全文获取类型
收费全文 | 37498篇 |
免费 | 6706篇 |
国内免费 | 6264篇 |
专业分类
化学 | 29586篇 |
晶体学 | 578篇 |
力学 | 1967篇 |
综合类 | 498篇 |
数学 | 3933篇 |
物理学 | 13906篇 |
出版年
2024年 | 143篇 |
2023年 | 794篇 |
2022年 | 1459篇 |
2021年 | 1488篇 |
2020年 | 1651篇 |
2019年 | 1790篇 |
2018年 | 1496篇 |
2017年 | 1411篇 |
2016年 | 2001篇 |
2015年 | 2029篇 |
2014年 | 2321篇 |
2013年 | 2977篇 |
2012年 | 3352篇 |
2011年 | 3355篇 |
2010年 | 2449篇 |
2009年 | 2353篇 |
2008年 | 2527篇 |
2007年 | 2162篇 |
2006年 | 2152篇 |
2005年 | 1929篇 |
2004年 | 1567篇 |
2003年 | 1316篇 |
2002年 | 1463篇 |
2001年 | 1197篇 |
2000年 | 945篇 |
1999年 | 751篇 |
1998年 | 538篇 |
1997年 | 392篇 |
1996年 | 424篇 |
1995年 | 338篇 |
1994年 | 308篇 |
1993年 | 274篇 |
1992年 | 239篇 |
1991年 | 189篇 |
1990年 | 152篇 |
1989年 | 115篇 |
1988年 | 78篇 |
1987年 | 73篇 |
1986年 | 73篇 |
1985年 | 59篇 |
1984年 | 24篇 |
1983年 | 35篇 |
1982年 | 8篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1971年 | 4篇 |
1959年 | 6篇 |
1957年 | 8篇 |
1936年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
881.
离子液体体系中1-丁烯二聚反应的研究 总被引:8,自引:0,他引:8
研究了在强酸性AlCl3/Et2AlCl/[BMIM]Cl型离子液体体系中过渡金属化合物对1-丁烯二聚反应的催化作用.结果表明,[BMIM]Cl对强酸性AlCl3/Et2AlCl催化剂催化1-丁烯高聚反应有明显的阻聚作用,并显著提高了1-丁烯二聚的选择性.在过渡金属化合物中,含镍化合物对1-丁烯二聚反应有最好的催化效果.在最佳反应条件下,1-丁烯的转化率可达95.1%,二聚产物C8烯的选择性为85.8%.同时,对1-丁烯二聚反应的机理进行了初步探讨. 相似文献
882.
Xian Zhao Daren Guan Xizhang Yi Guibao Xu Minhua Jiang 《International journal of quantum chemistry》2003,93(5):335-343
A dynamic Lie algebraic (DLA) formulation is applied to the study of nonlinear optical properties of the substituted benzenes. We have described the generation of the dynamic Lie algebra for the model Hamiltonian used in the present study. In terms of these elements of the dynamic algebra we express the evolution operator as a function of the group parameters, which can be determined by means of solving a system of coupled nonlinear differential equations. Thus, in terms of the density matrix operator formalism in statistical mechanics we obtain the statistical averages of the electric polarization and then derive readily an expression for the hyperpolarizability of the paradisubstituted benzenes. Comparisons with experimental observations and other quantum calculations of the hyperpolarizabilities for the paradisubstituted benzenes are made qualitatively and quantitatively. These results imply that the DLA method appears useful in describing the nonlinear optical phenomena in the substituted benzene molecules. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 335–343, 2003 相似文献
883.
884.
[reaction: see text] A new one-step reaction has been developed for converting 4-azido-4-deoxy-d-galactoside into 4-deoxy-d-erythro-hexos-3-ulose by phosphoramidites and tetrazole. It is proposed that the new reaction proceeds via an intramolecular Staudinger reaction of the phosphite intermediate and a tetrazole-catalyzed elimination reaction of the resultant phosphorimidate. Tetrazole appears to be playing a unique role by acting as a bifunctional catalyst to facilitate the elimination reaction. 相似文献
885.
在1.0mol/L硫酸介质中,微量锇(IV)的存在对KIO4氧化偶氮氯膦-pC的褪色反应有明显的催化作用,据此建立微量锇的催化光度分析法、方法的检出限为0.0002μg/mL,锇(IV)的含量在0.0006—0.003μg/mL之间有良好的线性关系,反应在水相中进行,应用于贵金属精矿中锇的测定,结果满意. 相似文献
886.
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
887.
水溶性金属卟啉肿瘤靶向磁共振成像造影剂的研究 总被引:5,自引:0,他引:5
利用显微荧光-阿达玛变换三维图像分析研究了Cu-TSPP,Mn-TSPP,Cu-TMAP,Mn-TMAP4种水溶性金属卟啉人细胞间质进入肿瘤细胞内的富集过程,对金属卟啉的自旋-晶格驰豫性能(R1)的天空结果表明,Mn(Ⅱ)卟啉配合物的R1、值结Gd-DTPA提高1.5-2倍。 相似文献
888.
Ling-Tian Tang Yu Wei Yi Wang Shao-Wen Hu Xin-Qi Liu Tai-Wei Chu Xiang-Yun Wang 《Journal of Molecular Structure》2004,686(1-3):25-30
The formation of charge-transfer (CT) complexes between N-methyl-6,7-methylenedioxy-tetrahydro-4-isoquinolone (MMDTIQ, the model molecule of alkaloids) and iodine monochloride has been studied with the density functional B3LYP method. The competition for ICl between n-donor(s) and π-donor in the same molecule has been compared for the first time. The results indicate that the electron-donating ability of various donor sites decreases in the following order: amino nitrogen>carbonyl oxygen>etheric oxygen≈aromatic ring. Complexes with a stoichiometry of 1:1 to 1:5 (MMDTIQ–ICl) might form. Among complexes with a given stoichiometry, the one in which the phenyl ring is involved in the binding is always the least stable. According to these results, in order to ensure an alkaloid iodinated, the amount of ICl should be far beyond that of alkaloids and a low polar solvent should be used, which is quite in agreement with our recent experimental results. 相似文献
889.
A novel cadmium(Ⅱ) isothiocyanate complex [Cd(N-MeIM)2(SCN)2]n(N-MeIM=N-methylimidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. The title compound crystallize in the Triclinic system, space group P1, with lattice parameters a=0.589 50(12) nm, b=0.785 70(16) nm, c=0.882 00(18) nm, α=110.98(3)°, β=106.49(3)°, γ=95.08(3)°, and Z=1. The title compound exhibits an infinite chain structure in which each pair of Cd atoms is bridged by two η-1,3-SCN- groups. The unique Cd atom lies on an inversion centre and the coordination sphere is completed by two N-MeIM N atoms to form a CdS2N4 octahedron. The polymeric chains are further extended into three-dimensional network via π…π stackings interactions between the imidazole rings. The cyclic voltammetry behaviors of the compound on glass carbon electrode showed a typical irreversible process. CCDC: 265283. 相似文献
890.
Liu H Zhang S Nie S Zhao X Sun X Yang X Pan W 《Chemical & pharmaceutical bulletin》2005,53(6):631-633
Methylacrylic acid/styrene cross-linked with divinylbenzene is a novel pH-sensitive ion exchange resin. Microspheres of this resin were characterized by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The microspheres showed a pulsatile swelling behavior when the pH of the media changed. The pH-sensitive microspheres were loaded with salbutamol sulfate and the drug-release characteristics were studied under both simulated gastric and intestinal pH conditions. The results obtained showed that the drug release also depended on the pH of the release media. 相似文献