全文获取类型
收费全文 | 1209篇 |
免费 | 44篇 |
国内免费 | 6篇 |
专业分类
化学 | 958篇 |
晶体学 | 14篇 |
力学 | 9篇 |
数学 | 74篇 |
物理学 | 204篇 |
出版年
2023年 | 6篇 |
2021年 | 7篇 |
2020年 | 21篇 |
2019年 | 26篇 |
2018年 | 13篇 |
2017年 | 5篇 |
2016年 | 20篇 |
2015年 | 22篇 |
2014年 | 33篇 |
2013年 | 53篇 |
2012年 | 62篇 |
2011年 | 70篇 |
2010年 | 40篇 |
2009年 | 50篇 |
2008年 | 98篇 |
2007年 | 61篇 |
2006年 | 71篇 |
2005年 | 74篇 |
2004年 | 82篇 |
2003年 | 57篇 |
2002年 | 54篇 |
2001年 | 32篇 |
2000年 | 25篇 |
1999年 | 7篇 |
1998年 | 14篇 |
1997年 | 8篇 |
1996年 | 14篇 |
1995年 | 13篇 |
1994年 | 14篇 |
1993年 | 9篇 |
1992年 | 17篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 16篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1927年 | 7篇 |
排序方式: 共有1259条查询结果,搜索用时 0 毫秒
21.
The time-resolved ESR signal of a triplet radical pair was detected upon excitation of a solid mixture of acridine and acridan at room temperature. The ZFS parameters of the triplet radical pair were determined to be D=−0.0100 cm−1 and E=0.00053 cm−1. The structure of the radical pair is discussed on the basis of the data. 相似文献
22.
Puchkaev AV Wakagi T Ortiz de Montellano PR 《Journal of the American Chemical Society》2002,124(43):12682-12683
The cytochrome P450 superfamily of enzymes catalyzes a broad range of oxidative processes involved in the metabolism of fatty acids, biosynthesis of sterols, and elimination of drugs and xenobiotics. Application of the unique properties of P450 enzymes as fine biocatalysts in biotechnology is limited due to their thermal instability and the requirement for auxiliary electron-donor proteins and cofactors. CYP119, a thermophilic P450 enzyme from Sulfolobus solfataricus, was characterized some time ago, but no high-temperature redox partners have been available for it. Here we report reconstitution of CYP119 with a novel high-temperature electron-donor system consisting of a ferredoxin and 2-oxoacid:ferredoxin oxidoreductase from Sulfolobus tokodaii strain 7 that, unlike all other known P450 electron-donor partners, utilizes coenzyme-A and pyruvic acid rather than NADH or NADPH as the source of electrons. The oxidation of lauric acid by the reconstituted system increased 16-fold as the temperature increased from 25 to 70 degrees C and was functional for more than 30 min at the higher temperature. This first in vitro high-temperature P450 catalytic system is a key step in the development of practical high-temperature monooxygenase systems. 相似文献
23.
Kobayashi S Miyamura H Akiyama R Ishida T 《Journal of the American Chemical Society》2005,127(25):9251-9254
A novel, highly active immobilized ruthenium catalyst, which can be successfully used in oxidation of alcohols to aldehydes and ketones, has been developed. In contrast to most immobilized catalysts, the Ru catalyst has activity that is higher than that of the original non-immobilized catalyst. In a batch system, the Ru catalyst was recovered and reused several times without loss of activity. The catalyst was also applied to a flow system, in which excellent conversions and yields were demonstrated. No leaching of Ru was observed in both cases. 相似文献
24.
Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations 总被引:1,自引:0,他引:1
Aqueous suspensions of hydrothermally synthesized titanate nanotubes and poly(diallyldimethylammonium chloride) (PDDA) have been employed to fabricate multilayer films on various substrates in a layer-by-layer fashion. Atomic force microscopy displays the dense coverage of the substrate surface by the nanotubes. UV-vis absorption spectroscopy confirms the consecutive growth of PDDA/nanotube layer pairs. Single crystalline Ag and Au nanoparticles with narrow size distribution spatially correlating with the nanotubes have been obtained by treating the nanotubes with AgNO(3) or HAuCl(4) aqueous solution followed by chemical reduction. The noble metal nanoparticles show a strong surface plasmon absorption band. A multilayer film construction of the noble-metal-loaded nanotubes has also been achieved. This process has been further extended to the heteroassembly of nanotubes/nanosheets in different layer sequences. 相似文献
25.
[6n]Paracyclophenediynes 2a-d (n = 3-6) having [4.3.2]propellatriene units were prepared as precursors of the corresponding [6n]paracyclophynes. Laser irradiation of 2a-d produced the negative ions of [6n]paracyclophynes 1a-d (n = 3-6) by extrusion of the indan fragments, which were detected by time-of-flight mass spectrometry. 相似文献
26.
Sadafumi NishiharaTomoyuki Akutagawa Tatsuo Hasegawa Shigeki FujiyamaToshikazu Nakamura Takayoshi Nakamura 《Journal of solid state chemistry》2002,168(2):661-667
Two polymorphs of monovalent [Ni(dmit)2]− (dmit2−=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)2], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)2]− molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)2], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)2]− dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)2]− arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K. 相似文献
27.
In acidic aqueous solution, a cobalt(III) complex containing monodentate N(9)-bound adeninate (ade(-)), cis-[Co(ade-kappaN(9))Cl(en)(2)]Cl (cis-[1]Cl), underwent protonation to the adeninate moiety without geometrical isomerization or decomposition of the Co(III) coordination sphere, and complexes of cis-[CoCl(Hade)(en)(2)]Cl(2) (cis-[2]Cl(2)) and cis-[Co(H(2)ade)Cl(en)(2)]Cl(3) (cis-[3]Cl(3)) could be isolated. The pK(a) values of the Hade and H(2)ade(+) complexes are 6.03(1) and 2.53(12), respectively, at 20 degrees C in 0.1 M aqueous NaCl. The single-crystal X-ray analyses of cis-[2]Cl(2).0.5H(2)O and cis-[3]Cl(2)(BF(4)).H(2)O revealed that protonation took place first at the adeninate N(7) and then at the N(1) atoms to form adenine tautomer (7H-Hade-kappaN(9)) and cationic adeninium (1H,7H-H(2)ade(+)-kappaN(9)) complexes, respectively. On the other hand, addition of NaOH to an aqueous solution of cis-[1]Cl afforded a mixture of geometrical isomers of the hydroxo-adeninato complex, cis- and trans-[Co(ade-kappaN(9))(OH)(en)(2)](+). The trans-isomer of chloro-adeninato complex trans-[Co(ade-kappaN(9))Cl(en)(2)]BF(4) (trans-[1]BF(4)) was synthesized by a reaction of cis-[2](BF(4))(2) and sodium methoxide in methanol. This isomer in acidic aqueous solution was also stable toward isomerization, affording the corresponding adenine tautomer and adeninium complexes (pK(a) = 5.21(1) and 2.48(9), respectively, at 20 degrees C in 0.1 M aqueous NaCl). The protonated product of trans-[Co(7H-Hade-kappaN(9))Cl(en)(2)](BF(4))(2).H(2)O (trans-[2](BF(4))(2).H(2)O) could also be characterized by X-ray analysis. Furthermore, the hydrogen-bonding interactions of the adeninate/adenine tautomer complexes cis-[1]BF(4), cis-[2](BF(4))(2), and trans-[2](BF(4))(2) with 1-cyclohexyluracil in acetonitrile-d(3) were investigated by (1)H NMR spectroscopy. The crystal structure of trans-[Co(ade)(H(2)O)(en)(2)]HPO(4).3H(2)O, which was obtained by a reaction of trans-[Co(ade)(OH)(en)(2)]BF(4) and NaH(2)PO(4), was also determined. 相似文献
28.
To gain knowledge about biological iron mobilization, tripodal monotopic and ditopic hydroxamate ligands (1 and 2) are prepared, and their iron-chelating properties are investigated. Ligands 1 and 2 contain three Ala-Ala-beta-(HO)Ala units and three [Ala-Ala-beta-(HO)Ala](2) units connected with tris(alanylaminoethyl)amine, respectively, and form six-coordinate octahedral complexes with iron(III) in aqueous solution. Ligand 1 and 1 equiv of iron give Fe-1, and ligand 2 and 1 or 2 equiv of iron produce Fe(1)-2, or Fe(2)-2. These complexes exhibit absorptions at lambda(max) 425 nm of epsilon 2800-3000/Fe, characteristic of tris(hydroxamato)iron(III) complexes, and preferentially assume the Delta-cis configuration. Loading of Fe(III) on 1, 2, and M(III)-loaded ligands (M-1 and M(1)-2, M = Al, Ga, In) with ammonium ferric oxalate at pH 5.4 is performed, and the second-order rate constants of loading with respect to Fe(III) and the ligand or M(III)-loaded ligands are determined. The rates of loading of Fe(III) on M-1 increase in the order Al-1 < Ga-1 < In-1, and those on M(1)-2 in the order Al(1)-2 < Ga(1)-2 < Fe(1)-2 < In(1)-2, indicating that the dissociation tendency of M(III) ions from the hydroxamate ligand is an important factor. The iron complexes formed with 2 are subjected to an iron removal reaction with excess EDTA in aqueous pH 5.4 solution at 25.0 degrees C, and the collected data are analyzed by curve-fitting using appropriate first-order kinetic equations, providing the rate constants for the upper site and the lower site of 2. Similar analysis for FeM-2 affords removal rate constants for Fe(up)-2, M(up)-2, and Fe(low)-2, and the iron residence probability at each site. The protonation constants of the hydroxamate groups for 1 and 2 (pK(1,) pK(2), pK(3), and pK(1,) pK(2)., pK(6)) are determined, and the proton-independent stability constants for Fe-1, the upper site of Fe(2)-2, and the lower site of Fe(1)-2 are 10(28), 10(29), and 10(28.5), respectively. 相似文献
29.
Kaori Suzuki Takayoshi Kobayashi Hiroyuki Ohtani Hiroshi Yesaka Saburo Nagakura Yoshinori Shichida Tôru Yoshizawa 《Photochemistry and photobiology》1980,32(6):809-811
Difference spectra between squid rhodopsin and its bathorhodopsin at room temperature were measured ca. 150 ps and ca. 500 ps after the excitation at 347.2 nm by a double-beam picosecond time-resolved spectrometer. The spectra measured showed a red shift of the isosbestic point between squid rhodopsin and its bathorhodopsin and a lower ΔAmax/ΔAmin value compared with those measured at low temperatures by conventional spectrophotometry. 相似文献
30.
Kazunori Takada Hiroya Sakurai Fujio Izumi Takayoshi Sasaki 《Journal of solid state chemistry》2004,177(1):372-376
Monolayer hydrate (MLH) NaxCoO2·y′H2O was obtained from superconducting bilayer hydrate (BLH) NaxCoO2·yH2O by partial extraction of H2O molecules between the CoO2 layers. Magnetization measurements indicated that electron densities in the CoO2 layer of the MLH phase remained unchanged after the water extraction. Nevertheless, superconductivity was completely suppressed in the MLH phase. This strongly suggests that the highly 2D nature in the BLH phase due to its thick insulating layers consisting of H2O molecules and Na+ ions plays an important role for inducing superconductivity. 相似文献