全文获取类型
收费全文 | 16831篇 |
免费 | 3262篇 |
国内免费 | 2313篇 |
专业分类
化学 | 12583篇 |
晶体学 | 238篇 |
力学 | 1049篇 |
综合类 | 142篇 |
数学 | 1778篇 |
物理学 | 6616篇 |
出版年
2024年 | 74篇 |
2023年 | 487篇 |
2022年 | 758篇 |
2021年 | 749篇 |
2020年 | 859篇 |
2019年 | 781篇 |
2018年 | 645篇 |
2017年 | 549篇 |
2016年 | 851篇 |
2015年 | 841篇 |
2014年 | 945篇 |
2013年 | 1280篇 |
2012年 | 1569篇 |
2011年 | 1514篇 |
2010年 | 992篇 |
2009年 | 996篇 |
2008年 | 1116篇 |
2007年 | 990篇 |
2006年 | 858篇 |
2005年 | 756篇 |
2004年 | 550篇 |
2003年 | 507篇 |
2002年 | 455篇 |
2001年 | 371篇 |
2000年 | 356篇 |
1999年 | 370篇 |
1998年 | 298篇 |
1997年 | 263篇 |
1996年 | 288篇 |
1995年 | 240篇 |
1994年 | 195篇 |
1993年 | 172篇 |
1992年 | 140篇 |
1991年 | 101篇 |
1990年 | 115篇 |
1989年 | 74篇 |
1988年 | 62篇 |
1987年 | 56篇 |
1986年 | 41篇 |
1985年 | 39篇 |
1984年 | 24篇 |
1983年 | 23篇 |
1982年 | 18篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 2篇 |
1973年 | 3篇 |
1957年 | 3篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
102.
Gong Y Xiang Y Yue B Xue G Bradshaw JS Lee HK Lee ML 《Journal of chromatography. A》2003,1002(1-2):63-70
Two bonded chiral stationary phases (CSPs), 8-aminoquinoline-2-ylmethyl- and 8-aminoquinoline-7-ylmethyl-diaza-18-crown-6-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl silica particles (non-porous, 1.5 microm), have been prepared and evaluated using capillary liquid chromatography at high pressures (> or = 8000 p.s.i.). High column efficiency (up to 400 000 plates m(-1)) was achieved for chiral separations. These CSPs with two recognition sites, i.e. substituted-diaza-18-crown-6 and beta-cyclodextrin combined with high chromatographic efficiency provide good resolution of a variety of enantiomers and positional isomers in relatively short times under reversed-phase conditions. After inclusion of a Ni (II) ion from the mobile phase, the positively charged crown ether-capped beta-cyclodextrin facilitates specific static, dipolar, and host-guest complexation interactions with solutes. 相似文献
103.
104.
固相萃取-气相色谱-质谱分析肉样中盐酸克伦特罗的残留量 总被引:25,自引:12,他引:25
建立了固相萃取 气相色谱 质谱联机分析肉样中盐酸克伦特罗残留量的方法。对盐酸克伦特罗在C1 8和离子交换固相萃取柱上的保留行为进行了研究 ,发现不同浓度盐酸克伦特罗的固相萃取回收率在 75 %~ 95 %之间 ;肉样中的加标回收率在 70 %~ 83 % ;相对标准偏差在 4 .95 %~ 1 3 .4 % ;最低检出限为 1 μg kg。盐酸克伦特罗的硅烷化产物 ,采用选择离子的模式进行检测 ( 86、2 4 3、2 62、2 77) ,衍生物的峰面积与样品浓度在0 .0 0 2 5 2~ 2 .0 2mg L范围内呈良好的线性关系 ,线性回归系数大于 0 .9999。 相似文献
105.
Hu H Qiao M Xie F Fan K Lei H Tan D Bao X Lin H Zong B Zhang X 《The journal of physical chemistry. B》2005,109(11):5186-5192
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface. 相似文献
106.
Zhang WW Li HF Liu L Xie JL Lu CS Zhou Y Ren XM Meng QJ 《Journal of colloid and interface science》2003,261(1):82-87
A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect. 相似文献
107.
108.
109.
过渡金属酞等配合物(MPC)用手均相液相氧化中作催化剂已有不少报导,象许多均相催化剂一样,MPC用于均相反应存在着难于从反应体系中分离出来的问题.把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法.我们曾尝试把MP。固载在分子筛载体和硅胶载体上,并用ESR研究其对O2的活化作用[1,2].本文报导MPc通过共价键键联固载在SiO2上,并研究其对O2的活化作用.1实验部分1.1试剂HSIC13为日本东京化成株式会社产品,二级试剂·发烟硫酸(SO。质量分数大于20%)为分析纯试剂.PCl5为化学纯试… 相似文献
110.
选择性氧化含氰基的对硝基苯硫醚 总被引:2,自引:0,他引:2
选择性氧化含氰基的对硝基苯硫醚岳国仁,王建华,张正(南京大学化学系南京210008)关键词含氰基硫醚,选择性氧化,四水合过硼酸钠据报道[1]对硝基苯磺酰基乙腈的合成,反应时间长,可采用四水合过硼酸钠(NaBO3·4H2O)作为氧化剂,受到重视[2,3... 相似文献