诺氟沙星与卵清蛋白相互作用的研究

应用荧光光谱法和紫外光谱法研究了诺氟沙星(NRF)与卵清蛋白(OVA)的相互作用,计算了诺氟沙星与卵清蛋白之间的结合常数和结合位点数。实验发现卵清蛋白的最大发射峰位于338 nm,当向该溶液中滴加诺氟沙星时,该发射峰强度明显减弱,且向长波长方向稍有移动。实验表明：随着温度升高,卵清蛋白的猝灭曲线斜率降低,证实了诺氟沙星与卵清蛋白的相互作用为单一的静态猝灭过程,同时随着溶液pH值的增大,诺氟沙星对卵清蛋白的猝灭程度逐渐降低。根据热力学参数确定了诺氟沙星与卵清蛋白之间主要以静电作用力相结合。最后利用紫外光谱法证明了诺氟沙星对卵清蛋白构象产生了影响。     

On Different Approaches to Estimate the Mass Fractal Dimension of Coal Aggregates

Several methods to measure the structures of coal aggregates are compared. Loose and compact coal aggregates were generated through flocculation of ultrafine coal particles (mean volume diameter of 12 μm) under specific shearing conditions. Aggregate structure in terms of mass fractal dimension, D_f, was determined using various methods; namely 2D and 3D image analysis, interpretation of intensity patterns from small angle light scattering, changes in aggregation state through light obscuration, and settling behavior. In this study, the measured values of D_f ranged from 1.84–2.19 for coal aggregates with more open structures, and around 2.27–2.66 for the compact ones. All of these approaches could distinguish structural differences between aggregates, albeit with variation in D_f values estimated by the different techniques. The discrepancy in the absolute values for fractal dimension is due to the different physical properties measured by each approach, depending on the assumptions used to infer D_f from measurable parameters. In addition, image analysis and settling techniques are based on the examination of individual aggregates, such that a large number of data points are required to yield statistically representative estimations. Light scattering and obscuration measure the aggregates collectively to give average D_f values of the particulate systems; consequently ignoring any structural variation between the aggregates, and leaving possible small contaminations undetected (e.g. by dust particles or air bubbles). Appropriate utilization of a particular method is thus largely determined by system properties and required data quality.     

脯氨酸催化的醛或酮反应中不同中间体的相互转换及异构平衡

烯胺、亚胺离子和恶唑烷酮是脯氨酸催化醛、酮反应中的关键中间体,在ωB97XD/6-311++G**理论水平上找到了连接其中任意两个中间体的过渡态. 计算结果表明无论在气相还是溶液中恶唑烷酮都是优势物种,这些物种是可以相互转化的,且异构平衡受控于所用溶剂和实验温度,这些物种存在与否以及发挥的作用取决于实验条件.提出了一条亚胺离子和恶唑烷酮通过亚胺水合物和恶唑烷酮水合物进行相互转换的新路径. 计算结果还表明在醛/酮与N-Boc亚胺的脯氨酸催化反应中,决速步骤是C-C键的形成而不是中间体的相互转换. 这些计算结果合理地解释了已有实验现象,并有利于优化醛、酮不对称有机催化反应的条件.     

动态超高压微射流对卵清蛋白微观结构的影响

采用圆二色谱(CD)、X射线衍射(XRD)、ANS荧光探针和紫外(UV)光谱研究了动态超高压微射流对卵清蛋白微观结构的影响。结果表明：卵清蛋白的微观结构的变化与处理压力有关,CD显示不同压力处理的卵清蛋白二级结构中的α-螺旋,β-折叠,β-转角和无规卷曲之间发生相互转化,二级结构的有序性提高;X射线衍射图谱直观显示不同压力处理的卵清蛋白晶体结构增加,160 MPa处理下结晶区最大,说明蛋白结构的有序性提高,与CD分析结果相似;ANS荧光探针光谱显示卵清蛋白的表面疏水性随着处理压力的增大而提高,120 MPa处理下达到最大;紫外光谱显示随着处理压力的增大,卵清蛋白最大紫外吸光值下降,卵清蛋白分子表面的具有紫外吸收的芳香氨基酸残基被包埋于分子内部,卵清蛋白的三维结构发生改变。     

Structural Characteristic of Folding/Unfolding Intermediate of Pokeweed Anti-viral Protein Revealed by Time-resolved Fluorescence

The structural feature of unfolding intermediate of pokeweed anti-viral protein (PAP) was characterized using time-resolved fluorescence spectroscopic methods to elucidate protein folding/unfolding process. CD and fluorescence spectra consistently demonstrated that the unfolding of PAP completed at 4 M of guanidine hydrochloride (GuHCl). The fluorescence resonance energy transfer (FRET) and time-resolve fluorescence depolarization analysis of Trp208 and Trp237 located in the C-terminal domain of PAP suggested that peculiar unfolding intermediate populated before reaching to the unfolding state. The FRET distance of Trp237 to Tyr182 was extended to more than 28 Å with keeping the compact conformation in the unfolding intermediate state populated in the presence of 2 M GuHCl. On the other hand, Trp208 maintained the energy transfer pair with Tyr72 near the active site, although the rotational freedom was increased a little. There results suggest that the most distinguished structural feature of the unfolding intermediate of PAP is the separation of C-terminal domain from N-terminal domain. FRET and fluorescence depolarization studies also showed that C-terminal domain would be more separated to liberate the segmental motions of Trp208 and Trp237 distinctly at the unfolding state.     

Study on the Interaction Between Water-Soluble CdTe Quantum Dots and Ovalbumin by Optical Spectroscopy

ABSTRACT

CdTe quantum dots (QDs) modified by 2-mercaptoethylamine hydrochloride (CA) and thioglycolic acid (TGA), respectively, were synthesized in aqueous medium. The interaction of CdTe QDs with ovalbumin has been investigated in depth by Fourier transform infrared spectroscopy (FTIR), UV-Vis absorption, fluorescence-quenching spectrometry, and resonance Rayleigh scattering spectroscopy (RRS). Fluorescence data show that the quenching type of ovalbumin by CA-CdTe QDs is static quenching with the binding constant being 10^?4 M^?1, and the number of binding sites being one. The calculated thermodynamic parameters demonstrate that the main binding forces are hydrophobic interaction and electrostatic attraction. In contrast, the quenching style of ovalbumin by TGA-CdTe QDs is verified to be dynamic quenching. Under suitable acidity conditions, the interaction of CA-CdTe QDs or TGA-CdTe QDs with ovalbumin leads to the remarkable enhancement of RRS, and the increments are found to be proportional to the concentration of ovalbumin in a certain range. A simple and highly sensitive RRS approach for determining ovalbumin is developed. In addition, the causes for the enhancement of RRS and the quenching of fluorescence are investigated to shed light on the quenching mechanism.     

同步辐射研究汽油火焰中的成分

利用同步辐射和分子束取样技术研究了汽油与氧气低压预混火焰的燃烧产物,得到汽油燃烧火焰中部的光电离飞行时间质谱图以及一些成分的电离能.与文献中的电离能比较后可以确定火焰中产物的具体结构.通过空间分布曲线着重分析了五种有害物质的反应过程,为建立燃烧反应动力学模型奠定了基础.     

Folding transitions of the square-diagonal lattice

We address the problem of “phantom” folding of the tethered membrane modeled by the two-dimensional square lattice, with bonds on the edges and diagonals of each face. Introducing bending rigidities K₁ and K₂ for respectively long and short bonds, we derive the complete phase diagram of the model, using transfer matrix calculations. The latter displays two transition curves, one corresponding to a first-order (ferromagnetic) folding transition, and the other to a continuous (anti-ferromagnetic) unfolding transition.     

纳米PIC-I分子聚集体的超辐射和Z-扫描研究

分子聚集体在非线性光学和集成光学等领域有潜在的应用前景。纳米结构一维染料分子J—聚集体有许多既不同于单个分子又不同于体材料的奇异性质，即超辐射和巨光学非线性。这种超辐射是由于在几个本征态内振于强度结合在一起，得到一巨跃迁偶极于，因而是超辐射的。跃迁速率与耦合分子个数N成正比。分子聚集体的J—吸收和超辐射发射是共振的。利用Z—扫描技术测量PIC在不同配比下的非线性折射率、非线性吸收系数和非线性极化率。观测到随着链长变短，样品的三阶非线性极化率增大。对这种非线性增强的机制进行了分析和讨论。     

不同物料和炭化方式制备生物炭结构性质的FTIR研究

红外光谱是了解生物炭结构性质特征的重要手段。通过采用傅里叶红外光谱技术(FTIR)对不同物料和制备方式的生物炭结构性质特征进行表征。结果表明：不同的物料制备的生物炭均具有羟基、芳香基及一些含氧基团的吸收峰,与活性碳有共同特征;但其他吸收峰,有着显著差异。高温炭化可以使玉米秸秆中—OH,—CH₃,—CH₂—,CO间发生缔合或消除,促进了芳香基团的形成。在不同炭化方式下,加热和微波炭化,对生物炭形成有着机理上差别,加热炭化可致使醇、酚中的—OH彼此结合或者消除,形成苯环类基团,而微波法能使得芳香基团钝化阻止其参与反应,使得苯环类物质得以更多形成。综上表明,红外光谱可较好反映生物炭的结构特征,揭示了生物炭主要含有—OH、芳香基团等活性基团。     

Comparative Study of the Interactions between Ovalbumin and five Antioxidants by Spectroscopic Methods

L-Ascorbic acid, α-tocopherol, procyanidin B3, β-carotene and astaxanthin are five classic dietary antioxidants. In this study, the interaction between the five antioxidants and ovalbumin was investigated by fluorescence spectroscopy, in combination with UV-vis absorption spectroscopy and circular dichroism (CD) spectroscopy. The quenching mechanism of ovalbumin by α-tocopherol is static quenching and the interaction between α-tocopherol and ovalbumin is synergistically driven by enthalpy and entropy. Electrostatic interactions and hydrophobic interactions play a major role in stabilizing the complex. For the other four antioxidants, the quenching mechanisms are all static quenching mechanisms at lower concentrations of antioxidants, but at higher concentrations of antioxidants, predominantly by the “sphere of action” quenching mechanisms. The binding processes of the other four antioxidants to ovalbumin are all entropy process and the major part of the action force is hydrophobic interactions. The binding constants of ovalbumin with the five antioxidants are in the following order as: astaxanthin > β-carotene > L-ascorbic acid > procyanidin B3 > α-tocopherol at 298 K. Synchronous fluorescence spectroscopy shows the interaction between L-ascorbic acid/β-carotene/astaxanthin and ovalbumin decreases the hydrophobicity of the microenvironment of tryptophan (Trp) and tyrosine (Tyr) residues. The hydrophobicity of Trp is increased while the hydrophility of Tyr is increased in the presence of α-tocopherol. However, the microenvironment of Trp and Tyr is not affected by procyanidin B3. The UV-vis absorption and CD spectra suggest that the interaction between the five antioxidants and ovalbumin leads to the loosening and unfolding of ovalbumin skeleton and exerts some influence on the natural secondary structure of ovalbumin. The study provides an accurate and full basic data for clarifying the binding mechanisms of L-ascorbic acid, α-tocopherol, procyanidin B3, β-carotene and astaxanthin interacting with ovalbumin and is helpful for understanding rational use of antioxidants as dietary supplements.     

Existence of temperature on the nanoscale

We consider a regular chain of quantum particles with nearest neighbor interactions in a canonical state with temperature T. We analyze the conditions under which the state factors into a product of canonical density matrices with respect to groups of n particles each and under which these groups have the same temperature T. In quantum mechanics the minimum group size n(min) depends on the temperature T, contrary to the classical case. We apply our analysis to a harmonic chain and find that n(min)=const for temperatures above the Debye temperature and n(min) proportional to T(-3) below.     

Folding and mixing in the Birkhoff-Shaw chaotic attractor

Some new visualization techniques are employed to elucidate the folding topology of the Birkhoff-Shaw chaotic attractor and the mixing action of trajectories wandering across its spirally wing-beak structure.     

Interactive Effects of Pressure,Temperature and Time on the Molecular Structure of Ovalbumin,Lysozyme and β-Lactoglobulin

The structure of three food proteins, ovalbumin, lysozyme and g -lactoglobulin were investigated when subjected to pressure, temperature and holding time. Structural effects were determined by the examination of circular dichroism spectra. Experiments were performed using pressures of up to 105 MPa, temperatures up to 79 °C and holding times of 30 minutes using experimental design methodology and compared with ultra high pressures (600 MPa). Examination of the spectra showed that the structure of the three proteins behaved differently to the processing conditions. g -lactoglobulin was found to be the least stable protein while lysozyme was the most stable protein. The higher pressure of 105 MPa was not sufficient to cause structural change when used at ambient conditions but when used in conjunction with raised temperatures and holding time, the applied energy was found to be sufficient to disrupt the protein structure.     

Condensation Behavior of Ag Aggregates on Liquid Surfaces

We report a condensation behavior of silver aggregates on silicone oil surfaces. The deposited Ag atoms diffuse and aggregate on the oil surface, and then form granular clusters and ramified islands. The apparent Ag coverage of the total area increases linearly with the nominal film thickness h for h 〈 0.9nm. However, the coverage exhibits a fluctuation behavior for 1.0 nm 〈 h〈 2.5 nm. It is found that the anomalous behavior of the coverage is resulted from a characteristic material condensation process in the aggregates.     

AFM Study on the Formation Mechanism and Microstructure of Ni Atomic Aggregates on Liquid Substrates

We study the formation mechanism and microstructure of nickel （Ni） atomic aggregates on the silicone oil surfaces by atomic force microscopy （AFM）. Initially, the deposited atoms nucleate and form the compact clusters on the liquid surfaces. Then they perform Brownian motion and adhere upon impact. Finally the branched aggregates are formed. The Ni aggregates exhibit granular structure. The mean size of the granularities in the aggregates is of the order of 10 nm and it decreases with the nominal film thickness. The experiment shows that the Ni aggregates perform a directional diffusion towards the sample edge. The interpretation for this phenomenon is presented.     

不同煤级煤的Raman谱特征及与XRD结构参数的关系

11种Cdaf在57.58%～94.01%的不同变质程度煤的拉曼光谱实验表明不同变质程度煤的拉曼光谱一级模都存在两个明显的振动峰,分别为较为宽缓的D峰(1 340～1 380 cm-1)和相对较为尖锐的G峰(1 580～1 600 cm-1)。将800～1 800 cm-1范围的谱图拟合为两个洛仑兹峰,每个峰的峰位置,峰强度以及半峰宽等拉曼参数与碳含量的相关关系分析结果显示：D峰位置和G峰位置随碳含量的增加分别向低波数和高波数区域移动;两峰的峰位差随碳含量的增加而增加;两峰的半峰宽FWHM-D,FWHM-G及两峰强度比I_D/I_G在碳含量75％～94％范围内与碳含量线性相关。发现XRD分析获得的d002和L_c与拉曼谱中的G峰位置及半峰宽存在着良好的相关性。与X射线衍射得到的晶粒尺寸L_a值相关性分析表明用Cancado公式和KW公式对L_a进行估算均是不合理的。     

Fluorescence Study on the Structure of Ionic Liquid Aggregates in Aqueous Solutions

Although ionic liquids are a relatively novel class of materials, it is well documented that they form micelles through aggregation of cation aliphatic tails. However, anion self-assembly has not yet been reported. In this study, we analyzed the intrinsic fluorescence of p-toluenesulfonate groups (tosylate) as part of the ionic liquid 1-ethyl-3-methylimidazolium tosylate ([emim][TOS]) and p-toluenesulfonic acid (pTSA), in aqueous solution. pTSA was found to have overlapping monomer and excimer emissions for chromophore concentrations from 10⁻³ to 1 M, whereas [emim][TOS], in the same conditions, showed monomer emission slightly broadened by much weaker excimer emission. These different photophysical behaviors of the same chromophore in the two compounds are explained by the formation of ion pairs by [emim][TOS], which can also be inferred from the loss of vibrational structure of the absorption spectra with respect to pTSA. Despite this different behavior regarding ion pairing, anion aggregation was observed in the excitation spectra of both pTSA and [emim][TOS]. While the absorption spectra corresponded to single chromophores, the excitation spectra changed from those characteristic of a single chromophore (below 10⁻³ M) to red-shifted narrow bands (above 0.1 M) typical of J aggregates. Between those concentrations, the excitation spectra split into blue- and red-shifted bands with relative intensities that changed with concentration as the chromophores rearranged in their clusters from head-to-head to head-to-tail aggregates. Differences between the absorption and excitation spectra were ascribed to aggregation-induced fluorescence enhancement.