J.Serb.Chem.Soc.65(10)681–689(2000) UDC 547.582.4:542.9:541.12.03 JSCS-2792 Original scientific paper Synthesis of some bis- and mono-2-hydroxybenzoic acid derivatives and the determination of their acidity constants EVGENIJA A. DJURENDIC , GYÖNGYI GY. VASTAG#, TERÉZIA M. SURÁNYI#, MIRJANA M. POPSAVIN# and KATARINA M. PENOV GASI# Institute of Chemistry, Faculty of Sciences, University of Novi Sad, Trg D. Obradovica 3, YU-21000 Novi Sad, Yugoslavia (Received 21 March, revised 14 June 2000) Several bis- and mono-2-hydroxybenzoic acid derivatives were synthesized by the reaction of methyl 2-hydroxybenzoate with some alcohols (diols, polyols and amino alcohols) and their acidity constants were determined in 60 % aqueous ethanol by the potentiometric titration method. It has been shown that the biochemical behaviour of these compounds is greatly dependent on their acidity. It appears that the ester derivatives are weaker acids than the amide derivatives and, therefore, can be potentially more involved in the processes of metal ions transport in plants, whereas the introduction of –OH and –CH3 groups has a very small effect on the biochemical properties. Keywords: 2-hydroxybenzoic acid derivatives, synthesis, acidity constants. J.Serb.Chem.Soc.65(10)691–694(2000) UDC 615.28/.281 JSCS–2793 Original scientific paper An alternative synthesis of clindamycin KEITH BOWDEN and GRAHAM P. STEVENS Department of Biological and Chemical Sciences, Central Campus, University of Essex, Wivenhoe Park, Colchester, Essex, UK, CO4 3SQ (Received 7 June 2000) A novel synthesis of clindamycin from lincomycin using Nchlorosuccinimide and triphenylphosphine is reported. This results in high yields and avoids the use of tetrachloromethane employed in the current manufacturing process. Keywords: clindamycin, N-chlorosuccinmide. J.Serb.Chem.Soc.65(10)695–708(2000) UDC 547.462.3:539.172.3 JSCS–2794 Original scientific paper Protonation of maleic and fumaric acid in aqueous sulfuric acid solutions KATICA JANKOVSKA1, LIDIJA SOPTRAJANOVA2 and ILINKA SPIREVSKA2 1Faculty of Metallurgy and Technology, Rudjer Boskovic bb, 91000 Skopje, Macedonia and 2Institute of Chemistry, Faculty of Natural Sciences and Mathematics, P.O. Box 162, 91001 Skopje, Macedonia (Received 26 January, revised 12 June 2000) The protonations of maleic and fumaric acid in an acidic medium (aqueous solutions of sulfuric acid) were followed spectrophotometrically at room temperature. The acid-base equilibria were characterised qualitatively and quantitatively. The pKBH+ values were determined using the Hammett equation, employing several acid functions in order to determine which of them describes best the protonation process of the studied organic acids. The thermodynamic pKBH+ values as well as those of the solvation parameters m, m* and f and of the thermodynamic protonation constants (or, rather, the pKa,p values) were also defermined. The method of characteristic vector analysis (CVA) was used to reconstruct the experimental spectra. Keywords: maleic acid, fumaric acid, protonation, spectrophotometry. J.Serb.Chem.Soc.65(10)709–713(2000) UDC 547.461.3:539.173:541.127 JSCS–2795 Original scientific paper Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition SLAVICA BLAGOJEVIC,1 NATASA PEJIC,1 SLOBODAN ANIC2 and LJILJANA KOLAR-ANIC2 1Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, YU11000 Belgrade and 2Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, P. O. Box 137, YU-11001 Belgrade, Yugoslavia (Received 26 April 2000) The kinetics of the Belousov-Zhabotinsky (BZ) oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III) was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5´10-3 min-1, was found. Keywords: kinetics, non-linear dynamics, oscillatory reaction, Belousov-Zhabotinsky reaction. J. Serb. Chem. Soc. 65(10)715–723(2000) UDC 632.952:541.183:549.67:582.28 JSCS-2796 Original scientific paper Kinetics of aflatoxin B1 and G2 adsorption on Ca-clinoptilolite ALEKSANDRA DAKOVIC, MAGDALENA TOMASEVIC-CANOVIC, VERA DONDUR1, ALEKSANDRA VUJAKOVIC and PREDRAG RADOSEVIC Institute for Technology of Nuclear and Other Mineral Raw Materials, P. O. Box 390, YU-11001, Belgrade, and 1Faculty of Physical Chemistry, P. O. Box 137, YU-11001 Belgrade, Yugoslavia (Received 26 March 2000) The kinetics of aflatoxins B1 and G2 adsorption on Ca-clinoptilolite at pH 2 and 7, in aqueous electrolyte at 37 ºC were studied. For both aflatoxins, the adsorption process begins with a fast reaction whereby most of the toxin is adsorbed in the first few minutes. This fast process is followed by the significantly slower process of aflatoxin bonding at active centers of mineral adsorbent. The initial rate method showed that the fast adsorption process of aflatoxin B1 and G2, at both pH values is a first order reaction, while the slow adsorption process of these aflatoxins is a zero order reaction. The adsorption indexes and adsorption rates for both examined toxins were pH dependent. In the investigated initial toxins concentration ranges (500–3000 mg/dm3), high adsorption indexes were achieved (> 80 %). Keywords: clinoptilolite, adsorption, aflatoxin B1, aflatoxin G2. J.Serb.Chem.Soc.65(10)725–731(2000) UDC 543.544.4/.7:547.261/546.212 JSCS–2797 Original scientific paper Influence of the stationary and mobile phase composition in ideal chromatographic systems on the log k values in column chromatography. I. ODS/methanol–water system T. J. JANJIC, G. VUCKOVIC# and M. B. CELAP# Faculty of Chemistry, University of Belgrade, P. O. Box 158, YU-11001 Belgrade, Yugoslavia (Received 18 May 2000) On the basis of the literature data it was established that in the case of ODS column chromatography with methanol as modifier the value log xs/x1 (where xs and x1 denote methanol mole fractions in the stationary and the mobile phase, respecitvely) is a linear function of the corresponding Bosch’s PmN parameter as well as of the log k value of the investigated substances. It was also found that the phase equilibrium in the system ODS/methanol-water is in accordance with the Everett’s equation for ideal systems (K = 10.88). Finally, a linear relationship between the log xs/x1 values and the volume fraction of methanol (j) was found in the range of 0.5–1.0, which corresponds to the linear part of the function log k = f(j), established experimentally by other authors. Keywords: C18 liquid chromatography, stationary phase composition, mobile phase composition, capacity factors, PmN parameter, log k pair linearity rule, proportionality rule, RPP scale. J.Serb.Chem.Soc.65(10)733–742(2000) UDC 543.544.42:661.183.7:547.261:547.722/.728 JSCS–2798 Original scientific paper Application of the Log k pair linearity rule and Proportionality rule to the RPP mobile phase scales estimation on diol-silica column TOMISLAV J. JANJIC, GORDANA VUCKOVIC# and MILENKO B. CELAP# Faculty of Chemistry, University of Belgrade, P. O. Box 158, YU-11001 Belgrade, Yugoslavia (Received 12 May 2000) By the application of the Log k pair linearity rule and the Proportionality rule to the previously published log k values for 27 compounds, obtained on diol-silica columns with acetonitrile, methanol and tetrahydrofuran as modifiers, the existence of common RPP scales was established. The obtained correlation coefficients of the linear function log k = f(RPP) were better than 0.9900 for 26 compounds in the first, 21 in the second and 20 in the third case. In addition, in the case of the two first modifiers a linear correlation between the obtained RPP values and mol % of modifier in the mobile phase was found. On the basis of this, the following simple linear function: log k = f(mol % of modifier) was proposed as a criterion for log k values judgement in practical work. A linear correlation was also established between intercept and slope of the function, in spite of the fact that the investigated compounds essentially differ in their descriptors. Keywords: column chromatography, diol-silica sorbent, log k pair linearity rule, proportinality rule, RPP scale. J.Serb.Chem.Soc.65(10)743–754(2000) UDC 546.65/654:546.226 33:534.24 JSCS–2799 Original scientific paper Lanthanide doped alkaline metal sulphates as candidates for EPR dosimetry JELENA PETKOVIC, IVANA MLADENOVIC, NIKOLA VUKELIC, MILOS MOJOVIC and GORAN BACIC Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12, YU-11001 Belgrade, Yugoslavia (Received 2 June 2000) The applicability of lanthanide doped alkaline metal sulphates as a new type of dosimeters for EPR dosimetery of ionizing radiation has been investigated in an attempt to obtain a dosimeter with better characteristics than the commonly used alanine dosimeter. Irradiation of samples doped with different lanthanides (Y, Ln, Gd) showed that the best sensitivity is obtained using dosimeters doped with Y2(SO4)3. Different procedures for manufacturing dosimeters were studied and an optimum procedure was established. The time stability of the EPR signal of the irradiated Y2(SO4)3 dosimeter was investigated using a 15N-PDT standard and no fading of the EPR signal was observed over at least two weeks. The dose dependence of alanine and Y2(SO4)3 doped K3Na(SO4)2 dosimeters irradiated in the range 20 Gy – 200 kGy was analysed using a combination of 1-hit and 2-hit mechanisms of free radicals creation. Keywords: lanthanide doped K3Na(SO4)2, electron paramagnetic resonance, dosimetry. J.Serb.Chem.Soc. 65(10)000-000(2000) UDC 542.4/.47::541.124 JSCS-2800 Original scientific paper An experimental study of the drying of granular materials in a packed bed passed by hot air the local humidity of the material ANCA MOISE and RADU Z. TUDOSE Department of Chemical Engineering, Iasi Technical University, Mangeron nr. 71, Iasi-6600, Romania (Received 26 July 1999, revised 14 June 2000) With the purpose of establishing the mechanism resposible for the drying of granular materials in a packed bed passed by a gaseous thermic agent, experimental kinetic study was perormed. In a pilot plant, the axial and radial distributions of the solid local humidity were determined in the nonsteady regime. The results show it is possible for three zones, each at a different state of dryness, to exist in the bed: one zone with initial humidity, one zone with variable humidity and one zone with dried material. Keywords: drying, packed bed, kinetics of drying.