全文获取类型
收费全文 | 1724篇 |
免费 | 62篇 |
国内免费 | 181篇 |
专业分类
化学 | 389篇 |
晶体学 | 8篇 |
力学 | 20篇 |
综合类 | 14篇 |
数学 | 1357篇 |
物理学 | 179篇 |
出版年
2024年 | 5篇 |
2023年 | 24篇 |
2022年 | 35篇 |
2021年 | 38篇 |
2020年 | 51篇 |
2019年 | 68篇 |
2018年 | 53篇 |
2017年 | 65篇 |
2016年 | 40篇 |
2015年 | 29篇 |
2014年 | 46篇 |
2013年 | 386篇 |
2012年 | 39篇 |
2011年 | 63篇 |
2010年 | 40篇 |
2009年 | 71篇 |
2008年 | 74篇 |
2007年 | 93篇 |
2006年 | 85篇 |
2005年 | 65篇 |
2004年 | 58篇 |
2003年 | 70篇 |
2002年 | 114篇 |
2001年 | 60篇 |
2000年 | 52篇 |
1999年 | 49篇 |
1998年 | 46篇 |
1997年 | 35篇 |
1996年 | 32篇 |
1995年 | 25篇 |
1994年 | 12篇 |
1993年 | 12篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1967条查询结果,搜索用时 15 毫秒
51.
Stephen D. Pastor David N. Rahni Nancy Khoury Stephen A. Koch 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1951-1956
The X-ray crystallographic analysis of 6,6-dimethyl-2,4,8,10-tetra-tert-octyl-dibenzo[d,f][1,3,2]dioxagermepin, 1 is reported. In the solid-state conformation of 1, the dihedral angle about the C─C sp2-sp 2 σ bond connecting the two aryl rings is 50.1°. The observed C2 symmetry in the solid-state conformation of 1 is consistent with the previously suggested solution conformation. 相似文献
52.
This communication describes a convenient synthesis of fused bicyclic pyrazolones in a one-pot reaction procedure. Modified protocols are also developed to access 5,5-bicyclic and bulky pyrazolones in good yields. The method reported herein represents a practical approach to structurally diversified bicyclic pyrazolones. 相似文献
53.
54.
Benjamin R. M. Lake Dr. Charlotte E. Willans 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16780-16790
The preparation of a series of imidazolium salts bearing N‐allyl substituents, and a range of substituents on the second nitrogen atom that have varying electronic and steric properties, is reported. The ligands have been coordinated to a copper(I) centre and the resulting copper(I)–NHC (NHC=N‐heterocyclic carbene) complexes have been thoroughly examined, both in solution and in the solid‐state. The solid‐state structures are highly diverse and exhibit a range of unusual geometries and cuprophilic interactions. The first structurally characterised copper(I)–NHC complex containing a copper(I)–alkene interaction is reported. An N‐pyridyl substituent, which forms a dative bond with the copper(I) centre, stabilises an interaction between the metal centre and the allyl substituent of a neighbouring ligand, to form a 1D coordination polymer. The stabilisation is attributed to the pyridyl substituent increasing the electron density at the copper(I) centre, and thus enhancing the metal(d)‐to‐alkene(π*) back‐bonding. In addition, components other than charge transfer appear to have a role in copper(I)–alkene stabilisation because further increases in the Lewis basicity of the ligand disfavours copper(I)–alkene binding. 相似文献
55.
Dr. Ryu Yamasaki Dr. Masato Ohashi Kyotaro Maeda Takuya Kitamura Minami Nakagawa Korehito Kato Tetsushi Fujita Ryohei Kamura Kazuto Kinoshita Dr. Hyuma Masu Prof. Dr. Isao Azumaya Prof. Dr. Sensuke Ogoshi Prof. Dr. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3415-3425
A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes. 相似文献
56.
Peng Sun Zihan Xia Zhongfang Li Ziwei Fan Fengqi He Qiang Liu Xiaoyan Yin 《Materials Today Chemistry》2022
A high-temperature proton exchange membrane with high proton conductivity over a wide humidity range still remains a challenge. PBI dendrimer containing triazine rings (TPBI) was synthesized to approach this aim considering its high content of hygroscopic terminal groups and of larger free volume. A novel proton conductor previously synthesized (zirconium 3-sulfopropyl phosphonate, ZrSP) was doped due to its good proton conductivity over a wide humidity range. TPBI was post-crosslinked with a tetrafunctional epoxy resin (N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, TGDDM) to enhance the mechanical stability at low cross-linking degrees, which allowed high doping levels of ZrSP, and thus, high conductivity. The prepared membranes (TPBI-TGDDM/ZrSP) showed good thermal stability, high proton conductivity over wide humidity range, and good dimensional stability. At suitable degrees of branching, TPBI-TGDDM/ZrSP exhibited superior mechanical property, oxidative stability, methanol barrier property, and membrane selectivity than its linear analog (mPBI-TGDDM/ZrSP). As ZrSP instead of PA was applied as the proton conductor, TPBI-TGDDM/ZrSP showed good durability of proton conductivity, especially in comparison with TPBI-TGDDM/PA, which highly retarded decline in conductivity caused by PA leaking. The proton conductivity at 180 °C of TPBI(20)-TGDDM(10)/ZrSP(50) achieved 142, 84.2 and 23.6 mS cm?1 at 100%, 50%, and 0 RH, respectively. 相似文献
57.
Adjoint triples and pairs are basic operators used in several domains, since they increase the flexibility in the framework in which they are considered. This paper introduces multi-adjoint algebras and several properties; also, we will show that an adjoint triple and its “dual” cannot be considered in the same framework.Moreover, a comparison among general algebraic structures used in different frameworks, which reduce the considered mathematical requirements, such as the implicative extended-order algebras, implicative structures, the residuated algebras given by sup-preserving aggregations and the conjunctive algebras given by semi-uninorms and u-norms, is presented. This comparison shows that multi-adjoint algebras generalize these structures in domains which require residuated implications, such as in formal concept analysis, fuzzy rough sets, fuzzy relation equations and fuzzy logic. 相似文献
58.
We study electron energies in a double concentric quantum ring with anisotropy in the rims heights in the presence of the external magnetic field applied along the symmetry axis. To this end, we consider a model in which the thickness grows linearly from the axis up to the inner rim with a slope different from one between the inner and the outer rims. The anisotropy in the rims heights originated by the presence in the structure of various valleys we simulate by periodic dependence of the slope on the radial direction. We show that the wave functions of the electron confined in such structure can be found analytically if the slopes in all radial directions are the same, and by using a simple exact diagonalization procedure otherwise. The behavior of the electron energies as functions of the magnetic field, rings radii and rims heights, as well as the number of the valleys and their depths is consistently described with our formalism. The entanglement of the states with different radial and orbital quantum numbers, the period and the amplitude of the Aharonov–Bohm oscillations are very sensible to any variations of the rims heights. 相似文献
59.
Minghui Zhou Marianne Lankelma Dr. Ir. Jarl Ivar van der Vlugt Prof. Dr. Bas de Bruin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11166-11172
The metalloradical activation of o-aryl aldehydes with tosylhydrazide and a cobalt(II) porphyrin catalyst produces cobalt(III)-carbene radical intermediates, providing a new and powerful strategy for the synthesis of medium-sized ring structures. Herein we make use of the intrinsic radical-type reactivity of cobalt(III)-carbene radical intermediates in the [CoII(TPP)]-catalyzed (TPP=tetraphenylporphyrin) synthesis of two types of 8-membered ring compounds; novel dibenzocyclooctenes and unprecedented monobenzocyclooctadienes. The method was successfully applied to afford a variety of 8-membered ring compounds in good yields and with excellent substituent tolerance. Density functional theory (DFT) calculations and experimental results suggest that the reactions proceed via hydrogen atom transfer from the bis-allylic/benzallylic C−H bond to the carbene radical, followed by two divergent processes for ring-closure to the two different types of 8-membered ring products. While the dibenzocyclooctenes are most likely formed by dissociation of o-quinodimethanes (o-QDMs) which undergo a non-catalyzed 8π-cyclization, DFT calculations suggest that ring-closure to the monobenzocyclooctadienes involves a radical-rebound step in the coordination sphere of cobalt. The latter mechanism implies that unprecedented enantioselective ring-closure reactions to chiral monobenzocyclooctadienes should be possible, as was confirmed for reactions mediated by a chiral cobalt-porphyrin catalyst. 相似文献
60.
LIN Hong-Wei 《结构化学》2007,26(7):773-776
A new Schiff base compound, C13H9Br2N3O2·CH3OH, isonicotinic acid [1-(3,5- dibromo-2-hydroxyphenyl)methylidene]hydrazide methanol, has been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The compound comprises a Schiff base moiety isonicotinic acid [1-(3,5-dibromo-2-hydroxyphenyl) methylidene]hydrazide and a methanol molecule. The crystal belongs to the triclinic system, space group P1 with a = 8.464(1), b = 9.511(2), c = 10.901(2) , α = 92.940(2), β = 110.456(2), γ = 96.040(2)o, Z = 2, V = 814.0(2) 3, Dc = 1.759 g/cm3, Mr = 431.09, λ(MoKα) = 0.71073 , μ = 4.994 mm-1, F(000) = 424, R = 0.0440 and wR = 0.1061. A total of 3284 unique reflections were collected, of which 2197 with I > 2σ(I) were observed. The molecule adopts a trans configuration about the C=N double bond. The dihedral angle between the benzene and pyridine rings is 22.0(4)o. The crystal structure is stabilized by intermolecular O-H···N and C-H···O hydrogen bonds, forming layers parallel to the ac plane. The preliminary biological tests show that the compound has potential antibacterial activities. 相似文献