全文获取类型
收费全文 | 2837篇 |
免费 | 95篇 |
国内免费 | 13篇 |
专业分类
化学 | 2263篇 |
晶体学 | 26篇 |
力学 | 34篇 |
数学 | 137篇 |
物理学 | 485篇 |
出版年
2022年 | 15篇 |
2021年 | 23篇 |
2020年 | 39篇 |
2019年 | 41篇 |
2018年 | 35篇 |
2017年 | 23篇 |
2016年 | 63篇 |
2015年 | 60篇 |
2014年 | 63篇 |
2013年 | 124篇 |
2012年 | 128篇 |
2011年 | 203篇 |
2010年 | 94篇 |
2009年 | 119篇 |
2008年 | 223篇 |
2007年 | 204篇 |
2006年 | 186篇 |
2005年 | 160篇 |
2004年 | 158篇 |
2003年 | 136篇 |
2002年 | 118篇 |
2001年 | 46篇 |
2000年 | 53篇 |
1999年 | 38篇 |
1998年 | 31篇 |
1997年 | 29篇 |
1996年 | 35篇 |
1995年 | 16篇 |
1994年 | 21篇 |
1993年 | 23篇 |
1992年 | 25篇 |
1991年 | 21篇 |
1990年 | 17篇 |
1989年 | 21篇 |
1988年 | 19篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 22篇 |
1984年 | 36篇 |
1983年 | 24篇 |
1982年 | 31篇 |
1981年 | 25篇 |
1980年 | 10篇 |
1979年 | 15篇 |
1978年 | 22篇 |
1977年 | 16篇 |
1976年 | 12篇 |
1975年 | 19篇 |
1974年 | 13篇 |
1973年 | 20篇 |
排序方式: 共有2945条查询结果,搜索用时 15 毫秒
41.
42.
Reaction of α-nitro olefins with secondary amines in the presence of palladium(O) catalyst affords allylic amines. 相似文献
43.
Masao Ikeda Takashi Nakamura Yu Nagase Koji Ikeda Yoshiro Sekine 《Journal of polymer science. Part A, Polymer chemistry》1981,19(10):2595-2607
For the purpose of studying the mechanism of thermal degradation of poly[(tetramethyl-p-silphenylene) Siloxane] (poly TMPS) a series of polymers with silphenylene and siloxane bonds in the main chain were prepared and subjected to thermogravimetry (TG) and pyrolysis study. Analyses of products from poly TMPS degradation (in vacuum at a constant temperature) by gas chromatography (GC), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC–MS) revealed that degradation occurs at the silphenylene bonds. The TG curves obtained in He for heating rates of 1,2,2.5,7.5, and 10°C/min were analyzed by the Ozawa method; activation energies of 39 ± 1 and 45 ± 2 kcal/mol were obtained respectively for the initial cleavage of the methyl side group and the later-stage scission of the main-chain silphenylene bond which leads to a major weight loss. The results agree with those obtained for other structurally similar polymers. 相似文献
44.
Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation. 相似文献
45.
Koji Kano Hirofumi Kawazumi Teiichiro Ogawa Junzo Sunamoto 《Chemical physics letters》1980,74(3):511-514
Fluorescence quenching of pyrene and pyrenedecanoic acid by various kinds of anilines has been studied in dipalmitoylphosphatidylcholine liposomes in gel phases. N,N-dimethylaniline and p-isopropyl-N,N-dimethylaniline caused anisotropic diffusional quenching, while N,N-dicetylaniline, a less mobile quencher, predominantly caused static quenching. These data suggested the location sites of both pyrenes and anilines in the membranes. 相似文献
46.
Kouichi Ohe Tomomi Yokoi Koji Miki Fumiaki Nishino Sakae Uemura 《Journal of the American Chemical Society》2002,124(4):526-527
The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3. 相似文献
47.
Photoaffinity labeled (3-diazoacetoxy)-9-cis-retinal (1) and (9-methylenediazoacetoxy)-9-cis-retinal (20) were synthesized and bound to absorption maxima at 465 and 460 nm respectively. Binding studies established that synthetic retinals 1 and 2 bind to the natural binding site and that the integrity of the diazoacetoxy photoaffinity label is preserved in the process. Incorporation of 3-(O14COCHN2)-labeled 9-cis retinal could be conveniently carried out in high yield using apomembrane solubilized in CHAPS as detergent to afford the pigment analog in a pure form. Photolysis of the diazoacetoxy group within the binding site led to 15–20%, crosslinking of rhodopsin as estimated by using radiocarbon containing labeled retinal 1 thus showing that this synthetic retinal is suitable for photoaffinity labeling of the active site in rhodopsin. Subsequent experiments to establish the site(s) of crosslinking by sequencing studies will then contribute to our knowledge of the structure of rhodopsin. 相似文献
48.
The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs. 相似文献
49.
Shin-Ichi Hirano Toshinobu Yogo Ko-Ichi Kikuta Wataru Sakamoto 《Journal of Sol-Gel Science and Technology》1994,2(1-3):329-334
The sol-gel processing is one of promising methods to fabricate well-derived integrated thin films at relatively low temperature. Ferroelectric niobates films do afford the possibilities for adding the values by the hybridization with semiconductor and/or electro-optic systems. The molecular level designing of the precursor solution was stressed as well as the control of key processing factors. The advantages of this sol-gel have been extended to prepare the ferroelectric Pb(Mg, Nb)O3-PbTiO3 solid solution films integrated on Si wafers. The crystallization of the films with desired crystal structure could be promoted by the controlled partial hydrolysis of designed alkoxide solution in the intermediate state and the pre-heated treatment of alkoxide-derived films in flow of water vapor and oxygen gas mixture. 相似文献
50.
Makoto OzawaTakaaki Taguchi Takayuki ItohYutaka Ebizuka Kevin I Booker-MilburnG.Richard Stephenson Koji Ichinose 《Tetrahedron》2003,59(44):8793-8798
A novel shunt product was isolated from a disruptant of the actVI-ORFA gene involved in the biosynthesis of actinorhodin (ACT) in Streptomyces coelicolor A3(2). Its structure was elucidated as 1,4-naphthoquinone-8-hydroxy-3-[3(S)-acetoxy-butyric acid], (S)-NHAB, based on NMR, MS, and CD spectroscopic data as well as a single crystal X-ray crystallographic analysis. The formation of (S)-NHAB involves a retro-Claisen type C-C bond cleavage of an ACT biosynthetic intermediate. Feeding experiments with [1-13C] and [2-13C] acetates indicated its biosynthetic origin as a single octaketide chain. The relevant gene product, Act-ORFA, which is a functionally unknown protein, is proposed to play a regulatory role related to the multi-enzymatic steps to ACT production, based on the metabolic profile of its disruptant and the wide distribution of actVI-ORFA homologues in the gene clusters for Streptomyces aromatic polyketides. 相似文献