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1.
The action of ultra violet rays of 260 nm on aqueous solutions of bases, nucleosides and nucleotides of DNA at 77°K is studied by electron spin resonance. It is shown that the free radicals observed are similar, with a few noteworthy exceptions to those induced by X-rays, under the same conditions of temperature, in the solid state. Contrary to what might be excepted on the basis of the results obtained by X-rays, the variation in the yield in paramagnetic centres in each sequence studied does not seem to be important.  相似文献   
2.
One-electron oxidation of two structurally similar CuII-diphenolate complexes, 1 and 2, creates EPR-silent CuII-phenoxyl complexes [1]+ and [2]+ that mimic the oxidized form of the enzyme galactose oxidase (GOase). Both model complexes display novel NIR absorptions assigned to phenolate-phenoxyl charge transfer that resemble a tyrosinate-tyrosyl charge-transfer band observed in the enzymatic system. [1]+ and [2]+ react with benzyl alcohol to form 0.5 equivs of benzaldehyde per complex; biomimetic reduction to CuI-phenol complexes is not observed, but such species may exist transiently. Initial kinetic studies show that [2]+ reacts faster with benzyl alcohol than does [1]+, despite being a significantly weaker oxidant (DeltaE degrees = 370 mV). This acceleration is ascribed to mechanistic differences: [2]+ appears to bind substrate prior to the rate-determining step. Large, nonclassical kinetic isotope effects confirm C-H bond cleavage as the rate-determining step in the reactions of both [1]+ and [2]+ with benzyl alcohol, as is the case for GOase.  相似文献   
3.
The reaction of a copper(I) complex with a sterically demanding secondary diamine ligand and O2 yields a tris(mu-hydroxy)tricopper(II) complex. This complex is a structural model of the proposed native intermediate in multicopper oxidases, with interesting structural, magnetic, and solution properties.  相似文献   
4.
The activation of dioxygen (O(2)) by Cu(I) complexes is an important process in biological systems and industrial applications. In tyrosinase, a binuclear copper enzyme, a mu-eta(2):eta(2)-peroxodicopper(II) species is accepted generally to be the active oxidant. Reported here is the characterization and reactivity of a mu-eta(2):eta(2)-peroxodicopper(II) complex synthesized by reacting the Cu(I) complex of the secondary diamine ligand N,N'-di-tert-butyl-ethylenediamine (DBED), [(DBED)Cu(MeCN)](X) (1.X, X = CF(3)SO(3)(-), CH(3)SO(3)(-), SbF(6)(-), BF(4)(-)), with O(2) at 193 K to give [[Cu(DBED)](2)(O(2))](X)(2) (2.X(2)). The UV-vis and resonance Raman spectroscopic features of 2 vary with the counteranion employed yet are invariant with change of solvent. These results implicate an intimate interaction of the counteranions with the Cu(2)O(2) core. Such interactions are supported further by extended X-ray absorption fine structure (EXAFS) analyses of solutions that reveal weak copper-counteranion interactions. The accessibility of the Cu(2)O(2) core to exogenous ligands such as these counteranions is manifest further in the reactivity of 2 with externally added substrates. Most notable is the hydroxylation reactivity with phenolates to give catechol and quinone products. Thus the strategy of using simple bidentate ligands at low temperatures provides not only spectroscopic models of tyrosinase but also functional models.  相似文献   
5.
We use cubic-phase plate imaging to demonstrate an order-of-magnitude improvement in the transverse resolution of three-dimensional objects reconstructed by extended depth-of-field tomography. Our algorithm compensates for the range shear of the cubic-phase approach and uses camera rotation to center the reconstructed volume on a target object point.  相似文献   
6.
7.
Abstract— –The photosensitization of amino acids by proflavine is studied using the technique of electron spin resonance spectroscopy. The analysis of the line shape as a function of the incident microwave power (both in the presence and absence of oxygen) and the dependence of the numbers of free radicals on the intensity of the incident light allow one to suggest that two types of radicals are formed. One is formed by a biphotonic process, the nature of the radicals being the same as in the case of ionising radiation, while the other is probably the RO2 radical formed as a result of photodynamic action.  相似文献   
8.
Synthesis of a new fluorescent probe specific for catechols   总被引:1,自引:0,他引:1  
[reaction: see text] The synthesis of a new fluorescent probe, specific for the catechol moiety, has been conducted by preparation of alpha,alpha-dibromomalonamides containing an appropriate fluorophore. N,N'-Bis-anthracen-9-ylmethyl-2,2-dibromomalonamide reacted with various catechols in the presence of cesium carbonate to generate highly fluorescent derivatives.  相似文献   
9.
10.
Multicopper oxidases catalyze the 4e- reduction of O2 to H2O. Reaction of the fully reduced enzyme with O2 produces the native intermediate (NI) that consists of four oxidized Cu centers, three of which form a trinuclear cluster site, all bridged by the product of full O2 reduction. The most characteristic feature of NI is the intense magnetic circular dichroism pseudo-A feature (a pair of temperature-dependent C-terms with opposite signs) associated with O --> Cu(II) ligand-to-metal charge transfer (LMCT) that derives from the strong Cu-O bonds in the trinuclear site. In this study, the two most plausible Cu-O structures of the trinuclear site, the tris-mu2-hydroxy-bridged and the mu3-oxo-bridged structures, are evaluated through spectroscopic and electronic structure studies on relevant model complexes, TrisOH and mu3O. It is found that the two components of a pseudo-A-term for TrisOH are associated with LMCT to the same Cu that are coupled by a metal-centered excited-state spin-orbit coupling (SOC), whereas for mu3O they are associated with LMCT to different Cu centers that are coupled by oxo-centered excited state SOC. Based on this analysis of the two candidate models, only the mu3-oxo-bridged structure is consistent with the spectroscopic properties of NI. The Cu-O sigma-bonds in the mu3-oxo-bridged structure would provide the thermodynamic driving force for the 4e- reduction of O2 and would allow the facile electron transfer to all Cu centers in the trinuclear cluster that is consistent with its involvement in the catalytic cycle.  相似文献   
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