全文获取类型
收费全文 | 255篇 |
免费 | 7篇 |
国内免费 | 3篇 |
专业分类
化学 | 180篇 |
晶体学 | 1篇 |
力学 | 16篇 |
数学 | 25篇 |
物理学 | 43篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2022年 | 2篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 4篇 |
2014年 | 14篇 |
2013年 | 8篇 |
2012年 | 25篇 |
2011年 | 12篇 |
2010年 | 18篇 |
2009年 | 13篇 |
2008年 | 18篇 |
2007年 | 12篇 |
2006年 | 15篇 |
2005年 | 18篇 |
2004年 | 10篇 |
2003年 | 15篇 |
2002年 | 19篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1896年 | 1篇 |
排序方式: 共有265条查询结果,搜索用时 15 毫秒
1.
Recent electron scattering experiments on the few-nucleon systems are presented. The interpretation of the data in terms of nucleon and meson degrees of freedom is discussed.Invited talk to the symposium Mesons and Light Nuclei IV, Bechyn, Czechoslovakia, September 5–10, 1988. 相似文献
2.
3.
The ideal way to prepare efficient, yet robust stationary phases for microanalytical high-resolution methods such as capillary chromatography and electrochromatography remains to be defined. In this contribution a one step sol-gel process is proposed for the production of monolithic, macroporous nanocomposite phases in fused silica capillaries, which require no additional derivatization, since they already bear the interactive (C8) moieties. The effect of the catalyst, the water content, the pH, as well as that of certain additives on monolith formation and porosity is investigated. Volume shrinkage and a tendency to crack were the major obstacles to overcome. Homogeneous stationary phases could be produced by applying a pH gradient during sol formation, thereby changing the catalytic principle from acidic (0.1 M HCl) to basic (gradual formation of OH– as a consequence of the hydrolysis of N-methylformamide). Gelation/coacervation of suchgels could be induced by the addition of N,N-diethylamine. The water content during sol formation was determined as decisive for pore formation, with 250% of the amount theoretically needed for complete hydrolysis of all precursors giving optimal results. The volume shrinkage problem during xerogel formation was resolved by integrating dialkyldialkoxysilane units (dimethyldiethoxysilane 35 mol%) into the silica network. 相似文献
4.
The conventional Gross reaction for the formylation of the tetrapropoxythiacalix[4]arene using TiCl4 affords the 18-(chloromethyl)-28-hydroxy-25,26,27-tripropoxythiacalix[4]arene substituted in the meta-position of the macrocycle. The p-tetraformyl-tetrapropoxythiacalix[4]arene, which is an interesting intermediate to the upper-rims functionalization of thiacalixarenes, was prepared with a very good yield using BuLi and N-formylpiperidine. 相似文献
5.
6.
7.
A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII 下载免费PDF全文
Henrique F. Carvalho Dr. João M. C. Teixeira Carlos T. B. Paula Prof. Petr Hermann Dr. Carlos Platas‐Iglesias Prof. Stephane Petoud Prof. Éva Tóth Prof. Carlos F. G. C. Geraldes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14834-14845
We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid= L1 ) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the GdIII complex may be sufficient for biological applications. A detailed structural study of the complexes by 1H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the 1H NMR paramagnetic shifts induced by YbIII. The water‐exchange rate of the GdIII complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$ =6.7×106 s?1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of LnIII ions emitting in both the visible (EuIII and TbIII) and NIR (PrIII, NdIII, HoIII, YbIII) spectral regions. The emission quantum yield determined for the YbIII complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$ =7.3(1)×10?3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI. 相似文献
8.
Qun Dang Zhibo Zhang Bingyu Tang Yang Song Ling Wu Tongqian Chen Stephane Bogen Vinay Girijavallabhan David B. Olsen Peter T. Meinke 《Tetrahedron letters》2014
To discover novel nucleosides as potential antiviral agents, 2′-spirolactam and 2′-spiropyrrolidine-containing nucleoside analogs were envisioned. Efficient synthetic routes were developed with an epoxide opening as the key step to establish the quaternary center at the 2′ position, leading to the design and synthesis of uridine analogs 8 and 21, prodrugs 13–16, and cytidine analog 11. 相似文献
9.
Qun Dang Zhibo Zhang Shuangsheng He Yaohong Liu Tongqian Chen Stephane Bogen Vinay Girijavallabhan David B. Olsen Peter T. Meinke 《Tetrahedron letters》2014
To discover novel nucleosides as potential antiviral agents, 4′-spirocyclic phosphono-nucleosides were designed to mimic the monophosphate of R-1479, a known nucleoside inhibitor of HCV NS5B. Bypassing the first kinase step to nucleoside monophosphate is viewed as advantageous since this phosphorylation is often observed as the rate-limiting transformation to the active NTP for many nucleosides. Efficient synthetic routes were developed with a triphenylphosphine–iodine cyclization reaction as the key step to form the tetrahydrofuran 4′-spirocycle. The desired 4′-spirocyclic phosphono-cytidine analogs 12a, 12b, and 16 were prepared in 11 steps. 相似文献
10.
We conjecture that the balanced complete bipartite graph K⌊n/2⌋,⌈n/2⌉ contains more cycles than any other n-vertex triangle-free graph, and we make some progress toward proving this. We give equivalent conditions for cycle-maximal triangle-free graphs; show bounds on the numbers of cycles in graphs depending on numbers of vertices and edges, girth, and homomorphisms to small fixed graphs; and use the bounds to show that among regular graphs, the conjecture holds. We also consider graphs that are close to being regular, with the minimum and maximum degrees differing by at most a positive integer k. For k=1, we show that any such counterexamples have n≤91 and are not homomorphic to C5; and for any fixed k there exists a finite upper bound on the number of vertices in a counterexample. Finally, we describe an algorithm for efficiently computing the matrix permanent (a #P-complete problem in general) in a special case used by our bounds. 相似文献