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排序方式: 共有341条查询结果,搜索用时 15 毫秒
1.
Oleinikova A Smolin N Brovchenko I Geiger A Winter R 《The journal of physical chemistry. B》2005,109(5):1988-1998
The formation of spanning hydrogen-bonded water networks on protein surfaces by a percolation transition is closely connected with the onset of their biological activity. To analyze the structure of the hydration water at this important threshold, we performed the first computer simulation study of the percolation transition of water in a model protein powder and on the surface of a single protein molecule. The formation of an infinite water network in the protein powder occurs as a 2D percolation transition at a critical hydration level, which is close to the values observed experimentally. The formation of a spanning 2D water network on a single rigid protein molecule can be described by adapting the cluster analysis of conventional percolation studies to the characterization of the connectivity of the hydration water on the surface of finite objects. Strong fluctuations of the surface water network are observed close to the percolation threshold. Our simulations also furnish a microscopic picture for understanding the specific values of the experimentally observed hydration levels, where different steps of increasing mobility in the hydrated powder are observed. 相似文献
2.
Experimental measurements of Tg for two series of lower homologues of polyethyleneoxide. differing in their end-groups, are discussed in terms of existing theories. Simple free-volume considerations predicting linear dependence of Tg on (molecular weight)?1 are inadequate in systems with end-groups capable of specific interactions (hydrogen bonding). Thermodynamic arguments show that the true Tg of infinitely long PEO chain is 220 ± 5°K. Suitable modification of parameters of the Gibbs-DiMarzio equations to account for the dependence of the free volume fraction on the concentration of end-groups results in good fit of the experimental data for hydroxyl-terminated samples and correctly predicts Tg(∞). Analysis of the data for chlorine-substituted oligomers suggests the existence of specific intermolecular interactions in the latter, involving chlorine atoms. 相似文献
3.
Piyarat Thanakoses Nagat Abd Alla Mostafa Mark T. Holtzapple 《Applied biochemistry and biotechnology》2003,107(1-3):523-546
Using the MixAlco process, biomass can be converted into carboxylic acids, which can be chemically converted into mixed alcohol
fuels. This study focused on the use of countercurrent fermentation to anaerobically convert sugarcane bagasse and chicken
manure to mixed carboxylic acids using a mixed culture of mesophilic microorganisms from terrestrial and marine sources. Bagasse
was pretreated with lime to increase digestibility. The continuum particle distribution model (CPDM) simulated continuous
fermentors based on data collected from batch experiments. This model saves considerable time in determining optimum operating
conditions. For an 80% bagasse/20% chicken manure fermentation with terrestrial inoculum at a volatile solids loading rate
(VSLR) of 7.36 g/(L of liquid·d) and a liquid residence time (LRT) of 8.88 d, total carboxylic acid productivity, total acid
selectivity, and yield were 2.49 g/(L of liquid·d), 0.581 g of total acid/g of VS digested, and 0.338 g of total acid/g of
VS fed, respectively, at a concentration of 18.7 g of total acid/L. At the same VSLR and LRT, fermentation with marine inoculum
gave higher total acid productivity, total acid selectivity, and yield than fermentation with terrestrial inoculum. For an
80% bagasse/20% chicken manure fermentation with marine inoculum at a VSLR of 3.83 g/(L of liquid·d) and an LRT of 12.1 d,
total carboxylic acid productivity, total acid selectivity, and yield were 1.38 g/(L of liquid·d), 0.667 g of total acid/g
of VS digested, and 0.359 g of total acid/g of VS fed, respectively, at a concentration of 16.2 g of total acid/L. 相似文献
4.
On the Constitution of Silicate Anions in Tetraethylammonium Silicates and their Aqueous Solutions Investigations by paperchromatography, 29Si-NMR spectroscopy and trimethylsilylation method show that concentrated solutions of tetraethylammonium (TEA) silicates with molar TEA:Si ratios from 2.8 to 1 contain mainly double three-ring silicate anions. Besides of these small amount of mono-, di-, tri-, tetra-, cyclotri-, cyclotetra-, double four-ring- and other polycyclic silicate anions are present. From these solutions a crystalline double three-ring silicate of the formula [N(C2H5)4]6[Si6O15] · 57 H2O could be obtained by crystallization at low temperature. Concentrated solutions with TEA:Si ratios of 0.8 to 0.6 contain mainly double three-, double four-, double five- an probably double six-ring silicate anions. From such solutions always the solid TEA-double four-ring silicate is obtained by crystallization. The reasons for the prefered formation of double ring silicate anions in TEA-silicate solutions and their crystallization are discussed. 相似文献
5.
Toxicity to algae is important characteristic of substances from ecologic point of view. The CORAL software (http://www.insilico.eu/coral) gives possibility to build up model of toxicity to algae using data on the molecular architecture and experimental toxicity, without additional data on physicochemical and/or biochemical parameters. Considerable improvement of the model is observed in the case of using the index of ideality of correlation (IIC) in the role of additional criterion of predictive potential. The IIC is calculated with using of the correlation coefficient between experimental and calculated values of endpoint for the calibration set, with taking into account the positive and negative dispersions between experimental and calculated values. The best model calculated with use the IIC is characterized (the validation set) by n?=?50, r2?=?0.947, RMSE?=?0.401 whereas, model calculated without use the IIC is characterized by n?=?50, r2?=?0.805, and RMSE?=?0.539. The suggested models are built up in accordance to five OECD principles. 相似文献
6.
Elka Kraleva Alla Spojakina Rumiana Edreva-Kardjieva Kveta Jiratova Lacezar Petrov 《Reaction Kinetics and Catalysis Letters》2007,92(1):111-119
HDS catalysts were prepared by loading H3PMo12O40 or H4PMo11V1O40 polyoxometallates on TiO2 (0.5 and 1.0 mmol (Mo+V)). Activity of the catalysts was tested in the HDS of thiophene. The activity of catalysts of low
concentration was 2–3 times higher than the activity of those of high concentration. Temperature programmed reduction (TPR)
and IR spectroscopy were used to determine the properties of the catalyst. TPR measurements proved that vanadium promotes
and stabilizes HDS activity due to an increase in the Mo5+/Mo4+ ratio. 相似文献
7.
The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed. 相似文献
8.
Dr. Alexander A. Larin Alexander V. Shaferov Dr. Alexander S. Kulikov Prof. Dr. Alla N. Pivkina Konstantin A. Monogarov Dr. Artem O. Dmitrienko Dr. Ivan V. Ananyev Dr. Dmitry V. Khakimov Prof. Dr. Leonid L. Fershtat Prof. Dr. Nina N. Makhova 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14628-14637
A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8–76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62–1.88 g cm−3), very high enthalpies of formation (846–1720 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.66–9.09 km s−1 and detonation pressures 25.0–37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN. 相似文献
9.
A new nickel(II) σ‐aryl complex, trans‐chloro(9‐phenanthrenyl)bis(triphenylphosphine)nickel(II), was used as a precatalyst for the Suzuki–Miyaura coupling reactions of aryl chlorides. The catalytic conditions were optimized by investigating the cross‐coupling of p‐chloroanisole with phenylboronic acid. The results show that this complex is efficient for both electron‐rich and electron‐deficient aryl chlorides, though it gives better yields for activated arylboronic acids than deactivated ones. All isolated cross‐coupled biaryl products have been characterized by 1H and 13C NMR, and their spectral data are consistent with those reported. Side products from the coupling of arylboronic acid with the precatalyst complex have also been isolated and characterized, which is helpful for understanding the coupling mechanism. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
10.
C. Lavilla A. Alla A. Martínez de Ilarduya E. Benito M.G. García‐Martín J.A. Galbis S. Muñoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3393-3406
Random poly(hexamethylene terephthalate‐co‐galactarate)s and poly(dodecamethylene terephthalate‐co‐galactarate)s copolyesters covering the whole range of compositions were obtained with weight‐average molecular weights of ~30,000–50,000 g mol?1 by melt polycondensation. They were thermally stable above 300 °C, and displayed Tg in the +20 to ?20 °C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 50 and 150 °C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress‐strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx‐diacid. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献