Intensification of Double Kinetic Resolution of Chiral Amines and Alcohols via Chemoselective Formation of a Carbonate–Enzyme Intermediate

Chiral amines and alcohols are synthons of numerous pharmaceutically-relevant compounds. The previously developed enzymatic kinetic resolution approaches utilize a chiral racemic molecule and achiral acyl donor (or acyl acceptor). Thus, only one enantiodivergent step of the catalytic cycle is engaged, which does not fully exploit the enzyme’s abilities. The first carbonate-mediated example of simultaneous double chemoselective kinetic resolution of chiral amines and alcohols is described. Herein, we established a biocatalytic approach towards four optically-pure compounds (>99% ee, Enantioselectivity: E > 200) via double enzymatic kinetic resolution, engaging chiral organic carbonates as acyl donors. High enantioselectivity was ensured by extraordinary chemoselectivity in lipase-catalyzed formation of unsymmetrical organic carbonates and engaged in a process applicable for the synthesis of enantiopure organic precursors of valuable compounds. This study focused not only on preparative synthesis, but additionally the catalytic mechanism was discussed and the clear impact of this rarely observed carbonate-derived acyl enzyme was shown. The presented protocol is characterized by atom efficiency, acyl donor sustainability, easy acyl group removal, mild reaction conditions, and biocatalyst recyclability, which significantly decreases the cost of the reported process.     

微波烧结Al_2O_3陶瓷的研究

简要介绍了微波烧结的特点,对 Ａｌ２ Ｏ３ 陶瓷的微波烧结过程进行了介绍和分析,并同常规烧结进行了对比实验,在此基础上得出了一些结论,为陶瓷微波烧结提供了实验依据     

钇掺杂对氧化铝膜的热稳定性及其孔结构的影响

以异丙醇铝和Y(NO3)3为主要原料,用溶胶-凝胶法制备掺杂钇的无支撑Al2O3膜,采用XRD、DTA-TG、BET等测试手段分析钇的掺杂对Al2O3膜的物相组成、热稳定性、以及Al2O3膜孔结构在不同煅烧温度时的影响.研究结果表明:掺杂钇能提高γ-Al2O3相向α-Al2O3相的转变温度和Al2O3膜的热稳定性.钇的掺杂也明显了改善了Al2O3膜在高温煅烧中的孔结构参数.     

Symbiotic N2 Fixation and N Uptake of Yellow and White Lupines Influenced by Spontaneous Rhizobia Infection and Substrate

Abstract

By using soil as substrate, white and yellow lupines (Lupinus albus L., Lupinus luteus L.) assimilated higher N amounts than under quartz sand conditions. This was caused by spontaneous infection of lupines with wild Rhizobia strains and also by an additional N uptake from the soil. In yellow lupines without inoculation in non-sterile soil, only the additional N uptake played a role. Differences in P and K supply as the cause of different N acquisition from soil and quartz sand could be excluded. As compared with white lupines, yellow lupines inoculated with Rhizobia had a high N₂ fixation that exceeded the effect of spontaneous infections. This result as well as the positive effect of spontaneous infections with soil-borne Rhizobia on white lupines indicates insufficient effectiveness of the strains used for inoculation on this plant species.     

Biosensors based on gold nanoelectrode ensembles and screen printed electrodes

Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated.     

The Process of Acetonitrile Synthesis over γ-Al2O3 Promoted by Phosphoric Acid Catalysts

The influence of principal parameters (reaction temperature, ratio of acetic acid and ammonia, composition of reactionary mixture and promotion of catalysts) on the selectivity and yield of the desired product was studied in the reaction of catalytic acetonitrile synthesis by ammonolysis of acetic acid. The processing of γ-Al₂O₃ by phosphoric acid increases amount of the centers, on which carries out reaction of acetamide dehydration. The kinetic model of a limiting stage of reaction – the acetamide dehydration to acetonitrile was suggested. In the process of ammonolysis of acetic acid it was demonstrated that the use of catalysts promoted by phosphoric acid and ratio NH₃:CH₃COOH=(3-4):1 at temperatures of a reactor 360-390°С leads to the increase of acetonitrile productivity to 0.7-0.8 g/cm³·h and allows to minimize formation of by-products.     

Single‐crystalline gold microplates grown on substrates by solution‐phase synthesis

Chemically synthesized single‐crystalline gold microplates have been attracting increasing interest because of their potential as high‐quality gold films for nanotechnology. We present the growth of tens of nanometers thick and tens of micrometers large single‐crystalline gold plates directly on solid substrates by solution‐phase synthesis. Compared to microplates deposited on substrates from dispersion phase, substrate‐grown plates exhibit significantly higher quality by avoiding severe small‐particle contamination and aggregation. Substrate‐grown gold plates also open new perspectives to study the growth mechanism via step‐growth and observation cycles of a large number of individual plates. Growth models are proposed to interpret the evolution of thickness, area and shape of the plates. It is found that the plate surface remains smooth after regrowth, implying the applicability of regrowth for producing giant plates as well as unique single‐crystalline nano‐structures.     

多孔氧化铝模板催化制备定向碳纳米管阵列

Well-aligned open-ended multi-walled carbon nanotube (MWCNT) arrays were prepared via chemical vapor deposition (CVD) method in porous anodic aluminum oxide (AAO) templates without depositing any transition metals as catalyst. Effects of the CVD temperature and heat treatment were studied in detail.Well-aligned open-ended MWCNT arrays were obtained at the CVD temperature above 600 ℃; when CVD temperature is reduced to around 550 ℃, CNTs, CNFs and other structures existed at the same time; no CNTs or carbon nanofibres (CNFs) could be found as the CVD temperature is below 500 ℃, and only amorphous carbon in the porous AAO template was found. Experimental results showed that the AAO template is catalytic during the CVD process, and it has the following two effects: to catalyze thermal decomposition of acetylene and to catalyze conversion of carbon decomposed from acetylene into CNTs or CNFs. Heat treatment could improve the graphitization degree, but it might also introduce new defects.     

铝酸钠溶液中苛性碱、碳酸碱和氧化铝含量的连续测定

利用自动电位滴定法, 选择葡萄糖酸钠配合铝酸钠溶液中的铝, 在滴定碱总量时保持氢氧化铝稳定而不沉淀析出, 不干扰测定. 再以氟化钾置换配合铝酸钠溶液中的铝, 同时放出与铝等化学计量的OH-, 通过酸碱滴定, 实现了在铝酸钠溶液中对苛性碱、 碳酸碱和氧化铝含量的连续测定. 此方法操作简便、 快速, 数据准确可靠.     

Kinetics of batch production of single-cell protein from cheese whey

A kinetic model for single-cell protein batch fermentation was developed using the numerical simultaneous integration approach of the fourth-order Runge-Kutta method. The model takes into account the effect of substrate inhibtion, maintenance energy, and cell death on the cell growth and substrate utilization during the fermentation process. The theoretical results obtained from the model compared well with the experimental data. The model was used to study the effect of the initial substrate concentration on the lag period, fermentation time, specific growth rate, population size, and cell productivity of batch fermentation. Increasing the initial substrate concentration increased the lag period and fermentation time and decreased the specific growth rate and cell yield. The growth limiting substrate concentration was 2.9 g/L, whereas the growth inhibiting substrate concentration was 69.0 g/L. Increasing the initial substrate concentration above 150 g/L significantly decreased the yeast population size.