全文获取类型
收费全文 | 4955篇 |
免费 | 106篇 |
国内免费 | 38篇 |
专业分类
化学 | 3052篇 |
晶体学 | 35篇 |
力学 | 224篇 |
数学 | 731篇 |
物理学 | 721篇 |
无线电 | 336篇 |
出版年
2021年 | 42篇 |
2020年 | 48篇 |
2019年 | 36篇 |
2018年 | 53篇 |
2017年 | 32篇 |
2016年 | 91篇 |
2015年 | 72篇 |
2014年 | 88篇 |
2013年 | 261篇 |
2012年 | 172篇 |
2011年 | 235篇 |
2010年 | 136篇 |
2009年 | 128篇 |
2008年 | 183篇 |
2007年 | 206篇 |
2006年 | 220篇 |
2005年 | 224篇 |
2004年 | 231篇 |
2003年 | 216篇 |
2002年 | 199篇 |
2001年 | 99篇 |
2000年 | 107篇 |
1999年 | 64篇 |
1998年 | 54篇 |
1997年 | 63篇 |
1996年 | 91篇 |
1995年 | 67篇 |
1994年 | 72篇 |
1993年 | 66篇 |
1992年 | 55篇 |
1991年 | 61篇 |
1990年 | 57篇 |
1989年 | 60篇 |
1988年 | 60篇 |
1987年 | 49篇 |
1986年 | 47篇 |
1985年 | 78篇 |
1984年 | 96篇 |
1983年 | 72篇 |
1982年 | 79篇 |
1981年 | 75篇 |
1980年 | 78篇 |
1979年 | 83篇 |
1978年 | 68篇 |
1977年 | 69篇 |
1976年 | 52篇 |
1975年 | 56篇 |
1974年 | 71篇 |
1973年 | 46篇 |
1972年 | 36篇 |
排序方式: 共有5099条查询结果,搜索用时 15 毫秒
111.
Schott D Sleigh CJ Lowe JP Duckett SB Mawby RJ Partridge MG 《Inorganic chemistry》2002,41(11):2960-2970
NMR studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its spectral features. In contrast, when L = AsMe(2)Ph, the ccc and cct-L forms are present in similar quantities and, hence, must have similar free energies; for this complex, however, the cct-CO isomer is also detectable. These complexes undergo a number of dynamic processes. For L(2) = dppe, an interchange of the hydride positions within the ccc form is shown to be accompanied by synchronized CO exchange and interchange of the two phosphorus atoms. This process is believed to involve the formation of a trigonal bipyramidal transition state containing an eta(2)-H(2) ligand; in view of the fact that k(HH)/k(DD) is 1.04 and the synchronized rotation when L(2) = dppe, this transition state must contain little H-H bonding character. Pathways leading to isomer interconversion are suggested to involve related structures containing eta(2)-H(2) ligands. The inverse kinetic isotope effect, k(HH)/k(DD) = 0.5, observed for the reductive elimination of dihydrogen from Ru(CO)(2)(H)(2)dppe suggests that substantial H-H bond formation occurs before the H(2) is actually released from the complex. Evidence for a substantial steric influence on the entropy of activation explains why Ru(CO)(2)(H)(2)dppe undergoes the most rapid hydride exchange. Our studies also indicate that the species [Ru(CO)(2)L(2)], involved in the addition of H(2) to form Ru(CO)(2)(H)(2)L(2), must have singlet electron configurations. 相似文献
112.
Roger L. Snowden 《Tetrahedron letters》1984,25(35):3835-3836
An efficient synthesis of dienediester 3, a key intermediate for drimane-related sesquiterpenes, is described starting from enal 4. 相似文献
113.
Renáta Oriňáková Hans-Dieter Wiemhöfer Jürgen Paulsdorf Veronika Barinková Anna Bednáriková Roger M. Smith 《Journal of Solid State Electrochemistry》2006,10(7):458-464
The electrochemical impedance method was applied during the electrochemical deposition of a binary Ni–Co coating on iron powder in a fluidised bed electrode system. The influence of the suspension density on the charge transfer in the course of the electro-deposition process was studied. At a potential of −900 mV (vs. Ag/AgCl/3 M KCl), when the binary Ni–Co layer was formed, the impedance data were characterised by two semicircles with the semicircle at high frequencies being larger in magnitude. A contribution of the diffusion process to the overall current was observed. The optimal suspension density for the charge transfer in the bed was 10×10−3–15×10−3 (i.e., 4–6 g of iron powder in 50 ml of electrolyte). The most probable mechanism of the charge transfer for the studied concentrations of powder particles is the convective mechanism. The iron particles dispersed in the electrolyte were considered to act as either a depolariser or an additional working electrode depending on the applied electrode potential and on the suspension density. 相似文献
114.
Chemosensors for the marine toxin saxitoxin 总被引:1,自引:0,他引:1
Gawley RE Pinet S Cardona CM Datta PK Ren T Guida WC Nydick J Leblanc RM 《Journal of the American Chemical Society》2002,124(45):13448-13453
Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed. 相似文献
115.
Roger Douillard 《Colloids and surfaces. B, Biointerfaces》1993,1(6):333-340
Knowledge of the equation of state of adsorbed or deposited layers of proteins at the air/water interface is of fundamental interest in the understanding of the surface activity of these molecules. Using scaling laws of current polymer theories, it has been shown that the equation of state of the interfacial layer in the semi-dilute regime should relate the surface pressure to the surface concentration through a power law. The exponent of this power law should reflect the quality of the solvent and the conformation of the adsorbed polypeptide chain. In the case of β-lactoglobulin layers, in the range of surface concentrations that should correspond to the semi-dilute regime, the relationship between surface pressure and surface concentration is expressed as a power law. The exponent of this power law is strongly influenced by the nature of the aqueous substrate and by the net charge of the protein molecule. The use of scaling laws gives a coherent view of the expansion of the polypeptide chain in the interfacial layer and of the relationship between surface concentration and surface pressure in the semi-dilute regime. This result favours a strong similarity between β-lactoglobulin and a polymer chain in the interfacial layer. It is concluded that current theories of polymer adsorption could be applied to interfacial protein layers. 相似文献
116.
Highly ordered mesoporous inorganic-organic hybrid thin films with covalently bonded carboxylic acid (-COOH) terminal groups on the pore surfaces were synthesized by evaporation induced self-assembly of tetraethoxysilane, organosilanes, and a nonionic surfactant followed by acid hydrolysis and characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, surface acoustic wave (SAW) based N2 sorption, and thermogravimetric analysis (TGA) techniques. 相似文献
117.
Naringenin is a natural widespread flavanone occurring in different foodstuffs that presents several important biological activities. Although its properties are well documented, its mechanisms of action are still controversial. The present article reports a conformational analysis of naringenin, using the semiempirical AM1 and ab initio methods, at the Hartree–Fock level of theory. The 3-21G, 3-21G*, 6-31G, and 6-31G** basis sets were used. The electron correlation effects were included through the Møller–Plesset second-order perturbation theory. The solvation of naringenin has been investigated through the standard SCRF, the supermolecule (SM), and the combined SM/SCRF models. The results have shown that there are two degenerate forms of naringenin, differing mainly by the orientation of a hydroxyl group (C4—OH). The energy barrier for the interconversion between them is ca. 6 kcal.mol–1, suggesting some conjugation between the -system of the aromatic B ring and the hydroxyl group (C4—OH). 相似文献
118.
A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ). 相似文献
119.
Roger M. Smith 《Chromatographia》1982,16(1):155-157
Summary The pungent principles of ginger and grains of paradise are examined using a reversed-phase HPLC column. An electrochemical detector is used to selectively detect the phenolic gingerols and shogaols. The retention indices of the compounds are compared using methanowater and acetonitrile-water as eluents.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献
120.
The 15N-NMR spectra of vitamin B12 analogues obtained in fully 15N-labelled form have been measured by direct and inverse (15N, 1H) correlated spectroscopy. All resonances, except those of the NH2 groups, have been assigned to individual N-atoms. The influences on δ (N) are analyzed and discussed which are caused by changing the α-face ligand from CN to H2O or CH3 and by switching the β-face ligand from the base-on to the base-off state. An implication of the correct resonance assignment on biosynthetic pathways is demonstrated. 相似文献