全文获取类型
收费全文 | 8857篇 |
免费 | 1124篇 |
国内免费 | 668篇 |
专业分类
化学 | 7004篇 |
晶体学 | 191篇 |
力学 | 923篇 |
综合类 | 23篇 |
数学 | 659篇 |
物理学 | 1849篇 |
出版年
2024年 | 22篇 |
2023年 | 64篇 |
2022年 | 169篇 |
2021年 | 203篇 |
2020年 | 391篇 |
2019年 | 244篇 |
2018年 | 208篇 |
2017年 | 261篇 |
2016年 | 387篇 |
2015年 | 381篇 |
2014年 | 408篇 |
2013年 | 648篇 |
2012年 | 596篇 |
2011年 | 487篇 |
2010年 | 447篇 |
2009年 | 580篇 |
2008年 | 629篇 |
2007年 | 674篇 |
2006年 | 554篇 |
2005年 | 448篇 |
2004年 | 457篇 |
2003年 | 405篇 |
2002年 | 322篇 |
2001年 | 224篇 |
2000年 | 210篇 |
1999年 | 233篇 |
1998年 | 200篇 |
1997年 | 147篇 |
1996年 | 103篇 |
1995年 | 114篇 |
1994年 | 68篇 |
1993年 | 65篇 |
1992年 | 52篇 |
1991年 | 40篇 |
1990年 | 25篇 |
1989年 | 29篇 |
1988年 | 22篇 |
1987年 | 17篇 |
1986年 | 18篇 |
1985年 | 15篇 |
1984年 | 23篇 |
1983年 | 4篇 |
1982年 | 14篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1970年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
The reaction of Cp2*UCl2 with HNSPh2 produces Cp2*UCl2(HNSPh2), which is the first structurally characterized complex of a sulfilimine. The hydrolysis of Cp2*UCl2(HNSPh2) with HNSPh2 · H2O yields a tetrauranium cluster whose heavy atom structure has been determined by x-ray diffraction and which is formulated as a UIV/UV complex: [Cp*(Cl)(HNSPh2)U(μ3-O)(μ2-O)2U(Cl)(HNSPh2)2]2. 相似文献
102.
Henrik Fanø Clausen 《Journal of solid state chemistry》2005,178(11):3342-3351
Two new metal organic framework (MOF) structures have been obtained from the Zn-terephthalic acid (H2BDC)-dimethyl formamide (DMF) system and examined by single-crystal X-ray diffraction: Zn(C8H4O4)(C3H7NO), 1, monoclinic C2/m, a=11.1369(5), b=14.0217(7), , β=106.316(1)°, , , Z=4, R1=0.060, wR2=0.169, S=1.27; Zn(HCO2)3(C2H8N), 2, trigonal , a=8.1818(1), , , , Z=6, R1=0.014, wR2=0.039, S=1.11. Contrary to previously published structures in the same system, the crystals were obtained by solvothermal synthesis at 381 K. Structure 1 consists of 2-D layers stacked in an offset manner to accommodate DMF moieties coordinated to Zn2+ within voids in adjacent layers. Structure 2 consists of a 3-D network constructed from Zn2+ ions bridged by deprotonated formic acid moieties. Over time, the structure of 1 rearranges to Zn(C8H4O4)(C3H7NO)(H2O) [monoclinic P21/n, a=6.6456(2), b=15.2232(5), , β=104.110(2)°, , , Z=4, R1=0.048, wR2=0.100, S=1.07], which is identical to the known MOF-2 structure, obtained by crystallization at ambient conditions. The three structures were determined from crystals with similar crystal habits picked from a single solvothermal synthesis batch. The study demonstrates that MOF syntheses can give not only multiple crystal structures under different conditions, but also that numerous different structures, including some that are metastable, can be formed under identical conditions. 相似文献
103.
M.E. Kletskii A.A. Millov A.V. Metelitsa M.I. Knyazhansky 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):857-270
The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S0, S1 and T1 potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S1 excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S1 twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism. 相似文献
104.
C. Cismaş I. Grosu G. Plé E. Condamine Y. Ramondenc L. Toupet I. Silaghi-Dumitrescu G. Nemeş A. Terec L. Muntean 《Structural chemistry》2005,16(4):369-377
The synthesis and stereochemistry of some new bis(1,3-oxathian-2-yl) derivatives are reported. The conformational behavior of these compounds and the orientation of their substituents are deduced from the NMR spectra, from the X-ray crystal structures of two compounds and from the ab-initio level calculations. The epimerization of diastereoisomers and the chair ⇌ 22,5-twist equilibria were studied by variable temperature NMR. 相似文献
105.
Carbonate Isostructural Anions [SnX3]5? in the Compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi The metallic shining compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi were prepared from the melt starting from adequate mixtures of the elements and SnO2. They crystallize in the hexagonal system (space group P63/mmc, No. 194, Z = 2) with the lattice constants mentioned in ?Inhaltsübersicht”?. In the structures of the isotypic compounds tin and the main group(V) elements build up trigonal planar anions [SnX3]5? with X = As, Sb, and Bi isostructural to the carbonate anion, oxygen forms isolated O2? ions. The bond lengths Sn? X are significantly shortened with respect to the sums of Pauling covalent radii. The atoms of the units [SnX3]5? are coordinated by alkali metal cations forming trigonal prisms and the O2? anions occupy octahedral holes. 相似文献
106.
New secondary and tertiary amine borane derivatives were prepared in a one-pot reaction starting from primary amine boranes. The reaction involves treatment of an amine borane with 2 equivalents of s-BuLi at −78 °C. In general, mixtures of mono and di metallated products were obtained. Alkyl iodides and benzyl chloride reacted with the lithiated amine, but aldehydes and ketones were reduced. Conversion was high as determined by NMR, but moderate to low yields were obtained after chromatography, possibly due to decomposition on silica. Crystal structures were obtained for the compounds 3a, 3b and 3c. 相似文献
107.
V.A. Ozeryanskii A.F. Pozharskii D.A. Shevchuk A.N. Chekhlov O.A. Dyachenko 《Tetrahedron》2005,61(17):4221-4232
A simple procedure for the synthesis of N,N,N′-trialkyl-1,8-diaminonaphthalenes is described. It consists in partial demethylation (dealkylation) of commercially available proton sponge [1,8-bis(dimethylamino)naphthalene] and some of its derivatives at heating with HBr-KI-DMF system. Limitation, scope and a possible mechanistic pathway for the reaction are discussed. For isomeric 8-dimethylamino-1-methylamino- and 1-dimethylamino-8-methylamino-4-nitronaphthalenes, X-ray measurements have been conducted. The first examples of complete realkylation reactions in the naphthalene proton sponges are reported. 相似文献
108.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
109.
Afarin Moezzi Marylin M. Olmstead Doris C. Pestana Philip P. Power 《无机化学与普通化学杂志》1995,621(11):1933-1938
The reaction of either Li2PPh or Li2AsPh with the diborane(4) derivative B2(NMe2)2Br2 affords the compounds [PhP(BNMe2)2]2 ( 1 ) or [PhAs(BNMe2)2]2 ( 2 ) in good yield. Both 1 and 2 have cyclic structures featuring non-planar P2B4 or As2B4 six-membered rings which have chair configurations. Although all four borons in each ring have planar coordination, the two phosphorus or arsenic centers have different degrees of pyramidalization. Bond distances within the rings indicate that the B? B, B? P or B? As bonds are single, whereas the exo-B? N bond lengths are consistent with significant π-bonding. The ring structures of 1 and 2 are in sharp contrast to the related boron-nitrogen species (t-BuN)2N4Me4 which has a nido-N2B4 framework. The attempted synthesis of the nitrogen analogue of 1 or 2 by using a similar approach did not result in the isolation of [PhN(BNMe2)2]2, instead the tetramino diborane(4) species [B(NMe2)NHPh]2 ( 3 ), which has a structure similar to other tetramine diborane(4) compounds, was isolated. 相似文献
110.
Transition structures associated with the C-C bond-formation step of the proline-catalyzed intermolecular aldol reaction
between acetone and isobutyraldehyde have been studies using density functional theory methods at the B3LYP/6-31G** computational
level. A continuum model has been selected to represent solvent effects. For this step, which is the stereocontrolling and
rate-determining step, four reactive channels corresponding to the syn and anti arrangement of the active methylene of the
enamine relative to the carboxylic acid group of l-proline and the re and si attack modes to both faces of the aldehyde carbonyl group have been analyzed. The B3LYP/6-31G**
energies are in good agreement with experiment, allowing us to explain the origin of the catalysis and stereoselectivity for
these proline-catalyzed aldol reactions.
Received: 2 April 2002 / Accepted: 18 July 2002 / Published online: 11 October 2002
Acknowledgements. This work was supported by research funds provided by the Ministerio de Educación y Cultura of the Spanish Government by
DGICYT (project PB98–1429). All the calculations were performed on a Cray–Silicon Graphics Origin 2000 of the Servicio de
Informática de la Universidad de Valencia. We are most indebted to this center for providing us with computer capabilities.
Correspondence to: L. R. Domingo e-mail: domingo@utopia.uv.es 相似文献