全文获取类型
收费全文 | 1850篇 |
免费 | 117篇 |
国内免费 | 6篇 |
专业分类
化学 | 1666篇 |
晶体学 | 12篇 |
力学 | 19篇 |
数学 | 122篇 |
物理学 | 154篇 |
出版年
2024年 | 3篇 |
2023年 | 27篇 |
2022年 | 77篇 |
2021年 | 104篇 |
2020年 | 80篇 |
2019年 | 58篇 |
2018年 | 36篇 |
2017年 | 39篇 |
2016年 | 78篇 |
2015年 | 71篇 |
2014年 | 87篇 |
2013年 | 113篇 |
2012年 | 184篇 |
2011年 | 134篇 |
2010年 | 84篇 |
2009年 | 66篇 |
2008年 | 107篇 |
2007年 | 112篇 |
2006年 | 88篇 |
2005年 | 84篇 |
2004年 | 73篇 |
2003年 | 57篇 |
2002年 | 47篇 |
2001年 | 13篇 |
2000年 | 6篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 10篇 |
1990年 | 10篇 |
1989年 | 11篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
1961年 | 2篇 |
1933年 | 1篇 |
排序方式: 共有1973条查询结果,搜索用时 0 毫秒
91.
Dr. Eduard E. Karslyan Dr. Alexandra O. Borissova Prof. Dr. Dmitry S. Perekalin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(20):5676-5679
A polycyclic aromatic ligand for site-selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7-tetramethoxy-9,10-dimethylanthracene initially reacts with [(C5H5)Ru(MeCN)3]BF4 to give the kinetic product with a [(C5H5)Ru]+ fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination. 相似文献
92.
A range of pyrazolidin-3-ones have been prepared and their activity as catalysts for iminium-ion promoted Diels-Alder reactions evaluated. Systematic variation of the C(5)- and N(2)-substituents indicates that the incorporation of an electron withdrawing substitutent at N(2) and either a Ph or CF3 substitution at C(5) results in optimal catalytic activity. The diastereoisomeric resolution of a model C(5)-Ph substituted pyrazolidinone and its ability to impart modest levels of asymmetric induction in the organocatalytic Diels-Alder reaction is also demonstrated. 相似文献
93.
R. Alan Aitken Bernd Fodi Michael H. Palmer Alexandra M.Z. Slawin Jing Yang 《Tetrahedron》2012,68(29):5845-5851
The structures of pyridazine N-oxide, pyrimidine N-oxide and pyrazine N-oxide have been determined by X-ray diffraction for the first time. Comparison with theoretical predictions of the equilibrium structures using the B3LYP method together with a cc-pVTZ basis set, show close agreement with the structural parameters observed, and experimental dipole moments, which suggests that the charge distribution is realistic. An ‘atoms in molecules’ (AIM) analysis of the computed wave-functions shows total electron densities rather different from the classical picture of a dative bond, whereas the same wave-functions subjected to Mulliken analysis show a more conventional view of the electron distribution. This latter procedure allows a bond dipole analysis of the N-oxide charge distribution. 相似文献
94.
95.
96.
Gerard van Doremaele Martin van Duin Maxence Valla Alexandra Berthoud 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):2877-2891
ARLANXEO Elastomers has developed and commercialized Keltan ACE™ technology, a class of half-sandwich cyclopentadienyl κ1-amidinate metal complexes, which are extremely active for the production of first-class ethylene/propylene/diene copolymers (EPDM). In this review, the development and some of the key features of the Keltan ACE™ catalyst system are presented. Many different ACE catalysts have been synthesized over the past years, including bridged and bimetallic catalysts. With Keltan ACE™, a complete range of EPDM products with similar polymer characteristics as their Ziegler–Natta (ZN) counterparts can be produced, including variations containing very high 5-ethylidene-2-norbornene (ENB) contents, controlled long chain branching, very high molecular weight, as well as oil-extended products. Moreover, other EPDM structures can be polymerized. The Keltan ACE™ catalyst technology also allows the production of EPDMs with very high amounts of dicyclopentadiene (DCPD) or 5-vinyl 2-norbornene (VNB) without excessive gelation and reactor fouling, that is, products that cannot or are extremely difficult to obtain via classical ZN catalysis. In a next step, high-VNB-EPDM can be postreactor modified, for example, via metathesis chemistry. In addition, EPDM polymers with a very broad or even bimodal molecular weight distribution can be obtained in a single reactor with certain ACE catalyst structures at particular activator/precatalyst ratios. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2877–2891 相似文献
97.
Krief A Destree A Durisotti V Moreau N Smal C Colaux-Castillo C 《Chemical communications (Cambridge, England)》2002,(6):558-559
Driving the equilibrium between selenides and osmium(VIII) reagents with selenoxides and osmium(VI) by a subsequent reaction (rearrangement of allyl selenoxides to allyl alcohols or addition of osmium(VIII) species on C=C double bonds) to one side, allows the transformation of methyl geranyl selenides to linalool and of methyl citronellyl selenoxide to 6,7-dihydroxy citronellyl selenide. 相似文献
98.
Kulbaba K Cheng A Bartole A Greenberg S Resendes R Coombs N Safa-Sefat A Greedan JE Stöver HD Ozin GA Manners I 《Journal of the American Chemical Society》2002,124(42):12522-12534
Pt(0)-catalyzed ring-opening precipitation copolymerization of [1]silaferrocenophanes fcSiMe(2) (3) and the spirocyclic cross-linker fcSi(CH(2))(3) (4) (fc = Fe(eta(5)-C(5)H(4))(2)) was used to prepare polyferrocenylsilane microspheres (PFSMSs) under mild conditions. By varying the reaction conditions, a wide variety of other morphologies was obtained. The effects of temperature, monomer ratio, solvent composition, catalyst concentration, and time on the observed morphology were investigated and interpreted in terms of a mechanism for microsphere formation. The most well-defined particles were formed using equimolar amounts of 3 and 4, in a 50:50 mixture of xylenes and decane at 60 degrees C with gentle agitation. Chemical oxidation of the polymeric microspheres led to positively charged particles (OPFSMSs) which underwent electrostatically driven self-assembly with negatively charged silica microspheres to form core-corona composite particles. Redox titration with controlled amounts of the one-electron oxidant [N(C(6)H(4)Br-p)(3)][PF(6)] in acetonitrile led to the oxidation of the outer 0.15 microm (ca. 32%) of the PFSMSs. The resulting OPFSMSs were reduced back to their neutral form by reaction with hydrazine in methanol. Pyrolysis of the PFSMSs led to spherical magnetic ceramic replicas with tunable magnetic properties that organize into ordered 2-D arrays at the air-water interface under the influence of a magnetic field. 相似文献
99.
100.