Advances in the chemical analysis and biological activities of chuanxiong

Chuanxiong Rhizoma (Chuan-Xiong, CX), the dried rhizome of Ligusticum chuanxiong Hort. (Umbelliferae), is one of the most popular plant medicines in the World. Modern research indicates that organic acids, phthalides, alkaloids, polysaccharides, ceramides and cerebrosides are main components responsible for the bioactivities and properties of CX. Because of its complex constituents, multidisciplinary techniques are needed to validate the analytical methods that support CX's use worldwide. In the past two decades, rapid development of technology has advanced many aspects of CX research. The aim of this review is to illustrate the recent advances in the chemical analysis and biological activities of CX, and to highlight new applications and challenges. Emphasis is placed on recent trends and emerging techniques.     

ChemInform Abstract: A 3D Purely Inorganic Porous Framework Based on Keggin Polyoxoanions.

K₂NaH₂ [BW₁₂O₄₀]·12H₂O, prepared by the conventional aqueous method, is characterized by single crystal XRD and IR spectroscopy.     

Nickel-catalyzed C-H direct amination of benzoxazoles with secondary amines

In this article, a facile, efficient and practical method for Ni-catalyzed direct C-H amination of benzoxazole with secondary amines has been developed. This procedure requires Ni(OAc)(2)·4H(2)O as catalyst, TBHP as oxidant and acid as the additive. A variety of substituted benzoxazol-2-amines were synthesized in moderate to good yields.     

Pd-Catalyzed asymmetric hydrogenation of 3-(toluenesulfonamidoalkyl)indoles

A series of 2-substituted 3-(toluenesulfonamidoalkyl)indoles was synthesized by application of (EtO)(2)POH or iodine as the catalyst, and was hydrogenated using chiral Pd catalyst, giving the 2,3-disubstituted indolines with up to 97% ee.     

Resonant cavity enhanced (RCE) photodetectors with flat-top and steep-edge spectral response

Flat-top and steep-edge spectral response of photodetectors is important for dense wavelength-division-multiplexed system. Realization of the flat-top and steep-edge response is very challenging. In the last two decades many methods have been proposed, but the spectral response linewidth is not acceptable to wavelength-division-multiplexes system. In this paper a novel RCE photodetector with flat-top and steep-edge spectral response is presented. Using the step shaped structure, designing multiple-step-type p-type In_0.67Ga_0.33As_0.7P_0.3 contact layer and adjusting the thickness of the absorption layer, a design with good flat-top performance is demonstrated such that the quantum efficiency is 51.161% in the flat-top passband, 0.5 and 3 dB bandwidths are 0.26 and 0.4 nm, respectively.     

Insights into quinaldic acid moiety formation in thiostrepton biosynthesis facilitating fluorinated thiopeptide generation

Thiostrepton (TSR), often referred as to a parent compound in the thiopeptide family, is a bimacrocyclic member that features a quinaldic acid (QA) moiety-containing side ring appended to the characteristic core system. QA biosynthesis requires an unusual ring-expanding conversion, showing a methyl transfer onto and a rearrangement of the indole part of L-tryptophan to give a quinoline ketone. Herein, we report that the process involves the activities of the radical methyltransferase TsrT, aminotransferase TsrA, dehydrogenase TsrE, and cyclase TsrD. TsrU, a stereospecific oxidoreductase, catalyzes the further conversion of the ketone into an enantiomerically pure S-alcohol. Elucidation of this chemistry, which is common in the biosynthesis of a number of thiopeptides sharing a QA side ring system, facilitates analog generation, as shown by the achievement of region-specific fluorination of thiostrepton with the improved antibacterial activity.     

Blockade of inflammatory responses by a small-molecule inhibitor of the Rac activator DOCK2

1. Download : Download high-res image (273KB)
2. Download : Download full-size image

Highlights? CPYPP binds to DOCK2 DHR-2 domain and inhibits its catalytic activity ? CPYPP inhibits DOCK2-mediated Rac activation in cells ? The structural features of CPYPP required for its inhibitory effect were revealed ? CPYPP inhibits lymphocyte migration and activation in vitro and in vivo     

Theoretical investigation on the chiral diamine-catalyzed epoxidation of cyclic enones: mechanism and effects of cocatalyst

The asymmetric epoxidation of 2-cyclohexen-1-one with aqueous H(2)O(2) as oxidant, 1,2-diaminocyclohexane as catalyst, and a Br?nsted acid trifluoroacetic acid (TFA) as cocatalyst has been studied by performing density functional theory calculations. It is confirmed that the catalyzed epoxidation proceeds via sequential nucleophilic addition and ring-closure processes involving a ketiminium intermediate. Four possible pathways associated with two Z isomers and two E isomers of ketiminium have been explored in detail. Our calculation indicates that these four pathways have high barriers and a small energy gap between two more favorable R and S pathways. We have analyzed the effects of the TFA anion and H(2)O on the activity and enantioselectivity of catalytic epoxidation. It is found that the TFA anion acts as a counterion to stabilize the transition states of the catalytic epoxidation by hydrogen-bond acceptance, leading to decreases in the barriers of the nucleophilic addition and ring-closure processes. The most significant decrease occurred in the ring-closure step of the Z-R-pathway, resulting in H-bond-induced enantioselectivity. Our calculations also show that water cooperates with TFA to further increase the reaction rate significantly.     

A hybrid finite element approach to modeling sound radiation from circular and rectangular ducts

A numerical model based on a hybrid finite element method is developed that seeks to join sound pressure fields in interior and exterior regions. The hybrid method is applied to the analysis of sound radiation from open pipes, or ducts, and uses mode matching to couple a finite element discretization of the region surrounding the open end of the duct to wave based modal expansions for adjoining interior and exterior regions. The hybrid method facilitates the analysis of ducts of arbitrary but uniform cross section as well the study of conical flanges and here a modal expansion based on spherical harmonics is applied. Predictions are benchmarked against analytic solutions for the limiting cases of flanged and unflanged circular ducts and excellent agreement between the two methods is observed. Predictions are also presented for flanged and unflanged rectangular ducts, and because the hybrid method retains the sparse banded and symmetric matrices of the traditional finite element method, it is shown that predictions can be obtained within an acceptable time frame even for a three dimensional problem.     

垂直于界面V型缺口尖端的应力奇异性及其应用

基于双材料垂直于界面V型缺口理论,给出了单一材料和双材料裂纹问题、V型缺口问题应力强度因子的统一定义,得到了应力外推法计算双材料K_I的公式,数值算例验证了本文方法的有效性.以双材料单向拉伸和三点弯曲模型为对象,深入研究了双材料中弹性模量、泊松比、缺口深度、缺口张角对缺口尖端奇异应力场的影响,获得了一定范围内各种参数变化对缺口尖端奇异应力场的影响规律,为异体材料形成的V型缺口在应力断料中的应用提供了必要的参考依据.