全文获取类型
收费全文 | 3241篇 |
免费 | 139篇 |
国内免费 | 20篇 |
专业分类
化学 | 2506篇 |
晶体学 | 7篇 |
力学 | 54篇 |
数学 | 466篇 |
物理学 | 367篇 |
出版年
2023年 | 15篇 |
2022年 | 19篇 |
2021年 | 27篇 |
2020年 | 71篇 |
2019年 | 49篇 |
2018年 | 29篇 |
2017年 | 41篇 |
2016年 | 75篇 |
2015年 | 101篇 |
2014年 | 105篇 |
2013年 | 176篇 |
2012年 | 227篇 |
2011年 | 228篇 |
2010年 | 161篇 |
2009年 | 129篇 |
2008年 | 225篇 |
2007年 | 215篇 |
2006年 | 219篇 |
2005年 | 204篇 |
2004年 | 160篇 |
2003年 | 132篇 |
2002年 | 156篇 |
2001年 | 68篇 |
2000年 | 55篇 |
1999年 | 60篇 |
1998年 | 45篇 |
1997年 | 52篇 |
1996年 | 58篇 |
1995年 | 44篇 |
1994年 | 31篇 |
1993年 | 23篇 |
1992年 | 24篇 |
1991年 | 14篇 |
1990年 | 19篇 |
1989年 | 16篇 |
1988年 | 4篇 |
1987年 | 11篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1983年 | 5篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1975年 | 3篇 |
1974年 | 6篇 |
1973年 | 3篇 |
1972年 | 5篇 |
1971年 | 4篇 |
排序方式: 共有3400条查询结果,搜索用时 93 毫秒
21.
The first basic mercurous tetrafluoroborate, Hg2(OH)[BF4], was obtained through a synproportionation reaction of red mercuric oxide, HgO, and elemental mercury in a 35% solution of HBF4 in water as colourless single crystals. The crystal structure (orthorhombic, Pbca, Z = 8, a = 985.0(1), b = 991.0(1), c = 1141.0(2) pm) contains [(HO)1/2—Hg—Hg—(OH)1/2]+ zig‐zag chains that are further connected via weak Hg—OH interchain interactions to layers between which the [BF4]— are located in an up and down fashion. 相似文献
22.
Leva S Lichte A Burmeister J Muhn P Jahnke B Fesser D Erfurth J Burgstaller P Klussmann S 《Chemistry & biology》2002,9(3):351-359
Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor. 相似文献
23.
Vanommeslaeghe K Van Alsenoy C De Proft F Martins JC Tourwé D Geerlings P 《Organic & biomolecular chemistry》2003,1(16):2951-2957
Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur. 相似文献
24.
Díaz MC Illescas BM Martín N Viruela R Viruela PM Ortí E Brede O Zilbermann I Guldi DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):2067-2077
A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c). 相似文献
25.
Summary The results of various quantum chemical calculations, the Hartree-Fock (HF) method, the Møller-Plesset perturbation theory (MP2), and the Hartree-Fock-Slater (HFS) method are compared. Atomic charges, dipole moments, topological properties of the electron density distribution and polarizabilities, and first hyperpolarizabilities are calculated. Atomic charges obtained with the HFS method are found to be very close to those calculated with the MP2 method, from which we conclude that the HFS method describes to some extent electron correlation effects. Performing an MP2 calculation after an HF calculation improves the molecular dipole moments considerably, yielding values close to the experimental ones. HFS calculations are computationally less demanding than MP2 and yield comparable results for the electron density distributions, dipole moments and polarizabilities. 相似文献
26.
[structure: see text] The addition reaction of azido-exTTFs to C(60) affords electroactive fullerotriazoline and azafulleroid dyads, which behave as amphoteric redox systems. Fluorescence experiments and transient absorption spectroscopy reveal that excitation of the fullerene moiety leads to radical pair lifetimes that are 2 orders of magnitude higher than those previously reported for related fullerotriazolines. 相似文献
27.
Demmers JA Rijkers DT Haverkamp J Killian JA Heck AJ 《Journal of the American Chemical Society》2002,124(37):11191-11198
In this report, we evaluate the validity of using hydrogen/deuterium exchange in combination with collision-induced dissociation mass spectrometry (CID MS) for the detailed structural and conformational investigation of peptides and proteins. This methodology, in which partly deuterated peptide ions are subjected to collision-induced dissociation in the vacuum of a mass spectrometer, has emerged as a useful tool in structural biology. It may potentially provide quantitatively the extent of deuterium incorporation per individual amino acid in peptides and proteins, thus providing detailed structural information related to protein structure and folding. We report that this general methodology has limitations caused by the fact that the incorporated deuterium atoms migrate prior or during the CID MS analysis. Our data are focused on a variety of transmembrane peptides, incorporated in a lipid bilayer, in which the near-terminal amino acids that anchor at the lipid-water interface are systematically varied. Our findings suggest that, under the experimental conditions we use, the extent of intramolecular hydrogen scrambling is strongly influenced by experimental factors, such as the exact amino acid sequence of the peptide, the nature of the charge carrier, and therefore most likely by the gas-phase structure of the peptide ion. Moreover, the observed scrambling seems to be independent of the nature of the peptide fragment ions (i.e., protonated B and Y' ' ions, and sodiated A and Y' ions). Our results strongly suggest that scrambling may be reduced by using alkali metal cationization instead of protonation in the ionization process. 相似文献
28.
Inderwildi OR Lebiedz D Deutschmann O Warnatz J 《The Journal of chemical physics》2005,122(15):154702
In this study, density functional theory calculations were performed to investigate the influence of oxygen preoccupation on the nitrogen oxide decomposition on rhodium. Besides gauging the coverage dependence of the adsorption energy of NO on the (111) rhodium facet, the influence of the initial oxygen coverage on the kinetics and thermodynamics of the nitrogen oxide decomposition reaction was also studied. The results are discussed with respect to a novel NOx decomposition catalyst. Furthermore, the influence of spin effects on the adsorption geometry as well as the adsorption energy is examined. It will be addressed why spin effects only have a minor influence on the behavior of NO on a rhodium surface. 相似文献
29.
Serum estradiol measurement by solid-phase chemiluminescence immunoassay and direct radioimmunoassay
Jozef de Boever Fortuna Kohen Marc Dhont Dirk Vandekerchkhove Georges van Maele 《Analytica chimica acta》1985
Estradiol017β is determined in serum extracts by solid-phase chemiluminescence immunoassay. The results are compared with those obtained from unextracted serum in routine conditions with a commercial radioimmunoassay (r.i.a.) kit. For the chemiluminescence procedure, a purified monoclonal antibody to estradiol-6-carboxymethyloxime/bovine serum albumin and the homologous chemiluminescent marker conjugate estradiol-6-carboxymethyloxime aminobutylethylisoluminol are used. Bound and free ligand are separated by washing and simple centrifugation. Results obtained by the chemiluminescence assay (y) and by r.i.a. (x) on 170 serum specimens from women during ovulation induction showed good correlation (y = 1.01x ? 16 with r = 0.95). The methods are similar in selectivity, detection limit (ca. 10 ng l?1) and precision (interassay relative standard deviation, 8–13%). 相似文献
30.
We report on a novel ultrafast two-dimensional infrared laser experiment that correlates vibrational bands of reactant and product of a photoreaction. The possibilities of this technique are demonstrated for the metal-to-ligand charge transfer (MLCT) in [Re(CO)3Cl(dmbpy)] (dmbpy = 4,4'-dimethyl-2,2'bipyridine) where we correlated the CO vibrational modes of the ground state and the MLCT state. A distinct vibrational mode is excited in the electronic ground state by an infrared laser pulse. This vibrational label survives the subsequent electronic excitation and can be followed in the excited electronic state. It is shown that the order of the vibrational energy levels is not preserved when exciting the molecule as was commonly assumed in the literature. 相似文献