Effect of sample and substrate electric properties on the electric field enhancement at the apex of SPM nanotips

Finite element (FE) models were built to define the optimal experimental conditions for tip-enhanced Raman spectroscopy (TERS) of thin samples. TERS experimental conditions were mimicked by including in the FE models dielectric or metallic substrates with thin dielectric samples and by considering the wavelength dependence of the dielectric properties for the metallic materials. Electromagnetic coupling between the substrate/sample and the SPM tips led to dramatic changes of both the spatial distribution and magnitude of the scattered electric field which depended on the substrate dielectric permittivity and excitation wavelength. Raman scattering as high as 10(8) with a spatial resolution of approximately 8 nm was estimated for gold SPM tips and gold substrate when excitation is performed at 532 nm (near-resonance wavelength). For dielectric samples (approximately 4 nm thick), the enhancement of Raman scattering intensity is estimated at approximately 10(5); this does not depend significantly on the sample dielectric permittivity for dielectric samples. These results suggest that TERS experimental conditions should be estimated and optimized for every individual application considering the geometric factors and electric properties of the materials involved. Such optimizations could enlarge the range of applications for TERS to samples eliciting weaker intrinsic Raman scattering, such as biological samples.     

An experimental and computer modelling study of the photochemical reaction of tert-butylguaiacylcarbinol sensitized by p-methoxypropiophenone in aerated dimethoxyethane solution

The kinetics of the photochemical reaction of tert-butylguaiacyl-carbinol sensitized by p-methoxypropiophenone in aerated dimethoxyethane solution were measured experimentally. In contrast with the same model system in oxygen-free solution, the concentration of the sensitizer in the presence of oxygen remained constant within the experimental error limits. This implies that a regenerative loop exists for the sensitizer which operates efficiently if oxygen is present. The efficiency of this regenerative loop seems to depend on the substrate concentration. The rate of substrate consumption was found to be considerably faster than the rate obtained previously for the oxygen-free system.

The kinetics of substrate and sensitizer consumption and product formation were also studied by computer modelling, employing a reaction set consisting of 91 elementary reactions and 58 different species. Using this reaction set the kinetics of the substrate consumption were simulated for 4 h with good agreement with the experimental results. The calculated yields of the various reaction products were in fairly good agreement with previous experimental results for a similar model system. For the sensitizer, however, a small disagreement with the experimental results still remains, implying that in our simulation the regenerative loop does not operate with sufficient efficiency. The most important pathways for substrate reaction are the different singlet oxygen channels and the hydrogen abstraction mode of reaction. The relative importance of these two pathways could not be determined quantitatively.     

Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces

The activation energy to reaction is a key quantity that controls catalytic activity. Having used ab inito calculations to determine an extensive and broad ranging set of activation energies and enthalpy changes for surface-catalyzed reactions, we show that linear relationships exist between dissociation activation energies and enthalpy changes. Known in the literature as empirical Br?nsted-Evans-Polanyi (BEP) relationships, we identify and discuss the physical origin of their presence in heterogeneous catalysis. The key implication is that merely from knowledge of adsorption energies the barriers to catalytic elementary reaction steps can be estimated.     

BZ类双催化及非催化化学振荡反应

本文报道以香草醛(以OA表示)为底物的双催化振荡反应以及以2,7-二羟基萘二酚(以DN表示)为有机底物的非催化振荡反应,对二类不同体系的振荡反应机理作了初步的探索。实验部分1.试剂和仪器实验中的反应物均采用分析纯,所有溶液均在去离子水中制备,测定时主要采用PXS-215型离子活度计,XWT-台式自动平衡记录仪。2.实验方法使用超级恒温槽,控制在所需温度下进行反应,以溴离子选择性电极测量并记录反应过程中电位随时间的变化来反映[Br~-]的变化,以Hg|Hg_2SO_4|K_2SO_4为参比电极,振荡现象也可以用HP8451紫外可见分光光度计测定特定波长的吸光率变化进行观察。     

Mechanism of nitrite formation by nitrate photolysis in aqueous solutions: the role of peroxynitrite, nitrogen dioxide, and hydroxyl radical

Photolysis of aqueous NO3(-) with lambda > or = 195 nm is known to induce the formation of NO2(-) and O2 as the only stable products. The mechanism of NO3- photolysis, however, is complex, and there is still uncertainty about the primary photoprocesses and subsequent reactions. This is, in part, due to photoisomerization of NO3(-) to ONOO(-) at lambda < 280 nm, followed by the formation of *OH and *NO2 through the decomposition of ONOOH (pKa = 6.5-6.8). Because of incomplete information concerning the mechanism of peroxynitrite (ONOOH/ONOO(-)) decomposition, previous studies were unable to account for all observations. In the present study aqueous nitrate solutions were photolyzed by monochromatic light in the range of 205-300 nm. It is shown that the main primary processes at this wavelength range are NO3(-) hv-->*NO2 + O*(-) (reaction 1) and NO3(-) hv--> ONOO(-) (reaction 2). Based on recent knowledge on the mechanisms of peroxynitrite decomposition and its reactions with reactive nitrogen and oxygen species, we determined Phi(1) and Phi(2) using different experimental approaches. Both quantum yields increase with decreasing the excitation wavelength, approaching Phi(1) = 0.13 and Phi(2) = 0.28 at 205 nm. It is also shown that the yield of nitrite increases with decreasing the excitation wavelength. The implications of these results on UV disinfection of drinking water are discussed.     

Photoinduced fluorescence enhancement in mono- and multilayer films of CdSe/ZnS quantum dots: dependence on intensity and wavelength of excitation light

Photoinduced fluorescence enhancement (PFE) behavior in mono- and multilayer films of CdSe/ZnS core/shell quantum dots (QDs) on glass substrates was investigated using various intensities and wavelengths of excitation light. CdSe/ZnS QDs capped with tri-n-octylphosphine oxide (TOPO) were produced using colloidal chemical synthesis, and mono- and multilayer QD films were fabricated on glass substrates by spin coating. The fluorescence quantum yield (QY) of the QD monolayer was greatly enhanced by continuous irradiation in a dry nitrogen atmosphere, whereas the QD multilayer showed a small enhancement of the QY or fluorescence intensity decay. In addition, the shorter the excitation wavelength, the more pronounced the PFE. The rate of increase of the QY increased with decreasing excitation intensities at any wavelength. These dependences were observed in both mono- and multilayer films. Our results suggest that the photoejection of electrons to the substrate is the origin of PFE. Assuming the charging effect of electrons trapped in the substrate, a phenomenological model is proposed to explain all of the experimental results, that is, the dependence on the intensity and wavelength of excitation light and the qualitative difference in PFE behavior between mono- and multilayer films.     

An experimental and theoretical study of the mechanism of stannylcupration of alpha,beta-acetylenic ketones and esters

The title reaction has been investigated by experimental and computational (DFT) techniques, and subsequently compared to the corresponding carbocupration reaction, with particular emphasis on the stereoselectivity. For stannylcupration of an ynone substrate, only the anti-addition product is observed, whereas for the corresponding ynoate substrate, the stereoselectivity can be affected by the reaction conditions: in the presence of methanol as proton donor, the initial syn-addition product can be trapped, whereas a syn/anti mixture is obtained in a non-protic solvent. This is in sharp contrast to the carbocupration of the same ynone substrate with a cyanocuprate (RCu(CN)Li), which is highly selective for syn-addition. The product selectivities can be understood from a detailed computational characterization of the reaction paths, and in particular from the relative stabilities of the vinyl cuprate and allenolate intermediates. It is suggested that the stereodetermining step is protonation of vinyl cuprate intermediates.     

Ketone-imide versus ketone-oxime reductive cross-coupling promoted by samarium diiodide: new mechanistic insight gained from a failed aminocyclopentitol synthesis

[reaction: see text] The intramolecular 1,6-ketone/imide reductive coupling promoted by samarium diiodide competes favorably with an alternative 1,5-ketone/oxime ether coupling in a keto-oxime substrate derived from D-glucosamine N-protected with a phthalimido group. This pinacol coupling reaction affords new homochiral alpha-hydroxylactam scaffolds that could be useful in diversity-oriented synthesis. A mechanistic proposal for this reaction that explains the experimental results is supported by DFT quantum-mechanical calculations on model compounds.     

Combining Q2MM modeling and kinetic studies for refinement of the osmium-catalyzed asymmetric dihydroxylation (AD) mnemonic

The interactions between the substrate and the ligand in the Sharpless AD reaction have been examined in detail, using a combination of substrate competition experiments and molecular modeling of transition states. There is a good agreement between computational and experimental results, in particular for the stereoselectivity of the reaction. The influence of each moiety in the second-generation ligand (DHQD)₂PHAL on the rate and selectivity of the reaction has been elucidated in detail.     

金催化炔基苯并二𫫇英环化合成8-羟基异香豆素的理论研究

Density functional theory（DFT） calculations were carried out on the gold-catalyzed cyclization of alkynyl benzodioxin to 8-hydroxy-isocoumarin reaction to show the molecular mechanism of the reaction. The conclusions obtained from this work are different from those in the previous experimental study. The results show that water molecule acts as both the reactant and the proton shuttle, and promotes the reaction with gold complexes under mild conditions. The nucleophilic addition site of water on the substrate is the C（sp³） atom on the side of the substrate far away from the oxabenzene ring, resulting in C（sp³）—O bond breaking in the substrate. The formation of new C—O bond and the cleavage of C—O bond in the substrate follow a step-by-step mechanism. The oxygen in the side-product acetone comes from the contribution of water in the reaction system. The regioselectivity of the reaction originates from the polarization of alkynyl π-electrons induced by substituents.     

Kinetic studies on the mechanism of the relative catalytic activities of surfactants in the oxidation of amino-acids by chloramine-T

The kinetics of oxidation of amino-acids by chloramine-T in the presence of two different surfactants (cationic and anionic surfactants) in acidic medium has been studied. The kinetic results show that the reaction is fractional and first order with respect to substrate and oxidant respectively. The influence of halides, ionic strength and solvent on the rate has been studied. The effect of surfactants on the reaction show that the reaction velocity is highly sensitive to the variation of surfactant concentration. The micelle-substrate binding constant (K) and co-operativity index have been calculated indicating the stability of the catalyst substrate micelles (complex) so formed. A probable reaction path has been suggested and discussed in the light of various experimental results and findings.     

克拉霉素与百里酚蓝荷移配合物的光度分析研究

利用克拉霉素与百里酚蓝在乙醇介质发生荷移反应,建立了荷移分光光度法测定克拉霉素含量的方法.结果表明,荷移反应生成1∶1型配合物,最大吸收波长为442 nm,表观摩尔吸光系数为ε=1.66×104L·mol-1·cm-1,克拉霉素测定线性范围为8.278～57.59 mg/L.     

2,3-二芳基马来酸酐环合反应机理的计算研究

在B₃LYP/6-311+G(d,p)//HF/3-21G水平上研究了2,3-二芳基马来酸酐环合反应机理.2,3-二芳基马来酸酐环合反应有两条反应途径:(1)反应过程中涉及的各种构型始终保持反式,即中心成环碳原子上的取代基团甲基或氢原子位于分子平面的异侧,这些构型具有C₂对称性;(2)反应过程中涉及的各种构型始终保持顺式,即中心成环碳原子上的取代基团甲基或氢原子位于分子平面的同一侧面,这些构型可具有Cs对称性.二芳基乙烯类化合物环合反应的位垒计算结果与Woodward-Hoffman原理一致,计算结果支持在环合碳原子上引入甲基能改善反应的热不可逆反应性能的实验结果.电荷分析表明,在环合碳原子上引入甲基,能增加二芳基乙烯类化合物体系对氧的稳定性,与实验结果一致.2,3-二芳基马来酸酐化合物的闭环结构的LUMO和HOMO能隙小于开环结构的能隙,说明闭环结构的最大吸收波长大于开环结构的最大吸收波长,与实验结果一致.     

Aspects of the mechanism of catalysis of glucose oxidase: A docking, molecular mechanics and quantum chemical study

The complex structure of glucose oxidase (GOX) with the substrate glucose was determined using a docking algorithm and subsequent molecular dynamics simulations. Semiempirical quantum chemical calculations were used to investigate the role of the enzyme and FAD co-enzyme in the catalytic oxidation of glucose. On the basis of a small active site model, substrate binding residues were determined and heats of formation were computed for the enzyme substrate complex and different potential products of the reductive half reaction. The influence of the protein environment on the active site model was estimated with a point charge model using a mixed QM/MM method. Solvent effects were estimated with a continuum model. Possible modes of action are presented in relation to experimental data and discussed with respect to related enzymes. The calculations indicate that the redox reaction of GOX differs from the corresponding reaction of free flavins as a consequence of the protein environment. One of the active site histidines is involved in substrate binding and stabilization of potential intermediates, whereas the second histidine is a proton acceptor. The former one, being conserved in a series of oxidoreductases, is also involved in the stabilization of a C4a-hydroperoxy dihydroflavin in the course of the oxidative half reaction.     

Synthesis and Studies of Some Ketosulfones,Part I

New ketosulfones have been prepared. Their chemical composition and structure were proved by analytical and spectral methods. The kinetics of 1,4-addition of arenesulfinic acids to 1,3-diphenyl-2-nitropropenone and 3-nitro-4-phenyl-3-butene-2-on were studied by LC. The overall reaction is second order, while it is first order regarding each reagent and substrate. On the basis of the experimental results for the dependence of rate constants on the temperature and the influence of the substituents on the rate, a probable mechanism of the nucleophilic addition was suggested.     

用嗜热菌蛋白酶催化合成天冬甜精并同时进行DL-苯丙氨酸甲酯的光学拆分

以DL-苯丙氨酸甲酯作原料,利用嗜热菌蛋白酶和固定化嗜热菌蛋白酶催化合成了天冬甜精,经拆分得到D-苯丙氨酸甲酯。实验结果表明,不仅天冬甜精产率高,而且D-苯丙氨酸甲酯的回收率好,光学纯度高。     

Factorial analysis optimization of a Diltiazem kinetic spectrophotometric quantification method

A Diltiazem kinetic spectrophotometric method was optimized by factorial analysis. The experimental method is based on a two-stage reaction of Diltiazem with hydroxylamine and a ferric salt: in the first stage there is a hydroxamic acid formation; and, in the second stage there is a red colour complex ferric hydroxamate formation. The variables under investigation were: solvent; hydroxylamine, sodium hydroxide and ammonium ferric sulphate concentrations; volume of perchloric acid; and, temperature. The responses of the reactional system were the maximum absorbance, the wavelength and the reaction time at maximum absorbance. Experimental design methodologies were used in the optimization. Fractional and full factorial designs followed by optimization Box-Behnken and central composite experimental designs were used. The observed optimum conditions were: methanol as reaction solvent; hydroxylamine concentration of 9.375%; sodium hydroxide concentration of 18.750%; ferric reagent concentration of 2.000%; minimum volume of perchloric acid to neutralize the sodium hydroxide; and, room temperature as reaction temperature. With this set of experimental conditions a reaction time of 10.5 s with maximum colour development at 512 nm wavelength was achieved.     

Thermoluminescence and a new organic light-emitting diode (OLED) based on triplet-triplet fluorescence of the trimethylenemethane (TMM) biradical

The results of an investigation of the thermoluminescence (TL) and electroluminescence (EL) of arylated methylenecyclopropanes 1, systems whose photoinduced electron-transfer (PET) chemistry has been thoroughly studied, are described. In both the TL and EL experiments with 1, electronically excited triplet trimethylenemethane (TMM) biradicals (3)2** are generated by back electron transfer (charge recombination) of a TMM radical cation (hole) 2*+, formed by isomerization of the substrate radical cation (hole, 1*+). The application of this chemistry to the design of new organic light-emitting diodes (OLEDs) is described. The mechanistic features of this reaction system have the potential of overcoming significant problems (e.g., quantum efficiency, difficulty obtaining long wavelength emission, and device durability) normally associated with OLEDs that rely on the use of organic closed-shell hydrocarbons.     

Properties of the Reactants and Their Interactions within and with the Enzyme Binding Cavity Determine Reaction Selectivities. The Case of Fe(II)/2-Oxoglutarate Dependent Enzymes

Fe(II)/2-oxoglutarate dependent dioxygenases (ODDs) share a double stranded beta helix (DSBH) fold and utilise a common reactive intermediate, ferryl species, to catalyse oxidative transformations of substrates. Despite the structural similarities, ODDs accept a variety of substrates and facilitate a wide range of reactions, that is hydroxylations, desaturations, (oxa)cyclisations and ring rearrangements. In this review we present and discuss the factors contributing to the observed (regio)selectivities of ODDs. They span from inherent properties of the reactants, that is, substrate molecule and iron cofactor, to the interactions between the substrate and the enzyme's binding cavity; the latter can counterbalance the effect of the former. Based on results of both experimental and computational studies dedicated to ODDs, we also line out the properties of the reactants which promote reaction outcomes other than the “default” hydroxylation. It turns out that the reaction selectivity depends on a delicate balance of interactions between the components of the investigated system.