Thermal Transport in Methane Hydrate by Molecular Dynamics and Phonon Inelastic Scattering

The heat conduction and thermal conductivity for methane hydrate are simulated from equilibrium molecular dynamics. The thermal conductivity and temperature dependence trend agree well with the experimental results. The nonmonotonic temperature dependence is attributed to the phonon inelastic scattering at higher temperature and to the confinement of the optic phonon modes and low frequency phonons at low temperature. The thermal conductivity scales proportionally with the van der Waals interaction strength, The conversion of a crystal-like nature into an amorphous one oecurs at higher strength. Both the temperature dependence and interaction strength dependence are explained by phonon inelastic scattering.

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering （CARS） spectroscopy with supercontinuum （SC）, the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.

Study on Molecular Chain Morphology of Konjac Glucomannan

The long-range structure of konjac glucomannan(KGM)is studied by using laser light scatter(LLS), gel permeation chromatography(GPC)and method of viscosidity. The weight-average molecular weight(Mw), root-mean-square ratio of gyration[(S2)1/2], second viral coefficient(A2)and multi-dispersion coefficient(Mw/Mn)are 1.04×106, 105. 0±0. 9 nm,(-1. 59±0.28)×10-3 mol ml g-2 and 1.015±0.003, respectively. Mark-Houwink equation is established as [η] = 5. 96×10-2Mw0.73 and the molecular chain parameters are as follows: ML=982. 82 nm-1, Lp = 27. 93 nm, d = 0. 74 nm, h = 0. 26 nm, L = l 054.11 nm. Further more molecular chain morphology of KGM is studied by using atom force microscope(AFM)and transmission electronic microscope(TEM), and the result shows that the KGM molecular is an extending semi-flexible linear chain without branch. Therefore, the image of molecular chain morphology confirms the deduction drawn by Mark-Houwink equation and molecular chain parameters.

CHARACTERIZATION OF MOLECULAR MASS OF SIX WATER-SOLUBLE POLYSACCHARIDE -PROTEIN COMPLEXES FROM GANODERMA TSUGAE MYCELIUM

Six water-soluble polysaccharide-protein complexes coded as GM1, GM2, GM3, GM4, GM5 and GM6 wereisolated from the mycelium of Ganoderma tsugae by extracting with 0.2 mol/L phosphate buffer solution at 25, 40 and80℃, water at 120℃, 0.5 mol/L aqueous NaOH solution at 25 and 65℃, consecutively. Their chemical components wereanalyzed by using IR, GC, HPLC and ^(13)C-NMR, and some new results were obtained. The four samples GM1, GM2, GM3and GM4 are heteropolysaccharide-prote in complexes, in which, α- (1→3) linked D-glucose is the major monosaccharidewhile galactose, mannose and ribose are the secondary ones. GM5 and GM6 are β-(1→3)-D-glucan-protein complexes. Theprotein content increased from 32% to 69% with the progress of isolation. Weight-average molecu1ar mass M_w and theintrinsic viscosity [η] of the GM samples in 0.5 mol/L aqueous NaCl solution at 25℃ were measured systematically by laserlight scartering (LLS), size exclusion chromatography (SEC) combined with LLS, and viscometry. The M_w of GM1 to GM6are 35.5, 46.8, 58.9, 41.6, 3.3 and 22.0×10~4, respectively. The conformation and molecular mass of the two fractions of sample GM5 were characterized satisfactorily by SEC-LLS without further fractionation.

Selection rules for electric multipole transition of triatomic molecule in scattering experiments

In the electron or x-ray scattering experiment,the measured spectra at larger momentum transfer are dominated by the electric dipole-forbidden transitions,while the corresponding selection rules for triatomic molecules have not been clearly elucidated.In this work,based on the molecular point group,the selection rules for the electric multipolarities of the electronic transitions of triatomic molecules are derived and summarized into several tables with the variation of molecular geometry in the transition process being considered.Based on the summarized selection rules,the electron energy loss spectra of H2O,CO2,and N2O are identified,and the momentum transfer dependence behaviors of their valence-shell excitations are explained.

SCATTERING FUNCTION OF POLYMER BLENDS

For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing 'ideal gases of the gravity centers of macromolecules'. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.

Selection rules for electric multipole transition of diatomic molecule in scattering experiments

The knowledge of the energy level structures of atoms and molecules is mainly obtained by spectroscopic experiments. Both photoabsorption and photoemission spectra are subject to the electric dipole selection rules （also known as optical selection rules）. However, the selection rules for atoms and molecules in the scattering experiments are not identical to those in the optical experiments. In this paper, based on the theory of the molecular point group, the selection rules are derived and summarized for the electric monopole, electric dipole, electric quadrupole, and electric octupole transitions of diatomic molecules under the first Born approximation in scattering experiments. Then based on the derived selection rules, the electron scattering spectra and x-ray scattering spectra of H2, N2, and CO at different momentum transfers are explained, and the discrepancies between the previous experimental results measured by different groups are elucidated.

DYNAMIC LIGHT SCATTERING STUDY ON TRANSLATION DIFFUSION OF 8-ARM STAR POLYSTYRENE IN GOOD AND THETA SOLVENTS

The technique of dynamic light scattering has been used to investigate the translation diffusion behavior of 8-arm star polystyrene (SPS)in a good solvent, tetrahydrofuran (THF) or benzene (BZ) and a theta solvent, cyclohexane (CH), by homodyne photon correlation spectroscopy .The intensityintensity autocorrelation function was analyzed by the method of cumulant. The translation diffusion coefficients have been obtained as a function of temperature and concentration. Under theta condition ,the non-concentration dependence of diffusion coefficient showed the unperturbed Gaussian state o the SPS molecular chain. The different hydrodynamic radii estimated from Stokes- Einstein equation reflected the stretch extent of the arm chain for regular star polymer. The data of diffusion activation energy of SPS in THF, BZ and CH were also obtained respectively.

LIGHT SCATTERING OF POLYSACCHARIDE FROM LACQUER IN AQUEOUS SOLUTION

The polysaccharide having weight-average molecular weight M_w=1. 09×10~5, isolated from the sap of lac trees (Vietnam), was separated into 12 fractions by aqueous-phase preparative gel permeation chromatography. The molecular weights and molecular weight distributions of the fractions were measured in aqueous 0.08M KCl/0.01 M NaAc and 0.4M KCl/0.05M NaAc at pH =7. 6 by light scattering, viscometry and gel permeation chromatography. The Mark-Houwink equation in aqueous 0.08M KCl/0.01M NaAc at 30℃ was found to be [η]= 2.28×10^(-2) M_w^(0.52) (cm^3/g), which indicated the polysaccharide chain in the aqueous solution to be a spherical random coil.

Raman Scattering Activities for Uniaxially Oriented Molecules

Raman scattering activities were derived for uniaxially oriented molecules. The unique axis of the molecules is assumed to rotate around one of the axes of space-fixed coordinate in a fixed orientation angle with respect to the axis, while the other two principal axes of the molecules are randomly oriented. Expressions for Raman scattering activities in terms of the elements of derived polarizability tensor are given as the function of orientation angle and are tabulated for various symmetries of point groups.

A modification potential method of calculating total cross sections of electrons scattering from complex molecules C2H6, C2F6, C6H6 and C6F6 at 100 eV-5000 eV

A complex optical model potential modified by incorporating the concept of bonded atom, which takes into consideration the overlapping effect of electron clouds between two atoms in a molecule, is first employed to calculate the total cross sections for electrons scattering from such complex molecules as C2H6, C2F6, C6H6 and C6F6 using the aclditivity rule model at Hartree-Fock level over the energy range from 100 eV to 5000 eV. The total cross sections are quantitatively compared with those obtained by experiments wherever available, and they are in good agreement with each other over a wide energy range. It is shown that the modified potential together with the additivity rule model is completely suitable for the calculation of total cross sections of electrons scattering from such complex molecules as C2H6, C2F6, C6H6 and C6F6 above 200 eV-300 eV.

Molecular Weight and Aggregation of Erwinia Gum in Aqueous Solutions

Erwinia(E) gum is composed of glucose, fucose, galactose and glucuronic acid. The weightaverage molecular weights M w, numberaverage molecular weights M n and intrinsic viscosities[η] of the four fractions and the unfractionated E gum in aqueous solutions at desired temperatures were studied by light scattering, membrane osmometry, size exclusion chromatography(SEC) and viscometry. The experimental results prove that E gum formed aggregates in the aqueous solution at 25 ℃ and the aggregates were broken gradually with increasing temperature. The dissociation of the aggregates of E gum in the aqueous solution started at 36 ℃, and was completed at around 90 ℃. The [η] values of E gum and its fractions are much higher than those of the conventional polymers with the similar molecular weights, and decrease with increasing NaCl concentration.

Elastic scattering of two ground-state N atoms

An interaction potential for an N2（X^1∑g^＋） molecule is constructed by using the highly accurate valence internally contracted multireference configuration interaction method and the largest basis set, aug-cc-pV6Z, in the valence range. The potential is used to investigate the elastic scattering of two N atoms at energies from 1.0×10^-11 to 1.0 × 10^-4 a.u. The derived total elastic cross sections are very large and almost constant at ultralow temperatures, and the shape of total elastic cross section curve is mainly dominated by the s-partial wave at very low collision energies. Three shape resonances are found in the total elastic cross sections. Concretely, the first one is very sharp and strong. It results from the g-partial-wave contribution and the resonant energy is 3.645 × 10^-6 a.u. The second one is contributed by the h-partial wave and the resonant energy is 1.752 × 10^-5 a.u. This resonance is broadened by those from the d- and f-partial waves. The third one comes from the l = 6 partial wave contribution and the resonant energy is 3.522 × 10^-5 a.u. This resonance is broadened by those from the g- and h-partial waves. The N2（X1∑g＋） molecular parameters, which are determined at the current theoretical level, achieve very high accuracy due to the employment of the largest correlation-consistent basis set in the valence range.

碱性蛋白酶酶解蛋白制备活性肽的质控研究

以胶原蛋白和大豆分离蛋白为主要研究对象,应用体积排阻色谱(SEC)结合多角度激光光散射(MALLS)及示差折光(RI)联用技术对碱性蛋白酶酶解蛋白制备肽段的过程进行了详细分析。在酶解过程中,不同来源的胶原蛋白(牛、鸡)和大豆分离蛋白在分子量分布、体系的分散度及粒径变化规律上表现出了典型的差异。结果表明,牛胶原蛋白在酶解开始时就迅速被降解产生了大量小分子肽段,鸡胶原蛋白相对于牛胶原蛋白在相同的酶解条件下更难产生小分子肽段,大豆分离蛋白随着酶的加入则是表现出了先聚集再降解的特性。SEC-MALLS技术可以有效把控蛋白酶解的过程以及体系中肽段分子量分布,该技术可以为活性肽产品的开发及品质检测提供依据。

基于分子干涉函数的光子-原子相干散射截面计算方法研究

X射线衍射在物质结构分析和材料无损检测领域有着广泛的应用,其基本物理原理为光子与物质发生的相干散射。传统的相干散射截面计算方法基于独立原子形状因子近似方法,忽略了光子动量转移较小时与原子发生相互作用时的分子干涉效应,影响相干散射截面的计算精度。因此,为了获得光子动量转移较小时精确的相干散射截面,本文在核数据处理程序NECP-Atlas中对基于分子干涉函数的光子-原子相干散射截面计算方法进行研究,利用分子动力学模拟方法计算分子干涉函数,对蒙特卡罗程序使用的ACE格式数据库中的原子形状因子进行修正,并给出了模拟得到的水分子和乙醇分子的分子干涉函数,对基于独立原子形状因子近似方法和考虑分子干涉效应计算得到的水和乙醇的散射成像结果进行了对比分析。数值结果显示:基于分子动力学模拟得到的分子干涉函数计算得到的水的散射成像结果与文献结果吻合较好;同时,当光子动量转移较小时,分子干涉效应对相干散射的次级光子角度分布有着显著影响。本文建立的光子-原子相干散射截面计算方法可显著提高光子动量转移较小时的相干散射次级光子角度分布计算精度,可为X射线衍射模拟提供数据基础。

拉曼光谱在细胞成像中的研究进展

细胞成像在生命科学与药物研究中具有重要意义。拉曼光谱作为一种非破坏性的振动光谱技术,结合非标记或探针标记技术可对细胞不同组分进行成像。由于自发拉曼光谱信号较弱,运用有效的增强手段可提高细胞成像的时间与空间分辨率。该文综述了表面增强拉曼光谱(SERS)、相干拉曼光谱(CRS)、共振拉曼光谱(RRS)等拉曼增强方法在线粒体、溶酶体和内质网等细胞器成像中的研究进展,以及上述方法在蛋白质、脂质、糖类和核酸等重要细胞生物分子成像中的应用。此外,还讨论了标记技术中拉曼探针的化学结构、增强因子、检出限等因素对细胞成像的影响,并分析了当前细胞拉曼成像的发展趋势、存在的挑战和可能的解决方案。

基于光学检测的分子间相互作用表征技术研究进展

分子间相互作用的表征技术是阐明细胞生物学事件、了解疾病发生机制、辅助药物研发的有力手段。近年来,分子间相互作用的表征技术发展迅速,不断向着高灵敏度、高通量、极短时间、极低检测限的方向发展。本文对表面等离子体共振、生物膜干涉、背向散射干涉以及微量热泳动这4种常见的、基于光学检测的分子间相互作用表征技术的原理、特点及最新应用进展进行了综述与比较,为分子间相互作用表征技术的选择提供参考。

Au溶胶中咖啡酸分子的表面增强拉曼光谱实验与理论研究

在加热条件下利用氯金酸与柠檬酸钠的还原反应制备出胶体金,并使用拉曼光谱仪测量出咖啡酸(CA)分子常规拉曼散射(NRS)光谱及其吸附在Au纳米颗粒上的表面增强拉曼散射(SERS)光谱。采用密度泛函理论(DFT)的B3LYP方法,选用6-31+G**基组作为C、H、O的计算基组,选用赝势基组LANL2DZ作为Au的计算基组。首先对体系结构进行优化,并在此基础上计算CA分子的NRS光谱及CA分子与Au纳米颗粒吸附后3种可能模型的SERS光谱。对比分析可知,CA分子上的羧基和羟基共同与Au团簇吸附的构型计算得到的结果与实验数据最符合。接着进一步对CA分子的振动模式进行了详细指认,结果表明,CA分子与Au纳米颗粒是通过CA分子上的羧基和羟基吸附在一起的。最后通过计算CA分子及CA分子与Au纳米颗粒吸附后的分子前线轨道,进一步确定了CA分子在Au溶胶中的吸附方式。

三通道Fabry-Perot标准具在瑞利测风激光雷达中的应用

描述了利用三通道Fabry-Perot(F-P)标准具作为鉴频器直接探测多普勒风场的原理。优化了三通道F-P标准具的设计参数。介绍了基于三通道F-P标准具研制的测风激光雷达接收机的结构。利用355 nm脉冲光,通过调节PZT电压来改变标准具的腔长,对标准具的透过率曲线进行了初步测量,并分析了标准具的参数,标准具的带宽和峰值透过率较设计时分别增大了13%和10%。介绍了利用四波束反演水平风场的方法。根据标准具参数和信噪比计算的速度灵敏度较设计时下降了0.09%,风速精度在40 km以下优于5 m/s。同时,与风廓线雷达进行了比对,对163组数据的风速差进行统计,平均值为0.22 m/s,标准差为1.67 m/s,表明两者有较高的一致性。

激光光散射法测定BAG分子量及其分子量分布

介绍了一种用于高能推进剂新型键合剂BAG分子量和分子量分布测定的激光光散射法。给出了该方法的实验原理、实验步骤。该法以合镍化钾的二甲基酰胺溶液溶剂和流动相,凝胶渗透色谱柱为分离体系,实验结果表明:准确度和精密度较好,可作为常规测定BAG分子量及其分布的方法。