全文获取类型
收费全文 | 4496篇 |
免费 | 832篇 |
国内免费 | 847篇 |
专业分类
化学 | 3253篇 |
晶体学 | 106篇 |
力学 | 412篇 |
综合类 | 53篇 |
数学 | 760篇 |
物理学 | 1591篇 |
出版年
2024年 | 7篇 |
2023年 | 61篇 |
2022年 | 120篇 |
2021年 | 147篇 |
2020年 | 247篇 |
2019年 | 167篇 |
2018年 | 173篇 |
2017年 | 196篇 |
2016年 | 230篇 |
2015年 | 216篇 |
2014年 | 234篇 |
2013年 | 433篇 |
2012年 | 275篇 |
2011年 | 286篇 |
2010年 | 236篇 |
2009年 | 309篇 |
2008年 | 299篇 |
2007年 | 330篇 |
2006年 | 269篇 |
2005年 | 262篇 |
2004年 | 232篇 |
2003年 | 244篇 |
2002年 | 203篇 |
2001年 | 155篇 |
2000年 | 120篇 |
1999年 | 99篇 |
1998年 | 122篇 |
1997年 | 90篇 |
1996年 | 83篇 |
1995年 | 51篇 |
1994年 | 50篇 |
1993年 | 33篇 |
1992年 | 34篇 |
1991年 | 37篇 |
1990年 | 14篇 |
1989年 | 15篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 15篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1973年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有6175条查询结果,搜索用时 15 毫秒
41.
《Angewandte Chemie (International ed. in English)》2017,56(12):3374-3378
A benzo‐fused double [7]carbohelicene (D7H) was synthesized through a regioselective cyclodehydrogenation of a tetranaphthyl‐p ‐terphenyl‐based precursor. The twisted (D7H‐1) and anti ‐folded (D7H‐2) conformers of D7H were separated by recrystallization, and their double helicene structures with overlapping terminal benzene rings were unambiguously elucidated by X‐ray crystallography. A record‐high isomerization barrier (46.0 kcal mol−1) in double helicenes was estimated based on density functional theory (DFT) calculation, which resulted in the excellent conformational stability of D7H. The physicochemical properties of D7H‐1 and D7H‐2 were investigated by UV/Vis absorption spectroscopy and cyclic voltammetry, displaying the variation of electronic structure upon conformational changes. The optical resolution of the racemic D7H‐1 was carried out by chiral HPLC, offering enantiopure D7H‐1‐(P ,P ) and D7H‐1‐(M ,M ), which were further characterized by circular dichroism spectroscopy. 相似文献
42.
Mechanochemical synthesis of dodecyl sulfate anion (DS−) intercalated Cu-Al layered double hydroxide
Dodecyl sulfate anion (DS−) was successfully intercalated into the gallery space of Cu-Al layered double hydroxides (LDH) by a non-heating mechanochemical route, in which basic cupric carbonate (Cu2(OH)2CO3) and aluminum hydroxide (Al(OH)3) were first dry ground and then agitated in SDS solution under ambient environment. The organics modified Cu-Al LDH showed good adsorption ability toward 2,4-dichlorophenoxyacetic acid (2, 4-D). The prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), CHS elemental analysis and Scanning electron microscopy (SEM). The LDH precursor prepared by ball-milling could directly react with SDS molecules forming a pure phase of DS− pillared Cu-Al LDH, which was not observed with the LDH product through the ion-exchange of DS− at room temperature. The process introduced here may be applied to manufacture other types of organic modified composites for pollutants removal and other applications. 相似文献
43.
对于聚集数据的线性模型,提出了广义聚集双参数估计的概念,给出了广义聚集双参数估计的两种相对效率,并得到了这两种相对效率的上界. 相似文献
44.
从矩阵几何解的角度出发,分析了七种类型的Geom/Geom/(Geom/Geom)/H 双输入排队系统.对这几个模型进行了描述,使用拟生灭过程探讨了各类模型的矩阵结构,并给出了其状态转移概率矩阵. 相似文献
45.
研究了非奇H-矩阵的判定问题.先给出了几个判定严格α-双链对角占优矩阵的充要条件,进一步利用矩阵对角占优理论得到了判定非奇H-矩阵的一些充分条件,推广和改进了已有的相关结果,并用数值算例说明了这些判定方法的有效性. 相似文献
46.
改进种群多样性的双变异差分进化算法 总被引:1,自引:0,他引:1
差分进化算法(DE)是一种基于种群的启发式随机搜索技术,对于解决连续性优化问题具有较强的鲁棒性.然而传统差分进化算法存在种群多样性和收敛速度之间的矛盾,一种改进种群多样性的双变异差分进化算法(DADE),通过引入BFS-best机制(基于排序的可行解选取递减策略)改进变异算子"DE/current-to-best",将其与DE/rand/1构成双变异策略来改善DE算法中种群多样性减少的问题.同时,每个个体的控制参数基于排序自适应更新.最后,利用多个CEC2013标准测试函数对改进算法进行测试,实验结果表明,改进后的算法能有效改善种群多样性,较好地提高了算法的全局收敛能力和收敛速度. 相似文献
47.
48.
Yongming Zhang 《数学学报(英文版)》2017,33(8):1039-1047
Let Y be a smooth projective surface defined over an algebraically closed field k with char k≠2, and let π : X →Y be a double covering branched along a smooth divisor. We show that y_X is stable with respect to π~*H if the tangent bundle y_Y is semi-stable with respect to some ample line bundle H on Y. 相似文献
49.
层状复合氢氧化物(LDHs)因其化学组成可调、比表面积大、生物相容性好等特点,目前在环境、能源和生物医药等领域广受关注.然而, LDHs在合成过程中由于其分子内作用力易发生团聚而导致其在基体中的分散不均匀,极大地限制了LDHs在实际中的应用.有机改性是改善LDHs分散性的有效方法,从表面改性和插层改性两个方面综述了近年来LDHs的有机改性方法,并介绍了其在阻燃、吸附、催化、气体阻隔、发光、储能和生物医药材料等领域的应用.最后对改性后LDHs未来的研究方向和应用领域进行了展望. 相似文献
50.
The hydrogenation of unsaturated carbons is a commonly used synthetic tool in pharmaceutical and industrial production. Recently, the Norton group realized highly selective hydrogenation of C=C bonds catalyzed by a rhodium hydride. Despite the great efforts made by experimentalists, details regarding the mechanism remained unclear. In this work, detailed DFT calculations were carried out to elucidate the principal features of this transformation. For enones we find that two possible competing mechanisms proposed by the experimental groups are computationally excluded, our proposed alternative mechanism with a total barrier of 20.0 kcal mol−1 is theoretically feasible, solvent methanol to also plays a crucial role in assisting β-hydrogenation in addition to being the hydrogen source for α-hydrogenation, and the cross-polarization of the substrate enone-conjugated system to result in an enhanced charge density of the α-carbon, which favors being hydrogenated first. For isolated alkenes, neither of the two possible competing mechanisms can be excluded computationally and which carbon atom is first hydrogenated depends on the electronic properties of the substrate itself. The combination of rhodium and C=C bonds changes the electronic properties of H on the rhodium hydride and enhances its hydrogenation activity. 相似文献