全文获取类型
收费全文 | 1462篇 |
免费 | 234篇 |
国内免费 | 117篇 |
专业分类
化学 | 1331篇 |
晶体学 | 11篇 |
力学 | 65篇 |
综合类 | 10篇 |
数学 | 64篇 |
物理学 | 332篇 |
出版年
2024年 | 4篇 |
2023年 | 36篇 |
2022年 | 75篇 |
2021年 | 118篇 |
2020年 | 99篇 |
2019年 | 98篇 |
2018年 | 74篇 |
2017年 | 58篇 |
2016年 | 78篇 |
2015年 | 97篇 |
2014年 | 74篇 |
2013年 | 157篇 |
2012年 | 66篇 |
2011年 | 72篇 |
2010年 | 56篇 |
2009年 | 58篇 |
2008年 | 49篇 |
2007年 | 57篇 |
2006年 | 39篇 |
2005年 | 48篇 |
2004年 | 51篇 |
2003年 | 55篇 |
2002年 | 67篇 |
2001年 | 18篇 |
2000年 | 24篇 |
1999年 | 32篇 |
1998年 | 33篇 |
1997年 | 20篇 |
1996年 | 15篇 |
1995年 | 20篇 |
1994年 | 15篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 8篇 |
1990年 | 1篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有1813条查询结果,搜索用时 15 毫秒
91.
本工作使用简单易得的三氟乙酸酐作为活化试剂,拓展了Stieglitz重排反应的底物适用范围,发展了一种通过C—C键断裂由苯乙基羟胺制备芳基伯胺的方法.该反应条件较为温和且对官能团具有较好的兼容性.机理研究表明,反应经历了活性三氟乙酸酯中间体的原位生成,并通过C—C和N—O键的断裂实现芳基迁移的过程. 相似文献
92.
Zechao Yang Lukas Fromm Tim Sander Julian Gebhardt Tobias A. Schaub Andreas Grling Milan Kivala Sabine Maier 《Angewandte Chemie (International ed. in English)》2020,59(24):9549-9555
Demonstrated here is a supramolecular approach to fabricate highly ordered monolayered hydrogen‐ and halogen‐bonded graphyne‐like two‐dimensional (2D) materials from triethynyltriazine derivatives on Au(111) and Ag(111). The 2D networks are stabilized by N???H?C(sp) bonds and N???Br?C(sp) bonds to the triazine core. The structural properties and the binding energies of the supramolecular graphynes have been investigated by scanning tunneling microscopy in combination with density‐functional theory calculations. It is revealed that the N???Br?C(sp) bonds lead to significantly stronger bonded networks compared to the hydrogen‐bonded networks. A systematic analysis of the binding energies of triethynyltriazine and triethynylbenzene derivatives further demonstrates that the X3‐synthon, which is commonly observed for bromobenzene derivatives, is weaker than the X6‐synthon for our bromotriethynyl derivatives. 相似文献
93.
Jana M. Holthoff Elric Engelage Robert Weiss Stefan M. Huber 《Angewandte Chemie (International ed. in English)》2020,59(27):11150-11157
Halogen bonding is often described as being driven predominantly by electrostatics, and thus adducts between anionic halogen bond (XB) donors (halogen‐based Lewis acids) and anions seem counterintuitive. Such “anti‐electrostatic” XBs have been predicted theoretically but for organic XB donors, there are currently no experimental examples except for a few cases of self‐association. Reported herein is the synthesis of two negatively charged organoiodine derivatives that form anti‐electrostatic XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self‐association of the anionic XB donors was observed in solid‐state structures, resulting in dimers, trimers, and infinite chains. In addition, co‐crystals with halides were obtained, representing the first cases of halogen bonding between an organic anionic XB donor and a different anion. The bond lengths of all observed interactions are 14–21 % shorter than the sum of the van der Waals radii. 相似文献
94.
95.
96.
在氮气环境下用PVT方法生长氮化铝过程中,氮面和铝面由于表面化学性质不同,生长的主要化学反应速度存在差异。原子在生长表面的迁移能力不同造成单晶表面生长方式差异较大。在基本相同条件下(生长温度、生长温差、生长气压、类似的籽晶、同一台生长设备)进行了铝、氮面氮化铝单晶晶体生长。为了更明显地表现铝氮面的差异,将同一片籽晶分为两半,翻转其中一半让铝氮面同时生长。铝面生长较好的区域形成了明显的晶畴,而氮面生长时生长较好的部分出现了明显的生长台阶,并出现了晶畴边界被生长台阶湮灭的生长现象,进一步通过AFM观测到铝面生长台阶平整但被缺陷所阻隔,晶畴发育明显为各晶畴独立生长。氮面生长台阶没有铝面规则但连续性较强,在原来晶畴边界位置也出现了连续的生长台阶(或台阶簇)。所以籽晶质量不高时氮面生长更容易提高晶体质量,后续的XRD测量结果也证明了氮面生长后的晶体质量明显高于铝面生长的晶体质量。 相似文献
97.
Inertia-induced cross-stream migration has been recently exploited for precise position of particles in confined channel flows. In this work, a three-dimensional finite volume based immersed boundary method has been developed to study the lateral migration and hydrodynamic self-assembly of neutrally-buoyant particles in pressure-driven flows. Simulation results show that, in 2D channel flows, the equilibrium position for a circular particle is closer to the centreline for larger particle Reynolds number due to the increasing flow rate, while in 3D square duct flow, the equilibrium position for a spherical particle is near a face centre and is closer to the wall for larger particle Reynolds number. Self-assembly of a pair of particles is observed in 3D square duct flows but not in 2D channel flows. Mechanisms for the self-assembly are discussed. 相似文献
98.
Ryosuke Matsui Erina Niijima Tomomi Imai Hiroyuki Kobayashi Akiko Hori Azusa Sato Yuko Nakamura Osamu Kitagawa 《Molecules (Basel, Switzerland)》2022,27(7)
The halogen bond has been widely used as an important supramolecular tool in various research areas. However, there are relatively few studies on halogen bonding related to molecular chirality. 3-(2-Halophenyl)quinazoline-4-thione derivatives have stable atropisomeric structures due to the rotational restriction around an N-C single bond. In X-ray single crystal structures of the racemic and optically pure N-C axially chiral quinazoline-4-thiones, we found that different types of intermolecular halogen bonds (C=S⋯X) are formed. That is, in the racemic crystals, the intermolecular halogen bond between the ortho-halogen atom and sulfur atom was found to be oriented in a periplanar conformation toward the thiocarbonyl plane, leading to a syndiotactic zig-zag array. On the other hand, the halogen bond in the enantiomerically pure crystals was oriented orthogonally toward the thiocarbonyl plane, resulting in the formation of a homochiral dimer. These results indicate that the corresponding racemic and optically pure forms in chiral molecules are expected to display different halogen bonding properties, respectively, and should be separately studied as different chemical entities. 相似文献
99.
ZHAO Xue CHEN De-Zhan WANG Zhen HAO Zhao-Ling 《结构化学》2007,26(8):980-987
5,8-Hihydroxyl-1,4-naphthazarin was taken as a model compound to explore the effect of halogen substitution on intramolecular proton transfer process. Calculations indicate that the substitution in the R2- and R4-positions far away from the active region has much weaker influence on the IPT process than that in the R1-and R3-positions. IPT barriers for substitution in the R1-position are higher than that of parent molecule. However, it is quite reverse for substitution in the R3-position. The IPT process is a proton transfer process coupled with charge separation and coulombic interaction would be dominant during this process. As for naphthazarin, halogen substitution would decrease the quantum yields of O2 but increase those of 1O2. 相似文献
100.