全文获取类型
收费全文 | 5196篇 |
免费 | 553篇 |
国内免费 | 323篇 |
专业分类
化学 | 3008篇 |
晶体学 | 56篇 |
力学 | 167篇 |
综合类 | 15篇 |
数学 | 510篇 |
物理学 | 1051篇 |
无线电 | 1265篇 |
出版年
2023年 | 71篇 |
2022年 | 82篇 |
2021年 | 151篇 |
2020年 | 148篇 |
2019年 | 167篇 |
2018年 | 130篇 |
2017年 | 123篇 |
2016年 | 207篇 |
2015年 | 241篇 |
2014年 | 272篇 |
2013年 | 365篇 |
2012年 | 413篇 |
2011年 | 390篇 |
2010年 | 289篇 |
2009年 | 313篇 |
2008年 | 352篇 |
2007年 | 294篇 |
2006年 | 284篇 |
2005年 | 256篇 |
2004年 | 202篇 |
2003年 | 221篇 |
2002年 | 180篇 |
2001年 | 105篇 |
2000年 | 73篇 |
1999年 | 73篇 |
1998年 | 66篇 |
1997年 | 53篇 |
1996年 | 41篇 |
1995年 | 42篇 |
1994年 | 37篇 |
1993年 | 30篇 |
1992年 | 33篇 |
1991年 | 25篇 |
1990年 | 20篇 |
1989年 | 18篇 |
1988年 | 10篇 |
1987年 | 16篇 |
1986年 | 8篇 |
1985年 | 15篇 |
1984年 | 18篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 28篇 |
1978年 | 28篇 |
1977年 | 49篇 |
1976年 | 18篇 |
1975年 | 18篇 |
1974年 | 11篇 |
1943年 | 10篇 |
排序方式: 共有6072条查询结果,搜索用时 15 毫秒
81.
K. Južnič 《Journal of Radioanalytical and Nuclear Chemistry》1988,126(4):315-322
Some properties of natural zeolite from Zaloka gorica, Slovenia, Yugoslavia were investigated to establish its applicability in solidification and for storage purposes of radioactive waste. It was found that this material is a rather good sorber for cesium, with a capacity of about 0.6 meq g–1. The migration rate of Cs+ in a system ion exchanger-aqueous solution was investigated and correlated with the sorption behaviour of cesium in a system. The leaching rate of cesium from concrete containing zeolite was measured. 相似文献
82.
K. Južnič 《Journal of Radioanalytical and Nuclear Chemistry》1977,40(1-2):217-220
The equilibria between the solution of TOA in toluene and mixtures of sulphuric and hydrochloric acid been studied. They were
characterized by ratios of stability constants of amine salts formed in the organic phase. 相似文献
83.
Koren AB Curtis MD Francis AH Kampf JW 《Journal of the American Chemical Society》2003,125(17):5040-5050
Syntheses are reported of new 4,4'-dialkyl-2,2'-bithiazole oligomers that have alkenoxy side chains that are capable of easy conversion to oligomers with functionalized side chains, e.g., terminally substituted hydroxy chains. The crystal structures of two representative oligomers (4,4',4' ',4' "-tetra-(2-propenoxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3P2) and 4,4',4' ',4' "-tetra-(3-hydroxypropyloxymethyl)-2,2',5',5' ',2' ',2' "-quaterthiazole (3H2)) were determined; 3P2 crystallizes in a pi-stacked motif with two molecules per unit cell, whereas 3H2 forms pi-stacks that are linked with hydrogen bonds to form infinite two-dimensional sheets with one molecule per unit cell. A comparison of the UV-vis spectra of the compounds in solution and in the solid state provides unequivocal evidence for the presence of a Davydov splitting, W(D) approximately 0.2 eV, in solid 3P2. The spectra are interpreted in the framework of molecular exciton theory to extract a value of the intermolecular transfer integral, J approximately 0.2 eV, for a total exciton bandwidth of ca. 0.8 eV. Monte Carlo calculations were used to determine the density of states of the exciton band and the absorption and emission line shapes of the 0 <-- 0 transition. It is suggested that the "three-humped" absorption profile typical of partially crystalline, regioregular polymers is the "optical signature" of pi-stacking. 相似文献
84.
Chi Chen Chang‐Wei Su Chun‐Wei Yeh Hui‐Ling Hu Jhy‐Der Chen Ju‐Chun Wang 《中国化学会会志》2006,53(2):299-303
The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl2‐4H2O afforded the complex MnCl2(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation. 相似文献
85.
采用多拷贝同时搜寻法(MCSS), 并结合现有微管抑制剂的SAR及3D-QSAR对β微管蛋白中Taxol(紫杉醇)结合腔的性质进行了分析. 结构研究结果表明, Taxol结合腔以疏水性质为主, 并指出官能团分布的具体位置: 在Phe270上方(Leu361-Pro272-Leu273-Leu228之间)的弧形区域、Asp26羧基下方及其与Glu22羧基之间、M-loop的中部, 以及Asp224内侧且靠近Arg276的胍基的位置. 而Asp224的内侧又是新提出的结合位点. 研究结果符合现有微管抑制剂的SAR, 为现有抗肿瘤药物的结构改造以及小分子微管抑制剂设计提供了理论依据. 相似文献
86.
Gottfried AC Wang J Wilson EE Beck LW Banaszak Holl MM Kampf JW 《Inorganic chemistry》2004,43(24):7665-7670
The combination of 2 equiv of bis[bis(trimethylsilyl)amide]germylene (5) with 2 equiv of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in tetrahydrofuran (THF) results in the ring-opening of 1 equiv of THF to form 2,2,8,8-tetrakis(1,1,1,3,3,3-hexamethyl-disilazan-2-yl)-5,16-diphenyl-7,9,14-trioxa-1,3,5,16,18,19-hexaaza-2,8-digerma-tricyclo[13.2.1.13,6]nonadeca-6(19),15(18)-diene-4,17-dione (6). This fast and nearly quantitative reaction builds a 15-membered ring from five different molecules. The new ring, structurally assigned by X-ray crystallography, contains a flexible methylene chain that moves rapidly on the NMR time scale. 相似文献
87.
三辛基氧化膦(TOPO)萃取铟的研究 总被引:2,自引:0,他引:2
本文研究了三辛基氧化膦(TOPO)自盐酸溶液中萃取铟的性能,其萃取率是随酸度的增加而增加。与P_(350)和TBP相比较,萃取能力大小顺序为:TOPO>P_(350)>TBP经斜率法和化学分析法研究确定,TOPO白盐酸溶液中萃取铟的反应为:In_((a))~(3+)+H_((a))~++4Cl_((a))~-+2TOPO_((o))F(?)HInCl_4·2TOPO_((o))IR和NMR研究证明:铟是以H[InCl_4]形式被萃入TOPO有机相中的。 相似文献
88.
This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce. 相似文献
89.
Renee J. Soukup-Hein Jeff Schneiderheinze Paul Mehelic Daniel W. Armstrong 《Chromatographia》2007,66(7-8):461-468
Previous work on the LC separation of peptides had shown that macrocyclic glycopeptide stationary phases to be selective for
peptides of five to thirteen amino acids in length. In this work, the selectivity of the teicoplanin stationary phase is compared
to that of a C18 stationary phase for seven diastereomeric enkephalin peptides. The teicoplanin stationary phase separated
all seven diastereomeric enkephalin peptides in a single chromatographic run. The insertion of d-amino acids into the primary enkephalin sequence produced areas of hydrophobicity that influenced retention order on the
C18 stationary phase. However, analogous trends are not observed on the teicoplanin stationary phase, which is more polar
and structurally diverse. Optimization of the mobile phase and the use of a step-gradient for the enkephalin separation on
the teicoplanin stationary phase is discussed. Also, the selectivity of macrocyclic glycopeptide stationary phases for peptides
of 14, 28, 30, and 36 amino acids also is investigated and compared to separation on a C18 stationary phase. A method for
eluting peptides with multiple basic amino acids, which tend to be strongly retained on the macrocyclic glycopeptide stationary
phases, is presented. 相似文献
90.
Investigation of the root extract of Antidesma pentandrum var. barbatum led to the isolation of seven new compounds, antidesmol ( 1 ), antidesmanins E ( 2 ) and F ( 3 ), antidesnone ( 4 ), antidesnol ( 5 ), barbatumols A ( 6 ) and B ( 7 ), together with 14 known compounds including sodium aristolochate‐I ( 10 ) and aristolochic acid‐I methyl ester ( 11 ). 相似文献