全文获取类型
收费全文 | 976篇 |
免费 | 28篇 |
国内免费 | 11篇 |
专业分类
化学 | 741篇 |
晶体学 | 9篇 |
力学 | 16篇 |
数学 | 70篇 |
物理学 | 179篇 |
出版年
2023年 | 5篇 |
2021年 | 13篇 |
2020年 | 17篇 |
2019年 | 20篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 29篇 |
2015年 | 13篇 |
2014年 | 17篇 |
2013年 | 49篇 |
2012年 | 57篇 |
2011年 | 60篇 |
2010年 | 44篇 |
2009年 | 29篇 |
2008年 | 53篇 |
2007年 | 66篇 |
2006年 | 48篇 |
2005年 | 59篇 |
2004年 | 62篇 |
2003年 | 55篇 |
2002年 | 28篇 |
2001年 | 20篇 |
2000年 | 21篇 |
1999年 | 16篇 |
1998年 | 11篇 |
1997年 | 11篇 |
1996年 | 12篇 |
1995年 | 5篇 |
1994年 | 8篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1985年 | 10篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 14篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1962年 | 3篇 |
排序方式: 共有1015条查询结果,搜索用时 15 毫秒
51.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
52.
The first total synthesis of mycestericin A (1) starting from tartrates is described. The Overman rearrangement of an allylic trichloroacetimidate generated a tetra-substituted carbon with nitrogen, and subsequent stereoselective transformations afforded the highly functionalized vinyl iodide. The cross-coupling of the vinyl iodide with a chiral organozinc species under Negishi conditions, followed by deprotection, completed the total synthesis of 1. 相似文献
53.
An analytical method for the determination of plutonium concentration and its isotope ratio (240Pu/239Pu) for settling particle samples by inductively coupled plasma mass spectrometry (ICP-MS) is presented. The generally used approach for Pu preconcentration by increasing the amount of samples is not applicable because of the small size of settling particle samples available for the analysis for Pu isotopes. Efforts were made to improve the sensitivity of a sector-field ICP-MS (SF-ICP-MS) and reduce the 238UH+ interference for Pu analysis by combining a high-efficiency sample introduction system (APEX-Q). An extremely low detection limit of 0.07 fg Pu was achieved, which allowed the determination of Pu isotope ratio at femtogram levels. The precision and accuracy of 240Pu/239Pu isotope ratio analysis were carefully examined with a certified Pu isotope standard (NBS-947) and an ocean sediment reference material (IAEA-368). Simple anion-exchange chromatography for the separation and purification of Pu was combined with the APEX-Q/SF-ICP-MS system to determine Pu isotopes in settling particles collected in the East China Sea continental margin. The obtained results supported a previous observation on the lateral transport of Pu containing particles in this continental margin. 相似文献
54.
Masatoshi Oue Akira Ishigaki Keiichi Kimura Yousuke Matsui Toshiyuki Shono 《Journal of polymer science. Part A, Polymer chemistry》1985,23(7):2033-2042
Poly- and bis(thiacrown ether) derivatives in which some oxygen atoms of benzocrown ether moiety are replaced by sulfur atoms have been synthesized. Their cation-binding abilities were investigated by using the solvent extraction method. The poly- and bis(benzothiacrown ether)s showed great affinity for silver ion, being more excellent in the affinity than the corresponding monocyclic analogs. They, however, possess very poor cation-binding ability for alkali and alkaline-earth metal ions. The poly- and bis(thiacrown ether)s also bind mercuric ions effectively, whereas the corresponding monomeric analogs do not at all. 相似文献
55.
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
56.
Ye S Zhou W Abe M Nishida T Cui L Uosaki K Osawa M Sasaki Y 《Journal of the American Chemical Society》2004,126(24):7434-7435
A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices. 相似文献
57.
Houjou H Kanesato M Hiratani K Mandon D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4576-4583
Novel diiron complexes with an Fe2(mu-OMe)2 core were studied as models of the active site of nonheme iron-containing enzymes. X-ray crystal structures of the complexes showed the existence of two types of ligand folding-parallel and twisted-both of which have four virtually equivalent phenolato groups sticking out from the Fe2O2 rhombic plane. Cyclic voltammetry measurements revealed two or more distinct redox waves in a region of relatively high potential, in addition to known Fe(II)/Fe(III) redox waves in a region of lower potential. These new peaks were assigned to the high-valence state of iron atoms, that is, Fe(III)Fe(IV) and Fe(IV)Fe(IV), resonating with the phenoxyl radical(s). The split width of the redox waves ranged from 0.14 to 0.20 eV, which may be a measure of the electronic interaction of the phenolate groups through the Fe2(mu-OMe)2 core. 相似文献
58.
Hui Zhao Shinji Mitsuiki Mikako Takasugi Masashi Sakai Masatoshi Goto Hiroaki Kanouchi Tatsuzo Oka 《Applied biochemistry and biotechnology》2012,166(7):1758-1768
Insoluble and hard-to-degrade animal proteins are group of troublesome proteins, such as collagen, elastin, keratin, and prion proteins that are largely generated by the meat industry and ultimately converted to industrial wastes. We analyzed the ability of the abnormal prion protein-degrading enzyme E77 to degrade insoluble and hard-to-degrade animal proteins including keratin, collagen, and elastin. The results indicate that E77 has a much higher keratinolytic activity than proteinase K and subtilisin. Maximal E77 keratinolytic activity was observed at pH 12.0 and 65 °C. E77 was also adsorbed by keratin in a pH-independent manner. E77 showed lower collagenolytic and elastinolytic specificities than proteinase K and subtilisin. Moreover, E77 treatment did not damage collagens in ovine small intestines but did almost completely remove the muscles. We consider that E77 has the potential ability for application in the processing of animal feedstuffs and sausages. 相似文献
59.
Cyclo[m]pyridine[n]pyrroles: hybrid macrocycles that display expanded π-conjugation upon protonation
Zhang Z Lim JM Ishida M Roznyatovskiy VV Lynch VM Gong HY Yang X Kim D Sessler JL 《Journal of the American Chemical Society》2012,134(9):4076-4079
Novel hybrid cyclo[m]pyridine[n]pyrroles have been synthesized using Suzuki coupling. Their NMR and optical spectroscopic features and solid state structural parameters provide support for the proposal that these species are best described as locally aromatic compounds devoid of long-range intersubunit conjugation. However, an extension of the π-conjugation in the macrocycles can be realized through protonation, as inferred from optical spectroscopic and X-ray diffraction-based structural studies. 相似文献
60.
Jinnouchi R Hatanaka T Morimoto Y Osawa M 《Physical chemistry chemical physics : PCCP》2012,14(9):3208-3218
A first principles theory combined with a continuum electrolyte theory is applied to adsorption of sulfuric acid anions on Pt(111) in 0.1 M H(2)SO(4) solution. The theoretical free energy diagram indicates that sulfuric acid anions adsorb as bisulfate in the potential range of 0.41 < U ≤ 0.48 V (RHE) and as sulfate in 0.48 V (RHE) < U. This diagram also indicates that sulfate inhibits formations of surface oxide and hydroxide. Charge analysis shows that the total charge transferred for the formation of the full coverage sulfate adlayer is 90 μC cm(-2), and that the electrosorption valency value is -0.45 to -0.95 in 0.41 < U ≤ 0.48 V (RHE) and -1.75 to -1.85 in U > 0.48 V (RHE) in good agreement with experiments reported in the literature. Vibration analysis indicates that the vibration frequencies observed experimentally at 1250 and 950 cm(-1) can be assigned, respectively, to the S-O (uncoordinated) and symmetric S-O stretching modes for sulfate, and that the higher frequency mode has a larger potential-dependence (58 cm(-1) V(-1)) than the lower one. 相似文献