全文获取类型
收费全文 | 2931篇 |
免费 | 82篇 |
国内免费 | 7篇 |
专业分类
化学 | 2250篇 |
晶体学 | 46篇 |
力学 | 21篇 |
数学 | 146篇 |
物理学 | 557篇 |
出版年
2023年 | 18篇 |
2022年 | 24篇 |
2021年 | 35篇 |
2020年 | 65篇 |
2019年 | 45篇 |
2018年 | 45篇 |
2017年 | 30篇 |
2016年 | 77篇 |
2015年 | 58篇 |
2014年 | 94篇 |
2013年 | 139篇 |
2012年 | 200篇 |
2011年 | 254篇 |
2010年 | 124篇 |
2009年 | 116篇 |
2008年 | 210篇 |
2007年 | 199篇 |
2006年 | 204篇 |
2005年 | 189篇 |
2004年 | 167篇 |
2003年 | 135篇 |
2002年 | 135篇 |
2001年 | 42篇 |
2000年 | 33篇 |
1999年 | 21篇 |
1998年 | 28篇 |
1997年 | 23篇 |
1996年 | 29篇 |
1995年 | 19篇 |
1994年 | 18篇 |
1993年 | 11篇 |
1992年 | 16篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 16篇 |
1982年 | 19篇 |
1981年 | 10篇 |
1980年 | 18篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 11篇 |
1975年 | 8篇 |
1974年 | 5篇 |
1967年 | 5篇 |
1966年 | 7篇 |
排序方式: 共有3020条查询结果,搜索用时 0 毫秒
181.
Dr. Yong-Sheng Wei Dr. Liming Sun Miao Wang Dr. Jinhua Hong Dr. Lianli Zou Hongwen Liu Dr. Yu Wang Dr. Mei Zhang Dr. Zheng Liu Prof. Yinwei Li Prof. Satoshi Horike Prof. Kazu Suenaga Prof. Qiang Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16147-16156
Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear FeIII2FeII complex (denoted as Fe3) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of FeII by other metal(II) ions (e.g., ZnII/CoII) via synthesizing isostructural trinuclear-complex precursors (Fe2Zn/Fe2Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities. 相似文献
182.
Daisuke Saito Dr. Tomohiro Ogawa Dr. Masaki Yoshida Junichi Takayama Dr. Satoshi Hiura Prof. Dr. Akihiro Murayama Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18882-18889
A series of assembled PtII complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups, [Pt(CN)2(R-impy)] (R-impyH+=1-alkyl-3-(2-pyridyl)-1H-imidazolium, R=Me ( Pt-Me ), Et ( Pt-Et ), iPr ( Pt- i Pr ), and tBu ( Pt- t Bu )). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield of 0.51–0.81 in the solid state at room temperature, originating from the triplet metal-metal-to-ligand charge transfer (3MMLCT) state. Their emission colors cover the entire visible region from red for Pt-Me to blue for Pt- t Bu . Importantly, Pt- t Bu is the first example that exhibits blue 3MMLCT emission. The 3MMLCT emission was proved and characterized based on the temperature dependences of the crystal structures and emission properties. The wide-range color tuning of luminescence using the 3MMLCT emission presents a new strategy of superfine control of the emission color. 相似文献
183.
Sayoko?Nagashima Satoshi?Kamiguchi Satoshi?Ohguchi Teiji?ChiharaEmail author 《Journal of Cluster Science》2011,22(4):647-660
Pyridine is allowed to react with methanol under a hydrogen stream in the presence of (H3O)2[(W6Cl8)Cl6]·6H2O supported on silica gel. When the temperature is raised above 200 °C, the catalytic activity of the cluster appears. Methylation of pyridine proceeds yielding 2-methylpyridine in 61% selectivity at 400 °C. The corresponding hexanuclear chloride clusters of niobium, molybdenum, and tantalum also catalyze the reaction. Ethanol affords the corresponding 2-ethylpyridine. When phenol is allowed to react with methanol in the presence of (H3O)2[(Mo6Cl8)Cl6]·6H2O supported on silica gel in the same manner, selective O-methylation proceeds yielding anisole in 57% selectivity at 150–200 °C. Above 250 °C, C-methylation predominates and provides o-cresol with 67% selectivity at 300 °C. The corresponding clusters of niobium, tantalum, and tungsten also catalyze the reaction. Ethanol and 1-propanol afford the corresponding 2-alkylphenols. Alkyl cations produced over weak Brønsted acid sites (H 0 ≈ +1.3) developed on the clusters are assumed as intermediates for both reactions. 相似文献
184.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献
185.
Satoshi Anezaki Yoshitaka Yamaguchi Masatoshi Asami 《Journal of organometallic chemistry》2011,696(11-12):2399-2405
New o-xylylene-linked bis(benzimidazolium) salts were synthesized in six-steps from C2-symmetric chiral 1,4-diol, 1,2-bis(1-hydroxypropyl)benzene, as a starting material. The silver complex of bis(benzimidazol-2-ylidene) was obtained on treatment of bis(benzimidazolium) salt with silver oxide. The reaction of the silver bis-NHC with [PdCl2(PhCN)2] afforded the bis-NHC complex of palladium. The X-ray diffraction studies on Pd complexes revealed that these complexes have distorted square planar geometry around the Pd center coordinating the NHC ligand in mutually cis-position. The arene ring of o-xylylene unit hanged over the Pd center and thus these complexes showed C1-symmetric structures. The variable temperature NMR spectroscopy revealed that these Pd complexes showed fluxional behavior between C1- and C2-symmetric structures in solution state. 相似文献
186.
A self-propelled object coupled with an enzyme reaction between urease and urea was investigated at the air/aqueous interface. A plastic object that was fixed to a urease-immobilized filter paper was used as a self-propelled object, termed a urease motor, placed on an aqueous urea solution. The driving force of the urease motor is the difference in the surface tension around the object. Oscillatory motion or no motion was triggered depending on the initial pH of the urea solution. Both the frequency and maximum speed of the oscillatory motion varied depending on the initial pH of the water phase. The mechanisms underlying the oscillatory motion and no motion were discussed in relation to the bell-shaped enzyme activity of urease in the enzyme reaction and the surface tension around the urease motor. 相似文献
187.
Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode 总被引:7,自引:0,他引:7
Tsuboyama A Iwawaki H Furugori M Mukaide T Kamatani J Igawa S Moriyama T Miura S Takiguchi T Okada S Hoshino M Ueno K 《Journal of the American Chemical Society》2003,125(42):12971-12979
Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32). 相似文献
188.
Density functional theory calculations were carried out for the title reactions. Ethylene oxide and methylamine were adopted as reactants. Amine clusters (dimer, trimer, tetramer, and pentamer) were considered, because the combination of one oxide and one amine molecule gave a large activation energy. An amine tetramer was found to react favorably with the oxide via various zwitterionic intermediates. A back-side S(N)2 nucleophilic attack of one amine and the subsequent proton relay up to the front side provide a stabilized reaction field. The amine-alcohol mixed reactant may react readily with the oxide, because the alcoholic O-H group is in contact with the oxide oxygen with the strong hydrogen-bond stabilization. 相似文献
189.
Oderaotoshi Y Cheng W Fujitomi S Kasano Y Minakata S Komatsu M 《Organic letters》2003,5(26):5043-5046
High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first example of an exo-selective cycloaddition. [reaction: see text] 相似文献
190.
Tatsuro Ouchi Hirotoshi Fujie Satoshi Jokei Yoshiomi Sakamoto Hidenori Chikashita Takeshi Inoi Otto Vogl 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2059-2074
Acryloyl-type polymer fixing 1-β-carbonylethyl-5-fluorouracil residues through D -glucofuranoses via ester bonds was synthesized by means of polymerization of the corresponding monomer and polymer reaction. In order to provide the water-soluble objective polymer, the copolymerization of the acryloyl-type monomer with acrylamide was carried out. The extent of release of 5-FU residues from the copolymer was investigated in the enzyme or nonenzyme system in vitro. Furthermore, the antitumor activities of the water-insoluble homopolymer and water-soluble copolymer obtained were tested in vivo. 相似文献