Advances in Enantioselective Construction of Trifluoromethoxylated Stereogenic Carbon Centers

In recent years,the trifluoromethoxy(OCF3)functional group has received extensive attention in phar-maceuticals,agrochemicals and material sciences.However,the methods for the enantioselective syn-thesis of trifluoromethoxylated stereogenic carbon centers are rare owing to the nature of easy decom-position of OCF3 anion and limited OCF3 reagent.And the asymmetric trifluoromethoxylation will be a hot research topic in near future due to the unique biological properties of a single isomer.This article mainly focuses on the recent advances in the enantioselectiveconstruction of trifluoromethoxylated stereogenic carbon centers.     

Preparation and characterization of covalently bonded PVA/Laponite/HAPI nanocomposite multilayer freestanding films by layer‐by‐layer assembly

The layer‐by‐layer (LBL) assembly technique is an attractive method to make functional multilayer thin films and has been applied to fabricate a wide range of materials. LBL materials could improve optical transmittance and mechanical properties if the film components were covalently bonded. Covalently bonded nanocomposite multilayer films were prepared by employing hydrophilic aliphatic polyisocyanate (HAPI) as the reactive component, to react with Laponite and polyvinyl alcohol (PVA). FT‐IR spectra suggested that HAPI reacted with Laponite and PVA at ambient temperature rapidly. Ellipsometry measurement showed that the film thickness was in linear growth. The influences of HAPI on the optical, mechanical and thermal properties of the films were investigated by UV‐Vis spectroscopy, tensile stress measurement, DSC and TGA. The obtained results showed that the optical transmittance and mechanical strength were enhanced when the film components were covalently bonded by HAPI. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 545–551     

A GENERALIZED RESULT ON THE POLYNOMIAL-LIKE ITERATIVE EQUATION

Most results on the polynomial-like iterative equation are given under the condition that the given function is monotone,while a work by L.Liu and X.Gong gets nonmonotone PM solutions with height 1 when the given function is of the same case.Removing the condition on height for the given function,we first give a method to assert the nonexistence of C⁰solutions,then present equivalent conditions for the existence of PM solutions with finite height.Finally,as an application of the equivalent conditions,we construct the PM solutions in the case that the given function has one fort.     

Simultaneous determination of calycosin‐7‐O‐β‐d‐glucoside,calycosin, formononetin,astragaloside IV and schisandrin in rat plasma by LC‐MS/MS: application to a pharmacokinetic study after oral administration of Shenqi Wuwei chewable tablets

A rapid, sensitive and reliable high‐performance liquid chromatography–mass spectrometry (LC‐MS/MS) method was developed and validated for simultaneous quantification of the five main bioactive components, calycosin, calycosin‐7‐O‐β‐d ‐glucoside, formononetin, astragaloside IV and schisandrin in rat plasma after oral administration of Shenqi Wuwei chewable tablets. Plasma samples were extracted using solid‐phase extraction separated on a CEC₁₈ column and detected by MS with an electrospray ionization interface in multiple‐reaction monitoring mode. Calibration curves offered linear ranges of two orders of magnitude with r > 0.995. The method had a lower limit of quantitation of 0.1, 0.02, 0.1, 1 and 0.1 ng/mL for calycosin, calycosin‐7‐O‐β‐d ‐glucoside, formononetin, astragaloside IV and schisandrin, respectively. Intra‐ and inter‐day precisions (relative standard deviation) for all analytes ranged from 0.97 to 7.63% and from 3.45 to 10.89%, respectively. This method was successfully applied to the pharmacokinetic study of the five compounds in rats after oral administration of Shenqi Wuwei chewable tablets. Copyright © 2014 John Wiley & Sons, Ltd.     

The Effect of Hispidulin,a Flavonoid from Salvia plebeia,on Human Nasopharyngeal Carcinoma CNE-2Z Cell Proliferation,Migration, Invasion,and Apoptosis

Nasopharyngeal carcinoma (NPC) is a common malignant head and neck tumor. Drug resistance and distant metastasis are the predominant cause of treatment failure in NPC patients. Hispidulin is a flavonoid extracted from the bioassay-guided separation of the EtOH extract of Salvia plebeia with strong anti-proliferative activity in nasopharyngeal carcinoma cells (CNE-2Z). In this study, the effects of hispidulin on proliferation, invasion, migration, and apoptosis were investigated in CNE-2Z cells. The [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] (MTT) assay and the colony formation assay revealed that hispidulin could inhibit CNE-2Z cell proliferation. Hispidulin (25, 50, 100 μM) also induced apoptosis in a dose-dependent manner in CNE-2Z cells. The expression of Akt was reduced, and the expression of the ratio of Bax/Bcl-2 was increased. In addition, scratch wound and transwell assays proved that hispidulin (6.25, 12.5, 25 μM) could inhibited the migration and invasion in CNE-2Z cells. The expressions of HIF-1α, MMP-9, and MMP-2 were decreased, while the MMPs inhibitor TIMP1 was enhanced by hispidulin. Moreover, hispidulin exhibited potent suppression tumor growth and low toxicity in CNE-2Z cancer-bearing mice at a dosage of 20 mg/kg/day. Thus, hispidulin appears to be a potentially effective agent for NPC treatment.     

Highly Dense Isolated Metal Atom Catalytic Sites: Dynamic Formation and In Situ Observations

Atomically dispersed noble‐metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface‐mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X‐ray diffraction. A combination of electron microscopy images with X‐ray absorption spectra demonstrated that the silver atoms were anchored on five‐fold oxygen‐terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation at low temperature. This work provides a general strategy for designing atomically dispersed noble‐metal catalysts with highly dense active sites.     

基于风险理念的黄土滑坡调查与编图研究

滑坡风险管理在国外已成为缓减地质灾害损失的重要手段,我国(香港地区除外)在滑坡风险管理方面起步较晚,尚处于探索阶段,目前正在开展的地质灾害详细调查项目尚没有很好地采用国际上流行的风险管理的理念和技术方法。本文以国土资源大调查部署实施的延安市宝塔区地质灾害详细调查示范项目为例,借鉴国际滑坡和工程边坡联合技术委员会制订的《土地利用规划滑坡易发性、危险性、风险区划指南》^[1] 及相关最新文献^[2~7],剖析了《滑坡崩塌泥石流灾害详细调查规范》和地质灾害详细调查项目实施中存在的问题及其与风险管理之间的差距。认为我国目前开展的地质灾害详细调查总体上属于中比例尺,还没有达到详细比例尺; 调查精度包括了高精度、中精度和低精度3种精度层次。提出了基于GIS、DEM、RS、地面调查等技术方法的黄土滑坡调查与编图的工作思路和技术路线。从1 :5万滑坡调查与风险编图、1 :1万滑坡调查与风险编图、村镇及重要基础设施滑坡调查与风险评估、典型滑坡点风险调查与评估4个方面,总结了基于风险管理理念的延安市宝塔区黄土滑坡调查与风险编图实例,旨在为《滑坡崩塌泥石流灾害详细调查规范》的修编和地质灾害详细调查项目更好地实施提供借鉴。     

The Active Sites of a Rod‐Shaped Hollandite DeNOx Catalyst

The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low‐temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod‐shaped morphology and one‐dimensional tunnels. Electron microscopy and synchrotron X‐ray diffraction determine the surface and crystal structures of the one‐dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X‐ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi‐tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions.     

pH/temperature double responsive behaviors and mechanical strength of laponite‐crosslinked poly(DEA‐co‐DMAEMA) nanocomposite hydrogels

A nanocomposite (NC) hydrogel crosslinked by inorganic Laponite XLG was successfully synthesized via in situ free radical polymerization of monomers N,N‐diethylacrylamide and (2‐dimethylamino) ethyl methacrylate (DMAEMA). Polymerization was carried out at room temperature due to the accelerating effect of DMAEMA. The as‐prepared hydrogels displayed controlled transformation in optical transmittance and volume in response to small diversification of environmental factors, such as temperature and pH. The compressive strength of swollen D_6:1G₆ hydrogels was as high as 2219 kPa while compressive strain was 95%. Cyclic compression measurement exhibited good elastic properties of NC hydrogels. This work provides a facile method for fabricating stimuli‐responsive hydrogels with superior mechanical property. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 876–884     

无处不在的化学——化学动力学

Starting from an example of how to extinguish a fire, this article illustrates how chemical dynamics plays a role in our life. It also introduces what is chemical dynamics and the contribution of Dutch chemist Jacobus H. van't Hoff to chemical dynamics. The horse racing analogy is used to illustrate how the amount of reactants, energy, catalysts and other factors affect the chemical reaction rate.