全文获取类型
收费全文 | 1249篇 |
免费 | 20篇 |
国内免费 | 16篇 |
专业分类
化学 | 661篇 |
晶体学 | 5篇 |
力学 | 59篇 |
数学 | 302篇 |
物理学 | 258篇 |
出版年
2019年 | 16篇 |
2017年 | 13篇 |
2016年 | 22篇 |
2015年 | 19篇 |
2014年 | 19篇 |
2013年 | 39篇 |
2012年 | 48篇 |
2011年 | 46篇 |
2010年 | 44篇 |
2009年 | 22篇 |
2008年 | 40篇 |
2007年 | 55篇 |
2006年 | 40篇 |
2005年 | 35篇 |
2004年 | 17篇 |
2003年 | 23篇 |
2002年 | 22篇 |
2001年 | 29篇 |
2000年 | 34篇 |
1999年 | 23篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 32篇 |
1995年 | 24篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 22篇 |
1991年 | 17篇 |
1990年 | 16篇 |
1989年 | 13篇 |
1988年 | 13篇 |
1987年 | 24篇 |
1986年 | 14篇 |
1985年 | 22篇 |
1984年 | 12篇 |
1983年 | 19篇 |
1982年 | 25篇 |
1981年 | 19篇 |
1980年 | 19篇 |
1979年 | 21篇 |
1978年 | 28篇 |
1977年 | 18篇 |
1976年 | 15篇 |
1975年 | 13篇 |
1974年 | 25篇 |
1973年 | 25篇 |
1971年 | 12篇 |
1970年 | 15篇 |
1969年 | 10篇 |
1967年 | 8篇 |
排序方式: 共有1285条查询结果,搜索用时 15 毫秒
41.
42.
43.
Isaiah R. Speight Dr. Igor Huskić Dr. Mihails Arhangelskis Dr. Hatem M. Titi Dr. Robin S. Stein Prof. Timothy P. Hanusa Prof. Tomislav Friščić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1811-1818
The “disappearing polymorph” phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal–organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C−H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs. 相似文献
44.
A. F. Isakovic A. Stein J. B. Warren S. Narayanan M. Sprung A. R. Sandy K. Evans‐Lutterodt 《Journal of synchrotron radiation》2009,16(1):8-13
Motivated by the anticipated advantageous performance of diamond kinoform refractive lenses for synchrotron X‐ray radiation studies, this report focuses on progress in designing, nanofabricating and testing of their focusing performance. The method involves using lift‐off and plasma etching to reproduce a planar definition of numerically determined kinoform refractive optics. Tests of the focusing action of a diamond kinoform refractive lens at the APS 8‐ID‐I beamline demonstrate angular control of the focal spot. 相似文献
45.
46.
R. S. Stein M. Sethumadhavan R. A. Gaudiana T. Adams D. Guarrera S. K. Roy 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):517-531
Abstract At present we have strong evidence that several members of a series of wholly-aromatic, para-linked, rodlike polyamides, polyesters, and polyesteramides form molecular composites with certain flexible-chain, thermoplastic polymers over a wide range of compositions. This paper reports on the initial results of an investigation of intermolecular interactions using spectroscopy and various scattering techniques as well as characterization of some of the mechanical and optical properties of these materials. The composites are made by two techniques: 1) photo-polymerization of a homogeneous solution of a rodlike polymer in a monomer containing a photoinitiation; 2) solvent evaporation from homogeneous solutions of very limited combinations of solvent, rodlike polymers and flexible polymers. While both of these techniques produce optically clear, nonscattering films of various thicknesses over the entire compositional range, e.g., 1–99 wt% of rodlike polymer, the latter is generally more convenient and has been used extensively in this study. Optical and electron microscopy, wide angle light scattering, and spectroscopic and thermal analysis support the view that these polymer combinations are truly molecularly dispersed. 相似文献
47.
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
48.
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
49.
Thomas Auth Dr. Christopher J. Stein Prof. Richard A. J. O'Hair Prof. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(7):e202103130
High-valent tetraalkylcuprates(iii ) and -argentates(iii ) are key intermediates of copper- and silver-mediated C−C coupling reactions. Here, we investigate the previously reported contrasting reactivity of [RMiii Me3]− complexes (M=Cu, Ag and R=allyl) with energy-dependent collision-induced dissociation experiments, advanced quantum-chemical calculations and kinetic computations. The gas-phase fragmentation experiments confirmed the preferred formation of the [RCuMe]− anion upon collisional activation of the cuprate(iii ) species, consistent with a homo-coupling reaction, whereas the silver analogue primarily yielded [AgMe2]−, consistent with a cross-coupling reaction. For both complexes, density functional theory calculations identified one mechanism for homo coupling and four different ones for cross coupling. Of these pathways, an unprecedented concerted outer-sphere cross coupling is of particular interest, because it can explain the formation of [AgMe2]− from the argentate(iii ) species. Remarkably, the different C−C coupling propensities of the two [RMiii Me3]− complexes become only apparent when properly accounting for the multi-configurational character of the wave function for the key transition state of [RAgMe3]−. Backed by the obtained detailed mechanistic insight for the gas-phase reactions, we propose that the previously observed cross-coupling reaction of the silver complex in solution proceeds via the outer-sphere mechanism. 相似文献
50.
Ironside MS Stein RS Duer MJ 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(1):49-55
A key problem in solid-state NMR is resolving overlapping isotropic signals. We present here a two-dimensional method which can enable sites with the same isotropic chemical shift to be distinguished according to their chemical shift anisotropy and asymmetry. The method involves correlating sideband spectra at different effective spinning rates using CSA-amplification pulse sequences. The resulting two-dimensional correlation pattern allows very accurate determination of the chemical shift principal values in addition to the recovery of parameters for two overlapping patterns which allows the resolution of overlapping signals. 相似文献