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211.
Heat and mass transfer in unsaturated porous media at a hot boundary: I. One-dimensional analytical model 总被引:2,自引:0,他引:2
We present a model of heat and mass transfer in an unsaturated zone of sand and silty clay soils, taking into account the effects of temperature gradients on the advective flux, and of the enhancement of thermal conduction by the process of latent heat transfer through vapor flow. The motivation for this study is to supply information for the planned storage of thermal energy in unsaturated soils and for hot waste storage. Information is required on the possibility of significant drying at a hot boundary, as this would reduce the thermal conductivity of a layer adjacent to the boundary and, thus, prevent effective heat transfer to the soil. This study indicates the possibility that the considered system may be unstable, with respect to the drying conditions, with the occurrence of drying depending on the initial and the boundary conditions. An analysis performed for certain boundary conditions of heat transfer and for given soil properties, disregarding the advective flux of energy, indicated that there are initial conditions of water content for which heating will not cause significant drying. Under these conditions, fine soils may be better suited for heat transfer at the hot boundary, due to their higher field capacity, although their heat conduction coefficients at saturation are lower than those of sandy soils. At present, these conclusions are limited to the range of 50–80°C. Potential effects of solute concentration at the hot boundary are indicated. 相似文献
212.
A generalization of the Navier-Stokes equation is developed to include laminar flow through a rigid isotropic granular porous medium of spatially varying permeability. The model is based on a theory of interspersed continua and the mean geometrical properties of an idealized granular porous microstructure. The derived momentum transport equations are applicable to granular porous media over the entire porosity range from zero through unity. No restriction with respect to flow velocity is imposed, except for the assumption of laminar flow within the pores. The results provide useful and versatile equations and substantiate many of the empirical equations currently in use. One of the major advantages of the generalized momentum equation is its adaptability to numerical simulation. 相似文献
213.
Targeting the Two Oncogenic Functional Sites of the HPV E6 Oncoprotein with a High‐Affinity Bivalent Ligand
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214.
Multiscale Modeling of the Active Site of [Fe] Hydrogenase: The H2 Binding Site in Open and Closed Protein Conformations
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Dr. Erik Donovan Hedegård Prof. Jacob Kongsted Prof. Ulf Ryde 《Angewandte Chemie (International ed. in English)》2015,54(21):6246-6250
A series of QM/MM optimizations of the full protein of [Fe] hydrogenase were performed. The FeGP cofactor has been optimized in the water‐bound resting state ( 1 ), with a side‐on bound dihydrogen ( 2 ), or as a hydride intermediate ( 3 ). For inclusion of H4 MPT in the closed structure, advanced multiscale modeling appears to be necessary, especially to obtain reliable distances between CH‐H4MPT+ and the dihydrogen (H2) or hydride (H?) ligand in the FeGP cofactor. Inclusion of the full protein is further important for the relative energies of the two intermediates 2 and 3 . We finally find that hydride transfer from 3 has a significantly higher barrier than found in previous studies neglecting the full protein environment. 相似文献
215.
Aryne‐Induced Novel Tandem 1,2‐Addition/(3+2) Cycloaddition to Generate Imidazolidines and Pyrrolidines
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Dr. Sharada P. Swain Yi‐Chun Shih Dr. Shwu‐Chen Tsay Joby Jacob Dr. Chun‐Cheng Lin Dr. Kuo Chu Hwang Dr. Jia‐Cherng Horng Prof. Dr. Jih Ru Hwu 《Angewandte Chemie (International ed. in English)》2015,54(34):9926-9930
A new “single‐flask” method was developed for the synthesis of imidazolidines and pyrrolidines with high stereoselectivity. First, a Schiff base was arylated with an aryne. Second, an intramolecular proton transfer took place from the methylene position to the anionic aryne ring. Third, the resultant ylide reacted with a second equivalent of the same Schiff base in situ or an electron‐deficient alkene through a (3+2) cycloaddition. These sequential tandem 1,2‐addition/(3+2) cycloaddition reactions led to the desired heterocycles in 63–88 % yields. 相似文献
216.
Jacob C. Timmerman Bradley D. Robertson Prof. Ross A. Widenhoefer 《Angewandte Chemie (International ed. in English)》2015,54(7):2251-2254
The cationic gold phosphine complex [{PCy2(o‐biphenyl)}Au(NCMe)]+SbF6? (Cy=cyclohexyl) catalyzes the intermolecular, anti‐Markovnikov hydroamination reaction of monosubstituted and cis‐ and trans‐disubstituted alkylidenecyclopropanes (ACPs) with imidazolidin‐2‐ones and other nucleophiles. This reaction forms 1‐cyclopropyl alkylamine derivatives in high yield and with high regio‐ and diastereoselectivity. NMR spectroscopic analysis of gold π‐ACP complexes and control experiments point to the sp hybridization of the ACP internal alkene carbon atom as controlling the regiochemistry of the ACP hydroamination reaction. 相似文献
217.
Energetic 2,2‐Dimethyltriazanium Salts: A New Family of Nitrogen‐Rich Hydrazine Derivatives
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Dr. Valérian Forquet Dr. Carlos Miró Sabaté Dr. Guy Jacob Dr. Yann Guelou Dr. Henri Delalu Dr. Chaza Darwich 《化学:亚洲杂志》2015,10(8):1668-1675
Amination of 1,1‐dimethylhydrazine with NH2Cl or hydroxylamine‐O‐sulfonic acid yields 2,2‐dimethyltriazanium (DMTZ) chloride ( 3 ) and sulphate ( 4 ), respectively. The DMTZ cation was paired with the nitrogen‐rich anions 5‐aminotetrazolate ( 5 ), 5‐nitrotetrazolate ( 6 ), 5,5′‐azobistetrazolate ( 7 ), and azide ( 8 ), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8 , which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X‐ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed. 相似文献
218.
A peptide has been designed so that its chelating affinity for one type of metal ion regulates its affinity for a second, different type of metal ion. The prochelator peptide (PCP), which is a fusion of motifs evocative of calcium loops and zinc fingers, forms a 1 : 2 Zn : peptide complex at pH 7.4 that increases its affinity for Zn2+ ∼3-fold in the presence of Tb3+ (log β2 from 13.8 to 14.3), while the 1 : 1 luminescent complex with Tb3+ is brighter, longer lived, and 20-fold tighter in the presence of Zn2+ (log K from 6.2 to 7.5). This unique example of cooperative, heterometallic allostery in a biologically compatible construct suggests the possibility of designing conditionally active metal-binding agents that could respond to dynamic changes in cellular metal status. 相似文献
219.
Mansoureh Shahalami Louxiang Wang Chu Wu Jacob H. Masliyah Zhenghe Xu Derek Y.C. Chan 《Advances in colloid and interface science》2015
The interaction between bubbles and solid surfaces is central to a broad range of industrial and biological processes. Various experimental techniques have been developed to measure the interactions of bubbles approaching solids in a liquid. A main challenge is to accurately and reliably control the relative motion over a wide range of hydrodynamic conditions and at the same time to determine the interaction forces, bubble–solid separation and bubble deformation. Existing experimental methods are able to focus only on one of the aspects of this problem, mostly for bubbles and particles with characteristic dimensions either below 100 μm or above 1 cm. As a result, either the interfacial deformations are measured directly with the forces being inferred from a model, or the forces are measured directly with the deformations to be deduced from the theory. The recently developed integrated thin film drainage apparatus (ITFDA) filled the gap of intermediate bubble/particle size ranges that are commonly encountered in mineral and oil recovery applications. Equipped with side-view digital cameras along with a bimorph cantilever as force sensor and speaker diaphragm as the driver for bubble to approach a solid sphere, the ITFDA has the capacity to measure simultaneously and independently the forces and interfacial deformations as a bubble approaches a solid sphere in a liquid. Coupled with the thin liquid film drainage modeling, the ITFDA measurement allows the critical role of surface tension, fluid viscosity and bubble approach speed in determining bubble deformation (profile) and hydrodynamic forces to be elucidated. Here we compare the available methods of studying bubble–solid interactions and demonstrate unique features and advantages of the ITFDA for measuring both forces and bubble deformations in systems of Reynolds numbers as high as 10. The consistency and accuracy of such measurement are tested against the well established Stokes–Reynolds–Young–Laplace model. The potential to use the design principles of the ITFDA for fundamental and developmental research is demonstrated. 相似文献
220.
Dr. Tian Qin Dr. Lara R. Malins Jacob T. Edwards Rohan R. Merchant Alexander J. E. Novak Jacob Z. Zhong Riley B. Mills Ming Yan Dr. Changxia Yuan Dr. Martin D. Eastgate Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2017,56(1):260-265
Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH3) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry. 相似文献