Hierarchically Structured Porous Silica Spheres by Microemulsion/Vesicle Templating for Hydrodesulfurization of Fluid Catalytic Cracking Diesel

A series of hierarchically structured porous silica sphere (HSPSS) materials are successfully fabricated by a facile, one‐step microemulsion/vesicle bimodal method in a multicomponent microemulsion system of P123/n‐butanol/1,3,5‐trimethylbenzene/KCl/H₂O (surfactant/cosurfactant/oil/salt/water). The pore structures of the obtained HSPSS products consist of mesocellular foam and mesostructured vesicles. In contrast to the traditional porous silica materials the new structures combine two separate, distinct mesophases with different‐sized mesovoids in a single porous sphere. Moreover, the proportion of every mesophase in obtained HSPSS can be easily adjusted by tuning the initially added amount of n‐butanol or KCl in this multicomponent microemulsion system. When the molar ratio of KCl/tetraethoxysilane is 2.15, the obtained HSPSS material is turned into uniform mesostructured vesicle silica spheres, which consist of many small diameter vesicle particles. The hydrodesulfurization (HDS) activity of fluid catalytic cracking diesel over the HSPSS was tested. HSPSS‐0.75‐1.43 catalyst support with multiple mesoporous structures shows the highest HDS efficiency (98.5%) among all the studied catalysts.     

Superior effect of a pi-acceptor ligand (phosphine-electron-deficient olefin ligand) in the Negishi coupling involving alkylzinc reagents

Palladium-catalyzed Negishi cross-coupling involving primary and secondary alkyls, even in the presence of beta-H, can be achieved at ambient temperature using chelating ligands containing a phosphine and an electron-deficient olefin. The superior effects of the ligands were shown not only in the desired cross-coupling product yields but also in the fast reaction at mild conditions. This reaction has been also scaled up to 50 g in 0.005 mol % catalyst (20,000 TONs) at room temperature.     

Organo[2-(hydroxymethyl)phenyl]dimethylsilanes as mild and reproducible agents for rhodium-catalyzed 1,4-addition reactions

Stable and reusable tetraorganosilicon reagents, alkenyl-, aryl-, and silyl[2-(hydroxymethyl)phenyl]dimethylsilanes, undergo 1,4-addition reactions to alpha,beta-unsaturated carbonyl acceptors under mild rhodium-catalysis. The reaction tolerates a diverse range of functional groups and is applicable to gram-scale synthesis. Use of a chiral diene ligand allows the achievement of the corresponding enantioselective transformations using the tetraorganosilicon reagents, providing the silicon-based approach to optically active ketones and substituted piperidones that serve as synthetic intermediates of pharmaceuticals. A rhodium alkoxide species is suggested to be responsible for a transmetalation step on the basis of the observed kinetic resolution of a racemic chiral phenylsilane in the enantioselective 1,4-addition reaction under the rhodium-chiral diene catalysis.     

Error estimation of a kind of rational spline

This paper deals with the approximation properties of a kind of rational spline with linear denominator when the function being interpolated is C³$C^3$ in an interpolating interval. Error estimate expressions of interpolating functions are derived, convergence is established, the optimal error coefficient, _ci$c_i$, is proved to be symmetric about the parameters of the rational interpolation and it is bounded. Finally, the precise jump measurements of the second derivatives of the interpolating function at the knots are given.     

Statistical properties and kinetics of end-end contact formation of unfolded polypeptides: a systematic molecular dynamics study

The authors have systematically examined the statistical properties of the unfolded states of series of polypeptides and the kinetics of their end-to-end contact (ring closure) formation by molecular dynamics simulations. The formation of an end-to-end contact follows a single-exponential decay as measured by the first-passage time. It is shown that the shifted Gaussian chain model can be applied to describe the dimensions of glycine-rich polypeptides at high temperature. However, notable deviation from the ideal Gaussian chain model was observed at lower temperatures particularly for those polypeptides without glycines, due to the tendency to form local structures.