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1.
Zahradnícková H Husek P Simek P Hartvich P Marsálek B Holoubek I 《Analytical and bioanalytical chemistry》2007,388(8):1815-1822
A rapid and simple method was developed for the determination of free amino acids (AAs) released from cyanobacteria. The procedure
involves trapping of AAs from the centrifuged cyanobacterial culture fluid on a cation-exchange resin, their release together
with the resin by direct treatment with the reaction medium, followed by immediate derivatization with a corresponding chloroformate.
The extractive alkylation transfers the analytes into an organic phase, an aliquot of which is subjected to GC analysis. Identification
and quantification of AAs was performed by GC/MS and GC/FID, respectively, using propyl chloroformate (PCF) as the derivatization
reagent. For chiral analysis, the cyanobacteria extracts were treated with 2,2,3,3,3-pentafluoropropyl chloroformate (PFPCF)
to create more volatile analytes. Separation of the AA enantiomers was accomplished on a Chirasil-Val capillary column and
the D/L enantiomeric ratios were determined. AAs of cyanobacteria are considered to be important for the assessment of energy flow
in an aquatic food web, nutrition value of cyanobacteria in a food web and for cell–cell communication within cyanobacteria.
The highest levels of AAs were found in the summer period at the beginning of the season (July). In the September and October
samples, the amount of AAs was lower, the number of D-AAs decreased and the D/L ratio was higher than in the July sample. Based on the obtained results it can be assumed that young populations excrete
AAs in higher concentrations and a different composition compared to actively growing populations.
Figure PFPCF derivatization scheme 相似文献
2.
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
3.
Yodthong Baimark Mangkorn Srisa-ard Jirasak Threeprom Nual-Anong Narkkong 《Colloid and polymer science》2007,285(13):1521-1525
Nanoparticle colloids of methoxy poly(ethylene glycol)-b-poly(D,L-lactide) (MPEG-b-PDLL) diblock copolymer were prepared by a modified spontaneous emulsification solvent diffusion method using acetone/ethanol
as the mixture organic solvents. The MPEG-b-PDLL was synthesized by ring-opening polymerization of D,L-lactide using stannous octoate and MPEG with molecular weight of 5,000 g/mol as the initiating system. The MPEG-b-PDLL obtained was an amorphous polymer with molecular weight of 73,600 g/mol. Influences of acetone/ethanol (v/v) ratios
and Tween 80 surfactant concentrations on characteristics of the colloidal nanoparticles were investigated and discussed.
Light-scattering analysis showed that average diameters of the surfactant-free colloidal nanoparticles were in the range of
86–124 nm. The nanoparticle sizes decreased as the ethanol ratio increased. The Tween 80 did not show the significant effect
on the nanoparticle sizes. Scanning electron micrographs of dried nanoparticles that demonstrated the aggregation of most
particles suggested they were the soft nanoparticles. However, the dried nanoparticle morphology can be observed from scanning
electron microscopy as having a spherical shape and smooth surfaces. 相似文献
4.
An enzymatic method for determining L-malic acid in wine based on an L-malate sensing layer with nicotinamide adenine dinucleotide (NAD+), L-malate dehydrogenase (L-MDH) and diaphorase (DI), immobilized by sol-gel technology, was constructed and evaluated. The sol-gel glass was prepared
with tetramethoxysilane (TMOS), water and HCl. L-MDH catalyzes the reaction between L-malate and NAD+, producing NADH, whose fluorescence (λ
exc = 340 nm, λ
em = 430 nm) could be directly related to the amount of L-malate. NADH is converted to NAD+ by applying hexacyanoferrate(III) as oxidant in the presence of DI. Some parameters affecting sol-gel encapsulation and the
pH of the enzymatic reaction were studied. The sensing layer has a dynamic range of 0.1–1.0 g/L of L-malate and a long-term storage stability of 25 days. It exhibits acceptable reproducibility [s
r(%)≈10] and allows six regenerations. The content of L-malic acid was determined for different types of wine, and polyvinylpolypyrrolidone (PVPP) was used as a bleaching agent
with red wine. The results obtained for the wine samples using the sensing layer are comparable to those obtained from a reference
method based on UV-vis molecular absorption spectrometry, if the matrix effect is corrected for. 相似文献
5.
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
6.
Substrate selectivity of Gluconobacter oxydans (ATCC 9937) for 2,5-diketo-d-gluconic acid (2,5-DKG) production was investigated with glucose, gluconic acid, and gluconolactone in different concentrations
using a resting-cell system. The results show that gluconic acid was utilized favorably by G. oxydans as substrate to produce 2,5-DKG. The strain was coupled with glucose dehydrogenase (GDH) and 2,5-DKG reductase for synthesis
of 2-keto-l-gulonic acid (2-KLG), a direct precursor of l-ascorbic acid, from glucose. NADP and NADPH were regenerated between GDH and 2,5-DKG reductase. The mole yield of 2-KLG of
this multienzyme system was 16.8%. There are three advantages for using the resting cells of G. oxydans to connect GDH with 2,5-DKG reductase for production of 2-KLG: gluconate produced by GDH may immediately be transformed into
2,5-DKG so that a series of problems generally caused by the accumulation of gluconate would be avoided; 2,5-DKG is supplied
directly and continuously for 2,5-DKG reductase, so it is unnecessary to take special measures to deal with this unstable
substrate as it was in Sonoyama’s tandem fermentation process; and NADP(H) was regenerated within the system without any other
components or systems. 相似文献
7.
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
8.
A. Yu. Spivak O. V. Knyshenko O. V. Ivanova M. I. Mallyabaeva E. S. Murtazina I. Yu. Ponedel’kina V. N. Odinokov 《Russian Chemical Bulletin》2007,56(12):2487-2490
The use of a combination of ionic liquid [bmim]PF6 with boron trifluoride etherate as the catalyst in the glycosylation of α-tocopherol and chromanol of vitamin K1 (naphthotocopherol) allowed us to obtain β-glycosides in high yield when β-anomer of peracetylated D-glucose was used. In addition, usually inactive α-anomers of peracetylated D-glucopyranose and D-galactopyranose were involved in this reaction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2401–2404, December, 2007. 相似文献
9.
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
10.
P. I. Abronina L. V. Backinowsky A. A. Grachev S. L. Sedinkin N. N. Malysheva 《Russian Chemical Bulletin》2005,54(5):1287-1293
Methyl 2,4-di-O-benzoyl-α-D-mannopyranoside was used as a key intermediate in the synthesis of 3,6-branched mannopentaoside bearing one terminal D-[1-13C]mannopyranose residue, viz., methyl 6-O-[3,6-di-O-(α-D-mannopyranosyl)-α-D-mannopyranosyl)-3-O-{α -D-[1-13C]mannopyranosyl}-α-D-mannopyranoside.
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. 1250–1255, May, 2005. 相似文献
11.
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
12.
V. Lukša V. StarkuvienE B. StarkuvienE R. Dagys 《Applied biochemistry and biotechnology》1997,62(2-3):219-231
AD-hydantoinase (5,6-dihydropyrimidine amidohydrolase) was purified to homogeneity fromBacillus circulans. Purification of two hundred forty-three-fold was achieved with an overall yield of 12%. The relative molecular mass of the
native enzyme is 212,000 and that of the subunit is 53,000. This enzyme is an acidic protein with an isoelectric point of
4.55. The enzyme is sensitive to thiol reagent and requires metal ions for its activity. The optimal conditions for the hydantoinase
activity are pH 8.0–10.0 and a temperature of 75‡C. The enzyme is the most stable in a pH range of 8.5–9.5 and up to 60‡C.
The enzyme is significantly stable not only at high temperatures but also on treatment with protein denaturant SDS. These
remarkable properties are used for the purification procedure. 相似文献
13.
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
14.
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
15.
The fluorescence of fluoresceinisothiocyanate-labeled concanavalin A (FITC-Con A) was quenched by forming an FITC-Con A–glycogen
conjugate and dequenched upon addition of sugars to the conjugate solution due to disaggregation of the conjugate. However,
fluorescence quenching was barely observed upon formation of FITC-Con A–dextran conjugate. The sugar-induced fluorescence
response of the FITC-Con A–glycogen conjugate depended significantly on the type of sugar: methylated α-D-glucose and α-D-mannose both induced high and rapid responses, while the responses to D-mannose and D-glucose were moderate. In contrast, no response was observed in the presence of D-galactose due to a lack of affinity to Con A. Thus, it is apparent that D-glucose and other sugars can be detected via the fluorescence of the FITC-Con A–glycogen conjugate.
相似文献
16.
L. T. Eremenko G. V. Oreshko G. V. Lagodzinskaya G. G. Aleksandrov I. L. Eremenko 《Russian Chemical Bulletin》2007,56(10):2097-2104
The reaction of 1,4:3,6-dianhydro-D-sorbitol 5-nitrate with POCl3 afforded mono-and bis(5-O-nitro-1,4:3,6-dianhydro-D-sorbit-2-yl) phosphorochloridates, whose hydrolysis resulted in phosphoric acid mono-and diesters. The subsequent treatment
of these compounds with bases gave sodium and cyclohexylammonium salts. The reactions of phosphorochloridates with phenol,
pentaerythritol dibromohydrin, and ethylenimine in the presence of organic bases afford mixed phosphates and phosphoramidates.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2026–2032, October, 2007. 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.
T. A. Mastryukova O. I. Artyushin M. P. Pasechnik E. V. Sharova I. L. Odinets V. P. Morgalyuk I. G. Tananaev G. V. Myasoedova B. F. Myasoedov 《Russian Chemical Bulletin》2005,54(11):2540-2544
The composition of complexes formed upon the extraction of UVI and ThIV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by 31P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO3 as the [UO2(L)2(NO3)2] complex, while thorium(IV) is extracted from 5 M HNO3 as the [Th(L)3(NO3)3]+·NO
3
−
complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO3 and L· (HNO3)2, respectively.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005. 相似文献
19.
M. A. Proskurnin V. V. Chernysh M. Yu. Kononets S. V. Pakhomova 《Russian Chemical Bulletin》2005,54(1):124-134
The potential of thermal lens spectrometry in the determination of stability constants of complex compounds was explored using copper(I) and iron(II) complexes with 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline as examples. Thermal lens spectrometry offers advantages over conventional spectrophotometry in the determination of stability constants both in aqueous and nonaqueous media. The overall and stepwise stability constants of iron(II) tris(1,10-phenanthrolinate), copper(I) bis(2,9-dimethyl-1,10-phenanthrolinate), and copper(I) bis(1,10-phenanthrolinate) were determined at levels as low as 10−8–10−6 mol L−1.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 123–133, January, 2005. 相似文献
20.
N. A. Ivanova Z. R. Valiullina O. V. Shitikova M. S. Miftakhov 《Russian Chemical Bulletin》2005,54(11):2698-2701
The reaction of methyl 3,6-anhydro-2,7-dideoxy-7-iodo-4,5-O-isopropylidene-D-allo-heptonate with 1,8-diazabicyclo[5.4.0]undec-7-ene affords methyl 3,6-anhydro-2,7-dideoxy-4,5-O-isopropylidene-D-ribo-hept-6-enonate, which undergoes the previously unknown rearrangement into a 2,2-dimethyl-1,3-dioxole derivative.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2610–2613, November, 2005. 相似文献