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1.
Spectrophotometric kinetic technique has been used to investigate the effect of cetyltrimethylammonium bromide (CTAB) and
sodium dodecyl sulfate (SDS) surfactants on the redox reaction of cerium(IV)+l-sorbose in aqueous sulfuric acid media. The anionic SDS has no effect, whereas the reaction rate increases in the presence
of cationic CTAB, which is due to favorable conditions provide by the cationic micelles. The reaction rate decreases with
[H2SO4], and no acid-dependent path has been observed. At constant [H2SO4], the rate of the reaction is dependent on the first powers of the l-sorbose and cerium(IV) concentrations. The CTAB-assisted reaction is retarded by addition of electrolytes (Na2SO4, NaNO3, and NaCl), which is attributed to the competition between electrolyte anions and cerium(IV)-sulfato species. Bromide ion
(of CTAB or externally added in the form of NaBr) is not oxidized by the cerium(IV) (as a main or side reaction). 相似文献
2.
The influence of surfactants (anionic and cationic) on the reactivity of the redox couple cerium(IV) and D-glucose was examined spectrophotometerically. Various kinetic parameters have been determined in the absence and presence of surfactants. The kinetics were followed by monitoring the disappearance of the absorbance of cerium(IV) at 385 nm. The reaction obeyed first-order kinetics with respect to [D-glucose] in both media. No effect of anionic micelles of sodium dodecyl sulfate (SDS) was observed due to electrostatic repulsion between the negative head group of SDS and reactive species of cerium(IV) (Ce(SO4)
3
2−
). A twofold increase in the oxidation rate was observed in the presence of cationic micelles of cetyltrimethylammonium bromide (CTAB). The observed catalytic role has been analyzed in terms of the Menger–Portnoy model. The effects of various inorganic salts (Na2SO4, NaNO3 and NaCl) were also studied in micellar media. 相似文献
3.
Shi Nian-Qing Prahl Kristine Hendrick Jim Cruz Jose Lu Ping Cho Jae-Yong Jones Sharon Jeffries Thomas 《Applied biochemistry and biotechnology》2000,84(1-9):201-216
Pichia stipitis CBS 6054 will grow on d-xylose, d-arabinose, and l-arabinose. d-Xylose and l-arabinose are abundant in seed hulls of maize, and their utilization is important in processing grain residues. To elucidate
the degradation pathway for l-arabinose, we obtained a mutant, FPL-MY30, that was unable to grow on d-xylose and l-arabinose but that could grow on d-arabinitol. Activity assays of oxidoreductase and pentulokinase enzymes involved in d-xylose, d-arabinose, and l-arabinose pathways indicated that FPL-MY30 is deficient in d-xylitol dehydrogenase (D-XDH), d- and l-arabinitol dehydrogenases, and d-ribitol dehydrogenase. Transforming FPL-MY30 with a gene for xylitol dehydrogenase (PsXYL2), which was cloned from CBS 6054 (Gen Bank AF127801), restored the D-XDH activity and the capacity for FPL-MY30 to grow on
l-arabinose. This suggested that FPL-MY30 is critically deficient in XYL2 and that the d-xylose and l-arabinose metabolic pathways have xylitolas a common intermediate. The capacity for FPL-MY30 to grow on d-arabinitol could proceed through d-ribulose. 相似文献
4.
Effects of anionic and cationic micelles on the oxidation of d-dextrose by diperiodatoargentate(III)
Mohd Yusuf Dar Mohammad Ilyas Parveen Kumar Zaheer Khan 《Colloid and polymer science》2006,285(3):315-321
The oxidative behavior of d-dextrose toward diperiodatoargentate(III) (DPA) has been studied in the absence and presence of anionic and cationic micelles of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), respectively. The kinetics is based on the reduction of silver(III) to silver(I) by d-dextrose under pseudo-first-order conditions. The monoperiodatoargentate(III) ions act as active oxidants in comparison to that of DPA. The reactions are first- and fractional-order dependence with respect to [DPA] and [d-dextrose], respectively. The reaction rates decrease with [H+] and [periodate]. The premicellar environment of SDS and CTAB strongly inhibits the reaction rate. Inhibition is due to favorable thermodynamic/electrostatic binding between the Ag(III) complex and CTAB monomer aggregates. A suitable mechanism involving a one-electron transfer (rate-determining step) from d-dextrose to the silver(III) species has been proposed. Activation parameters have been evaluated and discussed. 相似文献
5.
V. V. Potekhin 《Russian Chemical Bulletin》2007,56(5):875-882
The oxidation of lower aliphatic alcohols C1–C4 with dioxygen to form the corresponding carbonyl compounds in the presence of the PdII tetraaqua complexes and FeII-FeIII aqua ions in an aqueous medium was studied at 40–80 °C. The introduction of an aromatic compound (acetophenone, benzonitrile,
phenylacetonitrile, o-cyanotoluene, nitrobenzene) and FeII aqua ion instead of the FeIII aqua ion into the reaction system increases substantially the catalytic activity and the yield of the carbonyl compound.
The key role of the Pd species in the intermediate oxidation state stabilized by the aromatic additive in the catalytic cycle
of alcohol oxidation with dioxygen to the carbonyl compound was shown. An increase in the kinetic isotope effect with an increase
in the temperature of methanol oxidation indicates a change in the rate-determining step of alcohol oxidation with dioxygen
in the presence of PdII-FeII-FeIII and the aromatic compound. At temperatures below 60 °C, the catalytically active palladium species are mainly formed upon
the reduction of the PdII tetraaqua complex with the FeII aqua ion, whereas at higher temperatures the reaction between the alcohol and PdII predominates. The mechanism and kinetic equation of the process were proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 842–848, May, 2007. 相似文献
6.
Kabir-ud-Din Neelam Hazoor Zaidi Mohd Akram Zaheer Khan 《Colloid and polymer science》2006,284(12):1387-1393
Aqueous colloidal manganese dioxide (MnO2) was prepared via titration by using potassium permanganate and sodium thiosulphate in aqueous neutral medium. The kinetics of oxidation of d-glucose onto the surface of colloidal MnO2 have been studied spectrophotometrically. The results show that the rate of initial stage (nonautocatalytic path) increases with increasing the [d-glucose], [H+], and temperature and also upon addition of nonionic surfactant Triton X-100 (TX-100), which indicates that the surfactant enhances the concentration of d-glucose at the surface of the colloidal MnO2. Hydrogen bonding interaction seemingly arises between –OH groups of d-glucose and oxygen of the ether linkages of polyoxyethylene chain of TX-100. A possible mechanism of the oxidative degradation of d-glucose is discussed in terms of d-glucose/TX-100 and colloidal MnO2 interaction. 相似文献
7.
V. N. Leibzon L. V. Michalchenko M. Yu. Leonova V. P. Gultyai 《Russian Chemical Bulletin》2005,54(5):1203-1207
Small additives of iron(II) or copper(II) salts change the regioselectivity of 2,4,6-trinitrotoluene monoreduction with titanium(III) chloride affording predominantly less accessible 2-amino-4,6-dinitrotoluene over 4-amino-2,6-dinitrotoluene (from 25% when
the reduction occurs in the absence of the iron and copper salts to 70% in the presence of these salts). A possible mechanism
of the process is discussed.
Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1172–1176, May, 2005. 相似文献
8.
Boris U. Stambuk Mary Ann Franden Arjun Singh Min Zhang 《Applied biochemistry and biotechnology》2003,106(1-3):255-263
The kinetics and regulation of d-xylose uptake were investigated in the efficient pentose fermentor Candida succiphila, and in Kluyveromyces marxianus, which assimilate but do not ferment pentose sugars. Active high-affinity (K
m
∼ 3.8 mM; V
max ∼ 15 nmol/[mg·min]) and putative facilitated diffusion low-affinity (K
m
∼ 140 mM; V
max ∼ 130 nmol/[mg·min]) transport activities were found in C. succiphila grown, respectively, on xylose or glucose. K. marxianus showed facilitated diffusion low-affinity (K
m
∼ 103 mM; V
max ∼ 190 nmol/[mg·min]) transport activity when grown on xylose under microaerobic conditions, and both a low-affinity and an
active high-affinity (K
m
∼ 0.2 mM; V
max ∼ 10 nmol/[mg·min]) transport activity when grown on xylose under fully aerobic conditions. 相似文献
9.
J. Csapó J. Schmidt Zs. Csapó-Kiss É. Varga-Visi G. Pohn É. Csokona 《Chromatographia》2002,56(1):S169-S171
Summary In recent decades several methods have been developed for determination of the proportion of nitrogen-containing substances
passed from the rumen into the abomasum, or small intestine, which are of microbial origin. Recently, when examining thed-amino acid content of foodstuffs, particularly milk and milk products, it was observed that, in addition tod-alanine (d-Ala,d-glutamic acid (d-Glu) andd-aspartic acid (d-Asp) can also be detected in similar quantities, primarily in products which have links with bacterial activity. This gave
rise to the idea of examining the diaminopimelic acid (DAPA),d-Glu, andd-Asp content of bacteria extracted from the rumen of cattle, and that of chyme from the same cattle, to establish whetherd-Asp andd-Glu can be used to estimate protein of bacterial origin.
The investigations performed have provided evidence that bothd-Asp andd-Glu might be appropriate for determination of protein of bacterial origin. The results obtained using these two bacterial
markers (d-Asp andd-Glu) proved to the approximately 10% lower than those obtained using DAPA; this was not because of to error attributable
to the new markers but rather to the unreliability of determination using DAPA Analyses performed on samples of known bacterial
protein content indicate thatd-Asp andd-Glu gave almost identical results for bacterial protein content which were very close to the theoretical (calculated) values.
Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001. 相似文献
10.
Kinetics of hydrogen peroxide decomposition in the presence of the tetraaquapalladium(II) complex in an aqueous solution at
40–70 °C was studied. The reaction rate is the first order with respect to the concentration of both PdII and H2O2 and the negative first order with respect to perchloric acid. Using free radicals traps, the reaction mechanism was found
to differ from the traditional free-radical mechanism known for d-metal aqua ions and proceeds without generation of hydroxyl
radicals. The kinetic data obtained suggest a mechanism involving the formation of an intermediate palladium complex with
oxygen.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1077–1082, May, 2005. 相似文献
11.
Hamase K Takagi S Morikawa A Konno R Niwa A Zaitsu K 《Analytical and bioanalytical chemistry》2006,386(3):705-711
Using a column-switching HPLC system combining a micro-ODS column and a chiral column, the amounts of d-proline (d-Pro) have been determined in 18 tissues, plasma and urine of mice. To avoid the enzymatic degradation of d-amino acids in vivo, a mutant mouse strain lacking d-amino acid oxidase activity (ddY/DAO− mouse) was used. In the brain, relatively large amounts of d-Pro were observed in the anterior pituitary, posterior pituitary and pineal glands. In the peripheral tissues, the amounts
of d-Pro were high in the pancreas and kidney. Above all, it is surprising that the ddY/DAO− mice excreted large amounts of d-Pro in their urine (433 nmol/mL, 20 times that of l-Pro). The origin of d-Pro has also been investigated. By comparing germ-free mice and gnotobiotic mice, intestinal bacteria were shown to have
no effect on the urinary d-Pro amount. Concerning the dietary origin, a notable amount of d-Pro was still excreted in the urine after starvation for 4 days, suggesting that some of the d-Pro is produced in the mice. Age-dependent changes in the urinary d-Pro amount have also been investigated from the postnatal 1st month up to 12 months, and ddY/DAO− mice were found to excrete large amounts of d-Pro in the urine constantly throughout their lives.
Kenji Hamase is Associate Professor in the Department of Bioanalytical Chemistry, Graduate School of Pharmaceutical Sciences at Kyushu
University. His current research interests focus on the development of analytical methods for d-amino acids and the study of their physiological functions and diagnostic values. He received the Japanese Society for Analytical
Chemistry Award for Young Scientists in 2003, and the PSJ Award for Young Scientists in 2006. 相似文献
12.
Water soluble macroligands for vancomycin purification in affinity ultrafiltration have been prepared by coupling the ligandd-alanyl-d-alanine to dextran activated by tosyl chloride, carbonyldiimidazole, and chloroformate, respectively. Centrifugal ultrafiltration
has been used to study the equilibrium binding of vancomycin for the macroligands. The affinity binding can be described as
Langmuir type adsorption and is strongly affected by temperature. The binding between vancomycin and macroligand is an unusual
endothermic process that binding capacity of macroligand increases with temperature. Vancomycin has also been successfully
purified from fermentation liquor using the macroligand in a centrifugal ultrafiltration device. 相似文献
13.
A chiral liquid chromatographic method for determination of the enantiomeric purity of both l-carnitine and acetyl-l-carnitine is described. Separation of the enantiomers of dl-carnitine and acetyl-dl-carnitine was achieved on a commercial chiral column (Chiralcel OD-R) after derivatization with (alpha-bromo)methyl phenyl ketone. Introduction of this lipophilic UV chromophoric group to the carnitine and acetylcarnitine molecules improved their retention, resolution, and UV detection. The mobile phase was 74:26 (v/v) 0.5 mol L-1 sodium perchlorate–acetonitrile, pH 3.8, and the flow rate was 0.4 mL min-1. Detection was performed at 235 nm. The method is selective and reliable for determination of the enantiomeric purity of bulk drug substances l-carnitine and acetyl-l-carnitine. 相似文献
14.
Hiroshi Murata Iwao Satake Katumitu Hayakawa Masaru Tanokura 《Colloid and polymer science》2006,284(7):725-732
The conformation of poly(l-lysine) (PLL) was investigated in sodium alkanesulfonate CnSO3Na (n=8, 7) at various temperatures by circular dichroism spectrum measurements. C8SO3Na induced a double-step conformational change from a coil, to a β-sheet, and then to an α-helix, in which C7SO3Na induced a single-step coil-to-helix conformational change. Binding isotherms of C8SO3Na by PLL were constructed from the potentiometry of equilibrium concentration of the surfactant using a surfactant ion-selective electrode. The curves indicated the cooperative binding characteristic and were analyzed by a linear lattice model using the Bethe approximation. The thermodynamic parameters obtained from the model revealed that the binding of C8SO3Na by PLL was an entropy-driven process. The conformational change was observed at nearly full binding, presumably due to the surfactant clustering of the ordered conformation. 相似文献
15.
T. N. Kropacheva V. I. Kornev D. A. Loginov V. I. Meshcheryakov E. V. Mutseneck D. V. Muratov D. S. Perekalin L. S. Shul’pina A. R. Kudinov 《Russian Chemical Bulletin》2005,54(10):2354-2358
New dinuclear ruthenium manganese complexes of general composition (bpy)2Ru(L)MnClx(H2O)2 (L is 1,10-phenanthroline-5,6-dione, 3,3′-dicarboxy-2,2′-bipyridyl, or bis(pyrazolyl); x = 2 or 4) were synthesized by the reaction of (bpy)2Ru(L) with MnCl2 · 4H2O. These compounds and the starting mononuclear ruthenium complexes were studied by spectrophotometric and electrochemical
methods in MeCN. The position of the charge-transfer band RuII → L in the spectra depends on the donor-acceptor characteristics of the ligand L. For the dinuclear complex under study,
the formal potentials of reversible one-electron oxidation of RuII are in the range of 0.9–1.2 V (vs. the standard hydrogen electrode), whereas oxidation of MnII occurs at more positive (by 0.1–0.2 V) potentials.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2281–2285, October, 2005. 相似文献
16.
The micelle formation of a series of amphiphilic block copolymers in aqueous and NaCl solutions was studied by a fluorescent probe technique using pyrene as a "model drug". These copolymers were synthesized from poly (ethylene glycol) (PEG) and l-lactide by a new calcium ammoniate catalyst. They had fixed PEG block lengths (44, 104 or 113 ethylene oxide units) and various poly(l-lactide) (PLLA) block lengths (15–280 lactide units). The critical micelle concentration (cmc) was found to decrease with increasing PLLA content. The distinct dissimilarity of the cmc values of diblock and triblock copolymers based on the same block length of PEG provided evidence for the different configurations of their micelles. It was also observed that the introduction of NaCl salt significantly contributed to a decrease in the cmcs of the copolymers with short PEG and PLLA blocks, while it had less influence on the cmcs of copolymers with long PEG or PLLA blocks. The dependence of partition coefficients ranging from 0.2×105 to 1.9×105 on the PLLA content in the copolymer and on the micelle configuration was also discussed. The contribution of NaCl salt to increasing the partition of pyrene into a micellar phase was observed. 相似文献
17.
G. Sankar P. R. Sarode A. Srinivasan C. N. R. Rao S. Vasudevan J. M. Thomas 《Journal of Chemical Sciences》1984,93(3):321-334
A detailed investigation of sulphided Co/Mo/Al2O3 catalysts, their oxide precursors and several model oxides and sulphides of cobalt and molybdenum has been carried out using
x-ray photoelectron spectroscopy and x-ray absorption spectroscopy (xanes andexafs). Octahedrally coordinated Co(II) and Mo(IV) are shown to be present in a sulphidic environment on the surfaces of these
catalysts. The surface species contain an excess of sulphur, probably involving disulphide linkages. The surface compositions
of the catalysts examined conform to the general formula Co11 Mo
2n
IV
(2n + 3)S
2
2−
(2n -2)S2−. 相似文献
18.
M. P. Sobolevskaya V. A. Denisenko S. Fotso H. Laach N. I. Menzorova Yu. T. Sibirtsev T. A. Kuznetsova 《Russian Chemical Bulletin》2008,57(3):665-668
A new cyclic dipeptide, 3-a[(4-hydroxybenzyl)methyl]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione (1) together with the known compounds, 2,3-dihydroxybenzoic acid (2), and 6-(3-methylbut-2-enyl)isatin (3) were isolated from the actinobacterium Streptomyces sp. GW 33/1593. Compounds 1 and 2 possessed cytotoxic activity against the sea urchin Strongylocentrotus intermedius embryos.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 652–655, March, 2008. 相似文献
19.
Hasegawa H Fukushima T Lee JA Tsukamoto K Moriya K Ono Y Imai K 《Analytical and bioanalytical chemistry》2003,377(5):886-891
d-Lactic and l-lactic acids were simultaneously determined by means of a column-switching high-performance liquid chromatography (HPLC) with fluorescence detection. As a fluorescence reagent, 4-nitro-7-piperazino-2,1,3-benzoxadiazole (NBD-PZ) was employed for the fluorescence derivatization of lactic acid. The proposed HPLC system adopted both octylsilica (Cadenza CD-C8) and amylose-based chiral columns (CHIRALPAK AD-RH), which proved to give a sufficient enantiomeric separation of the lactic acid derivatives with a separation factor () of 1.32 and a resolution (Rs) of 1.98. Moreover, the features of the first elution of d-lactic acid peak in the proposed HPLC were convenient for the determination of trace amount of serum d-lactic acid, which is known to increase under diabetes. Intra-day and inter-day accuracies were in the range of 90.5–101.2 and 89.0–100.7%, and the intra-day and inter-day precisions were 0.3–1.2 and 0.4–4.8%, respectively. The proposed method was applied to determine d-lactic and l-lactic acids in human serum of normal subjects and diabetic patients, showing that both d-lactic and l-lactic acid concentrations were significantly increased in the serum of diabetic patients (n=31) as compared with normal subjects (n=21). This fact was found for the first time owing to the development of the proposed HPLC method which is able to determine d-lactic and l-lactic acid simultaneously. Finally, serum d-lactic acid concentrations determined by the proposed HPLC method were compared with those from a reported enzymatic assay, and the smaller p value between normal subjects and diabetic patients was shown by the proposed HPLC method. 相似文献
20.
Infrared absorption spectroscopy has been applied for the identification of the minerals associated with natural goethite
(α-FeO·OH) from Saudi Arabia. The thermal transformation of natural goethite as well as the effects of the presence of the
associated minerals on the reaction products were investigated. The results revealed that at 300°C protohematite is formed
which at 600°C is slightly crystallized. Further recrystallization and hematite formation takes place at 1000°C. It was also
found that the presence of other minerals found in goethite samples has no effect on the reaction products. 相似文献