正十二烷基硫酸钠在聚丙烯酰胺溶液中聚集的1H NMR研究

利用核磁共振自旋-晶格弛豫时间（T₁）、自旋-自旋弛豫时间（T₂）、自扩散系数（D）以及二维核Overhause增强谱（2D NOESY）技术研究了表面活性剂正十二烷基硫酸钠（SDS）在聚丙烯酰胺（PAM）浓度固定为10 g/L水溶液中的聚集. 结合与SDS水溶液体系核磁共振实验数据比较,得到了如下信息：（1） 当溶液中有PAM存在时,SDS分子的运动性下降,临界聚集浓度提前;（2） 随着SDS浓度的增加,PAM分子的自扩散性能下降,同时分子链的柔软性也下降了;（3） 2D NOESY谱结果表明,PAM与SDS分子间未发生直接的缔合作用.     

Dynamics ofLens culinaris agglutinin studied by red-edge excitation spectra and anisotropy measurements of 2-p-toluidinylnaphthalene-6-sulfonate (TNS) and of tryptophan residues

The fluorescence of 2-p-toluidinylnaphthalene-6-sulfonate bound toLens culinaris agglutinin and of the Trp residues of the protein was investigated. Red-edge excitation spectra and steady-state anisotropy as a function of temperature indicate that the TNS is bound rigidly. Red-edge excitation spectra, steady-state anisotropy as a function of sucrose and anisotropy decay experiments performed on Trp residues fluorescence prove that the internal fluorophore presents residual motion independent of the global rotation of the protein. Fluorescence anisotropy decay allows to calculate the rotational correlation time (351 ps) of this local motion. Quenching resolved emission anisotropy with iodide gives values equal to 0.257 and 0.112 for the anisotropies of the buried and the surface Trp residues, respectively. This result indicates that the Trp residues present at the surface of the protein have important local motions compared to those embedded in the protein matrix. The results obtained from TNS and Trp residues indicate that the agglutinin has different dynamic domains.     

Luminescence and anisotropy decays ofN-3-pyrene maleimide labeling IgG proteins and cells

The Py.M (N-3-Pyrene Maleimide) is a dye that covalently binds to reactive amino or sulfhycryl groups to give highly fluorescent protein conjugates. Measurements of luminescence lifetimes and anisotropy decays have been performed with a Phase and Modulation Fluorometer. Complexes of Py.M-antibody (IgG antimouse) and tumoral cells C6 labeled with Py.M have been investigated. The Py.M fluorescence in buffer solution and the protein and cells natural fluorescence have been checked. For Py.M-IgG and labeled cells, the fluorescence decays present interesting behaviours. The least-squares analysis of the experimental results on Py.M-IgG complex points out two lorentzian distributions centered at 74 ns and 11 ns, on the contrary, for the labeled cells, a discrete component at 100 ns and a lorentzian distribution centered at 5 ns are shown. In both systems a weak component lower than 1 ns is observed. The fluorescence decays, mainly the long lifetime one, are very sensitive to oxygen quenching, showing the high efficiency of O₂ quenching. For samples N₂ bubbled, the lifetime experimental resuits show a decrease of the oxygen accessibility from free probe in solution to Py.M-IgG complex and to labeled cells, compatible with a more compact packing of the probe binding site. The experimental results of anisotropy decays of degassed samples show for Py.M-IgG complexes a long rotation correlation time of about 200 ns at T=5°C, assigned to overall rotation of the protein, besides shorter correlation times attributable to inner protein motions. For labeled cells, the long rotation correlation time becomes of the order of 580 ns confirming a progressive increase of the stabilization of the binding site.     

Conformational differences of oxytocin and vasopressin as observed by fluorescence anisotropy decays and transient effects in collisional quenching of tyrosine fluorescence

We used gigahertz frequency-domain fluorometry to examine the tyrosyl fluorescence intensity and anisotropy decays of the single-tyrosine cyclic peptide hormones oxytocin and vasopressin. Acrylamide quenching and a distance-dependent quenching model for collisional quenching were used to evaluate the extent of tyrosyl exposure to the quencher and to provide increased resolution of the picosecond anisotropy decays. Analysis of the intensity decays using a lifetime distribution model shows different distributions for oxytocin and vasopressin. We found that the tyrosyl fluorescence of lysine-vasopressin, as revealed both by the lifetime Stern-Volmer plots and from the quenching analysis, is quenched more effectively than oxytocin. ForN-acetyltyrosinamide (NATyrA), oxytocin, and lysine-vasopressin, we recovered apparent diffusion coefficients for quenching of 4.7×10^–6, 0.44×10^–6, and 4.3×10^–6 cm²/s, respectively, the lower value for oxytocin suggesting a shielded environment for its tyrosyl residue. Tyrosyl anisotropy decays were recovered by global analysis of progressively quenched samples. Compared with oxytocin, vasopressin displayed a longer correlation time for overall rotational diffusion and a higher amplitude for picosecond segmented motions of its tyrosyl residue. All the data are consistent with a more extended and flexible solution structure for vasopressin than for oxytocin.Dedicated to Professor Alfons Kawski on the occasion of his 65th birthday.     

表面活性剂SDS/TX-100混合体系的NMR研究

用NMR测量了不同比例的SDS/TX-100混合溶液中质子化学位移,结合表面活性剂溶液的两态交换模型,分析了质子化学位移随浓度的变化趋势, 求出了不同比例混合溶液中两种表面活性剂各自的临界胶束浓度及混合胶束的临界胶束浓度. 依据理想混合溶液理论,预测了混合胶束的临界胶束浓度,计算了溶液中SDS与TX-100之间的相互作用参数和SDS在混合胶束中的摩尔分数. 根据所得参数讨论了混合胶束的形成过程. 利用文中和文献中混合体系的实验数据验证了协同作用理论改进前后的适用性,表明改进后的协同作用理论完善一些.     

The Conformational Changes of the Fungal Lipase from Humicola lanuginosa Induced by the Formation of Bile Salt and Mixed Micelles

The effect of sodium taurodeoxycholate and a mixture of sodium taurodeoxycholate/phosphatidyl-choline on the activation of fungal lipase from Humicola lanuginosa (HLL) was investigated by monitoring the specific activity and the changes in intrinsic protein fluorescence. A large increase in the inactivation rate was observed at about the critical micellar concentration of bile salt. On the contrary, a high activation of lipase was achieved by the presence of mixed micelles. Steady-state fluorescence quenching measurements were performed to resolve the fluorescence contribution of W89 residue in emission of four-tryptophan-containing HLL lipase. The W89 residue is located in the lid helix which participates in interfacial activation of the enzyme. The assignment of W89 residue was confirmed by use of the W89F mutant and inhibited form of lipase. The FQRS (fluorescence quenching resolved spectra) method was used to decompose the total emission spectrum of HLL lipase. The FQRS results show that the fluorescence of the W89 residue is similar in inhibited and inactivated HLL lipase and exhibits a maximum of emission at about 345 ± 1 nm (_ex = 295 nm). In the mixed micelle solution the fluorescence of the W89 residue may be resolved into two components, with fluorescence maxima at 337 and 347 nm, respectively (_ex = 295 nm). It is concluded that HLL lipase undergoes a conformational transition upon specific interactions with both anionic and mixed micelles, resulting in a change in the microenvironment of the W89 residue.     

Distance-dependent fluorescence quenching ofN-acetyl-l-tryptophanamide by acrylamide

We examined the time-dependent intensity decays ofN-acetyl-l-tryptophanamide (NATA) when collisionally quenched by acrylamide in propylene glycol over a range of temperatures. The intensity decays of NATA became increasingly heterogeneous in the presence of acrylamide. The NATA intensity decays were not consistent with the Collins-Kimball radiation boundary condition (RBC) model for quenching. The steady-state Stern-Volmer plots show significant upward curvature, and quenching of NATA by acrylamide was observed even in vitrified propylene glycol, where translational diffusion cannot occur during the lifetime of the excited state. These frequencydomain and steady-state data indicate a through-space quenching interaction between NATA and acrylamide, and the results are consistent with a rate constant for quenching that depends exponentially on the fluorophore-quencher separation distance. The exponential distance-dependent rate of quenching also explains the upward curvature of the Stern-Volmer plot, and the steady-state data aid in determining the interaction distance between NATA and acrylamide. These results suggest that the distance-dependent quenching rates need to be considered in the interpretation of acrylamide quenching of proteins.     

Limiting Dynamics for Spherical Models of Spin Glasses at High Temperature

We analyze the coupled non-linear integro-differential equations whose solution is the thermodynamical limit of the empirical correlation and response functions in the Langevin dynamics for spherical p-spin disordered mean-field models. We provide a mathematically rigorous derivation of their FDT solution (for the high temperature regime) and of certain key properties of this solution, which are in agreement with earlier derivations based on physical grounds. AMS (2000) Subject Classification: Primary: 82C44 Secondary: 82C31, 60H10, 60F15, 60K35     

Limiting Dynamics for Spherical Models of Spin Glasses at High Temperature

We analyze the coupled non-linear integro-differential equations whose solution is the thermodynamical limit of the empirical correlation and response functions in the Langevin dynamics for spherical p−spin disordered mean-field models. We provide a mathematically rigorous derivation of their FDT solution (for the high temperature regime) and of certain key properties of this solution, which are in agreement with earlier derivations based on physical grounds. AMS (2000) Subject Classification: Primary: 82C44, Secondery: 82C31, 60H10, 60F15, 60K35     

Determination of the in-plane anisotropy field in hexagonal systems via rotational magnetization: Theoretical model and Monte Carlo simulations

The magnetic anisotropy field in thin films with in-plane uniaxial anisotropy can be deduced from the VSM magnetization curves measured in magnetic fields of constant magnitudes. This offers a new possibility of applying rotational magnetization curves to determine the first- and second-order anisotropy constant in these films. In this paper we report a theoretical derivation of rotational magnetization curve in hexagonal crystal system with easy-plane anisotropy based on the principle of the minimum total energy. This model is applied to calculate and analyze the rotational magnetization process for magnetic spherical particles with hexagonal easy-plane anisotropy when rotating the external magnetic field in the basal plane. The theoretical calculations are consistent with Monte Carlo simulation results. It is found that to well reproduce experimental curves, the effect of coercive force on the magnetization reversal process should be fully considered when the intensity of the external field is much weaker than that of the anisotropy field. Our research proves that the rotational magnetization curve from VSM measurement provides an effective access to analyze the in-plane anisotropy constant K ₃ in hexagonal compounds, and the suitable experimental condition to measure K ₃ is met when the ratio of the magnitude of the external field to that of the anisotropy field is around 0.2. Supported by the National Natural Science Foundation of China (Grant Nos. 90505007 and 10774061) Recommended by LI FaShen     

Deuteron size effects on its elastic scattering from1H and4He

The effect of change in deuteron size on its elastic scattering from protons and alphas is investigated by varying the Hulthen parameters of the deuteron wave function in the scattering process. The cross sections forp-d scattering, calculated in the Born approximation, are found to increase substantially at backward angles even when the deuteron size is reduced by a small amount, whereas the shape of the angular distribution does not change significantly. For theα-d elastic scattering, interaction potential is obtained by folding the deuteron wave function and the optical potential for nucleon-scattering. The cross sections calculated atE _d = 13·7 MeV, shows that the first minimum around Θ_cm = 60° is deepend as the deuteron size is reduced, while at 52 MeV bombarding energy, the size effects are not very distinct. These observations are useful in the interpretation of deuteron cluster knockout reactions.     

Zn1-x-yNaxCoyO薄膜的脉冲激光沉积制备及表征

采用脉冲激光沉积技术,在Si(111)衬底上成功制备出不同含量Na,Co共掺的ZnO薄膜.利用X射线衍射仪、原子力显微镜、荧光光谱仪以及四探针电阻率测试台对薄膜的结构、表面形貌和光电性质进行了表征.重点讨论了不同掺杂浓度对薄膜光电性质的影响.结果表明:Na,Co共掺没有改变ZnO的六角纤锌矿结构且掺杂导致薄膜仅有的的紫外发光峰出现红移.当Na,Co掺杂浓度分别为10%时,峰值最强且红移最明显,发光峰波长为397 nm,薄膜的电阻率最低,达到了8.34×10^-1 Ω ·cm.深入讨论了 关键词： 脉冲激光沉积 1-x-yNa_xCo_yO薄膜')" href="#">Zn_1-x-yNa_xCo_yO薄膜 光电性质 红移     

蛋白质溶液结构及动力学的核磁共振研究

高场液相核磁共振技术作为解析高分辨率蛋白质结构的两大主要手段之一,在近二十几年的时间里得到了迅猛的发展. 一方面,随着谱仪硬件技术、核磁脉冲技术和蛋白质标记技术的不断发展,液相核磁共振技术所能够研究的蛋白质不断突破分子量的限制,可以达到几万,甚至几十万. 另一方面,液相核磁共振技术成功地应用于蛋白质分子动力学的研究中,是目前唯一能够对蛋白质多个位点同时进行动力学研究的实验方法,并且仍在不断地创新、发展和完善中. 本文从蛋白质溶液结构的解析和动力学的研究两个主要方面对液相核磁共振研究的基本方法进行简要的介绍,并结合实例介绍一些最新的研究进展.