全文获取类型
收费全文 | 1302篇 |
免费 | 163篇 |
国内免费 | 96篇 |
专业分类
化学 | 940篇 |
晶体学 | 3篇 |
力学 | 32篇 |
综合类 | 10篇 |
数学 | 327篇 |
物理学 | 249篇 |
出版年
2024年 | 4篇 |
2023年 | 19篇 |
2022年 | 31篇 |
2021年 | 27篇 |
2020年 | 63篇 |
2019年 | 64篇 |
2018年 | 39篇 |
2017年 | 41篇 |
2016年 | 65篇 |
2015年 | 60篇 |
2014年 | 73篇 |
2013年 | 123篇 |
2012年 | 100篇 |
2011年 | 86篇 |
2010年 | 86篇 |
2009年 | 64篇 |
2008年 | 80篇 |
2007年 | 68篇 |
2006年 | 69篇 |
2005年 | 49篇 |
2004年 | 44篇 |
2003年 | 40篇 |
2002年 | 30篇 |
2001年 | 17篇 |
2000年 | 24篇 |
1999年 | 21篇 |
1998年 | 28篇 |
1997年 | 33篇 |
1996年 | 14篇 |
1995年 | 15篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 13篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1972年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有1561条查询结果,搜索用时 15 毫秒
101.
近年路易斯酸B(C6F5)3催化的醛酮还原及胺化反应研究表明,缺电子的路易斯酸B(C6F5)3也可以作为一种"耐水"的催化剂在"有水"条件下进行催化反应.这些研究成果对进一步扩展受限路易斯酸碱对(FLPs)化学的研究领域和应用前景提供了更多可能.本文以硅烷作为还原剂,在路易斯酸B(C6F5)3催化下可在温和条件下实现醛与烷基羟胺类化合物的直接还原胺化反应,并且在还原过程中N-O键不会发生断裂,可中等至高产率地制备各种烷氧基取代的羟胺衍生物.对反应机理研究发现,在中性条件下苯甲醛与苄氧基羟胺的反应仅得到缩合中间产物肟醚,而在HCl或过量H2O的参与下苯甲醛与苄氧基羟胺的直接还原胺化均可顺利进行;对反应机理的研究表明苄氧基羟胺会与路易斯酸硼烷在过量H2O的参与下发生质子化,在硅烷的作用下转化成具有一定还原性的"硼氢化胺盐"活性中间体并进而促使中间产物肟醚的还原.对醛与羟胺的直接还原胺化反应研究表明,在"有水"条件下路易斯酸B(C6F5)3不仅仅是一种"耐水"的催化剂,在某些反应中水可能直接影响着催化反应,尤其是对醛酮的直接还原胺化反应.因此,继续深入研究有"水"条件下路易斯酸硼烷参与的催化反应机理不仅对FLPs化学的发展至关重要,对其他相应催化体系的研究也具有重要的参考价值. 相似文献
102.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(7):789-796
Three new metal(II)–cytosine (Cy)/5‐fluorocytosine (5FC) complexes, namely bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN3)diiodidocadmium(II) or bis(cytosine)diiodidocadmium(II), [CdI2(C4H5N3O)2], ( I ), bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN3)bis(nitrato‐κ2O,O′)cadmium(II) or bis(cytosine)bis(nitrato)cadmium(II), [Cd(NO3)2(C4H5N3O)2], ( II ), and (6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one‐κN3)aquadibromidozinc(II)–6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one (1/1) or (6‐amino‐5‐fluorocytosine)aquadibromidozinc(II)–4‐amino‐5‐fluorocytosine (1/1), [ZnBr2(C4H5FN3O)(H2O)]·C4H5FN3O, ( III ), have been synthesized and characterized by single‐crystal X‐ray diffraction. In complex ( I ), the CdII ion is coordinated to two iodide ions and the endocyclic N atoms of the two cytosine molecules, leading to a distorted tetrahedral geometry. The structure is isotypic with [CdBr2(C4H5N3O)2] [Muthiah et al. (2001). Acta Cryst. E 57 , m558–m560]. In compound ( II ), each of the two cytosine molecules coordinates to the CdII ion in a bidentate chelating mode via the endocyclic N atom and the O atom. Each of the two nitrate ions also coordinates in a bidentate chelating mode, forming a bicapped distorted octahedral geometry around cadmium. The typical interligand N—H…O hydrogen bond involving two cytosine molecules is also present. In compound ( III ), one zinc‐coordinated 5FC ligand is cocrystallized with another uncoordinated 5FC molecule. The ZnII atom coordinates to the N(1) atom (systematic numbering) of 5FC, displacing the proton to the N(3) position. This N(3)—H tautomer of 5FC mimics N(3)‐protonated cytosine in forming a base pair (via three hydrogen bonds) with 5FC in the lattice, generating two fused R22(8) motifs. The distorted tetrahedral geometry around zinc is completed by two bromide ions and a water molecule. The coordinated and nonccordinated 5FCs are stacked over one another along the a‐axis direction, forming the rungs of a ladder motif, whereas Zn—Br bonds and N—H…Br hydrogen bonds form the rails of the ladder. The coordinated water molecules bridge the two types of 5FC molecules via O—H…O hydrogen bonds. The cytosine molecules are coordinated directly to the metal ion in each of the complexes and are hydrogen bonded to the bromide, iodide or nitrate ions. In compound ( III ), the uncoordinated 5FC molecule pairs with the coordinated 5FC ligand through three hydrogen bonds. The crystal structures are further stabilized by N—H…O, N—H…N, O—H…O, N—H…I and N—H…Br hydrogen bonds, and stacking interactions. 相似文献
103.
《International journal of quantum chemistry》2018,118(17)
The derivative of molecular orbitals (MO) energies with respect to a bond length (dynamic orbital force [DOF]) is used to estimate the bonding/antibonding character of valence MOs along this bond, with a focus on lone pair MOs, in a series of small molecules: AH (A = F, Cl, Br), AH2 (A = O, S, Se), AX3 (A = N, P, As; X = H, F), and H2CO. The HOMO DOF agrees with the calculated variation of bond length and force constant in the corresponding ground state cation, and of bond length variation by protonation. These results also agree with available experimental data. It is worthy to note that the p‐type HOMOs in AH and AH2 are found bonding. The lone pair MO is bonding in NH3, while it is antibonding in PH3, AsH3, and AF3. 相似文献
104.
105.
Frustrated Lewis pair chemistry has taken a steep development in the recent years. It offers possibilities of developing new variants of known reactions and of finding new chemical transformations. This is demonstrated and described by the recently developed FLP‐formylborane chemistry, which has led to the formation of the unique (η2‐formylborane)FLP adducts and opened a way of preparing a genuine formylborane compound, which shows an interesting follow‐up chemistry. FLPs have helped finding phosphorus analogues of the enamine Stork reaction and the Claisen reaction. These reactions lead to new organophosphorus compounds and they make new phosphane/borane systems available. P/B FLPs add to a variety of small main group element oxides. They undergo 1,2‐addition reactions to CO2, SO2 and other heterocumulenes and they feature unique 1,1‐addition reactions to carbon monoxide, to isonitriles and even to nitric oxide (NO), the latter yielding examples of a new class of persistent nitroxide radicals, the FLPNO nitroxyls. Eventually, some remarkable radical reactions of FLPs and related compounds are briefly mentioned. 相似文献
106.
107.
广义Stirling数偶的理论及应用 总被引:3,自引:2,他引:3
The object of this expository paper is to sum up several results concerning generalized Stirling number (GSN) pairs investigated earlier by the author. Also expounded in some detail are two kinds of extended GSN pairs with applications (illustrative examples). 相似文献
108.
苏郇立 《纯粹数学与应用数学》2010,26(4):608-614
设X为紧度量空间,T为半群,本文研究了动力系统(X,T)上Li-Yorke对的存在性问题,证明了当(X,T)拓扑可迁且包含周期点时,在(X,T)上存在无限scrambled集.另外,列举了一些不包含Li-Yorke对的动力系统. 相似文献
109.
Dragomir
.
okovi 《组合设计杂志》2010,18(4):254-259
We show that 138 odd values of n<10000 for which a Hadamard matrix of order 4n exists have been overlooked in the recent handbook of combinatorial designs. There are four additional odd n=191, 5767, 7081, 8249 in that range for which Hadamard matrices of order 4n exist. There is a unique equivalence class of near‐normal sequences NN(36), and the same is true for NN(38) and NN(40). This means that the Yang conjecture on the existence of near‐normal sequences NN(n) has been verified for all even n⩽40, but it still remains open. © 2010 Wiley Periodicals, Inc. J Combin Designs 18: 254–259, 2010 相似文献
110.