全文获取类型
收费全文 | 1156篇 |
免费 | 49篇 |
国内免费 | 4篇 |
专业分类
化学 | 854篇 |
晶体学 | 20篇 |
力学 | 17篇 |
数学 | 68篇 |
物理学 | 250篇 |
出版年
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 20篇 |
2018年 | 16篇 |
2017年 | 13篇 |
2016年 | 29篇 |
2015年 | 27篇 |
2014年 | 18篇 |
2013年 | 41篇 |
2012年 | 73篇 |
2011年 | 75篇 |
2010年 | 45篇 |
2009年 | 48篇 |
2008年 | 70篇 |
2007年 | 57篇 |
2006年 | 63篇 |
2005年 | 66篇 |
2004年 | 59篇 |
2003年 | 49篇 |
2002年 | 42篇 |
2001年 | 25篇 |
2000年 | 28篇 |
1999年 | 9篇 |
1998年 | 15篇 |
1997年 | 13篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 14篇 |
1992年 | 23篇 |
1991年 | 20篇 |
1990年 | 18篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 13篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 6篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 11篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1972年 | 6篇 |
1969年 | 8篇 |
排序方式: 共有1209条查询结果,搜索用时 515 毫秒
61.
62.
63.
64.
Keiichi Kimura Akira Matsui Yoshiaki Inaki Kiichi Takemoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):1231-1241
Polymerization of acrylonitrile initiated by triazole-copper(II) complexes was studied in dimethylsulfoxide solution. It was found that the polymerization proceeds by a free radical mechanism; however, the complexes can hardly homopolymerize methyl methacrylate and styrene. Ability of the complexes to initiate polymerization seems to depend on the substituents of triazole, the sort of solvents, and the counterions of copper(n) salts. From the data of visible spectroscopy and the spin trapping, the initiation mechanism was discussed in terms of reduction of copper(II) followed by forming active species. 相似文献
65.
Takayoshi Kimura Tasunori Suzuki Keisuke Takata Akina Soga Yutsa Nomoto Tadashi Kamiyama Yousuke Nakai Hideo Matsui Masao Fujisawa 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1467-1474
The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K 1 expressed in terms of mole fractions and standard thermodynamic properties of formation (Δf H, Δf G, Δf S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group. 相似文献
66.
Yoshio Kobayashi Tsukasa Shirochi Takafumi Maeda Yusuke Yasuda Toshiaki Morita 《Surface and interface analysis : SIA》2013,45(9):1424-1428
This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu2+ (0.01 M (CH3COO)2Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10?4 M citric acid and 5 × 10?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H2 gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
67.
A series of liquid crystalline compounds having the difluoropropyleneoxy moiety (–OCF2C2H4–) as a linking group has been synthesized. The physical properties, i.e. dielectric anisotropy, birefringence, viscosity and phase transition temperatures, have been measured. This novel class of compounds shows a larger negative dielectric anisotropy than the corresponding compounds having a propyleneoxy (–OC3H6–) linking group. Their dielectric properties may be explained by the combined effect of fluorine atoms with large electron negativities and the electron donating feature of an oxygen atom substituted on the same carbon atom. The semi‐empirical quantum calculation method (AM1) also confirmed this dielectric behaviour of the difluoropropyleneoxy linkage group. 相似文献
68.
Takafumi Osuga Takashi Murase Manabu Hoshino Makoto Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(42):11368-11371
A tray‐shaped PdII3AuI3 complex ( 1 ) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with AuI followed by PdII clipping. Tray 1 is an efficient scaffold for the modular assembly of [3×n] AuI clusters. Treatment of 1 with the AuI3 tricyclic guest 2 in H2O/CH3CN (7:3) or H2O results in the selective formation of a [3×2] cluster ( 1 ⋅ 2 ) or a [3×3] cluster ( 1 ⋅ 2 ⋅ 1 ), respectively. Upon subsequent addition of AgI ions, these complexes are converted to an unprecedented Au3–Au3–Ag–Au3–Au3 metal ion cluster. 相似文献
69.
Copper‐Catalyzed CH Bond Direct Chalcogenation of Aromatic Compounds Leading to Diaryl Sulfides,Selenides, and Diselenides by Using Elemental Sulfur and Selenium as Chalcogen Sources Under Oxidative Conditions 下载免费PDF全文
Prof. Fumitoshi Shibahara Takafumi Kanai Eiji Yamaguchi Akika Kamei Takayuki Yamauchi Prof. Toshiaki Murai 《化学:亚洲杂志》2014,9(1):237-244
The reactions of aromatic compounds and elemental chalcogens catalyzed by a copper salt with molecular oxygen as an oxidant were carried out. The reaction of 3‐substituted imidazo[1,5‐a]pyridines and elemental sulfur in the presence of CuTC (copper(I) thiophenecarboxylate) gave the corresponding bisimidazopyridyl sulfides in good to quantitative yields. The reaction proceeded even under aerobic oxidation conditions. The use of a polar solvent was crucial for the reaction, and DMSO (dimethyl sulfoxide) in particular stimulated the reaction. The reaction could be applied to common aromatic compounds, such as N‐methyl indole and dialkyl anilines. The reaction of indole proceeded at the nucleophilic C3 position rather than at the acidic C2 position. In addition, the reaction of dialkyl anilines proceeded with an ortho, para orientation. The reactions of imidazopyridines and elemental selenium under similar conditions gave the corresponding bisimidazopyridyl diselenides along with bisimidazopyridyl monoselenides. The resulting diselenides were readily converted to the corresponding monoselenides with unreacted imidazopyridines under the same conditions. The reaction could be applied to the copolymerization of bifunctional bisimidazopyridines and elemental sulfur to give oligomeric copolymers in quantitative yield. 相似文献
70.
Dr. Atsuko Masuya-Suzuki Satoshi Goto Takafumi Kambe Dr. Ryunosuke Karashimada Dr. Yasuhiro Kubota Prof. Nobuhiko Iki 《ChemistryOpen》2021,10(1):46-55
We prepared Ln(III) (Ln=Eu, Gd, and Yb) complexes with a tripodal Schiff base, tris[2-(5-methylsalicylideneimino)ethyl]amine (H3L) and studied their photophysical properties. Upon ligand excitation, YbL showed Yb(III)-centered luminescence in the near-infrared region. While the overall quantum yield (0.60(1)%) of YbL in acetonitrile was moderate among the reported values for Yb(III) complexes, its radiative lifetime (0.33(2) ms) was significantly shorter than those reported previously. We propose that the ligand-to-metal charge-transfer (LMCT) state mediated the sensitization in YbL. The emission and excitation spectra of EuL indicated the participation of the LMCT state in the sensitization. The radiative lifetime (0.84(7) ms) for EuL in the solid state was rather short compared to those of reported Eu(III) complexes. Our results show that the Yb(III) complex with the Schiff base ligand has two features: the short radiative lifetime and the non-triplet sensitization path. 相似文献