N-苄叉基-2-氨基噻唑及其类似物的构象和分子内的扭曲驱动力

确定了N-苄叉基-2-氨基噻唑(2a)和N-对硝基苄叉基-2-氨基噻唑(2b)的晶体结构.结合已报道的N-对硝基苄叉基-2-氨基嘧啶(1a),N-对硝基苄叉基-2-氨基吡啶(1b)和N-苄叉基-3-氨基吡啶(2c)的晶体结构,利用AM1,RHF,DFT方法和6-311G,6-311G^**基组,优化每个分子的22个旋转构象(θ=0°～90°).由DFT法所得到的最优构象的扭角θ(1a,22°;1b,0°;1c,42°;2a、2b:0°)与实验值(1a,26°;1b,20°;1c,46°;2a,8.8°;2b,3.8°)最接近.尽管分子最优构象扭角的差异很大,但总电子能最稳定的构象都在θ=±42°附近.在任一分子、任何电子态中,离域的π体系总是失稳定的,全平面构象不是π体系最稳定的构象.无论是离域的还是定域的π体系,它们均倾向于扭曲的几何构象.π电子的离域是分子扭曲的驱动力之一.与经典观点相反,非键原子间的核排斥作用是分子扭曲的阻力,而不是动力.     

绍兴黄酒中ACE活性抑制肽的分离分析

首次将绍兴黄酒中的肽类组分进行大孔吸附树脂柱层析和高效凝胶过滤色谱以及反相色谱的多步提取纯化与抑制血管紧张素转换酶（AcE）活性试验,并首次利用基体辅助激光解吸电离-飞行时间串联质谱分析和液相色谱-电喷雾电离四极杆-飞行时间串联质谱联用分析鉴定出黄酒中4种ACE活性抑制肽的氨基酸序列为：VEDGGV、PST、NT和LY。     

New Prediction Model of Surface and Interfacial Energies Based on COSMO-UCE**

The nature and strength of intermolecular and surface forces are the key factors that influence the solvation, adhesion and wetting phenomena. The universal cohesive energy prediction equation based on conductor-like screening model (COSMO-UCE) was extended from like molecules (pure liquids) to unlike molecules (dissimilar liquids). A new molecular-thermodynamic model of interfacial tension (IFT) for liquid-liquid and solid-liquid systems was developed in this work, which can predict the surface free energy of solid materials and interfacial energy directly through cohesive energy calculations based on COSMO-UCE. The applications of this model in prediction of IFT for water-organic, solid (n-hexatriacontane, polytetrafluoroethylene (PTFE) and octadecyl-amine monolayer)-liquid systems have been verified extensively with successful results; which indicates that this is a straightforward and reliable model of surface and interfacial energies through predicting intermolecular interactions based on merely molecular structure (profiles of surface segment charge density), the dimensionless wetting coefficient R_A/C can characterize the wetting behavior (poor adhesive (non-wetting), wetting, spreading) of liquids on the surface of solid materials very well.     

Interacting Quantum Atoms Analysis of the Reaction Force: A Tool to Analyze Driving and Retarding Forces in Chemical Reactions

The analysis of the reaction force and its topology has provided a wide range of fruitful concepts in the theory of chemical reactivity over the years, allowing to identify chemically relevant regions along a reaction profile. The reaction force (RF), a projection of the Hellmann-Feynman forces acting on the nuclei of a molecular system onto a suitable reaction coordinate, is partitioned using the interacting quantum atoms approach (IQA). The exact IQA molecular energy decomposition is now shown to open a unique window to identify and quantify the chemical entities that drive or retard a chemical reaction. The RF/IQA coupling offers an extraordinarily detailed view of the type and number of elementary processes that take reactants into products, as tested on two sets of simple reactions.     

The Effect of Oleic Acid Emulsification using SPE on Fluorite and Dolomite Flotation**

Collector OA, oleic acid, is widely used industrially for fluorite flotation. Low selectivity, dispersibility and collecting capability of the OA collector are always observed. In this study, compared with flotation of dolomite, a collector mixture of OA and SPE (styrylphenol polyoxyethylene ether) demonstrated significantly better performances for the fluorite. An optimal mass ratio 4 : 1 OA : SPE was found, and the recovery of fluorite was increased from over 85 % to more than 94 % compared with pure OA. Furthermore, the dosage of the collector agent was reduced from 50 mg mL⁻¹ to 20 mg mL⁻¹, which did not negatively impact the recovery of dolomite. The results from the contact angle tests indicated that SPE selectively increased the surface hydrophobicity of fluorite but had little effect on dolomite. Besides, zeta potential measurements and IR analyses revealed that the addition of SPE led to strong chemical adsorption on the surface of fluorite, resulting in a significant difference in the flotation performances of the two minerals. Therefore, SPE-emulsified OA is corroborated to prompt more selectivity and collecting capability on flotation of fluorite over dolomite.     

工科无机化学中“分子结构和分子间力”的教学思考与探索

“分子结构和分子间力”在人们认识物质世界的过程中起着承上启下的重要作用。然而,在“新工科”建设背景下,化学教学内容要少而精,以强化专业的应用特色建设。对工科学生历年来对于共价键理论、分子间力和离子极化中易错或不易理解的相关内容进行了分析和讨论,旨在帮助学习者在认识物质世界的过程中能更好地在微观世界和宏观世界之间切换,并学会预测或解释物质的性质及其递变规律,同时落实化学核心素质及德育素质的培养。     

Ionization of the Conformers of cis Nanotubular Cyclic Peptides in the Gas Phase: Effect of Size and Conformation on Ionization

Cyclic peptides, because of their unique spatial conformations, simplicity, and limited conformational freedom, are widely used as model molecules for larger peptides in chemistry and biochemistry. In this work, the ionization energies and photoelectron spectra of different conformers of the cyclic peptides (n = 2–15) were calculated using the symmetry‐adapted cluster‐configuration interaction (SAC‐CI) method and D95 + (d,p) basis set in the gas phase. The calculated photoelectron spectra were used to study the electronic structures of the cyclic peptides. It was observed that the first ionization energy of the cyclic peptides decreases with the ring size, reaches a minimum, and then increases. In addition, the first ionization band of the cyclic peptides was assigned to the ionization of the lone electron pairs of the nitrogen atoms, although there are π electrons of the CO bond and the lone electron pairs of oxygen atoms in the structure of the peptides.     

Effect of the substituted benzene group on thermal and mechanical properties of epoxy resins initiated by cationic latent catalysts

Epoxy resins (DGEBA) were cured by cationic latent thermal catalysts, that is, N‐benzylpyrazinium hexafluoroantimonate (BPH) and N‐benzylquinoxalinium hexafluoroantimonate (BQH) to investigate the effect of substituted benzene group on cure kinetics and mechanical properties of epoxy system. Differential scanning calorimetry (DSC) was undertaken for activation energy of the system. It was also characterized in terms of flexural, fracture toughness, and Izod impact strengths for the mechanical tests. As a result, the cure reaction of both epoxy systems resulted in an autocatalytic kinetic mechanism accelerated by hydroxyl groups. Also, the conversion and cure activation energy of the DGEBA/BQH system were higher than those of DGEBA/BPH system. The mechanical properties of the DGEBA/BQH system were also superior to those of the DGEBA/BPH system, as well as the morphology. This was probably due to the consequence of the effect of the substituted benzene group of the BQH catalyst, resulting in increasing the crosslinking density and structural stability in the epoxy system studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2419–2429, 2004     

理论研究丁羟粘合剂化学键解离及其对力学性能的影响

端羟基聚丁烯(HTPB)是推进剂中的常用的粘合剂,老化是其贮存和使用中的重要问题。通过量子化学计算HTPB 与甲基二异腈酸酯(TDI)形成的网络模型简化结构中化学键的均裂解离能(BDE),分析了键能与老化分解的关系。键能计算结果证明可靠且可用于比较分析。与CH₂ 基团相连的C-O 键的BDE值最小,推测该键最弱并且在热老化过程会发生断裂分解,降解产物主要是CO₂。HTPB 中的烯丙基伯羟基与TDI 形成的聚氨酯中α-C-H 属于最弱的X-H(X=C, N)键,推测其容易受到自由基的进攻发生氢转移反应。对容易断裂分解的C-O 键,提出了可能的老化机理。计算的C-O 键断裂活化能与其解离能近似相等,热老化过程中断键生成自由基并通过无势垒过程释放出CO₂。整个过程的热老化半衰期是温度的指数衰减函数,表明随着温度的提高HTPB-TDI 聚氨酯老化加速。热力学计算证明老化形成的氨基自由基和烷基自由基能够重新结合。采用分子动力学动态分析方法,分析了HTPB-TDI 聚氨酯网络老化前后的结构变化及其对弹性力性质的影响,发现释放CO₂ 的过程伴随着体系密度降低。对假定的CO₂ 扩散聚集以及CO₂ 从体系中扩散消失的模型进行了模拟,发现拉伸模量和剪切模量在这两种情形下会增加。     

Influence of the Electromagnetic Forces on Momentum and Heat Transfer in a 3-Phase ac Plasma Reactor

A new 3-phase ac plasma reactor has been developed within the framework of research on hydrocarbon cracking for the production of carbon black and hydrogen. ^(1,2) One of the main characteristics of the system is related to the 3-phase, 50 Hz ac current plasma generator which induces a very particular arc motion affecting the heat and mass transfer inside the reactor. In a first step, the general flow inside the reactor in the absence of hydrocarbon injection has been studied. A simplified approach to characterize the heat and mass transfer inside the reactor is presented in this paper. The arc zone analysis is carried out simultaneously by a theoretical analysis of the electromagnetic forces and by an ultrahigh-speed cine-camera analysis. The flow in the reactor is modeled with a CFD commercial code. Results are compared with experimental temperature measurements.     

The Effect of DNA Sequence Directionality on G‐Quadruplex Folding

Sequence inversion in G‐rich DNA from 5′→3′ to 3′→5′ exerts a substantial effect on the number of structures formed, while the type of G‐quadruplex fold is in fact determined by the presence of K⁺ or Na⁺ ions. The melting temperatures of G‐quadruplexes adopted by oligonucleotides with sequences in the 5′→3′ direction are higher than those of their 3′→5′ counterparts with both KCl and NaCl. CD, UV, and NMR spectroscopy demonstrates the importance of primary sequence for the structural diversity of G‐quadruplexes. The changes introduced by mere sequence reversal of the G‐rich DNA segment have a substantial impact on the polymorphic nature of the resulting G‐quadruplexes and their potential physiological roles. The insights resulting from this study should enable extension of the empirical rules for the prediction of G‐quadruplex topology.     

磷酸铝分子筛骨架晶格能与骨架拓扑结构的关系

应用晶格能极小技术计算了１９种磷酸铝分子筛折骨架晶格能，采用一元线性回归分析、多元线性回归分析和人工神经网络误差反传算法（ＢＰ），将其骨架晶格能与骨架拓扑结构参数相关，预测结果与计算晶格能吻合，表明晶格能与配位序（Ｎ２－Ｎ３）具有良好的多元线性关系，利用多元线性回归方程对１０种结构的磷酸铝分子筛的骨架晶格能进行了预测。     

The Synergistic Effect of Cationic Moieties and GRGDSF‐Peptides in Hydrogels on Neural Stem Cell Behavior

This article reports the behavior of embryonic neural stem cells on a hydrogel that combines cationic, non‐specific cell adhesion motifs with glycine‐arginine‐glycine‐aspartic acid‐serine‐phenylalanine (GRGDSF)‐peptides as specific cell adhesion moieties. Therefore, three hydrogels are prepared by free radical polymerization that contains either a GRGDSF‐peptide residue ( P1 ), amino ethylmethacrylate as a cationic residue ( P2 ), or a combination of both motifs ( P3 ). For each gel, cross linker concentrations of 8 mol% is used to have a comparable gel stiffness of 8–9 kPa. The cell experiments indicate a synergistic effect of the non‐specific, cationic residues, and the specific GRGDSF‐peptides on embryonic neural stem cell behavior that is especially pronounced in the cell adhesion experiments by more than doubling the number of cells after 72 h when comparing P3 with P2 and is less pronounced in the proliferation and differentiation experiments.

     

The Electrochemical Surface Forces Apparatus: The Effect of Surface Roughness, Electrostatic Surface Potentials, and Anodic Oxide Growth on Interaction Forces, and Friction between Dissimilar Surfaces in Aqueous Solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with ? resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force-distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with ?-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal-ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg-Healy-Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force-distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)(3) phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.     

Electronic Substitution Effect on the Ground and Excited State Properties of Indole Chromophore: A Computational Study**

Indole, being the main chromophore of amino acid tryptophan and several other biologically relevant molecules like serotonin, melatonin, has prompted considerable theoretical and experimental interest. The current work focuses on the investigation of substitution effect on the ground and excited electronic states of indole using computational quantum chemistry. Having three close-lying excited electronic states, the vibronic coupling effect becomes extremely important yet challenging for the photophysics and photochemistry of indole. Here, we have evaluated the performance of time-dependent density functional theory against available experimental and ab initio results from the literature. The electronic effects on the excited states of indole and indole derivatives e. g. tryptophan, serotonin and melatonin are reported. A bathochromic shift has been observed in the absorption spectrum for the L_a state. The absorption wavelength increases in the order of indole<tryptophan <serotonin <melatonin. While the contribution of the in-plane small adjacent groups increases the electron density of the indole ring, the out-of-plane long substituent groups have minor effect. The absorption spectra calculated including the vibronic coupling are in good agreement with experiments. These results can be used to estimate the error in photophysical observables of indole derivatives calculated considering indole as a prototypical system.     

The effect of fiber orientation and stacking sequence on carbon/E-glass/epoxy intraply hybrid composites under dynamic loading conditions

This study investigated the dynamic mechanical properties of hybrid intraply carbon/E-glass epoxy composites with different orientations and stacking sequences under different loading conditions with increasing temperature. A neat epoxy and five various hybrid composites such as Carbon (0°)/E-glass (90°), Carbon (45°)/E-glass (135°), Carbon (90°)/E-glass (0°), Carbon/E-glass (alternating layer), and Carbon/E-glass (alternating layer 45°) were manufactured. Three-point bending test and dynamic mechanical test were conducted to understand the flexural modulus and viscoelastic behavior (storage modulus, loss modulus, and loss tangent) of the composites. Dynamic mechanical test was performed with the dual cantilever method, at four different frequencies (1, 5, 10, and 20 Hz) and temperatures ranging from 30 to 150°C. The experimental results of storage modulus, loss modulus, and loss tangents were compared with the theoretical findings of neat epoxy and various hybrid composites. The glass transition temperature (T_g) increased with the increase in frequency. A linear fit of the natural log of frequency to the inverse of absolute temperature was plotted in the activation energy estimation. The interphase damping (tanδ_i) between plies and the strength indicator (S_i) of the hybrid composites were estimated. It was observed that the neat epoxy had more insufficient storage and loss modulus and a high loss tangent at all the frequencies whereas hybrid composites had high storage and loss modulus and a low loss tangent for all the frequencies. Compared with other hybrid composites, Carbon (90°)/E-glass (0°) had higher strength and activation energy. The result of reinforcement of hybrid fiber in neat epoxy significantly increases the material's strength and stability at higher temperatures whereas decreasing free molecular movement.     

Effect of Coriolis and buoyancy forces on three-dimensional flow of chemically reactive tangent hyperbolic fluid subject to variable viscosity

Thermophoresis effect has wide range of applications in electro-static precipitators and in biology for calculating single biological macro molecules, such as genomic-length DNA and HIV virus in the micro channels. Current study deal with effects of Coriolis and buoyancy forces on the three-dimensional boundary layer flow of tangent hyperbolic fluid with thermo-migration and haphazard motion of nano-sized particles. Arrhenius kind of chemical reaction is taken along an exponentially stretchable surface. The main focus of current exploration is to execute shear thinning nano-liquid flow past an exponentially rotating stretchable surface under the influence of variable viscosity, mixed convection and activation energy. We are motivated to explore the features of three-dimensional shear thinning model combined under the features of mixed convention, variable viscosity, and activation energy. The mathematical model is designed to generate PDEs and converted them into ODEs by employing fractious transformation. The numerical outcomes are exhibited via graphs by employing Bvp4c numerical technique whereas the values of skin friction coefficient are calculated by monopolizing shooting method. Characteristics of the parameters appearing in modeling like the viscosity parameter, power-law index, local Weissenberg number, mix convection parameter, rotation parameter, Prandtl number and chemical reaction parameter are comprehensively analyzed through graphical behavior. The impact of governing parameters on skin friction, heat and mass transfer rates is illustrated through tables. The detail analysis anticipates that the elevation in Weissenberg number and porosity caused decline in velocity. Further, the temperature behaves doppositely analogous to development Prandtl besides the thermophoresis parameter.     

超声对鸡腿菇多糖结构及生物活性的影响

超声提取技术对多糖结构和生物活性的影响具有重要的生物学意义和潜在的应用价值. 研究了超声对鸡腿菇多糖结构和生物活性的影响机理. 通过HPLC, GC, GC-MS等技术鉴定了热水提取鸡腿菇多糖(WCP3a)和超声波提取鸡腿菇多糖(UCP3a)的一级结构, 采用邻苯三酚自氧化法检测了二者的体外抗氧化活性, 并对两者一级结构及生物活性的异同进行了比较. 结果显示, (1) WCP3a的单糖组成为甘露糖、葡萄糖和半乳糖三种, 而UCP3a的单糖组成为甘露糖和葡萄糖两种|(2) WCP3a的糖苷键型为1→4,6甘露糖、1→甘露糖、1→3葡萄糖和1→2,6半乳糖|UCP3a的糖苷键型为1→4,6甘露糖、1→甘露糖、1→3葡萄糖和1→4葡萄糖|(3) WCP3a和UCP3a均能有效清除超氧阴离子, 并且UCP3a对超氧阴离子的清除效果更显著|(4)首次发现超声波可引起化学断键及原子重排, 导致多糖的组成单位单糖结构发生变化--半乳糖转化为葡萄糖, 其转化率随超声功率呈先增大后减小的趋势|随着超声时间的延长, 转化率同样呈先增大后减小的趋势.     

取代基对氮自由基稳定性影响的ab initio研究

用UHF／4-31G基组，全构型优化，研究了九个氮自由基NHR（R＝CH3，CF3，CCl3，CN，NH2，CHO，OH，COOH，F）的构型和稳定化能ΔE，它们的ΔE分别为25．24，－38．53，－20．59，21．46，19．96，58．82，73．69，31．75，63．85kJ•mol-1，表明，除CF3，CCl3以外，其余七个取代基对氮自由基起稳定化作用．