CF3C(O)F水合作用的热力学和动力学理论研究

由于氟氟烃（CFCs）对大气臭氧层有破坏作用，人们拟以另外的化合物来代替它，CF3CX2H（X＝H，CI，F）可能是一类合适的取代物．但人们对它及其反应产物对大气的影响还不清楚.CFaC（0）F是CFaCX。H大气光氧化过程的终产物之一[1－3］，其在大气中的后继反应行为将直接关系到CF2     

Rigid nanoscopic containers for highly dispersed, stable metal and bimetal nanoparticles with both size and site control

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.     

Oxidation of heme to beta- and delta-biliverdin by Pseudomonas aeruginosa heme oxygenase as a consequence of an unusual seating of the heme

The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO.     

Computational and experimental studies of the effect of substituents on the singlet-triplet energy gap in phenyl(carbomethoxy)carbene

The effect of aromatic substitution on the singlet-triplet energy gap in substituted phenyl(carbomethoxy)carbene (X-Ph-C-CO(2)CH(3), PCC) has been explored by time-resolved infrared (TRIR) spectroscopy and gas-phase computational methods. The ground state of para-substituted PCC is calculated to change from the triplet state in p-NO(2)-PCC (Delta G(ST) = 6.1 kcal/mol) to the singlet state in p-NH(2)-PCC (Delta G(ST) = -2.8 kcal/mol). The absence of solvent perturbation in the TRIR spectra of p-N(CH(3))(2)-PCC (which should have electronic properties similar to p-NH(2)-PCC) and parent PCC is consistent with their ground states lying > +/-2 kcal/mol from the next available electronic state, in line with the computational results. The observation of solvent perturbation in the TRIR spectra of p-OCH(3)-PCC and p-CH(3)-PCC implies that their ground states lie < +/-1 kcal/mol from their next available electronic state. This is in agreement with our computational results, which predict a gas-phase Delta G(ST) of -0.8 and 1.6 kcal/mol for p-OCH(3)-PCC and p-CH(3)-PCC as compared to Delta G(ST) values of -3.9 and -1.3 kcal/mol from polarizable continuum model (PCM) calculations with acetonitrile as a solvent. Gas-phase computational results for the meta- and ortho-substituted PCC species are also presented, along with selected linear free energy (LFE) relationships for the para and meta species.     

基于RPR的高生存性网络

弹性分组环(RPR)技术定义了一种新型的媒体接入控制(MAC)层协议,采用了共享介质传输和空间复用协议以及低于50 ms的故障恢复保护的弹性机制,支持服务等级协定(SLA,Service Level Agreement),即插即用,基于MAC的高速交换,可承载具有突发性的IP业务,同时支持传统的语音传送,是未来城域网技术的重要发展方向.光纤技术的飞速发展使得RPR不再仅仅局限于城域网,还可以用于广域网.文章在基于RPR的低于50 ms的故障恢复保护的基础上,提出了具有高生存性的解决方案.     

过硫酸盐活化高级氧化新技术

过硫酸盐在热、光、过渡金属催化等条件激活下产生强氧化性的硫酸根自由基·SO₄^-。基于·SO₄^-的过硫酸盐活化“高级氧化技术”在环境污染治理领域的应用,是刚刚发展起来的崭新的研究方向,具有广阔的应用前景。本文在分析其基本原理的基础上,综述了过硫酸盐活化技术在国内外土壤地下水有机污染原位修复、难降解有机废水处理等环境污染治理方面的研究进展,并就存在问题进行了研究展望。     

Unveiling Latent Structure of Venture Capital Syndication Networks

Venture capital (VC) is a form of private equity financing provided by VC institutions to startups with high growth potential due to innovative technology or novel business models but also high risks. To against uncertainties and benefit from mutual complementarity and sharing resources and information, making joint-investments with other VC institutions on the same startup are pervasive, which forms an ever-growing complex syndication network. Attaining objective classifications of VC institutions and revealing the latent structure of joint-investment behaviors between them can deepen our understanding of the VC industry and boost the healthy development of the market and economy. In this work, we devise an iterative Loubar method based on the Lorenz curve to make objective classification of VC institutions automatically, which does not require setting arbitrary thresholds and the number of categories. We further reveal distinct investment behaviors across categories, where the top-ranked group enters more industries and investment stages with a better performance. Through network embedding of joint investment relations, we unveil the existence of possible territories of top-ranked VC institutions, and the hidden structure of relations between VC institutions.     

One-Step Calcination to Gain Exfoliated g-C3N4/MoO2 Composites for High-Performance Photocatalytic Hydrogen Evolution

The difficulty of exposing active sites and easy recombination of photogenerated carriers have always been two critical problems restricting the photocatalytic activity of g-C₃N₄. Herein, a simple (NH₄)₂MoO₄-induced one-step calcination method was successfully introduced to transform bulk g-C₃N₄ into g-C₃N₄/MoO₂ composites with a large specific surface area. During the calcination, with the assistance of NH₃ and water vapor produced by ammonium molybdate, the pyrolytical oxidation and depolymerization of a g-C₃N₄ interlayer were accelerated, finally realizing the exfoliation of the g-C₃N₄. Furthermore, another pyrolytical product of ammonium molybdate was transformed into MoO₂ under an NH₃ atmosphere, which was in situ loaded on the surface of a g-C₃N₄ nanosheet. Additionally, the results of photocatalytic hydrogen evolution under visible light show that the optimal g-C₃N₄/MoO₂ composite has a high specific surface area and much improved performance, which is 4.1 times that of pure bulk g-C₃N₄. Such performance improvement can be attributed to the full exposure of active sites and the formation of abundant heterojunctions. However, with an increasing feed amount of ammonium molybdate, the oxidation degree of g-C₃N₄ was enhanced, which would widen the band gap of g-C₃N₄, leading to a weaker response ability to visible light. The present strategy will provide a new idea for the simple realization of exfoliation and constructing a heterojunction for g-C₃N₄ simultaneously.     

5-呋喃基-1-苯并噻唑基吡唑啉类荧光化合物的合成及光谱分析

吡唑啉衍生物具有高的蓝色荧光,并且具有高量子效率,很易于用作发光材料中电子传输层。依据Schellhammer经验中化学结构与荧光性关系,在吡唑啉的1-位引入了苯并噻唑基,3-位引入苯基衍生物,使其具有荧光性,5-位引入呋喃基作为助色团,可使荧光波长红移,增加荧光性。文章设计并合成了六种5-位引入呋喃基苯并噻唑吡唑啉类荧光化合物,通过红外光谱、荧光光谱、1HNMR、元素分析对合成的化合物进行了表征,表明这类化合物具有良好的荧光性,其最大发射波长在440～460 nm之间,经过分析得知其荧光强度的大小与衍生物中不同的取代基有关。