全文获取类型
收费全文 | 4478篇 |
免费 | 148篇 |
国内免费 | 36篇 |
专业分类
化学 | 3280篇 |
晶体学 | 44篇 |
力学 | 114篇 |
数学 | 653篇 |
物理学 | 571篇 |
出版年
2023年 | 18篇 |
2022年 | 38篇 |
2021年 | 49篇 |
2020年 | 81篇 |
2019年 | 85篇 |
2018年 | 57篇 |
2017年 | 50篇 |
2016年 | 115篇 |
2015年 | 104篇 |
2014年 | 96篇 |
2013年 | 191篇 |
2012年 | 316篇 |
2011年 | 369篇 |
2010年 | 149篇 |
2009年 | 148篇 |
2008年 | 308篇 |
2007年 | 284篇 |
2006年 | 325篇 |
2005年 | 288篇 |
2004年 | 240篇 |
2003年 | 233篇 |
2002年 | 187篇 |
2001年 | 57篇 |
2000年 | 46篇 |
1999年 | 32篇 |
1998年 | 40篇 |
1997年 | 54篇 |
1996年 | 75篇 |
1995年 | 38篇 |
1994年 | 37篇 |
1993年 | 33篇 |
1992年 | 34篇 |
1991年 | 18篇 |
1990年 | 30篇 |
1989年 | 21篇 |
1988年 | 28篇 |
1987年 | 21篇 |
1986年 | 19篇 |
1985年 | 52篇 |
1984年 | 35篇 |
1983年 | 19篇 |
1982年 | 37篇 |
1981年 | 28篇 |
1980年 | 26篇 |
1979年 | 27篇 |
1978年 | 18篇 |
1977年 | 16篇 |
1976年 | 17篇 |
1975年 | 13篇 |
1974年 | 12篇 |
排序方式: 共有4662条查询结果,搜索用时 0 毫秒
71.
Highly ordered mesoporous inorganic-organic hybrid thin films with covalently bonded carboxylic acid (-COOH) terminal groups on the pore surfaces were synthesized by evaporation induced self-assembly of tetraethoxysilane, organosilanes, and a nonionic surfactant followed by acid hydrolysis and characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, surface acoustic wave (SAW) based N2 sorption, and thermogravimetric analysis (TGA) techniques. 相似文献
72.
Clark SB Turnipseed SB Nandrea GJ Madson MR Hurlbut JA Sofos JN 《Journal of AOAC International》2002,85(5):1009-1014
A confirmatory method is described for phenylbutazone (PB) residues in bovine kidney tissue. Ground kidney tissue is diluted with water, and the mixture is made basic with 25% ammonium hydroxide in water; the lipids are extracted with ethyl and petroleum ethers. The ether layer is discarded, and the tissue is acidified with 6N HCl. PB residues are extracted with tetrahydrofuranhexane (1 + 4). The extract is passed through a silica solid-phase extraction column, and the eluate is evaporated to dryness. The residue is dissolved in acidified acetonitrile-water-acetic acid (50 + 49.4 + 0.6). A single quadrupole mass spectrometer coupled to a liquid chromatograph with an electrospray interface is used to confirm the identity of the PB residues in the kidney extract. Negative-ion detection with selected-ion monitoring of 4 ions is used. Sets of control and fortified-control kidney tissues (at 50, 100, and 200 ppb PB) and several kidney tissue field samples were analyzed for method validation. The method was tested further during the course of a survey to determine the incidence of PB residues in bovine kidney samples obtained from slaughterhouses across the country. In addition, the method was tested for use with an ion-trap mass spectrometer coupled to a liquid chromatograph, which allowed confirmation of PB at lower levels (5-10 ppb) in kidney tissue. 相似文献
73.
Gary A. Baker Jeffrey D. Jordan Frank V. Bright 《Journal of Sol-Gel Science and Technology》1998,11(1):43-54
We investigate the effects of controlled poly(ethylene glycol) (PEG) doping on the behavior of pyrene, rhodamine 6G (R6G), and acrylodan-labeled bovine serum albumin (BSA-Ac) sequestered within tetramethylorthosilicate (TMOS)-derived sol-gel-processed materials. To probe the dipolarity of the local environment within the composite we performed static fluorescence measurements on pyrene as the composites aged. We found that small levels of PEG loading effected significant enhancements in the local dipolarity surrounding the average pyrene molecule. Time-resolved fluorescence anisotropy measurements were used to follow the rotational reorientation dynamics of R6G as the composites aged. As the PEG loading increased, the R6G reorientational mobility increased. Nitrogen adsorption techniques were used to quantify the effects of PEG doping level on the surface area and final xerogel pore features. A large reduction in surface area was observed with PEG doping, but no detectable change in pore size was noted. The effects of PEG doping on a biomolecule were probed by following the time-resolved fluorescence anisotropy decay of BSA-Ac. These results showed that PEG doping resulted in increased biomolecule dynamics relative to that found for a neat, undoped TMOS-derived composites. Together these results show that PEG doping can be used to tune the sol-gel-processed composite dipolarity, alter the mobility of dopants sequestered within the composite, control analyte acessibility to the sensing chemistry, and modulate the internal dynamics within a biodopant. 相似文献
74.
Kaster Jeffrey A. Michelsen Donald L. Velander William H. 《Applied biochemistry and biotechnology》1990,(1):469-484
A microbubble dispersion (MBD) was used to supply oxygen for aerobic fermentations in a standard 2 L stirred tank fermenter.
The microbubble dispersion was formed using only surfactants produced naturally. Growth rates ofSaccharomyces cerevisiae cultures were found to be equal or greater with MBD sparging than with gas sparging. The oxygen transfer coefficent with
MBD sparging was found to be 190/h and independent of impeller speed from 100–580 rpm. The oxygen transfer coefficient with
air sparging rose from 55 to 132/h over the same range of impeller speeds. Power requirements for the fermenter systems were
estimated. 相似文献
75.
Ruifeng Liu Paula R. Moody Alex S. Vanburen Jeffrey A. Clark Joel A. Krauser Dennis R. Tate 《Vibrational Spectroscopy》1996,10(2):325-329
Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results. 相似文献
76.
77.
Jeffrey Kovac 《Foundations of Chemistry》2002,4(2):163-171
Traditional philosophy of science regards theoretical reasoning, based on the example of Euclidian geometry, as the hallmark
of a mature science. There is, however, a parallel tradition of practical reasoning based on specific cases that goes back
to Aristotle. In this paper I argue that practical reasoning is an essential part of the practice of chemistry and should
be understood and appreciated on its own merits rather than regarded as a symbol of the immaturity and inferiority of chemistry
as a science.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
78.
The distances and orientations among reactant centers in the active site of coenzyme B12-dependent ethanolamine deaminase from Salmonella typhimurium have been characterized in the Co(II)-product radical pair state by using X-band electron paramagnetic resonance (EPR) and two-pulse electron spin-echo envelope modulation (ESEEM) spectroscopies in the disordered solid state. The unpaired electron spin in the product radical is localized on C2. Our approach is based on the orientation-selection created in the EPR spectrum of the biradical by the axial electron-electron dipolar interaction. Simulation of the EPR line shape yielded a best-fit Co(II)-C2 distance of 9.3 A. ESEEM spectroscopy performed at four magnetic field values addressed the hyperfine coupling of the unpaired electron spin on C2 with 2H in the C5' methyl group of 5'-deoxyadenosine and in the beta-2H position at C1 of the radical. Global ESEEM simulations (over the four magnetic fields) were weighted by the orientation dependence of the EPR line shape. A Nelder-Mead direct search fitting algorithm was used to optimize the simulations. The results lead to a partial model of the active site, in which C5' is located a perpendicular distance of 1.6 A from the Co(II)-C2 axis, at distances of 6.3 and 3.5 A from Co(II) and C2, respectively. The van der Waals contact of the C5'-methyl group and C2 indicates that C5' remains close to the radical species during the rearrangement step. The C2-Hs-C5' angle including the strongly coupled hydrogen, Hs, and the C5'-Hs orientation relative to the C1-C2 axis are consistent with a linear hydrogen atom transfer coordinate and an in-line acceptor p-orbital orientation. The trigonal plane of the C2 atom defines sub-spaces within the active site for C5' radical migration and hydrogen atom transfers (side of the plane facing Co(II)) and amine migration (side of the plane facing away from Co(II)). 相似文献
79.
Physical and chemical strategies that place designed molecules in spatially separated regions of surfactant-templated mesostructured silicate thin films are used to prepare films containing rhodamine 6G (R6G), lanthanide complexes, and both simultaneously. Fluorescence and photoexcitation spectra of R6G in amorphous and structured thin films show that it is located inside the surfactant micelles of structured thin films. A silylated ligand that binds lanthanides condenses to form part of the silica framework and causes the lanthanide to localize in the silica. Luminescence and photoexcitation spectra show that energy transfer from the metal complex to R6G occurs in the films. R6G quenches Tb emission in a concentration-dependent manner. Energy transfer efficiency is calculated using the Tb luminescence lifetime, and this quantity is used to calculate the distance between Tb and R6G with the aid of Forster theory. 相似文献
80.
Hwu SJ Ulutagay-Kartin M Clayhold JA Mackay R Wardojo TA O'Connor CJ Krawiec M 《Journal of the American Chemical Society》2002,124(42):12404-12405
Two novel copper(II) arsenates Na5ACu4(AsO4)4Cl2 (A = Rb, Cs) were synthesized by conventional solid-state methods using reactive molten salt media. These compounds are isostructural and crystallize in an orthorhombic lattice (Fmmm, No. 69; Z = 8). The cell constants are a = 14.632(3) A, b = 18.872(2) A, c = 14.445(3) A, V = 3989(1) A3, for A = Rb; a = 14.638(3) A, b = 18.990(4) A, c = 14.418(3) A, V = 4008(1) A3, for A = Cs. Single-crystal structure studies reveal a new composite framework consisting of alternating covalent and ionic lattices. The covalent lattice contains highly oriented oligomeric mu-oxo [Cu4O12]16- tetrameric units with a cyclo-S8-like Cu4O4 magnetic core that resembles the building block of layered cuprates. The ionic slab consists of a novel framework of mixed alkali metal chloride lattice and rarely seen Na6O8 clusters. Similar to organic-inorganic hybrid materials, the title compounds present a new class of host-guest chemistry via salt inclusion reactions. 相似文献