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2.
The pH mediated intra-molecular association and inter-molecular aggregation of a range of amphiphilic poly(l-lysine iso-phthalamide) polymers have been investigated in aqueous solution over a range of pH values and concentrations. The desired functionality of these novel bioresponsive amphiphilic polymers was achieved by incorporating pendant hydrophilic carboxyl groups along the polymer backbone, via the l-lysine moiety, balanced by a degree of hydrophobicity introduced via the iso-phthaloyl moiety. Incorporation of low levels of bis-functional Cy3 (poly-Cy3) and/or Cy5 dye (poly-Cy3/5 or poly-Cy5) co-monomers in the responsive polymer backbone allowed detailed probing of the pH mediated hydrophobic association using a combination of optical spectroscopic techniques. Both steady-state fluorescence spectroscopy and fluorescence lifetime measurements of poly-Cy3 revealed a conformational transition at pH 4.5. Thus, below a critical pH the polymer collapsed into a compact globular structure (hypercoil) bringing the fluorophore molecules into close proximity with one another. This resulted in a dramatic reduction in fluorescence intensity and fluorescent lifetime in the single fluorophore systems (poly-Cy3) accompanied by a red shift in the maximum emission wavelength. Observed redshifts in the emission maxima and enhancements of fluorescent lifetimes with increasing polymer concentration suggested the formation of polymer aggregates. Fluorescence resonance energy transfer (FRET) was measured in mixtures of single fluorophore containing poly-Cy3 (donor) and poly-Cy5 (acceptor) and dual fluorophore containing poly-Cy3 (donor)/Cy5 (acceptor) in an effort to distinguish between intra-molecular versus inter-molecular association. The relevance of the results with respect to potential in vivo applications (drug delivery and biodiagnostics) is discussed. 相似文献
3.
The N-oxide group of the cellulose solvent N-methylmorpholine-N-oxide showed a strong preference for the axial position compared with N-methyl as determined by NMR experiments and computational studies. In solvents with negligible solvent-solute interaction, about 95% of the NMMO molecules obtained a typical chair conformation with an axial N-O (1) while 5% had an equatorial N-O (2) at room temperature (25 °C). Other conformations (boat and twist) are energetically largely disfavored. N-Benzylmorpholine-N-oxide was prepared as reference compound possessing 100% axial N-O. Aprotic solvents of increasing polarity slightly shifted the conformation equilibrium towards the more polar conformer 2. The effect of protic solvents, capable of forming H-bonds, was more pronounced, with water increasing the percentage of 2 to 25% of the total population. Addition of sugar model compounds reversed this effect, so that formation of 2 was suppressed and exclusively 1 was found, indicating a strong interaction between the latter conformer and the carbohydrate. 相似文献
4.
化学法制备含锆沥青中锆的形态解析 总被引:1,自引:0,他引:1
采用X光电子能谱、X光衍射和背散射对含锆沥青中锆的存在方式进行了表征,结合实验现象推断出含锆沥青中锆是以氧化锆的方式存在的。含锆沥青制备过程中的反应实际上是氯化锆的水解和氧氯化锆的热分解反应,由于水解和生成的氯化氢气体的逸出,使新生成的氧化锆颗粒难以粘结在一起,从而在沥青中精细分散。在含锆沥青中的氧化锆颗粒在几微米尺度上,较粉末掺杂几十微米的颗粒有较大的改善。 相似文献
5.
c-Met is a transmembrane receptor tyrosine kinase and an important therapeutic target for anticancer drugs. In the present study, we systematically investigated the influence of a range of parameters on the correlation between experimental and calculated binding free energies of type II c-Met inhibitors. We especially focused on evaluating the impact of different force fields, binding energy calculation methods, docking protocols, conformation sampling strategies, and conformations of the binding site captured in several crystallographic structures. Our results suggest that the force fields, the protein flexibility, and the selected conformation of the binding site substantially influence the correlation coefficient, while the sampling strategies and ensemble docking only mildly affect the prediction accuracy. Structure-activity relationship study suggests that the structural determinants to the high binding affinity of the type II inhibitors originate from its overall linear shape, hydrophobicity, and two conserved hydrogen bonds. Results from this study will form the basis for establishing an efficient computational docking approach for c-Met type II inhibitors design. 相似文献
6.
This work is encouraged by the growing interest and recent success of quantum mechanics‐based methods in modeling of thermodynamic properties in the field of chemical engineering and life sciences. Among those, the COSMO‐RS model has become one of the most popular methods to predict phase equilibria in complex bio‐related systems. Recently, we have shown that the quality of predictions of n‐octanol/water and micelle/water partition coefficients is improved when the weighted mixtures of conformers are used to represent molecules, thereby demanding that the conformation analysis is performed for each component of the system. In this paper, different methods for performing the conformational search are evaluated. Micelle/water partition coefficients of solutes from different homologous series in aqueous solutions of Triton X100 as well as the n‐octanol/water partitioning of three common drugs (aminopinicillanic acid, ampicillin, and penicillin G) are calculated and compared with experimental data. Conformational analysis is made by the HyperChem program for the molecules placed in vacuum as well as by using the molecular dynamics simulation in a solvent medium (n‐octanol and water). It is demonstrated that molecular dynamics simulation is a promising tool to conduct conformational analysis. Along with the possibility of providing the conformers for large surfactant and pharmaceutical molecules, the method accounts for the solvent in a realistic manner. The results for micelle/water partition coefficients illustrate that n‐octanol is a reasonable approximation for the “micelle‐like” medium in molecular dynamics (MD) simulations. Predicted n‐octanol/water partition coefficients of three penicillins are in a good agreement with literature data and values calculated by a common quantitative structure‐activity relationship (QSAR). 相似文献
7.
随着北京奥运会的临近和全民健身运动的推广,全国各地均在进行不同程度的体育场馆新建、改建、扩建工程,体育建筑设计也逐渐进入更深入的专业化设计领域。该文基于体育场馆的空间特点,简要介绍了一些体育场馆内部常用声学材料的特点及使用。 相似文献
8.
The physicochemical and conformational properties of globulin (BG) and albumin (BA) fractions from common buckwheat seeds were characterised, and compared with those of buckwheat protein isolate (BPI). The polyphenol contents were also evaluated. The polyphenol content in BA was much higher than that in BG, and most of the polyphenols in the BA was in the free form, whilst that in the BG and BPI was mainly in the protein-bound form. The BA had higher content of uncharged polar amino acids, but lower acidic amino acids than BG. The protein solubility-pH profile of the BG and BA were very different, especially at pH 4.0–6.0. Far-UV and near-UV CD and intrinsic fluorescence spectra indicated that the secondary and/or tertiary conformations of BA were much more flexible than those of BG, but also more easily affected by the polyphenols. The results indicated that the properties of BG and BA varied considerably, and were largely dependent upon their polyphenol levels and the interactions of the polyphenols and the proteins. 相似文献
9.
The properties of NMOB/cadmium arachidate alternated multilayers 总被引:2,自引:0,他引:2
Hui Ai Yubo Fan Lei Tao Yi Fang Fenggang Tao Gongming Wang Wencheng Wang 《Thin solid films》1999,350(1-2):219-222
100 bilayers 2-nitro-5-(N-methyl-N-octadecyl)aminobenzoic acid (NMOB) and cadmium arachidate (CdA) alternated Langmuir–Blodgett (LB) film was fabricated. The thickness of NMOB monolayer is 2.85 nm measured by small angle X-ray diffraction. It shows that NMOB molecule stands vertically in the alternated film. A DFT method, B3LYP, was used to calculate the energies of various conformations of NMOB with 4-31G* basis set. The computational results show that the tilted conformation is the most stable and the energy difference between this conformation and the vertical one is 31 kJ/mol. The refractive indices of NMOB/CdA alternated films were also determined at different wavelengths by waveguide measurement. 相似文献
10.
Water-soluble polymers were degraded by ozone, and the degradation rate defined by the change of weight average polymerization degree per unit time was obtained. The degradation rate of poly(oxyethylene) (PEG) was proportional to the 1.5 to 2.0 power of the polymerization degree, and was 20 to 60 times that of poly(acrylamide) (PAAm). The experimental results of PEG and PAAm were correlated as a function of polymerization degree, temperature, dissolved ozone concentration and OH? ion concentration. The degradation rate of poly(sodium acrylate)(PANa) was proportional to the 2.0 power of the polymerization degree when no other electrolyte was added. However, the degradation rate of PANa decreased with the increase in NaCl concentration, and approached that of PAAm in the range of high NaCl concentrations. 相似文献