Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections

We report re-optimization of a recently proposed long-range corrected (LC) hybrid density functional [J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2008, 128, 084106] to include empirical atom-atom dispersion corrections. The resulting functional, omegaB97X-D yields satisfactory accuracy for thermochemistry, kinetics, and non-covalent interactions. Tests show that for non-covalent systems, omegaB97X-D shows slight improvement over other empirical dispersion-corrected density functionals, while for covalent systems and kinetics it performs noticeably better. Relative to our previous functionals, such as omegaB97X, the new functional is significantly superior for non-bonded interactions, and very similar in performance for bonded interactions.     

Tandem addition/cyclization reaction of organozinc reagents to 2-alkynyl aldehydes: highly efficient regio- and enantioselective synthesis of 1,3-dihydroisobenzofurans and tetrasubstituted furans

The enantioselective addition of organozinc reagents to some 2-alkynyl benzaldehydes and the subsequent regioselective cyclization step was performed in one pot to form chiral 1,3-dihydroisobenzofurans with good product yields and excellent regio- and enantioselectivities. In the case of 2-alkynylcycloalkene aldehydes, tetrasubstituted furans were obtained in good product yields through a 1, 5-hydride shift of the preformed cyclization product.     

Preparation of a novel molecularly imprinted polymer by a sol-gel process for on-line solid-phase extraction coupled with high performance liquid chromatography to detect trace enrofloxacin in fish and chicken samples

A molecularly imprinted functionalized sol-gel has been prepared by using enrofloxacin (ENRO) as a template, 3-aminopropyltriethoxysilane as the functional monomer, tetraethoxysilicane as a cross-linker. This ENRO-imprinted polymer was evaluated by static, kinetic adsorption and selective experiments. The polymer displays good selectivity, and fast kinetics in terms of adsorption and desorption. The material was applied as a sorbent for on-line determination of trace ENRO by high performance liquid chromatography, with a focus on biological matrices. At a loading flow rate of 1.0 mL min^-1 for sampling 50 mL, the enrichment factor and limit of detection (LOD; at S/N?=?3) are 566 and 8 ng L^-1, respectively. The peak area precision (the LOD for nine replicate detections of 0.1 µg L^-1 ENRO) is 4.4%. ENRO in fish and chicken muscle was determined at three spiked levels with recoveries ranging from 70% to 82%.     

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利用太阳能光解水制氢和降解有机污染物对解决能源和环境问题具有重要意义，而可见光响应催化剂的研制是实现太阳光高效利用的关键。本文从可见光响应光催化剂的设计思路出发，从电子能带结构、固溶体结构和微观复合结构三方面介绍了目前光催化剂的研究进展和发展方向。     

Assessment of Joule heating and its effects on electroosmotic flow and electrophoretic transport of solutes in microfluidic channels

Joule heating is inevitable when an electric field is applied across a conducting medium. It would impose limitations on the performance of electrokinetic microfluidic devices. This article presents a 3-D mathematical model for Joule heating and its effects on the EOF and electrophoretic transport of solutes in microfluidic channels. The governing equations were numerically solved using the finite-volume method. Experiments were carried out to investigate the Joule heating associated phenomena and to verify the numerical models. A rhodamine B-based thermometry technique was employed to measure the solution temperature distributions in microfluidic channels. The microparticle image velocimetry technique was used to measure the velocity profiles of EOF under the influence of Joule heating. The numerical solutions were compared with experimental results, and reasonable agreement was found. It is found that with the presence of Joule heating, the EOF velocity deviates from its normal "plug-like" profile. The numerical simulations show that Joule heating not only accelerates the sample transport but also distorts the shape of the sample band.     

Theoretical Study of Adsorption and Dehydrogenation of C2H4 on Cu(410)?

Adsorption and dehydrogenation of ethylene on Cu(410) surface are investigated with firstprinciples calculations and micro-kinetics analysis. Ethylene dehydrogenation is found to start from the most stable π-bonded state instead of the previously proposed di-σ-bonded state. Our vibrational frequencies calculations verify the π-bonded adsorption at step sites at low coverage and low surface temperature and di-σ-bonded ethylene on C-C dimer (C₂H₄-CC) is proposed to be the species contributing to the vibrational peaks experimentally observed at high coverage at 193 K. The presence of C₂H₄-CC indicates that the dehydrogenation of ethylene on Cu(410) can proceed at temperature as low as 193 K.     

Bifunctional cinchona alkaloids-catalyzed asymmetric [4+2] cycloaddition reaction of β,γ-unsaturated α-keto esters with oxazolones

A highly enantioselective [4+2] cycloaddition reaction of β,γ-unsaturated α-keto esters with oxazolones was realized with readily available cinchona alkaloids as the catalysts. Using this reaction, a series of highly functionalized δ-lactones with adjacent α-quaternary-β-tertiary stereocenters were obtained in high yields (up to 97%) and with good-to-excellent enantioselectivities (up to 97% ee).     

低共熔溶剂中原位合成ZIF-8膜及其气体分离性能

在α-氧化铝载体上,采用原位合成法,在尿素/氯化胆碱低共熔溶剂中合成了ZIF-8膜。采用X射线衍射(XRD)和扫描电子显微镜(SEM)对合成的ZIF-8膜进行了表征。考察了反应溶液浓度、降温速率对ZIF-8膜合成的影响。通过优化合成条件合成了表面平整致密,厚度为8 μm的ZIF-8膜。采用Wicke-Kallenbach技术对优化条件下合成的ZIF-8膜进行了单组分气体渗透和双组分混合气体分离性能表征。在室温(293 K)下,ZIF-8膜对H2/CO2、H2/O2、H2/N2、H2/CH4双组分气体的分离系数分别为7.4、5.2、9.1、13.8,均大于相应的努森扩散分离系数,说明合成的ZIF-8膜具有分子筛分性能。     

Investigation of Structural Evolution of SnO2 Nanosheets towards Electrocatalytic CO2 Reduction

In‐depth understanding of the catalytic active sites is of paramount importance for the design of efficient electrocatalysts for CO₂ conversion. Here we highlight the structural evolution of SnO₂ nanosheets for electrocatalytic CO₂ reduction. The transformation of SnO₂ into metallic Sn would occur on the surface of catalyst during the catalytic process, followed by enhanced selectivity and activity for the conversion of CO₂ to HCOOH. Electrocatalytic characterization and structural analysis demonstrate that the metallic Sn derived from structural evolution plays a dominant role in the CO₂ reduction to HCOOH. This work deepens the understanding of the catalytic mechanism and provides a new pathway for the rational design of advanced electrocatalysts for CO₂ reduction.     

Fluorobenziodoxole−BF3 Reagent for Iodo(III)etherification of Alkynes in Ethereal Solvent

A combination of fluorobenziodoxole (FBX) and BF₃ ? OEt₂ in cyclopentyl methyl ether promotes regio‐ and stereoselective addition of benziodoxole and methoxy groups to alkynes. This difunctionalization reaction tolerates a variety of functionalized internal and terminal alkynes to afford trans‐β‐alkoxyvinylbenziodoxoles, which represent versatile precursors to stereochemically well‐defined multisubstituted vinyl ethers. The reaction is proposed to involve cleavage of the I?F bond of FBX by BF₃, followed by electrophilic activation of the alkyne by the resulting cationic I^III species that triggers the nucleophilic addition of the ethereal oxygen.