全文获取类型
收费全文 | 5154篇 |
免费 | 191篇 |
国内免费 | 12篇 |
专业分类
化学 | 3686篇 |
晶体学 | 40篇 |
力学 | 91篇 |
数学 | 494篇 |
物理学 | 1046篇 |
出版年
2023年 | 30篇 |
2022年 | 46篇 |
2021年 | 51篇 |
2020年 | 71篇 |
2019年 | 59篇 |
2018年 | 44篇 |
2017年 | 37篇 |
2016年 | 165篇 |
2015年 | 145篇 |
2014年 | 126篇 |
2013年 | 232篇 |
2012年 | 275篇 |
2011年 | 318篇 |
2010年 | 210篇 |
2009年 | 143篇 |
2008年 | 279篇 |
2007年 | 267篇 |
2006年 | 248篇 |
2005年 | 223篇 |
2004年 | 223篇 |
2003年 | 178篇 |
2002年 | 170篇 |
2001年 | 134篇 |
2000年 | 92篇 |
1999年 | 87篇 |
1998年 | 55篇 |
1997年 | 63篇 |
1996年 | 68篇 |
1995年 | 63篇 |
1994年 | 48篇 |
1993年 | 48篇 |
1992年 | 76篇 |
1991年 | 41篇 |
1990年 | 62篇 |
1989年 | 39篇 |
1988年 | 62篇 |
1987年 | 38篇 |
1986年 | 42篇 |
1985年 | 58篇 |
1984年 | 52篇 |
1983年 | 36篇 |
1982年 | 36篇 |
1981年 | 42篇 |
1980年 | 48篇 |
1979年 | 40篇 |
1978年 | 40篇 |
1977年 | 44篇 |
1976年 | 29篇 |
1975年 | 32篇 |
1967年 | 26篇 |
排序方式: 共有5357条查询结果,搜索用时 0 毫秒
101.
Brett D. Jones Jessica R. Chittum Sehmuz Akalin Asta B. Schram Jonathan Fink Christine Schnittka Michael A. Evans Carol Brandt 《School science and mathematics》2015,115(8):404-415
The primary purpose of this study was to examine the ways in which a 12‐week afterschool science and engineering program affected middle school students' motivation to engage in science and engineering activities. We used current motivation research and theory as a conceptual framework to assess 14 students' motivation through questionnaires, structured interviews, and observations. Students reported that during the activities they perceived that they were empowered to make choices in how to complete things, the activities were useful to them, they could succeed in the activities, they enjoyed and were interested in the hands‐on activities and some presentations, they felt cared for by the facilitators and received help when they were stuck or confused, and they put forth effort. Based on our examination of data across our three data sources, we identified motivating opportunities that were provided to students during the activities. These motivating opportunities can serve as examples to help both formal and informal science educators better connect motivation theory to practice so that they can create motivating opportunities for students. Furthermore, this study provides a methodological example of how students' motivation can be examined during the context of authentic science and engineering instruction. 相似文献
102.
Bessenrodt Christine; Malle Gunter; Olsson Jorn B. 《Journal London Mathematical Society》2006,73(2):493-505
We investigate the problem of finding a set of prime divisorsof the order of a finite group, such that no two irreduciblecharacters are in the same p-block for all primes p in the set.Our main focus is on the simple and quasi-simple groups. Forresults on the alternating and symmetric groups and their doublecovers, some combinatorial results on the cores of partitionsare proved, which may be of independent interest. We also studythe problem for groups of Lie type. The sporadic groups (andtheir relatives) are checked using GAP. 相似文献
103.
A series of new amphiphilic polymers containing various amounts of N-methyl-4-vinylpyridinium units as hydrophilic part and N-dodecylacrylamide or N-decylacrylamide units as hydrophobic part have been prepared by quaternizing the cognate copolymers. Their behaviour in aqueous solutions has been studied by viscometry, as well as by fluorescence spectroscopy and tensiometry. Results are discussed in detail and a conformational model of the macromolecules at the interface (water/methylcyclohexane) is proposed in relation to the formation of microdomains in the aqueous media. 相似文献
104.
A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure. 相似文献
105.
Frontispiece: Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes 下载免费PDF全文
106.
Volkers PI Boyke CA Chen J Rauchfuss TB Whaley CM Wilson SR Yao H 《Inorganic chemistry》2008,47(15):7002-7008
This report describes routes to iron dithiolato carbonyls that do not require preformed iron carbonyls. The reaction of FeCl 2, Zn, and Q 2S 2C n H 2 n (Q (+) = Na (+), Et 3NH (+)) under an atmosphere of CO affords Fe 2(S 2C n H 2 n )(CO) 6 ( n = 2, 3) in yields >70%. The method was employed to prepare Fe 2(S 2C 2H 4)( (13)CO) 6. Treatment of these carbonylated mixtures with tertiary phosphines, instead of Zn, gave the ferrous species Fe 3(S 2C 3H 6) 3(CO) 4(PR 3) 2, for R = Et, Bu, and Ph. Like the related complex Fe 3(SPh) 6(CO) 6, these compounds consist of a linear arrangement of three conjoined face-shared octahedral centers. Omitting the phosphine but with an excess of dithiolate, we obtained the related mixed-valence triiron species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (-). The highly reducing all-ferrous species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (2-) is implicated as an intermediate in this transformation. Reactive forms of iron, prepared by the method of Rieke, also combined with dithiols under a CO atmosphere to give Fe 2(S 2C n H 2 n )(CO) 6 in modest yields under mild conditions. Studies on the order of addition indicate that ferrous thiolates are formed prior to the onset of carbonylation. Crystallographic characterization demonstrated that the complexes Fe 3(S 2C 3H 6) 3(CO) 4(PEt 3) 2 and PBnPh 3[Fe 3(S 2C 3H 6) 4(CO) 4] feature high-spin ferrous and low-spin ferric as the central metal, respectively. 相似文献
107.
Reuther G Tan KT Vogel A Nowak C Arnold K Kuhlmann J Waldmann H Huster D 《Journal of the American Chemical Society》2006,128(42):13840-13846
Many proteins involved in signal transduction are equipped with covalently attached lipid chains providing a hydrophobic anchor targeting these molecules to membranes. Despite the considerable biological significance of this membrane binding mechanism for 5-10% of all cellular proteins, to date very little is known about structural and dynamical features of lipidated membrane binding domains. Here we report the first comprehensive study of the molecular dynamics of the C-terminus of membrane-associated full-length lipidated Ras protein determined by solid-state NMR. Fully functional lipid-modified N-Ras protein was obtained by chemical-biological synthesis ligating the expressed water soluble N-terminus with a chemically synthesized (2)H or (13)C labeled lipidated heptapeptide. Dynamical parameters for the lipid chain modification at Cys 181 were determined from static (2)H NMR order parameter and relaxation measurements. Order parameters describing the amplitude of motion in the protein backbone and the side chain were determined from site-specific measurements of (1)H-(13)C dipolar couplings for all seven amino acids in the membrane anchor of Ras. Finally, the correlation times of motion were determined from temperature dependent relaxation time measurements and analyzed using a modified Lipari Szabo approach. Overall, the C-terminus of Ras shows a versatile dynamics with segmental fluctuations and axially symmetric overall motions on the membrane surface. In particular, the lipid chain modifications are highly flexible in the membrane. 相似文献
108.
Schwan KC Adolf A Thoms C Zabel M Timoshkin AY Scheer M 《Dalton transactions (Cambridge, England : 2003)》2008,(37):5054-5058
The halogenation of Lewis-acid/base-stabilised phosphanylboranes () and arsanylboranes () with CX(4) (X = Cl, Br) leads selectively to the substitution of both protons at the pentel atom and the new compounds [(CO)(5)W(X(2)PBH(2).NMe(3))] (: X = Cl, : X = Br) and [(CO)(5)W(X(2)AsBH(2).NMe(3))] (: X = Cl, : X = Br), respectively, are obtained. The new products were comprehensively characterised by spectroscopic methods and by X-ray crystallography. While compounds and show an antiperiplanar arrangement of the Lewis acid (W(CO)(5)) and the Lewis base (NMe(3)) in the solid state, a synclinal arrangement in and , respectively, was observed. Computational calculations of the optimised antiperiplanar and synclinal geometries of the compounds and in the gas phase slightly favour the antiperiplanar arrangement of the Lewis acid and the Lewis base for both compounds. 相似文献
109.
Bibal C Santini CC Chauvin Y Vallée C Olivier-Bourbigou H 《Dalton transactions (Cambridge, England : 2003)》2008,(21):2866-2870
A new family of hydroxytris(pentafluorophenyl)borate anions [B(C6F5)3OH](-) associated with organic and aprotic cations c+ (imidazolium, pyrrolidinium and phosphonium) has been prepared by a general one-pot synthesis that implies the chloride borate analogues [B(C6F5)3Cl](-)[c]+. The [c]+[B(C6F5)3OH](-) salts have been isolated and fully characterized. The borate anion [B(C6F5)3OH](-) has been shown to protonate the Zr-Me bond in the Cp2ZrMe2 complex forming CH4 and the first published example of anionic [Cp2Zr(Me)OB(C6F5)3](-) species. Standard spectroscopic methods demonstrate the covalent character of the Zr metal center and the anionic character of the boron atom. This protonolysis methodology using [B(C6F5)3OH](-) anion affords a new route for the incorporation of a covalently bonded anionic functionality on organometallic complexes. This provides a new way to immobilize transition metal complexes in ionic liquids. 相似文献
110.
Becker K Da Como E Feldmann J Scheliga F Csanyi ET Tretiak S Lupton JM 《The journal of physical chemistry. B》2008,112(16):4859-4864
Single oligo(phenylene-vinylene) molecules constitute model systems of chromophores in disordered conjugated polymers and can elucidate how the actual conformation of an individual chromophore, rather than that of an overall polymer chain, controls its photophysics. Single oligomers and polymer chains display the same range of spectral properties. Even heptamers support pi-electron conjugation across approximately 80 degrees curvature, as revealed by the polarization anisotropy in excitation and supported by quantum chemical calculations. As the chain becomes more deformed, the spectral linewidth at low temperatures, often interpreted as a sign of aggregation, increases up to 30-fold due to a reduction in photophysical stability of the molecule and an increase in random spectral fluctuations. The conclusions aid the interpretation of results from single-chain Stark spectroscopy in which large static dipoles were only observed in the case of narrow transition lines. These narrow transitions originate from extended chromophores in which the dipoles induced by backbone substituents do not cancel out. Chromophores in conjugated polymers are often thought of as individual linear transition dipoles, the sum of which make up the polymer's optical properties. Our results demonstrate that, at least for phenylene-vinylenes, it is the actual shape of the individual chromophore rather than the overall chromophoric arrangement and form of the polymer chain that dominates the spectroscopic properties. 相似文献