全文获取类型
收费全文 | 550篇 |
免费 | 5篇 |
国内免费 | 6篇 |
专业分类
化学 | 390篇 |
力学 | 15篇 |
数学 | 82篇 |
物理学 | 74篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 22篇 |
2012年 | 37篇 |
2011年 | 44篇 |
2010年 | 23篇 |
2009年 | 27篇 |
2008年 | 31篇 |
2007年 | 33篇 |
2006年 | 51篇 |
2005年 | 41篇 |
2004年 | 32篇 |
2003年 | 29篇 |
2002年 | 23篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 9篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1978年 | 4篇 |
1973年 | 2篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1964年 | 1篇 |
1919年 | 1篇 |
1916年 | 1篇 |
1896年 | 2篇 |
排序方式: 共有561条查询结果,搜索用时 109 毫秒
1.
Erik Fooladi Bjrn Dalhus Christian Rmming Mats Tilset 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):m567-m569
In the title compound, [Rh(CH3)2(C2H3N)(C9H21N3)](C24H20B), the geometry around the RhIII centre is distorted octahedral, with elongated Rh—N bonds trans to the metal‐bonded methyl groups. The metal‐containing cations are located in channels formed by an anionic supramolecular mesh, in which aromatic π–π interactions between anionic [B(Ph)4]? units play a major role. 相似文献
2.
Mats Gyllenberg 《Journal of Differential Equations》2004,205(1):50-76
For time-periodic dissipative and irreducible type-K competitive Kolmogorov systems, it is proved that there is a canonically defined countable family F of unordered, disjoint invariant sets with the property that, for every persistent trajectory whose ω-limit set is not a cycle, there exists a unique trajectory in some element of F such that these two trajectories are asymptotic and the corresponding points in these two trajectories are K-related. 相似文献
3.
Richard Becker Mladen Prester Ping Hui Lin Mats Johnsson Ivica Zivkovic 《Journal of solid state chemistry》2007,180(3):1051-1059
Two new isostructural cobalt selenite halides Co5(SeO3)4Cl2 and Co5(SeO3)4Br2 have been synthesized. They crystallize in the triclinic system space group P−1 with the following lattice parameters for Co5(SeO3)4Cl2: a=6.4935(8) Å, b=7.7288(8) Å, c=7.7443(10) Å, α=66.051(11)°, β=73.610(11)°, γ=81.268(9)°, and Z=1. The crystal structures were solved from single-crystal X-ray data, R1=3.73 and 4.03 for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively. The new compounds are isostructural to Ni5(SeO3)4Br2.Magnetic susceptibility measurements on oriented single-crystalline samples show anisotropic response in a broad temperature range. The anisotropic susceptibility is quantitatively interpreted within the zero-field splitting schemes for Co2+ and Ni2+ ions. Sharp low-temperature susceptibility features, at TN=18 and 20 K for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively, are ascribed to antiferromagnetic ordering in a minority magnetic subsystem. In isostructural Ni5(SeO3)4Br2 magnetically ordered subsystem represents a majority fraction (TN=46 K). Nevertheless, anisotropic susceptibility of Ni5(SeO3)4Br2 is dominated at low temperatures by a minority fraction, subject to single-ion anisotropy effects and increasing population of Sz=0 (singlet) ground state of octahedrally coordinated Ni2+. 相似文献
4.
We define a smooth functional calculus for a non-commuting tuple of (unbounded) operators Aj on a Banach space with real spectra and resolvents with temperate growth, by means of an iterated Cauchy formula. The construction is also extended to tuples of more general operators allowing smooth functional calculii. We also discuss the relation to the case with commuting operators. 相似文献
5.
Mats J. Sundell Esko O. Pajunen Osmo O. E. Hormi Jan H. Nsman 《Journal of polymer science. Part A, Polymer chemistry》1993,31(9):2305-2311
The synthesis of some divinyl monomers—bis(vinylphenyl)ethane ( 2 ), bis(vinylbenzyloxy)hexane ( 3a ), and bis(vinylbenzyloxy)dodecane ( 3b ) is reported. Copolymers of the new monomers and styrene were evaluated as an alternative to divinylbenzene-crosslinked polymers for use as matrices and absorbents. The mechanical properties and the amount of residual double bonds in the copolymers were compared. It was found that the new copolymers, unlike the divinylbenzene-crosslinked polymers, retained their mechanical strength even at high crosslinking degrees. Stress at break values of 79, 68, and 18 N/mm2 were found for the polymers crosslinked with 20 mol % of 3a, 2 , and divinylbenzene; 5, 25 and 45% of the divinyl units in these polymers were left as pendant double bonds. Porous styrene– 2 copolymers were synthesized and shown to have lower surface areas than the corresponding divinylbenzene-crosslinked polymers. The pore size distribution showed that this was due to the absence of the smallest pores which are found in the divinylbenzene-crosslinked polymers in between heavily crosslinked nodules. © 1993 John Wiley & Sons, Inc. 相似文献
6.
Gustafsson MG 《Journal of chemical information and modeling》2005,45(5):1244-1255
This work shows that independent component analysis (ICA) can be used to obtain statistically independent and, therefore, chemically interpretable latent variables (LVs) in multivariate regression. Two novel algorithms based on ICA are introduced and compared with two classical methods on simulated data: principal component regression and partial least-squares regression. All methods compared yield accurate predictions, but only those based on ICA yield LVs that are chemically interpretable. Practical limitations of ICA-based regression with respect to the underlying assumptions, sample size, and measurement noise are discussed and illustrated by means of simulations. 相似文献
7.
The development of microwave-accelerated protocols for palladium(0)-catalyzed carbonylative cyclization of unsaturated aryl bromides and chlorides is described. By employing o-bromostyryl derivatives lacking substituents on the vinylic bond, molybdenum hexacarbonyl-mediated in situ carbonylation delivered a set of indan-1-one products in high yield after only 20 min of heating. Without the addition of the tri-tert-butylphosphine releasing Fu-salt ((t-Bu)(3)PHBF(4)), only incomplete conversions of sluggish o-styryl bromides and chlorides were realized. Internal and chemoselective palladium(0)-catalyzed Heck arylations of enamides afforded suitable starting materials for subsequent rapid ring-closing reactions. Microwave-heated intramolecular in situ carbonylation of these electron-rich and sterically congested olefins conveniently afforded eight functionalized 3-acylaminoindanone derivatives in a novel synthetic process. Attempted carbonylative annulation of electron-poor o-bromocinnamic acid derivatives furnished only the corresponding lactones via a competing hydroxycarbonylation-Michael addition reaction sequence. 相似文献
8.
Weigelt J Wikström M Schultz J van Dongen MJ 《Combinatorial chemistry & high throughput screening》2002,5(8):623-630
NMR based screening has become an important tool in the pharmaceutical industry. Methods that provide information on the location of small molecule binding sites on the surface of a drug target (e. g. SAR-by-NMR and related techniques) are of particular interest. In order to extend the applicability of such techniques to drug targets of higher molecular weight, selective labeling strategies may be employed. Dual-amino acid selective labeling and site directed non-native amino acid replacement (SNAAR) allow for the selective detection of NMR resonances of a specific amino acid residue. This results in significantly reduced spectral complexity, which not only enables application to higher molecular weight systems, but also eliminates the need for sequential resonance assignment in order to identify the binding site. Regio-selective (or segmental) labeling of an entire protein domain of a multi domain protein may also be achieved. Labeling only a selected part of a multi domain protein (e. g. a catalytic or ligand binding domain) is an attractive way to simplify the spectral interpretation without disturbing the system under study. 相似文献
9.
Dimethylformamide (DMF) acts as an efficient source of carbon monoxide and dimethylamine in the palladium-catalyzed aminocarbonylation (Heck carbonylation) of p-tolyl bromide to provide the dimethylamide. Addition of amines to the reaction mixture in excess delivers the corresponding aryl amides in good yields. The amines employed, benzylamine, morpholine, and aniline, all constitute good reaction partners. The reaction proceeds smoothly with bromobenzene and more electron-rich aryl bromides, but electron-deficient aryl bromides fail to undergo aminocarbonylation. The reactions are conducted at 180-190 degrees C for 15-20 min with microwave heating in a reaction mixture containing imidazole and potassium tert-butoxide: the latter is required to promote decomposition of the DMF solvent at a suitable rate. The beneficial effects of controlled microwave irradiation as an energy source for the rapid heating of the carbonylation reaction mixture are demonstrated. The carbonylation procedure reported herein, which relies on the in situ generation of carbon monoxide, serves as a convenient alternative to other carbonylation methods and is particularly applicable to small-scale reactions where short reaction times are desired and the direct use of carbon monoxide gas is impractical. 相似文献
10.
Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics 总被引:1,自引:0,他引:1
Petrignani A Andersson PU Pettersson JB Thomas RD Hellberg F Ehlerding A Larsson M van der Zande WJ 《The Journal of chemical physics》2005,123(19):194306
Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer. 相似文献