化学酶法动态动力学拆分胺类化合物研究进展

论述了动态动力学拆分的原理,介绍了化学酶法拆分消旋体胺类化合物的反应和近年来的研究进展;指出手性胺是构成许多中间体的基础化合物,化学酶法动态动力学拆分是制备单一手性胺类化合物的重要方法.     

Novel α-arylnitriles synthesis via Ni-catalyzed cross-coupling of α-bromonitriles with arylboronic acids under mild conditions

An applicable and easy-handling Ni-catalyst can be used to promote direct arylation of α-bromonitriles with various arylboronic acids to construct α-arylnitriles under mild conditions. The methodology tolerates β-hydrogens and functional groups in the substrates.     

Chiral salen-metal derivatives of polyoxometalates with asymmetric catalytic and photocatalytic activities

Immobilization of the chiral salen-metal complex [Mn(III)(salen)(H(2)O)(2)ClO(4)] on the Keggin-type polyoxometalate (POM) skeletons leads to the isolation of POM derivatives functionalized with chiral salen-metal complexes, which represent the first examples of introducing chiral salen-metal complexes into the POM systems.     

Hydrothermal synthesis, structures, and luminescent properties of zinc(II) and cadmium(II) phosphonates with a 3D framework structure using terephthalate as second linkers

By introduction of 1,4-benzenedicarboxylic acid as a second organic ligand, two new divalent metal(II) phosphonates with a 3D framework structure, namely, [Zn(HL1)(bdc)(0.5)] (1) and [Cd(1.5)(HL2)(bdc)(0.5)] (2) (H(2)L1 = H(2)O(3)PCH(NH(2))C(6)H(5), H(3)L2 = H(2)O(3)PCH(2)-NC(5)H(9)-COOH, H(2)bdc = HOOCC(6)H(4)COOH), have been synthesized under hydrothermal conditions. The two compounds show three-dimensional (3D) framework structure with infinite two-dimensional (2D) networks pillared by H(2)bdc. For compound 1, the {ZnO(4)} polyhedra are interconnected by phosphonate groups into a 2D layer, and the adjacent layers are further cross-linked via the bdc(2-) anions to generate a three-dimensional framework structure with two types of channel system along the c-axis. A notable feature of compound 1 is the presence of alternate left- and right-handed helical chains in the structure. In compound 2, the inorganic chains, composed of {Cd(1)O(7)}, {Cd(2)O(4)} and {CPO(3)} polyhedra, are linked by HL2(2-) ligands to form a double layer structure in the ab plane, and the adjacent layers are further linked by the bdc(2-) anions to form a 3D framework structure with one-dimensional channel systems along the a-axis. Luminescence properties of compounds 1 and 2 have also been studied.     

New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances

BiOCl/BiOI composites with a visible light response were prepared by a simple hydrothermal method. Even though both single BiOCl and BiOI show low photocatalytic activity, BiOCl/BiOI composites provide enhanced efficiency in decomposing organic compounds including Methyl Orange (MO) and Rhodamine B (RhB). Furthermore, the 20%BiOCl/BiOI composite shows the highest efficiency for decomposing MO, while the highest performance is observed for the degradation of RhB over 70%BiOCl/BiOI composite. A possible photocatalytic mechanism has been proposed based on the relative experiments and the band positions of BiOCl and BiOI.     

1,1-carboboration of 1-alkynes: a conceptual alternative to the hydroboration reaction

Strongly electrophilic boranes R-B(C(6)F(5))(2) react readily with a variety of 1-alkynes by means of a 1,1-carboboration reaction to yield alkenylborane products, which can subsequently be used as reagents in metal catalyzed cross-coupling reactions.     

Qualitative and quantitative analyses of Epimedium wushanense by high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry

A new HPLC-DAD-ESI-MS(n) method was developed for rapid separation, characterization and quantitation of flavonoids in Epimedium wushanense, a popular Chinese herbal medicine. For qualitative identification, a total of 37 compounds were characterized from the underground and aerial parts of E. wushanense. Among them, 28 compounds were prenylated flavonoids, and 23 were confirmed by comparing with reference standards. For quantitative analysis, 12 major flavonoids including kaempferol glycosides, desmethylicaritin glycosides, and icaritin glycosides were simultaneously determined by HPLC/UV. Samples were separated on a Waters Symmetry C(18) column at 35 °C eluted with a gradient three-component mobile phase of acetonitrile, methanol, and water containing 0.03% v/v formic acid. All the flavonoids showed good linearity (r(2) ≥0.9997). The recoveries varied from 92.6 to 106.1% at three concentration levels. This method was applied to the determination of 20 samples of different geographical sources, harvesting time, and plant parts. Contents of the predominant flavonoid, epimedin C, ranged from 1.4 to 5.1% in aerial parts and 1.0 to 2.8% in underground parts. The methods established in this paper were simple and reliable and could be used for the quality control of E. wushanense.     

Multiple solutions for the laminar flow in a porous pipe with suction at slowly expanding or contracting wall

In this paper, the asymptotic solution for the similarity equation of the laminar flow in a porous pipe with suction at expanding and contracting wall has been obtained using the singular perturbation method. However, this solution neglects exponentially small terms in the matching process. To take into account these exponentially small terms, a method involving the inclusion of exponentially small terms in a perturbation series was used to find the two solutions analytically. The series involving the exponentially small terms and expansion ratio predicts dual solutions. Furthermore, the result indicates that the expansion ratio has much important influence on the solutions. When the expansion ratio is zero, it is a special case that Terrill has discussed.     

Existence of optimal solutions for general stochastic linear complementarity problems

In this paper we show the solvability of the expected residual minimization (ERM) formulation for the general stochastic linear complementarity problem (SLCP) under mild assumptions. The properties of the ERM formulation are dependent on the choice of NCP functions. We focus on the ERM formulations defined by the “min” NCP function and the penalized FB function, both of which are nonconvex programs on the nonnegative orthant.     

Representing a Functional Curve by Curves with Fewer Peaks

In this paper, we study the problems of (approximately) representing a functional curve in 2-D by a set of curves with fewer peaks. Representing a function (or its curve) by certain classes of structurally simpler functions (or their curves) is a basic mathematical problem. Problems of this kind also find applications in applied areas such as intensity-modulated radiation therapy (IMRT). Let f\bf f be an input piecewise linear functional curve of size n. We consider several variations of the problems. (1) Uphill–downhill pair representation (UDPR): Find two nonnegative piecewise linear curves, one nondecreasing (uphill) and one nonincreasing (downhill), such that their sum exactly or approximately represents f\bf f. (2) Unimodal representation (UR): Find a set of unimodal (single-peak) curves such that their sum exactly or approximately represents f\bf f. (3) Fewer-peak representation (FPR): Find a piecewise linear curve with at most k peaks that exactly or approximately represents f\bf f. Furthermore, for each problem, we consider two versions. For the UDPR problem, we study its feasibility version: Given ε>0, determine whether there is a feasible UDPR solution for f\bf f with an approximation error ε; its min-ε version: Compute the minimum approximation error ε ^∗ such that there is a feasible UDPR solution for f\bf f with error ε ^∗. For the UR problem, we study its min-k version: Given ε>0, find a feasible solution with the minimum number k ^∗ of unimodal curves for f\bf f with an error ε; its min-ε version: given k>0, compute the minimum error ε ^∗ such that there is a feasible solution with at most k unimodal curves for f\bf f with error ε ^∗. For the FPR problem, we study its min-k version: Given ε>0, find one feasible curve with the minimum number k ^∗ of peaks for f\bf f with an error ε; its min-ε version: given k≥0, compute the minimum error ε ^∗ such that there is a feasible curve with at most k peaks for f\bf f with error ε ^∗. Little work has been done previously on solving these functional curve representation problems. We solve all the problems (except the UR min-ε version) in optimal O(n) time, and the UR min-ε version in O(n+mlog m) time, where m<n is the number of peaks of f\bf f. Our algorithms are based on new geometric observations and interesting techniques.