有机溶剂对酶催化活性和选择性的影响

有机溶剂中酶的结构与功能与在水中有很大的不同, 通过调整反应介质可系统地改善酶针对目标反应的活性和选择性。重点阐述了溶剂对酶催化反应的活性和选择性的影响及其控制策略, 给出了酶催化选择性的热力学预测模型。     

非水反相微乳中NaCl纳米粒子的制备

在乙醇/Brij 30/十六烷反相微乳中利用无水NaAc与HCl反应制备了水可溶性晶态NaCl纳米粒子,平均粒径为 60 nm.与在甲酰胺/AOT/正庚烷反相微乳中制备的粒径约为1 μm的NaCl粒子进行比较,表明在特定条件下,非水微乳可以作为合成水可溶性纳米粒子的有效介质.     

Relative effectiveness of pretreatments on performance of Rhizomucor miehei lipase in nonpolar reaction media

Enzymes can be used in nonpolar reaction media to modify waterinsoluble substrates. A variety of pretreatments, applied to the enzyme prior to introduction to the nonpolar media, can improve enzyme activity. However, the various pretreatments have not been studied using directly comparable conditions, nor have they been applied simultaneously to test for interactive effects. This work evaluates pretreatment of lipase with various classes of additives. The pretreated lipase is used to catalyze esterification between citronellol and acetic acid in a medium of n-hexane. The effectiveness of a particular pretreatment is presented in terms of relative performance (RP), which is equal to the number of times faster the pretreated lipase catalyzes the reaction relative to untreated lipase. The individual and interactive effects of the pretreatment factors were studied and compared. Buffer salts had a much stronger performance-enhancing effect than nonbuffer salts; pretreatment with 90% (w/w) sodium phosphate yielded lipase with an RP of approx 64. A strong interaction was found between the treatments with sodium phosphate and pH adjustment. These treatments may mitigate the inhibitory effect of acetic acid. Activating effects of phase interfaces and active-site protectants are shown to be complementary to other treatments, demonstrating that they likely act by distinct mechanisms.     

Influence of electrolyte characteristics on the electrochemical parameters of electrical double layer capacitors

Electrical double layer capacitors based on ideally polarizable nanoporous carbon electrodes in propylene carbonate with the addition of different 1 M Me₃EtNBF₄, Me₂Et₂NBF₄, MeEt₃NBF₄, Et₄NBF₄, Et₃PrNBF₄ and Et₃BuNBF₄ electrolytes have been tested by cyclic voltammetry, chronoamperometry and electrochemical impedance methods. The limits of ideal polarizability, low-frequency limiting capacitance and series resistance, time constant, Ragone plots (energy density vs. power density dependencies) and other characteristics have been discussed. The influence of the electrolyte molar mass on the electrochemical characteristics of the nanoporous carbon electrode cells has been established. The applicability limits of the Srinivasan and Weidner model have been tested.     

Tracking X‐ray‐derived redox changes in crystals of a methylamine dehydrogenase/amicyanin complex using single‐crystal UV/Vis microspectrophotometry

X‐ray exposure during crystallographic data collection can result in unintended redox changes in proteins containing functionally important redox centers. In order to directly monitor X‐ray‐derived redox changes in trapped oxidative half‐reaction intermediates of Paracoccus denitrificans methylamine dehydrogenase, a commercially available single‐crystal UV/Vis microspectrophotometer was installed on‐line at the BioCARS beamline 14‐BM‐C at the Advanced Photon Source, Argonne, USA. Monitoring the redox state of the intermediates during X‐ray exposure permitted the creation of a general multi‐crystal data collection strategy to generate true structures of each redox intermediate.     

Electrochemical methylation of a chelate anionic NiI complex with methylcobaloxime. Partial modeling of the action mechanism of the active center of acetyl-CoA synthase

Electrochemically generated anions of Co and Ni chelate complexes can be alkylated with BuⁿBr, BuⁿI, and (dmgH)₂CoMe (dmgH is the dimethylglyoximate anion). Unlike the anionic Co complexes, the anionic Ni complex cannot be alkylated with BuⁿBr; however, it reacts with stronger alkylating agents (BuⁿI and (dmgH)₂CoMe). It is assumed that the electrochemical alkylation of the Ni complex with (dmgH)₂CoMe can serve as a model for alkylation occurring in biological synthesis of acetyl coenzyme A. Reactions of some Co chelate anions with BuⁿI can proceedvia the reduction of the latter. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 55–58, January, 2000.     

Voltammetry of Benzo[a]pyrene in Aqueous and Nonaqueous Media: Adsorptive Stripping Voltammetric Determination at Pencil Graphite Electrode

A detailed study of the electrochemical oxidation of Benzo[a]pyrene (BaP) at the glassy carbon and pencil graphite electrodes was carried out in aqueous and nonaqueous media. Using square‐wave stripping mode, the compound yielded a well‐defined voltammetric response at pencil graphite electrode in acetate buffer, pH 4.8 at +1.13 V (vs. Ag/AgCl) (a preconcentration step being carried out at a fixed potential of +0.70 V for 180 s). The process could be used to determine BaP concentrations in the range 0.25–1.25 μM, with a detection limit of 0.027 μM (6.82 μg L^?1). The applicability to assay of spiked human urine samples was also illustrated.     

SE‐30 Graphite Composite Electrode: An Alternative for the Development of Electrochemical Biosensors

A new graphite composite electrode was constructed by mixing graphite powder with chromatography stationary phase, SE‐30, as the binder. The electrochemical behavior of the new electrode has been evaluated and compared with that of traditional carbon paste electrode (CPE). The proposed electrode provides a remarkable increase in the rate of electron transfer of biomolecules such as nicotinamide adenine dinucleotide (NADH), cysteine, ascorbic acid and catechol and shows a low surface fouling effects. The electrode shows highly promising results when used as an amperometic sensor for biocompounds such as NADH.     

Application of 1-Alkyl-3-methylimidazolium-Based Ionic Liquids as Background Electrolytes in Nonaqueous Capillary Electrophoresis for the Analysis of Coptidis Alkaloids

Interest in ionic liquids (ILs) for their potential in analytical chemistry is increasing because they are environmentally benign and are good separation solvents. The aim of the presented investigation was to verify whether ILs would be a suitable background electrolyte (BGE) in nonaqueous capillary electrophoresis (NACE) for organic cations analysis of the closely related analogues. In this study, a novel and very simple NACE method has been established for analyzing seven quaternary alkaloids in Coptis rhizome using 1-alkyl-3-methylimidazolium tetrafluoroborate-based ionic liquid as BGE. The effects of the alkyl group, imidazolium counterion (anionic part), along with the concentration of IL, are investigated and discussed. Baseline separation, high efficiencies, and symmetrical peaks of the seven alkaloids were obtained. The separation mechanism could be hydrophobic and hydrogen-bonding interactions between the alkaloids and the imidazolium cations. The optimum conditions were 70 mM 1-decyl-3-methylimidazolium tetrafluoroborate (1D-3MI-TFB) methanol solution (apparent pH 2.66) and 30 kV applied voltage. The detection was performed at 254 nm. Seven quaternary alkaloids in Coptis rhizome were separated within 14 min. The proposed NACE separation procedure is highly reproducible and can be applied in the qualitative and quantitative analysis of Coptidis alkaloids.     

非水溶液滴定法测定普卢利沙星的含量

以0.1mol.L-1高氯酸为滴定液,结晶紫为指示剂,用非水滴定法测定普卢利沙星。重复测定普卢利沙星含量平均值为99.4%(n=6),相对标准偏差为0.1%。该方法准确简便、重复性好,可作为普卢利沙星含量测定的有效方法。