全文获取类型
收费全文 | 11964篇 |
免费 | 1860篇 |
国内免费 | 1929篇 |
专业分类
化学 | 12255篇 |
晶体学 | 351篇 |
力学 | 74篇 |
综合类 | 53篇 |
数学 | 133篇 |
物理学 | 2887篇 |
出版年
2024年 | 41篇 |
2023年 | 189篇 |
2022年 | 401篇 |
2021年 | 440篇 |
2020年 | 601篇 |
2019年 | 478篇 |
2018年 | 430篇 |
2017年 | 418篇 |
2016年 | 634篇 |
2015年 | 652篇 |
2014年 | 690篇 |
2013年 | 1167篇 |
2012年 | 760篇 |
2011年 | 689篇 |
2010年 | 650篇 |
2009年 | 728篇 |
2008年 | 776篇 |
2007年 | 836篇 |
2006年 | 780篇 |
2005年 | 742篇 |
2004年 | 629篇 |
2003年 | 541篇 |
2002年 | 385篇 |
2001年 | 294篇 |
2000年 | 296篇 |
1999年 | 233篇 |
1998年 | 205篇 |
1997年 | 179篇 |
1996年 | 182篇 |
1995年 | 147篇 |
1994年 | 97篇 |
1993年 | 78篇 |
1992年 | 68篇 |
1991年 | 41篇 |
1990年 | 39篇 |
1989年 | 39篇 |
1988年 | 37篇 |
1987年 | 27篇 |
1986年 | 23篇 |
1985年 | 24篇 |
1984年 | 14篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1973年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
L. F. Chertanova B. I. Buzykin A. A. Gazikasheva M. P. Sokolov 《Russian Chemical Bulletin》1992,41(12):2162-2167
The crystal and molecular structures of the products of the halogenation of the dimorpholide of ethoxyvinylphosphonic acid were determined by the method of x-ray structure analysis. It was established that (dimorpholinophosphoryl)chloroacetaldehyde only exists in the crystals as the Z-enol [(Z)-1-hydroxy-2-(dimorpholinophosphoryl)-2-chloroethene] with intra- and intermolecular H-bonds (=CH...O=P and OH...O=P). The (dimorpholinophosphoryl)dibromomethane forms centrosymmetric eight-membered cyclic dimers in the crystals due to intermolecular CH...O=P H-bonds. The structure of the morpholine and phosphoryl groups in both compounds was discussed.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2730–2737, December, 1992. 相似文献
72.
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence. 相似文献
73.
Crystals of 4(C2H5)4N+F– · 11H2O are orthorhombic, space groupPna21, witha=16.130(3),b=16.949(7),c=17.493(7) Å, andZ=4. The structure was shown to be a clathrate hydrate containing infinite chains of edge-sharing (H2O)4F– tetrahedra extending parallel to thea axis. The chains are laterally linked by bridging water molecules to form a three-dimensional hydrogen-bonded anion/water framework. The ordered (C2H5)4N+ cations occupy the voids in two open channel systems running in theb andc directions. FinalR
F
=0.091 for 2278 observed MoK data measured at 22°C.
Supplementary Data: relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82010 (20 pages).Dedicated to Professor H. M. Powell. 相似文献
74.
Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on
nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The
distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows
a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen
bonds. The frequency shows a cos6θ dependence as compared to cos2θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides. 相似文献
75.
A. V. Afonin 《Russian Chemical Bulletin》1996,45(5):1142-1144
The analysis of the effect of the solvents on the proton chemical shifts in1H NMR spectra of 2-vinyloxypyridine indicates that the C—H...N interaction of weak intramolecular hydrogen bond type hinders the formation of intermolecular hydrogen C—H...X and C-H... bonds. The protonating solvents reduce the intramolecular C—H...N interaction due to association with the N atom of the pyridine cycle.Translated fromIzvestiya Akademii Nauk. Seriya Khimieheskaya, No. S, pp. 1202–1204, May, 1996. 相似文献
76.
Safoklov B. B. Atovmyan E. G. Nikonova L. A. Tkachev V. V. Aldoshin S. M. 《Russian Chemical Bulletin》2002,51(12):2224-2229
Pyrrole-2-carbaldehyde isonicotinoylhydrazone (1) and its hydrate [1·H2O] (2) were studied by single-crystal X-ray diffraction analysis. The introduction of the pyrrole substituent into N"-substituted isonicotinic hydrazide (INH) causes the intramolecular redistribution of the electron density compared to those in INHs studied earlier, which increases the basicity of the hydrazone nitrogen atom (N") involved in intermolecular hydrogen bonding. This effect has not been observed in the structures of N"-substituted INHs and benzhydrazides studied previously. Intermolecular hydrogen bonds play a decisive role in the formation of the crystal structures of 1 and 2. 相似文献
77.
I. I. Chuev S. M. Aldoshin E. G. Atovmyan D. B. Frolov A. N. Utenyshev 《Russian Chemical Bulletin》1996,45(4):851-855
N-Thenylidene- andN-(o-nitrobenzylidene)hydrazides of isonicotinic acid have been studied by X-ray structural analysis and IR spectroscopy. In the crystalline state, these molecules are linked through intermolecular N—H ... Npy hydrogen bonds. Carbonyl groups are not involved in intermolecular hydrogen bonds. However, it was found that the C=O group participates in an attractive interaction with the sulfur atom of the thiophene group. The energy of this interaction is comparable with the energies of intermolecular C=O ... H—N hydrogen bonds in amides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 896–900, April, 1996. 相似文献
78.
S. V. Fedorov A. Yu. Rulev N. N. Chipanina A. M. Shulunova V. G. Nenajdenko E. S. Balenkova D. A. Tyurin V. K. Turchaninov 《Russian Chemical Bulletin》2005,54(1):103-107
The molecular structures of β-amino-α-bromovinyl trifluoromethyl ketones was studied by UV, IR, 1H, 13C, and 15N NMR spectroscopy and using the density functional (B3LYP/6-31G(d,p) and PBE/QZ3P) and ab initio riMP2/cc-pVTZm quantum-chemical calculations. Factors affecting stabilization of the EZE-conformation of the molecules, which is atypical of analogous unsubstituted amino enones, are considered.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 102–106, January, 2005. 相似文献
79.
Transference numbers of HCl(aq) solutions at 25°C, from 0.01 to 13.6 mol-kg–1(m) have been obtained by measuring the emf of cells with transference using hydrogen gas/platinum electrodes. Good agreement is obtained at concentrations up to 1 m with all previous data, and our results strongly corroborate those of King and Spiro over the 2–8m concentration range. The transference numbers of the hydronium ion fit the empirical equation,
H
HCl
= 0.821 + 0.0457m
1/2 – 2.476×10–2m – 1.90×10–4
m
2 – 1.45×10–5
m
3 the maximum deviation in T
H
HCl
being 0.003. 相似文献
80.
Homogeneity and structure of organically modified polysiloxane networks prepared by sol-gel co-condensation, as well as location and nature of water molecules and silanol groups were studied by 1D and 2D solid-state NMR. 1H–29Si and 1H–1H interatomic distances were estimated from variable contact-time CP/MAS experiments, 1H NMR chemical shifts and off-resonance WISE NMR. A structure model of these networks is proposed and discussed. The fraction of proton-inaccessible units Q4 in the networks decreases with increasing amounts of dimethylsiloxane (D) and methylsiloxane (T) units. In contrast to systems prepared by co-condensation of tetraethoxysilane (TEOS) with dimethyl(diethoxy)silane (DMDEOS), proton-inaccessible units form essential fraction in networks prepared by co-condensation of TEOS with methyl(triethoxy)silane (MTEOS). The proton-accessible part of the networks with high O/Si ratios is nano-heterogeneous phase, which is composed of water containing Q
i
particles separated by copolymer domains. The overall homogeneity and uniformity of binding sites around silanol groups increases by co-condensation TEOS with DMDEOS or MTEOS, while the amount of physisorbed water as well as the hydrogen bond strength decreases, as compared with neat silica gel prepared by polycondensation of TEOS. 相似文献