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1.
The kinetics and mechanism of the substitution reaction between [Cr(H2O)6]3+ and l-Dopa in aqueous medium has been studied over the range 1.8 ≤ pH ≤ 2.6, 1.68 × 10−2 mol dm−3 ≤ [Dopa] ≤ 5.04 × 10−2 mol dm−3, I = 0.1 mol dm−3 (KNO3) at 50 °C. The reaction takes place via an outer sphere association between Cr3+ and l-Dopa followed by chelation. The product was characterized by physicochemical and infrared spectroscopic methods. The antiparkinsonian activity of the product was found to be higher than that of l-Dopa.  相似文献   

2.
Aloe vera L., a member of Liliaceae, is a medicinal plant and has a number of curative properties. We describe here the development of tissue culture method for high-frequency plantlet regeneration from inflorescence axis-derived callus cultures of sweet aloe genotype. Competent callus cultures were established on 0.8% agar-gelled Murashige and Skoog’s (MS) basal medium supplemented with 6.0 mg l−1 of 2,4-dichlorophenoxyacetic acid (2,4-D) and 100.0 mg l−1 of activated charcoal and additives (100 mg l−1 of ascorbic acid, 50.0 mg l−1 each of citric acid and polyvinylpyrrolidone, and 25.0 mg l−1 each of l-arginine and adenine sulfate). The callus cultures were cultured on MS medium containing 1.5 mg l−1 of 2,4-D, 0.25 mg l−1 of Kinetin (Kin), and additives with 4% carbohydrate source for multiplication and long-term maintenance of regenerative callus cultures. Callus cultures organized, differentiated, and produced globular embryogenic structures on MS medium with 1.0 mg l−1 of 2,4-D, 0.25 mg l−1 of Kin, and additives (50.0 mg l−1 of ascorbic acid and 25.0 mg l−1 each of citric acid, l-arginine, and adenine sulfate). These globular structures subsequently produced shoot buds and then complete plantlets on MS medium containing 1.0 mg l−1 of 6-benzylaminopurine and additives. A hundred percent regenerated plantlets were hardened in the greenhouse and stored under an agro-net house/nursery. The regeneration system defined could be a useful tool not only for mass-scale propagation of selected genotype of A. vera, but also for genetic improvement of plant species through genetic transformation.  相似文献   

3.
The oxidation of l-valine (l-val) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 3.0 × 10−3 mol dm−3 was studied spectrophotometrically at 298 K and follows the rate law;
where K 4, K 5 and K 6 are the equilibrium constants for the different steps involved in the mechanism, k is the rate constant for the slow step of the reaction. The appearance of [l-val] term in both numerator and denominator explains the observed less than unit order in [l-val]. Similarly the appearances of [H3IO6 2−] and [OH] in the denominator obey the experimental negative less than unit order in [H3IO6 2−] and [OH], respectively. The oxidation reaction in alkaline medium proceeds via a DPC-l-valine complex, which decomposes slowly in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test and spectroscopic studies.  相似文献   

4.
Cytosolic fumarase, a key enzyme for the accumulation of fumaric acid in Rhizopus oryzae, catalyzes the dehydration of l-malic acid to fumaric acid. The effects of carbon–nitrogen ratio on the acid production and activity of cytosolic fumarase were investigated. Under nitrogen limitation stress, the cytosolic fumarase could keep high activity. With the urea concentration decreased from 2.0 to 0.1 g l−1, the cytosolic fumarase activity increased by 300% and the production of fumaric acid increased from 14.4 to 40.3 g l−1 and l-malic acid decreased from 2.1 to 0.3 g l−1. Cytosolic fumarase could be inhibited by substrate analog 3-hydroxybutyric acid. With the addition of 3-hydroxybutyric acid (50 mM) in the fermentation culture, fumaric acid production decreased from 40.3 to 14.1 g l−1 and l-malic acid increased from 0.3 to 5.4 g l−1.  相似文献   

5.

Abstract  

Oxidation of the amino acid l-phenylalanine by diperiodatocuprate(III) in alkaline medium at constant ionic strength of 0.25 mol dm−3 was studied spectrophotometrically at different temperatures (298–313 K). The reaction between diperiodatocuprate(III) and l-phenylalanine in alkaline medium exhibits 1:2 stoichiometry. Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) as the reactive oxidant species has been proposed, proceeding through the formation of a complex and reaction of the intermediate of l-phenylalanine with monoperiodatocuprate(III) to give the products. The products were identified by spot test, infrared (IR), and gas chromatography-mass spectrometry (GC-MS). The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to the slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. The isokinetic temperature was also calculated and found to be 331 K.  相似文献   

6.
Iodine determination in food samples was performed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Sample masses up to 500 mg of bovine liver, corn starch, milk powder, or wheat flour were completely combusted using the MIC system. Ammonium nitrate (6 mol l−1 solution, 50 μl) was used as an aid for ignition and vessels were charged with 15 bar of O2. The use of H2O, 0.9 mmol l−1 H2O2, 10 to 50 mmol l−1 (NH4)2CO3 and 56 mmol l−1 tetramethylammonium hydroxide was investigated as absorbing solutions, as well as the suitability of performing a reflux step after the combustion process. Digestion of food samples by pressurized microwave-assisted acid digestion, microwave-assisted extraction and conventional extraction of iodine in alkaline solution were also evaluated. Iodine recoveries higher than 99% were obtained using MIC and 50 mmol l−1 (NH4)2CO3 or 56 mmol l−1 tetramethylammonium hydroxide as absorbing solution and with 5 min for the reflux step. Accuracy was evaluated using certified reference materials (bovine muscle, corn bran, and milk powder) and agreement better than 97% was obtained. The limit of quantification by MIC and further ICP-MS determination was 0.002 μg g−1. Blanks were always low and no memory effects were observed. Digestion by MIC allowed the processing of up to eight samples by each run in 25 min with high efficiency of digestion (residual carbon content lower than 1%) providing a suitable medium for further iodine determination by ICP-MS.  相似文献   

7.
Quenched phosphorescence was used, for the first time, as detection mode in the chiral separation of methotrexate (MTX) enantiomers by electrokinetic chromatography. The detection is based on dynamic quenching of the strong emission of the phosphorophore 1-bromo-4-naphthalene sulfonic acid (BrNS) by MTX under deoxygenated conditions. The use of a background electrolyte with 3 mg/mL 2-hydroxypropyl-β-cyclodextrin and 20% MeOH in 25 mM phosphate buffer (pH 7.0) and an applied voltage of 30 kV allowed the separation of l-MTX and its enantiomeric impurity d-MTX with sufficient resolution. In the presence of 1 mM BrNS, a detection limit of 3.2 × 10−7 M was achieved, about an order of magnitude better than published techniques based on UV absorption. The potential of the method was demonstrated with a degradation study and an enantiomeric purity assessment of l-MTX. Furthermore, l-MTX was determined in a cell culture extract as a proof-of-principle experiment to show the applicability of the method to biological samples.  相似文献   

8.
Summary The potential of capillary zone electrophoresis has been investigated for the separation and quantitative determination of some quinolone antibiotics. The influence of different conditions, such as the nature and concentration of the electrophoretic electrolyte, on migration time, peak symmetry, efficiency and resolution was studied. A buffer consisting of 100mm HEPES adjusted to pH 8.5 containing 10% (v/v) acetonitrile was found to furnish a very efficient and stable electrophoretic system for the separation of exoxacin, ciprofloxacin, ofloxacin, oxolinic acid, nalidixic acid and pipemedic acid. A linear relationship between concentration and peak area for each compound was obtained in the concentration range 0.25–40 μg mL−1; detection limits were approximately 0.25 ng mL−1. It was demonstrated that the method can be used for the simultaneous determination of these six antibiotics in serum and urine samples.  相似文献   

9.
The kinetics of the intra-molecular electron transfer of an adduct of l-ascorbic acid and the [Fe3IIIO(CH3COO)6(H2O)3]+ cation in aqueous acetate buffer was studied spectrophotometrically, over the ranges 2.55 ≤ pH ≤ 3.74, 20.0 ≤ θ ≤ 35.0 °C, at an ionic strength of 0.50 and 1.0 mol dm−3 (NaClO4). The reaction of l-ascorbic acid and the complex cation involves the rapid formation of an adduct species followed by a slower reduction in the iron centres through consecutive one-electron transfer processes. The final product of the reaction is aqueous iron(II) in acetate buffer. The proposed mechanism involves the triaqua and diaqua-hydroxo species of the complex cation, both of which form adducts with l-ascorbic acid. At 25 °C, the equilibrium constant for the adduct formation was found to be 86 ± 15 and 5.8 ± 0.2 dm3 mol−1 for the triaqua and diaqua-hydroxo species, respectively. The kinetic parameters derived from the rate expression have been found to be: k 0 = (1.12 ± 0.02) × 10−2 s−1 for the combined spontaneous decomposition and k 1 = (4.47 ± 0.06) × 10−2 s−1H 1 = 51.0 ± 2.3 kJ mol−1, ΔS 1 = −100 ± 8 J K−1 mol−1), k 2 = (4.79 ± 0.38) × 10−1 s−1H 2 = 76.5 ± 0.8 kJ mol−1, ΔS 2 = 6 ± 3 J K−1 mol−1) for the triaqua and diaqua-hydoxo species, respectively.  相似文献   

10.
The kinetics of oxidation of l-cystine by diperiodatoargentate(III) (DPA) in alkaline medium at a constant ionic strength of 0.10 mol dm−3 was studied spectrophotometrically. The reaction exhibits a 1:2 stoichiometry (l-cys:DPA) and is first order in [DPA]. The order in both [l-cystine] and [alkali] changes from first to zero order as their concentrations increase. Added periodate retards the rate of reaction. The effects of added products have been investigated. The active species of silver(III) is identified as monoperiodatoargentate(III) (MPA). The oxidation is thought to proceed via an MPA–l-cystine complex, which decomposes in a rate-determining step to give a free radical followed by a fast step to give the products. The products were identified by spot test, IR and GC–MS. The reaction constants involved in different steps of the mechanism were evaluated. The activation parameters with respect to the slow step of the mechanism were computed and discussed.  相似文献   

11.
Aqueous solution of water soluble colloidal MnO2 was prepared by Perez-Benito method. Kinetics of l-methionine oxidation by colloidal MnO2 in perchloric acid (0.93 × 10−4 to 3.72 × 10−4 mol dm−3) has been studied spectrophotometrically. The reaction follows first-order kinetics with respect to [H+]. The first-order kinetics with respect to l-methionine at low concentration shifts to zero order at higher concentration. The effects of [Mn(II)] and [F] on the reaction rate were also determined. Manganese (II) has sigmoidal effect on the rate reaction and act as auto catalyst. The exact dependence on [Mn(II)] cannot be explained due to its oxidation by colloidal MnO2. Methionine sulfoxide was formed as the oxidation product of l-methionine. Ammonia and carbon dioxide have not been identified as the reaction products. The mechanism with the observed kinetics has been proposed and discussed.  相似文献   

12.
The kinetics of oxidation of l-lysine by diperiodatoargentate(III) (DPA) in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm−3 was studied spectrophotometrically. The oxidation products are aldehyde, 5-aminopentanal and Ag(I). The main products were identified by spot test, IR and GC-MS. The stoichiometry is [l-lysine]:[DPA] = 1:1. The reaction is first order with respect to diperiodatoargentate(III) concentrations, whereas the order with respect to l-lysine and alkali concentrations changes from first order to zero order as the l-lysine and alkali concentrations are increased. The effects of added products, periodate, ionic strength, and dielectric constant of the reaction medium were investigated. Based on the experimental results, a mechanism involving complex formation between DPA species and l-lysine is proposed. The reaction constants involved in the mechanism were evaluated. The activation parameters with respect to the slow step of the mechanism were determined and discussed.  相似文献   

13.
The coordination behaviour of the tripeptide glycyl-l-phenylalanyl-glycine (H-Gly-Phe-Gly-OH) with Au(III), Pd(II), and Pt(II) in both solution and in the solid state has been investigated experimentally. In addition, quantum chemical calculations have been carried out with a view to obtain the structures and spectroscopic properties of the ligand and its complexes. Both in solution and in the solid state the tripeptide interacts in a tetradentate manner with the Au(III) and Pd(II) ions through the NH2, two deprotonated amide N atoms and the COOgroup, forming [Au(H-Gly-Phe-Gly-OH)H−2)] × H2O and [Pd(H-Gly-l-Phe-Gly-OH)H−2)]Na × H2O complexes. The MN3O chromophores are calculated to be near planar. Interaction with cisplatin leads to the formation of a mononuclear complex with tridentate coordination of the ligand by NH2 and two N- atoms from the deprotonated amide groups ([Pt(H-Gly-l-Phe-Gly-OH)H−2)NH3] × 2H2O). The fourth coordination position of the Pt(II) is occupied by an NH3 ligand. The PtN4 chromophore is flat with a deviation from planarity of 0.3°. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

14.
Summary The chromatographic resolution of the enantiomers of sulindac has been achieved using a Chiralpak AD CSP (10 μm, 250×4.6 mm) with a mobile phase of hexane: ethanol (85∶15 v/v) containing trifluoroacetic acid (0.05% v/v) at a flow rate of 1.0 mL min−1. Under these conditions the enantiomers eluted with separation and resolution factors of 1.43 and 2.46 respectively. Semipreparative isolation of the enantiomers and their characterization by circular dichroism spectroscopy and NMR, in the presence of a chiral shift reagent, indicated that the elution order was (−)-(S)- before (+)-(R)-sulindac. The enantiomeric composition of sulindac in urine following administration of the racemic drug to man was determined by sequential achiral-chiral chromatography. Achiral analysis was carried out using a Spherisorb S5 ODS2 stationary phase (5 μm, 250×4.6 mm) and a mobile phase of aqueous acetic acid (2% v/v; pH 3.5): acetonitrile: THF (50∶48∶2 by volume) at a flow rate of 1.0 mL min−1. The HPLC eluate containing sulindac (retention time 4.9 min) was collected and following workup, the enantiomeric composition of the drug was determined using the CSP. Over the 24 h collection period sulindac was excreted predominantly as theR-enantiomer, but the enantiomeric composition was found to vary markedly with time which is presumably associated with the complex metabolism of the drug.  相似文献   

15.
A simple and new isocratic normal phase chiral HPLC method has been developed for the determination of enantiomeric purity of pemetrexed disodium (l-enantiomer) in bulk drugs with a short run time of about 20 min. Chromatographic separation of l and d-enantiomers of pemetrexed disodium was achieved on an amylose based chiral stationary phase using a mobile phase consists of hexane, ethanol and trifluoro acetic acid. The resolution between the enantiomers was found to be more than 2.0. The system precision and method precision were found to be within 5% RSD for the distomer (d-enantiomer) at its specification level (i.e. not more than 1.0% w/w). The limit of detection and limit of quantification of distomer were 1.6 and 5 μg mL−1, respectively for 10 μL injection volume. The percentage recovery of distomer was ranged from 90.6 to 105.7 in bulk drug samples. The test solution was found to be stable in the diluent for 48 h. The method was found to be specific for the enantiomers of pemetrexed disodium and can be conveniently used for the quantification of undesired d-enantiomer present in the bulk drug samples of pemetrexed disodium.  相似文献   

16.
Summary A sensitive HPLC method with marbofloxacin (MAR) as internal standard and fluorescence detection is described for the analysis of ofloxacin (OFL) enantiomers in plasma samples. Plasma samples were prepared by adding phosphate buffer (pH 7.4, 0.1m), then extracted with trichloromethane.S-OFL,R-OFL, and the internal standard were separated on a reversed-phase column with water-methanol, 85.5∶14.5, as mobile phase. The concentrations ofS-OFL andR-OFL eluting from the column (retention times 7.5 and 8.7 min, respectively) were monitored by fluorescence detection withλ ex = 331 andλ em = 488 nm. The detection and quantitation limits were 10 and 20 ng mL−1, respectively, forS-OFL and 11 and 21 ng mL−1 forR-OFL. Response was linearly related to concentration in the range 10 to 2500 ng mL−1. Recovery was close to 93% for both compounds. The method was applied to determination of the enantiomers of OFL in plasma samples collected during pharmacokinetic studies.  相似文献   

17.
Synthesis of small oligopeptide brushes (oligo(S-benzyl-l-cysteine)) onto polyelectrolyte functionalized silica microparticles was developed. Poly(vinyl amine) (PVAm) adsorbed from salt-free and KCl 10−1 mol L−1 aqueous solution onto silica microparticles was chemically and naturally cross-linked by epichlorohydrin and CO2, respectively. After the adsorption of PVAm onto microporous silica particles and stabilization by cross-linking, five repeated coupling reactions of Boc-S-benzyl-l-cysteine were performed. To test the protein interactions with the newly designed surface, human serum albumin (HSA) has been selected as a model protein. X-ray photoelectron spectroscopy, total organic carbon, potentiometric and polyelectrolyte titrations, and electrokinetic analysis were employed to obtain information about the polyelectrolyte adsorption and the amount of the amino acid S-benzyl-l-cysteine that was covalently bound to the solid surface and for determination of the protein amount adsorbed onto functionalized surface. The amount of HSA adsorbed onto modified silica microparticles decreased in order: silica/PVAm-cross-linked (silica/PVAm-C) (8.00 mg g−1) > silica/PVAm-C/S-benzyl-l-cysteine (6.34 mg g−1) > silica (4.86 mg g−1) > silica/PVAm-C/(S-benzyl-l-cysteine)5 (1.86 mg g−1).  相似文献   

18.
Bacillus subtilis NX-2 produces γ-polyglutamic acid (γ-PGA) when using glucose and l-glutamate as carbon sources. The conversion of carbon sources into γ-PGA was analyzed with the 13C-NMR method after enriching the media with 13C-labeled glucose. The results showed that the percentage of γ-PGA monomers derived from glucose was relatively low, approximately 6% and 9%, respectively, with an initial glucose concentration of 30 and 40 g L−1. It was concluded that glucose was utilized mainly as the growth-limiting substrate for cell growth and supplied the required energy during γ-PGA biosynthesis, while l-glutamate was preferred as the main substrate for γ-PGA formation. To achieve an efficient conversion of l-glutamate and enhance the γ-PGA production, a fed-batch culture was proposed by feeding of glucose. By this method, supplied l-glutamate (40 g L−1) was completely depleted, and γ-PGA yield was attained 42 g L−1.  相似文献   

19.
Summary An HPLC column-switching method has been developed and validated for the enantioselective determination of (R)- and (S)-carvedilol in human plasma. Sample preparation was performed either off-line, by extraction with trichloromethane and back-extraction into 0.01m aqueous citric acid which was injected on to a LiChrosorb RP 8 column, or on-line, by injecting diluted (0.1m formic acid) plasma on to a LiChrosorb ADS column. In both instances separation was performed by gradient elution and on-line transfer of the fraction containing, the carvedilol on to an enantioselective Teicoplanin column. The enantiomers of carvedilol were separated isocratically by use of methanol-acetonitrile-triethylammonium acetate, 70:30:0.05 (v/v/w), as mobile phase. With fluorescence detection the limits of quantitation were 0.30 ng mL−1 for (R)-carvedilol and 0.26 ng mL−1 for (S)-carvedilol; these were sufficient to enable investigation of the effect of exercise on plasma concentrations of (R)- and (S)-carvedilol after oral administration of either the racemate or the pure enantiomers. Although the operating conditions were optimized for sample preparation by on-line deproteination on a LiChrospher RP 18 ADS column, the complete method was insufficiently rugged for analysis of large numbers of plasma samples—the enantioselectivity of the Teicoplanin column deteriorated too rapidly because of the transfer of enantioselectivity-poisoning interferences which could not be suppressed sufficiently. In contrast the liquid-liquid sample-extraction procedure combined with column switching resulted in a analytical method with long-term stability. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001  相似文献   

20.
In this study, an efficient procedure was developed for callus induction and regeneration of kiwifruit (Actinidia deliciosa) using different organs of shoots developed under in vitro conditions. Effects of explants source and media (M1, 1.0 mg l−1 BA + 2.0 mg l−1 2,4-D–M2, 1.0 mg l−1 NAA + 2.0 mg l−1 2,4-D) on initiation of callus were examined in order to obtain callus for organogenesis. The best callus for plant regeneration was obtained from leaf explants on Murashige and Skoog’s medium (MS) supplemented with M2. Formation of callus from leaf of kiwifruit (A. deliciosa) was cultured in MS medium containing different concentration of N6-benzylaminopurin (BA; 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 mg l−1) for callus proliferation and plant regeneration. Although the first shoot formation was appeared in medium containing 6.0 and 8.0 mg l−1 BA, the best shoots formation was obtained in medium with 4.0 mg l−1 BA.  相似文献   

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