疏水条件下甾体化合物的分离及环糊精的作用

分别应用胶束电动毛细管色谱法（ＭＥＣＣ）、反相色谱法和串联柱ＨＰＬＣ法分离 左旋十八甲基炔诺酮（ＬＮＧ）、睾酮（Ｔ）、孕酮（Ｐ－雌二醇（Ｅ２）等甾体化合物ＭＥＣＣ分离在未涂层毛细管柱上进行。当电泳缓冲溶液为含２０ｍｍｏｌ／Ｌ的２,６－二甲基－β环糊精（（ＤＭ－β－ＣＤ）添加剂和５０ｍｍｏｌ／Ｌ的十二烷基硫酸钠（ＳＤＳ）的１０ｍｍｏ／Ｌ四硼酸钠（ＰＨ９．２）时,可实现快速分离。通过与反相色谱法和串联     

反相高效液相色谱法测定尿中吡啶醚和脱氧吡啶醚

尿中吡啶醚（ｐｙｒｉｄｉｎｏｌｉｎｅ,ＰＹＤ）和脱氧吡啶醚（ｄｅｏｘｙｐｙｒｉｄｉｎｏｌｉｎｅ,ＤＰＤ）是骨代谢特异的生化指标。应用高效液相色谱法（ＨＰＬＣ）建立了尿中ＰＹＤ和ＤＰＤ的测定方法。尿液用６ｍｏｌ／ＬＨＣｌ水解后,以纤维素ＣＦ１小柱提取,然后用ＨＰＬＣ测定;色谱系统为ＳｐｈｅｒｉｓｏｒｂＣ１８反相色谱柱,流动相组成为１５％甲醇添加０．１％七氟丁酸,流速为１．２ｍＬ／ｍｉｎ。系统的检测限：ＰＹＤ为１０ｎｍｏｌ／Ｌ,ＤＰＤ为７ｎｍｏｌ／Ｌ;回收率：ＰＹＤ为９１．５％,ＤＰＤ为１０６．１％;日内变异     

高效液相色谱手性流动相法拆分甲状腺素对映体

运用高效液相色谱手性流动相法（ＨＰＬＣ－ＣＭＰ）对影响甲状腺素对映体（Ｄ－,Ｌ－Ｔ４）分离方法的因素：三乙胺（ＴＥＡ）浓度,流动相ｐＨ值,铜离子（Ｃｕ２＋）浓度,Ｌ－脯氨酸（Ｌ－ｐｒｏ）浓度,柱温以及流动相的流速进行了系统的研究。同时,考察了色谱方法分离Ｔ４对映体的线性关系,精密度和准确度。线性响应范围为０．６～３．２　ｎｍｏｌ　（Ｄ－,Ｌ－Ｔ４）,线性相关系数为ｒＤ－Ｔ４＝０．９９８０,ｒＬ－Ｔ４＝０．９９９０,日内和日间的精密度分别为ＲＳＤ＜２．３％（ｎ＝６）,ＲＳＤ＜３．１５％（ｎ＝５）。结果表明本实验所得的色谱条件较文献报道的优越,分离条件简单,重现性好。ＨＰＬＣ－ＣＭＰ法测定甲状腺素对映体其意义在于该方法可为定量测定药品及人体血液中Ｄ－,Ｌ－Ｔ４两种异构体,为治疗药物监测（ＴＤＭ）和药物不良反应监测（ＡＤＲｓ）提供了依据。     

水中痕量有机污染物质富集技术的发展——聚氨酯类泡沫富…

用聚氨酯类泡沫（ＰＵＦ）富集回收蒸馏水，自来水与河水中的多环芳烃，方法简便，回收率高，适于现场采集各种不同类型的水样，ＧＣ／ＭＳ分析中，氚化芘在１Ｌ蒸馏水中检出限为２６ｎｇ／Ｌ，而在ＨＰＬＣ／ＦＬＤ分析中，苯并（ｋ）荧蒽，苯并（ａ）芘，二苯并（ａ，ｈ）蒽，苯并（ｇｈｉ）在１Ｌ蒸馏水中的检出限分别为０．８６，０．５１，２．１和３．０ｎｇ／Ｌ。     

应用反相高效液相色谱法分离L，D－多肽非对映异构体

 应用反相高效液相色谱法（ＲＰ－ＨＰＬＣ）研究了５对Ｌ，Ｄ－多肽非对映异构体在不同条件下的分离情况。通过改换色谱柱、改变流动相的组成及梯度淋洗条件，发现其中的２对（Ｂｏｃ－Ａｌａ－Ｌ，Ｄ－Ａｌａ－ＧｌｙＯＢｚｌ和Ｂｏｃ－Ｇｌｙ－Ｌ，Ｄ－Ａｌａ－ＶａｌＯＢｚｌ）可以得到较好的分离，分离度分别为１．１和１．６，因此这２对Ｌ，Ｄ－多肽非对映异构体可以作为研究接肽反应消旋情况的模型体系。     

应用反相高效液相色谱法分离L，D－多肽非对映异构体

应用反相高效液相色谱法（ＲＰ－ＨＰＬＣ）研究了５对Ｌ，Ｄ－多肽非对映异构体在不同条件下的分离情况。通过改换色谱柱、改变流动相的组成及梯度淋洗条件，发现其中的２对（Ｂｏｃ－Ａｌａ－Ｌ，Ｄ－Ａｌａ－ＧｌｙＯＢｚｌ和Ｂｏｃ－Ｇｌｙ－Ｌ，Ｄ－Ａｌａ－ＶａｌＯＢｚｌ）可以得到较好的分离，分离度分别为１．１和１．６，因此这２对Ｌ，Ｄ－多肽非对映异构体可以作为研究接肽反应消旋情况的模型体系。     

T（3－BrP）PS_4卟啉用于高效液相色谱法测定微量钴、锌、铜

新显色剂５，１０，１５，２０－四（３－溴－４－磺酸苯基）卟啉，即Ｔ（３－ＢｒＰ）ＰＳ_４，与Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）离子生成螯合物，可在岛津ＣＬＣＯＤＳ柱上用离子对反相高效液相色谱法（ＨＰＬＣ）分离。流动相为２７＋７３的乙腈＋水，内含２０ｍｍｏｌ／Ｌ的乙酸＋乙酸钠缓冲液（ｐＨ６．０）和１０ｍｍｏｌ／Ｌ的四乙基碘化铵（ＴＥＡ·Ｉ）。检测波长为４２０ｎｍ。应用于茶叶、桔皮和紫米中微量钴、锌，铜离子的测定中，结果满意。     

微生物脱硫过程中的产物分析

ｌ 引 言微生物脱除矿物燃料中的杂环有机硫分为微生物降解脱硫和微生物催化脱硫，前一途径中菌株通过断裂有机化合物的Ｃ－Ｃ键，降解模型化合物二苯并噻吩（ＤＢＴ）生成含硫水溶性产物从燃料中脱除，破坏了碳氢化合物的碳骨架，引起燃烧值的降低。后一途径中微生物或它们的酶催化氧化ＤＢＴ的杂环硫原子，生成二苯并噻吩砜（ＤＢＴＯ２）及终产物 ２－羟基联苯（ＨＢＰ）和硫酸盐（‘４Ｓ’途径），保留了整个碳氢化合物的骨架。本研究用ＤＢＴ作为唯一硫源筛选不同菌种，通过液相色谱（ＨＰＬＣ）和液相色谱／质叙质谱联用（ＬＣ／ＭＳ…     

STUDIES ON SEPARATION AND DETERMINATION OF THE COUMARINS IN MURRAYA PANICULATA（L）JACK BY RP－HPLC

ＳＴＵＤＩＥＳ　ＯＮ　ＳＥＰＡＲＡＴＩＯＮ　ＡＮＤ　ＤＥＴＥＲＭＩＮＡＴＩＯＮ　ＯＦ　ＴＨＥ　ＣＯＵＭＡＲＩＮＳ　ＩＮ　ＭＵＲＲＡＹＡ　ＰＡＮＩＣＵＬＡＴＡ（Ｌ）ＪＡＣＫ　ＢＹ　ＲＰ－ＨＰＬＣＳＴＵＤＩＥＳＯＮＳＥＰＡＲＡＴＩＯＮＡＮＤＤＥＴＥＲＭＩ...     

毛细管区带电泳在氧氟沙星含量分析中的应用

氧氟沙星（ＯＦ）是第三代喹诺酮类药物中效果最好的广谱抗菌素之一。由于它在ｐＨ２～１１范围内难溶于水与醇，给用ＨＰＬＣ法检测其含量带来一定困难。本文报告了用毛细管区带电泳（ＣＺＦ）分离检测该药的方法。由于使用ｐＨ调制样品引入技术，克服了其溶解性不好给ＨＰＬＣ法所带来的困难。其实验条件为：５０ｍｍｏｌ／Ｌ硼砂（ｐＨ１．５）为电泳缓冲液，２８０ｎｍ为紫外检测波长，２５ｋＶ为电泳电压。样品由高差进样方式引入分离毛细管（５．１２ｃｍ×５０μｍｉ．ｄ．，有效分离长度为３８．５ｃｍ）。用磺胺作内标，ＯＦ在４８～５３０ｍｇ／Ｌ及５８０～９７０ｍｇ／Ｌ范围内可进行定量分析。保留时间（ｔｒ）及相对紫外吸收（Ａ（样品）／Ａ（内标））的日内－ＲＳＤ值分别小于１．０％和２．４％（ｎ＝６）。     

反应碰撞的动力学李代数描述

提出一种李代数方法描述分子反应碰撞问题．给出了含有主要动力学参量的S-矩阵元、分子碰撞跃迁几率以及反应体系能量统计平均值随时间演化的解析表达式．讨论了一个简单排斥势场中的原子-双原子分子共线反应体系，以阐明这种新方法的要点。     

Dynamics and scaling of polymers in a dilute solution: analytical treatment in two and higher dimensions

We consider the dynamical scaling of a single polymer chain in good solvent. In the case of two-dimensional systems, Shannon and Choy [Phys. Rev. Lett. 79, 1455 (1997)] have suggested that the dynamical scaling for a dilute polymer solution breaks down. Using scaling arguments and analytical calculations based on the Zimm model, we show that the dynamical scaling of a dilute two-dimensional polymer system holds when the relevant dynamical quantities are properly extracted from finite systems. Most important, the polymer diffusion coefficient in two dimensions scales logarithmically with system size, in excellent agreement with our extensive computer simulations. This scaling is the reason for the failure of the previous attempts to resolve the dynamical scaling of dilute two-dimensional polymer systems. In three and higher dimensions our analytic calculations are in agreement with previous results in the literature.     

Classical theory of collisional entropy production

A classical dynamical theory of elementary collision processes is formulated in analogy to the quantum theory of the dynamical scattering matrix, which can be defined for a pure quantum stationary scattering state. The elements of this matrix are probability amplitudes for transitions between internal states defined for given values of a reaction coordinate. The squared magnitudes of these amplitudes, modeled in the proposed classical theory, define normalized internal state population distributions suitable for information theoretical analysis. Statistical entropy and surprisal are defined as dynamical functions of a reaction coordinate. This formalism differs fundamentally from concepts based on the classical Liouville equation.     

将A-L理论推广到无限维李代数

为使由Alhassid与Levine所提出的动力学李代数方法（简称A－L理论）能适用于更多的散射体系，在h(∞)中引入了有效集合C（有限维）的概念．按照微扰理论的意义，C中的代数元所对应的群参量是较低次微扰的结果，而不属于C的代数元所对应的群参量则相当于较高次做扰所产生的修正结果．因此可以近似地利用C来代替h(∞)．这样，不仅简化了计算程序并且对于很多具有现实意义的散射过程的计算成为可能．     

Dynamical arrest, percolation, gelation, and glass formation in model nanoparticle dispersions with thermoreversible adhesive interactions

We report an experimental study of the dynamical arrest transition for a model system consisting of octadecyl coated silica suspended in n-tetradecane from dilute to concentrated conditions spanning the state diagram. The dispersion's interparticle potential is tuned by temperature affecting the brush conformation leading to a thermoreversible model system. The critical temperature for dynamical arrest, T*, is determined as a function of dispersion volume fraction by small-amplitude dynamic oscillatory shear rheology. We corroborate this transition temperature by measuring a power-law decay of the autocorrelation function and a loss of ergodicity via fiber-optic quasi-elastic light scattering. The structure at T* is measured using small-angle neutron scattering. The scattering intensity is fit to extract the interparticle pair-potential using the Ornstein-Zernike equation with the Percus-Yevick closure approximation, assuming a square-well interaction potential with a short-range interaction (1% of particle diameter). (1) The strength of attraction is characterized using the Baxter temperature (2) and mapped onto the adhesive hard sphere state diagram. The experiments show a continuous dynamical arrest transition line that follows the predicted dynamical percolation line until ? ≈ 0.41 where it subtends the predictions toward the mode coupling theory attractive-driven glass line. An alternative analysis of the phase transition through the reduced second virial coefficient B(2)* shows a change in the functional dependence of B(2)* on particle concentration around ? ≈ 0.36. We propose this signifies the location of a gel-to-glass transition. The results presented herein differ from those observed for depletion flocculated dispersion of micrometer-sized particles in polymer solutions, where dynamical arrest is a consequence of multicomponent phase separation, suggesting dynamical arrest is sensitive to the physical mechanism of attraction.     

Microscopic models of mode-coupling theory: The F(12) scenario

We provide extended evidence that mode-coupling theory (MCT) of supercooled liquids for the F(12) schematic model admits a microscopic realization based on facilitated spin models with tunable facilitation. Depending on the facilitation strength, one observes two distinct dynamical glass transition lines-continuous and discontinuous-merging at a dynamical tricritical-like point with critical decay exponents consistently related by MCT predictions. The mechanisms of dynamical arrest can be naturally interpreted in geometrical terms: the discontinuous and continuous transitions correspond to bootstrap and standard percolation processes, in which the incipient spanning cluster of frozen spins forms either a compact or a fractal structure, respectively. Our cooperative dynamical facilitation picture of glassy behavior is complementary to the one based on disordered systems and can account for higher-order singularity scenarios in the absence of a finite temperature thermodynamic glass transition. We briefly comment on the relevance of our results to finite spatial dimensions and to the F(13) schematic model.     

Response of solid Ne upon photoexcitation of a NO impurity: a quantum dynamics study

The ultrafast geometrical rearrangement dynamics of NO doped cryogenic Ne matrices after femtosecond laser pulse excitation is studied using a quantum dynamical approach based on a multi-dimensional shell model, with the shell radii being the dynamical variables. The Ne-NO interaction being only weakly anisotropic allows the model to account for the main dynamical features of the rare gas solid. Employing quantum wave packet propagation within the time dependent Hartree approximation, both, the static deformation of the solid due to the impurity and the dynamical response after femtosecond excitation, are analysed. The photoinduced dynamics of the surrounding rare gas atoms is found to be a complex high-dimensional process. The approach allows to consider realistic time-dependent femtosecond pulses and the effect of the pulse duration is clearly shown. Finally, using the pulse parameters of previous experiments, pump-probe signals are calculated and found to be in good agreement with experimental results, allowing for a clear analysis of the ultrafast mechanism of the energy transfer into the solid.     

Multinanoparticle Translocations in Phospholipid Membranes:Translocation Modes and Dynamic Processes

Multinanoparticles interacting with the phospholipid membranes in solution were studied by dissipative particle dynamics simulation. The selected nanoparticles have spherical or cylindrical shapes, and they have various initial velocities in the dynamical processes. Several translocation modes are defined according to their characteristics in the dynamical processes, in which the phase diagrams are constructed based on the interaction strengths between the particles and membranes and the initial velocities of particles. Furthermore, several parameters, such as the system energy and radius of gyration, are investigated in the dynamical processes for the various translocation modes. Results elucidate the effects of multiparticles interacting with the membranes in the biological processes.     

INVERSION OF A NONLINEAR DYNAMICAL MODEL FROM THE OBSERVATION

A technique for inversion of a nonlinear dynamical model from the observations has been developed, and examined by using the Lorenz system. The results show that the Lorenz system can be accurately inversed by using the observation data set. This technique will be broadly used in establishing the nonlinear dynamical model from an actual data set.