JSCS Vol 61, No. 9
 
J. Serb. Chem. Soc. 61(9)703-715(1996) 
UDC 535.337:621:3.001.5:621.3.029 
JSCS-2284 
Review paper

Review
BROADBAND DIELECTRIC RELAXATION SPECTROSCOPY AT 10-4 Hz

P. PISSIS and A. KANAPITSAS

Department of Physics, National Technical University of Athens, 
Zografou Campus, 15780 Athens, Greece

(Received 17 July 1995)
1. Introduction
2. Fundamentals of DRS
3. PHEA hydrogels
4. Water and glass-forming liquids in confined geometries
5. Polyurethane blends
6. Conclusions

Key words: dielectric relaxation spectroscopy, relaxation mechanisms, poly(hydroxyethyl-acrylate) hydrogels; water, glass-forming liquids, copolymers.

J. Serb. Chem. Soc. 61(9) 717-727 (1996) 
UDC 546.11:541.571.9:547.96 
JSCS-2285 
Review paper

Review

STUDY OF HYDROGEN BONDING NETWORKS IN PROTEINS BY HIGH RESOLUTION NMR SPECTROSCOPY

NENAD JURANIC, MARTIN MONCRIEFFE, ELIZABETH KURIAN, FRANKLYN G. PRENDERGAST
and SLOBODAN MACURA

Department of Biochemistry and Molecular Biology, Mayo Graduate School, 
Mayo Clinic and Mayo Foundation, Rochester, MN 55905, U.S.A.

((Received 24 July 1995)
1. Introduction
2. Hydrogen bonding in proteins
3. High resolution NMR and hydrogen bonding
4. Hydrogen bonding and protein structure
5. Conclusion

Key words: high resolution NMR spectroscopy, protein, hydrogen bond, structure, stability.

J. Serb. Chem. Soc. 61(9)729-743(1996) 
UDC 543.51:539.194:539.125.5 
JSCS-2286 
Review paper

Review
MOLECULAR VIBRATIONAL SPECTROSCOPY WITH NEUTRONS

J. TOMKINSON

ISIS Facility Rutherford Appleton Laboratory, 
Chilton; Oxon, OX10 OQX, UK

(Received 25 May 1996)
1. Introduction
2. Neutron spectroscopy of H-bonds
3. Instrumentation
4. Applicatons
5. Prospects for future work
6. Conclusion

Key words: molecular vibrations, neutron spectroscopy, vibrational band intensities, hydrogen bond.

J. Serb. Chem. Soc. 61(9) 745-753 (1996) 
UDC 537.533.2:531.758 
JSCS-2287 
Original scientific paper

CALCULATION OF THE ELECTRON NUMBER DENSITY SPATIAL DISTRIBUTION IN THE ICAP

ZORAN RASPOPOVIC1, IVANKA HOLCLAJTNER-ANTUNOVIC2, VELJKO GEORGIJEVIC3
and MIRJANA TRIPKOVIC1

1Institute of Physics, P.O.Box 57, YU-11080 Belgrade - Zemun, 
2Faculty of Physical Chemistry, University of Belgrade, P.O.Box 137, YU-11001 Belgrade and 
3Faculty of Civil Engineering, University of Belgrade, P.O.Box 895, YU-11001, Belgrade, Yugoslavia

(Received 24 July 1995, revised 14 March 1996)
A computer simulation is used to calculate the spatial distributions of electron number density in inductively coupled argon plasma. The calculated and experimental results obtained for standard conditions in analytical atomic spectroscopy are compared with other authors' experimental results.

Key words: electron number density, inductively coupled plasma, mathematical modelling.

J. Serb. Chem. Soc. 61(9) 755-758 (1996) 
UDC 546.11:541.571.9:547.263 
JSCS-2288 
Original scientific paper
HYDROGEN-BONDED COMPLEXES OF 1,1,1-TRICHLORO-2-METHYL-2-PROPANOL WITH SOME ETHERS AND KETONES

LJUBINKA J. BOGUNOVIC1, UBAVKA B. MIOC2, SLOBODAN V. RIBNIKAR2
and BILJANA R. STANISAVLJEV2

1Faculty of Technology and Metallurgy, University of Belgrade, 
Karnegijeva 4, P.O.Box 494, YU-11001 Belgrade, and 
2Faculty of Physical Chemistry, University of Belgrade, Studentski trg 16, 
P.O.Box 137, YU-11001 Belgrade, Yugoslavia

(Received 24 July 1995)
The interaction by hydrogen bond formation of 1,1,1-trichloro-2-methyl-2-propanol with some ethers and acetone was investigated in CCl4 by means of IR spectroscopy. Equilibrium constants and enthalpies of complex formation were determined. The dependence of the spectroscopic parameters, equilibrium constants and enthalpies of complex formation on the proton donating and proton accepting power of the interacting carbinol and ether are discussed. The results are compared with those of earlier sudies on the complexes of trimethylcarbinol with ketones and ethers.

Key words: IR spectra, molecular complexes, hydrogen bond, 1,1,1-trichloro-2-methyl-2-propanol

J. Serb. Chem. Soc. 61(9) 759-765 (1996) 
UDC 661.878/661.635/:543.42 
JSCS-2289 
Original scientific paper

SPECTROSCOPIC INVESTIGATION OF THE EFFECTS OF MONOVALENT CATIONS ON 
THE DYNAMICS OF PROTONIC SPECIES IN THE HYDRATES OF 12-TUNGSTOPHOSPHORIC 
ACID SALTS


UBAVKA B. MIOC1, MILORAD DAVIDOVIC2, BILJANA R. STANISAVLJEVIC1, MARIJA R. TODOROVIC3, ZORAN P. NEDIC1 and SNEZANA USKOKOVIC4

1Faculty of Physical Chemistry, University of Belgrade, P.O. Box 137, YU-11001 Belgrade, 
2The Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11001 Belgrade, 
3Faculty of Chemistry, University of Belgrade, P.O.Box 158, YU-11001 Belgrade and 
4Faculty of Pharmacy, University of Belgrade, P.O.Box 146, YU-11001 Belgrade, Yugoslavia

(Received 24 July 1995)
Heteropoly acids are well known as superionic protonic conductors at room temperature. The conductivity depends upon the temperature and relative humidity of the surrounding. Recent results show that the conductivity is very much affected by monovalent exchange counter-ions. In this work the effect of monovalent ions (Li+, Na+, K+ and Cs+) on the nature and structure of hydrogen bonds, the presence of different protonic species as charge carriers, and the dynamic equilibrium of proton species as a function of temperature and ion characteristics were investigated.

Key words: IR spectra, hydrogen bond, protonic species, 12-tungstophosphoric acid salts.

J. Serb. Chem. Soc. 61(9) 767-771 (1996) 
UDC 661.878/661.635/:543.42 
JSCS-2290 
Original scientific paper

ANTICOAGULANT EFFECT OF TUNGSTOPHOSPHORIC ACID SALT STUDIED BY 
IR SPECTROSCOPY

UBAVKA B. MIOC1, VESNA S. KUNTIC2, ZORAN P. NEDIC1, IVANA M. FILIPOVIC3
and SVETISLAV B. JELIC3

1Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, YU-11000 Belgrade, 
2Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, YU-11000 Belgrade and 
3Institute of Oncology and Radiology, YU-11000 Belgrade, Yugoslavia

(Received 24 July 1995 revised 19 February 1996)
The influence of the Li and Na salts of 12-tungstophosphoric acid H3PW12O46 (WPA) was tested for in vitro effects on blood coagulation. It was found that only Li3WPA shows anticoagulant effects, but compared with WPA activity, the activity of Li salt is diminished. IR spectroscopy was used to define the reaction between these salts and coagulation proteins. The appearance of bands characteristic of oxonium ion (H3O+) in the IR spectra indicates blocking of the active center of the protein through a very strong hydrogen bond.

Key words: IR spectra, anticoagulant effect, hydrogen bond, tungstophosphoric acid salts.

J. Serb. Chem. Soc. 61 (9) 773-776 (1996) 
UDC 535.33:541.571.9:547.582.4 
JSCS-2291 
Original scientific paper

INFRARED STUDY OF N-H... HIDROGEN BONDING. 
N-METYLBENZAMIDE - AROMATIC DONOR SYSTEM

ALEKSANDAR D. NIKOLIC, IVANA I. IVANCEV-TUMBAS, SLOBODAN D. PETROVIC1 and
DUSAN G. ANTONOVIC1

Faculty of Natural Sciences and Mathematics, YU-21000 Novi Sad and 
1Faculty of Technology and Metallurgy, YU-11000 Belgrade, Yugoslavia

(Received 26 September 1995, revised 17 May 1996)
The present paper reports the results of an infrared study in the region of the fundamental NH stratching vibration for six N-methylbenzamide-aromatic donor systems. The thermodynamic properties for 1:1 NMBA-aromatic donor complexes are given. The contribution of the charge transfer mechanism to the hydrogen bonding in the studied systems is considered.

Key words: hydrogen bond, N-methylbenzamide IR spectra

J. Serb. Chem. Soc. 61 (9) 777-783 (1996) 
UDC 547.268.19:543.42 
JSCS-2292 
Original scientific paper

HERTZIAN SPECTROSCOPY OF PHYTOL AND OF ITS SOLUTIONS. 
INTERPRETATION OF THE DYNAMICS AND CONSTANTS OF THE SYSTEM

ZORAN A. FIDANOVSKI1 and MILESA Z. SRECKOVIC2

1VTI VJ, Katani}eva 15, YU-11000 Belgrade, and 
2Faculty of Electrical Engineering, University of Belgrade, 
Bulevar revolucije 73, YU-11000 Belgrade, Yugoslavia

(Received 24 July 1995, revised 15 May 1996)
For a series of organic solvents, as well as various concentrations of their mixtures, a series of Rayleigh-Brillouin spectra was recorded. The spectral data with reference to the central line were separately evaluated, with respect to other optical and thermodynamic parameters. From the data obtained the acoustical features of phytol and some other solvents were qualitatively and quantitatively estimated by determining the speed of hypersound. The distances were measured very carefully for all four components of the scattered light. From the data for the scattered light, the dipole moment of phytol was determined. On the basis of experimental values for the Rayleigh line, the contributions of the nonlinear behaviour of phytol and other organic solvents were estimated.

Key words: Raileigh-Brilloun spectra, phytol, dipol molecular moments, hypersound.

J. Serb. Chem. Soc. 61 (9) 785-792 (1996) 
UDC 546.98:541.428.49:535.243 
JSCS-2293 
Original scientific paper

SPECTROPHOTOMETRIC INVESTIGATION OF COMPLEX FORMATION BETWEEN HMPAO AND PALLADIUM(II) IONS

NADEZDA S. VUKICEVIC, KATARINA D. KARLJIKOVIC-RAJIC1, DRAGAN S. VESELINOVIC2,
NADEZDA M. VANLIC-RAZUMENIC and SNEZANA M. USKOKOVIC1

Vinca Institute of Nuclear Sciences,, Deptarment of Radiosotopes, P.O. Box 522, YU-11001 Belgrade, 
1Faculty of Pharmacy, Department of Analytical Chemistry, P.O. Box 146, YU-11224 Belgrade and 
2Faculty of Physical Chemistry, P.O.Box 137, YU-11001 Belgrade, Yugoslavia

(Received 24 July 1995)
A system containing palladium(II) ions and dioxime HMPAO (H2L; L2- = 4,8-diaza-3,6,6,9-tetramethylundecane-2,10-dione dioximate ion) was investigated within a pH range of 2.0 to 7.5 (I = 0.5 mol dm-3) using spectrophotometric measurements. Experimental data proved the formation of two different complex types: one with excessive Pd(II) ions (lmax = 370 nm) and the other with excessive HMPAO, lmax = 240 nm, HMPAO to Pd(II) ratio 1:1, and a relative stability constant log b' = 4.64 ± 0.05, at 293 K. The probable structure of the complex [Pd(HL)]+ in solution is also suggested.

Key words: UV - VIS spectra, palladium(II) complexes, HMPAO complexes.

J. Serb. Chem. Soc. 61 (9) 793-796 (1996) 
UDC 547.753:537.753 
JSCS-2294 
Original scientific paper

ELECTRONIC SPECTRA OF SOME ISOINDOLONE DERIVATIVES

MARIJA KAKAS, IMRE GUTH, AGNES KAPOR and IVAN JANIC

Institute of Physics, Faculty of Science, University of Novi Sad, Trg D. Obradovica, 4, YU-21000 Novi Sad, Yugoslavia

(Received 31 July 1995)
The absorption (293 K), luminescence and excitation spectra (293 and 77 K) of 12b-p-tolyl-perhydro-1,3-benzoxazino [2,3-a]-isoindolone (1) and 2-(2-hydroxyethyl)-1-p-tolyl-4,5,6,7-tetrahydro-3(1H)-isoindolone (2) were examined in solution, and the luminescence and excitation spectra were examined in polycrystalline form. An analysis of the electronic spectra indicates that the lowest excited singlet and triplet electronic state in these molecules are of the pp*-type. The large probability of intersystem conversion to triplet state appears in the polycrystalline form of 2 and solution of 1. The rotation of the tolyl group in 2 due to excitation at room temperature, causes internal degradation of the excited singlet state and an absence of fluorescence. The molecules keep their solid state conformation in solution, too, at least in the ground electronic state.

Key words: electronic spectra, isoindolone derivatives.

J. Serb. Chem. Soc. 61 (9) 797-801 (1996) 
UDC 547.565.3:541.515:53.083.2 
JSCS-2295 
Original scientific paper

ESR SPIN-TRAPPING STUDIES OF INFLUENCE OF PHENOLIC COMPOUNDS ON HYDROXYL RADICAL FORMATION

BOZIDAR LJ. MILIC, SONJA M. DJILAS and JASNA M. CANADANOVIC-BRUNET

Faculty of Technology, University of Novi Sad, Bulevar Cara Lazara 1, YU-21000 Novi Sad, Yugoslavia

(Received 24 July 1995, revised 15 Jun 1996)
The influence of some phenolic compounds, such as catechol, pyrogallol, resorcinol, vanillin, salicylic acid and 5-aminosalicylic acid, on the hydroxyl radical formation was studied by electron spin resonance (ESR) using the spin trapping method. The results of the investigation show that phenolic compounds, which possess a catechol residue, enhance the formation of the hydroxyl radical during the oxido-reductive reactions of ferric compound, a thylendiaminotetraacetic acid with hydrogen peroxide in sodium phosphate buffer at pH 7.4. The ferric ions are reduced by the phenolic compounds forming ferous ions which react with the hydrogen peroxide in a Fenton type reaction and increase the concentraton of hydroxyl radicals.

Key words: hydroxyl radical, phenolic compounds, Fenton type reaction, ESR spin trapping method.

J. Serb. Chem. Soc. (9) 803-808 (1996) 
UDC 546.26:620.197.6:543.51 
JSCS-2296 
Original scientific paper

MASS SPECTROMETRIC STUDY OF GLASSY CARBON SURFACE STABILITY
ALEKSANDRA PERIC1, OLIVERA NESKOVIC2, MIOMIR VELJKOVIC2, KIRO ZMBOV2,
MIODRAG MILETIC2,MILA LAUSEVIC1 and ZORAN LAUSEVIC2

1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O.Box 494, YU-11000 Belgrade, and 
2Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11000 Belgrade, Yugoslavia

(Received 24 July 1996)
The combinaton of temperature-programmed desorption (TPD) and quadrupole mass spectrometry was used to investigate glassy carbon surface stability. TPD experiments provide valuable information about the nature and the stability of the surface oxide groups. Samples of pure glassy carbon, and glassy carbon modified by metal (silver, palladium) deposition were analysed. Mass spectrometric analysis showed that the thermal decomposition of surface oxide species results in desorption of H2O, CO and CO2, these being the major gas products. Desorption energies were calculated using the peak-position method. On the basis of the TPD spectra obtained and the desorption energies, it was concluded that the metal deposition stabilizes the glassy carbon surface.

Key words: mass spectra, temperature-programmed desorption (TPD), glassy carbon.

J. Serb. Chem. Soc. 61 (9) 809-816 (1996) 
UDC 622.337:66.095:541.52 
JSCS-2297 
Original scientific paper

INVESTIGATION OF POLYCYCLIC BIOMARKER TRANSFORMATION DURING HYDROUS PYROLYSIS OF OIL SHALE BY GC-MS

TATJANA L. GLUMICIC1, MIRJANA M. SABAN1,2, JOZEF J. COMOR3, SMILJANA S. MILOJKOVIC3, and NIKOLA P. DOGOVIC4

1Centre of Chemistry, Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, YU-11000 Belgrade, 
2Department of Chemistry, University of Belgrade, P.O. Box 158, YU-11000 Belgrade, 
3The Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11001 Belgrade and 
4Military Technical Institute, YU-11000 Belgrade

(Received 24 July 1995)
In order to simulate maturational changes of the organic matter, hydrous pyrolysis of immature oil shale from Vranje was carried out at 280 and 300 oC for 48 and 96 h under constant pressure of 12-13 MPa. Using a gas chromatographic - mass spectrometric method (GC-MS) on the basis of m/z = 191 and m/z = 217 fragmentograms, polycyclic alkanes, steranes and terpanes, isolated from bitumens and hydrous pyrolysates were analysed. The observed differences in the compositions of polycyclic alkanes isolated from bitumens and hydrous pyrolysates made possible the investigation of the structural changes of these biomarkers at the molecular level druing hydrous pyrolysis.

Key words: mass spectra, hydrous pyrolysis, bitumen, polycyclic alkanes, maturation parameters.

J. Serb. Chem. Soc. 61 (9) 817-821 (1996) 
UDC 547.592.2:628:35:543.544.25 
JSCS-2298 
Original scientific paper

GC-MS IN CRUDE OIL CORRELATION STUDIES - EFFECTS OF BIODEGRADATION ON STERANE AND TERPANE MATURATION PARAMETERS

BRANIMIR S. JOVANČIĆEVIĆ1,2, LJUBICA Z. TASIC1, PREDRAG S. POLIC1,2, JOVAN M. NEDELJKOVIC3, ANATOLY K. GOLOVKO4 and DRAGOMIR K. VITOROVIC1,2

1Department of Chemistry, Faculty of Science, University of Belgrade, P.O.Box 158, YU-11001 Belgrade, 
2Centre of Chemistry, ICTM, Njegoseva 12, YU-11000 Belgrade; 
3Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11001 Belgrade, Yugoslavia and 
4Institute of Petroleum Chemistry, Academichesky Ave, 3, 634055 Tomsk, Russia

(Received 24 July 1995)
GC-MS was applied in order to determine the effects of biodegradation on steranes and terpanes in crude oils. Sterane and terpane maturation parameters were correlated in 36 crude oils, biodegraded to various degrees (28 samples originate from the SE part of the Pannonian Basin, Yugoslavia, and 8 samples were obtained from the oil fields of Eastern Russia). The absence of any correlation between terpane maturation parameters indicated that terpane isomers are highly altered during biodegradation. On the other hand, satisfactory correlation between sterane parameters indicated that their abundance and distribution is less affected by microbial activity, and it can be concluded that sterane parameters represent more reliable maturation parameters.

Key words: GS-MS spectra, steranes, terpanes, maturation parameters.

J. Serb. Chem. Soc. 61 (9) 823-830 (1996) 
UDC 550.41:553.96:543.51 
JSCS-2299 
Original scientific paper

GC-MS IN ORGANIC GEOCHEMISTRY OF COAL-ESTIMATION OF THE ORIGIN AND DEGREE OF CARBONIFICATION IN COAL FROM THE KOSOVO BASIN (YUGOSLAVIA)

ZORAN M. MILIČEVIC1, MIRJANA M. SABAN2,3, BRANIMIR S. JOVANCICEVIC2,3, and
JOVAN M. NEDELJKOVIC4

1Faculty of Economics, University of Pristina, Cara Dusana bb, YU-38000 Pristina, 
2Faculty of Chemistry, University of Belgrade, P.O.Box 158, YU-11001 Belgrade, 
3Centre of Chemistry, ICTM, Njegoseva 12, Belgrade and 
4Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11001 Belgrade, Yugoslavia

(Received 24 July 1995, revised 22 March 1996)
Biological markers in the alkane fraction of coal from the central and southern parts of the Kosovo basin (Yugoslavia) were analyzed by using computerized gas chromatography-mass spectrometry (GC-MS). The presence of tricyclic diterpanes with pimarane and abietane structure and tetracyclic diterpane 16a(H) phyllocladane indicated that coniferous resins participated in the formation of the organic mater of Kosovo basin coal. The presence of De-A lupane proved the partipication of dicotyledonous gymnosperms in the formation of the organic matter, while the presence of pentacyclic triterpanes with hopane structure indicated that the degradation of the organic substance was caused by microorganisms of the bacterial type. The results of the GC-MS analysis of the biomarkers were used to estimate the degree of carbonification of the investigated coal. The presence of diterpanes with pimarane structure and the presence of monoaromatic hopane structure (D-ring), and the absence of 16a(H) phyllocladane and 18a(H)22,29,30 trisnorhopane (Ts), confirmed that Kosovo basin coal is of a low carbonification degree.

Key words: gas chromatography-mass spectrometry, biomarkers, terpanes, coal, Kosovo basin.

J. Serb. Chem. Soc. 61 (9) 831-840 (1996) 
UDC 541.23-001.4:539.183.2 
JSCS-23000 
Original scientific paper

A STABLE ISOTOPY STUDY OF GEOTHERMAL WATERS IN SERBIA

NADA R. MILJEVIC1, DUSAN D. GOLOBOCANIN1 and MIHAILO G. MILIVOJEVIC2

1Vinca Institute of Nuclear Sciences, P.O.Box 522, YU-11001 Belgrade, and 
2Faculty of Mining and Geology, Djusina 7, YU-11000 Belgrade, Yugoslavia

(Received 24 July 1995)
An investigation of the stable isotope compositions of thermal waters in central Serbia was initiated in 1986 to provide an isotope database for geothermal resource assessment purposes. Samples of water at 66 locations from various sources (thermal springs, dug wells, and boreholes) were collected for conventional isotope hydrological analysiss (D, 18O, 13C). Most of the examined waters are of the Na-(Ca)-Mg-HCO3(SO4)-(Cl) type, with temperatures ranging from 16 to 111 °C. The deuterium and 18O compositions are in wide range from -42 to -106 ‰ for DD and between -3.3 and -12.9 ‰ for d18O. The isotopic data on DD and D18O for the thermal waters indicate their meteoric origin. An evaluation of the actual temperature in depth of the geothermal reservoirs was performed for the case of the oxygen-18 shift appearance in discharged waters.

Key words: mass spectra, isotope analyses, thermal waters.