JSCS Vol 69, No. 6

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Impresum http://www.shd.org.rs/HtDocs/SHD/PDFicon.gif35 KBContent of Vol 69, No. 6 http://www.shd.org.rs/HtDocs/SHD/PDFicon.gif35 KB;  Instruction for authors http://www.shd.org.rs/HtDocs/SHD/PDFicon.gif37 KB

J. Serb. Chem. Soc. 69 (6) 413–420 (2004)
UDC 66.095.213+541.143:547.288.4
JSCS – 3168
Original scientific paper

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Photochemical and Beckmann rearrangement of (Z)-cholest-4-en-6-one oxime


*Center for Chemistry, ICTM, P. O. Box 473, 11001 Belgrade and
**Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, P. O. Box 158, 11001 Belgrade, Serbia and Montenegro

(Received 27 November 2003)
Beckmann rearrangement of (Z)-cholest-4-en-6-one oxime (4) (prepared in 4 steps starting from cholest-5-en-3b-ol (1)) with thionyl chloride in dioxane solution afforded an enAMide-type lactAM, i.e., 7-aza-B-homocholest-4-en-6-one (6) as a single product. Photoreaction of the sAMe compound in methanol or benzene-acetic acid solution gave a mixture of products, with the formation of the parent ketone 3 and the occurrence of Z/E isomerization, while the lactAM 6 was obtained only when the reaction was performed in methanol and then in very low yield (7 %).

Keywords: (Z)-cholest-4-en-6-one oxime, 7-aza-B-homocholest-4-en-6-one, Beckmann rearrangement, photoreaction.


J. Serb. Chem. Soc.69 (6) 421–429 (2004)
UDC 530.145:661.46+547.655
JSCS – 3169
Original scientific paper

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Regioselectivity of the bromination of 1-oxo-1,2,3,4-tetrahydronaphthalene and 6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphthalene, and thiabiscyclanones synthesis on their basis


Department of Chemistry, N. G. Chernyshevskii Saratov State University, 83 Astrakhanskaya Street, Saratov 410012, Russia and
*Russian Antiplague Research Institute “Microbe”, 46 Universitetskaya Street, Saratov 410005, Russia

(Received 6 August, revised 21 November 2003)
Abstract: On the basis of quantum chemical (PM3 and RHF/6-31G*) study, the regioselectivity of the bromination of 1-oxo-1,2,3,4-tetrahydronaphthalene (1) and 6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphthalene (2) at their alicyclic and aromatic fragments was quantum chemically substantiated and confirmed experimentally. It was found that the above compounds undergo aromatic at the a-methylene position. The conditions for bromination at the positions 5, 8 of benzannelated ring were established. For the first time, non- and 2,2’-dibromosubstituted with respect to the oxo group bis(6,7-dimethyl-1-oxo-1,2,3,4-tetrahydronaphth-2-yl) sulphides (7, 8a, b) were obtained. The latter were found to show promise as stabilizing agents for the storage of cholera sera.

Keywords: 1-oxo-1,2,3,4-tetrahydronaphthalene, bromination, reactivity, quantum chemical study, sulphur-containing 1,5-diketones.

J. Serb. Chem. Soc. 69 (6) 431–439 (2004)
UDC 541.44:54–128:541.124
JSCS – 3170
Original scientific paper

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An approach to quantum chemical consideration of "hydride" transfer reactions


Department of Chemistry, N. G. Chernyshevskii Saratov State University, 83 Astrakhanskaya Street, Saratov 410012, Russia

(Received 6 August, revised 27 November 2003)
An approach to the quantum chemical study of "hydride ion" transfer has been proposed, according to which the sequences of changes in ionization potentials, enthalpies and free energies of the affinities to the hydride ion, to the hydrogen atom and to the proton of substrates molecules and their derivatives (cations, radicals, anions), are compared with the experimentally substantiated series of "hydride" mobility. It has been established that the experimental series of "hydride" mobility for six chalcogenopyrans based on "semicyclic" 1,5-diketones is in conformity with the computed ionization potentials of the molecules, and with the affinity of the corresponding radicals to the hydrogen atom involved in the transfer. The direct splitting-out of the hydride ion and the primary deprotonation of the substrates followed by the withdrawal of two electrons was elucidated to be unlikely. Feasible are the mechanisms of "hydride" mobility, the first step of which consists of electron or hydrogen atom transfer from the chalcogenopyrans molecules.

Keywords: "hydride" transfer, reaction mechanisms, theory – experiment correlation, quantum chemical consideration, chalcogenopyrans.

J. Serb. Chem. Soc. 69 (6) 441–453 (2004)
UDC 678.744+547.495.1:543.067
JSCS – 3171
Original scientific paper

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DynAMical mechanical analysis of photocrosslinked hyperbranched urethane acrylates


The "Vinca" Institute of Nuclear Sciences, The Laboratory of Radiation Chemistry and Physics "GAMa", P. O. Box 522, 11001 Belgrade and
*DugaNova Ltd., Viline vode 6, 11000 Belgrade, Serbia and Montenegro

(Received 17 October 2002, revised 17 December 2003)
A series of acrylate functionalized sAMples based on hyperbranched hydroxy-terminated polyesters with different molecular weights and different degrees of acrylation were synthesized. The obtained urethane acrylates were slightly yellow viscose liquids. Their composition was characterized by FTIR and 1H-NMR spectroscopy and their molecular weights were measured by GPC. All the synthesized sAMples were diluted with 25 wt.% 1,4-butanediol dimethacrylate (BDDM). The rheological properties of the uncured sAMples and the dynAMic mechanical properties of the UV cured sAMples were exAMined. All the sAMples exhibit Newtonian behavior, which indicates the absence of physical entanglements in these polymers. The viscosity increases with increasing number of acrylic groups per molecule. The glass transition temperature of the UV cured sAMples increases with increasing the number of acrylic groups per molecule. The value of the storage modulus in the rubber-elastic plateau and the cross-link density increase with increasing number of acrylic groups per molecule. The formed networks are inhomogeneous and the residual unsaturation is the highest in the sAMples with the largest number of acrylic groups per molecule.

Keywords: urethane acrylate, hyperbranched hydroxy-terminated polyester, FTIR, 1H-NMR, GPC, rheology, UV curing, dynAMic mechanical properties.

J. Serb. Chem. Soc. 69 (6) 455–460 (2004)
UDC 678–13:539.217+546.9
JSCS – 3172
Original scientific paper

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Noble metals binding on macroporous poly(GMA-co-EGDMA) modified with ethylenediAMine


ICTM - Center for Chemistry, Njegoseva 12, Belgrade 
*Faculty of Technology and Metallurgy, Karnegijeva 4, Belgrade and
**Vinca Institute of Nuclear Sciences, Chemical DynAMics Laboratory, P. O. Box 522, Belgrade, Serbia and Montenegro

(Received 28 July 2003, revised 8 January 2004)
Macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), p(GME), was synthesized by suspension copolymerization and modified by reaction of the pendant epoxy groups with ethylenediAMine. The sorption rate and capacity of the modified copolymer, p(GME)-en for Rh(III), Au(III) and Pt(IV) ions were determined in batch experiments under non-competitive conditions. The uptake of Rh(III) was faster than those of Au(III) and Pt(IV). The sorption capacity for Pt(IV) was determined in the pH range 0.9–6.0. The maximum Pt(IV) uptake capacity onto p(GME)-en at pH 5.5 was 1.30 mmol/g.

Keywords: macroporous copolymers, modification, sorption, noble metals.

J. Serb. Chem. Soc. 69 (6) 461–475 (2004)
UDC 547.539.211.2+547.21:535.32
JSCS – 3173
Original scientific paper

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Changes of refractive indices in ternary mixtures containing
chlorobenzene + n-hexane + (n-heptane or n-octane) at 298.15 K


Laboratorio de Propiedades Fisicas. Centro de Apoyo Cientifico y Tecnólogico a la Investigación (C.A.C.T.I.),
Universidad de Vigo, 36200 Vigo, España and
*DepartAMent d’Enginyeria Quimica, Escola TPcnica Superior d’Enginyeria Quimica, Universitat Rovira i Virgili,
Avinguda Països Catalans 26, CAMpus Sescelades, 43007 Tarragona, España

(Received 11 August, revised 5 December 2003)
The refractive indices of ternary mixtures of chlorobenzene + n-hexane + (n-heptane or n-octane) have been measured at 298.15 K and at atmospheric pressure over the whole composition diagrAM. ParAMeters of polynomial equations which represent the composition dependence of physical and derived properties are gathered. The experimental refractive indices and the ternary derived properties are compared with the data obtained using several predictive semi-empirical models. The use of the Soave–Redlich–Kwong (SRK) and the Peng–Robinson (PR) cubic equations of state with the Van der Waals one-fluid mixing rule, which incorporate different combining rules to predict refractive indices on mixing, are tested against the measured results, good agrement being obtained.

Keywords: refractive index, chlorobenzene, alkanes, cubic equation of state.

J. Serb. Chem. Soc. 69 (6) 477–483 (2004)
UDC 582.685:543.23
JSCS – 3174
Original scientific paper

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Kinetic determination of morin nanoAMounts


Faculty of Natural Science and Mathematics, Department of Chemistry, University of Nis, Visegradska 33, 18000 Nis, Serbia and Montenegro

(Received 22. September, revised 10 December 2003)
A kinetic-spectrophotometric method is proposed for the determination of morin. The method is based on the inhibition effect of morin on the oxidation of C6H5COONa by hydrogen peroxide in the presence of the complex Fe(II)-AA(ascorbic acid), which acts as a catalyst. The concentration range for the determination of morin is one of the lowest achieved so far (a linear calibration graph was obtained for morin from 2.255–22.55 ng cm-3). The limit of detection of the method is 0.28 ng cm-3. The relative error ranges between 1.42 to 5.10 % for the given concentration interval. Kinetic equations are proposed for the investigated process. The effects of certain foreign ions upon the reaction rate were determined in order to assess the selectivity of the method. The major advantages of this kinetic-spectrophotometric assay are its sensitivity, selectivity, reproducibility, speed and simplicity.

Keywords: kinetic method, morin, determination.

J. Serb. Chem. Soc. 69 (6) 485–491 (2004)
UDC 546-98'131+543.4/.5:615.9
JSCS – 3175
Original scientific paper

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Spectrophotometric investigation of fAMotidine-Pd(II) complex and its analytical application in drug analysis


Institute of Inorganic Chemistry, Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, 11000 Belgrade and
*Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-14, Belgrade, Serbia and Montenegro

(Received 12 September 2003, revised 19 January 2004)
By using different spectrophotometric methods, it was found that fAMotidine and palladium(II) ions form a complex, Pd(II) : fAMotidine = 1:1, which has an absorption maximum at 345 nm. The formation of the complex between fAMotidine and palladium(II) chloride in Britton–Robinson buffer solution in the pH range 2.23–8.50 was studied. The conditional stability constant of the complex at the optimum pH 2.62 and ionic strength 0.5 M was found to be log K’ = 3.742 ± 0.025. The Beer’s law was verified over the fAMotidine concentration range from 5×10-5 – 6×10-4 M. The proposed method was found to be suitable for accurate and sensitive analysis of fAMotidine both as the substance (RSD = 1.02–1.80 %) and its dosage forms (RSD = 1.75–1.83 %).

Keywords: fAMotidine, palladium(II) chloride, complexometry, spectrophotometry, drug determination.


J. Serb.Chem. Soc. 69 (6) 493–502 (2004)
UDC 661.834:543.4/.6:621.319.1
JSCS – 3176
Original scientific paper

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Phonon anomalies in optical spectra of LiNbO3 single crystals


*Institute of Physics, Pregrevica 118, P. O. Box 68, 11080 Zemun, Serbia and Montenegro,
**Institute of Physics, Montanuniversitaet Leoben, Franz Josef Strasse 18, 8700 Leoben, Austia and
***Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia and Montenegro

(Received 29. October, revised 25 December 2003)
LiNbO3 single crystals were grown by the Czochralski technique in an air atmosphere. The critical crystal diAMeter Dc = 1.5 cm and the critical rate of rotation wc = 35 rpm were calculated by equations from the hydrodynAMics of the melt. The domain inversion was carried out at 1430 K using a 3.75 V/cm electric field for 10 min. The obtained crystals were cut, polished and etched to determine the presence of dislocations and single domain structures. The optical properties were studied by infrared and RAMan spectroscopy as a function of temperature. With decreasing temperature, an atypical behaviour of the phonon modes could be seen in the ferroelectrics LiNbO3. The obtained results are discussed and compared with published data.

Keywords: litium niobate, Czochralski tecnique, single crystal, RAMan spectroscopy, infrared spectroscopy, ferroelectrics.

J. Serb. Chem. Soc. 69 (6) 503–505 (2004)
Book  review

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Nova Acta Leopoldina, No. 330, Vol. 88
Deutsche Akademie der Naturforscher Leopoldina, Halle (Saale), 2003 ISBN 3–8047–2038–2, 160 pages, price: 28.80 Eur

This publication may be viewed as an issue of Nova Acta Leopoldina, in particular its number 330 and volume 88, but (as this reviewer prefers) also as a separate book. Anyway, it contains papers presented at a scientific conference, held in Göttingen on October 11 to 13, 2001, under the auspices of the German Academy of Natural Sciences Leopoldina, the Göttingen Academy of Sciences, and the French Academy of Sciences, The book contains 8 articles (that this reviewer will refer to as chapters), preceded by in introduction written by Herbert W. Roesky,
In the "Introduction" (pp. 7–9) Roesky recalls that a language is a system of verbal signs which are typical for a community of people who want to express what they think and who want to be understood by the other members of the community. Because modern chemistry and mathematics began... to discover that there are a lot of things they share, the purpose of this conference was to bring chemists and mathematicians together, in order that they could better understood each other. This is best expressed by Peter Deuflhard, who, by studying the relations of the scientific languages of chemistry and mathematics, concludes: The common clear message from these comparisons is that chemical intuition may pave the way for mathematical concepts just as chemical concepts may gain from mathematical precisioning. Along this line, significant improvements in chemical research and engineering have already been possible -- and can be further expected in the future from the dialogue between the two scientific languages.
The first chapter is "Chemistry as an Ideographic Language" by Guy Ourisson (pp. 11-18). It briefly outlines the wealth of information contained in a structural formula of an organic compound. What the paper does not mention is that such formulas have also a mathematical content, recognized already in the middle of the 19th century.
The second chapter "Transition Metal-Based Machines and Motors at the Molecular Level" (pp. 19–38) is written by Jean-Paul Collin and four coauthors. It contains exactly what the title says and is nothing but a well–written (chemical) review article.
The next chapter is "Virtual Crystallography" by Olaf Delgado-Friedrichs (pp. 39–49). It describes the author's original and interesting combinatorial and geometric researches, related to crystallography.
Follows "A Comparison of Related Concepts in Computational Chemistry and Mathematics" by Peter Deuflhard (pp. 51–66). This text goes to the very center of the theme. It considers three mathematical concepts (intrinsic low-dimensional manifolds, Galerkin's method for constructing special Hilbert spaces, and geometrical conformations) and connects them with three fields of physico-chemical research (quasistationary state approximation in chemical kinetics, lumping in polymer kinetics, and molecular conformational analysis).
The fifth chapter "The Essence of Chemical Thinking Beyond Mathematical Equations" by Jerzy Haber (pp. 67–80) has the AMbition to demonstrate that chemistry is based on an interplay of theory, comprising phenomenological inductive laws and deductive theory, experiments, and chemical intuition, and that chemistry developed its own ideographic language, whose semiotic rules permit to understand reaction mechanisms. In spite of these abstract claims, the article mainly outlines the author's own (experimental) research of catalytic oxidation of hydrocarbons. A few philosophical thoughts are found only at the end of the text, whereas mathematics is completely absent.
The next chapter is “Analysis of Chemical Reaction Systems – What Are Mathematics Able to Do, How Far Has Chemistry to Help?” by Jürgen Warnatz (pp. 81–108). It provides exAMples for how complex phenomena encountered in chemical and industrial processes are modelled by mathematical methods. These will be found interesting by both chemists and mathematicians.
The "Poetic Suggestion in Chemical Science" (pp. 109–139), written by (Sir) John Meurig Thomas, expresses some thoughts on the artistic and poetic aspects of both mathematics and chemistry, richly illustrated by facts and pictures from their past and present. Although the entire book is full of high-quality and beautiful figures, this chapter is really a piece of art. It would be good to make this article available to high-school students, before they decide what they will be studying – the number of those choosing chemistry would increase significantly.
The last chapter "Combustion: From Mathematical Models to Practical Devices", by Jürgen Wolfrum (pp. 141–160), is a fine survey of the physical chemistry of combustion, however with very few details on its mathematical modelling.
There is a total of 218 references quoted in this book. Not a single one is from the Journal of Mathematical Chemistry or MATCH Communications in Mathematical and in Computer Chemistry, the only two journals devoted to mathematics-related researches in chemistry. Not a single quotation is from the Journal of Computational Chemistry or Journal of Chemical Information and Computer Sciences or Computers &AMp; Chemistry, the three main journals for publishing computer-aided researches in chemistry. Not a single quotation is from Theoretical Chemistry Accounts (former Theoretica Chimica Acta) or International Journal of Quantum Chemistry, the leading journals for theoretical chemistry. This says something about the modes by which the authors of the book were invited or selected, and the connection of the contents of the book to contemporary scientific activities, lying on the border between mathematics and chemistry, sometimes referred to as Mathematical Chemistry.
In spite of the above, there is no doubt that the book “Chemistry and Mathematics: Two Scientific Languages of the 21st Century” is a valuable attempt to improve understanding, communication, and cooperation between mathematicians and chemists. From a technical point of view, the book is a masterpiece.

Ivan Gutman 
Faculty of Science, University of Kragujevac
Kragujevac, Serbia and Montenegro

J.Serb.Chem.Soc. 69(6)507–509(2004)

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The Devision of Analytical Chemistry
of the Federation of European Chemical Societies
and Professional Institutions (FECS)

European Analytical Column No. 32
(January 2004)

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