全文获取类型
收费全文 | 3148篇 |
免费 | 118篇 |
国内免费 | 36篇 |
专业分类
化学 | 1764篇 |
晶体学 | 14篇 |
力学 | 53篇 |
数学 | 806篇 |
物理学 | 665篇 |
出版年
2023年 | 21篇 |
2022年 | 15篇 |
2021年 | 64篇 |
2020年 | 42篇 |
2019年 | 61篇 |
2018年 | 82篇 |
2017年 | 53篇 |
2016年 | 112篇 |
2015年 | 110篇 |
2014年 | 117篇 |
2013年 | 198篇 |
2012年 | 186篇 |
2011年 | 241篇 |
2010年 | 129篇 |
2009年 | 145篇 |
2008年 | 177篇 |
2007年 | 175篇 |
2006年 | 166篇 |
2005年 | 158篇 |
2004年 | 168篇 |
2003年 | 111篇 |
2002年 | 105篇 |
2001年 | 54篇 |
2000年 | 34篇 |
1999年 | 30篇 |
1998年 | 41篇 |
1997年 | 40篇 |
1996年 | 46篇 |
1995年 | 32篇 |
1994年 | 28篇 |
1993年 | 27篇 |
1992年 | 29篇 |
1991年 | 25篇 |
1990年 | 17篇 |
1989年 | 10篇 |
1988年 | 12篇 |
1986年 | 14篇 |
1985年 | 17篇 |
1984年 | 15篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 14篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1978年 | 11篇 |
1977年 | 16篇 |
1976年 | 11篇 |
1974年 | 9篇 |
1973年 | 9篇 |
1956年 | 11篇 |
排序方式: 共有3302条查询结果,搜索用时 15 毫秒
81.
Intermediate diradicals which occur in the Paterno–Büchi photocycloaddition and in the Norrish type I photoreactions have been calculated taking into account the spin–orbit coupling (SOC) between the singlet (S) and triplet (T) states. Reaction paths for the photocycloaddition of formaldehyde to ethene and the diradical products of the α-cleavage of cyclohexanone have been optimized by the MNDO CI method for a number of different singlet and triplet states. SOC integrals are calculated by an effective one-electron approximation. Intermediate diradicals in the Paterno–Büchi reaction and the SOC effects are also studied ab initio with CAS SCF geometry optimization in a TZV basis set. Both methods predict a large SOC matrix element between the S and T states in the course of the C–C attack, while the SOC integral is two orders of magnitude smaller for the diradical produced in the C–O attack. In the Norrish type I photoreaction the oxygen atom also produces some nonzero contribution to the SOC integral which governs intersystem crossing in a ·C–C· diradical. For the diradicals produced by the α-cleavage of cyclohexanone a vibronic interaction is responsible for the SOC mixing between the lowest S and T states. The importance of one-center versus two-center SOC contributions in diradicals is briefly discussed. 相似文献
82.
Zlatopolskiy BD Loscha K Alvermann P Kozhushkov SI Nikolaev SV Zeeck A de Meijere A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4708-4717
The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylprolines, cis-5 and trans-5, and also feeding experiments with enantiomerically pure samples of the deuterium-labeled 3-(2'-nitrocyclopropyl)alanine, (2S)-3,3-[D2]15 and (2S)-2,2'-[D2]15, and 4-(Z)-propenylproline 2',4-[D2]-(2S,4R)-5. The latter five amino acids were prepared for the first time and allowed one to unequivocally assign the hitherto unknown absolute configurations of the last four stereocenters in hormaomycin 1 a. As a bonus, some new information about the biosynthesis of this molecule has also been gathered. 相似文献
83.
Roy Aleksan Isard Dunietz Boris Kayser 《Zeitschrift fur Physik C Particles and Fields》1992,54(4):653-659
The weak phase γ is conventionally probed by theB s→ρ 0 mode. The predicted rate is tiny. Even if aB s→ρ 0 K s rate difference could be established, it would not be clear that sin 2γ had been measured, because amplitudes with other weak phases may contribute significantly. Non-CP eigenstates, such asB s →D s ± K ?, have a two-fold advantage overB s→ρ 0 K s. Their rates are orders of magnitude above that forB s→ρ 0 K s, and they probe theCP-violating phase γ, without any contamination from other weak phases. Detailed time-dependent studies of non-CP eigenstates remove possible final-state phases and extract the weak phase γ. 相似文献
84.
The blue oxidases, laccase and ascorbate oxidase, contain three spectroscopically distinct copper binding sites, two of which are EPR detectable in the oxidized Cu(II) state, called type 1 (T1) and type 2 (T2). The three dimensional structure of ascorbate oxidase has recently been determined (Messerschmidt A.et al.: J. Mol. Biol.206, 513 (1989)) while that of laccase has not. We have therefore carried out comparative electron spin echo envelope modulation (ESEEM) measurements on ascorbate oxidase, laccase and laccase in which T1 Cu(II) was substituted with Hg(II) in order to obtain structural information about the copper sites in laccase. The ESEEM results clearly show that there are as many histidines in laccase as in ascorbate oxidase, i.e., at least two at each site. Orientation selective ESEEM experiments showed that in the T1 site in both enzymes the two remote (uncoordinated) nitrogens are magnetically inequivalent and have different hyperfine interactions. Furthermore, the isotropic hyperfine constants of both remote nitrogens in laccase T1 are larger than those in ascorbate oxidase T1. In laccase T2 two remote nitrogens show similar hyperfine couplings and the modulation depth is significantly deeper than in ascorbate oxidase. Finally, it is suggested that the difference between the NQR frequencies of the remote nitrogens in T1 and T2 in both oxidases can be attributed to the alkyl group of the side chain being adjacent to the bound imidazole in T1 and to the remote nitrogen in T2. This is in accordance with the known X-ray structure of ascorbate oxidase. 相似文献
85.
Boris Leaf 《Foundations of Physics》1982,12(6):583-606
86.
Heat capacities of concentrated multicomponent aqueous electrolyte solutions at various temperatures
Boris S. Krumgalz Ilan A. Malester Irving J. Ostrich Frank J. Millero 《Journal of solution chemistry》1992,21(7):635-649
The specific heat capacities of the aqueous multicomponent system NaCl +KCl+MgCl2+CaCl2 with ionic strength between 8.3 and 9.6 (resembling Dead Sea waters) were measured between 15°C and 45°C. The obtained data were fitted to an empirical equation as a function of concentration and temperature. The thermodynamic functions of the studied multicomponent system were found to be strongly influenced by changes in MgCl2 concentrations. The application of Young's rule to such concentrated systems was checked at 25°C. The calculated (by Young's rule) specific heat capacitiesC
p and apparent molar heat capacities Cp, of these multicomponent electrolyte solutions were in reasonable agreement with the measured values (–0.008 J-g–1-K–1 and –2.6 J-mol–1-K–1, respectively). 相似文献
87.
Kocher N Henn J Gostevskii B Kost D Kalikhman I Engels B Stalke D 《Journal of the American Chemical Society》2004,126(17):5563-5568
The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment. 相似文献
88.
Le Guennic B Hieringer W Görling A Autschbach J 《The journal of physical chemistry. A》2005,109(21):4836-4846
The circular dichroism spectra of the tris-bidentate metal complexes Lambda-[M(phen)3]2+, with M = Fe, Ru, Os and phen = 1,10-tris-phenanthroline, are investigated computationally, employing time-dependent density functional theory. Good agreement with experimental spectra is obtained for Ru and Os. The Lambda-[Os(phen)3]2+ spectrum is analyzed in detail. It is shown how relativistic effects red shift CD bands where the Os 5d-orbital participates to a large extent in the excitations. Further, the participation of the metal in the ligand pi --> pi exciton CD is determined to be of the order of 10%. Though solvent effects can have a noticeable effect on individual transitions and rotatory strengths, they are demonstrated to have only a very small overall effect on the resulting simulated CD spectra. For Lambda-[Fe(phen)3]2+, the results are shown to be rather sensitive to the choice of the applied hybrid and nonhybrid density functionals, and the optimized geometries based thereupon. In particular, the sign pattern of the lower-energy part (up to 33 x 10(3) cm(-1)) of the Lambda-[Fe(phen)3]2+ CD spectrum is difficult to reproduce. Some combinations of functionals and geometries yield good agreement with experiment, but no "best" approach can be devised based on the available results. Possible sources of errors in the spectrum of Lambda-[Fe(phen)3]2+ due to deficiencies in the functionals and the exchange-correlation kernels are investigated. 相似文献
89.
Total selenium content and its distribution in the soluble and insoluble protein-bound fractions obtained after aqueous extraction of antarctic krill samples were determined. About 26% of the total selenium (2.4 g g–1 dry weight) was found in the supernatant; the rest was in the pellet. Isolation of low molecular selenium-containing fractions was also performed by enzymatic digestion of the protein, followed by size-exclusion chromatography in conjunction with atomic absorption spectrometry. From the applied various proteinases (pronase E, subtilisin Carlsberg, trypsin, chymotrypsin, proteinase and proteinase N from Bacillus subtilis and Novo 0.6 MPX enzyme), the treatment with pronase E led to best recovery of selenium. About 96% of the total Se was found in the hydrolysate, mainly in low molecular weight fractions. Eighty percent of the Se species were in fractions with molecular weights in the range of amino acids and short peptides. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC-ICP-MS) allowed the identification of selenomethionine and the assumption that selenocystine or its derivatives were the main species in these fractions. 相似文献
90.