全文获取类型
收费全文 | 77177篇 |
免费 | 16893篇 |
国内免费 | 6754篇 |
专业分类
化学 | 69872篇 |
晶体学 | 780篇 |
力学 | 3022篇 |
综合类 | 378篇 |
数学 | 7174篇 |
物理学 | 19598篇 |
出版年
2024年 | 143篇 |
2023年 | 965篇 |
2022年 | 1707篇 |
2021年 | 1849篇 |
2020年 | 2966篇 |
2019年 | 4244篇 |
2018年 | 2588篇 |
2017年 | 2064篇 |
2016年 | 5403篇 |
2015年 | 5499篇 |
2014年 | 5840篇 |
2013年 | 7079篇 |
2012年 | 6830篇 |
2011年 | 6048篇 |
2010年 | 5473篇 |
2009年 | 5316篇 |
2008年 | 5026篇 |
2007年 | 4142篇 |
2006年 | 3651篇 |
2005年 | 3418篇 |
2004年 | 2888篇 |
2003年 | 2510篇 |
2002年 | 3403篇 |
2001年 | 2536篇 |
2000年 | 2132篇 |
1999年 | 1349篇 |
1998年 | 738篇 |
1997年 | 696篇 |
1996年 | 624篇 |
1995年 | 544篇 |
1994年 | 438篇 |
1993年 | 442篇 |
1992年 | 328篇 |
1991年 | 341篇 |
1990年 | 286篇 |
1989年 | 220篇 |
1988年 | 191篇 |
1987年 | 133篇 |
1986年 | 129篇 |
1985年 | 122篇 |
1984年 | 103篇 |
1983年 | 56篇 |
1982年 | 58篇 |
1981年 | 36篇 |
1980年 | 30篇 |
1979年 | 18篇 |
1978年 | 19篇 |
1976年 | 20篇 |
1975年 | 17篇 |
1973年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Sesquiterpene esters from the fruits of Celastrus orbiculatus 总被引:1,自引:0,他引:1
Three new beta-dihydroagarofuran sesquiterpene esters, 6 alpha-acetoxy-9 beta-benzoyloxy-1 beta-cinnamoyloxy-8 beta-butanoyloxy-beta-dihydroagarofuran (1), 6 alpha-acetoxy-9 beta-benzoyloxy-1 beta-cinnamoyloxy-8 beta-(2-methylbutanoyloxy)-beta-dihydroagarofuran (2), and 6 alpha-acetoxy-1 beta,8 beta-dibenzoyloxy-9 beta-hydroxy-beta-dihydroagarofuran (6), together with three known compounds (3-5) were isolated from the fruits of Celastrus orbiculatus THUNB. Their structures were elucidated on the basis of spectroscopic methods. Compound 4 showed moderate activity in inhibiting LPS-induced nitric oxide production in murine macrophage RAW264.7 cells with an IC(50) value of 43.7 microM. 相似文献
992.
993.
A new series of thiophene‐ and furan‐containing chromophores with a chiral prolinol donor and a sulfone acceptor has been synthesized. The UV‐vis absorptions, second‐order nonlinear optical properties, and X‐ray crystal structures are described. 相似文献
994.
995.
QuanZhenHUANG GongZhenCHENG HaiBoZHANG SongTaoDING XiaoBingYANG XiaoHaiZHOU GaoYongZHANG 《中国化学快报》2005,16(4):497-500
The Q-band position of tin-centered 5, 9, 14, 18, 23, 27, 32, 36-octabutoxy 2, 3-phthalocyanine(SnNc(OBu)8) exhibits dramatic red-shift as mixed with SnCl2 in CH2Cl2. 相似文献
996.
997.
Simple complexes connected through C-H...S and C-H...N interactions are investigated: CH4...NH3, C2H4...NH3, C2H2...NH3, CH4...SH2, C2H4...SH2, and C2H2...SH2. Ab initio and DFT calculations are performed (SCF, MP2, B3LYP) using different basis sets up to the MP2/aug-cc-pVQZ//MP2/aug-cc-pVDZ level of approximation. The Bader theory is applied since MP2/6-311++G(d,p) wave functions are used to find and to characterize bond critical points in terms of electron densities and their Laplacians. The influence of hybridization on the properties of C-H...S and C-H...N systems is also studied showing that the strength of such interactions increases in the following order: C(sp3)-H...Y, C(sp2)-H...Y, C(sp)-H...Y, where Y = S, N--it is in line with the previous findings on C-H...O hydrogen bonds. The results also show that CH4...SH2 and C2H4...SH2 complexes should be rather classified as van der Waals interactions and not as hydrogen bonds. The frequency associated with the C-H stretch of C(sp3)-H...S is blue-shifted. 相似文献
998.
Piotr Kujawa Annie Audibert‐Hayet Joseph Selb Franoise Candau 《Journal of Polymer Science.Polymer Physics》2004,42(9):1640-1655
Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (NH). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (NH = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the NH value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (NH = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004 相似文献
999.
A Novel Dimeric Coumarin from Clausena lenis 总被引:1,自引:0,他引:1
HongPingHE ShunTingCHEN YueMaoSHEN ChangXiangCHEN YiBinZHAO XiaoJiangHAO 《中国化学快报》2003,14(11):1150-1153
A novel dimeric coumarin (1), a dimeric of seselin named diseselin A, was isolated from the aerial part of Clausena lenis. The structure was elucidated based on the MS, 1D and 2D NMR data. 相似文献
1000.
Oliver Moers Violeta Latorre Karl‐Heinz Nagel Armand Blaschette Peter G. Jones 《无机化学与普通化学杂志》2003,629(1):83-90
Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH3SO2)2N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P21/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P21/n, Z′ = 1), where A— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO2)2NH. In KA and RbA, the anion is distorted into a rare C1 conformation, whereas the standard C2 conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O6N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ1O‐bonding ligands; however, the coordination number for Cs+ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding. 相似文献