全文获取类型
收费全文 | 879篇 |
免费 | 36篇 |
专业分类
化学 | 790篇 |
晶体学 | 2篇 |
力学 | 16篇 |
数学 | 22篇 |
物理学 | 85篇 |
出版年
2022年 | 4篇 |
2021年 | 11篇 |
2020年 | 35篇 |
2019年 | 20篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 24篇 |
2015年 | 20篇 |
2014年 | 21篇 |
2013年 | 35篇 |
2012年 | 48篇 |
2011年 | 55篇 |
2010年 | 37篇 |
2009年 | 22篇 |
2008年 | 66篇 |
2007年 | 57篇 |
2006年 | 53篇 |
2005年 | 48篇 |
2004年 | 42篇 |
2003年 | 23篇 |
2002年 | 24篇 |
2001年 | 14篇 |
2000年 | 24篇 |
1999年 | 14篇 |
1998年 | 11篇 |
1997年 | 6篇 |
1996年 | 15篇 |
1995年 | 9篇 |
1994年 | 12篇 |
1993年 | 16篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1973年 | 8篇 |
1972年 | 3篇 |
1967年 | 3篇 |
1942年 | 2篇 |
1866年 | 7篇 |
排序方式: 共有915条查询结果,搜索用时 359 毫秒
61.
62.
63.
Muhammad Nawaz Tahir Markus Messerschmidt Michael Klein Victor Martinez Patrick Theato Nadine Metz Sonngard Hartmann Ute Kolb Vadim Ksenofontov Franz Renz Wolfgang Tremel 《Polyhedron》2009,28(9-10):1728-1733
The precursor [FeIII(L)Cl (L = N,N′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN)8]4? yields a star shaped nona-nuclear cluster, [MoIV{(CN)FeIII(L)}8]Cl4. This Fe8Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mössbauer spectroscopy. This molecule was deposited on TiO2 nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis spectroscopy (high-resolution) transmission electron microscopy ((HR)TEM) and Mössbauer spectroscopy. High- and low-temperature Mössbauer spectra indicate that the spin state transition of the free cluster molecules is preserved after surface binding. The above results emphasize the possibility of fabricating molecule-based low-dimensional structures by using traditional bottom-up approaches based on the electrostatic interaction between the cluster cations and polymer functionalized nanowires. These results can be generalized for the application to both charged and non-charged molecules. 相似文献
64.
Tomohiro Hirano Shuhei Masuda Shou Nasu Koichi Ute Tsuneyuki Sato 《Journal of polymer science. Part A, Polymer chemistry》2009,47(4):1192-1203
Radical polymerization of N,N‐dimethylacrylamide (DMAAm) was investigated in the presence of tartrates, such as diethyl L ‐tartrate, diisopropyl L ‐tartrate, and di‐n‐butyl L ‐tartrate, in toluene at low temperatures. Syndiotactic polymers were obtained in the presence of tartrates, whereas isotactic polymers were obtained in the absence of tartrates. The syndiotactic‐specificity increased with increasing amount of tartrates and with decreasing polymerization temperature. NMR analysis suggested that DMAAm and tartrates formed a 1:1 complex through double hydrogen bonding. A mechanism for the syndiotactic‐specific radical polymerization of DMAAm is proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1192–1203, 2009 相似文献
65.
Tomohiro Hirano Shou Nasu Akihiro Morikami Koichi Ute 《Journal of polymer science. Part A, Polymer chemistry》2009,47(23):6534-6539
Radical polymerization of N‐methylacrylamide (NMAAm), N,N‐dimethylacrylamide (DMAAm), and N‐methyl‐N‐phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereospecificity of the radical polymerization of acrylamide derivatives depended on the N‐substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534–6539, 2009 相似文献
66.
ABSTRACTHere we report on the synthesis and mesomorphic properties of a series of imino-linked dimeric molecules. In order to improve our understanding of the structure–NTB phase correlations, we have studied the impact of geometric and electronic factors arising from varying mesogenic units, different spacer lengths and from the ratio (n/m) between the lengths of terminal chains (n) and spacer (m). From the perspective of the molecular geometry, the results show that the stability of the NTB phase results from increasing effective molecular bending and with the broadening of the mesogenic unit, in particular near the spacer, and that the n/m ratio plays a substantial role in conjunction with the specific mesogenic unit. A computational study of the electronic properties shows that a broadening of the mesogenic core in the vicinity of the spacer is associated with an increased anisotropy of the electrostatic potential distribution. Within a given series of materials our study suggests that the incidence of the NTB phase and its thermal stability are governed by the synergy of specific geometrical factors and the anisotropy of the electrostatic potential distribution of the mesogenic core. 相似文献
67.
The push-pull characters of a large series of donor-acceptor substituted azo dyes—71 structures in all—have been quantified by the NN double bond lengths, dNN, the 15N NMR chemical shift differences, Δδ15N, of the two nitrogen atoms and the quotient, π∗/π, of the occupations of the antibonding π∗, and bonding π orbitals of this partial NN double bond. The excellent correlation of the occupation quotients with the bond lengths strongly infers that both π∗/π and dNN are excellent parameters for quantifying charge alternation in the push-pull chromophore and the molecular hyperpolarizability, β0, of these compounds. By this approach, selected compounds can be appropriately considered as viable candidates for nonlinear optical (NLO) applications. 相似文献
68.
Mario Barbatti Jiří Pittner Marek Pederzoli Ute Werner Roland Mitrić Vlasta Bonačić-Koutecký Hans Lischka 《Chemical physics》2010
Non-adiabatic dynamics simulations were performed for pyrrole at time-dependent density functional theory level using the trajectory surface hopping approach. Initial conditions were prepared based on the UV-absorption spectrum so as to simulate monochromatic absorption in three distinct spectral regions. The results showed predominance of the NH-stretch mechanism for excited-state relaxation. With increasing initial energy, however, other mechanisms are activated as well, even though they still occurred for a minor fraction of the trajectories. Dynamics starting at the origin of the absorption spectrum exhibited internal conversion to the ground state with a time constant of 20 fs. In contrast, dynamics starting at higher energies gave rise to much longer time constants for internal conversion near 200 fs. 相似文献
69.
70.
Wang X Zeng L Wiens M Schlossmacher U Jochum KP Schröder HC Müller WE 《Micron (Oxford, England : 1993)》2011,42(5):401-411
In the present study we examined material from the Ashikule Basin of Tibet. Chemical analyses were performed by use of energy dispersive X-ray spectroscopy and electron probe microanalysis to clarify whether the varnish layers that had developed on the surface of the rhyolite are indeed composed of varnish bodies and silica glaze. Electron microscopic analyses revealed that the surface of the varnish is covered both by filamentous hyphae bacterial and cocci-shaped forms. Within the varnish mineral layer in those samples two forms of bacteria-like microorganisms exist; cocci as tightly packed bacterial aggregates [within varnish bodies], and bacillus-like microorganisms [within the varnish matrix, that surrounds the varnish bodies]. The bacillus-like forms are embedded in a network of filaments that have diameters between 35 and 45 nm. These bacilli with the surrounding filaments are assumed to have been involved in biofilm formation (synthesis of extracellular polymeric substances) prior to their live burial. We concluded that the formation of the varnish layers was for the most part biogenically driven by microorganisms. 相似文献