全文获取类型
收费全文 | 2346篇 |
免费 | 49篇 |
专业分类
化学 | 1663篇 |
晶体学 | 34篇 |
力学 | 29篇 |
数学 | 79篇 |
物理学 | 590篇 |
出版年
2022年 | 15篇 |
2021年 | 16篇 |
2020年 | 21篇 |
2019年 | 29篇 |
2018年 | 18篇 |
2017年 | 17篇 |
2016年 | 41篇 |
2015年 | 43篇 |
2014年 | 45篇 |
2013年 | 115篇 |
2012年 | 89篇 |
2011年 | 109篇 |
2010年 | 65篇 |
2009年 | 66篇 |
2008年 | 111篇 |
2007年 | 108篇 |
2006年 | 109篇 |
2005年 | 107篇 |
2004年 | 113篇 |
2003年 | 85篇 |
2002年 | 97篇 |
2001年 | 71篇 |
2000年 | 51篇 |
1999年 | 29篇 |
1998年 | 26篇 |
1997年 | 23篇 |
1996年 | 28篇 |
1995年 | 15篇 |
1994年 | 22篇 |
1993年 | 23篇 |
1992年 | 27篇 |
1991年 | 33篇 |
1990年 | 29篇 |
1989年 | 25篇 |
1988年 | 28篇 |
1987年 | 30篇 |
1986年 | 23篇 |
1985年 | 53篇 |
1984年 | 43篇 |
1983年 | 30篇 |
1982年 | 34篇 |
1981年 | 41篇 |
1980年 | 31篇 |
1979年 | 43篇 |
1978年 | 36篇 |
1977年 | 22篇 |
1976年 | 32篇 |
1975年 | 22篇 |
1974年 | 18篇 |
1973年 | 15篇 |
排序方式: 共有2395条查询结果,搜索用时 15 毫秒
91.
ESR signals with g = 2.08 and 2.13 due to Ni were observed for evaporated (Ge0.32Se0.32Te0.32As0.4) 100-xNix and films respectively. The large increase of the electrical conductivity by the addition of Ni is discussed in connection with the ESR signal. Bulk glasses prepared by melt-quenching are also investigated for comparison. 相似文献
92.
We examine the role of the non-locality of the potential in the two-body scattering by taking the nucleon-Σ system as an example. We employ a non-local potential for the nucleon-Σ channel which has the characteristic features of the quark model and reproduces the phase shifts of widely used local potentials. We use inverse scattering methods to obtain the equivalent local potential from the non-local potential, and show that the obtained local potential has a strong short range repulsion. 相似文献
93.
The basic model for incompressible two-phase flows with phase transitions consistent with thermodynamics is studied. The latter means that the total energy is conserved and the total entropy is nondecreasing. We consider the case of constant but non-equal densities of the phases, complementing our previous paper (Prüss et?al. in Evol Equ Control Theory 1:171–194, 2012) where the case of equal densities is analyzed. The local well-posedness of such problems is proved by means of the technique of maximal L p -regularity, in a configuration where the interface is nearly flat and initial data are small. 相似文献
94.
T. Idehara I. Ogawa Y. Shimizu T. Tatsukawa 《International Journal of Infrared and Millimeter Waves》1998,19(6):803-816
Higher harmonic operation of gyrotrons is necessary to obtain high frequencies. Some gyrotrons included in the Gyrotron FU series developed at Fukui University have achieved operation at the third and even fourth harmonics of the electron cyclotron frequency. The output lies in the millimeter to submillimeter wavelength range and the output powers are several watts to several tens of watts. In this paper, the gyrotrons and the conditions under which they operate are described in detail. 相似文献
95.
96.
Electrophoretic mobilities, mu, and diffusion coefficients, D, of a small ion (molecular weight 579) were determined in dependence on the viscosity, eta, of aqueous buffer solutions containing ethylene glycol, or polyethylene glycol (PEG) with average molecular weights of 400, 20000, 100000 or 2000000, respectively, as additives. The values for mu and D are inversely proportional to the viscosity for the solutions with small-sized additives (ethylene glycol and PEG400), in accordance to Walden's rule. In contrast, for the longest polymers the mobilities and the diffusion coefficients approximate the values observed for pure water, and are nearly independent of the viscosity. This result agrees with the model of fractional free volume and the obstruction theory. For solutions with equal viscosity, three ranges can be differentiated for mu and D in relation to the size of the additive: for small additives, on the one hand, and the long-chained polymers, on the other hand, the values for mu and D are nearly independent of the size of the additive. In contrast, a pronounced increase of mu and D is found with increasing polymer size in the molecular weight range between 20000 and 100000. The ratio mu/D, occurring in a number of expressions for the plate height contributions, exhibits a remarkably small change over the entire polymer size and viscosity range (between 1 and 7 cP) under consideration. Consequently, the separation efficiency, expressed by the plate number, is found to be nearly constant, and is independent of viscosity. 相似文献
97.
Llorenç Rubert Dr. Md Faizul Islam Dr. Andrew B. Greytak Rahul Prakash Mark D. Smith Dr. Rosa Maria Gomila Prof. Dr. Antonio Frontera Prof. Dr. Linda S. Shimizu Dr. Bartolome Soberats 《Angewandte Chemie (International ed. in English)》2023,62(46):e202312223
We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development. 相似文献
98.
meso-Pentafluorophenyl- substituted [40]nonaphyrin(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH(4) to [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn(II) or Cu(II) ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH(4) and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn(II)-Pd(II)-Pd(II)) and 13 (Cu(II)-Pd(II)-Pd(II)) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C--H bond activation while the other is bound in an NNC fashion with single C--H bond activation. Multi-metal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (<0.6 eV), despite their nonplanar conformations. 相似文献
99.
Yong S. Chong Dr. William R. Carroll William G. Burns Mark D. Smith Ken D. Shimizu Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(36):9117-9126
An atropisomeric molecular balance was developed to study face‐to‐face arene–arene interactions. The balance has a large central 1,4,5,8‐naphthalene diimide surface that forms intramolecular arene–arene interactions with two pendent arms. The balance adopts distinct syn and anti isomers with varying numbers of intramolecular interactions. Thus, the strength of the arene–arene interaction could be quantitatively measured by NMR spectroscopy from the anti/syn ratios. The size of the arene arms was easily varied, which allowed examination of the relationship between arene size and strength of the interaction. A nonlinear size dependence was observed in solution with larger arene arms having a disproportionately stronger arene–arene interaction. The intramolecular arene–arene interactions were also characterized in the solid state by X‐ray crystallography. These studies were facilitated by the kinetic stability of the syn and anti isomers at room temperature due to the high isomerization barrier (ΔG=27.0 kcal mol?1). Thus, the anti isomer could be selectively isolated and crystallized in its folded conformation. The X‐ray structures confirmed that the anti isomers formed two strong intramolecular arene–arene interactions with face‐to‐face geometries. The solid‐state structure analysis also reveals that the rigid framework may contribute to the observed nonlinear size trend. The acetate linker is slightly too long, which selectively destabilizes the balances with smaller arene arms. The larger arene arms are able to compensate for the longer linker and form effective intramolecular arene–arene interactions. 相似文献
100.
Lars J. Wesenberg Erika Diehl Till J. B. Zähringer Carolin Dörr Dr. Dieter Schollmeyer Dr. Akihiro Shimizu Prof. Dr. Jun-ichi Yoshida Prof. Dr. Ute A. Hellmich Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17574-17580
The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non-protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against castrate-resistant prostate cancer. Further improvement of the structure led to significantly increased cancer cell line toxicity. Thus, exploiting environmentally benign electrooxidation, we present a new versatile and powerful method based on direct C−H activation that is applicable for example the production of medicinally relevant compounds. 相似文献