全文获取类型
收费全文 | 4359篇 |
免费 | 76篇 |
国内免费 | 33篇 |
专业分类
化学 | 2826篇 |
晶体学 | 34篇 |
力学 | 229篇 |
数学 | 752篇 |
物理学 | 627篇 |
出版年
2022年 | 27篇 |
2021年 | 33篇 |
2020年 | 37篇 |
2019年 | 28篇 |
2018年 | 42篇 |
2016年 | 76篇 |
2015年 | 59篇 |
2014年 | 70篇 |
2013年 | 235篇 |
2012年 | 140篇 |
2011年 | 199篇 |
2010年 | 113篇 |
2009年 | 113篇 |
2008年 | 163篇 |
2007年 | 172篇 |
2006年 | 177篇 |
2005年 | 194篇 |
2004年 | 208篇 |
2003年 | 193篇 |
2002年 | 183篇 |
2001年 | 89篇 |
2000年 | 97篇 |
1999年 | 50篇 |
1998年 | 46篇 |
1997年 | 52篇 |
1996年 | 74篇 |
1995年 | 62篇 |
1994年 | 60篇 |
1993年 | 58篇 |
1992年 | 53篇 |
1991年 | 51篇 |
1990年 | 53篇 |
1989年 | 54篇 |
1988年 | 45篇 |
1987年 | 42篇 |
1986年 | 47篇 |
1985年 | 72篇 |
1984年 | 72篇 |
1983年 | 63篇 |
1982年 | 79篇 |
1981年 | 67篇 |
1980年 | 79篇 |
1979年 | 78篇 |
1978年 | 69篇 |
1977年 | 58篇 |
1976年 | 48篇 |
1975年 | 57篇 |
1974年 | 66篇 |
1973年 | 48篇 |
1972年 | 41篇 |
排序方式: 共有4468条查询结果,搜索用时 31 毫秒
101.
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
102.
Atkinson CE Aliev AE Motherwell WB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(8):1714-1723
A binding site optimisation protocol for the design of artificial enzymes based on "small molecule-small molecule" binding studies by diffusion NMR is presented. Since the reaction chosen was the hydrolysis of ester 1 ([4-(4-carboxy-1-oxobutyl)-aminobenzyl]-phenethyl ester), an analogous phosphonate ester 2 ([4-(4-carboxy-1-oxobutyl)-aminobenzyl]-phosphonic phenethyl ester) was selected as a suitable transition state analogue (TSA). The key objective of the NMR studies was to find a unit with functional groups capable of binding to the acidic sites of the TSA. Nine dipeptides, mainly with basic and hydroxyl groups, were used and their affinity to the TSA was studied by measuring the change in the diffusion coefficient, D(pep), upon binding by pulse field gradient NMR. The value of D(pep) at 298 K in D(2)O at pD 5, 7 and 10 was measured both in free solution, and mixtures containing one dipeptide and the TSA. As both components are low molecular weight species with M < 500, a TSA-to-dipeptide ratio of 10:1 was used to detect significant changes in D(pep). The results revealed that dipeptides with basic residues show higher affinity to the TSA than those with hydroxyl or aliphatic side chains in aqueous solutions. The dipeptide showing the most significant relative change in D(pep) was H-Arg-Arg-OH, and the binding constant was estimated to be 86 L M(-1) by measuring D(pep) at varying concentrations of the TSA. In addition, binding of the TSA to a new water-soluble polymer with a polyallylamine backbone and randomly distributed Arg-Arg binding sites was examined, and the binding constant was estimated to be > or =1500 L M(-1). As confirmed by further catalytic activity tests, polymers containing Arg-Arg as a binding site are capable of significant rate accelerations in the hydrolysis of ester 1. 相似文献
103.
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
104.
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
105.
In this paper, we present a rheological study of a compact layer of highly swollen gel beads. The flow regimes of these systems are modelled by an elastic sinusoid moving in a Newtonian fluid. This model predicts a yield stress varying with the square root of the elastic modulus of the gel bead. The slope at the origin (at zero velocity) of the flow curve is expected to depend only on geometrical parameters and on the solvent viscosity. The experimental data are in qualitative agreement with the theoretical predictions. 相似文献
106.
Using the density functional method, the stabilities of highly hydrogenated and fluorinated [80]fullerenes, both empty and containing the Sc3N molecule, have been calculated. Addition of 44 atoms to i-Sc3NC80 is predicted to be most favorable due to the formation of six octahedrally located benzenoid rings, while addition of up to 52 atoms (consistent with preliminary fluorination data) gives a structure stabilized by the presence of four benzenoid rings. The most stable isomers at this addition level have been determined and the relative stabilities of a number of C80H52, C80F52, and i-Sc3NC80H52 species calculated. The hydrogenation of the i-Sc3NC80 has been computed to be more difficult than the corresponding partner, C80. From the geometrical point of view, the Sc3N molecule is planar in the parent [80]fullerene but is calculated to be pyramidal in some of the hydrogenated/fluorinated derivatives. Moreover, in these it has fixed locations due to orbital interactions arising from deformation of the cage and the presence of localized double bonds. 相似文献
107.
Hyperfine structures of transitions in the a 3Πu ← X1Σg system of Na2 have been accurately measured by Doppler-free laser excitation spectroscopy in a collimated molecular beam. The hyperfine patterns are quantitatively explained and the reduced matrix elements of the magnetic dipole hf interaction determined from a least-squares fit to the measured line positions. 相似文献
108.
109.
Christian Bellec Daniel Bertin Roger Colau StPhane Deswarte Pierre Maitte Claude Viel 《Journal of heterocyclic chemistry》1979,16(8):1611-1616
Z α-Cyano-β-nitrostyrenes were prepared by nitration with dinitrogentetroxide of the corresponding α-cyanostyrenes. Elsomers were obtained by photoirradiation of Z isomers. The electrochemical reduction of these cyanonitro compounds generates the α-cyanooximes which lead, according to the experimental conditions(ring closure or hydrolysis), either to 5-aminoisoxazoles or to β-ketonitriles. 相似文献
110.
The kinetics of the gas-phase reaction of the NO3 radical with naphthalene have been investigated at 150 torr O2 + 590 torr N2 and 600 torr O2 + 140 torr N2 at 298 ± 2 K. Relative rate measurements were carried out in reacting NO3? N2O5-naphthalene-propene-O2? N2 mixtures by longpath Fourier transform infrared absorption spectroscopy. A rate constant ratio for the reactions of O2 and NO2 with the NO3-naphthalene adduct of k/k < 4 × 10?7 was obtained from the competition between O2 and NO2 for reaction with the NO3-naphthalene adduct and thermal decomposition of the adduct back to reactants. Atmospheric pressure ionization MS/MS measurements of the nitronaphthalene products of the NO3 radical-initiated reaction of naphthalene are consistent with the proposed reaction mechanism, and the atmospheric implications of the data are discussed. © 1994 John Wiley & Sons, Inc. 相似文献