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51.
An Object-Based Shale Permeability Model: Non-Darcy Gas Flow,Sorption, and Surface Diffusion Effects
Shale samples consist of two major components: organic matter (OM) and inorganic mineral component (iOM). Each component has its distinct pore network topology and morphology, which necessitates generating a model capable of distinguishing the two media. We constructed an object-based model using the OM and iOM composition of shale samples. In the model, we integrated information such as OM population and size distribution, as well as its associated pore-size distribution. For the iOM part, we used mineralogy and pore-size information derived from X-ray diffraction, scanning electron microscopy, and nitrogen sorption measurements. Our proposed model results in millimeter-scale 2D realizations of shale samples by honoring OM and mineral types, their compositions, shapes, and size distributions. The model can capture heterogeneities smaller than 1 mm. We studied the effects of different gas flow processes and found that Knudsen diffusion and gas slippage dominate the flow, but surface diffusion has little impact on total gas flow. 相似文献
52.
Three‐Dimensional Branched and Faceted Gold–Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution Electrocatalysis
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Dr. Lucy Gloag Dr. Tania M. Benedetti Dr. Soshan Cheong Dr. Yibing Li Dr. Xuan‐Hao Chan Prof. Lise‐Marie Lacroix Prof. Shery L. Y. Chang Dr. Raul Arenal Dr. Ileana Florea Dr. Hector Barron Dr. Amanda S. Barnard Dr. Anna M. Henning Prof. Chuan Zhao Prof. Wolfgang Schuhmann Prof. J. Justin Gooding Prof. Richard D. Tilley 《Angewandte Chemie (International ed. in English)》2018,57(32):10241-10245
Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low‐index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close‐packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low‐index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts. 相似文献
53.
Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses
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Dr. Andrew Ballard Dr. Hiwa O. Ahmad Dr. Stefania Narduolo Lucy Rosa Nikki Chand Dr. David A. Cosgrove Dr. Peter Varkonyi Dr. Nabil Asaad Dr. Simone Tomasi Dr. Niklaas J. Buurma Dr. Andrew G. Leach 《Angewandte Chemie (International ed. in English)》2018,57(4):982-985
Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. 相似文献
54.
55.
A series of acrylic acid and 4(5)-vinylimidazole copolymers for a non-hydrous proton transferring membrane used in polymer electrolyte membrane for fuel cell (PEMFC) are reported. The feed ratio of each monomer results in the variation of copolymer as evaluated by Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (1H-NMR). Differential scanning calorimeter and thermal gravimetric analyzer confirm the thermal properties of copolymer films with Tg at 105-177 °C and Td above 230 °C. The simultaneous analysis of wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) suggests the thermal performance about the decrease in domain size as a consequence of the loss of moisture content in the membrane and the increase in domain size as a consequence of chain mobility after Tg. The proton conductivities under anhydrous condition of the copolymer membranes are in the range of 10−2 S/cm even up to 120 °C. 相似文献
56.
Ye L Miao C Brook MA Pelton R 《Langmuir : the ACS journal of surfaces and colloids》2008,24(17):9341-9343
Photocatalytic TiO 2 was derivatized with an amino silane to give a positively charged colloidal suspension in water. UV irradiation of the cationic titania oxidized the organo silane coating converting the titania to a negatively charged colloid. Irradiation of mixed suspensions of cationic titania and cationic polyvinylamine microgel induced catastrophic flocculation. Electrophoresis and XPS evidence suggests that the UV removed the amine groups from the titania resulting in heteroflocculation of anionic titania with cationic microgel particles. 相似文献
57.
Doye JP Louis AA Lin IC Allen LR Noya EG Wilber AW Kok HC Lyus R 《Physical chemistry chemical physics : PCCP》2007,9(18):2197-2205
The ability to control the crystallization behaviour (including its absence) of particles, be they biomolecules such as globular proteins, inorganic colloids, nanoparticles, or metal atoms in an alloy, is of both fundamental and technological importance. Much can be learnt from the exquisite control that biological systems exert over the behaviour of proteins, where protein crystallization and aggregation are generally suppressed, but where in particular instances complex crystalline assemblies can be formed that have a functional purpose. We also explore the insights that can be obtained from computational modelling, focussing on the subtle interplay between the interparticle interactions, the preferred local order and the resulting crystallization kinetics. In particular, we highlight the role played by "frustration", where there is an incompatibility between the preferred local order and the global crystalline order, using examples from atomic glass formers and model anisotropic particles. 相似文献
58.
Agibert SA Moreira MB Ratusznei SM Rodrigues JA Zaiat M Foresti E 《Applied biochemistry and biotechnology》2007,136(2):193-206
The effect of temperature on the performance of an anaerobic sequencing biofilm batch reactor (ASBBR) with liquid-phase recirculation
was assessed. Assays were performed using a recirculation velocity of 0.20 cm/s, 8-h cycles, and an average treated synthetic
wastewater volume of 2 L/cycle with a concentration of 500 mg of Chemical Oxygen Demand (COD)/L. Operation temperatures were
15, 20, 25, 30, and 35°C. At 25, 30, and 35°C, organic matter removal efficiencies for filtered samples ranged from 81 to
83%. At lower temperatures, namely 15 and 20°C, removal efficiency decreased significantly to 61 and 65%, respectively. A
first-order model could be fitted to the experimental concentration profile values. The first-order kinetic parameter value
of this model varied from 0.46 to 0.81 h1 considering the lowest and highest temperature studied. Moreover, analysis of the removal profile values allowed fitting
of an Arrhenius-type equation with an activation energy of 5715 cal/mol. 相似文献
59.
Polymeric micelle systems of hydroxycamptothecin based on amphiphilic N-alkyl-N-trimethyl chitosan derivatives 总被引:5,自引:0,他引:5
This research investigated the possible utilization of amphiphilic N-octyl-N-trimethyl chitosan (OTMCS) derivatives in solublization and controlled release of 10-hydroxycamptothecin (10-HCPT), a hydrophobic anticancer drug. The release behavior of the 10-HCPT-OTMCS micelles was measured and compared to that of a commercial 10-HCPT lyophilized powder in vitro and in vivo. This research also examined the effects of chemical structure of the chitosan derivatives and the micellar preparation conditions on the encapsulation efficiency, drug loading content, and particle size of the polymeric micelles. The results showed that these chitosan derivatives were able to self-assemble and form spherical shape polymeric micelles with an average particle size range of 24–280 nm and a drug loading content of 4.1–32.5%, depending on the modified structures and loading procedures. The solubility of 10-HCPT in aqueous fluid was increased about 80,000-fold from 2 ng/ml in water to 1.9 mg/ml in OTMCS micellar (degree of octyl and trimethyl substitution is 8% and 54%, respectively) solution. In addition, OTMCS was able to modulate the in vitro release of 10-HCPT and improve its pharmacokinetic properties and lactone ring stability in vivo. These data suggested the possible utilization of the amphiphilic micellar chitosan derivatives as carriers for hydrophobic drugs for improving their delivery and release properties. 相似文献
60.
Douglas B. Grotjahn Aldo J. Apponi Matthew A. Brewster Ju Xin Lucy M. Ziurys 《Angewandte Chemie (International ed. in English)》1998,37(19):2678-2681
The simplest alkali metal acetylides MCCH were made in the gas phase for the first time (see drawing), and their bond lengths were determined by millimeter/submillimeter spectroscopy of their isotopomers. The M−C bond lengths rCM are the shortest known for organoalkali metal compounds. In the case of LiCCH, the experimentally determined Li−C distance of 1.888 Å has an estimated accuracy of ±0.0005 Å, which should allow a rigorous test of theoretical methods. 相似文献