全文获取类型
收费全文 | 1677篇 |
免费 | 63篇 |
国内免费 | 8篇 |
专业分类
化学 | 1327篇 |
晶体学 | 31篇 |
力学 | 23篇 |
数学 | 171篇 |
物理学 | 196篇 |
出版年
2023年 | 9篇 |
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 23篇 |
2019年 | 31篇 |
2018年 | 17篇 |
2017年 | 21篇 |
2016年 | 39篇 |
2015年 | 36篇 |
2014年 | 40篇 |
2013年 | 97篇 |
2012年 | 112篇 |
2011年 | 115篇 |
2010年 | 55篇 |
2009年 | 68篇 |
2008年 | 116篇 |
2007年 | 108篇 |
2006年 | 100篇 |
2005年 | 93篇 |
2004年 | 94篇 |
2003年 | 80篇 |
2002年 | 65篇 |
2001年 | 12篇 |
2000年 | 29篇 |
1999年 | 12篇 |
1998年 | 24篇 |
1997年 | 23篇 |
1996年 | 18篇 |
1995年 | 15篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 16篇 |
1986年 | 6篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 24篇 |
1979年 | 15篇 |
1978年 | 14篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有1748条查询结果,搜索用时 15 毫秒
71.
72.
Kyoungmin Kang Kosuke Sakamoto Dr. Yoshihiro Nishimoto Prof. Dr. Makoto Yasuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4930-4934
The regioselective anti-carboindation of ynamides by using InBr3 and silylated nucleophiles was developed to synthesize (Z)-β-(carbonylamino)alkenylindiums. The X-ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti-addition fashion. In contrast to reported syn-carbometalations of ynamides by using organometallics, a cooperation of InBr3 and silylated nucleophiles to ynamides achieved an anti-addition, which was supported by DFT calculations. The scope of substrates included various ynamides and silylated nucleophiles, such as silyl ketene acetals and silyl ketene imines. The transformation of synthesized alkenylindiums by iodination, radical coupling, and Pd-catalyzed cross-coupling successfully afforded trisubstituted enamines with high regio- and stereoselectivities. 相似文献
73.
74.
Yoshihiro Hamaya 《Journal of Difference Equations and Applications》2013,19(9):805-817
We introduce the concept of the second Liapunov differences in difference equations and show that, in the autonomous case, the second variations can guarantee the existence of solutions tending to zero while others starting arbitrarily near 0 go to ∞. These are based on Yorke's results for ordinary differential equations. 相似文献
75.
Yoshihiro Abe Hideo Hosono Takayuki Kamae Kouichi Kawashima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):113-116
Abstract Protons in alkaline-earth phosphate glasses give much higher mobility than those in silicate glasses. This is caused by the difference in O-H bonding state. Protons in P-OH form a strong hydrogen bonding with oxygen anion, resulting in formation of weak O-H bond. The electrical conductivity of the glasses is proportional to the square of the proton concentration. The activation energy for the conduction is related to νOH, peak wavenumber of infrared absorption band (around~3000 cm?1), due to fundamental O-H stretching vibration. The mobility of protons increases with decreasing νOH, which depends on the species of ions included in the phosphate glasses. 相似文献
76.
Yoshimi Kurimura Masahiro Saito Kyota Hiramatsu Yoshihiro Sairenchi 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9-11):1275-1292
Electron transfer reactions of Co(NH3)5PAA (PAA = polyacrylic acid) with either the polyanionic polymer-bound ferrous chelate, Fe11P-SS (P-SS = vinylbenzylaminediacetate-co-styrenesulfonate) or the uncharged polymer-bound ferrous chelate, Fe11P-VPRo (P-VPRo = vinylbenzylaminediacetate-co-vinylpyrrolidone), and the Ru(bpy)2+ 3 photosensitized reduction of Co(NH3)5PAA have been investigated in aqueous solutions at pH 5.4, I = 0.06 (I is ionic strength), and 25°C. For the ferrous chelate reductions, the second-order rate constants for Fe11-PSS and Fe11P-VPRo were almost equal to that for the corresponding nonpolymer-bound ferrous chelate, Fe11BDA (BDA = benzylaminediacetate). The results indicate that there is no appreciable steric hindrance due to the polymer chains of the polymer-bound ferrous chelates and that the effect of columbic repulsion force between the polyanion chains can be ignored for the reaction of Co(NH3)5PAA with Fe11P-SS. The results also suggest that there are two kinds of the pendant Co(III) species, “reactive” and “inert.” The inert Co(III) species are shielded by the polymer chains from attack of the Fe(II) chelates that are present in the bulk solutions. A similar reaction behavior was observed in the Ru(bpy)2+ 3 photosensitized reduction of Co(NH3)5PAA at pH 5.4. For the Co(III) complex having an extremely few Co(III) complex moieties on the polymer chain, almost all of the Co(III) groups were hardly reduced by the excited state of Ru(bpy)2+ 3, and reverse quenching occurred due to binding of the Ru(bpy)2+ 3 to the polyacrylic acid chain of the polymer complex. On the other hand, for Co(NH3)5PAA with a relatively large number of the Co(III) moieties on the polymer chain, lifetime measurements at a higher concentration of the Ru(bpy)2+ 3 showed a double-exponential fit, which suggests that there are two parallel decay processes. The fast and slow components mainly correspond to the decays: Ru(bpy)2+ 3 quenched by Co(III) and reverse quenching due to binding of Ru(bpy)2+ 3 into the compact polymer chains. 相似文献
77.
Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co2(CO)8) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co2(CO)8-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed. 相似文献
78.
Kiyofumi Katagiri Keiko Ohta Kunihito Koumoto Kei Kurosu Yoshihiro Sasaki Kazunari Akiyoshi 《Colloid and polymer science》2013,291(6):1375-1380
Novel organic–inorganic hybrid nanoparticles consisting of polymer–hydrogel nanoparticles (nanogels) and iron oxide were developed for potential biomedical applications. Hybrid nanoparticles were prepared by a simple procedure using polysaccharide nanogels as a reactive site for iron oxide formation. The hybrid nanoparticles have a narrow size distribution with a diameter of approximately 30 nm and show high colloidal stability. These nanohybrid particles could be used as a contrast medium for magnetic resonance imaging or for magnetic hyperthermia therapy. 相似文献
79.
Yoshihiro Shigemasa Kuninori Oogaki Nasuo Ueda Ruka Hakashima Ken-Ichi Harada Naohito Takeda 《Journal of carbohydrate chemistry》2013,32(3):325-330
Abstract The formose reaction, by which a complex mixture of sugars and sugar alcohols (the so-called formose) are produced by the base-catalyzed condensation of formaldehyde, has received much attention in connection with the prebiotic synthesis of carbohydrates2 and the microbial utilization of formose.3–5 Formose, however, has not been useful yet, because of the complexity of this product mixture (Fig. 1a). Therefore, it seemed desirable to make the reaction more selective. 相似文献
80.
Yoshihiro Shigemasa Takaaki Ueda Hiroyuki Saimoto 《Journal of carbohydrate chemistry》2013,32(4):669-673
Abstract The formose reactions2 in N,N-dimethylformamide (DMF) catalyzed by 2-(dimethylamino)ethanol and thiamine hydrochloride, have been found to give rise to dihydroxyacetone and DL-glycero-tetrulose selectively at 1.1 M and 3.0 M of formaldehyde concentration, respectively. In our consecutive study on the formose reaction in DMF, it has been fortunately found that the distribution of products is able to be controlled by the amount of water added to the reaction mixture. We describe herein the first example of the favored formation of DL-2-C-hydroxymethyl-3-pentu-lose (GP-191) in the formose reaction using DMF-H2O solvent, and it's isolation and structure elucidation. 相似文献