全文获取类型
收费全文 | 30054篇 |
免费 | 3557篇 |
国内免费 | 6545篇 |
专业分类
化学 | 33352篇 |
晶体学 | 212篇 |
力学 | 728篇 |
综合类 | 217篇 |
数学 | 1419篇 |
物理学 | 4228篇 |
出版年
2024年 | 39篇 |
2023年 | 489篇 |
2022年 | 736篇 |
2021年 | 1155篇 |
2020年 | 1733篇 |
2019年 | 1366篇 |
2018年 | 1369篇 |
2017年 | 1247篇 |
2016年 | 1441篇 |
2015年 | 1338篇 |
2014年 | 1950篇 |
2013年 | 2988篇 |
2012年 | 1756篇 |
2011年 | 2059篇 |
2010年 | 1576篇 |
2009年 | 1753篇 |
2008年 | 1875篇 |
2007年 | 2005篇 |
2006年 | 1855篇 |
2005年 | 1719篇 |
2004年 | 1631篇 |
2003年 | 1400篇 |
2002年 | 849篇 |
2001年 | 688篇 |
2000年 | 659篇 |
1999年 | 529篇 |
1998年 | 490篇 |
1997年 | 423篇 |
1996年 | 410篇 |
1995年 | 421篇 |
1994年 | 356篇 |
1993年 | 271篇 |
1992年 | 290篇 |
1991年 | 190篇 |
1990年 | 153篇 |
1989年 | 132篇 |
1988年 | 121篇 |
1987年 | 74篇 |
1986年 | 79篇 |
1985年 | 80篇 |
1984年 | 68篇 |
1983年 | 35篇 |
1982年 | 53篇 |
1981年 | 45篇 |
1980年 | 30篇 |
1979年 | 29篇 |
1978年 | 27篇 |
1977年 | 31篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Ligand-promoted copper-catalyzed cascade reactions have become a robust tool for the synthesis of cyclic compounds. Although numerous ligands have been developed, this review focuses on the introduction of commercially available 1,10-phenanthroline-promoted copper-catalyzed cascade reactions in recent years. Moreover, based on original articles, this review highlights product yields in the presence and absence of the ligand, and the possible mechanistic role of the ‘copper/1,10-phenanthroline’ catalytic system. 相似文献
52.
Mahdieh Darroudi Sara Ranjbar Mohammad Esfandiar Mahsima Khoshneviszadeh Mahshid Hamzehloueian Mehdi Khoshneviszadeh Yaghoub Sarrafi 《应用有机金属化学》2020,34(12):e5962
In the present work, novel 5-((1-benzyl-1,2,3-triazol-4-yl)methoxybenzylidene)-2-(arylamino)thiazol-4-one thiazolone incorporated triazole derivatives have been designed as tyrosinase inhibitors. The compounds were synthesized through click reaction in good yield. Moreover, the antityrosinas activity of the synthesized derivatives was evaluated. In the search for establishing a click copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction under strict conditions, in terms of a novel air-stable, a recyclable and efficient magnetic catalyst was planned for new triazole derivatives as a well-organized copper iodide supported on the functionalized Fe3O4@SiO2 core-shell (CuI/Fe3O4@SiO2(TMS-EDTA) nanoparticles). The engineered nanocatalyst synthesized for the first time and characterized by different methods, including FT-IR spectroscopy, XRD, FESEM, EDX, TEM, TGA, and BET analysis. The excellent catalytic performance in ethanol with high surface area (351.7 m2g−1) and short reaction time for diverse functional groups (120–200 min), no use of toxic solvents, reusability of the catalyst, and using eco-friendly conditions are the advantageous of this work. Moreover,the nanocatalyst can be used at least five times without any significant decrease in the yield of the reaction. The thiazolidine-triazole derivatives 9a , 9c , 9e , and 9 g showed promising tyrosinase inhibitory activity with IC50 values in the range of 5.90–9.81 μM. The compounds were found to be considerably more potent tyrosinase inhibitors than the reference inhibitor kojic acid (IC50 = 18.36 μM). 相似文献
53.
In this research, the main emphasis has been focused on the preparation of a novel Fe3O4-supported propane-1-sulfonic acid-grafted graphene oxide quantum dots (Fe3O4@GOQD-O-(propane-1-sulfonic acid)) that it was readily synthesized via a five-step procedure as a hitherto unreported magnetic nanocatalyst. This newly prepared Fe3O4@GOQD-O-(propane-1-sulfonic acid) nanocomposite was structurally well-established by different analytical techniques including Fourier transform infrared (FT-IR), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), thermal gravimetric analysis (TGA), field emission gun-scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM) and vibrating sample magnetometer (VSM) analyses. The high catalytic performance of this nanocomposite was exhibited in one-pot synthesis of dihydropyrano[2,3-c]pyrazole and 4H-chromene derivatives under mild conditions. Low reaction times, excellent yields of the products, benignity of the catalyst, easy reaction work-up and magnetic recyclability of the catalyst are the main advantages of the present protocol. Also, our research indicated that the Fe3O4@GOQD-O-(propane-1-sulfonic acid) could be reused up to five times without considerable loss of catalytic activity. 相似文献
54.
Consider an elastic thin three-dimensional body made of a periodic distribution of elastic inclusions. When both the thickness of the beam and the size of the heterogeneities tend simultaneously to zero the authors obtain three different one-dimensional models of beam depending upon the limit of the ratio of these two small parameters. 相似文献
55.
《化学:亚洲杂志》2018,13(14):1791-1796
The development of highly efficient bioorthogonal reactions is of paramount importance for the research fields of biomaterials and chemical biology. We found that the o,o′‐difluorinated aromatic azide was able to react with triphenylphosphine to produce water‐stable phosphanimine. To further improve the efficiency of this kind of nonhydrolysis Staudinger reaction, a tetrafluorinated aromatic azide was employed to develop a faster nonhydrolysis Staudinger reaction with a rate of up to 51 m −1 s−1, as revealed by high‐performance liquid chromatography (HPLC) analysis and fluorescence kinetics. As a proof‐of‐concept study, the highly efficient Staudinger reaction was successfully used for chemoselective fluorescence labeling of proteins and nucleic acids (DNA and RNA) as well as for protein polyethyleneglycol (PEG)ylation. We believe that this bioorthogonal reaction can provide a broadly useful tool for various bioconjugations. 相似文献
56.
硒是动植物及人体生长必需的十五种微量元素之一,具有清除体内自由基、抗氧化、增强免疫力等功能,但其安全剂量的范围却很窄。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体,粒径范围在17~200 nm之间,平均粒径138 nm。XRD衍射图谱中的特征峰与FeS2衍射图谱中各峰位置基本一致,因此判定硫铁矿中主要化学组分为FeS2,且图谱中基本没有杂峰,表明制备过程中并未混入杂质,样品纯度较高。实验结果表明,该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪(XPS)对硫铁矿去除水体中SeO2-3的机理进行了研究。研究结果表明, (1)在较为广泛的实验pH范围(pH 2.2~11.5),硫铁矿均能有效去除水体中SeO2-3,去除效率(除pH值7.8以外)均达到90%以上;(2)硫铁矿与SeO2-3发生反应后,其主要组成元素的XPS特征峰结合能有所减小,表明硫铁矿表面发生了一定化学变化;(3)酸碱环境下硫铁矿去除SeO2-3的机理不完全相同,酸性环境下,硫铁矿对SeO2-3的去除是单纯的氧化还原过程,即硫铁矿中被酸活化的S2-2将SeO2-3还原为单质Se(0),并且酸性越强,SeO2-3去除效果越好;碱性环境下,SeO2-3的去除过程中氧化还原与络合反应并存,硫铁矿表面有络合态Fe(OH)SeO3和单质Se(0)两种存在形态,且碱性越强,络合态Fe(OH)SeO3含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-3为代表的可变价金属阴离子提供重要理论依据和应用基础。 相似文献
57.
The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO2Me) by Cp2TaH3 and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η2-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η2-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc. 相似文献
58.
《中国化学快报》2020,31(9):2353-2357
NiS2 has become a research hotspot of anode materials for Na-ion batteries due to its high theoretical specific capacity. However, the volume effect, the dissolution of polysulfide intermediates and the low conductivity during the charge/discharge process lead to the low specific capacity and poor cycling stability. NiS2/rGO nanocomposite was prepared by a facile two-step process: GO was prepared by modified Hummers method, and then NiS2/rGO nanocomposite was synthesized by l-cys assisted hydrothermal method. NiS2/rGO nanocomposite shows excellent cycle performance and rate performance, which could be attributed to the mesoporous structure on the graphene skeleton with high conductivity. Besides, the chemical constraint of a unique SO bond on NiS2 could inhibit the dissolution of intermediates and the loss of irreversible capacity. 相似文献
59.
利用玻色化方法可以避免超对称可积系统中反对易费米场带来的计算困难. 本文以N=1超对称mKdVB系统为例, 利用玻色化方法, 将其转化为只有玻色场的耦合系统. 应用标准的WTC方法, 证明了该耦合系统具有Painlevé性质. 运用Painlevé截断方法, 可以得到玻色化后超对称mKdVB系统的非局域对称. 为了求解与非局域对称相关的Lie第一性原理, 引入新的场将玻色化后系统拓展为更大的系统. 通过引入新的场, 该非局域对称局域化为Lie点对称. 因此, 可以利用Lie点对称约化方法研究拓展后的系统, 得到超对称mKdVB系统的孤子与其他孤波相互作用解. 相似文献