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131.
Photocatalytic Systems. XLIV. On the Intervalence Charge Transfer Behaviour of Ion Pairs of Octacyanomolybdate [Mo(CN)8]4? ions are forming coloured ion pairs with FeIII, CuII, UVIO2, and VIVO, the long-wavelength absorption band of which could be assigned to an intervalence charge-transfer transition. From the solvent dependence of the IT band, interionic distances could be estimated. 相似文献
132.
The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-butyldimethylsilyl ketene acetal of methyl acetate adds nearly instantaneously to aromatic and olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl ether adducts. 相似文献
133.
H.-D. Bauer Reinhold Rennekamp Jürgen Thomas 《Analytical and bioanalytical chemistry》1998,361(6-7):515-521
Concerning the conventional TEM-imaging as well as the analytical procedures the capabilities are pointed out: electron diffraction,
energy dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS). The possibilities of investigation
of both nanocrystalline materials and multilayers are discussed, accompanied by examples of current investigations: At alloys,
produced by intense milling, at single nanocrystals the imaging by diffraction contrast was successful, the analysis has failed
because of the sample thickness. By means of energy spectroscopic imaging multilayers from Fe-SiB/NbCu and Fe/Cr as well as
Al2O3/TiN have been characterized.
Received: 15 July 1997 / Revised: 16 February 1998 / Accepted: 21 February 1998 相似文献
134.
N-Substituted oxazolidin-2,4-diones have been synthesized in a novel one-pot reaction by reacting cyanohydrins stepwise with 1,1′-carbonyldiimidazole and primary amines followed by acidic hydrolysis of the intermediate 4-imino-oxazolidin-2-ones. Their microwave-assisted conversion into α-hydroxyamides was accomplished by treatment with catalytic amounts of sodium methoxide in methanol. 相似文献
135.
The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout. 相似文献
136.
Thomas R. Gengenbach Zoran R. Vasic Sheng Li Ronald C. Chatelier Hans J. Griesser 《Plasmas and Polymers》1997,2(2):91-114
The properties and composition of plasma polymer surfaces stored in air can change considerably over time, especially as a
result of oxidative reactions. When plasma polymers contain an element other than O, it is possible to probe for mechanisms
in addition to oxidation that contribute to the aging of the surface. Plasma polymers containing N were fabricated from either
1,3-diaminopropane (DAP),n-heptylamine (nHA), or allylamine (AA), and studied by X-ray photo-electron spectroscopy (XPS) and air/water contact angles
(CA). For each of the plasma polymers, a multiexponential increase in the O/C ratio was observed over time using XPS. The
N/C ratios remained constant (AA) or decreased somewhat (nHA and DAP). In contrast, the trends in CA values differed, declining
for the nHA surfaces, rising for the AA, and changing little for the DAP. Surface roughness, assessed by scanning tunnelling
or atomic force microscopy, did not change over time. The diverse adjustments in the polarity of each surface and the similar
compositional changes between them are reconcilable if the aging of the plasma polymer surface is a manifestation of the superposition
of concurrent oxidative reactions and partial surface reorientation; the former introduce polar groups and the latter transports
then from the surface to deeper regions beyond the CA probe depth but within the XPS analysis depth. These processes vary
between different plasma polymers. Data for the alkylamine plasma polymers is also compared with that for two plasma polymers
fabricated from methanol. The change in composition, but not polarity, of the DAP surface after 4 days of storage demonstrates
the importance of using multiple techniques to characterize the aging of plasma polymer surfaces. 相似文献
137.
Structures of New SeII and TeII Complexes Containing 2,2-Dicyanethylene-1,1-dithiolate, 2,2-Dicyanethylene-1,1-thioselenolate, and 2,2-Dicyanethylene-1,1-diselenolate (NBu4)2{Se[S2C?C(CN)2]2} ( I ), (AsPh4)2 · {Te[SSeC?C(CN)2]2} ( II ), and (NBu4)2{Te[Se2C?C(CN)2]2} ( III ) containing the bidentate chelate ligands 2,2-dicyanethylene-1,1-dithiolate i-mnt , 2,2-dicyanethylene-1,1-thioselenolate i-mnts , and 2,2-dicyanethylene-1,1-diselenolate i-mns have been prepared and characterized by X-ray structure analysis. The central units consist of [M(X? X)2E2]2? (M = Se, Te; X? X = ligand; E = lone-pair) with fourfold coordinated SeII and TeII, respectively. The complex anions [Se(i-mnt)2E2]2? as well as [Te(i-mnts)2E2]2? show a trapezoide distortion with d(Se? S) = 2.276(5); 2.287(5); 2.803(5); 2.789(5) Å and d(Te? Se) = 2.611(2); 2.617(3); d(Te? S) = 2.889(5); 2.935(4) Å. In III there are centrosymmetric complex anions [Te(i-mns)2E2]2? with nearly identical Te? Se-bond-lengths: 2.674(3) and 2.692(2) Å. These Te? Se bonds are elongated compared to usual Te? Se bonds. 相似文献
138.
Ronald D. Ley Lee A. Applegate R. Steven Padilla Thomas D. Stuart 《Photochemistry and photobiology》1989,50(1):1-5
Several lines of evidence support the hypothesis that ultraviolet radiation (UVR) is involved in the etiology of cutaneous melanoma in humans. However, progress in understanding the mechanisms involved in induction of melanotic tumors by UVR has been hindered by lack of a suitable animal model. During the course of multiple exposures (3 times/wk for 70 wk) of the South American opossum, Monodelphis domestica, to UVR, we first observed the appearance of areas of dermal melanocytic hyperplasia (MH) on the exposed skin. Post-UVR exposure to photoreactivating light (320-500 nm) suppressed the occurrence of MH. We also observed at 100 weeks from first exposure that 10 of 46 surviving animals had developed melanotic tumors which arose, presumably, from areas of MH. Tumors on three of the 10 animals have been classified as malignant melanomas based on metastasis to lymph nodes. We conclude from these results that UVR can act as a complete carcinogen for melanoma induction and, based on the photoreactivation of MH induction, that DNA damage is involved in melanoma formation. 相似文献
139.
Thomas Geiger Richard Nottenberg Mary-Lou Plaprat Michael Grtzel 《Helvetica chimica acta》1982,65(8):2507-2516
Light-induced interfacial electron transfer from two p-InP electrodes differing in the amount of majority carrier doping to a number of electron relays ( R ) dissolved in aqueous solution was investigated. The material with the lower carrier density (0.71 × 1018 cm?3) exhibited much better wavelength response and quantum yield for electron transfer than the electrode doped with 2.3 × 1018 cm?3 charge carriers. Using cobalt (III) sepulcrate, Co (sep)3+, as an electron relay a polychromatic light to electrical energy conversion efficiency of 18% was obtained. The potential of this relay for use in a regenerative photoelectrochemical cell is briefly discussed. 相似文献
140.
Palladium (0)-catalyzed allylic substitution reactions employing triorganoindium reagents have been investigated. In situ generated vinyl- and arylindiums react with substituted and unsubstituted cyclohex-2-enyl esters in the presence of 1-3 mol % Pd(2)(dba)(3) to produce vinyl- or arylcyclohexenes in moderate to excellent yields. The stereoselectivity of this process was also examined, and evidence is presented that the reaction proceeds with inversion of stereochemical configuration. 相似文献