Nickel-catalyzed cross-electrophile allylation of vinyl bromides and the modification of anti-tumour natural medicine β-elemene

Herein, we present a facile and efficient allylation method via Ni-catalyzed cross-electrophile coupling of readily available allylic acetates with a variety of substituted alkenyl bromides using zinc as the terminal reductant. This Ni-catalyzed modular approach displays excellent functional group tolerance and a broad substrate scope, which the creation of a series of 1,4-dienes including several structurally complex natural products and pharmaceutical motifs. Moreover, the coupling strategy has the potential to realize enantiomeric control. The practicality of this transformation is demonstrated through the potent modification of the naturally antitumor active molecule β-elemene.

Herein, we present a facile and efficient allylation method via Ni-catalyzed cross-electrophile coupling of readily available allylic acetates with a variety of substituted alkenyl bromides using zinc as the terminal reductant.     

Effect of Thermal Processing on the Metabolic Components of Black Beans on Ultra-High-Performance Liquid Chromatography Coupled with High-Field Quadrupole-Orbitrap High-Resolution Mass Spectrometry

An ultra-high-performance liquid chromatography coupled with high-field quadrupole-orbitrap mass spectrometry (UHPLC-QE-MS) histological platform was used to analyze the effects of two thermal processing methods (cooking and steaming) on the nutritional metabolic components of black beans. Black beans had the most amino acids, followed by lipids and polyphenols, and more sugars. Multivariate statistical analysis indicated that heat processing significantly affected the metabolic component content in black beans, with effects varying among different components. Polyphenols, especially flavonoids and isoflavones, were highly susceptible. A total of 197 and 210 differential metabolites were identified in both raw black beans and cooked and steamed black beans, respectively. Cooking reduced the cumulative content of amino acids, lipids, polyphenols, sugars, and nucleosides, whereas steaming reduced amino acid and lipid content, slightly increased polyphenol content, and significantly increased sugar and nucleoside content. Our results indicated that metabolic components were better retained during steaming than cooking. Heat treatment had the greatest impact on amino acids, followed by polyphenols, fatty acids, sugars, and vitamins, indicating that cooking promotes the transformation of most substances and the synthesis of a few. The results of this study provide a basis for further research and development of nutritional products using black beans.     

Linker engineering in metal–organic frameworks for dark photocatalysis

Dark reactions featuring continuous activity under light off conditions play a critical role in natural photosynthesis. However, most artificial photocatalysts are inactive upon the removal of the light source, and the artificial photocatalysts with dark photocatalysis abilities have been rarely explored. Herein, we report a Ti-based metal–organic framework (MOF), MIL-125, exhibiting the capability of dark photocatalytic hydrogen production. Remarkably, the introduction of different functional groups onto the linkers enables distinctly different activities of the resulting MOFs (MIL-125-X, X = NH₂, NO₂, Br). Dynamic and thermodynamic investigations indicate that the production and lifetime of the Ti³⁺ intermediate are the key factors, due to the electron-donating/-withdrawing effect of the functional groups. As far as we know, this is the first report on dark photocatalysis over MOFs, providing new insights into the storage of irradiation energy and demonstrating their great potential in dark photocatalysis due to the great MOF diversity.

A Ti-based MOF with long-lived Ti³⁺ can achieve dark photocatalysis. The different groups on the organic linker modulate electron storage ability and the lifetime of Ti³⁺, significantly regulating dark photocatalytic activity in H₂ production.     

LBO晶体超光滑表面抛光机理

胶体SiO2抛光LBO晶体获得无损伤的超光滑表面,结合前人对抛光机理的认识,探讨了超光滑表面抛光的材料去除机理,分析了化学机械抛光中的原子级材料去除机理.在此基础上,对胶体SiO2抛光LBO晶体表面材料去除机理和超光滑表面的形成进行了详细的描述,研究抛光液的pH值与材料去除率和表面粗糙度的关系.LBO晶体超光滑表面抛光的材料去除机理是抛光液与晶体表面的活泼原子层发生化学反应形成过渡的软质层,软质层在磨料和抛光盘的作用下很容易被无损伤的去除.酸性条件下,随抛光液pH值的减小抛光材料的去除率增大;抛光液pH值为4时,获得最好的表面粗糙度.     

免疫算法在双闭环直流调速系统中的应用

文中对双闭环直流调速系统控制器的选择进行了分析,并借鉴免疫算法强大的寻优能力,提出了基于免疫算法的调速系统控制器参数整定方法.为了分析比较,实际应用中采用了三种控制器参数整定方法,比较结果说明,免疫算法在调速系统控制器参数整定中的应用是更加有效的.通过在单晶炉拉晶过程的应用,证明该方法可行性和正确性.     

Pyrene分子(小片石墨晶体)的电子传导特性

利用量子理论中基于Green函数的tight-binding方法,对pyrene分子的电子传导和电子流分布进行了理论研究。在考虑到界面耦合和Hopping积分的情况下,得出了电子透射谱和流分布的模拟结果。结果显示透射与电子的能量紧密相关;谱的振荡特征是能级量子化的结果;流分布有着特定的方向,并且在每一个原子点上符合Kirchhoff量子流守恒定律。另外还发现了桥接pyrene分子的正负能开关特性。     

The Optimal Error Estimate of the Fully Discrete Locally Stabilized Finite Volume Method for the Non-Stationary Navier-Stokes Problem

This paper proves the optimal estimations of a low-order spatial-temporal fully discrete method for the non-stationary Navier-Stokes Problem. In this paper, the semi-implicit scheme based on Euler method is adopted for time discretization, while the special finite volume scheme is adopted for space discretization. Specifically, the spatial discretization adopts the traditional triangle P1−P0 trial function pair, combined with macro element form to ensure local stability. The theoretical analysis results show that under certain conditions, the full discretization proposed here has the characteristics of local stability, and we can indeed obtain the optimal theoretic and numerical order error estimation of velocity and pressure. This helps to enrich the corresponding theoretical results.     

ACTIVE CONTROL OF A FLEXIBLE CANTILEVER PLATE WITH MULTIPLE TIME DELAYS

Active control of a flexible cantilever plate with multiple time delays is investigated using the discrete optimal control method. A controller with multiple time delays is presented. In this controller, time delay effect is incorporated in the mathematical model of the dynamic system throughout the control design and no approximations and assumptions are made in the controller derivation, so the system stability is easily guaranteed. Furthermore, this controller is available for both small time delays and large time delays. The feasibility and efficiency of the proposed controller are verified through numerical simulations in the end of this paper.     

Numerical Study on Entropy Generation of the Multi-Stage Centrifugal Pump

The energy loss of the multi-stage centrifugal pump was investigated by numerical analysis using the entropy generation method with the RNG k-ε turbulence model. Entropy generation due to time-averaged motion and velocity fluctuation was mainly considered. It was found that the entropy generation of guide vanes and impellers account for 71.2% and 23.3% of the total entropy generation under the designed flow condition. The guide vanes are the main hydraulic loss domains and their entropy generation is about 9 W/K, followed by impellers. There are vortices at the tongue of the guide vane inlet as well as flow separations in the impellers, which lead to entropy generation. The fluid impacts the outer surface of the guide vanes, resulting in the increase in entropy generation. There are refluxes near the guide vane tongues which also increase the entropy generation of this part. The entropy generation distribution of the guide vanes and impellers was investigated, which found that the positive guide vane has more entropy generation compared with the reverse guide. The entropy generation of the blade suction surface is higher compared with the pressure surface. This study indicated that the entropy generation method has distinct advantages in the assessment of hydraulic loss.     

Cloning,Expression, Purification,and Characterization of β-Galactosidase from Bifidobacterium longum and Bifidobacterium pseudocatenulatum

Expression and purification of β-galactosidases derived from Bifidobacterium provide a new resource for efficient lactose hydrolysis and lactose intolerance alleviation. Here, we cloned and expressed two β-galactosidases derived from Bifidobacterium. The optimal pH for BLGLB1 was 5.5, and the optimal temperature was 45 °C, at which the enzyme activity of BLGLB1 was higher than that of commercial enzyme E (300 ± 3.6 U/mg) under its optimal conditions, reaching 2200 ± 15 U/mg. The optimal pH and temperature for BPGLB1 were 6.0 and 45 °C, respectively, and the enzyme activity (0.58 ± 0.03 U/mg) under optimum conditions was significantly lower than that of BLGLB1. The structures of the two β-galactosidase were similar, with all known key sites conserved. When o-nitrophenyl-β-D-galactoside (oNPG) was used as an enzyme reaction substrate, the maximum reaction velocity (V_max) for BLGLB1 and BPGLB1 was 3700 ± 100 U/mg and 1.1 ± 0.1 U/mg, respectively. The kinetic constant (K_m) of BLGLB1 and BPGLB1 was 1.9 ± 0.1 and 1.3 ± 0.3 mmol/L, respectively. The respective catalytic constant (k_cat) of BLGLB1 and BPGLB1 was 1700 ± 40 s⁻¹ and 0.5 ± 0.02 s⁻¹, respectively; the respective k_cat/K_m value of BLGLB1 and BPGLB1 was 870 L/(mmol∙s) and 0.36 L/(mmol∙s), respectively. The K_m, k_cat and V_max values of BLGLB1 were superior to those of earlier reported β-galactosidase derived from Bifidobacterium. Overall, BLGLB1 has potential application in the food industry.