JSCS Vol 74, No. 4

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J. Serb. Chem. Soc. 74 (4) 359–366 (2009)
UDC 582.998.2:57.083.32:66.095.11:66.02; JSCS–3837; doi: 10.2298/JSC0904359S; Original scientific paper

Chemical modification of Art v 1, a major mugwort pollen allergen, by cis-aconitylation and citraconylation
DRAGANA STANIĆ, LIDIJA BURAZER*, MARIJA GAVROVIĆ-JANKULOVIĆ**, RATKO M. JANKOV** and TANJA ĆIRKOVIĆ VELIČKOVIĆ**
Institute for Chemistry, Technology and Metallurgy – Center for Chemistry, Njegoševa 12, P.O. Box 473, 11001 Belgrade, Serbia

*Institute of Virology, Vaccines and Sera – Torlak, Vojvode Stepe 458, P.O. Box 1, 11221 Belgrade, Serbia

**Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11001 Belgrade, Serbia

(Received 19 September, revised 6 November 2008)

Art v 1 is the major allergen of mugwort (Artemisia vulgaris) pollen, a significant cause of hay fever all over Europe. Specific immunotherapy is the only treatment modality for allergic disease. Application of modified allergens makes the treatment safer and more efficient. In this work, two out of three (citraconic anhydride, cis-aconitic anhydride, 2,3-dimethylmaleic anhydride) tested anhydrides were proven to be suitable for chemical modifications of allergens. Art v 1 was modified by cis-aconitylation and citraconylation in order to obtain derivatives of Art v 1 that may be suitable for further immunological testing. Acylation of Art v 1 gave derivatives (caaArt v 1 and citArt v 1) with about 80 % modified AMino groups. The derivatives were in the monomeric form and had drAMatically reduced pI values. Both derivatives were relatively stable at neutral pH values, while the acyl groups undergo hydrolysis under acidic conditions. Modification of allergens by cis-aconitylation and citraconylation could be a new tool for obtaining allergoids.

 

Keywords: allergoid; mugwort pollen; Art v 1; chemical modification; allergen-specific immunotherapy.

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J. Serb. Chem. Soc. 74 (4) 367–377 (2009)
UDC 616.33:615.37:633.852.73:633.879.1; JSCS–3838; doi: 10.2298/JSC0904367D; Original scientific paper

Phytochemical analysis and gastroprotective activity of an olive leaf extract
DRAGANA DEKANSKI, SNEŽANA JANIĆIJEVIĆ-HUDOMAL*, VANJA TADIĆ**, GORAN MARKOVIĆ**, IVANA ARSIĆ** and DUŠAN M. MITROVIĆ***
Biomedical Research, R &AMp; D Institute, Galenika a.d., Pasterova 2, 11000 Belgrade, Serbia

*Pharmacology Department, School of Medicine, University of Priština (Kosovska Mitrovica), Serbia

**Institute for Medicinal Plant Research “Dr Josif Pančić”, Tadeuša Košćuška 1, 11000 Belgrade, Serbia

***Institute of Medical Physiology, School of Medicine, University of Belgrade, Višegradska 26, 11000 Belgrade, Serbia


(Received 8 September, revised 7 November 2008)

Some medicinal features of olive leaf have been known for centuries. It has been traditionally used as an antimicrobial and to prevent and treat diabetes mellitus and heart disease. Whether olive leaf, a natural antioxidant, influences the gastric defense mechanism and exhibits gastroprotection against experimentally-induced gastric lesions remains unknown. In this study, the content of total phenols, total flavonoids and tannins in olive leaf extract (OLE) were determined. Seven phenolic compounds were identified and quantified (oleuropein, caffeic acid, luteolin, luteolin-7-O-glucoside, apigenin-7-O-glucoside, quercetin, and chryseriol). Furthermore, the protective activity of the OLE in gastric mucosal injury induced by a corrosive concentration of ethanol was investigated. In relation to the control group, pretreatment with OLE (40, 80 and 120 mg kg-1) significantly (p < 0.001) attenuated the gastric lesions induced by absolute ethanol. The protective effect of the OLE was similar to that obtained with a reference drug, ranitidine. The results obtained indicate that OLE possesses significant gastroprotective activity, and that the presence of compounds with antioxidative properties would probably explain this effect.

 

Keywords: olive leaf extract; phenols; flavonoids; tannins; gastroprotection.

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J. Serb. Chem. Soc. 74 (4) 379–388 (2009)
UDC 577.112.383+66.097.8+547.995; JSCS–3839; doi: 10.2298/JSC0904379B;  Original scientific paper

Inhibition of trypsin by heparin and dalteparin, a low molecular weight heparin
OLIVERA M. BOSNIĆ, KRISTINA R. GOPČEVIĆ*, MIROSLAV M. VRVIĆ** and IVANKA M. KARADŽIĆ*

School of Medicine, Department of Physiology, University of Belgrade, Višegradska 26, 11000 Belgrade, Serbia

*School of Medicine, Department of Chemistry, University of Belgrade, Višegradska 26, 11000 Belgrade, Serbia

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

(Received 28 August, revised 19 September 2008)

The interaction between trypsin, a prototype S1 serine protease, with heparin and its low molecular weight derivative dalteparin were investigated. Direct inhibition of the proteolytic activity of trypsin by heparin and dalteparin, used in concentrations typical for their clinical application, was detected. The half-maximum inhibition of the trypsin activity was achieved at 15.25±1.22 mg/mL for heparin and was estimated to be at 58.47±15.20 mg/mL for dalteparin. Kinetic analyses showed that heparin and its low molecular weight derivative dalteparin inhibited trypsin by occupation of an exosite, producing noncompetitive and mixed inhibition, respectively. Heparin as a noncompetitive inhibitor with constant of inhibition Ki1,2 = 0.151±0.019 mM and dalteparin with Ki1 = 0.202±0.030 mM and Ki2 = 0.463±0.069 mM in mixed inhibition both represent moderate inhibitors of serine protease trypsin. The obtained constants of inhibition indicate that under the clinically applied concentrations of heparin and dalteparin, trypsins and their homolog S1 serine proteases could be directly inhibited, influencing the delicate control of proteolytic reactions in homeostasis.

 

Keywords: serine proteases; heparin; dalteparin; inhibition.

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J. Serb. Chem. Soc. 74 (4) 389–400 (2009)
UDC 546.982–386:548.7:535.441; JSCS–3840; doi: 10.2298/JSC0904389K; Original scientific paper

Palladium(II) complexes with R2edda derived ligands. Part I. Reaction of diisopropyl (S,S)-2,2'-(1,2-ethanediyldiimino)-dipropanoate with K2[PdCl4]
BOJANA B. KRAJČINOVIĆ*, GORAN N. KALUĐEROVIĆ*,**, DIRK STEINBORN**, HARRY SCHMIDT**, CHRISTOPH WAGNER**, KURT MERZWEILER**, SREĆKO R. TRIFUNOVIĆ*** and TIBOR J. SABO****
*Department of Chemistry, Institute of Chemistry, Technology and Metallurgy, Studentski trg 14, 11000 Belgrade, Serbia

**Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Straße 2, D-06120 Halle, Germany

***Department of Chemistry Faculty of Science, University of Kragujevac, 34000 Kragujevac, Serbia

****Faculty of Chemistry, University of Belgrade, P.O. Box 158, 11001 Belgrade, Serbia

(Received 24 June, revised 6 October 2008)

The reaction of K2[PdCl4] with (S,S)-(i-Pr)2eddip diester (diiso-propyl (S,S)-2,2’-(1,2-ethanediyldiimino)dipropanoate) resulted in {PdCl2[(S,S)-(i-Pr)2eddip-κ2N,N’]} (1) and {PdCl[(S,S)-(i-Pr)eddip-κ2N,N’,κO]} (2) with one hydrolyzed ester group. The compounds were characterized by spectroscopic methods and it was proved that the reaction is diastereoselective (1H- and 13C-NMR) in the case of 2 (one diastereoisomer of four possible). The structure of 2 was determined by X-ray diffraction analysis, indicating that the product is the (R,R)-N,N’ configured isomer. In contrast, the reaction yielding 1 produced two of three possible diastereoisomers. DFT calculations support the formation of two diastereoisomers of 1 and of one diastereoisomer of 2.

 

Keywords: palladium complexes; crystal structure; EDDP ligands; DFT calculations.

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J. Serb. Chem. Soc. 74 (4) 401–406 (2009)

UDC 546.763’723–386:66.095.62.094.25; JSCS–3841; doi: 10.2298/JSC0904401Y; Original scientific paper

 

Synthesis and characterization of novel oxo-bridged, trinuclear mixed-metal complexes of Cr(III) and Fe(III)

MOHAMMAD YAZDANBAKHSH, IMAN KHOSRAVI and HAMAN TAVAKKOLI

Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran

 

(Received 3 October 2008)

Two new heterotrinuclear p-chlorobenzoates, [Fe2CrO(C7H4O2Cl)6(py)3]NO3 (1) and [Cr2FeO(C7H4O2Cl)6(py)3]NO3 (2) were prepared as nitrate salts and characterized by elemental analyses (CHN), spectroscopic (infrared, electronic) studies and atomic absorption spectroscopy. These complexes are a new type of oxo-bridged mixed-metal complex in which the carboxylate ligand is p-chlorobenzoic acid. Bridging coordination modes for the carboxylates were indicated by the presence of nasym (M2M’O) vibrations in the infrared spectra.

 

Keywords: carboxylates; oxo-bridged complexes; p-chlorobenzoic acid; IR spectra.

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J. Serb. Chem. Soc. 74 (4) 407–415 (2009)        

UDC 547.466.64+544.72.023.221+66.097.8:620.193; JSCS–3842; doi: 10.2298/JSC0904407Z; Original scientific paper

 

Electrochemical and molecular simulation studies on the corrosion inhibition of L-glutAMine monolayers

on an iron surface

ZHE ZHANG*, SHENHAO CHEN*,**, YUANYUAN FENG***, YUNQIAO DING*, JUANJUAN ZHOU* and HENGLEI JIA*

*Department of Chemistry, Shandong University, Jinan 250100, P.R. China

**State Key Laboratory for Corrosion and Protection, Shenyang 110016, P.R. China

***Department of Chemistry Qufu Normal University, Qufu 273165, P.R. China

 

(Received 19 September, revised 10 November 2008)

L-GlutAMine was used to form monolayers for the inhibition of the corrosion of iron in 0.50 mol dm-3 H2SO4. The protection ability of the films was exAMined by electrochemical impedance spectroscopy. The mechanism of adsorption is discussed using quantum chemical calculations and molecular simulations. Scanning electron microscopy was applied to confirm the formation of L-glutAMine monolayers and the inhibitive effect. The results indicate that the molecules of L-glutAMine are able to form films on the surface of iron and longer immersion time of the iron electrode in the solution results in a stronger inhibition ability of the films. The films are formed spontaneously by the adsorption of L-glutAMine with a specific affinity of its head-group to the iron surface, hence, the densely and ordered monolayers can be considered as self-assembled.

 

Keywords: L-glutAMine; iron; corrosion; self-assembled monolayer; EIS.

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J. Serb. Chem. Soc. 74 (4) 417–425 (2009)

UDC 633.822+66.061:665.52/.54; JSCS–3843; doi: 10.2298/JSC0904417Z; Original scientific paper

 

Supercritical CO2 extraction of mentha (Mentha piperita L.) at different solvent densities

ZORAN ZEKOVIĆ, ŽIKA LEPOJEVIĆ, SLAVICA MILIĆ, DUŠAN ADAMOVIĆ* and IBRAHIM MUJIĆ**

University of Novi Sad, Faculty of Technology, Department of Biotechnology and Pharmaceutical Engineering, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia

*Institute of Field and Vegetable Crops, Maksima Gorkog 30, 21000 Novi Sad, Serbia

**University of Bihać, Biotechnical Faculty, Kulina Bana 2, 77000 Bihać, Bosnia and Herzegovina

 

(Received 20 May, revised 28 October 2008)

The chemical composition of mentha essential oil and mentha extracts obtained at different pressures/temperatures by supercritical fluid extraction (SFE) were studied by GC–MS. The menthol content was also determined spectrophotometrically. The predominant compounds in the essential oil and in the CO2 extract obtained at 100 bar were L-menthon and menthole but at higher pressures (from 150 to 400 bar), squalene was dominant. The equation of Naik et al. was used for modelling the mentha–supercritical CO2 system.

 

Keywords: Mentha piperita L.; essential oil; supercritical fluid extraction; extraction pressure and temperature; GC–MS.

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J. Serb. Chem. Soc. 74 (4) 427–440 (2009)

UDC 536.2:536.7+547.321’212:541.18.045; JSCS–3844; doi: 10.2298/JSC0904427Z; Original scientific paper

 

Local heat transfer coefficients during the evaporation of 1,1,1,2-tetrafluoroethane (R-134a) in a plate heat exchanger

EMILA ŽIVKOVIĆ, STEPHAN KABELAC* and SLOBODAN ŠERBANOVIĆ

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade, Serbia

*Helmut Schmidt University of the Federal Armed Forces, Holstenhofweg 85, D-22043 HAMburg, Germany

 

(Received 10 June, revised 30 October 2008)

The evaporation heat transfer coefficient of the refrigerant R-134a in a vertical plate heat exchanger was investigated experimentally. The area of the plate was divided into several segments along the vertical axis. For each of the segments, the local value of the heat transfer coefficient was calculated and presented as a function of the mean vapor quality in the segment. Owing to the thermocouples installed along the plate surface, it was possible to determine the temperature distribution and vapor quality profile inside the plate. The influences of the mass flux, heat flux, pressure of system and the flow configuration on the heat transfer coefficient were also taken into account and a comparison with literature data was performed.

 

Keywords: plate heat exchanger; evaporation; R-134a; heat transfer coefficient.

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J. Serb. Chem. Soc. 74 (4) 441–453 (2009)        

UDC 669.018.9:678.632:546.26–037; JSCS–3845, doi: 10.2298/JSC0904441S; Original scientific paper

 

Composite material based on an ablative phenolic resin and carbon fibers

VINETA SREBRENKOSKA, GORDANA BOGOEVA-GACEVA* and DIMKO DIMESKI

Faculty of Technology, Goce Delčev University, Krste Misirkov b.b., P.O. Box 201, 2000 Štip, R. Macedonia

*Faculty of Technology and Metallurgy, Sts.Cyril and Methodius University, MK-1000 Skopje, R. Macedonia

 

(Received 27 July 2007, 12 February 2009)

In this study, a technological procedure for the production of a molding compound based on short carbon fibers and an ablative phenol–formaldehyde resin for high temperature application was optimized. The starting raw materials were characterized and molding compounds with different fiber/matrix ratios and different fiber lengths were obtained. From the different laboratory sAMples, molded parts were made by thermocompression. The basic mechanical and thermal properties of the composites were determined. From the obtained results, the optimal fiber/matrix ratio was determined for a production of molding compound for high temperature application. The molding process of the composite material was optimized and all the parAMeters for good mechanical properties and high thermal stability of the composite were obtained. Optimization of the composite molding process was performed by the application of a numerical method for a planned experiment, i.e., a full three-factorial experimental design with variance of all three parAMeters (fiber length, temperature and time of the press cycle) on two levels. The obtained mechanical properties (flexural strength: 247 MPa, modulus: 27.6 GPa, impact resistance: 110 (for test moldings 10 mm´10 mm) and 91 kJ/m2 (for test moldings 15 mm´15 mm)) justified the application of this composite material in the automotive, leisure, military and other industries where high temperature resistance and high mechanical strength is required.

 

Keywords: molding compound; phenol–formaldehyde resin; carbon fibers; composites; thermocompression.

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J. Serb. Chem. Soc. 74 (4) 455–460 (2009)

UDC 504.521+665.7:628.516.000.57; JSCS–3846; doi: 10.2298/JSC0904455M; Original scientific paper

 

Bioremediation of soil heavily contAMinated with crude oil and its products: composition of the microbial consortium

JELENA S. MILIĆ, VLADIMIR P. BEŠKOSKI, MILA V. ILIĆ, SAMIRA A. M. ALI*, GORDANA Đ. GOJGIĆ-CVIJOVIĆ and MIROSLAV M. VRVIĆ*

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

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

 

(Received 23 June, revised 16 July 2008)

Bioremediation, a process that utilizes the capability of microorganism to degrade toxic waste, is emerging as a promising technology for the treatment of soil and groundwater contAMination. The technology is very effective in dealing with petroleum hydrocarbon contAMination. The aim of this study was to exAMine the composition of the microbial consortium during the ex situ experiment of bioremediation of soil heavily contAMinated with crude oil and its products from the Oil Refinery Pančevo, Serbia. After a 5.5-month experiment with biostimulation and bioventilation, the concentration of the total petroleum hydrocarbons (TPH) had been reduced from 29.80 to 3.29 g/kg (89 %). In soil, the dominant microorganism population comprised GrAM-positive bacteria from actinomycete-Nocardia group. The microorganisms which decompose hydrocarbons were the dominant microbial population at the end of the process, with a share of more than 80 % (range 107 CFU/g). On the basis of the results, it was concluded that a stable microbial community had been formed after initial fluctuations.

 

Keywords: bioremediation; microbial consortia; petroleum contAMination.

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J. Serb. Chem. Soc. 74 (4) 461–470 (2009)

UDC 551.351.2+539.16:628.518:539.16:539.163; JSCS–3847; doi: 10.2298/JSC0904461R; Original scientific paper

 

Radioactivity of sand from several renowned public beaches and assessment of the corresponding environmental risks

MIRJANA B. RADENKOVIĆ, SAEED MASAUD ALSHIKH*, VELIBOR B. ANDRIĆ and ŠĆEPAN S. MILJANIĆ*

Vinča Institute of Nuclear Sciences, Radiation and Environmental Protection Department, P.O. Box 522, 11001 Belgrade, Serbia

*Faculty of Physical Chemistry, University of Belgrade, P.O. Box 276, 11001 Belgrade, Serbia

 

(Received 9 June, revised 17 July 2008)

The radiological risk due to the presence of natural and man-made radionuclides in beach sands from several renowned seaside and riverbank public beaches was estimated in this study. The exposure levels to terrestrial radiation of the beaches were determined, as well as hazards due to human use of the analyzed sands in industry and in building constructions. Specific radionuclides concentrations in the sand sAMples were determined by standard gAMma-spectrometry. The corresponding radiation hazards arising due to the use of sand as a building material were estimated by three different radiological hazard indices. The total absorbed gAMma dose rate in the air was determined and the corresponding annual effective dose outdoors was estimated. The obtained data are relevant both from human health and environmental monitoring aspects.

 

Keywords: environmental radioactivity; sand; radiological hazard indices; gAMma spectrometry; dose rates.

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J. Serb. Chem. Soc. 74 (4) 471–476 (2009)

UDC 543+061.3(4); EuCheMS news

 

EUCHEMS NEWS

European analytical column No. 37 from the Division of Analytical Chemistry (DAC) of the European Association for Chemical and Molecular Sciences (EuCheMS)

BO KARLBERG, MANFRED GRASSERBAUER* and JENS E. T. ANDERSEN**

Department of Analytical Chemistry, Stockholm University, SE-10691 Stockholm, Sweden

*Vienna University of Technology, Department of Chemistry, Getreidemarkt 9, A-1060 Wien, Austria

**Department of Chemistry, Technical University of Denmark, Building 207, DK-2800 Lyngby, Denmark

 

INTRODUCTORY COMMENTS FROM THE CHAIRMAN OF DAC

The European Analytical Column has again a somewhat different format. We have once more invited a guest columnist to give their views on various matters related to Analytical Chemistry in Europe. This year we have invited Professor Manfred Grasserbauer of the Vienna University of Technology to present some of the current challenges for European analytical chemistry. During the period 2002–2007 Professor Grasserbauer was Director of the Institute for Environment and Sustainability, Joint Research Centre of the European Commission, Ispra. There is no doubt that many challenges exist at the present time for all of us representing a major branch of chemistry, nAMely analytical chemistry.

The global financial crisis is affecting all branches of chemistry but analytical chemistry in particular since our discipline by tradition has many close links to industry. We notice already now a decreased industrial commitment with respect to new research projects and sponsoring of conferences. It is therefore important that we strengthen our efforts and that we keep our presence at analytical chemistry meetings and conferences unchanged.

Recent activities of DAC and details regarding the major analytical-chemistry event this year in Europe, Euroanalysis XV in Innsbruck, are also reported.

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April 14, 2009.
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