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1.
Cass T. Miller Francisco J. Valdés-Parada Sassan Ostvar Brian D. Wood 《Transport in Porous Media》2018,122(3):611-632
The thermodynamically constrained averaging theory (TCAT) has been used to develop a simplified entropy inequality (SEI) for several major classes of macroscale porous medium models in previous works. These expressions can be used to formulate hierarchies of models of varying sophistication and fidelity. A limitation of the TCAT approach is that the determination of model parameters has not been addressed other than the guidance that an inverse problem must be solved. In this work we show how a previously derived SEI for single-fluid-phase flow and transport in a porous medium system can be reduced for the specific instance of diffusion in a dilute system to guide model closure. We further show how the parameter in this closure relation can be reliably predicted, adapting a Green’s function approach used in the method of volume averaging. Parameters are estimated for a variety of both isotropic and anisotropic media based upon a specified microscale structure. The direct parameter evaluation method is verified by comparing to direct numerical simulation over a unit cell at the microscale. This extension of TCAT constitutes a useful advancement for certain classes of problems amenable to this estimation approach. 相似文献
2.
Jiang Wang Brian P. Cary Peyton D. Beyer Samuel H. Gellman Daniel J. Weix 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(35):12209-12213
Synthesis of the C?C bonds of ketones relies upon one high‐availability reagent (carboxylic acids) and one low‐availability reagent (organometallic reagents or alkyl iodides). We demonstrate here a ketone synthesis that couples two different carboxylic acid esters, N‐hydroxyphthalimide esters and S‐2‐pyridyl thioesters, to form aryl alkyl and dialkyl ketones in high yields. The keys to this approach are the use of a nickel catalyst with an electron‐poor bipyridine or terpyridine ligand, a THF/DMA mixed solvent system, and ZnCl2 to enhance the reactivity of the NHP ester. The resulting reaction can be used to form ketones that have previously been difficult to access, such as hindered tertiary/tertiary ketones with strained rings and ketones with α‐heteroatoms. The conditions can be employed in the coupling of complex fragments, including a 20‐mer peptide fragment analog of Exendin(9–39) on solid support. 相似文献
3.
Gui‐Ping Zhu Kian‐Soo Ong Karen Siew‐Ling Chong Jia‐Feng Yao Hu‐Lin Huang Fei Duan 《Electrophoresis》2019,40(6):845-850
Micro‐structure patterned substrates attract our attention due to the special and programmable wettabilities. The interaction between the liquid and micro/nano structures gives rise to controllable spreading and thus evaporation. For exploration of the application versatility, the introduction of nanoparticles in liquid droplet results in interaction among particles, liquid and microstructures. In addition, temperature of the substrates strongly affects the spreading of the contact line and the evaporative property. The evaporation of sessile droplets of nanofluids on a micro‐grooved solid surface is investigated in terms of liquid and surface properties. The patterned nickel surface used in the experiments is designed and fabricated with circular and rectangular shaped pillars whose size ratios between interval and pillars is fixed at 5. The behavior is firstly compared between nanofluid and pure liquid on substrates at room temperature. For pure water droplet, the drying time is relatively longer due to the receding of contact line which slows down the liquid evaporation. Higher concentrations of nanoparticles tend to increase the total evaporation time. With varying concentrations of graphite at nano scale from 0.02% to 0.18% with an interval at 0.04% in water droplets and the heating temperature from 22 to 85°C, the wetting and evaporation of the sessile droplets are systematically studied with discussion on the impact parameters and the resulted liquid dynamics as well as the stain. The interaction among the phases together with the heating strongly affects the internal circulation inside the droplet, the evaporative rate and the pattern of particles deposition. 相似文献
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Jennifer M. Ruddock Nikola Zotev Brian Stankus Haiwang Yong Darren Bellshaw Sbastien Boutet Thomas J. Lane Mengning Liang Sergio Carbajo Wenpeng Du Adam Kirrander Michael Minitti Peter M. Weber 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(19):6437-6441
Time‐resolved pump–probe gas‐phase X‐ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N?C bond length of 1.45±0.02 Å and a C?N?C bond angle of 118°±4°. 相似文献
6.
Derek Yiren Ong Zhihao Yen Asami Yoshii Julia RevilloImbernon Ryo Takita Shunsuke Chiba 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5046-5051
New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH‐ZnI2 system delivers alcohols and NaH‐ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines. 相似文献
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8.
Transition Metal Chemistry - (η5-Dp)Ru(PPh3)2H (Dp?=?C8H9?, 1,2-dihydropentalenyl) was synthesized in 90% yield by reaction of (η5-Dp)Ru(PPh3)2Cl with sodium formate.... 相似文献
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10.
David Tong Jackie Wu Nathan Bazinski Donghyun Koo Naresh Vemula Prof. Dr. Brian L. Pagenkopf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(67):15244-15247
Cycloadditions of strained carbocycles promoted by Lewis acids are powerful methods to construct heterocyclic frameworks. In fact, the formal [3+2] cycloadditions of donor–acceptor (DA) cyclopropanes with nitriles has seen particular success in synthesis. In this work, we report on the first [4+2] cycloaddition of nitriles with DA cyclobutanes by Lewis acid activation. Tetrahydropyridine derivatives were obtained in up to 91 % yield from various aryl-activated cyclobutane diesters and aliphatic or aromatic nitriles. 相似文献