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91.
92.
Krivdin LB Chernyshev KA Rosentsveig GN Ushakova IV Rosentsveig IB Levkovskaya GG 《Magnetic resonance in chemistry : MRC》2007,45(11):980-984
Configurational assignment of seven synthesized N-arylsulfonylimines of alpha-polychloroaldehydes has been carried out by means of experimental measurements and high-level ab initio calculations of their (13)C--(13)C, (13)C--(1)H and (15)N--(1)H spin-spin coupling constants. The title compounds were shown to exist in solution solely in the form of E isomers, in line with thermodynamic reasoning. 相似文献
93.
Koptyug IV Kovtunov KV Burt SR Anwar MS Hilty C Han SI Pines A Sagdeev RZ 《Journal of the American Chemical Society》2007,129(17):5580-5586
We demonstrate the creation and observation of para-hydrogen-induced polarization in heterogeneous hydrogenation reactions. Wilkinson's catalyst, RhCl(PPh3)3, supported on either modified silica gel or a polymer, is shown to hydrogenate styrene into ethylbenzene and to produce enhanced spin polarizations, observed through NMR, when the reaction was performed with H2 gas enriched in the para spin isomer. Furthermore, gaseous phase para-hydrogenation of propylene to propane with two catalysts, the Wilkinson's catalyst supported on modified silica gel and Rh(cod)(sulfos) (cod = cycloocta-1,5-diene; sulfos = -O3S(C6H4)CH2C(CH2PPh2)3) supported on silica gel, demonstrates heterogeneous catalytic conversion resulting in large spin polarizations. These experiments serve as a direct verification of the mechanism of heterogeneous hydrogenation reactions involving immobilized metal complexes and can be potentially developed into a practical tool for producing catalyst-free fluids with highly polarized nuclear spins for a broad range of hyperpolarized NMR and MRI applications. 相似文献
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96.
Kirill Tsiberkin 《Transport in Porous Media》2018,121(1):109-120
The study considers an effect of the nonlinear inertial terms in the Brinkman filtration equation on the characteristics of coupled flows in a pure fluid and porous medium in the frameworks of two independent problems. The first problem is the forced boundary-layer flow overlying the Darcy–Brinkman porous medium. The Prandtl theory is used, and the self-similar equations are built to describe it. It is shown that the inertial terms have a valuable effect on the boundary-layer structure because of the large velocity gradient in the transition zone. The boundary-layer thickness in a porous medium rapidly grows at large Reynolds numbers. The velocity magnitude and gradient at the interface also change. The second independent problem is an analysis of the inertial terms effect on the flow stability. The neutral curves of the full and linearized flow models are built using the shooting method. They have different short-wave asymptotic, but there are no significant changes in the critical Reynolds numbers and corresponding wave numbers. 相似文献
97.
Kirill Tsiberkin 《Transport in Porous Media》2018,125(2):259-269
The study considers the forced boundary-layer flow overlying the Darcy–Brinkman porous medium and gives a quantitative analysis of the nonlinear inertial terms in the Brinkman filtration equation. The inertial terms are shown to be larger than the Darcy’s drag near the porous medium interface. The applicability range of boundary-layer approach is determined. It is suitable in high-permeable media with moderate velocities of an external flow. If it is slow enough, the inertial terms can be omitted in spite of interface effect. On the other hand, fast external flow produces the filtration with large pore-scale Reynolds number; therefore, the Forchheimer’s drag should be taken into account. It is shown the Brinkman term as well as inertial terms have a significant role in boundary-layer formation within the porous medium. 相似文献
98.
Diels-Alder ligation of peptides and proteins 总被引:2,自引:0,他引:2
de Araújo AD Palomo JM Cramer J Seitz O Alexandrov K Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(23):6095-6109
The development of the Diels-Alder cycloaddition as a new method for the site-specific chemoselective ligation of peptides and proteins under mild conditions is reported. Peptides equipped with a 2,4-hexadienyl ester and an N-terminal maleimide react in aqueous media to give cycloadducts in high yields and depending on the amino acid sequence with high stereoselectivity. Except for the cysteine SH group the transformation is compatible with all amino acid side chain functional groups. For ligation to proteins the hexadienyl group was attached to avidin and streptavidin noncovalently by means of complex formation with a biotinylated peptide or by covalent attachment of a hexadienyl ester-containing label to lysine side chains incorporated into the proteins. Site-specific attachment of the hexadienyl unit into a Rab protein was achieved by means of expressed protein ligation followed by protection of the generated cysteine SH by means of Ellman's reagent. The protein reacted with different maleimido-modified peptides under mild conditions to give the fully functional cycloadducts in high yield. The results demonstrate that the Diels-Alder ligation offers an advantageous and technically straightforward new opportunity for the site-specific equipment of peptides and proteins with further functional groups and labels. It proceeds under very mild conditions and is compatible with most functional groups found in proteins. Its combination with other ligation methods, in particular expressed protein ligation is feasible. 相似文献
99.
Genzer J Efimenko K Fischer DA 《Langmuir : the ACS journal of surfaces and colloids》2006,22(20):8532-8541
The goal of this study is to elucidate the formation of molecular gradients made of semifluorinated organosilanes (SFOs) on flat substrates by using a methodology developed by Chaudhury and Whitesides (Science 1992, 256, 1539). We use surface-sensitive combinatorial near-edge X-ray absorption fine structure (combi-NEXAFS) spectroscopy to measure the position-dependent concentration and orientation of SFO molecules in SFO molecular gradients on flat silica surfaces. Using the combi-NEXAFS data, we establish the correlation between the fraction of the F(CF(2))(8)(CH(2))(2)- species on the substrate and the average tilt angle of the -(CF(2))(8)F group in the SFO as a function of the deposition gas medium (air vs nitrogen) and the end group around the silicon atom (monofunctional vs trifunctional). In addition, we utilize the gradient geometry to comprehend the mechanism of formation of SFO self-assembled monolayers (SAMs). Specifically, we provide evidence that depending on the nature of the end group in the SFO and the vapor phase the SFO molecules add themselves into the existing SAMs either as individual molecules or as multimolecular complexes. 相似文献
100.
Krivdin LB Larina LI Chernyshev KA Rulev AY 《Magnetic resonance in chemistry : MRC》2006,44(2):178-187
Configurational assignment of seven azomethines obtained from the alpha-functionally substituted and nonsubstituted alpha,beta-unsaturated aldehydes has been performed on the basis of experimental measurements and the high-level ab initio calculations of their 1J(C,C) and 1J(C,H), involving the alpha-imino carbon that demonstrated the marked stereochemical dependence of both coupling constants upon the orientation of the nitrogen lone pair in the diverse isomers of the title azomethines. 相似文献