A 3-D numerical heat transfer model for silica aerogels based on the porous secondary nanoparticle aggregate structure

A 3-D finite volume numerical model based on the porous secondary nanoparticle random aggregate structure was developed to predict the total thermal conductivity of silica aerogels. An improved 3-D diffusion-limited cluster–cluster aggregation (DLCA) method was used to generate an approximately real silica aerogel structure. The model includes the effects of the random and irregular nanoparticle aggregate structure for silica aerogels, solid–gas coupling, combined conduction and radiation, nanoparticle and pore sizes, secondary nanoparticle porosity and contact length between adjacent nanoparticles. The results show that the contact length and porosity of the secondary aerogel nanoparticle significantly affect the aerogel microstructure for a give density and, thus, greatly affect the total thermal conductivity of silica aerogels. The present model is fully validated by experimental results and is much better than the model based on a periodic cubic array of full density primary nanoparticles, especially for higher densities. The minimum total thermal conductivity for various silica aerogel microstructures can be well predicted by the present model for various temperatures, pressures and densities.     

An organocatalytic Michael-aldol cascade: formal [3+2] annulation to construct enantioenriched spirocyclic oxindole derivatives

An efficient organocatalytic Michael-aldol cascade reaction for the asymmetric synthesis of spirocyclic oxindole derivatives fused with tetrahydrothiophenes has been developed through a formal [3+2] annulation strategy.     

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

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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.