全文获取类型
收费全文 | 205篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 120篇 |
力学 | 3篇 |
数学 | 25篇 |
物理学 | 60篇 |
出版年
2020年 | 2篇 |
2013年 | 37篇 |
2012年 | 2篇 |
2011年 | 7篇 |
2010年 | 2篇 |
2008年 | 6篇 |
2007年 | 11篇 |
2006年 | 8篇 |
2005年 | 6篇 |
2004年 | 3篇 |
2003年 | 3篇 |
2002年 | 4篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1996年 | 10篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 2篇 |
1989年 | 5篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1968年 | 2篇 |
1961年 | 5篇 |
1960年 | 1篇 |
1958年 | 2篇 |
1957年 | 3篇 |
1956年 | 2篇 |
1954年 | 3篇 |
1951年 | 1篇 |
1948年 | 2篇 |
1947年 | 2篇 |
1942年 | 1篇 |
1941年 | 1篇 |
1939年 | 3篇 |
1937年 | 2篇 |
1935年 | 3篇 |
1934年 | 2篇 |
1928年 | 1篇 |
排序方式: 共有208条查询结果,搜索用时 15 毫秒
101.
Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation. 相似文献
102.
103.
104.
A priori evaluations, using Hartree-Fock self-consistent-field (SCF) theory or density-functional theory (DFT), of the current passing between two electrodes through a single bridging molecule result in predicted conductivities that may be up to one to two orders of magnitude larger than observed ones. We demonstrate that this is, in part, often due to the improper application of the computational methods. Conductivity is shown to arise from tunneling between junction states of the electrodes through the molecule; these states are inherently either quasi two-fold or four-fold degenerate and always comprise the (highest occupied molecular orbital) HOMO band at the Fermi energy of the system. Frequently, in previous cluster based molecular conduction calculations, closed-shell SCF or Kohn-Sham DFT methods have been applied to systems that we demonstrate to be intrinsically open shell in nature. Such calculations are shown to induce artificial HOMO-LUMO (LUMO-lowest unoccupied molecular orbital) band splittings that Landauer-based formalisms for steady-state conduction interpret as arising from extremely rapid through-molecule tunneling at the Fermi energy, hence, overestimating the low-voltage conductivity. It is demonstrated that these shortcomings can be eliminated, dramatically reducing calculated current magnitudes, through the alternate use of electronic-structure calculations based on the spin-restricted open-shell formalism and related multiconfigurational SCF of DFT approaches. Further, we demonstrate that most anomalies arising in DFT implementations arise through the use of hybrid density functionals such as B3LYP. While the enhanced band-gap properties of these functionals have made them the defacto standard in molecular conductivity calculations, we demonstrate that it also makes them particularly susceptible to open-shell anomalies. 相似文献
105.
106.
E W Kadish KM Sintic PJ Khoury T Govenlock LJ Ou Z Shao J Ohkubo K Reimers JR Fukuzumi S Crossley MJ 《The journal of physical chemistry. A》2008,112(3):556-570
Through-porphyrin electronic communication is investigated using "linear-type" and "corner-type" bis(quinoxalino)porphyrins in free-base form and their ZnII, CuII, NiII, and PdII derivatives. These compounds are porphyrins with quinoxalines fused on opposite or adjacent beta,beta'-pyrrolic positions; they were synthesized from 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)-porphyrin-2,3,12,13- and -2,3,7,8-tetraone, respectively, by reaction with 1,2-phenylenediamine. The degree of electron spin delocalization into the fused rings in the pi-radical anions of the free-base and metal(II) bisquinoxalinoporphyrins was elucidated by electrochemistry, UV-vis absorption, and electron spin resonance (ESR) spectra of the singly reduced species and density functional theory calculations. Hyperfine splitting patterns in the ESR spectra of the pi-radical anions show that symmetric molecules have delocalized electron spin, indicating that significant inter-quinoxaline interactions are mediated through the central porphyrin unit, these interactions being sufficient to guarantee through-molecule conduction. However, when molecular symmetry is broken by tautomeric exchange of the inner nitrogen hydrogens in the free-base porphyrin with a corner-type quinoxaline substitution pattern, the pi-radical anion becomes confined so that one quinoxaline group is omitted from spin delocalization. This indicates the appearance of a unidirectional barrier to through-molecule conduction, suggesting a new motif for chemically controlled rectification. 相似文献
107.
There is considerable current interest in the design and constructionof directly executable modelling languages for mathematicalprogramming. The present research extends contemporary modellinglanguages by specifying a type calculus for an extended dimensionalsystem that determines if the model is well formed in the sensethat the objective function and constraints consist of homogeneouscomponents. Each variable, coefficient, constant, function,constraint, input, and output of the model is assigned a typethat consists of its concepts, quantities, and units of measurementwith optional scale factors. In checking the composition offunctions and constraints, the system can do automatic unitconversions and apply user-supplied conversions. The systemallows a hierarchy of concepts that provides inheritance ofquantities and automatic concept conversion. In addition, eachset in a model is typed so the system can check the validityof operations on indices. 相似文献
108.
109.
R. M. Sandstedt W. J. Eva W. F. Geddes B. Frisell M. J. Blish M. M. Rainess A. I. Krupkin L. Reimers L. Karácsonyi E. Unna D. K. Mecham C. E. Bode C. O. Swanson E. Munz C. H. Bailey L. H. Bailey Fr. Láska B. Rund P. A. Wawilin B. I. Rudoschewskaja G. A. Weiss A. L. Schinkarenko W. A. Ignatowitsch P. Glassmann J. Kantorer W. Whale 《Analytical and bioanalytical chemistry》1939,116(7-8):256-261
110.
The value of recent methods of identification of organic substances by means of the micro melting point apparatus is investigated, using 3 groups of closely related substances (benzoic acid derivatives, barbituric acid derivatives, and sulphonamids).The experiments show that a combination of the melting point determination with an observation of sublimation and conversion during heating and, moreover, with the observation of the conversion of crystallised melting drops etc. very markedly increases the value of the determination.The preparation of derivatives from quantities below l mg can be performed more rapidly and more simply than the preparation of larger amounts. The melting point determination of the derivatives is of the greatest value for the identification of the respective substances.On the other hand, the melting point determination on eutectic mixtures of the substance in question with a test substance is found to be of much lower value as a method of identification, if there is a possibility for the occurrence of a number of closely related substances having the same melting point ; such substances often have the same eutectic melting point with the same test substance.The determination of the index of refraction of molten substances (i.e., the determination of the temperature interval within which the molten mass has the same index of refraction as a glass powder of a known index of refraction) is an excellent method of identification, since the scattering of the temperature intervals found for related substances is of the same magnitude, and for not related substances is considerably higher, than the scattering of their melting points. 相似文献