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991.
S He AT Lam Y Jeune-Smith H Hess 《Langmuir : the ACS journal of surfaces and colloids》2012,28(29):10635-10639
The nanoscale architecture of binding sites can result in complex binding kinetics. Here, the adsorption of streptavidin and neutravidin to biotinylated microtubules is found to exhibit negative cooperativity due to electrostatic interactions and steric hindrance. This behavior is modeled by a newly developed kinetic analogue of the Fowler-Guggenheim adsorption model. The complex adsorption kinetics of streptavidin to biotinylated structures needs to be considered when these intermolecular bonds are employed in self-assembly and nanobiotechnology. 相似文献
992.
A thiouronium-based solid-phase synthesis of a 1,3,5-triazine scaffold has been developed. The key feature of the synthesis is the use of a readily accessible solid-supported thiouronium salt as a primary precursor for the stepwise assembly of the 1,3,5-triazine substrate. The sulfur linker employed in the synthesis is stable under both acidic and basic conditions and is versatile enough to provide access to monocyclic, bicyclic, and spirocyclic compounds with the 1,3,5-triazine scaffold. By using this synthetic strategy, a representative set of 79 compounds containing the 1,3,5-triazine scaffold were prepared. 相似文献
993.
Qiang Wei Haiqin Deng Yunbo Cai Jacky W. Y. Lam Jie Li Jingzhi Sun Meng Gao Anjun Qin Ben Zhong Tang 《Macromolecular rapid communications》2012,33(16):1356-1361
The 1,3‐dipolar cycloaddition of azides and active internal alkynes has been well studied, but is rarely utilized as a tool for polymer preparation. In this work, an efficient polymerization route is developed. Polycycloaddition of diazide ( 4 ) and bis(benzoylethynyl)‐benzenes and ‐butane ( 3 ) at elevated temperature has produced the first examples of soluble 1,4,5‐trisubstituted polytriazoles P I with satisfactory molecular weights (M w up to 16 400) in excellent yields (up to 98.6%). All the obtained polymers are thermally stable, losing merely 5% of their weights at temperatures higher than 367 °C. They exhibit higher refractive indices than some commercial plastics and can be crosslinked upon UV irradiation to generate a 3D photopattern with high resolution. The metal‐free feature of such a methodology offers a facile tool to prepare functional materials free from the contamination of metal species. 相似文献
994.
Dezhi Xu Mozhen Wang Xuewu Ge Michael Hon‐Wah Lam 《Macromolecular rapid communications》2012,33(22):1945-1951
Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization. 相似文献
995.
Y Wang L Davidow AC Arvanites J Blanchard K Lam K Xu V Oza JW Yoo JM Ng T Curran LL Rubin AP McMahon 《Chemistry & biology》2012,19(8):972-982
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996.
Ordered mesoporous aluminas with high surface areas (up to 783 m2/g), large pore volumes (up to 0.82 cm3/g) and the presence of complementary micropores (up to 0.17 cm3/g) are synthesized with Pluronic® F127 or P123 triblock copolymers in a one-pot synthesis of metal alkoxide, template and cosolvent molecules such as 1,3,5-trimethylbenzene or 1,3,5-triisopropylbenzene in an acidic ethanol solution at 15 °C. Materials are characterized by nitrogen adsorption analysis, small-angle X-ray diffraction and transmission electron microscopy. 相似文献
997.
将核酸适配体作为胰蛋白酶固定化介质,制备了一种新型的微流控芯片酶反应器,并与高效液相色谱-串联质谱联用,搭建了在线分析平台;分别使用标准蛋白及混合蛋白样品对芯片的酶解效率及联用平台的分析能力进行了初步评价。结果表明,5 ng肌红蛋白经该平台分析后肽段覆盖率可达到37%;对500 ng混合蛋白进行3次平行分析,肽段覆盖率及相对标准偏差分别为44.3%、6.5%(牛血清白蛋白), 65.0%、2.7%(肌红蛋白)和62.0%、5.6%(细胞色素c);初步实验表明,该在线分析平台具有检测灵敏度高、重现性好、酶解效率高的特点,有望在蛋白质组学分析中发挥重要作用。 相似文献
998.
Discrete DNA decorations of Pt nanoparticles (PtNPs) are realized for the first time, which provide a valence control over the quasi-molecular self-assembly of Au-Pt bimetallic heteronanostructures with DNA as the guide. 相似文献
999.
Villano SM Huynh LK Carstensen HH Dean AM 《The journal of physical chemistry. A》2012,116(21):5068-5089
The unimolecular reactions of hydroperoxy alkyl radicals (QOOH) play a central role in the low-temperature oxidation of hydrocarbons as they compete with the addition of a second O(2) molecule, which is known to provide chain-branching. In this work we present high-pressure rate estimation rules for the most important unimolecular reactions of the β-, γ-, and δ-QOOH radicals: isomerization to RO(2), cyclic ether formation, and selected β-scission reactions. These rate rules are derived from high-pressure rate constants for a series of reactions of a given reaction class. The individual rate expressions are determined from CBS-QB3 electronic structure calculations combined with canonical transition state theory calculations. Next we use the rate rules, along with previously published rate estimation rules for the reactions of alkyl peroxy radicals (RO(2)), to investigate the potential impact of falloff effects in combustion/ignition kinetic modeling. Pressure effects are examined for the reaction of n-butyl radical with O(2) by comparison of concentration versus time profiles that were obtained using two mechanisms at 10 atm: one that contains pressure-dependent rate constants that are obtained from a QRRK/MSC analysis and another that only contains high-pressure rate expressions. These simulations reveal that under most conditions relevant to combustion/ignition problems, the high-pressure rate rules can be used directly to describe the reactions of RO(2) and QOOH. For the same conditions, we also address whether the various isomers equilibrate during reaction. These results indicate that equilibrium is established between the alkyl, RO(2), and γ- and δ-QOOH radicals. 相似文献
1000.
Calculations were carried out for 25 isotopologues of the title reaction for various combinations of (35)Cl, (37)Cl, (12)C, (13)C, (14)C, H, and D. The computed rate constants are based on harmonic vibrational frequencies calculated at the CCSD(T)/aug-cc-pVTZ level of theory and X(ij) vibrational anharmonicity coefficients calculated at the CCSD(T) /aug-cc-pVDZ level of theory. For some reactions, anharmonicity coefficients were also computed at the CCSD(T)/aug-cc-pVTZ level of theory. The classical reaction barrier was taken from Eskola et al. [J. Phys. Chem. A 2008, 112, 7391-7401], who extrapolated CCSD(T) calculations to the complete basis set limit. Rate constants were calculated for temperatures from ~100 to ~2000 K. The computed ab initio rate constant for the normal isotopologue is in good agreement with experiments over the entire temperature range (~10% lower than the recommended experimental value at 298 K). The ab initio H/D kinetic isotope effects (KIEs) for CH(3)D, CH(2)D(2), CHD(3), and CD(4) are in very good agreement with literature experimental data. The ab initio (12)C/(13)C KIE is in error by ~2% at 298 K for calculations using X(ij) coefficients computed with the aug-cc-pVDZ basis set, but the error is reduced to ~1% when X(ij) coefficients computed with the larger aug-cc-pVTZ basis set are used. Systematic improvements appear to be possible. The present SCTST results are found to be more accurate than those from other theoretical calculations. Overall, this is a very promising method for computing ab initio kinetic isotope effects. 相似文献