有机共轭体系电子转移反应的溶剂重组能

应用Marcus双球模型计算溶剂重组能λs时,在AM1法优化给受体几何构型基础上,提出了共轭体系电子云分布的扁球模型,并用统计的方法求出了rD/A.同时依照Miller等的处理办法,结合其他理论及实验证据将电子转移交叉反应中联苯分子的扭转能计入溶剂重组能λs中,从而用实验速率常数拟合出含扭转能的λs值.此实验拟合值与扁球法得到的λs计算值吻合得很好.通过比较理论值与实验值,发现了给受体间距的大小、受体分子的变化、溶剂的不同对λs计算值相对λs实验值的偏差的影响,直接证实了电子给受体的耦合作用,溶剂分子参与的超交换电子转移及溶质溶剂分子表面相互作用等量子因素造成的实际反应体系对溶剂经典连续介质模型的偏离.     

Electron Transfer and Charge Transfer: Twin Themes in Unifying the Mechanisms of Organic and Organometallic Reactions

The broad varieties of organic and organometallic reactions merge into a common unifying mechanism by considering all nucleophiles and electrophiles as electron donors (D) and electron acceptors (A), respectively. Comparison of outer-sphere and inner-sphere electron transfers with the aid of Marcus theory provides the thermochemical basis for the generalized free energy relationship for electron transfer (FERET) in Equation (37) and its corollaries in Equations (43) and (44) that have wide predictive applicability to electrophilic aromatic substitutions, olefin additions, organometallic cleavages, etc. The FERET is based on the conversion of the weak nucleophile–electrophile interactions extant in the ubiquitous electron donor—acceptor (EDA) precursor complex [D, A] to the radical ion pair [D^⊕, A^?], for which the free energy change can be evaluated from the charge-transfer absorption spectra according to Mulliken theory. FERET analysis thus indicates that the charge-transfer ion pairs [D^⊕, A^?] are energetically equivalent to the transition states for nucleophile/electrophile transformations. The behavior of such ion pairs can be directly observed immediately following the irradiation of the charge-transfer bands of various EDA complexes with a 25-ps laser pulse. Such studies confirm the radical ion pair [Arene^⊕, NO₂] as a viable intermediate in electrophilic aromatic nitration, as presented in the electron-transfer mechanism between arenes and the nitryl cation (NO) electrophile.     

The accelerated development of an optimized synthesis of 1,2,4-oxadiazoles: application of microwave irradiation and statistical design of experiments

Herein, we report the development of an optimized microwave-assisted synthesis of 1,2,4-oxadiazoles. The chemistry development process was significantly accelerated by employing a statistical software package (MODDE 6.0™) to guide in the optimization of the reaction conditions. The resulting optimized reaction conditions were then utilized in the synthesis of a focused library of 1,2,4-oxadiazoles.     

Maillard and Hydrolytic Reactions in Subcritical Water Extraction of Bioactive Compounds from Licorice

Nowadays, subcritical water extraction (SWE) techniques are extensively investigated worldwide, while the thermal reactions that inevitably occur under subcritical water conditions are rarely studied. In order to investigate the behaviors of the different reactions during SWE of bioactive compounds from licorice, the Maillard reaction process was accessed via their products and the hydrolytic reaction was analyzed according to the kinetic parameters. In addition, the contents of total phenolics and flavonoids in the extracts obtained at the different temperatures were determined and total antioxidant capacities were evaluated by HPLC-ABTS⁺. The results showed that flavonoids and phenolics from licorice as well as new compounds generated via the Maillard reaction contributed to the antioxidant activity of the extracts. The fluorescence, color and absorbance of the extracts showed that the degree of the Maillard reaction increased with the rise of the extraction temperature. The kinetics of extraction for glycyrrhizic acid showed that it was firstly extracted by diffusion, and then was hydrolyzed into glycyrrhetinic acid 3-O-mono-β-D-glucuronide and glycyrrhetinic acid following a first-order mechanism. These findings could provide deep insights into the SWE process and a new method for producing glycyrrhetinic acid 3-O-mono-β-D-glucuronide and glycyrrhetinic acid.     

Influence of the Electron Transfer Rate on Electrochemically Controlled Hydrogen Bonding

Hydrogen bonding is an essential interaction in natural and artificial systems. Its strength can be modulated by employing process known as Electrochemically Controlled Hydrogen bonding (ECHB). Although these processes are assumed to operate under thermodynamic control no experimental evidence for kinetic control exists. In this work, ECHB processes where studied using electrogenerated radical anions from 5-nitroimidazole derivatives as receptor molecules and 1,3-diethylurea as hydrogen bond donor species. Results revealed that kinetic control occurs due to an increase in the internal reorganization energy of the receptor molecule, which cause a decrease in electron transfer rate. Electronic structure calculations and experimental K_b values suggested that kinetic limitations were the product of a competition between intra and intermolecular hydrogen bonding formation during the global process.     

肽链体系中的长程电子转移: 多肽构象和旁链间距对电子转移矩阵元的影响

用AM1半经验方法,优化了吲哚和苯酚中性分子、正离子自由基和负离子自由基的几何构型。用线性反应坐标近似和溶剂效庆的类导体屏蔽模型（COSMO）构造吲哚正离子和苯酚中性分子间电子转移的双势阱,用以估算多肽链中色氨酸和酪氨酸之间的电子转移的反应热和内重组能。优化TrpH-(Pro)n-TyrOH(n=0-3)多肽模型分子的结构和构象,用能级分裂因子的极小值方法计算了这些多肽体系的电子转移矩阵元。     

巴比妥酸的质子迁移异构化反应及其芳香性的密度泛函研究

用密度泛函理论方法,在B3LYP/6-31G水平上研究了巴比妥酸的醇式和酮式结构的分子内质子迁移异构化反应,对反应势能面的研究发现,该化合物可能存在6种中间体和12种过渡态,对反应物、产物和过渡态进行了几何构型优化,在同一水平下计算了单点能量,并用频率振动模式和内稟坐标(IRC)确证了过渡态的存在,反应的活化能最小为107.50kJ·mol-1,最大为330.84kJ·mol-1。在GIAO-HF/6-31G//B3LYP/6-31G水平对反应物、产物,中间体和过渡态的非相关性化学位移(NICS)进行了计算,利用NICS值对反应过程中芳香性进行分析,发现如果分子中的C5与C6存在双键或者形成过渡态的四员环状结构,分子就有不同程度的芳香性,如果有C6上的羟基氢迁移到C5上,C5-C6以单键相结合,则分子就没有芳香性。     

Optimization and statistical analysis of Au-ZnO/Al2O3 catalyst for CO oxidation

In our former work [Catal. Today 174 (2011) 127], 12 heterogeneous catalysts were screened for CO oxidation, and Au-ZnO/Al₂O₃ was chosen and optimized in terms of weight loadings of Au and ZnO. The present study follows on to consider the impact of process parameters (catalyst preparation and reaction conditions), in conjunction with catalyst composition (weight loadings of Au and ZnO, and the total weight of the catalyst), as the optimization of the process parameters simultaneously optimized the catalyst composition. The optimization target is the reactivity of this important reaction. These factors were first optimized using response surface methodology (RSM) with 25 experiments, to obtain the optimum: 100 mg of 1.0%Au-4.1%ZnO/Al₂O₃ catalyst with 220 °C calcination and 100 °C reduction. After optimization, the main effects and interactions of these five factors were studied using statistical sensitivity analysis (SA). Certain observations from SA were verified by reaction mechanism, reactivity test and/or characterization techniques, while others need further investigation.     

Rate Study for Electron Transfer of Sml2 to the Carbonyl Compounds and the Sulfoxides

The rate constants for the electron transfer of samarium diiodide to 2-heptanal, 2-methyl valeraldehyde and diphenyl sulfoxide were obtained for the first time. The reaction is first order in these substrates and there are hints that the reaction rate has a strong steric dependence. HMPA exhibited a profound catalytic effect but t-BuOH did not. The effect of temperature on reaction rates was also obtained.     

蛋白质结构建模的后期优化策略

以Lip8为研究对象, 以分级开放式优化和组合优化为优化策略, 分别采取四种不同的优化手段对相同的初始模型进行了优化, 同时比较了含水体系与不含水体系的优化过程, 最终获得8个相应优化后的蛋白模型. 采用Procheck, Errat, Profile 3D及Ramachandran 图等方法对上述8个模型进行评估. 通过比较各项评估结果, 研究了不同优化方法对最终模型准确性的影响, 结果表明, 优化过程中采用分级开放式策略, 同时考虑显性溶剂(水)体系和加入分子动力学优化的优化方法可以获得相对最优结构.     

A DOE Approach to Investigate the Influence of Process-Parameters and Composition on the Stability of Emulsions Stabilized by Marine Polysaccharides Prepared by High-Pressure Homogenization

The influence of pre-homogenization conditions (speed and duration at a rotor–stator system), homogenization pressure, and quantitative composition of the emulsions on the droplet size and stability of the resulting emulsions is investigated using design of experiments. A mix of marine polysaccharides (e.g., alginate and fucoidane) from Ascophyllum nodosum is used as emulsifier to form O/W-emulsions with medium-chained triglycerides. It was found that the amount of emulsifier is the most relevant parameter for emulsions' stability whereas the influence of the homogenization pressure is more distinct at low polysaccharide contents. In contrast, the parameters of pre-homogenization do not influence the droplet size significantly.      

Influence of the Phenological Stage and Harvest Date on the Bioactive Compounds Content of Green Pepper Fruit

Green pepper fruit is often consumed before it is completely ripe. However, the influence of the phenological stage in which the green pepper is consumed as a potential influencing factor in its bioactive compounds content and antioxidant capacity remains unknown. In addition, no literature is available concerning the bioactive compounds changes in ‘Lamuyo’ green peppers along its developmental and growth cycle. For this, two different approaches have been carried out, one using twelve different phenological stages (S1 to S12), and in the other, seven different harvest dates (from 27 February to 20 April). Moreover, bioactive compounds changes during 21 days of postharvest storage at 8 °C were investigated. In this study, bioactive compounds (ascorbic acid, dehydroascorbic acid, and total phenolic content) and the total hydrophilic and lipophilic (TAA-H and TAA-L) antioxidant activity were analysed. In addition, total soluble solids, total acidity, individual sugars, and organic acids were determined. Vitamin C levels increased along the phenological stages and harvest dates due to significant increases in ascorbic and dehydroascorbic acid levels. Our results show that the total phenol content decreases as vegetables develop and subsequently increases both as ripening begins and by the last harvest date. Furthermore, TAA-H was also greater by the phenological stage S12 and the 20 April harvest date. In conclusion, the phenological stage and harvest date are key factors that significantly influence the bioactive compounds of green peppers, and those that appear by S12 and 20 April could be more beneficial to health.     

Rapid Optimization of Reaction Conditions Based on Comprehensive Reaction Analysis Using a Continuous Flow Microwave Reactor

Generally, the flow method has the advantage of a precise control over the reaction parameters and a facile modification of the reaction conditions, while a continuous flow microwave reactor allows for the quick optimization of reaction conditions owing to the rapid uniform heating. In this study, we developed a “9+4+1 method” to optimize reaction conditions based on comprehensive reaction analysis using a flow microwave reactor. The proposed method is expected to contribute to the synthesis of various fine and bulk chemicals by reducing cost and wastage, and by conserving time.     

Gas Electron Diffraction and its Influence on the Solution of the Phase Problem in Crystal Structure Determination

We studied, and performed research for our Ph.D. degrees in the area of gas electron diffraction. Our mentor was Lawrence Brockway. a pioneer in this subject. At that time, research in gas electron diffraction was in its early stages of development. In 1941, the distinguished Peter Debye wrote a theoretical paper concerning gas electron diffraction which challenged ones capability to develop the necessary experimental equipment and to further advance the theoretical developments so as to greatly extend the science of gas electron diffraction. We carried these thoughts in mind when we joined the Naval Research Laboratory, where the opportunity to design and produce excellent equipment was readily available. In the course of pursuing this research area, one of the findings was the existence of non-negativity as a condition for the results of a diffraction experiment for gaseous substances. When we became interested in the field of crystal structure determination, the familiarity with non-negativity which was needed in the study of gases, led to a search for the necessary and sufficient condition for a Fourier series to be non-negative. The search was successful and has played an important part in crystal structure determination. Some early applications to complicated structures are described.     

The Role of a Dipeptide Outer‐Coordination Sphere on H2‐Production Catalysts: Influence on Catalytic Rates and Electron Transfer

The outer‐coordination sphere of enzymes acts to fine‐tune the active site reactivity and control catalytic rates, suggesting that incorporation of analogous structural elements into molecular catalysts may be necessary to achieve rates comparable to those observed in enzyme systems at low overpotentials. In this work, we evaluate the effect of an amino acid and dipeptide outer‐coordination sphere on [Ni(P^Ph₂N^Ph‐R₂)₂]²⁺ hydrogen production catalysts. A series of 12 new complexes containing non‐natural amino acids or dipeptides was prepared to test the effects of positioning, size, polarity and aromaticity on catalytic activity. The non‐natural amino acid was either 3‐(meta‐ or para‐aminophenyl)propionic acid terminated as an acid, an ester or an amide. Dipeptides consisted of one of the non‐natural amino acids coupled to one of four amino acid esters: alanine, serine, phenylalanine or tyrosine. All of the catalysts are active for hydrogen production, with rates averaging ～1000 s^?1, 40 % faster than the unmodified catalyst. Structure and polarity of the aliphatic or aromatic side chains of the C‐terminal peptide do not strongly influence rates. However, the presence of an amide bond increases rates, suggesting a role for the amide in assisting catalysis. Overpotentials were lower with substituents at the N‐phenyl meta position. This is consistent with slower electron transfer in the less compact, para‐substituted complexes, as shown in digital simulations of catalyst cyclic voltammograms and computational modeling of the complexes. Combining the current results with insights from previous results, we propose a mechanism for the role of the amino acid and dipeptide based outer‐coordination sphere in molecular hydrogen production catalysts.     

Double Group Transfer Reactions: Role of Activation Strain and Aromaticity in Reaction Barriers

Double group transfer (DGT) reactions, such as the bimolecular automerization of ethane plus ethene, are known to have high reaction barriers despite the fact that their cyclic transition states have a pronounced in‐plane aromatic character, as indicated by NMR spectroscopic parameters. To arrive at a way of understanding this somewhat paradoxical and incompletely understood phenomenon of high‐energy aromatic transition states, we have explored six archetypal DGT reactions using density functional theory (DFT) at the OLYP/TZ2P level. The main trends in reactivity are rationalized using the activation strain model of chemical reactivity. In this model, the shape of the reaction profile ΔE(ζ) and the height of the overall reaction barrier ΔE^≠=ΔE(ζ=ζ^TS) is interpreted in terms of the strain energy ΔE_strain(ζ) associated with deforming the reactants along the reaction coordinate ζ plus the interaction energy ΔE_int(ζ) between these deformed reactants: ΔE(ζ)=ΔE_strain(ζ)+ΔE_int(ζ). We also use an alternative fragmentation and a valence bond model for analyzing the character of the transition states.     

Proton Transfer Influence on Geometry and Electron Density in Benzoic Acid–Pyridine Complexes

The influence of the proton transfer on the geometry of donor and acceptor molecule in benzoic acid–pyridine complexes is investigated by theoretical calculations at the B3LYP/6‐311++G** level of theory. Systematic shifts of the H‐atom in the H‐bond are reflected in the geometry of the COOH group and the lengths of aromatic ring bond lengths of the proton acceptor. Changes in electron densities have been studied by atoms in molecules analysis. A systematic natural bond orbital analysis has been performed to study the proton transfer mechanism. Two donor orbitals are engaged in the proton transfer process which is accompanied by a change in orbital delocalization of H‐atom that can switch between two donor orbitals so the path of proton transfer in intermolecular H‐bond is not determined by the orbital shape. Theoretical results have been confirmed by experimental results published previously.