全文获取类型
收费全文 | 196篇 |
免费 | 12篇 |
专业分类
化学 | 150篇 |
力学 | 1篇 |
数学 | 42篇 |
物理学 | 15篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 1篇 |
2019年 | 7篇 |
2018年 | 1篇 |
2017年 | 6篇 |
2016年 | 4篇 |
2015年 | 9篇 |
2014年 | 4篇 |
2013年 | 8篇 |
2012年 | 9篇 |
2011年 | 10篇 |
2010年 | 10篇 |
2009年 | 7篇 |
2008年 | 13篇 |
2007年 | 17篇 |
2006年 | 15篇 |
2005年 | 17篇 |
2004年 | 11篇 |
2003年 | 7篇 |
2002年 | 1篇 |
2001年 | 5篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1964年 | 1篇 |
1955年 | 1篇 |
1948年 | 3篇 |
排序方式: 共有208条查询结果,搜索用时 312 毫秒
11.
Heikki Joela 《Chemical physics letters》1974,28(2):236-238
The radical anion of tetraline was prepared by reduction in 1,2-dimethoxyethane and measured at ?80° and ?93°C. Coupling constants, all triplets, are: 7.03, 2.17, 1.94, 1.75, 0.51 and 0.19 G. 相似文献
12.
Lahtinen P Korpi H Haavisto E Leskelä M Repo T 《Journal of combinatorial chemistry》2004,6(6):967-973
A simple and efficient parallel screening method to evaluate the catalytic activities of homogeneous copper complexes for the oxidation of benzylic alcohols in aqueous solutions with molecular oxygen is reported. Copper(II) sulfate was treated in situ with 22 nitrogen donor ligands, and the catalytic activities of these combinations were studied at four different pH values with two substrates (benzyl alcohol and 3,4-dimethoxy benzyl alcohol (veratryl alcohol)), resulting in 176 oxidation experiments in the primary screening stage. Copper complexes based on N,N,N',N'-tetramethyl ethylenediamine (TMEDA), 9,10-diaminephenanthrene (DAPHEN), and 1,2-diaminocyclohexane (DACH) were determined to be the most active catalysts. In the second screenings, the influence of reaction conditions on Cu(DACH)-, Cu(TMEDA)-, and Cu(DAPHEN)-catalyzed reactions were investigated in more detail. It was found that highly basic reaction conditions favor the reaction with the exception of Cu(TMEDA), which is active at a lower pH range. Under optimized conditions, Cu(DAPHEN) catalyzes the transformation of veratryl alcohol to the corresponding aldehyde with 100% conversion. 相似文献
13.
Viscous overstability (oscillatory instability) may play an important role in the formation of small scale structure in dense planetary rings such as Saturn's B ring. We investigate the growth and saturation of such modes in local particle simulations. Starting from a hydrodynamic model, we develop a set of ordinary differential equations to model the evolution of the amplitudes of the linearly overstable modes in the nonlinear regime. The NASA/ESA space probe Cassini can make direct observations of these modes in Saturn's rings, including their sizes and temporal development. 相似文献
14.
Konu J Chivers T Tuononen HM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(43):12977-12987
The lithium salts of the chalcogenocarbonyl dianions [(E)C(PPh2S)2]2? (E=S ( 4 b ), Se ( 4 c )) were produced through the reactions between Li2[C(PPh2S)2] and elemental chalcogens in the presence of tetramethylethylenediamine (TMEDA). The solid‐state structure of {[Li(TMEDA)]2[(Se)C(PPh2S)2]}—[{Li(TMEDA)}2 4 c ]—was shown to be bicyclic with the Li+ cations bis‐S,Se‐chelated by the dianionic ligand. One‐electron oxidation of the dianions 4 b and 4 c with iodine afforded the diamagnetic complexes {[Li(TMEDA)]2[(SPh2P)2CEEC(PPh2S)2]} ([Li(TMEDA)]2 7 b (E=S), [Li(TMEDA)]2 7 c (E=Se)), which are formally dimers of the radical anions [(E)C(PPh2S)2]? . (E=S ( 5 b ), Se ( 5 c )) with elongated central E? E bonds. Two‐electron oxidation of the selenium‐containing dianion 4 c with I2 yielded the LiI adduct of a neutral selone {[Li(TMEDA)][I(Se)C(PPh2S)2]}—[{LiI(TMEDA)} 6 c ]—whereas the analogous reaction with 4 b resulted in the formation of 7 b followed by protonation to give {[Li(TMEDA)][(SPh2P)2CSS(H)C(PPh2S)2]}—[Li(TMEDA)] 8 b . Attempts to identify the transient radicals 5 b and 5 c by EPR spectroscopy in conjunction with DFT calculations of the electronic structures of these paramagnetic species and their dimers are also described. The crystal structures of [{Li(TMEDA)}2 4 c ], [{LiI(TMEDA)} 6 c ] ? C7H8, [Li(TMEDA)]2 7 b? (CH2Cl2)0.33, [Li(THF)2]2 7 b , [Li(TMEDA)]2 7 c , [Li(TMEDA)] 8 b? (CH2Cl2)2 and [Li([12]crown‐4)2] 8 b were determined and salient structural features are discussed. 相似文献
15.
The nature of metal-metal bonding in group 13 dimetallenes REER (E = Al, Ga, In, Tl; R = H, Me, (t)Bu, Ph) was investigated by use of quantum chemical methods that include HF, second order M?ller-Plesset perturbation theory (MP2), coupled cluster (CCSD(T)), complete active space with (CASPT2) and without (CAS) second order perturbation theory, and two density functionals, namely, B3LYP and M06-2X. The results show that the metal-metal interaction in group 13 dimetallenes stems almost exclusively from static and dynamic electron correlation effects: both dialuminenes and digallenes have an important singlet diradical component in their wave function, whereas the bonding in the heavier diindenes and, in particular, dithallenes is dominated by closed shell metallophilic interactions. The reported calculations represent a systematic attempt to determine the metal and ligand dependent bonding changes in these systems. 相似文献
16.
Common design principles apply to design of mechanical and biological machine structures. Most of the main properties of machines and creatures are determined by programmed genetics. These determine the geometry, material selection, functioning of machines and biological creatures and the fitness for service. The present approach of innovation and optimum design is based on basic mechanics with fuzzy goal formulations and heuristics, like axiomatic design. These models are combined synergistically to formulate the desired properties of the machines. First, engineering mechanics and heuristics are shown to have a finalistic guidance on the conceptual design of optimal fluid conveying channels consisting of a branch and a closing device. Then a multi-objective algorithm is tested in an industrial case study design of a preloaded screw fastened flange plate and it is shown to be a reliable tool for testing and innovating new solutions. The goals and constraints are modellled consistently by the same goal function form. The joints have to be reliable against risks of separation, relaxation, fatigue and creep fracture due to pressure differences. Compared to conventional results it gives nearly the same technical and safety functions even at half the cost. This approach is useful for optimizing new concepts and also existing machine designs showing possibilities for notable cost savings. 相似文献
17.
The use of a TDI camera is restricted to cases of viewing from the direction of the surface normal. Our previous work indicated that a TDI camera can be used with viewing angles up to 30° from the surface normal which extends the usability of TDI for visual inspection applications. The objective of this paper is to examine the use of a TDI camera at a non-zero viewing angle under vibration conditions. The effects caused by vibration of the surface to be viewed become critical when using a TDI camera at non-zero viewing angles. A method of approximating the TDI performance under vibration conditions was determined and evaluated experimentally. The resulting measurements support the approximating method developed here. 相似文献
18.
Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rudy M. Brown Dr. Javier Borau Garcia Juuso Valjus Christopher J. Roberts Dr. Heikki M. Tuononen Dr. Masood Parvez Prof. Roland Roesler 《Angewandte Chemie (International ed. in English)》2015,54(21):6274-6277
A Ni0‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand. 相似文献
19.
Sami-Pekka Hirvonen Mikko Mänttäri Valter Wigren Mikko Salomäki Carita Kvarnström Heikki Tenhu 《Colloid and polymer science》2011,289(9):1065-1072
Poly(benzimidazobenzophenanthroline) (BBL) was prepared according to literature method and modified with poly(ethylene oxide)
in a one pot synthesis. After precipitation in aqueous sodium carbonate solution and subsequent purification, aqueous dispersions
were prepared by ultrasonication. Particle sizes in the dispersions ranged from few tens of nanometers to several micrometers
and most of the particles had sizes of 50–250 nm. Further studies indicated that the colloidal stability is a combined result
of steric stabilization caused by excluded volume interactions of PEO chains on particle surface and electrostatic stabilization
by the dissociated carboxylic acid groups on the particle surface. The product could be processed into uniform films 20–30 nm
in thickness by spin coating onto gold-plated silicon substrates having aminethiol monolayer as the top most layer. 相似文献
20.
The following results are obtained.
- -
- An open neighbornet U of X has a closed discrete kernel if X has an almost thick cover by countably U-close sets.
- -
- Every hereditarily thickly covered space is aD and linearly D.
- -
- Every t-metrizable space is a D-space.
- -
- X is a D-space if X has a cover {Xα:α<λ} by D-subspaces such that, for each β<λ, the set ?{Xα:α<β} is closed.