全文获取类型
收费全文 | 607篇 |
免费 | 12篇 |
国内免费 | 4篇 |
专业分类
化学 | 423篇 |
晶体学 | 17篇 |
力学 | 2篇 |
数学 | 34篇 |
物理学 | 147篇 |
出版年
2023年 | 3篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 6篇 |
2018年 | 4篇 |
2016年 | 10篇 |
2015年 | 11篇 |
2014年 | 12篇 |
2013年 | 26篇 |
2012年 | 21篇 |
2011年 | 27篇 |
2010年 | 14篇 |
2009年 | 15篇 |
2008年 | 20篇 |
2007年 | 34篇 |
2006年 | 33篇 |
2005年 | 36篇 |
2004年 | 25篇 |
2003年 | 32篇 |
2002年 | 30篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 12篇 |
1998年 | 4篇 |
1997年 | 16篇 |
1996年 | 6篇 |
1995年 | 10篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1978年 | 15篇 |
1977年 | 12篇 |
1976年 | 12篇 |
1975年 | 7篇 |
1974年 | 7篇 |
1973年 | 11篇 |
1961年 | 2篇 |
排序方式: 共有623条查询结果,搜索用时 15 毫秒
1.
The composition of nickel hexacyanoferrate(II) complexes depends on the ratios of sodium hexacyanoferrate(II) and nickel nitrate solutions mixed. The adsorption behavior of nickel hexacyanoferrate(II) is described; acid treatment of Ni2Fe(CN)6 accelerates the adsorption rate of cesium, but does not increase the adsorption capacity. The Ni—Cs exchange ratios of Ni2Fe(CN)6 are discussed. In concentrated salt solutions, the distribution coefficients of 59Fe, 60Co, 65Zn. 137Cs, 95Zr and 144Ce are determined together with those of 85Sr and 106Ru. A simple determination of 137Cs in sea water containing 59Fe, 60Co, 65Zn, 95Zr, 144Ce, 85Sr and 106Ru is described. 相似文献
2.
Novel synthesis of heterocyclic spirans by tandem cycloaddition to sulfur-containing heterocumulenes
Yoshiki Ohshiro Hitoshi Nanimoto Hiroyuki Tanaka Mitsuo Komatsu Toshio Agawa Noritake Yasuoka Yasushi Kai Nobutami Kasai 《Tetrahedron letters》1985,26(25):3015-3018
Novel Ni(C0)4-promoted tandem cycloadditions of diphenylcyclo- propenone to isothiocyanates and to CS2 were found to provide new heterocyclic spirans, pyrroline-2-one-5-spiro-5′-thiolene-4′-ones and a thiolene-2-one-5-spiro-5′-thiolene-4′-one, respectively, in moderate yields. 相似文献
3.
The relationship between the chemical structure of nematic liquid crystals and their pretilt angles 总被引:1,自引:0,他引:1
About 50 different additives in one or more of three different nematic mixtures have been investigated to clarify the relationship between the chemical structure of the liquid crystal and the pretilt angle on a polyimide surface. The pretilts found for cells have been explained within our recently proposed population distribution model. For compounds with cyano-groups at one end, we find that the in-plane order is governed both by the surface-mesogen interaction and by the relative strength of the intermolecular interactions in the nematic phase. This strength is nearly linear in alkyl chain length for the compounds investigated. Changes in the strength due to variations in the core of the molecules can be calculated easily by using group contributions from the known Parachors. The in-plane order can be treated as a simple product of the contributions from the liquid crystal and from the polyimide. Different polar end groups will give different angles between the surface and the optical axis of the individual mesogens in the first monolayer. The cyano-group gives the highest angle and alkyl groups the lowest. For nitro-compounds the dimers formed are so strongly bound that they do not break up at the surface. Nitro-compounds will thus act as dialkyl compounds. For dialkyl compounds the pretilt angles are dominated by the difference between the chain lengths at the two ends of the molecule. 相似文献
4.
Kowalczyk P Jaroniec M Kaneko K Terzyk AP Gauden PA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10530-10536
In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method. 相似文献
5.
Kazuhiro Watanabe Noboru Akino Tetsuo Aoyagi Noboru Ebisawa Yukio Fujiwara Atsusi Honda Takashi Inoue Takao Itoh Mikito Kawai Minoru Kazawa Junichi Koizumi Masaaki Kuriyama Kenji Miyamoto Naoki Miyamoto Kazuhiko Mogaki Yoshihiro Ohara Tokumichi Ohga Yoshikazu Okumura Hiroshi Oohara Katsumi Ohshima Fujio Satoh Kazuhiko Shimizu Syunji Takahashi Hirotsugu Usami Katsutomi Usui Masahiro Yamamoto Takeshi Yamazaki 《Radiation Physics and Chemistry》1997,49(6):631-639
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D− ion beam. In the preliminary experiment using one ion source, a D− ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D− beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID− < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H− ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator. 相似文献
6.
Toshiko Kido Katsumi Hashizume Kenji Soda Kozi Asada ‡ 《Photochemistry and photobiology》1978,28(4-5):729-732
Abstract— 2-Nitropropane dioxygenase (EC 1. 13. 11) of the yeast Hansenula mrakii catalyzes the oxygenative denitrification of 2-nitropropane as follows:
The enzyme is significantly inhibited by superoxide dismutase and various scavengers for superoxide such as cytochrome c , epinephrine, thiols and polyhydric phenols. The scavengers added to the reaction mixture were oxidized or reduced. The addition of superoxide dismutase and the omission of 2-nitropropane or oxygen prevented the oxidation and the reduction of the scavengers. The enzyme catalyzes the formation of nitrite from 2-nitropropane by KO2 added anaerobically.
One mole of NADH is bound per mole of the enzyme and predominantly the pro-R hydrogen of bound NADH is transferred to superoxide formed enzymatically or provided externally. The enzyme shows incomplete stereospecificity for hydrogen transfer from NADH. 相似文献
The enzyme is significantly inhibited by superoxide dismutase and various scavengers for superoxide such as cytochrome c , epinephrine, thiols and polyhydric phenols. The scavengers added to the reaction mixture were oxidized or reduced. The addition of superoxide dismutase and the omission of 2-nitropropane or oxygen prevented the oxidation and the reduction of the scavengers. The enzyme catalyzes the formation of nitrite from 2-nitropropane by KO
One mole of NADH is bound per mole of the enzyme and predominantly the pro-R hydrogen of bound NADH is transferred to superoxide formed enzymatically or provided externally. The enzyme shows incomplete stereospecificity for hydrogen transfer from NADH. 相似文献
7.
Ogata H Mizoguchi Y Mizuno N Miki K Adachi S Yasuoka N Yagi T Yamauchi O Hirota S Higuchi Y 《Journal of the American Chemical Society》2002,124(39):11628-11635
The carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F has been characterized by X-ray crystallography and absorption and resonance Raman spectroscopy. Nine crystal structures of the [NiFe]hydrogenase in the CO-bound and CO-liberated forms were determined at 1.2-1.4 A resolution. The exogenously added CO was assigned to be bound to the Ni atom at the Ni-Fe active site. The CO was not replaced with H(2) in the dark at 100 K, but was liberated by illumination with a strong white light. The Ni-C distances and Ni-C-O angles were about 1.77 A and 160 degrees, respectively, except for one case (1.72 A and 135 degrees ), in which an additional electron density peak between the CO and Sgamma(Cys546) was recognized. Distinct changes were observed in the electron density distribution of the Ni and Sgamma(Cys546) atoms between the CO-bound and CO-liberated structures for all the crystals tested. The novel structural features found near the Ni and Sgamma(Cys546) atoms suggest that these two atoms at the Ni-Fe active site play a role during the initial H(2)-binding process. Anaerobic addition of CO to dithionite-reduced [NiFe]hydrogenase led to a new absorption band at about 470 nm ( approximately 3000 M(-1)cm(-1)). Resonance Raman spectra (excitation at 476.5 nm) of the CO complex revealed CO-isotope-sensitive bands at 375/393 and 430 cm(-1) (368 and 413 cm(-1) for (13)C(18)O). The frequencies and relative intensities of the CO-related Raman bands indicated that the exogenous CO is bound to the Ni atom with a bent Ni-C-O structure in solution, in agreement with the refined structure determined by X-ray crystallography. 相似文献
8.
Yatsuhisa Nagano Yuhji Achiba Kenji Sato Katsumi Kimura 《Chemical physics letters》1982,93(5):510-514
Kenetic energies and angular distributions of photoelectrons emitted by three-photon ionization fo atomic iron through two-photon resonant state e7DJ and e5 DJ, were measured, by using visible lasers. J-resolved photoelectron bands attributab to the a6DJ and a4Fj ionic states are reported. 相似文献
9.
Frieder W. Lichtenthaler Jürgen Klotz Katsumi Nakamura 《Tetrahedron: Asymmetry》2003,14(24):3973-3986
The dimethyl esters of the 2,6-anhydro-3-deoxy-hept-2-enaric acids with
-xylo,
-lyxo,
-arabino,
-lyxo- and
-ribo-configuration were synthesized from
-galactose and
-mannose, respectively, and further characterized by their di-O-acetyl and di-O-benzoyl derivatives. Comparison of their physical data with those of Daucus carota derived products revealed (−)-daucic acid to have
-lyxo-configuration 46 rather than the previously assigned
-xylo stereochemistry 1. Dimethyl daucate 43 could be converted by acid-induced ring contraction and dehydration into naturally occurring (+)-osbeckic acid 47, thereby proving its (S)-configuration. Configurational identity in the pyranoid rings of (−)-daucic acid and KDO, together with available biosynthetic evidence on chelidonic acid 4, a leaf closing factor, suggests a joint, KDO 8-P-based pathway for their biosynthesis in plants. 相似文献
10.
Phenols are ethynylated at the ortho position with silylated chloroethyne in the presence of a catalytic amount of GaCl3 and lithium phenoxide. The lithium salt is essential for the catalysis, and addition of 2,6-di(tert-butyl)-4-methylpyridine inhibits desilylation and hydration of the products. The reaction can be applied to various substituted phenols giving the ortho-ethynylated products in high yields, and the turnover numbers based on GaCl3 are between 8 and 10. The reaction mechanism involves addition of in situ formed phenoxygallium to the haloethyne followed by the elimination of GaCl3. 相似文献