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11.
12.
Meyer GJ 《Inorganic chemistry》2005,44(20):6852-6864
Strategies toward the realization of molecular control of interfacial charge transfer at nanocrystalline semiconductor interfaces are described. Light excitation of coordination compounds, based on (dpi)6 transition metals, anchored to wide band-gap semiconductors, such as TiO2, can initiate electron-transfer processes that ultimately reduce the semiconductor. Such photoinduced charge-separation processes are a key step for solar energy conversion. The thermodynamics and kinetic rate constants for three different interfacial charge separation mechanisms are discussed. Tuning the energetic position of the semiconductor conduction band relative to the molecular sensitizer has provided new insights into interfacial charge transfer. Supramolecular compounds that efficiently absorb light, promote interfacial electron transfer, and feature additional functions such as intramolecular electron transfer when bound to semiconductor surfaces have also been studied. New approaches for enhancing charge-separation lifetimes for solar energy conversion are presented. 相似文献
13.
Gerald Koitz Walter Fabian Hans-Werner Schmidt Hans Junek 《Monatshefte für Chemie / Chemical Monthly》1981,112(8-9):973-985
The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).
Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet. 相似文献
14.
Generalizing the work of Einstein and Mayer, it is assumed that at each point of space-time there exists a vector-spinor space with Nv vector dimensions and Ns spinor dimensions, where Nv=2k and Ns=2
k, k3. This space is decomposed into a tangent space with4 vector and4 spinor dimensions and an internal space with Nv–4 vector and Ns–4 spinor dimension. A variational principle leads to field equations for geometric quantities which can be identified with physical fields such as the electromagnetic field, Yang-Mills gauge fields, and wave functions of bosons and fermions. 相似文献
15.
The hydride transfer process between the isoalloxazine moiety of flavins and the nicotinamide moiety of NAD(P)H has been explored by using density functional theory based reactivity index in the 1-methylnicotinamide-lumiflavine model system. Based on crystallographic data available, we have found that the group softness index helps to locate and orientate reactive regions in these interacting molecules while the electrophilicity index successfully describes the reactivity pattern of this system. 相似文献
16.
Boisguerin P Leben R Ay B Radziwill G Moelling K Dong L Volkmer-Engert R 《Chemistry & biology》2004,11(4):449-459
SPOT synthesis permits parallel synthesis and screening of thousands of cellulose membrane-bound peptides to study protein-protein interactions in a proteomic context. Recognition of C-terminal residues is one of the most common binding features of PDZ domains. Unfortunately, most solid support-bound peptide libraries lack a free C terminus due to C-terminal fixation on the solid support. To overcome this restriction, we developed a robust methodology based on our previous strategy for generating peptides with authentic C termini. To validate this improved method, we screened a human peptide library of 6223 C termini with the syntrophin PDZ domain. Furthermore, using the same library, new peptide ligands derived from membrane proteins and receptors were found for the ERBIN PDZ domain. Finally, we identified the protein kinase breakpoint cluster region, which is known as a negative regulator of cell proliferation and oncogenic transformation, as an ERBIN ligand. 相似文献
17.
J. D. Petke Gerald M. Maggiora‡ Lester Shipman‡ Ralph E. CHRISTOFFERSEN‡ 《Photochemistry and photobiology》1979,30(2):203-223
Abstract— Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying excited singlet and triplet states of ethyl pheophorbide a (Et-Pheo a) and ethyl chlorophyllide a (Et-Chl a), and are employed in an analysis of the electronic absorption spectra of these systems. In both molecules the visible spectrum is found to consist of transitions to the two lowest-lying 1(π, π*) states, S1 and S2. The configurational compositions of S1 and S2 in both molecules are similar, and are described qualitatively in terms of a four-orbital model. The S1← S0 transition in each case is predicted to be intense, and is largely in-plane y-polarized, while the S2← S0 transition is predicted to be extremely weak and in-plane polarized. The orientation of the S2← S0 transition dipole is not conclusively established in the present calculations. The Soret band in both molecules is composed of transitions to no less than ten states (S3-S12 in Et-Chl a and S3-S7S9-S12. and S14 in Et-Pheo a), which exhibit primarily (π, π*) character. The configurational compositions of these states are generally a complex mixture of excitations from both occupied macrocyclic π molecular orbitals and occupied orbitals with electron density in the cyclopen-tanone ring and the carbomethoxy chain. No clear correspondences are evident between respective Soret states of the two systems. Transitions to these states are generally intense and display a variety of in-plane polarizations. Two additional Soret states of Et-Pheo a, S8 and S13, exhibit primarily (n. π*) character. S8 is characterized by excitations from u and non-bonding regions of the carbomethoxy chain, while S13 is described by n →π* excitations involving the nitrogen atom of ring II. No corresponding (n, π*) states were found for Et-Chl a. In both molecules the lowest two triplet states, T1 and T2, are found to lie lower in energy than S1. while T, and S1 are approximately degenerate. The configurational compositions of T1-T4 of both molecules are nearly identical, and may be described by a four-orbital model. However, the compositions of T1-T4 differ sharply from those of S1 and S2. A number of higher-lying 3(π, π*) states of both molecules (T5-T13 in Et-Chi a and T8-T9, T11-T13 in Et-Pheo a) are found to have energies similar to the singlet Soret states, relative to S0. They are characterized by a complex mixture of configurations which do not include significant contributions involving the four-orbital model. In addition, two 3(n, π*) states of Et-Pheo a, T10 and T14, are found, which are somewhat analogous to S8 and S13. Additional data presented include the charge distributions and molecular dipole moments of the S0. S1, and T1 states of both molecules, as well as energies and oscillator strengths of computed Sn←S1 and Tn←1 transitions. 相似文献
18.
Reactions of 2-t-butyl-4-methyl-2,4-dihydropyrrolo[3,4-b]indoles with N-aryl-maleimides have been investigated. The formation of 1:1-cycloadducts is influenced by substituents at 1,3-position. The consecutive transformations of these intermediates can be controlled by nucleophilic solvents or reagents. Ring opening reactions occur at the labile N,O-acetal group of the cycloadducts followed by eliminaton or addition reactions. 相似文献
19.
Skin of the lizard, Anolis carolinensis, is remarkably sensitive to light. Illuminated in vitro with visible light from a tungsten source (110 W (m-2)), skin changes from brilliant green to dark brown (50% reduction in reflectance) within 2-4 min as a result of dispersion of melanin from a perinuclear position within dermal melanophores into superficial dendritic processes. Reversal of the process, reaggregation of pigment, will occur within 2.0 min upon return to darkness. This photic response can be initiated with light levels as low as 5.0 W m(-2) and is maximized by light levels only 5% that of midwinter sunshine. Pigment dispersion in response to both melanocyte simulating hormone and to light is inhibited by cytochalasin-B, indicating that microfilaments may be the motor element for pigment movement in that direction. Colchicine, but not cytochalasin-B, totally blocks pigment reaggregation following melanocyte stimulating hormone exposure and partially blocks it in the dark phase of the photic response. The results of this study are consistent with a model for pigment movement in A. carolinensis that provides microfilaments for pigment dispersion and microtubule involvement in both dispersion and aggregation. Finally, because it is readily visible, easily quantified, rapid and reversible, photic response in the skin of A. carolinensis is recommended as a valuable model system for the study of saltatory movement of organelles within cells. 相似文献
20.
As part of a fundamental study of the behaviour of mixed plastics during reprocessing and in service, blends of low density polyethylene (LDPE) and polyvinyl chloride (PVC) have been investigated. It was found that Young's modulus increased steadily from pure LDPE to pure PVC whereas both tensile strength at break and elongation at break passed through a minimum at about 5% PVC. Optical and scanning electron microscope studies have related this mechanical behaviour to morphological changes in the two phase system under stress. 相似文献