全文获取类型
收费全文 | 47254篇 |
免费 | 9601篇 |
国内免费 | 3207篇 |
专业分类
化学 | 49317篇 |
晶体学 | 566篇 |
力学 | 898篇 |
综合类 | 152篇 |
数学 | 3193篇 |
物理学 | 5936篇 |
出版年
2024年 | 36篇 |
2023年 | 174篇 |
2022年 | 442篇 |
2021年 | 581篇 |
2020年 | 1624篇 |
2019年 | 2968篇 |
2018年 | 1341篇 |
2017年 | 1044篇 |
2016年 | 3825篇 |
2015年 | 4020篇 |
2014年 | 4044篇 |
2013年 | 4849篇 |
2012年 | 3917篇 |
2011年 | 3215篇 |
2010年 | 3605篇 |
2009年 | 3550篇 |
2008年 | 3251篇 |
2007年 | 2483篇 |
2006年 | 2161篇 |
2005年 | 2211篇 |
2004年 | 1882篇 |
2003年 | 1701篇 |
2002年 | 2429篇 |
2001年 | 1631篇 |
2000年 | 1489篇 |
1999年 | 541篇 |
1998年 | 183篇 |
1997年 | 132篇 |
1996年 | 125篇 |
1995年 | 81篇 |
1994年 | 62篇 |
1993年 | 70篇 |
1992年 | 53篇 |
1991年 | 71篇 |
1990年 | 37篇 |
1989年 | 44篇 |
1988年 | 16篇 |
1987年 | 30篇 |
1986年 | 17篇 |
1985年 | 28篇 |
1984年 | 15篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1973年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Jaeyoung Ko Janggyoo Choi Soo Kyung Bae Jinwoong Kim Kee Dong Yoon 《Journal of separation science》2013,36(24):3860-3865
A rapid and efficient high‐performance counter‐current chromatography (HPCCC) method was developed to separate five oligostilbenes from the roots of Vitis amurensis. An n‐hexane/ethyl acetate/methanol/water system (4:8:4:10, v/v/v/v) was selected as an optimal two‐phase solvent system of which the upper phase was used as the stationary phase and the lower phase was used as the mobile one. Partition coefficient values for the target compounds under these optimized conditions were 0.28 ( 1 , ampleosin A), 7.12 ( 2 , (+)‐g‐viniferin), 2.26 ( 3 , vitisin A), 5.38 ( 4 , wilsonol C), and 11.23 ( 5 , vitisin B). Flow‐rate gradient HPCCC (4 mL/min in 0–70 min, 8 mL/min in 70–250 min) was applied to isolate the target compounds in as high purity as possible within the shortest possible run time. Under these conditions, ampelopsin A (12.1 mg), (+)‐g‐viniferin (10.4 mg), vitisin A (2.8 mg), wilsonol C (3.2 mg), and vitisin B (37 mg) were isolated with >95% purity from 150 mg of enriched oligostilbene extract. Although the KD of the last eluted compound, vitisin B (KD = 11.23), was relatively large, it was eluted in 115–145 min using the two‐phase solvent system. This study shows that HPCCC is an efficient tool for the isolation and purification of natural products. 相似文献
992.
Amayreh Mousa Chanbasha Basheer Abdul Rahman Al‐Arfaj 《Journal of separation science》2013,36(12):2003-2009
Dispersive liquid–liquid microextraction method was developed for the determination of the amount of phthalate esters in bottled drinking water samples and dispersive liquid–liquid microextraction samples were analyzed by GC–MS. Various experimental conditions influencing the extraction were optimized. Under the optimized conditions, very good linearity was observed for all analytes in a range between 0.05 and 150 μg/L with coefficient of determination (R2) between 0.995 and 0.999. The LODs based on S/N = 3 were 0.005–0.22 μg/L. The reproducibility of dispersive liquid–liquid microextraction was evaluated. The RSDs were 1.3–5.2% (n = 3). The concentrations of phthalates were determined in bottled samples available in half shell. To understand the leaching profile of these phthalates from bottled water, bottles were exposed to direct sunlight during summer (temperature from 34–57°C) and sampled at different intervals. Result showed that the proposed dispersive liquid–liquid microextraction is suitable for rapid determination of phthalates in bottled water and di‐n‐butyl, butyl benzyl, and bis‐2‐ethylhexyl phthalate compounds leaching from bottles up to 36 h. Thereafter, degradation of phthalates was observed. 相似文献
993.
Quan‐Bin Han Wai‐Lun Tang Cai‐Xia Dong Hong‐Xi Xu Zhi‐Hong Jiang 《Journal of separation science》2013,36(7):1304-1310
Two‐phase solvent system plays crucial role in successful separation of organic compounds using counter‐current chromatography (CCC). An interesting two‐phase solvent system, composed of chloroform/ethyl acetate/methanol/water, is reported here, in which both phases contain sufficient organic solvents to balance their dissolving capacities. Adjusting the solvent system to get satisfactory partition coefficients (K values) for target compounds becomes relatively simple. This solvent system succeeded in sample preparation of aconitine (8.07 mg, 93.69%), hypaconitine (7.74 mg, 93.17%), mesaconitine (1.95 mg, 94.52%) from raw aconite roots (102.24 mg, crude extract), benzoylmesaconine (34.79 mg, 98.67%) from processed aconite roots (400.01 mg, crude extract), and yunaconitine (253.59 mg, 98.65%) from a crude extract of Aconitum forrestii (326.69 mg, crude extract). 相似文献
994.
Karine Vuignier Szabolcs Fekete Pierre‐Alain Carrupt Jean‐Luc Veuthey Davy Guillarme 《Journal of separation science》2013,36(14):2231-2243
In the present study, three types of silica‐based monoliths, i.e. the first and second generations of commercial silica monolithic columns and a wide‐pore prototype monolith were compared for the analysis of large biomolecules. These molecules possess molecular weights between 1 and 66 kDa. The gradient kinetic performance of the first‐generation monolith was lower than that of the second generation, for large biomolecules (>14 kDa) but very close with smaller ones (1.3–5.8 kDa). In contrast, the wide‐pore prototype column was particularly attractive with proteins larger than 19 kDa (higher peak capacity). Among these three columns, the selectivity and retention remained quite similar but a possible larger number of accessible and charged residual silanols was noticed on the wide‐pore prototype material, which led to unpredicted small changes in selectivity and slightly broader peaks than expected. The peak shapes attained with the addition of 0.1% formic acid in the mobile phase remained acceptable for MS coupling, particularly for biomolecules of less than 6 kDa. It was found that one of the major issues with all of these silica‐based monoliths is the possible poor recovery of large biomolecules (principally with monoclonal antibody fragments of more than 25 kDa). 相似文献
995.
A mathematical model is constructed and solved that could describe the dynamic behavior of the adsorption of a solute of interest in single and stratified columns packed with partially fractal porous adsorbent particles. The results show that a stratified column bed whose length is the same as that of a single column bed, provides larger breakthrough times and a higher dynamic utilization of the adsorptive capacity of the particles than those obtained from the single column bed, and the superior performance of the stratified bed becomes especially more important when the superficial velocity of the flowing fluid stream in the column is increased to accommodate increases in the system throughput. This occurs because the stratified column bed provides larger average external and intraparticle mass transfer and adsorption rates per unit length of packed column. It is also shown that increases in the total number of recursions of the fractal and the ratio of the radii between larger and smaller microspheres that make up the partially fractal particles, increase the intraparticle mass transfer and adsorption rates and lead to larger breakthrough times and dynamic utilization of the adsorptive capacity of the particles. The results of this work indicate that highly efficient adsorption separations could be realized through the use of a stratified column comprised from a practically reasonable number of sections packed with partially fractal porous adsorbent particles having reasonably large (i) total number of recursions of the fractal and (ii) ratio of the radii between larger and smaller microspheres from which the partially fractal particles are made from. It is important to mention here that the physical concepts and modeling approaches presented in this work could be, after a few modifications of the model, applied in studying the dynamic behavior of chemical catalysis and biocatalysis in reactor beds packed with partially fractal porous catalyst particles. 相似文献
996.
997.
Dhirendra Kumar Dr. K. R. Justin Thomas Ching‐Chiao Lin Prof. Jwo‐Huei Jou 《化学:亚洲杂志》2013,8(9):2111-2124
A series of pyrenoimidazoles that contained various functional chromophores, such as anthracene, pyrene, triphenylamine, carbazole, and fluorene, were synthesized and characterized by optical, electrochemical, and theoretical studies. The absorption spectra of the dyes are dominated by electronic transitions that arise from the pyrenoimidazole core and the additional chromophore. All of the dyes exhibited blue‐light photoluminescence with moderate‐to‐high quantum efficiencies. They also displayed high thermal stability and their thermal‐decomposition temperatures fell within the range 462–512 °C; the highest decomposition temperature was recorded for a carbazole‐containing dye. The oxidation propensity of the dyes increased on the introduction of electron‐rich chromophores, such as triphenylamine or carbazole. The application of selected dyes that featured additional chromophores such as pyrene, carbazole, and triphenylamine as blue‐emissive dopants into multilayered organic light‐emitting diodes with a 4,4′‐bis(9H‐carbazol‐9‐yl)biphenyl (CBP) host was investigated. Devices that were based on triphenylamine‐ and carbazole‐containing dyes exhibited deep‐blue emission (CIE 0.157, 0.054 and 0.163, 0.041), whereas a device that was based on a pyrene‐containing dye showed a bright‐blue emission (CIE 0.156, 0.135). 相似文献
998.
A new bridging ligand, 2,3‐di(2‐pyridyl)‐5‐phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN‐CNN‐type coordination mode. The reaction of dpppzH with cis‐[(bpy)2RuCl2] (bpy=2,2′‐bipyridine) affords monoruthenium complex [(bpy)2Ru(dpppzH)]2+ ( 12+ ) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)2Ru(dpppz)Ru(Mebip)]3+ ( 23+ ) was prepared from complex 12+ and [(Mebip)RuCl3] (Mebip=bis(N‐methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)2Ru(dpppz)Pt(C?CPh)]2+ ( 42+ ) has been prepared from complex 12+ , in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λmax=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3‐di(2‐pyridyl)‐5,6‐diphenylpyrazine. 相似文献
999.
Hongki Kim Dr. Taejoon Kang Hyoban Lee Hyunseong Ryoo Dr. Seung Min Yoo Prof. Dr. Sang Yup Lee Prof. Dr. Bongsoo Kim 《化学:亚洲杂志》2013,8(12):3010-3014
The direct transfer of single‐crystalline Au nanowires (NWs) onto Au substrates was achieved by a simple attachment and detachment process. In the presence of a lubricant, Au NWs grown vertically on a sapphire substrate were efficiently moved to an Au substrate through van der Waals interactions. We demonstrate that the transferred Au NWs on the Au substrate can act as sensitive, reproducible, and long‐term‐stable surface‐enhanced Raman scattering (SERS) sensors by detecting human α‐thrombin as well as Pb2+ and Hg2+ ions. These three biochemically and/or environmentally important analytes were successfully detected with high sensitivity and selectivity by Au NW‐SERS sensors bound by a thrombin‐binding aptamer. Furthermore, the as‐prepared sensors remained in working order after being stored under ambient conditions at room temperature for 80 days. Because Au NWs can be routinely transferred onto Au substrates and because the resultant Au NW‐SERS sensors are highly stable and provide with high sensitivity and reproducibility of detection, these sensors hold potential for practical use in biochemical sensing. 相似文献
1000.