全文获取类型
收费全文 | 3706篇 |
免费 | 199篇 |
国内免费 | 22篇 |
专业分类
化学 | 2812篇 |
晶体学 | 49篇 |
力学 | 94篇 |
数学 | 233篇 |
物理学 | 739篇 |
出版年
2024年 | 3篇 |
2023年 | 25篇 |
2022年 | 62篇 |
2021年 | 99篇 |
2020年 | 80篇 |
2019年 | 101篇 |
2018年 | 72篇 |
2017年 | 65篇 |
2016年 | 127篇 |
2015年 | 131篇 |
2014年 | 178篇 |
2013年 | 245篇 |
2012年 | 316篇 |
2011年 | 389篇 |
2010年 | 211篇 |
2009年 | 193篇 |
2008年 | 265篇 |
2007年 | 223篇 |
2006年 | 222篇 |
2005年 | 194篇 |
2004年 | 151篇 |
2003年 | 130篇 |
2002年 | 129篇 |
2001年 | 49篇 |
2000年 | 56篇 |
1999年 | 33篇 |
1998年 | 25篇 |
1997年 | 18篇 |
1996年 | 17篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 14篇 |
1992年 | 9篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有3927条查询结果,搜索用时 328 毫秒
61.
Lee JH Je J Schlautmana MA Carraway ER 《Chemical communications (Cambridge, England)》2003,(2):270-271
The maximum intensity, Imax, and time required to reach the maximum emission, taumax, for 1-aminopyrene monitored in 1,1'-oxalyldi-4-methylimidazole (OD4MI) chemiluminescence (CL) reactions are approximately 61 times higher and 16 times faster than their respective values for bis(2,4,6-trichlorophenyl)oxalate (TCPO) CL reactions in the presence of imidazole (ImH). 相似文献
62.
Owen S. Jeong B. C. Poole P. S. Macaskie L. E. 《Applied biochemistry and biotechnology》1992,(1):693-707
Tributyl phosphate (TBP), a plasticizer and solvent, is used in nuclear fuel reprocessing, generating TBP wastes laden with
residual uranium. ACitrobacter sp. accumulated heavy metals via a phosphohydrolase(s) that precipitated metals with inorganic phosphate liberated from an
organic phosphate “donor” molecule (TBP). Mutant analysis suggested that TBP hydrolysis was not attributable to a previously
documented acid phosphatase (monoesterase). Purified monoesterase had little activity against phospho di- and triesters, had
no requirement for Mg2+ or Mn2+, and was EDTA-resistant. Conversely, TBP cleavage by immobilized cells was enhanced by Mg2+, and ininhibited by Mn2+ and EDTA. A separate phosphotri/diesterase was implicated. 相似文献
63.
Sang Chul Shim Chil Hoon Doh Tae Jeong Kim Hak Ki Lee Ki Doo Kim 《Journal of heterocyclic chemistry》1988,25(5):1383-1385
Ethanolic tetracarbonylhydridoferrate combined with adipaldehyde is very efficient for the selective transformation of an amino group into perhydroazepine. A large variety of both aliphatic and aromatic amines react with adipaldehyde in the presence of tetracarbonylhydridoferrate at room temperature and carbon monoxide to give the corresponding N-alkyl- and N-arylperhydroazepines in good to excellent yields. 相似文献
64.
Jae Ha Kim Young Tae Jeong Seong Ihl Woo 《Journal of polymer science. Part A, Polymer chemistry》1994,32(15):2979-2987
Highly active catalysts for copolymerization have been prepared by the precipitation of MgCl2/ToCl4 complex with or without high surface area silica. Copolymerization of ethylene and 1-butene has been tested by using the prepared catalysts at various concentrations of 1-butene. The catalytic activities are 20–80 kg/g Ti h. The rate of copolymerization is strongly affected by the addition of 1-butene. The decay rate of copolymerization is first order with respect to time. Analyses of copolymers with solvent extraction, DSC, IR, XRD, and NMR were performed. Ethylene reactivity ratio (k11) for TiCl4/MgCl2/THF catalyst is calculated to be about 26 by NMR spectrum. © 1994 John Wiley & Sons, Inc. 相似文献
65.
Preparation of Silver Nanoparticles through Alcohol Reduction with Organoalkoxysilanes 总被引:1,自引:0,他引:1
Hoe Jin Hah Sang Man Koo Sang Hoon Lee 《Journal of Sol-Gel Science and Technology》2003,26(1-3):467-471
Silver nanoparticles of narrow size distribution were prepared through the chemical reduction in an alcohol solution with several organoalkoxysilanes. In this system, organoalkoxysilanes served as a stabilizer, protecting silver nanoparticles from aggregation. The changes in size and morphology of colloidal silver nanoparticles were investigated with the addition of organoalkoxysilanes such as 3-aminopropyltriethoxysilane (APS), methyltriethoxysilane (MTS), phenyltrimethoxysilane (PTS), vinyltriethoxysilane (VTS), and 3-glycidoxypropyltrimethoxysilane (GPS) as stabilizers. The organic functional groups of organoalkoxysilanes interact with silver ions and clusters, which stabilize silver nanoparticles in the system. The silver nanoparticles obtained were characterized with transmission electron microscopy (TEM), UV-vis spectroscopy, etc. 相似文献
66.
Dong Won Kim Young Shin Jeon Young Kyu Jeong Moo Yul Suh Kih Soo Joe 《Journal of Radioanalytical and Nuclear Chemistry》1995,189(2):219-227
The chromatographic separation of lithium isotopes was investigated by chemical exchange with the recently synthesized polymer-bound dibenzo pyridino diamide azacrown (DBPDA) and reduced dibenzo pyridino diamide azacrown (RDBPDA). Column chromatography was employed for the determination of the effect of solvents and ligand conformation on the separation coefficients. The maximum separation coefficients, , for the DBPDA and RDBPDA at 20.0±0.02°C with acetonitrile as eluent, were found to be 0.034±0.002 and 0.035±0.002, respectively. The isotope separation coefficient and adsorption capability of the lithium ion on the DBPDA and RDBPDA were only slightly dependent on ligand structure, but strongly dependent on the solvent. DBPDA and RDBPDA appeared to have almost the same value for the isotope separation coefficient of lithium. 相似文献
67.
Jin Seok Choi Younjoo Lee Eunmyoung KimNakcheol Jeong Hosung YuHogyu Han 《Tetrahedron letters》2003,44(8):1607-1610
The development of the 2-(4-trifluoromethylphenylsulfonyl)ethoxycarbonyl (Tsc) function, a novel base-sensitive amino-protecting group, and its application to the preparation of DNA-binding polyamides are described. Pyrrole-imidazole polyamides were synthesized by an efficient solid-phase method under conditions compatible with Fmoc chemistry using two Tsc-protected amino acids, Tsc-Py-OH 1a and Tsc-Im-OH 1b. 相似文献
68.
A supercritical fluid chromatographic (SFC) procedure for the quantitation of three major polyprenols present in the leaves of Ginkgo biloba was developed. In contrast to previously reported high-performance liquid chromatographic (HPLC) methods, the SFC method does not require extensive pre-purification for polyprenol analysis. The SFC analytical procedure described shows a very broad range of linearity and detects many known polyprenol isoprenologs with baseline separation. Dodecaprenol was used as the internal standard. The coefficient of variation of the method was 5.8% for the quantitation of C85, C90 and C95 polyprenols. The SFC assay results showed that the content of polyprenols in ginkgo leaves were higher than the previously published values. In addition, the chromatogram of the highly concentrated leaf extract revealed the presence of an isoprenolog (C120) not previously detected by HPLC methods. 相似文献
69.
Kim SH Tamrazi A Carlson KE Daniels JR Lee IY Katzenellenbogen JA 《Journal of the American Chemical Society》2004,126(15):4754-4755
We present the first example of a nuclear hormone receptor microarray, using for illustration the ligand-binding domains of the two estrogen receptors, ERalpha-LBD and ERbeta-LBD. The proteins are printed and allowed to attach to aldehyde slides; the efficiency of attachment depends on whether the LBD is liganded with agonists (low attachment) versus liganded with antagonists or unliganded (high attachment). This suggests that attachment is orientation specific and involves principally a single lysine residue. The attached ERs retain good ligand-binding activity that can be assessed using an estradiol-fluorophore conjugate, and specific and ER subtype-selective binding of ligands can be determined conveniently in competitive binding assays. This powerful new, high-throughput technique to study ligand binding to ER-LBDs can be extended to other nuclear hormone receptors and adapted to assay the recruitment of coregulator proteins. 相似文献
70.
A synthetic strategy for the preparation of cyclic peptide mimetics based on SET-promoted photocyclization processes 总被引:2,自引:0,他引:2
Yoon UC Jin YX Oh SW Park CH Park JH Campana CF Cai X Duesler EN Mariano PS 《Journal of the American Chemical Society》2003,125(35):10664-10671
A novel method for the synthesis of cyclic peptide analogues has been developed. The general approach relies on the use of SET-promoted photocyclization reactions of peptides that contain N-terminal phthalimides as light absorbing electron acceptor moieties and C-terminal alpha-amidosilane or alpha-amidocarboxylate centers. Prototypical substrates are prepared by coupling preformed peptides with the acid chloride of N-phthalimidoglycine. Irradiation of these substrates results in the generation of cyclic peptide analogues in modest to good yields. The chemical efficiencies of these processes are not significantly affected by (1) the lengths of the peptide chains separating the phthalimide and alpha-amidosilane or alpha-amidocarboxylate centers and (2) the nature of the penultimate cation radical alpha-heterolytic fragmentation process (i.e., desilylation vs decarboxylation). An evaluation of the effects of N-alkyl substitution on the amide residues in the peptide chain showed that N-alkyl substitution does not have a major impact on the efficiencies of the photocyclization reactions but that it profoundly increases the stability of the cyclic peptide. 相似文献