全文获取类型
收费全文 | 844篇 |
免费 | 28篇 |
专业分类
化学 | 568篇 |
晶体学 | 11篇 |
力学 | 18篇 |
数学 | 90篇 |
物理学 | 185篇 |
出版年
2021年 | 7篇 |
2020年 | 7篇 |
2017年 | 7篇 |
2016年 | 16篇 |
2015年 | 12篇 |
2014年 | 11篇 |
2013年 | 29篇 |
2012年 | 34篇 |
2011年 | 30篇 |
2010年 | 22篇 |
2009年 | 20篇 |
2008年 | 41篇 |
2007年 | 34篇 |
2006年 | 38篇 |
2005年 | 57篇 |
2004年 | 27篇 |
2003年 | 25篇 |
2002年 | 28篇 |
2001年 | 15篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 22篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 19篇 |
1992年 | 9篇 |
1991年 | 13篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 22篇 |
1983年 | 15篇 |
1982年 | 14篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 15篇 |
1976年 | 11篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 11篇 |
1972年 | 5篇 |
1968年 | 7篇 |
1966年 | 9篇 |
排序方式: 共有872条查询结果,搜索用时 31 毫秒
71.
Brajendra K. Singh Christian V. Stevens Davy R.J. Acke Erik V. Van der Eycken 《Tetrahedron letters》2009,50(1):15-4274
A continuous flow procedure has been elaborated for the copper(II)-mediated N- and O-arylation of a range of compounds with arylboronic acids using a commercial microreactor setup. The compounds could be continuously generated in good yields paving the way for efficient scalability. 相似文献
72.
A. Tschirsch Elmar Goldberg und A. B. Stevens 《Fresenius' Journal of Analytical Chemistry》1907,46(5):347-349
Ohne Zusammenfassung 相似文献
73.
74.
ABSTRACTLiquid-crystalline dimers and bimesogens have attracted much attention due to their propensity to exhibit the spontaneously chiral twist-bend mesophase (NTB), most often by dimers with methylene spacers. Despite their relative ease of synthesis, the number of ether-linked twist-bend materials significantly lags behind those of methylene-linked compounds. In this work, we have prepared and studied a range of ether-linked bimesogens homologous in structure to the FFO9OCB; as with methylene-linked systems, it appears that it is molecular topology and the gross molecular shape that are the primary drivers for the formation of this phase of matter. Dimers and bimesogens are well studied within the context of the twist-bend phase; however, present understanding of this mesophase in oligomeric systems lags far behind. We report our recent efforts to prepare further examples of oligomeric twist-bend nematogens, including further examples of our ‘n+1’ methodology, which may allow the synthesis of high-purity, monodisperse materials of any given length to be prepared. We have observed that there is a tendency for these materials to exhibit highly ordered soft-crystalline mesophases as opposed to the twist-bend phase. 相似文献
75.
Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given. 相似文献
76.
Given a totally real field F and a prime integer p which is unramified in F, we construct p-adic families of overconvergent Hilbert modular forms (of non-necessarily parallel weight) as sections of, so called, overconvergent Hilbert modular sheaves. We prove that the classical Hilbert modular forms of integral weights are overconvergent in our sense. We compare our notion with Katz’s definition of p-adic Hilbert modular forms. For F = ?, we prove that our notion of (families of) overconvergent elliptic modular forms coincides with those of R. Coleman and V. Pilloni. 相似文献
77.
Naijue Zhu Danielle Lightsey Jiawang Liu Maryam Foroozesh Kathleen M. Morgan Edwin D. Stevens Cheryl L. Klein Stevens 《Journal of chemical crystallography》2010,40(4):343-352
Abstract
The single-crystal X-ray structures and in vivo activities of three aryl acetylenic inhibitors of cytochromes P450 1A1, 1A2, 2A6, and 2B1 have been determined and are reported herein. These are 1-ethynylpyrene, 1-propynylpyrene, and 4-propynylpyrene. To investigate electronic influences on the mechanism of enzyme inhibition, the experimental electron density distribution of 1-ethynylpyrene has been determined using low-temperature X-ray diffraction measurements, and the resulting net atomic charges compared with various theoretical calculations. A total of 82,390 reflections were measured with Mo Kα radiation to a (sinθ/λ)max = 0.985 Å−1. Averaging symmetry equivalent reflections yielded 8,889 unique reflections. A least squares refinement procedure was used in which multipole parameters were added to describe the distortions of the atomic electron distributions from spherical symmetry. A map of the model electron density distribution of 1-ethynylpyrene was obtained. Net atomic charges calculated from refined monopole population parameters yielded charges that showed that the terminal acetylenic carbon atom (C18) is more negative than the internal carbon (C17). Net atomic charges calculated by ab initio, density functional theory, and semi-empirical methods are consistent with this trend suggesting that the terminal acetylenic carbon atom is more likely to be the site of oxidation. This is consistent with the inhibition mechanism pathway that results in the formation of a reactive ketene intermediate. This is also consistent with assay results that determined that 1-ethynylpyrene acts as a mechanism-based inhibitor of P450s 1A1 and 1A2 and as a reversible inhibitor of P450 2B1. Crystallographic data: 1-ethynylpyrene, C18H10, P21/c, a = 14.571(2) Å, b = 3.9094(5) Å, c = 20.242(3) Å, β = 105.042(2)°, V = 1,113.5(2) Å3; 1-propynylpyrene, C19H12, P21/n, a = 8.970(2) Å, b = 10.136(1) Å, c = 14.080(3) Å, β = 99.77(2)°, V = 1,261.5(4) Å3; 4-propynylpyrene, C19H12, Pbca, a = 9.904(1) Å, b = 13.174(2) Å, c = 19.401(1) Å, V = 2,531.4(5) Å3. 相似文献78.
79.
S. A. Waksman K. R. Stevens A. Rippel G. Behr H. Wiangke Pfeiffer R. R. Le G. Worsley und F. J. Nutman 《Fresenius' Journal of Analytical Chemistry》1934,96(3-4):151-155
Ohne Zusammenfassung 相似文献
80.
Andrew L. Korich Amanda R. Walker Christopher Hincke Caitlin Stevens Peter M. Iovine 《Journal of polymer science. Part A, Polymer chemistry》2010,48(24):5767-5774
Boronic acid end‐functionalized polycaprolactone (PCL) polymers were synthesized by ring‐opening polymerization using a pinacol boronate ester‐containing (Bpin) initiator. The polymerization provides access to boron‐terminated polymers (i.e. Bpin‐PCL‐OH) with narrow molecular weight distributions (PDI = 1.09). Postsynthetic manipulation of the polymer's terminal hydroxyl group by copper‐catalyzed azide‐alkyne cycloaddition chemistry provides a series of bis end‐functionalized polymers with significant structural diversity at the termini. Deprotection of the boronate ester end group was accomplished with an acidic solid phase DOWEX resin. The boronate ester deprotection methodology does not result in hydrolysis of the polymeric backbone. The boronic acid‐tipped polymers were converted into star polymer assemblies using thermal dehydration and ligand‐facilitated trimerization. Thermal dehydration of (HO)2B‐PCL‐OAc to the corresponding boroxine‐based star polymer assembly was inefficient and lead to degradation products. Ligand‐facilitated trimerization using either pyridine or 7‐azaindole as the Lewis base was efficient and mild. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献