全文获取类型
收费全文 | 1901篇 |
免费 | 84篇 |
国内免费 | 12篇 |
专业分类
化学 | 1202篇 |
晶体学 | 11篇 |
力学 | 109篇 |
数学 | 343篇 |
物理学 | 332篇 |
出版年
2023年 | 12篇 |
2022年 | 22篇 |
2021年 | 50篇 |
2020年 | 48篇 |
2019年 | 34篇 |
2018年 | 36篇 |
2017年 | 39篇 |
2016年 | 70篇 |
2015年 | 81篇 |
2014年 | 68篇 |
2013年 | 106篇 |
2012年 | 124篇 |
2011年 | 148篇 |
2010年 | 70篇 |
2009年 | 83篇 |
2008年 | 140篇 |
2007年 | 112篇 |
2006年 | 93篇 |
2005年 | 96篇 |
2004年 | 79篇 |
2003年 | 58篇 |
2002年 | 61篇 |
2001年 | 25篇 |
2000年 | 26篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 22篇 |
1996年 | 17篇 |
1995年 | 11篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 13篇 |
1980年 | 11篇 |
1979年 | 13篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1974年 | 5篇 |
1970年 | 3篇 |
排序方式: 共有1997条查询结果,搜索用时 31 毫秒
21.
The [2 + 2]-cycloaddition of dichloroketene (prepared in situ from CCl3COCl and Zn(Cu)) with three alkynes 1a–c to form 2,3-dimethyl-( 2a ), 2,3-diethyl-( 2b ) and 3-butyl-4,4-dichlorocyclobut-2-enone ( 2c ) proceeds rapidly in the absence of POCl3. The primary products 2a–c rearrange in situ to the 2,4-dichlorocyclobut-2-enones 3a–c under the influence of ZnCL2 produced during the reaction. ZnCl2 converts both 2a and 3a into a 4:6 equilibrium mixture of the two; this isomerization does not occur with LiCl. The Cl-atoms of both 2a , b and 3a , b and of 2c may reductively be removed with Zn(Cu) in AcOH/pyridine to afford the alkylcyclobutenones 4a-c . Without pyridine, this reduction gives ca. 1:1 mixtures of the double-bond isomers 4 and 5 in low yields. The cyclobutenones 2c and 4c may be deuterated by CD3COOD in the presence of pyridine. D -Atom is introduced into 2c at C(4) and at C(γ), and into 4c at C(2) and C(4). A mechanism for this deuteration is considered, which does not involve a cyclobutadienolate 7 , but rather a cyclobutenolate of type 8 . The reductions of 2 and 3 to 4 might also pass through the same type of intermediate 8 . 相似文献
22.
Martin R. Bryce Peter J. Skabara Adrian J. Moore Andrei S. Batsanov Judith A.K. Howard Vanessa J. Hoy 《Tetrahedron》1997,53(52):1002-17794
Reactions of tetrathiafulvalenyllithium (TTF-Li) with a range of aldehydes and ketones have been explored for the first time, to provide an efficient route to mono-functionalised TTF derivatives of general formulae TTF-CH(OH)R (R = alkyl, phenyl, tetrathiafulvalenyl and ferrocenyl) and TTF-CR(OH)R′ (R = alkyl, phenyl, R′ = alkyl, phenyl, tetrathiafulvalenyl, ferrocenyl, and R-R′ = fluorenyl). Subsequent transformations involving the reactive alcohol group of some of these compounds are reported. The structures of the three title compounds have been established by single-crystal X-ray analysis. 相似文献
23.
Christophe Bongars Peter Bougeard Adrian Bury Christopher J. Cooksey Michael D. Johnson Stewart Mitchell Paul A. Owens Famida Rajah 《Journal of organometallic chemistry》1985,289(1):163-171
5-Methylhex-5-enylcobaloxime reacts with carbon tetrachloride and with fluorotrichloromethane at 80–100°C to give substantially pure 1-methyl-1-(β,β,β-trichloroethyl)- and 1-methyl-1-β-fluoro-β,β-dichloroethyl)-cyclopentane. Hex-5-enylco-baloxime also gives trichloroethylcyclopentane from carbon tetrachloride, but the yield is dependent on the concentration of carbon tetrachloride. Similar cyclisation to give trichloroethyl- or fluorodichloroethyltetrahydrofuran is observed in the reactions of hex-3-oxo-5-enylcobaloxime with carbon tetrachloride and fluorotrichloromethane. However, no cyclisation was observed in the reactions of the ester, hex-2-one-3-oxo-5-enylcobaloxime, with carbon tetrachloride. These reactions are believed to take place by attack of a polyhalogenomethyl radical at the terminal unsaturated carbon of the organic ligand, followed either by an intramolecular homolytic displacement in which the carbon radical at position-5 attacks carbon-1 with displacement of cobaloxime(II), or by a halogen atom abstraction. 相似文献
24.
Potter CV Freshwater J Dean JL Kybett AP Kidd R James M Saxton H 《Chemical Society reviews》2004,33(9):567-572
In January 2003, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC)--a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)? 相似文献
25.
26.
Reaction of N-phenyl maleimide (NPM) with silica surfaces modified with a self-assembled monolayer of (aminopropyl)triethoxysilane (APTES) was investigated using infrared spectroscopy (FTIR), elemental analysis, and titration assays. This reaction is of interest as a test case for using amine-maleimide coupling for immobilization of biomolecules. Addition of NPM to surface APTES residues was consistently sub-stoichiometric, with typical yields of about 75% on monolayers with a coverage of 1.15 APTES residues/nm2. Titration analysis found negligible presence of imide alkene C=C bonds in modified supports, indicating that addition of NPM to APTES proceeded via amine attack at the imide olefinic bond. FTIR measurements also revealed presence of amide bands which intensified over periods of 10 h. These observations were attributed to a slower secondary process in which APTES amines attack imide carbonyls to produce amide linkages. Stability of NPM-modified surfaces was examined under room temperature storage in pH 7 buffer up to 72 h and for 2 h exposure to buffer at temperatures up to 90 degrees C. It was found that stability was determined by robustness of APTES-silica attachment, with about 30% loss under the harshest conditions investigated. 相似文献
27.
Kinetic studies on the substitution reaction between [Fe(4)S(4)Cl(4)](2-) and Bu(t)NC or Et(2)NCS(2)(-) are reported. The binding of small molecules and ions to Fe-S clusters is a fundamental step in substitution reactions but can be difficult to follow directly because these reactions are rapid and often associated with small spectroscopic changes. A novel kinetic method is reported which allows the time course of molecule and ion binding to Fe-S clusters to be followed by monitoring the lability of the cluster. Using a stopped-flow, sequential-mix apparatus, [Fe(4)S(4)Cl(4)](2-) and L (L = Et(2)NCS(2)(-) or Bu(t)NC) are rapidly mixed, and after a known time (delta) the resulting solution is mixed with a solution of PhS(-). The thiolate substitutes for the chloro ligands on the cluster, in a reaction which is easy to follow because of the large change in the visible absorption spectrum. The rate of this substitution is extremely sensitive to whether L is bound to the cluster or not. By correlation of delta with the rate of the reaction with PhS(-), the time course of the reaction between [Fe(4)S(4)Cl(4)](2-) and L can be mapped out. In studies where L = Bu(t)NC this technique has allowed the detection of an intermediate ([Fe(4)S(4)Cl(4)(CNBu(t))](2-)) which cannot be detected spectrophotometrically. In further studies, the substitution reactions of [Fe(4)S(4)Cl(4)](2-) with PhS(-), Et(2)NCS(2)(-), or Bu(t)NC are all perturbed by the addition of Cl(-). In all cases a common pathway for substitution is evident, but with Et(2)NCS(2)(-) an additional, slower pathway becomes apparent under conditions where the common pathway is completely inhibited by Cl(-). 相似文献
28.
Teplý F Stará IG Starý I Kollárovic A Saman D Vyskocil S Fiedler P 《The Journal of organic chemistry》2003,68(13):5193-5197
A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes. 相似文献
29.
Leslie D. Field Adrian V. George Trevor W. Hambley Peter Turner Brian J. Wallace 《Journal of organometallic chemistry》1997,540(1-2):95-99
Reaction of cis-[FeH2(dmpe)2](1) with diphenylbutadiyne results in an insertion into both of the iron-hydride bonds to form an iron metallocycle. Spectroscopic and crystallographic data of [Fe(PhHCC2CHPh)(dmpe)2] (3) show 1,4-diphenylbutatriene is symmetrically bound to the metal via the central double bond. The reaction to form the metallocyclic complex is greatly accelerated by application of external pressure. A 41% yield of (3) is isolated after two days at atmospheric pressure or after approximately 75 min at 800MPa. 相似文献
30.
The solubilization of styrene by poly(butyl methacrylate-g-methoxypoly(ethylene glycol)) and poly(methyl methacrylate-g-methoxypoly(ethylene glycol)) graft copolymers has been examined. From turbidity measurements the solubility limit of the monomer in the micelles was obtained and the distribution coefficients were evaluated. Dynamic light scattering revealed that below the solubility limit, solubilization leads to a slight increase in micelle size, while above the solubility limit, there is a dramatic increase in particle size and turbidity as oil-in-water emulsions are formed through coalescence of monomer-swollen micelles. Polymerizations carried out below the solubility limit using the graft copolymer micelles as templates resembled microemulsion polymerizations in nature and led to very fine sterically stabilized polystyrene latex particles. Through careful control of the monomer concentration and the polymerization temperature it was possible to obtain spherical nanosize latex particles with similar size to those of the micelle precursors (10 nm) up to 11% monomer by weight. Polymerizations above the solubility limit, on the other hand, showed similarities with emulsion polymerizations and resulted in larger particles with higher polydispersity. 相似文献