全文获取类型
收费全文 | 39349篇 |
免费 | 5765篇 |
国内免费 | 3662篇 |
专业分类
化学 | 27200篇 |
晶体学 | 370篇 |
力学 | 2301篇 |
综合类 | 241篇 |
数学 | 4740篇 |
物理学 | 13924篇 |
出版年
2024年 | 111篇 |
2023年 | 766篇 |
2022年 | 1237篇 |
2021年 | 1362篇 |
2020年 | 1466篇 |
2019年 | 1342篇 |
2018年 | 1174篇 |
2017年 | 1079篇 |
2016年 | 1650篇 |
2015年 | 1659篇 |
2014年 | 2039篇 |
2013年 | 2678篇 |
2012年 | 3340篇 |
2011年 | 3334篇 |
2010年 | 2245篇 |
2009年 | 2116篇 |
2008年 | 2307篇 |
2007年 | 2079篇 |
2006年 | 1972篇 |
2005年 | 1683篇 |
2004年 | 1427篇 |
2003年 | 1092篇 |
2002年 | 998篇 |
2001年 | 788篇 |
2000年 | 725篇 |
1999年 | 848篇 |
1998年 | 715篇 |
1997年 | 661篇 |
1996年 | 748篇 |
1995年 | 629篇 |
1994年 | 570篇 |
1993年 | 505篇 |
1992年 | 474篇 |
1991年 | 388篇 |
1990年 | 339篇 |
1989年 | 255篇 |
1988年 | 243篇 |
1987年 | 217篇 |
1986年 | 158篇 |
1985年 | 193篇 |
1984年 | 163篇 |
1983年 | 139篇 |
1982年 | 118篇 |
1981年 | 106篇 |
1980年 | 88篇 |
1979年 | 60篇 |
1978年 | 53篇 |
1976年 | 56篇 |
1975年 | 54篇 |
1974年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
921.
Chemical Constituents of Ailanthus triphysa 总被引:2,自引:0,他引:2
Two new compounds,8(14),15-isopimaradiene-2α,3α,19-triol(1),and 6α,7β-dihydroxy-17(20)-cis-5α-pregna-16-one(2),together with four known copounds,a oxygenated rare phyllocladane,phyllocladan-16α,19-diol(3),kaempferol-3-0-β-D-galactopyranosied,kaempferol-3-0-α-L-rhamnopyranoside and scopoletin, were isolated from the leaves of Ailanthus tripysa.Structures of 1-3 were elucidated on the basis of spectroscopic data as compared with related compounds. 相似文献
922.
In Situ IR Spectroscopic Studies on Molybdenum Nitride Catalysts: Active Sites and Surface Reactions
Recent IR spectroscopic studies on the surface properties of fresh Mo2N/-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/-Al2O3, both Mo+ (0<<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm-1, due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/-Al2O3 catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/-Al2O3 catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites. 相似文献
923.
Ren Xiaoming Wu Peiheng Zhang Wenwei Meng Qingjin Chen Xiaoyuan 《Transition Metal Chemistry》2002,27(4):394-397
Ion-pair complexes consisting of the [Fe(mnt)2]– anion and [RBzPy]+ cations [R = NO2
(1) or Cl (2)] have been prepared and characterized by elemental analysis and i.r. spectroscopy. The single crystal structure of (1) shows that the [Fe(mnt)2]– anions are dimeric, and that the coordination geometry of each Fe atom is square pyramidal. The most significant structural feature of (1) is that anions and cations form completely separate columns and – interactions occur within the cation columns. Thermal variations of
m
T for the complexes indicated antiferromagnetic coupling within the dimer. 相似文献
924.
A novel heteronuclear complex, [Tb2Zn2L10(bipy)(H2O)2]2 (HL = -methylacrylic acid, bipy = 4,4-bipyridine), was synthesized and characterized by elemental analysis and i.r. absorption spectra. Its structure, determined by X-ray diffraction, is a discrete octanuclear molecule, in which two ZnII ions are linked by a bipy molecule and between TbIII ions, or TbIII and ZnII ions are bridged by bidentate -methylacrylato groups. The temperature dependence of the magnetic susceptibility of the complex shows strong ferromagnetic interaction between the terbium atoms. 相似文献
925.
Zartler ER Hanson J Jones BE Kline AD Martin G Mo H Shapiro MJ Wang R Wu H Yan J 《Journal of the American Chemical Society》2003,125(36):10941-10946
The crucial step in drug discovery is the identification of a lead compound from a vast chemical library by any number of screening techniques. NMR-based screening has the advantage of directly detecting binding of a compound to the target. The spectra resulting from these screens can also be very complex and difficult to analyze, making this an inefficient process. We present here a method, RAMPED-UP NMR, (Rapid Analysis and Multiplexing of Experimentally Discriminated Uniquely Labeled Proteins using NMR) which generates simple spectra which are easy to interpret and allows several proteins to be screened simultaneously. In this method, the proteins to be screened are uniquely labeled with one amino acid type. There are several benefits derived from this unique labeling strategy: the spectra are greatly simplified, resonances that are most likely to be affected by binding are the only ones observed, and peaks that yield little or no information upon binding are eliminated, allowing the analysis of multiple proteins easily and simultaneously. We demonstrate the ability of three different proteins to be analyzed simultaneously for binding to two different ligands. This method will have significant impact in the use of NMR spectroscopy for both the lead generation and lead optimization phases of drug discovery by its ability to increase screening throughput and the ability to examine selectivity. To the best of our knowledge, this is the first time in any format that multiple proteins can be screened in one tube. 相似文献
926.
The design, synthesis and evaluation of a pentacyclic scaffold, CWO-324 to mimic saframycin A is described. CWO-324 is readily synthesized in five steps from 1,4-diacetyl-piperazine-2,5-dione and 2,5-dimethoxybenzaldehyde. CWO-324 was found to scission DNA, binds to bases 69-83(5′-GCAGTCAGG CACCGT-3′) of Hind III/Rsa I from plasmid pBR322 DNA in a foot-printing study and possesses anti-tumor activity. 相似文献
927.
Two novel polysiloxane-based polymers, which contain metal complexes, have been prepared. To prepare the Co(TACN)3+(2) (TACN= 1,4,7-triazacyclononane) based polymers, an orthoamide derivative of TACN was added to bromobutane-substituted methylpolysiloxane and hydrolyzed with base. Co(II) was then coordinated to the TACN, followed by cobalt oxidation to make polymer A or followed by N-octyl TACN coordination and cobalt oxidation to make polymer B. In both materials, TACN forms thermodynamically and kinetically stable Co(TACN)3+(2) complexes in which the six coordination sites of the Co(III) are occupied by nitrogens from the TACN. The polymers were coated on fused-silica capillary columns and spherical silica particles, which were used for capillary electrophoresis and capillary electrochromatography, respectively. The open and packed columns showed strong and pH-independent reversed electroosmotic flow. 相似文献
928.
H2PtCl6可被一系列的酸处理定形聚偕胺肟树脂所吸附,吸附容量的大小与处理树脂的质子酸的Pka值有关.认为是解高度低的酸所处理的树脂上的伯胺基成盐的机会较少,即树脂的吸附中心保留着较多的空穴,有利于H2PtCl6的接近而被吸附下来.吸附动力学的研究表明化学反应是吸附速度的控制因素。 相似文献
929.
930.
Nuclei from the normal mouse liver were partially digested with micrococcal nuclease, followed by DNA extraction, agarose gel clectrophoresis and dot blot hybridization with ~(32)P-labeled cDNA probes of CPS_1 and ACT complex, It was clearly shown that the CPS_1 genes were distributed on the monomer, dimer. and trimer of nucleosomes, while the genes coding for ACT complex were distributed on the condensed oligonucleosomes. An opposite manner of distribution of CPS_1 and ACT complex genes was, however, noted in the case of ascites hepatoma cells, in which the specific activity of ACT was 13 times higher than that in the normal liver, while that of CPS_1 was remarkably reduced. Similar patterns of change in mRNA level of CPS_1 and ACT complex were observed in the normal mouse liver and ascites hepatoma cells, indicating a close relationship between chromatin structure and gene expression of these enzymes. 相似文献