全文获取类型
收费全文 | 3313篇 |
免费 | 78篇 |
国内免费 | 22篇 |
专业分类
化学 | 2066篇 |
晶体学 | 11篇 |
力学 | 145篇 |
数学 | 495篇 |
物理学 | 696篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 78篇 |
2021年 | 114篇 |
2020年 | 100篇 |
2019年 | 81篇 |
2018年 | 58篇 |
2017年 | 46篇 |
2016年 | 129篇 |
2015年 | 92篇 |
2014年 | 134篇 |
2013年 | 168篇 |
2012年 | 223篇 |
2011年 | 253篇 |
2010年 | 143篇 |
2009年 | 123篇 |
2008年 | 199篇 |
2007年 | 197篇 |
2006年 | 208篇 |
2005年 | 195篇 |
2004年 | 146篇 |
2003年 | 127篇 |
2002年 | 126篇 |
2001年 | 49篇 |
2000年 | 23篇 |
1999年 | 29篇 |
1998年 | 32篇 |
1997年 | 38篇 |
1996年 | 36篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 17篇 |
1992年 | 7篇 |
1991年 | 15篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 15篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 9篇 |
排序方式: 共有3413条查询结果,搜索用时 15 毫秒
11.
Some results on configurations realizing minimum blocking sets of a finite projective plane are obtained by introducing a suitable attraction property.Dedicated to Professor M. Scafati Tallini on the occasion of her 65th birthday 相似文献
12.
Carlo Mealli Stefano Midollini Simonetta Moneti Thomas A. Albright 《Helvetica chimica acta》1983,66(2):557-569
The reaction of [(C3Ph3)Ni(PPh3)2]ClO4 with P(CH2CH2PPh2)3(pp3) and NaBPh4 yields the [(C3Ph3)Ni(pp3)]BPh4-complex. After long exposure of the solution of this compound in acetone/butanol to the air a new derivative [(C3Ph3)-Ni(pp2po)]BPh4· 0.5 C4H9OH, where pp2po is (Ph2PCH2CH2)2P(CH2 CH2POPh2), is obtained. Complete X-ray analysis has been carried out for the latter complex: a=18.303 (5); b=29.445 (6), c=13.305 (5) Å, β=112.70 (9)°; space group monoclinic, P21/a, Z=4. Disorder problems were encountered in the refinement of the structure. The best R is 0.093. One of the arms of the parent pp3-molecule, not coordinated to the metal, undergoes oxidation. The Ni-atom, coordinated by the three remaining P-atoms of the ligand, is also linked in a roughly η3-mode to the cyclopropenium ligand. The geometry of the molecule is examined in detail. Extended HMO-calculations were performed to interpret how the variation of P? Ni? P angles affects the bonding between the NiP3- and C3H3-fragments. The conclusion is that the overall energy of the complex may be lowered in spite of a weakening of the Ni-cyclopropenium linkage. Extensions are made to other systems containing a linkage between a metal and a X3-ring (X=P,As). 相似文献
13.
14.
The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)). 相似文献
15.
The authors study an example, suggested by E. De Giorgi, of a second-order uniformly elliptic partial differential operator in divergence form with continuous coefficients on a smooth domain in the plane such that the associated harmonic measure on the boundary is not absolutely continuous with respect to the ordinary surface measure. 相似文献
16.
Piero Dalla Croce Paola Del Buttero Stefano Mayorana Raffaele Vistocco 《Journal of heterocyclic chemistry》1978,15(3):515-517
Thiete 1,1-dioxide reacts with 2 moles of α-chlorobenzalphenylhydrazine and methyl phenylhydrazonochloroacetate in the presence of triethylamine leading to the pyrazole derivatives 6 and 7 whose structure and mechanism of formation are discussed. 相似文献
17.
Amidoalkyl radicals, generated from amides by Mn(OAc)3 in acetic acid react with phenyl substituted alkenes to generate five-membered lactones or lactams. Ultrasound at ambient temperature significantly accelerates these single electron transfer reactions even when compared with conventional conditions under reflux or simple mechanical stirring. In some cases sonication leads to unusual products. 相似文献
18.
Pro. Stefano Polezzo 《Theoretical chemistry accounts》1975,38(3):211-221
A direct method of minimization of the energy expression for closed and open shell systems in LCAO-MO density matrix formalism is presented. The method makes use of a unitary transformation acting directly on the density matrices. Expressions of the gradient and second energy derivatives are worked out. Some preliminary calculations to test the rate of minimization using a variable metric method have been made on H2S and SO molecules and have given satisfactory results.[/p] 相似文献
19.
20.
Federica Mastroiacovo Francesca Biagioni Paola Lenzi Gloria Lazzeri Michela Ferrucci Stefano Puglisi-Allegra Alessandro Frati Ferdinando Nicoletti Francesco Fornai 《Molecules (Basel, Switzerland)》2022,27(10)
The brain area which surrounds the frankly ischemic region is named the area penumbra. In this area, most cells are spared although their oxidative metabolism is impaired. area penumbra is routinely detected by immunostaining of a molecule named Heat Shock Protein 70 (HSP70). Within the area penumbra, autophagy-related proteins also increase. Therefore, in the present study, the autophagy-related microtubule-associated protein I/II-Light Chain 3 (LC3) was investigated within the area penumbra along with HSP70. In C57 black mice, ischemia was induced by permanent occlusion of the distal part of the middle cerebral artery. Immunofluorescence and electron microscopy show that LC3 and HSP70 are overexpressed and co-localize within the area penumbra in the same cells and within similar subcellular compartments. In the area penumbra, marked loss of co-localization of HSP70 and LC3-positive autophagy vacuoles, with lysosomal-associated membrane protein 1 (LAMP1) or cathepsin-D-positive lysosome vacuoles occurs. This study indicates that, within the area penumbra, a failure of autophagolysosomes depends on defective compartmentalization of LC3, LAMP1 and cathepsin-D and a defect in merging between autophagosomes and lysosomes. Such a deleterious effect is likely to induce a depletion of autophagolysosomes and cell clearing systems, which needs to be rescued in the process of improving neuronal survival. 相似文献