全文获取类型
收费全文 | 41054篇 |
免费 | 7431篇 |
国内免费 | 5993篇 |
专业分类
化学 | 29547篇 |
晶体学 | 556篇 |
力学 | 2718篇 |
综合类 | 693篇 |
数学 | 5006篇 |
物理学 | 15958篇 |
出版年
2024年 | 113篇 |
2023年 | 733篇 |
2022年 | 1375篇 |
2021年 | 1421篇 |
2020年 | 1585篇 |
2019年 | 1604篇 |
2018年 | 1338篇 |
2017年 | 1399篇 |
2016年 | 1812篇 |
2015年 | 1953篇 |
2014年 | 2415篇 |
2013年 | 2965篇 |
2012年 | 3641篇 |
2011年 | 3760篇 |
2010年 | 2732篇 |
2009年 | 2649篇 |
2008年 | 2930篇 |
2007年 | 2559篇 |
2006年 | 2491篇 |
2005年 | 2081篇 |
2004年 | 1661篇 |
2003年 | 1348篇 |
2002年 | 1357篇 |
2001年 | 1199篇 |
2000年 | 962篇 |
1999年 | 884篇 |
1998年 | 653篇 |
1997年 | 636篇 |
1996年 | 610篇 |
1995年 | 499篇 |
1994年 | 455篇 |
1993年 | 354篇 |
1992年 | 303篇 |
1991年 | 323篇 |
1990年 | 254篇 |
1989年 | 219篇 |
1988年 | 174篇 |
1987年 | 154篇 |
1986年 | 132篇 |
1985年 | 110篇 |
1984年 | 91篇 |
1983年 | 79篇 |
1982年 | 68篇 |
1981年 | 52篇 |
1980年 | 55篇 |
1979年 | 35篇 |
1977年 | 27篇 |
1976年 | 29篇 |
1975年 | 26篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
951.
Pd(OAc)2/FePc催化环己烯氧化合成环己酮的研究 总被引:6,自引:0,他引:6
考察了几种Fe-大环配合物与Pd(OAc)2组成的双组分催化体系,在乙腈酸性水溶液中环己烯经合成环己酮的催化活性,实验结果表明,其中以酞菁失(FePc)与Pd(OAc)2组成的催化体系活性最高,而FeTPPCl与Pd(OAc)2催化体系,虽然催化活性较高,但催化剂的稳定性较低,各种因素对Pd(OAc)2/FePc催化活催化影响的研究结果指出,在无水和酸存在的非水溶液中,Pd(OAc)2/FePc对 相似文献
952.
Preparation of a sulfonated fused-silica capillary and its application in capillary electrophoresis and electrochromatography 总被引:1,自引:0,他引:1
In the present paper, two new methods, sol-gel and chemical bonding methods, were proposed for preparation of sulfonated fused-silica capillaries. In the sol-gel method, a fused-silica capillary was coated with the sol solution obtained by hydrolysis of 3-mercaptopropyltrimethoxysilane (MPTS) and tetramethoxysilane, and followed by age; while in the chemical bonding method, a capillary was chemically bonded directly with MPTS. Then, both the resulting capillaries were oxidized with an aqueous solution of hydrogen peroxide solution (H2O2) (30%, m/m) to obtain the sulfonated capillaries. The electroosmotic flow (EOF) for the sulfonated capillaries was found to remain almost constant within the studied pH range, and greater than that of the uncoated capillary. However, the coating efficiency of the capillary prepared by chemical bonding method was higher than that by sol-gel method, by comparing their magnitude of the EOF, the degree of disguise of the silanol and reproducibility of preparation procedure. The effects of the electrolyte's concentration and the content of methanol (MeOH) on the EOF were also studied. Especially, the study of the apparent pH (pH*) on the EOF in a water-MeOH system was reported. Finally, capillary electrophoretic separation of seven organic acids was achieved within 6.5 min under optimal condition using the chemically bonded sulfonated capillary. Moreover, separation of four alkaloids on the sulfonated capillary was compared with that on uncoated capillary in different conditions. Ion-exchange mechanism was found to play a key role for separation of these four basic analytes on the sulfonated capillary. 相似文献
953.
采用草酸沉淀法,通过填加表面活性剂四丁基溴化铵、十六烷基三甲基溴化铵和金属离子K+,Mg2+,Ba2+,制备出稀土发光材料Y2O3Eu3+,利用XRD与激发和发射光谱等测试手段对样品的结构与光学性能进行了表征,考察了同时加入不同表面活性剂和金属离子对Y2O3Eu3+的结构和发光性质的影响.结果表明加入表面活性剂和金属离子对发光材料Y2O3Eu3+的发光性能有较大的影响,其中以同时加入四丁基溴化铵和Ba2+以及加入十六烷基三甲基溴化铵和Mg2+对Y2O3Eu3+粉体的发光性能影响最大. 相似文献
954.
本文是含咔唑化合物及其聚合物系列研究的一部分,以对-溴苯酚为原料,经过乙烯基醚化,再同咔唑反应、合成了新的单体,N-(p-乙烯氧基苯基)咔唑(NEOPC),经过元素分析、NMR和IR等对NEOPC进行分析鉴定,研究了它的聚合行为。 相似文献
955.
956.
亚氨基二乙酸—硅胶键合相的合成及其在核苷酸分析中的应用 总被引:2,自引:1,他引:2
以大孔微球硅胶(30nm,8μm)为基体,经γ-氨丙基三乙氧基硅烷活化与间隔臂氯代环氧丙烷反应后,再与螯合剂亚氨基二乙酸键合,后者与铜离子(Ⅱ)螯合后,构成定位金属离子亲和色谱固定相。用磷酸盐缓冲溶液(pH=7.0)作流动相,经紫外吸收检测(260nm)对核苷酸混合物进行了高效液相色谱分析,取得较满意的结果。 相似文献
957.
本文报道用环加成-芳构化串连反应制备多取代芳香族化合物的方法。将1-氯-2-卤-3-苯硒基-1,3-丁二烯(5)与丁炔二酸二甲酯进行Diels-Alder反应时,能直接生成多取代的芳香族化合物4-苯硒基-5-卤代邻苯二甲酸二甲酯(4)。若用2-卤素-3-苯硒基-1,3-丁二烯(1)与丁炔二酸二甲酯进行Diels-Alder反应,只得到正常的加成产物4-苯硒基-5-卤素-1,4-环己二烯-1,2-二甲酸二甲酯(3),需再用DDQ处理,才得到多取代芳香族化合物(4)。 相似文献
958.
Yuan L Feng W Yamato K Sanford AR Xu D Guo H Gong B 《Journal of the American Chemical Society》2004,126(36):11120-11121
Highly efficient, one-step macrocyclizations leading to the formation of macrocyclic hexa(aramides) in high yields (69-82%) are described. The one-step macrocyclizations were facilitated by the preorganization or folding of the backbones of uncyclized precursors in the course of macrocyclization. The preorganization of backbones was achieved by the presence of localized three-centered hydrogen bonds that were adopted in the design of a class of closely related, backbone-rigidified foldamers. The macrocyclization involved reactions between diacid chloride 1 and diamine 2. The crude reaction mixtures and products were conveniently examined by mass spectrometric method (MALDI-TOF). Compared to most traditional one-step macrocyclizations that usually require high dilution conditions and often lead to very low overall yields of the desired products, cyclic hexamers 3 were obtained as the overwhelmingly major product under a variety of reaction conditions, suggesting the generality of this approach. 相似文献
959.
Zn3V3O8 two-dimensional micro sheets are successfully synthesized by combination of solvothermal method and heat treatment. The Zn3V3O8 has better electrochemical performances after calcinations. 相似文献
960.
The synthesis of p-MPAQ and the electroanalytical chemical properties of the nickel(II)-p-MPAQ complex are reported in this paper. A sensitive adsorptive cathodic stripping procedure for trace nickel determination was developed. For a 3-min preconcentration time the detection limit is 3.0 × 10−11M. 相似文献