全文获取类型
收费全文 | 27977篇 |
免费 | 3700篇 |
国内免费 | 3138篇 |
专业分类
化学 | 20337篇 |
晶体学 | 353篇 |
力学 | 1388篇 |
综合类 | 234篇 |
数学 | 3516篇 |
物理学 | 8987篇 |
出版年
2023年 | 438篇 |
2022年 | 478篇 |
2021年 | 691篇 |
2020年 | 906篇 |
2019年 | 926篇 |
2018年 | 788篇 |
2017年 | 751篇 |
2016年 | 1120篇 |
2015年 | 1140篇 |
2014年 | 1351篇 |
2013年 | 1901篇 |
2012年 | 2274篇 |
2011年 | 2509篇 |
2010年 | 1763篇 |
2009年 | 1734篇 |
2008年 | 1932篇 |
2007年 | 1759篇 |
2006年 | 1580篇 |
2005年 | 1392篇 |
2004年 | 1107篇 |
2003年 | 883篇 |
2002年 | 809篇 |
2001年 | 702篇 |
2000年 | 568篇 |
1999年 | 529篇 |
1998年 | 478篇 |
1997年 | 419篇 |
1996年 | 452篇 |
1995年 | 384篇 |
1994年 | 367篇 |
1993年 | 341篇 |
1992年 | 319篇 |
1991年 | 276篇 |
1990年 | 232篇 |
1989年 | 191篇 |
1988年 | 167篇 |
1987年 | 128篇 |
1986年 | 141篇 |
1985年 | 154篇 |
1984年 | 101篇 |
1983年 | 64篇 |
1982年 | 71篇 |
1981年 | 53篇 |
1980年 | 52篇 |
1979年 | 58篇 |
1978年 | 40篇 |
1976年 | 37篇 |
1975年 | 32篇 |
1974年 | 40篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
采用高稳定、高灵敏的纳米金/多孔二氧化硅复合材料作为SERS基底,构建了一种二维薄层色谱-表面增强拉曼散射(TLC-SERS)联用方法,该技术结合了薄层色谱(TLC)的快速分离功能和SERS定性定量分析的优点,提高了分离能力。采用对巯基苯胺作为探针分子研究了基底的均匀性和批-批重复性。Mapping扫描实验表明,24个测量点峰强度的相对标准偏差(RSD)为5.9%,说明该基底具有良好的点-点重复性。9个批次基底信号值的RSD为7.5%。将该基底用于糖精钠的检测,线性范围为0.1~200 mg/L,检出限为0.06 mg/L。用于实际样品测定,检测出饮料中糖精钠为141 mg/L,水果中为18 mg/L,10 min内能完成分析测试。该方法灵敏度高,特异性强,前处理方式简单,实现了饮料及水果中糖精钠的快速检测。 相似文献
992.
液相色谱-质谱联用(简称液质联用,LC-MS)将色谱的高分离效能与质谱强大的结构测定功能结合,不仅实现了对复杂混合物更准确的定性定量分析,而且简化了样品的前处理过程,使样品分析更简便,在药物分析、食品与环境分析以及生物样品检测等众多领域得到了广泛的应用。作为LC-MS的核心组成部分,液质接口的作用是将LC的液体引入,发生电离,并将生成的离子传输进MS。因此,接口离子化技术的改进直接影响了LC-MS的发展和应用。为了获得更高的灵敏度和更广泛的适用性,研究人员一直致力于离子化技术的研究,以促进分析物的解吸,提高其电离和传输效率,减少基质效应的干扰。本文针对近年来LC-MS接口离子化技术的改进和发展,从离子化原理出发,对接口离子源的构造、影响电离的因素、以及相关的应用进行综述,探讨其优缺点,并对LC-MS接口离子化技术的发展趋势进行了展望。 相似文献
993.
本文主要介绍了一系列基于二茂铁骨架的三齿配体:f-amphox、f-ampha、f-amphol和f-amphamide的合成及其应用。这四类手性膦氮配体的铱络合物可以高活性(TON高达1 000 000)、高转化率(>99%)、高对映选择性(>99% ee)地催化(官能团化)酮等底物的不对称氢化反应。该系列配体成功地应用于地诺帕明、苯福林和沙丁胺醇等手性医药中间体的不对称合成。与传统路线相比,这些合成方法更高效,副产物更少,“三废”排放量更低。 相似文献
994.
硫镍基赝电容超级电容器具有较高的比电容和功率密度等优点,是下一代理想的储能装置之一,但其实际应用受到其活性材料的制约,如导电性低和循环性能差等。研究者围绕增强硫镍基赝电容电极材料导电性和提升循环稳定性进行了大量的研究工作。其中,构建自支撑的电极材料被认为是一种降低活性材料和集流体之间界面电阻的有效方法。本文综述了制备自支撑硫镍基赝电容电极的常见方法,并就活性材料的形貌与性能关系进行了总结,主要着眼于集流体改性、离子掺杂、复合材料构建及形貌调控优化等。最后对自支撑硫镍基赝电容电极材料的研究方向进行了展望。 相似文献
995.
Lin Yan Ling-Hui Wang Xie Li Ao Li Qi-Min Xiao 《Phosphorus, sulfur, and silicon and the related elements》2020,195(9):740-746
AbstractTreatment of the starting complex [Fe2(CO)6{μ-SCH2CH(CH2OH)S}] (1) with 2-(diphenylphosphino)benzoic acid in the presence of N,N’-dicyclohexylcarbodiimide and 4-dimethylaminopyridine gave the corresponding ester derivative [Fe2(CO)6{μ-SCH2CH(CH2O2CC6H4PPh2-2)S}] (2) in 92% yield. Further treatment of complex 2 with one equivalent of Me3NO · 2?H2O as the decarbonylating agent yielded diphenylphosphino-substituted complex [Fe2(CO)5{μ-SCH2CH(CH2O2CC6H4PPh2-2)S}] (3) in 79% yield. Both complexes were characterized by elemental analysis, spectroscopy, as well as by X-ray crystallography. Additionally, the electrochemical properties of these complexes were studied by cyclic voltammetry. 相似文献
996.
Shijie Ding Lingyu Kong Yanjuan Jin Jinbao Lin Chao Chang Huaying Li Erqiang Liu Haitao Liu 《先进技术聚合物》2020,31(4):873-884
Fused deposition molding (FDM) is one of the most widely used three‐dimensional (3D) printing technologies. This paper explores the influence of the forming angle on the tensile properties of FDM specimens. Orthogonal layering details were studied through experiments, theory, and finite element simulations. The stiffness and strength of the specimens were analyzed using the classical laminated plate theory and the Tsai–Wu failure criterion. The experimental process was simulated using finite element simulations. Results show that it is feasible to predict the stiffness and strength of FDM specimens using classical laminated plate theory and the Tsai–Wu failure criterion. A molding angle of 45° leads to specimens with maximized tensile properties. Numerical simulations show that changing the molding angle changes the internal stress and deformation fields inside samples, leading to FDM samples with different mechanical properties due to the orthogonal layers at different molding angles. 相似文献
997.
Haixiao Fang Hang Zhang Lin Li Yun Ni Riri Shi Zheng Li Xuekang Yang Bo Ma Chengwu Zhang Qiong Wu Changmin Yu Naidi Yang Shao Q. Yao Wei Huang 《Angewandte Chemie (International ed. in English)》2020,59(19):7536-7541
Monoamine oxidases have two functionally distinct but structurally similar isoforms (MAO‐A and MAO‐B). The ability to differentiate them by using fluorescence detection/imaging technology is of significant biological relevance, but highly challenging with available chemical tools. Herein, we report the first MAO‐A‐specific two‐photon fluorogenic probe ( F1 ), capable of selective imaging of endogenous MAO‐A enzymatic activities from a variety of biological samples, including MAO‐A‐expressing neuronal SY‐SY5Y cells, the brain of tumor‐bearing mice and human Glioma tissues by using two‐photon fluorescence microscopy (TPFM) with minimal cytotoxicity. 相似文献
998.
David W. Burke Chao Sun Ioannina Castano Nathan C. Flanders Austin M. Evans Edon Vitaku David C. McLeod Robert H. Lambeth Lin X. Chen Nathan C. Gianneschi William R. Dichtel 《Angewandte Chemie (International ed. in English)》2020,59(13):5165-5171
Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates. 相似文献
999.
Jing Guo Yan‐Zhong Fan Yu‐Lin Lu Shao‐Ping Zheng Cheng‐Yong Su 《Angewandte Chemie (International ed. in English)》2020,59(22):8661-8669
Although the photodimerization of acenaphthylene (ACE) has been known for 100 years, the asymmetric cycloaddition of its 1‐substituted derivatives is unknown. Herein, we report a supramolecular photochirogenic approach in which a homochiral and photoactive Δ/Λ‐[Pd6(RuL3)8]28+ metal–organic cage (Δ/Λ‐MOC‐16) is used as a supramolecular reactor for the enantioselective exited‐state photocatalysis of 1‐Br‐ACE. Owing to preorganization of the substrates by the supramolecular cage, stereochemical control of the triplet state, and nanospace transfer of energy and chirality, the cycloaddition of ACE proceeded with high selectivity for the formation of anti over syn stereoisomers, whereas the regio‐, stereo‐, and enantioselective cycloaddition of unsymmetrical 1‐Br‐ACE showed effective enantiodifferentiation of a pair of anti head‐to‐head stereoisomers. The enzyme‐mimicking photocatalysis was verified by catalytic turnover, rate enhancement, and competing‐guest inhibition experiments. 相似文献
1000.
Xiaokai Ding Dong Luo Jiaxiang Cui Huixian Xie Qingqing Ren Zhan Lin 《Angewandte Chemie (International ed. in English)》2020,59(20):7778-7782
Voltage decay and capacity fading are the main challenges for the commercialization of Li‐rich Mn‐based layered oxides (LLOs). Now, a three‐in‐one surface treatment is designed via the pyrolysis of urea to improve the voltage and capacity stability of Li1.2Mn0.6Ni0.2O2 (LMNO), by which oxygen vacancies, spinel phase integration, and N‐doped carbon nanolayers are synchronously built on the surface of LMNO microspheres. Oxygen vacancies and spinel phase integration suppress irreversible O2 release and help lithium ion diffusion, while N‐doped carbon nanolayer mitigates the corrosion of electrolyte with excellent conductivity. The electrochemical performance of LMNO after the treatment improves significantly; the capacity retention rate after 500 cycles at 1 C is still as high as 89.9 % with a very small voltage fading rate of 1.09 mV cycle?1. This three‐in‐one surface treatment strategy can suppress the voltage decay and capacity fading of LLOs. 相似文献