全文获取类型
收费全文 | 1485篇 |
免费 | 9篇 |
国内免费 | 2篇 |
专业分类
化学 | 706篇 |
晶体学 | 6篇 |
力学 | 47篇 |
数学 | 382篇 |
物理学 | 355篇 |
出版年
2022年 | 8篇 |
2021年 | 15篇 |
2020年 | 13篇 |
2019年 | 8篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 25篇 |
2015年 | 19篇 |
2014年 | 20篇 |
2013年 | 49篇 |
2012年 | 39篇 |
2011年 | 630篇 |
2010年 | 31篇 |
2009年 | 37篇 |
2008年 | 47篇 |
2007年 | 44篇 |
2006年 | 31篇 |
2005年 | 62篇 |
2004年 | 34篇 |
2003年 | 32篇 |
2002年 | 23篇 |
2001年 | 23篇 |
2000年 | 15篇 |
1999年 | 9篇 |
1998年 | 15篇 |
1997年 | 15篇 |
1996年 | 11篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1980年 | 5篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1972年 | 4篇 |
1969年 | 4篇 |
1968年 | 7篇 |
1966年 | 5篇 |
1965年 | 4篇 |
1937年 | 4篇 |
排序方式: 共有1496条查询结果,搜索用时 62 毫秒
1.
Laurens Kooijman Dr. Matthias Schuster Christian Baumann Simon Jurt Dr. Frank Löhr Dr. Boris Fürtig Prof. Dr. Peter Güntert Prof. Dr. Oliver Zerbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21151-21158
To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR. 相似文献
2.
3.
Angla Schwartz Lszl Szab Katalin Pusztay-Szab Istvn Hermecz Zoltn Mszros 《Journal of heterocyclic chemistry》1987,24(3):655-660
Ultraviolet-visible spectra of 4-oxo 1 and 4-imino 2 quinolizines or their monocyclic tautomers 3, 4 have been studied in neutral, acidic and basic ethanolic solution as well as in dimethyl sulfoxide and chloroform. Ring B of 4-oxo and 6-unsubstituted 4-imino compounds can be cleaved by sodium ethanolate more or less easily. Ring B of 6-methyl-4-iminoquinolizines is very unstable and they are present mainly in the monocyclic form which are partly dissociated in ethanol and dimethyl sulfoxide especially in higher dilution or in the presence of sodium ethanolate. In dilute acidic ethanol or chloroform, the dissociation is suppressed and in the latter solvent and in some cases, absorption bands can be observed due to a small amount of the 4-imino-6-methylquinolizines. In acidic solution of compounds 3B=C, 3D, 4E, 4F=G having simultaneously cyano and ethoxycarbonyl groups in 1 and 3 position, not simple reprotonation occurs but irreversible changes can be observed. 相似文献
4.
The aim of the paper is to investigate the limit behaviour of the least squares estimator of the shift parameter of nearly unstable, nearly stable, and nearly explosive AR(1) models. Both zero start and stationary cases are treated. Connection with the maximum likelihood estimator of the shift parameter of continuous time AR(1) processes is also discussed. 相似文献
5.
Katalin E. Kövér Dušan Uhr?&#x;n Victor J. Hruby 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,130(2):162-168
A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert1increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time. 相似文献
6.
Monika Schuster Robert Inführ Claudia Turecek Jürgen Stampfl Franz Varga Robert Liska 《Monatshefte für Chemie / Chemical Monthly》2006,4(4):843-853
To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials
which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component
for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers.
These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials.
Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and
commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated
by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials
prepared by 3D-photoshaping. 相似文献
7.
Analysis of K-shell excitation spectra of gas-phase molecules containing at least two atoms of either B, C. N. O or F reveals the existence of a striking correlation between the bond length of the atomic pair. the sum of their atomic numbers and the associated α-shape resonance energy. Empirical rules are established which allow the derivation of intramolecular distances with accuracies reliably better than ± 0.05 A from the K-.shell absorption spectrum of one of the atoms in the Molecule. 相似文献
8.
Valentina Domenici Carlo Alberto Veracini Katalin Fodor-Csorba Giacomo Prampolini Ivo Cacelli Andrjia Lebar Bostjan Zalar 《Chemphyschem》2007,8(16):2321-2330
The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules. 相似文献
9.
Vladislav?Tomi?i?Email author Vjekoslav?Butorac Jadranka?Viher Vladimir?Simeon 《Journal of solution chemistry》2005,34(6):613-616
The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO3−(aq) centered at ≈200 nm was studied in the temperature range 10–70 ∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion. 相似文献
10.
Ruth-Maria Olk A. Rhr J. Sieler K. Khler R. Kirmse W. Dietzsch E. Hoyer B. Olk 《无机化学与普通化学杂志》1989,577(1):206-216
Coordination Chemistry of 1,3-Dithiole-2-thione-4,5-diselenolate (dsit) — Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III) bis-chelates of 1,3-dithiole-2-thione-4,5-diselenolate (dsit) of general type (Bu4N)n[M(dsit)2] (n = 2: M ? Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M ? Ni, Au) are described. By comparison of the ir, 13C nmr, epr spectra, cyclovoltammetric data, and x-ray investigations (nickel-bis-chelates) of chelates of dsit and those of the chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of selenium for sulfur substitution on position 4 and 5 of the heterocyclic ligand are discussed. 相似文献