全文获取类型
收费全文 | 4855篇 |
免费 | 1380篇 |
国内免费 | 454篇 |
专业分类
化学 | 1353篇 |
晶体学 | 20篇 |
力学 | 882篇 |
综合类 | 74篇 |
数学 | 412篇 |
物理学 | 3948篇 |
出版年
2024年 | 9篇 |
2023年 | 44篇 |
2022年 | 138篇 |
2021年 | 159篇 |
2020年 | 168篇 |
2019年 | 155篇 |
2018年 | 159篇 |
2017年 | 212篇 |
2016年 | 272篇 |
2015年 | 220篇 |
2014年 | 360篇 |
2013年 | 371篇 |
2012年 | 345篇 |
2011年 | 364篇 |
2010年 | 260篇 |
2009年 | 302篇 |
2008年 | 337篇 |
2007年 | 320篇 |
2006年 | 304篇 |
2005年 | 269篇 |
2004年 | 211篇 |
2003年 | 211篇 |
2002年 | 193篇 |
2001年 | 172篇 |
2000年 | 147篇 |
1999年 | 142篇 |
1998年 | 107篇 |
1997年 | 95篇 |
1996年 | 105篇 |
1995年 | 78篇 |
1994年 | 73篇 |
1993年 | 51篇 |
1992年 | 51篇 |
1991年 | 38篇 |
1990年 | 25篇 |
1989年 | 32篇 |
1988年 | 19篇 |
1987年 | 30篇 |
1986年 | 20篇 |
1985年 | 21篇 |
1984年 | 20篇 |
1983年 | 12篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 10篇 |
1979年 | 13篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1969年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有6689条查询结果,搜索用时 15 毫秒
31.
Young Eun Jeun Joon Ho Park Joo Yeon Kim Prof. Hyun S. Ahn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(18):4039-4043
Mixed-metal oxyhydroxides—especially those of Ni and Fe—are one of the most active classes of materials known for catalyzing the oxygen evolution reaction (OER). Here, nanoparticulate mixed metal oxyhydroxides (of Ni, Fe, and Co) were prepared on an electrode surface by electrochemical reaction of a precursor solution encapsulated in aqueous nanodroplets (AnDs), with each of the droplets containing 10 s of attoliters of fluid. Electrode reactions and synthesis can be monitored in situ by electrochemistry as single AnD stochastically lands and interacts with the working electrode. Resultant metal oxyhydroxide nanoparticles can be size and composition controlled precisely by modulating the precursor solution stored in the AnD. Nanoparticulate metal oxyhydroxides were implemented as catalysts for the OER and exhibited superior catalysis compared to their thin-film counterparts, demonstrating a hundred-thousand-fold enhancement in atom efficiency at comparable turnover rates. 相似文献
32.
33.
Fansheng Ning Heng Zhu Huijiao Yan Jiguo Liu Shahid Aziz Hidayat Hussain Xiangyun Song Lei Xie Zhaoqing Meng Guiyun Cao Daijie Wang 《Journal of separation science》2023,46(16):2300053
In this work, the preparative separation of quinolyridine alkaloids from seeds of T. lanceolata by conventional and pH-zone-refining counter-current chromatography. Traditional counter-current chromatography separation was performed by a flow-rate changing strategy with a solvent system of ethyl acetate-n-butanol-water (1:9:10, v/v) and 200 mg sample loading. Meanwhile, the pH-zone-refining mode was adopted for separating 2.0 g crude alkaloid extracts with the chloroform-methanol-water (4:3:3, v/v) solvent system using the stationary and mobile phases of 40 mM hydrochloric acid and 10 mM triethylamine. Finally, six compounds, including N-formylcytisine (two conformers) ( 1 ), N-acetycytisine (two conformers) ( 2 ), (-)-cytisine ( 3 ), 13-β-hydroxylthermopsine ( 4 ), N-methylcytisine ( 5 ), and thermopsine ( 6 ) were successfully obtained in the two counter-current chromatography modes with the purities over 96.5%. Moreover, we adopted nuclear magnetic resonance and mass spectrometry for structural characterization. Based on the obtained findings, the pH-zone-refining mode was the efficient method to separate quinolyridine alkaloids relative to the traditional mode. 相似文献
34.
Vitamin E represents a group of lipophilic phenolic compounds, including α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol, and α-tocotrienol, β-tocotrienol, γ-tocotrienol, and δ-tocotrienol isomers. Different forms of vitamin E have been proven to exhibit varying biological activities. However, due to their structural similarities, the separation of vitamin E isomers is a challenging task. Therefore, it is crucial to establish an efficient method for isolating individual isomers. In this study, co-current countercurrent chromatography was employed to isolate vitamin E isomers from commercial capsules using a n-heptane-methanol-water (10:9.5:0.5, v/v) solvent system. The partition coefficients of the main constituents in the capsules ranged from 0.94 to 6.23, requiring over 450 min for a complete separation. To improve separation efficiency, a co-current elution mode was implemented and the flow rates of the two liquid phases as well as sample amount were examined. The results suggested that increasing the flow rate of the stationary phase and sample size could result in more effective separation, shorter separation time, and higher yield. It proved that co-current countercurrent chromatography was an effective method for the separation of vitamin E isomers. 相似文献
35.
36.
设计合成了一种新的C3对称性含膦三足体衍生物N',N',N'-三(亚磷酸三乙酯)缩氨三乙酸(L)及其Eu(Ⅲ)配合物.用1H NMR、13C NMR、红外光谱、元素分析、差热-热重及紫外光谱对其组成和结构进行分析和表征.结果表明,三足体衍生物与稀土苦味酸盐(Eu(pic)3·6H2O)形成了1:1配合物Eu(pic)3L.综合运用紫外-可见吸收光谱法、荧光光谱法和循环伏安法研究了Eu(pic)3L与小牛胸腺DNA之间的结合模式,结果表明,配合物Eu(pic)3L与DNA之间以嵌插形式发生相互作用.将该配合物作为杂交探针,对其在DNA电化学传感器方面的应用进行了探讨.结果发现,该配合物在修饰单链DNA的电极检测作用下,无明显的电化学信号响应,而当将其用于检测杂交双链DNA时,出现了明显信号,并且该配合物的DNA传感器对互补序列、错配序列及非互补序列都有良好的选择作用. 相似文献
37.
38.
In this article, we present a Python‐based library of high quality semi‐global potential energy surfaces for 50 polyatomic molecules with up to six atoms. We anticipate that these surfaces will find widespread application in the testing of new potential energy surface construction algorithms and nuclear ro‐vibrational structure theories. To this end, we provide the ability to generate the energy derivatives required for Taylor series expansions to sixth order about any point on the potential energy surface in a range of common coordinate systems, including curvilinear internal, Cartesian, and normal mode coordinates. The PyPES package, along with FORTRAN, C, MATLAB and Mathematica wrappers, is available at http://sourceforge.net/projects/pypes-lib . © 2015 Wiley Periodicals, Inc. 相似文献
39.
Juan de Torres Petru Ghenuche Satish Babu Moparthi Victor Grigoriev Jérôme Wenger 《Chemphyschem》2015,16(4):782-788
Zero‐mode waveguides (ZMWs) can confine light into attoliter volumes, which enables single molecule fluorescence experiments at physiological micromolar concentrations. Of the fluorescence spectroscopy techniques that can be enhanced by ZMWs, Förster resonance energy transfer (FRET) is one of the most widely used in life sciences. Combining zero‐mode waveguides with FRET provides new opportunities to investigate biochemical structures or follow interaction dynamics at micromolar concentrations with single‐molecule resolution. However, prior to any quantitative FRET analysis on biological samples, it is crucial to establish first the influence of the ZMW on the FRET process. Here, we quantify the FRET rates and efficiencies between individual donor–acceptor fluorophore pairs that diffuse into aluminum zero‐mode waveguides. Aluminum ZMWs are important structures thanks to their commercial availability and the large amount of literature that describe their use for single‐molecule fluorescence spectroscopy. We also compared the results between ZMWs milled in gold and aluminum, and found that although gold has a stronger influence on the decay rates, the lower losses of aluminum in the green spectral region provide larger fluorescence brightness enhancement factors. For both aluminum and gold ZMWs, we observed that the FRET rate scales linearly with the isolated donor decay rate and the local density of optical states. Detailed information about FRET in ZMWs unlocks their application as new devices for enhanced single‐molecule FRET at physiological concentrations. 相似文献
40.
Histidine‐modified organic‐silica hybrid monolithic column for mixed‐mode per aqueous and ion‐exchange capillary electrochromatography 下载免费PDF全文
Sheng Tang Shujuan Liu Xiaojing Liang Xiaofen Tang Xingcai Wu Yong Guo Xia Liu Shengxiang Jiang 《Journal of separation science》2015,38(12):2046-2052
A novel organic‐silica hybrid monolith was prepared through the binding of histidine onto the surface of monolithic matrix for mixed‐mode per aqueous and ion‐exchange capillary electrochromatography. The imidazolium and amino groups on the surface of the monolithic stationary phase were used to generate an anodic electro‐osmotic flow as well as to provide electrostatic interaction sites for the charged compounds at low pH. Typical per aqueous chromatographic behavior was observed in water‐rich mobile phases. Various polar and hydrophilic analytes were selected to evaluate the characteristics and chromatographic performance of the obtained monolith. Under per aqueous conditions, the mixed‐mode mechanism of hydrophobic and ion‐exchange interactions was observed and the resultant monolithic column proved to be very versatile for the efficient separations of these polar and hydrophilic compounds (including amides, nucleosides and nucleotide bases, benzoic acid derivatives, and amino acids) in highly aqueous mobile phases. The successful applications suggested that the histidine‐modified organic‐silica hybrid monolithic column could offer a wide range of retention behaviors and flexible selectivities toward polar and hydrophilic compounds. 相似文献