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991.
992.
993.
Blagojević SM Anić SR Cupić ZD Pejić ND Kolar-Anić LZ 《Physical chemistry chemical physics : PCCP》2008,10(44):6658-6664
The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained. 相似文献
994.
Petković H Sandmann A Challis IR Hecht HJ Silakowski B Low L Beeston N Kuscer E Garcia-Bernardo J Leadlay PF Kendrew SG Wilkinson B Müller R 《Organic & biomolecular chemistry》2008,6(3):500-506
The production of epothilone mixtures is a direct consequence of the substrate tolerance of the module 3 acyltransferase (AT) domain of the epothilone polyketide synthase (PKS) which utilises both malonyl- and methylmalonyl-CoA extender units. Particular amino acid motifs in the active site of AT domains influence substrate selection for methylmalonyl-CoA (YASH) or malonyl-CoA (HAFH). This motif appears in hybrid form (HASH) in epoAT3 and may represent the molecular basis for the relaxed specificity of the domain. To investigate this possibility the AT domains from modules 2 and 3 of the epothilone PKS were examined in the heterologous DEBS1-TE model PKS. Substitution of AT1 of DEBS1-TE by epoAT2 and epoAT3 both resulted in functional PKSs, although lower yields of total products were observed when compared to DEBS1-TE (2% and 11.5% respectively). As expected, epoAT3 was significantly more promiscuous in keeping with its nature during epothilone biosynthesis. When the mixed motif (HASH) of epoAT3 within the hybrid PKS was mutated to HAFH (indicative of malonyl-CoA selection) it resulted in a non-productive PKS. When this mixed motif was converted to YASH (indicative of methylmalonyl-CoA selection) the selectivity of the hybrid PKS for methylmalonyl-CoA showed no statistically significant increase, and was associated with a loss of productivity. 相似文献
995.
Iliyas A Eić M Zahedi-Niaki MH Vasenkov S 《The journal of physical chemistry. B》2008,112(12):3821-3825
The tracer zero-length column (ZLC) method has been employed to study the diffusion of toluene in one-dimensional ZSM-12 and SAPO-5 zeolites. A significant deviation in the shape of the measured tracer exchange curves from monoexponential behavior was observed for toluene diffusion in both adsorbents in the limit of long-time asymptotes. In contrast, water/ZSM-12 and acetylene/SAPO-5 systems exhibit tracer exchange curves that are close to monoexponential behavior. Monoexponential curves are usually observed for systems obeying normal (Fickian) diffusion. Such diffusion is expected for the latter two systems because the diameters of both sorbates are less than the radii of their corresponding host channels. The differences in the shape of the tracer exchange curves for large and small sorbates can be explained by assuming the occurrence of anomalous, single-file diffusion for large sorbates in narrow, one-dimensional channels. 相似文献
996.
An interpretative strategy (factorial design experimentation+total resolution analysis+chromatogram simulation) was employed to optimize the separation of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene) in temperature-programmed gas chromatography (GC). Also, the retention behavior of PAHs in the same GC system was studied by a feed-forward artificial neural network (ANN). GC separation was investigated as a function of one (linear temperature ramp) or two (linear temperature ramp+the final hold temperature) variables. The applied interpretative approach resulted in rather good agreement between the measured and the predicted retention times for PAHs in both one and two variable modeling. The ANN model, strongly affected by the number of input experiments, was shown to be less effective for one variable used, but quite successful when two input variables were used. All PAHs, including difficult to separate peak pairs (benzo(k)fluoranthene/benzo(b)fluoranthene and indeno(1,2,3-c,d)pyrene/dibenzo(a,h)anthracene), were separated in a standard (5% phenyl-95% dimethylpolysiloxane) capillary column at an optimum temperature ramp of 8.0 degrees C/min and final hold temperature in the range of 260-320 degrees C. 相似文献
997.
D. Krstić M. Çolović M. B. Kralj P. Trebše K. Krinulović V. Vasić 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2008,82(4):663-668
The influence of malathion and its four main degradation products found in irradiated solutions (malaoxon, isomalathion, diethyl
maleate and O,O-dimethyl phosphate) on acetylcholinesterase (AChE) of free and immobilized bovine erythrocytes was investigated.
The concentration-dependent responses to malathion and related organophosphates, malaoxon and isomalathion, of both AChE bioassays
used were obtained. The IC
50 values for free and immobilized AChE (3.7 ± 0.2) × 10−4 M/(1.6 ± 0.1) × 10−4, (2.4 ± 0.3) × 10−6/(3.4 ± 0.1) × 10−6 M, and (3.2 ± 0.3) × 10−6 M/(2.7 ± 0.2) × 10−6 M were obtained in the presence of malathion, malaoxon and isomalathion, respectively. However, diethyl maleate inhibited
AChE activity at concentrations ≥ 10 mM, while O,O-dimethyl phosphate did not noticeably affect enzyme activity at all investigated
concentrations. The relation between the structure of the compounds and their ability to inhibit enzyme activity was discussed.
The article is published in the original. 相似文献
998.
Condić-Jurkić K Perchyonok VT Zipse H Smith DM 《Journal of computational chemistry》2008,29(14):2425-2433
High level ab initio and density functional calculations have been employed to determine the most appropriate manner in which to truncate an arginine-bound carboxylate motif, using the substrate mechanism of Pyruvate Formate-Lyase as a case study. The results show that, both qualitatively and quantitatively, a neutral carboxylic acid provides a more realistic approximation to the salt bridge arrangement than does a bare anionic carboxylate substituent. 相似文献
999.
R. Jaćimović P. Makreski V. Stibilj T. Stafilov 《Journal of Radioanalytical and Nuclear Chemistry》2008,278(3):795-799
Major and trace element contents in iron ore reference materials were investigated using k
0-instrumental neutron activation analysis (k
0-INAA). To avoid iron interferences, radiochemical separation was developed (k
0-RNAA). The determination of the investigated elements in the inorganic phase from hydrochloric acid solution was performed
after radiochemical separation of iron by diisopropyl ether. It was found that after the Fe elimination, the limit of detection
for some elements was much lower that enables their direct determination. The distribution of 39 elements (with intermediate/medium
and long half-life radionuclides) after Fe removal was investigated. 相似文献
1000.
Baosić R Radojević A Radulović M Miletić S Natić M Tesić Z 《Biomedical chromatography : BMC》2008,22(4):379-386
The lipophilicity of a series of Schiff base ligands and their complexes with nickel(II) and copper(II) has been determined by reversed-phase thin-layer chromatography using binary dioxane-water mobile phase. Chelate ligands were prepared by condensation of diamine and the corresponding beta-diketone. Copper(II) and nickel(II) complexes with chelate ligands containing ethane-1,2-diamine or propane-1,2-diamine as the amine part and pentane-2,4-dione and/or 1-phenylbutane-1,3-dione, pentane-2,4-dione and/or 1,1,1-trifluoropentane-2,4-dione, or 1,1,1-trifluoropentane-2,4-dione and/or 1-phenylbutane-1,3-dione as the beta-diketone part were synthesized. Some of investigated compounds were screened for their in vitro antifungal activity against Sacharomyces cerevisiae and antibacterial activity against Escherichia coli. Chromatographically obtained lipophilicity parameters were correlated both with calculated n-octanol-water partition coefficient C log P and antimicrobial activities. Satisfactory correlations were obtained. Chromatographic data proved to be reliable parameters for describing the lipophilic properties of the investigated compounds. Additionally, the principal components analysis was performed on the data chromatographically obtained. This statistical method was useful for distinguishing compounds and objective comparison of their lipophilicity parameters. 相似文献