1,3-取代方酸衍生物非线性光学性质的从头算和半经验方法的比较研究

The structures of 1,3-substituted squaraine derivatives Sq1 ～ Sq12 were fully optimized by ab initio HF method with 6-31G* basis set level,and the electronic structures of Sq1 ～ Sq12 were also calculated. Based on the optimized structures,the electronic spectra were obtained by the CIS / 6-31G* method,which suggested that the max absorption wavelength mainly resulted from the electronic transition from HOMO to LUMO. The second nonlinear optical coefficients（β0）were calculated using ab initio CPHF method at 6-31G* basis set level and FF / AM1,FF / PM3,FF / MNDO,FF / MINDO3 methods. A systematic comparison between the results was carried out. It indicated that the second nonlinear optical coefficients were affected dramatically by the properties of five-membered hetero-rings. β0 can be enhanced by introducing pyrrole,thiazole and oxazole. The position of five-membered rings containing two heteroatoms which were connected with four-membered squaraine rings also affected β0 .     

甲氧基苯基偶氮衍生物电子结构与二阶NLO性质的HF/FF方法研究

采用量子化学HF方法在6-31G水平上优化6个甲氧基苯基偶氮衍生物分子的几何构型，利用HF／6-31G。方法计算它们的偶极矩、电荷分布、前线分子轨道能级并结合有限场(FF)方法计算二阶非线性光学系数．结果表明，偶氮苯衍生物分子具有很好的共轭性，在给吸电子基团作用下，电荷转移明显，展现示出较强的极性．偶氮苯衍生物分子与苯乙烯、Schiff碱类衍生物相似，也具有很好二阶非线性光学活性，同时六元杂环取代的偶氮苯衍生物分子二阶非线性光学系数比未取代的大，五元杂环取代结果相反．     

Fluorine-containing carbocations. III. Alkylation of polyfluorobenzenes with polyfluorinated α,α-difluorobenzyl cations and generation of polyfluorinated α-fluorodiphenylmethyl cations

Alkylation of incompletely fluorinated benzenes with polyfluorinated α,α-difluorobenzyl cations in an SbF₅ medium results in the formation of polyfluorinated α-fluorodiphenylmethyl cations whose precursors are the primary products of alkylation, i.e. the corresponding polyfluorinated α,α-difluorodiphenylmethanes. The influence of substituents on the ¹⁹F chemical shifts and spin-spin coupling constants J(FF) has been analysed in terms of their effects on contributions of the resonance structures controlling the positive charge distrubution on the coplanarity of the phenyl rings and the plane of the α-carbon bonds.     

Molecular dynamic simulations of self-assembled alkylthiolate monolayers on an Au(III) surface

Molecular dynamics simulations incorporating explicit gold atoms in the simulations have been carried out for alkanethiol self-assembled monolayers chemisorbed on the Au(III) surface. The structural properties of the monolayer are evaluated for two force fields: one in which the Au--S--C bond is fixed (FF I), and the other in which it is flexible (FF II). The influence of these force fields on the structural properties of HS(CH2)14CH3 on the structured Au surface is compared at different temperatures. FF I yields greater tilt angles and a smaller film thickness when compared with FF II. Both of the force fields predict that the tilt angles do not follow a monotonic decrease with temperature but show minima around 200 K. Simulations carried out at different chain lengths at 300 K reveal that FF II predicts a greater film thickness than FF I; however, the difference is within 1 A.     

Finite‐field method with unbiased polarizable continuum model for evaluation of the second hyperpolarizability of an open‐shell singlet molecule in solvents

The static second hyperpolarizability γ of the complexes composed of open‐shell singlet 1,3‐dipole molecule involving a boron atom and a water molecule in aqueous phase are investigated by the finite‐field (FF) method combined with a standard polarized continuum model (PCM) and with a newly proposed unbiased PCM (UBPCM). On the basis of the comparison with the results calculated by the FF method using the full quantum and the quantum‐mechanical/molecular‐mechanical and molecular‐dynamics (QM/MM‐MD) treatments, the present FF‐UBPCM method is demonstrated to remedy the artificial overestimation of the γ caused by standard FF‐PCM calculations and to well reproduce the FF‐QM/MM‐MD and FF‐full‐QM results with much lower costs. © 2013 Wiley Periodicals, Inc.     

Fluorine-fluorine spin-spin coupling constants in aromatic compounds: correlations with the delocalization index and with the internuclear separation

This paper describes a new empirical approach for the evaluation of fluorine-fluorine spin-spin coupling constants (J(FF)) in aromatic compounds. The correlations between J(FF) and the delocalization index calculated within the framework of the theory of atoms in molecules (AIM) and with the fluorine-fluorine internuclear separation are investigated. Both the internuclear separation and the delocalization index are found to be highly correlated with J(FF). A regression model in which the experimental J(FF) coupling constant is fitted exponentially to the internuclear separation and linearly to the delocalization index yields a squared correlation coefficient as high as 0.96 for a data set consisting of 33 coupling constants spread over a range of 85 Hz.     

果糖低温快速热解制备糠醛的机理研究

果糖低温快速热解制备5-羟甲基糠醛(HMF)的过程中,糠醛(FF)是一种重要的副产物。通过Py-GC/MS(快速热解-气相色谱/质谱联用)实验考察果糖低温快速热解过程中FF的形成特性。结果表明,FF的产率和相对含量都随着热解温度的提高先增大后减小,并在350℃时达到最大值,最高相对峰面积含量达到11.6%。此外,通过密度泛函理论计算,研究果糖热解形成FF的四条可能途径,计算结果表明,果糖热解形成FF的最优途径为路径2,即果糖首先经历一个协同的六元环过渡态,C5-C6键断裂的同时C6位羟基上的氢与C4位的羟基发生脱水反应,脱出一分子甲醛和一分子水,生成含C4=C5双键的二氢呋喃中间体,随后C2位上的羟基与C1位上的氢通过一个四元环过渡态又脱出一分子水,生成的烯醇中间体中烯醇氢与C3位的羟基最后经历一个六元环的过渡态再脱出一分子水,最终形成FF。     

Prediction of cyclohexane-water distribution coefficient for SAMPL5 drug-like compounds with the QMPFF3 and ARROW polarizable force fields

We present the performance of blind predictions of water—cyclohexane distribution coefficients for 53 drug-like compounds in the SAMPL5 challenge by three methods currently in use within our group. Two of them utilize QMPFF3 and ARROW, polarizable force-fields of varying complexity, and the third uses the General Amber Force-Field (GAFF). The polarizable FF’s are implemented in an in-house MD package, Arbalest. We find that when we had time to parametrize the functional groups with care (batch 0), the polarizable force-fields outperformed the non-polarizable one. Conversely, on the full set of 53 compounds, GAFF performed better than both QMPFF3 and ARROW. We also describe the torsion-restrain method we used to improve sampling of molecular conformational space and thus the overall accuracy of prediction. The SAMPL5 challenge highlighted several drawbacks of our force-fields, such as our significant systematic over-estimation of hydrophobic interactions, specifically for alkanes and aromatic rings.     

Kinetic, mechanistic, and thermodynamic investigations on ferrofluid-catalyzed oxidation of L-ascorbic acid by hydrogen peroxide in acidic aqueous solution

The reduction of ferrofluid (FF) by L-ascorbic acid (H(2)A) and the reoxidation of the reduced FF to its original form by hydrogen peroxide have been investigated in aqueous acidic medium. The rate of reduction of FF was found to be first order with respect to [H(2)A] and [FF] and independent with respect to [H(2)O(2)] and ionic strength. The rate of reduction of FF increased with increasing pH (2.5-4.0), having an inverse first order dependence in [H(+)]. With increasing temperature (15-45 degrees C), the rate of reduction was increased in line with the Arrhenius equation. Based on experimental evidence and results a mechanism, operative to reduce FF and reoxidize the reduced FF by H(2)O(2), which makes the system catalytic, is suggested. Thermodynamic quantities associated with FF-catalyzed oxidation of H(2)A by H(2)O(2) were determined and compared with other closely related systems.     

Force field development for cofactors in the photosystem II

We present a set of force field (FF) parameters compatible with the AMBER03 FF to describe five cofactors in photosystem II (PSII) of oxygenic photosynthetic organisms: plastoquinone‐9 (three redox forms), chlorophyll‐a, pheophytin‐a, heme‐b, and β‐carotene. The development of a reliable FF for these cofactors is an essential step for performing molecular dynamics simulations of PSII. Such simulations are important for the calculation of absorption spectrum and the further investigation of the electron and energy transfer processes. We have derived parameters for partial charges, bonds, angles, and dihedral‐angles from solid theoretical models using systematic quantum mechanics (QM) calculations. We have shown that the developed FF parameters are in good agreement with both ab initio QM and experimental structural data in small molecule crystals as well as protein complexes. © 2012 Wiley Periodicals, Inc.     

Force field development for organic molecules: Modifying dihedral and 1–n pair interaction parameters

We comprehensively illustrate a general process of fitting all‐atom molecular mechanics force field (FF) parameters based on quantum mechanical calculations and experimental thermodynamic data. For common organic molecules with free dihedral rotations, this FF format is comprised of the usual bond stretching, angle bending, proper and improper dihedral rotation, and 1–4 scaling pair interactions. An extra format of 1–n scaling pair interaction is introduced when a specific intramolecular rotation is strongly hindered. We detail how the preferred order of fitting all intramolecular FF parameters can be determined by systematically generating characteristic configurations. The intermolecular Van der Waals parameters are initially taken from the literature data but adjusted to obtain a better agreement between the molecular dynamics (MD) simulation results and the experimental observations if necessary. By randomly choosing the molecular configurations from MD simulation and comparing their energies computed from FF parameters and quantum mechanics, the FF parameters can be verified self‐consistently. Using an example of a platform chemical 3‐hydroxypropionic acid, we detail the comparison between the new fitting parameters and the existing FF parameters. In particular, the introduced systematic approach has been applied to obtain the dihedral angle potential and 1–n scaling pair interaction parameters for 48 organic molecules with different functionality. We suggest that this procedure might be used to obtain better dihedral and 1–n interaction potentials when they are not available in the current widely used FF. © 2014 Wiley Periodicals, Inc.     

Group electronegativity and Fukui function studies of the substituent effects in aromatic and inorganic systems

The group electronegativities (GE ) of molecular fragments, including the environmental contributions due to both the electrostatic interactions and electron distribution relaxation, and the Fukui function (FF ) indices of the charge sensitivity analysis (CSA ) are correlated with the known substituent effects in molecular systems. The semiempirical CSA in the atoms-in-molecules (AIM ) resolution has been applied to substituted benzenes and square platinum complexes treated as illustrative examples. The calculated FF indices and GE are both shown to constitute adequate reactivity criteria that qualitatively reproduce the known substituent effects. The FF index (second-order property) is found to be a more sensitive detector of the substituent influence than is the corresponding GE parameter (first-order property). © 1992 John Wiley & Sons, Inc.     

Honeycomb self-assembled peptide scaffolds by the breath figure method

The self-assembly of molecules into desired architectures is currently a challenging subject for the development of supramolecular chemistry. Here we present a facile "breath figure" assembly process through the use of the self-assembled peptide building block diphenylalanine (L-Phe-L-Phe, FF). Macroporous honeycomb scaffolds were fabricated, and average pore size could be regulated, from (1.00±0.18) μm to (2.12±0.47) μm, through the use of different air speeds. It is indicated that the honeycomb formation is humidity-, solvent-, concentration-, and substrate-dependent. Moreover, water molecules introduced from "breath figure" intervene in the formation of hydrogen bonds during FF molecular self-assembly, which results in a hydrogen bond configuration transition from antiparallel β sheet to parallel β sheet. Meanwhile, as a result of the higher polarity of water molecules, the FF molecular array is transformed from laminar stacking into a hexagonal structure. These findings not only elucidate the FF molecule self-assembly process, but also strongly support the mechanism of breath figure array formation. Finally, human embryo skin fibroblast (ESF) culture experiments suggest that FF honeycomb scaffolds are an attractive biomaterial for growth of adherent cells with great potential applications in tissue engineering.     

The additivity of substituent effects upon J(FF) in polysubstituted fluorobenzenes: An update

Substituent effects upon ³J(FF) are demonstrated to be additive, and a previous analysis of ⁴J(FF) and ⁵J(FF) in polysubstituted fluorobenzenes is updated.     

Comparsion of an immunochromatographic strip with ELISA for simultaneous detection of thiamphenicol,florfenicol and chloramphenicol in food samples

Rapid and sensitive indirect competitive enzyme‐linked immunosorbent assays (ic‐ELISA) and gold nanoparticle immunochromatographic strip tests were developed to detect thiamphenicol (TAP), florfenicol (FF) and chloramphenicol (CAP) in milk and honey samples. The generic monoclonal antibody for TAP, FF and CAP was prepared based on a hapten [D ‐threo‐1‐(4‐aminophenyl)‐2‐ dichloroacetylamino‐1,3‐propanediol], and the haptenwas linked to a carrier protein using the diazotization method. After the optimization of several parameters (coating, pH, sodium chloride content and methanol content), the ic‐ELISA was established. The quantitative working range for TAP was 0.11–1.36 ng/mL, with an IC₅₀ of 0.39 ng/mL. The optimized ELISA showed cross‐reactivity to CAP (300%) and FF (15.6%), with IC₅₀ values of 0.13 and 2.5 ng/mL, respectively. The analytical recovery of TAP, FF and CAP in milk and honey samples in the ic‐ELISA ranged from 81.2 to 112.9%. Based on this monoclonal antibody, a rapid and sensitive immunochromatographic test strip was also developed. This strip had a detection limit of 1 ng/mL for TAP, FF and CAP in milk and honey samples. Moreover, the test was completed within 10 min. Our results showed that the proposed ic‐ELISA and immunochromatographic test strip method are highly useful screening tools for TAP, FF and CAP detection in milk and honey samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Direct comparisons of experimental and calculated neutron structure factors of pure solvents as a method for force field validation

In the present letter, we directly compare neutron structure factors calculated from force field (FF)-based molecular dynamics simulations with experimental structure factors for water, methanol, and tetrahydrofuran (THF). For water, the difference in the measured structure factors is more significant than differences between the FFs. It is shown that the inclusion of electronic polarization in the force field improves the agreement with experiment for the more-polar methanol, whereas the results are comparable for the additive and polarizable FF models of the less-polar THF. The data presented here confirm that comparing the calculated scattering profiles from FF-based MD simulations to measured neutron structure factors is a promising method for FF validation and development.     

Wet effluent diffusion denuder technique and the determination of volatile organic compounds in air. II. Monoterpenes

In this work, a comparative study for the fractionation of Trichoderma reesei cellulases on five different hydrophobic interaction chromatography adsorbents (Butyl-Sepharose 4 FF, Phenyl-Sepharose 6 FF, Octyl-Sepharose 4 FF, Epoxy-Sepharose CL-6B and Polypropylene glycol-Sepharose CL-6B) is shown. The influence of the mobile phase composition on the chromatographic behaviour of T. reesei cellulases complex was evaluated using different concentrations of ammonium sulphate in the eluent buffer. A selective separation of beta-glucosidase with two-fold increase in specific activity and good recoveries of cellobiase activity were obtained with Butyl-Sepharose 4 FF and Phenyl-Sepharose 6 FF using 7% (w/v) ammonium sulphate in the eluent buffer. A beta-glucosidase fractionation was also obtained with Epoxy-Sepharose CL-6B, using 13% (w/v) of the salt in the mobile phase.     

Photoluminescence of Diphenylalanine Peptide Nano/Microstructures: From Mechanisms to Applications

Diphenylalanine (Phe‐Phe, FF) molecules, which can self‐assemble into highly ordered nano/microstructures, have increasingly aroused intense interests due to their special optical properties. In this review, recent advances in photoluminescence (PL) of supramolecular architectures of FF‐based peptide and the underlying mechanisms are highlighted. Mainly deep ultraviolet emission at around 285 nm and/or blue emission at ≈450 nm are observed in various FF peptide structures and its derivatives, which are primarily interpreted by quantum confinement effects, shallow radiative traps, and electron delocalization via hydrogen bonds in β‐ sheet structures. Furthermore, current applications of such fluorescent peptide nano/microstructures are also reviewed here, e.g., probing the number of water molecules confined in FF, temperature sensing, and visualization of deep ultraviolet beam. Yet, the PL mechanism is still under fierce debate and the application based on fluorescence is constantly under exploration. Thus, this review is endeavored to boost future explorations on the PL of the bioinspired FF peptide nano/microstructures.