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.     

Applications of Titanium Dioxide Nanostructure in Stomatology

Breakthroughs in the field of nanotechnology, especially in nanochemistry and nanofabrication technologies, have been attracting much attention, and various nanomaterials have recently been developed for biomedical applications. Among these nanomaterials, nanoscale titanium dioxide (nano-TiO₂) has been widely valued in stomatology due to the fact of its excellent biocompatibility, antibacterial activity, and photocatalytic activity as well as its potential use for applications such as dental implant surface modification, tissue engineering and regenerative medicine, drug delivery carrier, dental material additives, and oral tumor diagnosis and treatment. However, the biosafety of nano-TiO₂ is controversial and has become a key constraint in the development of nano-TiO₂ applications in stomatology. Therefore, in this review, we summarize recent research regarding the applications of nano-TiO₂ in stomatology, with an emphasis on its performance characteristics in different fields, and evaluations of the biological security of nano-TiO₂ applications. In addition, we discuss the challenges, prospects, and future research directions regarding applications of nano-TiO₂ in stomatology that are significant and worthy of further exploration.     

变形镜部分驱动器断电失效对校正性能的影响

变形镜在长期工作的过程中,压电陶瓷驱动器因累积疲劳效应会导致其失效,从而导致校正性能的降低.从变形镜的影响函数出发,将失效驱动器的电压置零,采用有限元方法建立变形镜疲劳失效模型,重点分析畸变波前的形态分布、入射光束的类型和驱动器的排布方式等对校正能力的影响.实验结果表明,在部分驱动器失效的情况下,变形镜应当根据高斯型随...     

Design,Synthesis, and In Vitro and In Vivo Antifungal Activity of Novel Triazoles Containing Phenylethynyl Pyrazole Side Chains

A series of triazole derivatives containing phenylethynyl pyrazole moiety as side chain were designed, synthesized, and most of them exhibited good in vitro antifungal activities. Especially, compounds 5k and 6c showed excellent in vitro activities against C. albicans (MIC = 0.125, 0.0625 μg/mL), C. neoformans (MIC = 0.125, 0.0625 μg/mL), and A. fumigatus (MIC = 8.0, 4.0 μg/mL). Compound 6c also exerted superior activity to compound 5k and fluconazole in inhibiting hyphae growth of C. albicans and inhibiting drug-resistant strains of C. albicans, and it could reduce fungal burdens in mice kidney at a dosage of 1.0 mg/kg. An in vivo efficacy evaluation indicated that 6c could effectively protect mice models from C. albicans infection at doses of 0.5, 1.0, and 2.0 mg/kg. These results suggested that compound 6c deserves further investigation.     

PROGRESSIVE DAMAGE ARREST MECHANISM IN TAILORED LAMINATED PLATES WITH A CUTOUT

This study addresses the effectiveness of a simple stiffness tailoring concept to delay damage initiation, control damage progression, and improve residual strength in tensile-loaded composite plates with a central circular cutout. The tailoring concept is to simply reposit all axially oriented （0°） material into regions near the edge of the plate away from the cutout. This tailoring is done in a way so as not to affect the weight of the plate. This accomplishes several beneficial changes in the way that the plate resists loading with no increases in material cost or weight. Lowering the axial stiffness of the laminate surrounding the cutout lowers the stress concentration. Increasing the axial stiffness near edges of the plate attracts loading away from the vicinity of the cutout to further lower stresses in the critical cutout region. This study focuses on in-plane response including damage progression and residual strength as a function of the degree of tailoring and cutout size. Strength and stiffness properties typical of IM7/8551-7 preperg material were assumed and a modified version of the Hashin failure criteria was used to identify the local damage. Results show that tailoring can significantly increase the damage initiation load and the residual strength. In some cases, observed evidence shows that tailoring performs as a damage arrest mechanism.     

Palladium-catalyzed hydrosilylation of ynones to access silicon-stereogenic silylenones by stereospecific aromatic interaction-assisted Si–H activation

Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes. However, the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult. Here we report a highly enantioselective hydrosilylation of ynones, a type of carbonyl-activated alkynes, using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand. The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94% yield, 20:1 regioselectivity and 98:2 enantioselectivity. The density functional theory(DFT) calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity, in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-π interaction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond.     

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.     

FOURIER ANALYSIS OF TEMPORAL AND SPATIAL OSCILLATIONS OF TUNNELING CURRENT IN SCANNING TUNNELING MICROSCOPY

Partially oxidized Si(111) surfaces and surfaces of highly oriented pyrolytic graphite (HOPG) were studied by two different ultrahigh vacuum scanning tunneling microscope (UHV-STM) systems and by an STM system working under ambient conditions, respectively. The STM current images of partially oxidized Si(111) surfaces and HOPG surfaces were analyzed by one/two-dimensional fast Fourier transformation (1D-FFT/2D-FFT). The phenomenon of temporal oscillations of tunneling current on the partially oxidized Si(111) surfaces was detected with both UHV-STM systems. Temporal as well as spatial oscillations of tunneling current appeared in highly resolved STM current images of the Si(111) surfaces simultaneously, but both kinds of oscillations could be discriminated according to their different influence on the 2D-FFT spectra of the current images, while varying the scanning range and rate. On clean HOPG surfaces only spatial oscillations of tunneling current induced by the surface structure were observed.     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究

本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明,对于[ScO(CO₂)_n]⁺体系,在n≤4时,形成了溶剂化结构;在n=5时,形成了碳酸盐结构,实现了二氧化碳的转化. 对于[YO(CO₂)_n]⁺体系,需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO₂)_n]⁺体系中,只发现了溶剂化结构,没有观察到碳酸盐结构. 理论计算表明,[YO(CO₂)_n]⁺体系拥有最小的溶剂化结构向碳酸盐结构转化能垒,[LaO(CO₂)_n]⁺体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

Pogostone Enhances the Antibacterial Activity of Colistin against MCR-1-Positive Bacteria by Inhibiting the Biological Function of MCR-1

The emergence of the plasmid-mediated colistin resistance gene mcr-1 has resulted in the loss of available treatments for certain severe infections. Here we identified a potential inhibitor of MCR-1 for the treatment of infections caused by MCR-1-positive drug-resistant bacteria, especially MCR-1-positive carbapenem-resistant Enterobacteriaceae (CRE). A checkerboard minimum inhibitory concentration (MIC) test, a killing curve test, a growth curve test, bacterial live/dead assays, scanning electron microscope (SEM) analysis, cytotoxicity tests, molecular dynamics simulation analysis, and animal studies were used to confirm the in vivo/in vitro synergistic effects of pogostone and colistin. The results showed that pogostone could restore the bactericidal activity of colistin against all tested MCR-1-positive bacterial strains or MCR-1 mutant–positive bacterial strains (FIC < 0.5). Pogostone does not inhibit the expression of MCR-1. Rather, it inhibits the binding of MCR-1 to substrates by binding to amino acids in the active region of MCR-1, thus inhibiting the biological activity of MCR-1 and its mutants (such as MCR-3). An in vivo mouse systemic infection model, pogostone in combination with colistin resulted in 80.0% (the survival rates after monotherapy with colistin or pogostone alone were 33.3% and 40.0%) survival at 72 h after infection of MCR-1-positve Escherichia coli (E. coli) ZJ487 (blaNDM-1-carrying), and pogostone in combination with colistin led to one or more order of magnitude decreases in the bacterial burdens in the liver, spleen and kidney compared with pogostone or colistin alone. Our results confirm that pogostone is a potential inhibitor of MCR-1 for use in combination with polymyxin for the treatment of severe infections caused by MCR-1-positive Enterobacteriaceae.