全文获取类型
收费全文 | 910篇 |
免费 | 28篇 |
国内免费 | 7篇 |
专业分类
化学 | 737篇 |
晶体学 | 4篇 |
力学 | 6篇 |
数学 | 23篇 |
物理学 | 175篇 |
出版年
2023年 | 6篇 |
2022年 | 10篇 |
2021年 | 18篇 |
2020年 | 31篇 |
2019年 | 29篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 17篇 |
2015年 | 18篇 |
2014年 | 26篇 |
2013年 | 38篇 |
2012年 | 56篇 |
2011年 | 60篇 |
2010年 | 31篇 |
2009年 | 27篇 |
2008年 | 64篇 |
2007年 | 48篇 |
2006年 | 50篇 |
2005年 | 51篇 |
2004年 | 40篇 |
2003年 | 28篇 |
2002年 | 38篇 |
2001年 | 19篇 |
2000年 | 14篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 13篇 |
1996年 | 18篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 15篇 |
1992年 | 9篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 4篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1972年 | 3篇 |
排序方式: 共有945条查询结果,搜索用时 15 毫秒
1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
2.
Takumi Watanabe Yuichiro Nishizawa Haruka Minato Dr. Chihong Song Prof. Dr. Kazuyoshi Murata Prof. Dr. Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8934-8938
The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications. 相似文献
3.
Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described. 相似文献
4.
H. Yamaguchi K. Kanisawa S. Miyashita Y. Hirayama 《Physica E: Low-dimensional Systems and Nanostructures》2004,23(3-4):285
We studied the structural, electrical, and mechanical properties of an InAs thin film grown on GaAs (1 1 1)A substrates by molecular beam epitaxy. In contrast to conventionally used (0 0 1) surfaces, where Stranski–Krastanov growth dominates the highly mismatched heteroepitaxy, layer-by-layer growth of InAs can be established. One of the largest advantages of this unique heteroepitaxial system is that it provides a two-dimensional electron gas system in the near-surface region without the problem of electron depletion. We review the fundamental properties and applications of this unique heteroepitaxial system. 相似文献
5.
A new method for rotation and brightness invariant pattern recognition was proposed by applying multiple circular harmonic expansions to the joint transform correlator. The amplitudes of the multiple orders of circular harmonic expansions made from a detecting image were synthetically modified to respond to the same auto-correlation peaks. These modified circular harmonic expansions were arranged in the input plane as reference patterns together with an arbitrary target pattern, and the correlation signals between them were calculated in the subtracted joint transform correlator. The fraction of the correlation-peak intensities between the target and the references were extracted as a new discrimination parameter. This new parameter performs pattern recognition under rotation and brightness invariance with good discriminability. Its high discriminability has been proved in computer simulations using the face image patterns of many individuals. 相似文献
6.
7.
K. Suzuki S. Miyashita K. Takashina Y. Hirayama 《Physica E: Low-dimensional Systems and Nanostructures》2004,20(3-4):232
We investigate the quantum Hall effect (QHE) in the InAs/GaSb hybridized electron–hole system grown on a conductive InAs substrate which act as a back-gate. In these samples, the electron density is constant and the hole density is controlled by the gate-voltage. Under a magnetic field perpendicular to the sample plane, the QHE appears along integer Landau-level (LL) filling factors of the net-carriers, where the net-carrier density is the difference between the electron and hole densities. In addition, longitudinal resistance maxima corresponding to the crossing of the extended states of the original electron and hole LLs make the QHE regions along integer-νnet discontinuous. Under tilted magnetic fields, these Rxx maxima disappear in the high magnetic field region. The results show that the in-plane magnetic field component enhances the electron–hole hybridization and the formation of minigaps at LL crossings. 相似文献
8.
9.
Katsunori Nishimura Rie Hidaka Fumitoshi Hirayama Hidetoshi Arima Kaneto Uekama 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):85-88
Geometries, electronic properties and NMR-shielding of cucurbit[5]uril, decamethylcucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril,
and cucurbit[8]uril are investigated with DFT calculations. All molecules are highly symmetrical with a distinct geometric
flexibility. In addition with a characteristic partial charge distribution these findings account for their chemical complex
building ability. 相似文献
10.