Heterogeneous oxidation of cyclohexanone catalyzed by TS-1:Combined experimental and DFT studies

The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite TS-1 using aqueous H2O2 as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H2O2 was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H2O2 was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H2O2 catalyzed by a hollow TS-1 zeolite wereε-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite.     

Synthesis of polybutadienes with controllable microstructure by a novel binary Nd(3-NBSO3)3/alkylaluminum catalyst system

The polymerization of 1,3-butadiene was examined by using a novel halogen-free neodymium m-nitrobenzenesulfonate(Nd(3-NBSO3)3·donors)/alkylaluminum binary catalyst system. The catalyst showed fairly high activity and controllable selectivity. The microstructure of the resultant polymer was adjustable by variation of electron donor and/or the alkylaluminum. 13C-NMR and thermal analysis demonstrate that the produced polybutadienes have stereo-block chain structures of cis-1,4 and trans-1,4 segments with adjustable Tm and Tc. The neodymium sulfonate-based catalyst is believed to be significant in regulating the chain structure of polydienes and in exploring 1,3-diene polymerization mechanism.     

Conversion of phenylacetonitrile in supercritical alcohols within a system containing small volume of water

The reaction of phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water was studied. The effects of various operating conditions, such as reaction temperature, reaction time, the mole ratio of phenylacetonitrile/water/methanol or ethanol on the product yield were systematically investigated. The optimal yield of methyl phenylacetate for phenylacetonitrile in supercritical methanol in a system containing a small volume of water was 70 % at 583 K and 2.5 h. The optimal yield of ethyl phenylacetate for phenylacetonitrile in supercritical ethanol with a small volume of water was 80 % at 583 K and 1.0 h. At the same time, a feasible mechanism was proposed for phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water.     

在碱金属/液氨作用下两类还原反应的机理探讨

碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Birch还原反应。一般认为这两种反应均生成了自由基负离子中间体。本文结合近几年的文献报道,对它们的机理进行进一步的探讨。     

UV‐Responsive Supramolecular Vesicles with Double Hydrophobic Chains

In order to improve the stability of polymeric vesicles, supramolecular vesicles are developed via self‐assembly of the inclusion of γ‐cyclodextrin (γ‐CD) and 1‐pyrenemethyl palmitate (Py‐pal). The inclusion has one hydrophilic head and double hydrophobic tails, which looks like the phospholipid. From the transmission electron microscopy (TEM) image, it can be observed that the average diameter of supramolecular vesicles is approximately 55 nm and there is a huge cavity in supramolecular vesicles. Due to the photo‐breakable ester of Py‐pal, supramolecular vesicles are broken under UV irradiation. Supramolecular vesicles are used as UV‐responsive drug carriers to release the hydrophilic drug such as doxorubicin hydrochloride (DOX•HCl).

     

Improved thermal and mechanical properties of bacterial cellulose with the introduction of collagen

Composite films comprised of bacterial cellulose (BC) and collagen (COL) were developed using BC hydrogel membranes as the base material and COL as the reinforcing material. Glutaraldehyde (GT) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC·HCl) were then used as cross-linking agents to prepare cross-linked BC/COL composite films by a wet chemical method. The effects of chemical cross-linking on the thermal and mechanical properties of composite films were investigated in detail. The COL molecules were adsorbed and deposited inside of 3D nanofiber networks of BC, coated on the surface of BC fibers. Chemical bonds formed between BC molecules, and between BC and COL molecules after cross-linking. Compared with BC, the obtained composite films showed 57.9 and 70.8% improvement in tensile strength after being cross-linked by GT and EDC·HCl, respectively. Cross-linking also enhanced the thermal stability of the specimens.     

On Galvin’s theorem for compact Hausdorff right-topological semigroups with dense topological centers

We generalize an important theorem of Fred Galvin from the Stone-Cˇech compactification βT of any discrete semigroup T to any compact Hausdorff right-topological semigroup with a dense topological center;and then apply it to Ellis' semigroups to prove that a point is distal if and only if it is IP*-recurrent, for any semiflow(T, X) with arbitrary compact Hausdorff phase space X not necessarily metrizable and with arbitrary phase semigroup T not necessarily cancelable.     

A new block preconditioner for complex symmetric indefinite linear systems

Using the equivalent block two-by-two real linear systems and relaxing technique, we establish a new block preconditioner for a class of complex symmetric indefinite linear systems. The new preconditioner is much closer to the original block two-by-two coefficient matrix than the Hermitian and skew-Hermitian splitting (HSS) preconditioner. We analyze the spectral properties of the new preconditioned matrix, discuss the eigenvalue distribution and derive an upper bound for the degree of its minimal polynomial. Finally, some numerical examples are provided to show the effectiveness and robustness of our proposed preconditioner.     

A Complete Solution to the Existence of ‐Cycle Frames of Type

The existence problem of a ‐cycle frame of type is now solved for any quadruple .