全文获取类型
收费全文 | 4341篇 |
免费 | 286篇 |
国内免费 | 837篇 |
专业分类
化学 | 4549篇 |
晶体学 | 81篇 |
力学 | 131篇 |
综合类 | 54篇 |
数学 | 311篇 |
物理学 | 338篇 |
出版年
2024年 | 2篇 |
2023年 | 57篇 |
2022年 | 60篇 |
2021年 | 75篇 |
2020年 | 160篇 |
2019年 | 175篇 |
2018年 | 183篇 |
2017年 | 176篇 |
2016年 | 190篇 |
2015年 | 145篇 |
2014年 | 189篇 |
2013年 | 437篇 |
2012年 | 506篇 |
2011年 | 239篇 |
2010年 | 196篇 |
2009年 | 239篇 |
2008年 | 288篇 |
2007年 | 291篇 |
2006年 | 253篇 |
2005年 | 226篇 |
2004年 | 211篇 |
2003年 | 176篇 |
2002年 | 144篇 |
2001年 | 97篇 |
2000年 | 124篇 |
1999年 | 104篇 |
1998年 | 92篇 |
1997年 | 72篇 |
1996年 | 63篇 |
1995年 | 47篇 |
1994年 | 40篇 |
1993年 | 23篇 |
1992年 | 49篇 |
1991年 | 25篇 |
1990年 | 28篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有5464条查询结果,搜索用时 234 毫秒
131.
Eu(Ⅲ)、Tb(Ⅲ)、Ho(Ⅲ)、Tm(Ⅲ)和Lu(Ⅲ)与N,N′-二(邻羟基亚甲基)乙二胺配合物的研究 总被引:1,自引:0,他引:1
Dutt曾合成稀土离子与N,N′-二(邻羟基亚甲基)乙二胺的稀土双希夫碱配合物。但未见报道Eu(Ⅲ),Tb(Ⅲ),Ho(Ⅲ),Tm(Ⅲ),Lu(Ⅲ)与双希夫碱N,N′-二(邻羟基亚甲基)乙二胺的配合物。本工作合成了这5种双希夫碱配合物。 所用稀土氧化物纯度大于99.9%(上海跃龙化工厂)。水杨醛(CP,用前经减压蒸馏提纯)。稀土硝酸盐Ln(NO_3)_3·xH_2_由稀土氧化物与硝酸反应制得。其余试剂均为分析纯。 仪器为Perkin-Elmer 240-C元素分析仪;Nicolet-5DX型红外光谱仪,KBr压片;岛津UV- 相似文献
132.
2,6-二羟甲基吡啶(1)经活性MnO_2氧化得到2,6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应,得到N-取代的1,5-二(邻硝基苯氧基)-3-氮杂戊烷(3a~3c),再经水合肼/Raney Ni还原,获得N-取代的1,5-二(邻氨基苯氧基)-3-氮杂戊烷(4a~4c)。利用Ba~(2 )作为模板离子,(2)分别与(4a~4c)反应,合成了一类新的含吡啶环系西佛碱大环配合物Ⅰ~Ⅲ,配合物Ⅰ、Ⅲ经与NaBH_4的乙醇溶液还原解络,得到氮杂大环自由配体Ⅳ和Ⅴ。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、~1H NMR、MS等证实了它们的结构和组成。 相似文献
133.
Simanenko Yu. S. Popov A. F. Prokop'eva T. M. 《Theoretical and Experimental Chemistry》2003,39(5):288-295
Among hydroxamate ions (typical nucleophiles), anomalously high nucleophilicity relative to 4-nitrophenyl diethyl phosphonate is seen in anions which have general basic catalytic sites that provide anchimeric assistance for proton transfer in the transition state. 相似文献
134.
The microcalorimetric method was used to study the antibacterial activity of two newly synthesized Schiff basecompounds(H_2L~(3')and H_2L~3)on Escherichia coli,trying to obtain the action on both of multiplying bacteria andnon-multiplying bacteria at one experiment.The metabolic power-time curves of the bacteria treated with the com-pounds were obtained,and the thermokinetic parameters were analyzed,from which the antibacterial activities ofthese compounds were evaluated.The results showed that both of the two compounds have good activity on aerobicmultiplying metabolism of E.coli,with the value of IC_(50)75.8 and 168.8 mg/L respectively,but have not effectiveaction on fermentation metabolism of E.coli.The action of the compounds on the non-multiplying metabolism wasinvestigated by taking the heat output of E.coli in the stationary phase as the guideline of the activity.The value ofMSC_(50)(minimum stationary-cidal concentration 50)of them is 118 and 187.5 mg/L,respectively.So,H_2L~(3')hasstronger antibacterial action on E.coli than H_2L~3 either for multiplying bacteria or non-multiplying bacteria,andtheir activity on the aerobic multiplying bacteria of E.coli is mainly shown.It does strongly suggest that the calo-rimetric method should play an important role in the fight against the drug-resistant bacteria. 相似文献
135.
用氨基三氮唑硫代丙酸乙酯与取代苯甲醛反应,合成了6个新型的5-氨基-1H-1,2,4-三氮唑-3-硫代-2′-丙酸乙酯类Schiff碱,其结构经^1H NMR,IR,MS和元素分析表征。 相似文献
136.
A new Co(II) complex with tridentate Schiff base ligand with a N,N,O donor set has been synthesized and characterized by single X-ray technique and spectroscopic techniques. The thermochemical properties have been studied. X-ray structure analysis of the title compound Co(II)L2 [HL = 2-methyl-6-(2′-hydroxybenzylideneamino) pyridine] shows that the polyhedron around Co(II) is a distorted tetrahedron, and the self-assembly via intermolecular π-π interactions leads to a three-dimensional network. Crystal data for the title complex C26H22CoN4O2: Monoclinic, space group Ia, a = 11.741(7) Å, b = 8.149(5) Å, c = 22.764(16) Å, β = 98.530(12)°, V = 2154(2) Å3, Z = 4. 相似文献
137.
The polymer bound Schiff‐base ligand (PS‐SalGlu) has been prepared from polystyrene bound salicylaldehyde and glutamic acid, and its complex (PS‐SalGlu‐Co) has also been synthesized. The polymer ligand and its complex were characterized by infrared spectroscopy, small area X‐ray photoelectron spectroscopy, and inductively coupled plasma‐atomic emission spectro (ICP‐AFS). In the presence of the complex, cyclohexene can be effectively oxidized by molecular oxygen without reductant. The long‐chain linear aliphatic olefins, such as 1‐octene, 1‐decene, 1‐dodecene and 1‐tetradecene, can be directly oxidized by molecular oxygen catalyzed by PS‐SalGlu‐Co, which affords the 1,2‐epoxy alkane. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
138.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
139.
一种西佛碱侧链型液晶高分子的合成及表征 总被引:2,自引:0,他引:2
一种西佛碱侧链型液晶高分子的合成及表征邹友思,林国良,姚青青,戴李宗,潘容华(厦门大学化学系厦门361005)关键词联苯,西佛碱,侧链型,液晶高分子,基团转移聚合Finkellnann等提出的柔性基去偶合概念’]已在侧链型液晶高分子的研究中得到了证实... 相似文献
140.
A new zirconia-based stationary phase (DPZ) was prepared by modifying zirconia with dodecylamine-N,N-dimethylenephosphonic acid (DDPA). DDPA was adsorbed on zirconia with only one phosphonic group, with the other being free.
Besides the hydrophobic interaction provided by nonpolar dodecyl, DPZ also has dipolar interaction, ion-exchange or electrostatic
repellent interaction provided by the free phosphonic group and amino group at different conditions. Separation of bases on
this stationary phase was achieved with satisfaction owing to the various retention mechanisms. The influence of methanol
content, pH value, ion types, and ionic strength of mobile phase are studied in detail.
Translated from Chinese Journal of Chromatography, 2005, 23(1) (in Chinese) 相似文献