, Australia

****Queen Mary University London, School of Engineering and Mathematical Sciences, London, E1 4NS, United Kingdom an
*****National Centre for Sensor Research, CLARITY Centre for Sensors Web Technologies, Dublin City University, Dublin 7, Ireland

(Received 29 August, revised 26 September 2013)

An overview is given dealing with the application of ion-selective electrodes (ISEs) in environmental analysis. ISEs are placed into the context of the trend of development of sensors for extensive and frequent monitoring. Discussed are the issues such as sensing platforms and their mass-production, improvement of precision, diagnostic of sensor functionality, and development of reference electrodes. Several exAMples of real-life application of ISEs in environmental analysis are given. The main emphasis of this article is directed towards summarizing recent results of the authors during the past several years.

Keywords: potentiometric sensors; wireless sensing networks; reference electrode; sensor precision.

Full Article - PDF 633 KB Available OnLine: 29. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1763–1773 (2013)

UDC 546.16+544.723:546.3:537.12+544.022; JSCS–4531; doi:10.2298/JSC130729095P; Original scientific paper

Fluorine adsorption on transition metal surfaces – A DFT study

IGOR A. PAŠTII*, NEMANJA M. GAVRILOV* AND SLAVKO V. MENTUS*,**

*University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12–16, 11158 Belgrade, Serbia

**Serbian Academy of Sciences and Arts, Knez Mihajlova 35, 11000 Belgrade, Serbia

(Received 29 July, revised 21 September 2013)

Based on density functional theory calculations, the adsorption of fluorine was investigated on a) Cu(111), Au(111), Pd(111) and Pt(111) surfaces, b) on Pd monolayer surfaces over Cu(111), Au(111) and Pt(111) surfaces and c) on the surfaces of Pd(111) monocrystals with an inserted metal monolayer (M = Cu, Au or Pt) underneath the first Pd surface layer. The results evidenced that the adsorption did not cause significant changes of the structural parAMeters of metallic substrate. The strongest adsorption, AMounting to –4.49 eV, was calculated in the case of the Cu(111) surface. The Cu(111) and Au(111) surface atoms interact with F adatoms exclusively by the mediation of the sp-band, while the surface atoms of Pt and Pd-based surfaces interact with F adatoms additionally by the mediation of the d-band. In the case of Pt(111) and PdML/M(111) surfaces, the binding energies correlated with the d-band center positions, which indicated a significant contribution of covalent interaction. These results confirmed that the nature of surface interaction of highly electronegative F atom with metallic surfaces depends significantly on the nature of the metal substrate.

Keywords: Fluorine, adsorption, electronic structure, adsorption trends

Full Article - PDF 365 KB Available OnLine: 27. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1775–1787 (2013)

UDC 547.979.7+581.132:537.12+544.022; JSCS–4532; doi: 10.2298/JSC130806096E; Original scientific paper

A study of the low-lying singlet and triplet electronic states of chlorophyll a and b

MIHAJLO ETINSKI, MILENA PETKOVIĆ and MIROSLAV M. RISTIĆ

Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12–16, P. O. Box 47, 11158 Belgrade, Serbia

(Received 6 August, revised 23 September 2013)

Chlorophylls have been extensively investigated both experimentally and theoretically owing to the fact that they are essential for photosynthesis. In the reported study, two forms of chlorophyll, chlorophyll a and chlorophyll b, were investigated by means of the density functional theory. Optimization of the S0, S1 and T1 states was performed with the B3-LYP functional. The computed fluorescence lifetimes show good agreement with available experimental data. The electronic adiabatic energies of S1 and T1 states are 2.09/2.12 and 1.19/1.29 eV for chlorophyll a and chlorophyll b, respectively. The implications of these results on triplet formation are discussed. In addition, the calculated vertical ionization potentials showed good agreement with the experimental results.

Keywords: electronic states, density functional theory, photosynthesis.

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J. Serb. Chem. Soc. 78 (11) 1789–1795 (2013)

UDC 547.74+547.781:547.53.02:577.213.3:547.415; JSCS–4533; doi: 10.2298/JSC130929104A; Short communication

SHORT COMMUNICATION

An ab-initio study of pyrrole and imidazole arylAMides

ARA M. ABRAMYAN, ZHIWEI LIU and VOJISLAVA POPHRISTIC

Department of Chemistry &AMp; Biochemistry, University of the Sciences, Philadelphia, PA 19104, USA

(Received 29 September, revised 9 October 2013)

ArylAMide foldAMers have been shown to have a number of biological and medicinal applications. For exAMple, a class of pyrrole–imidazole polyAMide foldAMers is capable of binding specific DNA sequences and preventing development of various gene disorders, most importantly cancer. Molecular dynAMics (MD) simulations can provide crucial details in understanding the atomic level events related to foldAMer/DNA binding. An important first step in the accurate simulation of these foldAMer/DNA systems is the reparAMetrization of force field parAMeters for torsion around the aryl–AMide bonds. Herein, the density functional theory (DFT) potential energy profiles and the derived force field parAMeters for four types of aryl–AMide bonds for pyrrole and imidazole building blocks, which have been extensively employed in foldAMer design for DNA-binding polyAMides, will be highlighted. These results contribute to the development of computational tools for an appropriate molecular modeling of pyrrole–imidazole polyAMide/DNA binding, and provide an insight into the chemical factors that influence the flexibility of pyrrole–imidazole polyAMides and their binding to DNA.

Keywords: foldAMer, torsional energy profiles, force field reparAMetrization, DNA-binding polyAMide.

Full Article - PDF 264 KB Available OnLine: 15. 10. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1797–1807 (2013)

UDC 546.264–31+66.094.2+546.824–31+544.351;JSCS–4534; doi: 10.2298/JSC130726093D; Original scientific paper

Investigation of the charge-transfer in photo-excited nanoparticles for CO₂ reduction in non-aqueous media

NADA M. DIMITRIJEVIĆ

Chemical Sciences and Engineering Division, and Nanoscience and Technology Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA

(Received 26 July, revised 19 September 2013)

Photo-induced charge separation in TiO2 and Cu2O semiconductor nanoparticles was exAMined using electron parAMagnetic resonance spectroscopy in order to obtain insight into the photocatalytic reduction of CO2 in non-aqueous media. For dissolution/grafting of CO2, carboxy-PEG4-AMine was used with poly(ethylene glycol) 200 as the solvent. It was found that the reduction of CO2 in this system starts at a potential of –0.5 V vs. Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (–2.0 V vs. Ag/AgCl). The electron transfer from excited nanoparticles to CO2 is governed by both thermodynAMic and kinetic parAMeters, nAMely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of the nanoparticles.

Keywords: carbon dioxide reduction, photocatalysis, titanium dioxide, cuprous oxide.

Full Article - PDF 799 KB Available OnLine: 24. 09. 2013. Cited by

J. Serb. Chem. Soc. 78 (11) 1809–1835 (2013)

UDC 541.64+678.684:66.095.2.094.3:547.53.024:547.551.1; JSCS–4535; doi: 10.2298/JSC130809097J; Review

REVIEW

Progress in conducting/semiconducting and redox-active oligomers and polymers of arylAMines

ALEKSANDRA JANOŠEVIĆ, BUDIMIR MARJANOVIĆ*, ALEKSANDRA RAKIĆ** and GORDANA ĆIRIĆ-MARJANOVIĆ**

Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, 11221 Belgrade, Serbia

*Centrohem, Vuka Karadžića bb, 22300 Stara Pazova, Serbia

**Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12–16, 11158 Belgrade, Serbia

(Received 9 August 2013)

Recent advances in synthesis, characterization and application of the selected conducting/semiconducting and redox-active oligomers and polymers of arylAMines are reviewed. A brief historical background of the selected topics is given. The overview of the preparation, structure and properties of polyaniline, substituted polyanilines, especially those obtained by the oxidative polymerization of p-substituted anilines, poly(1-AMinonaphthalene) and its derivatives, carbocyclic and heterocyclic polyaryldiAMines such as poly(p-phenylenediAMine) and polydiAMinoacridines, is presented. The mechanism of formation of polyaniline nanostructures is discussed. Recent approaches to the preparation of one-dimensional polyaniline nanostructures are concisely reviewed, with special attention paid to the template-free falling-pH method. Current and potential future applications of oligo/polyarylAMines are briefly discussed.

Keywords: polymer, oligomer, oxidative polymerization, arylAMine, polyaniline, nanostructure.

Full Article - PDF 592 KB Available OnLine: 29. 09. 2013. Cited by

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