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排序方式: 共有480条查询结果,搜索用时 992 毫秒
91.
Spin labeled 2'-deoxyuridine, in which a significant fraction of the spin density is delocalized from a nitroxide radical to the DNA base residue, was prepared as a crystalline solid, stable at ambient conditions. The crystal packing, which includes multiple hydrogen bonds, leads to one-dimensional chains of molecules with predominant intrachain ferromagnetic coupling and weaker interchain antiferromagnetic coupling. 相似文献
92.
Prakash S Alia A Gast P de Groot HJ Matysik J Jeschke G 《Journal of the American Chemical Society》2006,128(39):12794-12799
Photochemically induced dynamic nuclear polarization (photo-CIDNP) is observed in photosynthetic reaction centers of the carotenoid-less strain R26 of the purple bacterium Rhodobacter sphaeroides by (13)C solid-state NMR at three different magnetic fields (4.7, 9.4, and 17.6 T). The signals of the donor appear enhanced absorptive (positive) and of the acceptor emissive (negative). This spectral feature is in contrast to photo-CIDNP data of reactions centers of Rhodobacter sphaeroides wildtype reported previously (Prakash, S.; Alia; Gast, P.; de Groot, H. J. M.; Jeschke, G.; Matysik, J. J. Am. Chem. Soc. 2005, 127, 14290-14298) in which all signals appear emissive. The difference is due to an additional mechanism occurring in RCs of R26 in the long-living triplet state of the donor, allowing for spectral editing by different enhancement mechanisms. The overall shape of the spectra remains independent of the magnetic field. The strongest enhancement is observed at 4.7 T, enabling the observation of photo-CIDNP enhanced NMR signals from reaction center cofactors in entire bacterial cells allowing for detection of subtle changes in the electronic structure at nanomolar concentration of the donor cofactor. Therefore, we establish in this paper photo-CIDNP MAS NMR as a method to study the electronic structure of photosynthetic cofactors at the molecular and atomic resolution as well as at cellular concentrations. 相似文献
93.
Wolfgang Dreyer Maren Hantke Gerald Warnecke 《Continuum Mechanics and Thermodynamics》2014,26(4):521-549
We study averaging methods for the derivation of mixture equations for disperse vapor bubbles in liquids. The carrier liquid is modeled as a continuum, whereas simplified assumptions are made for the disperse bubble phase. An approach due to Petrov and Voinov is extended to derive mixture equations for the case that there is a phase transition between the carrier liquid and the vapor bubbles in water. We end up with a system of balance laws for a multi-phase mixture, which is completely in divergence form. Additional non-differential source terms describe the exchange of mass, momentum and energy between the phases. The sources depend explicitly on evolution laws for the total mass, the radius and the temperature of single bubbles. These evolution laws are derived in a prior article (Dreyer et al. in Cont Mech Thermodyn. doi:10.1007/s00161-0225-6, 2011) and are used to close the system. Finally, numerical examples are presented. 相似文献
94.
Tran BL Washington MP Henckel DA Gao X Park H Pink M Mindiola DJ 《Chemical communications (Cambridge, England)》2012,48(10):1529-1531
Treatment of d(1) [(nacnac)TiCl(Ntol(2))] with NaN(3) results in NaCl formation and N(2) ejection to yield the first four coordinate, parent imide [(nacnac)Ti=NH(Ntol(2))] (nacnac(-)=[ArNC(CH(3))](2)CH, Ar = 2,6-iPr(2)C(6)H(3), tol = 4-CH(3)C(6)H(4)). 相似文献
95.
In this paper we use a Renormalization Group (RG) method to study the long-time asymptotics of nonlinear diffusion equations with time-dependent diffusion coefficients and nonlinearities which are marginal (or critical) with respect to the RG operator. These equations describe the time evolution of the average concentration of a passive scalar being advected by a random velocity field. We prove that, besides the expected diffusive behavior, there is an extra logarithmic correction which is the imprint of the critical nonlinearity. 相似文献
96.
Rajca A Boratyński PJ Olankitwanit A Shiraishi K Pink M Rajca S 《The Journal of organic chemistry》2012,77(5):2107-2120
We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. All compounds have planar "azaacene" moieties. The experimental band gaps E(g) ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S(1) state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O(2)). For two oligomers with "tetraazanonacene" moieties, potentials of E(4+/3+) ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations. 相似文献
97.
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100.
Dr. A. Gastón Orrillo Dr. Andrea M. Escalante Dr. Maitena Martinez-Amezaga Dr. Ignacio Cabezudo Dr. Ricardo L. E. Furlan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1118-1127
Dynamic multilevel systems can be assembled from molecular building blocks through two or more reversible reactions that form covalent bonds. Molecular networks of dynamic multilevel systems can exhibit different connectivities between nodes. The design and creation of molecular networks in multilevel systems require control of the crossed reactivity of the functional groups (how to connect nodes) and the conditions of the reactions (when to connect nodes). In recent years, the combination of orthogonal and communicating reactions, which can be simultaneous or individually activated, has produced a variety of systems that have given rise to macrocycles and cages, as well as molecular motors and multicomponent architectures on surfaces. A given set of reactions can lead to systems with unique responsiveness, compositions, and functions as a result of the relative reactivities. In this Concept article, different molecular networks from synthetic systems that can be produced by combinations of different reaction types are discussed. Moreover, applications of this chemistry are highlighted, and future perspectives are envisioned. 相似文献