Synthesis of unnatural pentahydroxylated pyrrolizidines: 5-epi- and 5,7a-di-epi-hyacinthacine C1

Stereocontrolled synthesis of 5-epi- and 5,7a-di-epi-hyacinthacine C₁ (7 and 8), two potential glycosidase inhibitors are described using α,β-unsaturated ketone 9 as homochiral starting material. The key step in the synthesis is the highly diastereoselective dihydroxylation reaction of 9, that allows the obtention of a single bis-hydroxylated ketone (10). Further derivatization into two epimeric mesylate esters followed by internal cyclization form the pyrrolizidinic compounds 7 and 8. This type of compounds can be useful in glycobiology due to their ability to inhibit carbohydrate-processing enzymes.     

Determination of enzyme activity inhibition by FTIR spectroscopy on the example of fructose bisphosphatase

A mid-infrared enzymatic assay for label-free monitoring of the enzymatic reaction of fructose-1,6-bisphosphatase with fructose 1,6-bisphosphate has been proposed. The whole procedure was done in an automated way operating in the stopped flow mode by incorporating a temperature-controlled flow cell in a sequential injection manifold. Fourier transform infrared difference spectra were evaluated for kinetic parameters, like the Michaelis–Menten constant (K _M) of the enzyme and V _max of the reaction. The obtained K _M of the reaction was 14 ± 3 g L⁻¹ (41 μM). Furthermore, inhibition by adenosine 5′-monophosphate (AMP) was evaluated, and the K _M^App value was determined to be 12 ± 2 g L⁻¹ (35 μM) for 7.5 and 15 μM AMP, respectively, with V _max decreasing from 0.1 ± 0.03 to 0.05 ± 0.01 g L⁻¹ min⁻¹. Therefore, AMP exerted a non-competitive inhibition.     

A simple and efficient one-step, regioselective, enzymatic glucosylation of arbutin by α-glucosidase

4-Hydroxyphenyl-β-isomaltoside has been synthesized by α-glucosidase assisted transglycosylation between arbutin as acceptor and sucrose as donor molecules, respectively. Optimum conditions for the transglucosylation reaction were 40 °C for 20 h with 10 mM arbutin and 1.5 M sucrose in a 100 mM sodium citrate/phosphate buffer at pH 5.0. The new glucoside was obtained in a 50% molar yield with respect to arbutin.     

Hydrolysis rates of alkyl and aryl sulfinamides: evidence of general acid catalysis

Sulfinamides are important in enantioselective synthesis, as rare post-translational modifications of proteins and as isosteres of the amide bond. Little is known about the rates of hydrolysis for aliphatic sulfinamides or the mechanism of hydrolysis. In this Letter, we show that sulfinamides hydrolyse by predominantly a non-specific acid/base catalysis with phosphate buffer but by varying the buffer concentration, it was possible to determine the hydrolysis rates of a range of sulfinamides with water through non-linear least squares regression.     

酶催化脂肪族聚酯的合成

脂肪族聚酯是一种可生物降解的新型高聚物,可通过化学催化、发酵和酶催化来合成.酶催化合成聚酯是一种新型的环境友好绿色化学技术,可以在温和条件下高效的合成聚酯,有着传统聚合方法难以比拟的优势.尤其是特种酶的应用,为传统方法难以合成的聚酯,开辟了一条新的合成途径.本文综述了脂肪酶催化缩聚、酯交换、内酯开环聚合等聚酯合成方法,并讨论了反应参数(如溶剂、温度、酶和单体的浓度)对反应的影响.     

尿素酶固载于纳米二氧化钛多孔膜上的尿素生物传感器

在钛丝基体上沉积一层纳米二氧化钛(TiO2)多孔膜,然后直接将尿素酶吸附在TiO2膜上。基于TiO2膜的pH响应,发展了一种廉价的、易于微型化的pH敏尿素酶传感器。采用石英微天平、红外光谱和紫外可见光谱等手段研究尿素酶在TiO2膜上的物理固载行为。由于纳米TiO2在紫外光下光自洁特性可获得高度洁净的表面,石英微天平研究表明在光自洁后的TiO2膜上尿素酶的吸附具有很好的重复性和稳定性,吸附量为0.22mmol/g,吸附平衡常数k为3.15×105L/mol。采用电位法测定了尿素酶/TiO2复合膜电极的性能及其影响因素,在1.0 mmol/L pH 7~8 PBS,35℃,尿素的响应范围为8.5×10-5~1.5×10-1mol/L,相关系数r为0.993 7,检出限为6×10-5mol/L。     

Characterisation of poly(neutral red) modified carbon film electrodes; application as a redox mediator for biosensors

The polymer redox mediator, poly(neutral red) (PNR), has been synthesised and characterised electrochemically to investigate the best electropolymerisation and mediation conditions for application in enzyme biosensors and to clarify the mechanism of action. Neutral red was electropolymerised by potential cycling on carbon film electrode substrates by allowing the monomer to be oxidised during the full 20 cycles of polymerisation or reducing the positive limit of the potential window after the first 2 cycles to impede monomer oxidation with a view to obtaining longer polymer chains and a lesser degree of branching. Comparison was made with glassy carbon substrates. The PNR films on carbon film electrodes were characterised using cyclic voltammetry and electrochemical impedance spectroscopy, as well as in glucose biosensors prepared with PNR. Glucose oxidase enzyme was immobilised by encapsulation in silica sol-gel and compared with that obtained by cross-linking with glutaraldehyde. The biosensors were evaluated by chronoamperometry in 0.1 M phosphate buffer saline solution, pH 7.0, and showed evidence of electron transfer between the enzyme cofactor flavin adenine dinucleotide and PNR dissolved in the enzyme layer competing with PNR-mediated electrochemical degradation of H₂O₂ formed during the enzymatic process. This paper is dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday.     

应用大孔吸附树脂从农药废水中回收毕克草

毕克草为一种新型除草剂,通常情况下很难被降解,本文利用物理吸附原理通过自行制备的大孔吸附树脂从农药水中对其进行了回收,回收效果良好,同时也达到了废水处理的目的。优化的最佳实验条件:室温下,pH=1.0以及流速为5BV/h时,对COD为15000mg/L的毕克草废水吸附处理后,其出水可达《污水综合排放标准》(GB89—1996)中的一级排放标准;洗脱再生时,室温下,用95%的乙醇洗脱,流速为2BV/h,(即2倍树脂床体积/h)回收率可达98.4%,纯度达93.7%,总流程一次可处理该废水240mL。