全文获取类型
收费全文 | 3990篇 |
免费 | 99篇 |
国内免费 | 23篇 |
专业分类
化学 | 2666篇 |
晶体学 | 37篇 |
力学 | 61篇 |
数学 | 616篇 |
物理学 | 732篇 |
出版年
2021年 | 29篇 |
2020年 | 66篇 |
2019年 | 56篇 |
2018年 | 44篇 |
2017年 | 23篇 |
2016年 | 77篇 |
2015年 | 77篇 |
2014年 | 76篇 |
2013年 | 140篇 |
2012年 | 199篇 |
2011年 | 230篇 |
2010年 | 119篇 |
2009年 | 106篇 |
2008年 | 204篇 |
2007年 | 170篇 |
2006年 | 176篇 |
2005年 | 183篇 |
2004年 | 167篇 |
2003年 | 161篇 |
2002年 | 140篇 |
2001年 | 68篇 |
2000年 | 63篇 |
1999年 | 43篇 |
1998年 | 38篇 |
1997年 | 49篇 |
1996年 | 69篇 |
1995年 | 68篇 |
1994年 | 56篇 |
1993年 | 60篇 |
1992年 | 65篇 |
1991年 | 53篇 |
1990年 | 50篇 |
1989年 | 54篇 |
1988年 | 43篇 |
1987年 | 49篇 |
1986年 | 41篇 |
1985年 | 74篇 |
1984年 | 60篇 |
1983年 | 66篇 |
1982年 | 66篇 |
1981年 | 59篇 |
1980年 | 62篇 |
1979年 | 42篇 |
1978年 | 50篇 |
1977年 | 36篇 |
1976年 | 27篇 |
1975年 | 41篇 |
1974年 | 39篇 |
1973年 | 41篇 |
1972年 | 18篇 |
排序方式: 共有4112条查询结果,搜索用时 31 毫秒
141.
Laser-ablated W atoms react with CH4 in excess argon to form the CH3-WH, CH2=WH2, and CH[triple bond]WH3 molecules with increasing yield in this order of product stability. These molecules are identified from matrix infrared spectra by isotopic substitution. Tungsten methylidene and methylidyne hydride molecules are reversibly interconverted by alpha-H transfers upon visible and ultraviolet irradiations. Matrix infrared spectra and DFT/B3LYP calculations show that CH[triple bond]WH3 is a stable molecule with C3v symmetry, but other levels of theory were required to describe agostic distortion for CH2=WH2. Analogous reactions with Cr gave only CH3-CrH, which is calculated to be by far the most stable product. 相似文献
142.
Gies P Roy C McLennan A Pailthorpe M Hilfiker R Osterwalder U Monard B Moseley H Sliney D Wengraitis S Wong J Human S Bilimis Z Holmes G 《Photochemistry and photobiology》2003,77(1):58-67
In recent years the need to standardize measurement protocols for quantifying the degree of ultraviolet radiation (UVR) protection provided by clothing has led to the introduction of a number of standards around the world. To date, these standards have specified spectral measurements of UVR transmission by clothing and fabrics. Development of a standard test method has become an important part of the testing process, and this article presents results from an intercomparison involving 10 independent testing laboratories and 11 different UVR transmission measurement instruments. In addition to comparing the measured ultraviolet protection factors (UPF), this intercomparison also incorporates detailed scan results from all 10 laboratories and highlights differences in performance of the various instruments in different wavelength regions. Careful examination of these differences can indicate where changes to the systems could be made to allow improvements both in equipment performance and in agreement of the final results. The variability in the measurements of UPF in this study suggest that the protection categories in standards may need to be broadened. 相似文献
143.
144.
Reza Dabesrani Robert H. Sik Donald G. Davis George Dubay Colin F. Chignell 《Photochemistry and photobiology》1993,58(3):367-373
Abstract— The photochemistry, photophysics, and photosensitization (Type I and II) of indomethacin (IN) (N-[p-chlorobenzoyl]-5-methoxy-2-methylindole-3-acetic acid) has been studied in a variety of solvents using NMR, high performance liquid chromatography-mass spectroscopy, transient spectroscopy, electron paramagnetic resonance in conjunction with the spin trapping technique, and the direct detection of singlet molecular oxygen (l O2) luminescence. Photodecomposition of IN (λex > 330 nm) in degassed or air-saturated benzene proceeds rapidly to yield a major (2; N-[p-chlorobenzoyl]-5-methoxy-2-methyl-3-methylene-indoline) and a minor (3; N-[p-chlorobenzoyl]-5-methoxy-2, 3-dimethyl-indole) decarboxylated product and a minor indoline (5; 1-en-5-methoxy-2-methyl-3-methylene-in-doline), which is formed by loss of the p-chlorobenzoyl moiety. In air-saturated solvents two minor oxidized products 4 (N-[p-chlorobenzoyl]-5-methoxy-2-methylindol-3-aldehyde) and 6 (5-methoxy-2-methyl-indole-3-aldehyde) are also formed. When photolysis was carried out in 18O2-saturated benzene, the oxidized products 4 and 6 contained 18O, indicating that oxidation was mediated by dissolved oxygen in the solvent. In more polar solvents such as acetonitrile or ethanol, photodecomposition is extremely slow and inefficient. Phosphorescence of IN at 77 K shows strong solvent dependence and its emission is greatly reduced as polarity of solvent is increased. Flash excitation of IN in degassed ethanol or acetonitrile produces no transients. A weak transient is observed at 375 nm in degassed benzene, which is not quenched by oxygen. Irradiation of IN (λex > 325 nm) in N2-gassed C6H6 in the presence of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) results in the trapping of two carbon-centered radicals by DMPO. One adduct was identified as DMPO/.COC6H4-p-CI, while the other was probably derived from a radical formed during IN decarboxylation. In air-saturated benzene, (hydro) peroxyl and alkoxyl radical adducts of DMPO are observed. A very weak luminescence signal from 1O2 at 1268 nm is observed initially upon irradiation (λex= 325 nm) of IN in air-saturated benzene or chloroform. The intensity of this 1O2 signal increases as irradiation is continued suggesting that the enhancement in 1O2 yield is due to photoproduct(s). Accordingly, when 2 and 3 were tested directly, 2 was found to be a much better sensitizer of 1O2 than IN. In air-saturated ethanol or acetonitrile no IN 1O2 luminescence is detected even on continuous irradiation. The inability of IN to cause phototoxicity may be related to its photo stability in polar solvents, coupled with the low yield of active oxygen species (1O2, O2?-) upon UV irradiation. 相似文献
145.
Two important considerations in the design of an aerobic particulate immobilized cell bioreactor are the provision of sufficient
oxygen to maintain the desired metabolism of the immobilized organism, and the biomass holdup (which is proportional to the
number of immobilized cell particles in the reactor).
The Circulating Bed Reactor, a reactor developed for use with those forms of immobilization that result in particles of essentially
neutral buoyancy, operates with an expanded bed of circulating particles. The particle number density attainable in such a
reactor has been found to be dependent upon the circulation cell aspect ratio, the individual particle properties, the static
bed voidage of the particles, and the superficial gas velocity. The oxygen mass transfer characteristics have been found to
be dependent upon the circulatory nature of the system, the particle (solids) holdup, the particle porosity, and the superficial
gas velocity. 相似文献
146.
M. OKeeffe A. Conneely K. M. Cooper D. G. Kennedy L. Kovacsics Andrea Fodor P. P. J. Mulder J. A. van Rhijn G. Trigueros 《Analytica chimica acta》2004,520(1-2):125-131
Use of nitrofuran drugs in food-producing animals has been prohibited within the EU because they may represent a public health risk. Monitoring compliance with the ban has focused on the detection of protein-bound nitrofuran metabolites which, in contrast to the parent compounds, are stable and persist in animal tissues. As part of the “FoodBRAND” project, an extensive survey of pork was undertaken across 15 European countries. Samples (n = 1500) purchased at retail outlets were analysed for the nitrofuran metabolites AOZ, AMOZ, AHD and SEM using LC–MS/MS determination of nitrobenzaldehyde derivatives. Limits of quantification for the method were 0.1 μg/kg (AOZ, AMOZ), 0.2 μg/kg (SEM) and 0.5 μg/kg (AHD). Of the 1500 samples tested, measurable residues of nitrofuran metabolites were confirmed in 12 samples (0.8% incidence overall) of which 10 samples were purchased in Portugal (AOZ, 0.3 μg/kg; AMOZ, 0.2–0.6 μg/kg) and one sample each in Italy (AMOZ, 1.0 μg/kg) and Greece (AOZ, 3.0 μg/kg). 相似文献
147.
Mehrzad Mehran William J. Cooper Nahid Golkar Michael G. Nickelsen Eric R. Mittlefehldt Edward Guthrie Walter Jennings 《Journal of separation science》1991,14(11):745-750
The retention behavior of a heterogeneous group of solutes has been examined on seven different stationary phases under isothermal and temperature-programmed conditions. Both ΔHv (enthalpy of solute vaporization from the stationary phase) and ΔSv (entropy of solute vaporization from the stationary phase) values were determined for each solute – stationary phase combination under isothermal conditions. Both program rate and carrier gas velocity were shown to affect solute elution order. Unless these and other experimental factors discussed are controlled, column equivalency studies based on solute elution order have dubious value. 相似文献
148.
Interpretation of the chemical and spectral (IR., UV., 1H- and 13C-NMR.) properties of the antitumor antibiotic hedamycin (C41H50N2O11) suggests that the molecule contains a methyl substituted 1-hydroxyanthraquinone nucleus, an α, β-unsaturated ketone, two sugar-like tetrahydropyran rings ( 4 and 8 ) and an aliphatic chain 2 , presumably with an epoxy group (see the Scheme). 相似文献
149.
Katherine E. BashfordMatthew B. Burton Stuart CameronAnthony L. Cooper Rebecca D. HoggPeter D. Kane David A. MacManusChristopher A. Matrunola Christopher J. Moody Avril A.B. Robertson Mark R. Warne 《Tetrahedron letters》2003,44(8):1627-1629
The Bohlmann-Rahtz reaction has been used to prepare 2,3,6-trisubstituted pyridines suitable for use in library synthesis. The synthesis of piperidine substituted nicotinic acid derivative 9 has been optimised and carried out on a large scale to give ca. 500 g of scaffold which was used in the generation of the pyridine library 11. 相似文献
150.
Keyes TE Leane D Forster RJ Coates CG McGarvey JJ Nieuwenhuyzen MN Figgemeier E Vos JG 《Inorganic chemistry》2002,41(22):5721-5732
A detailed spectroscopic and electrochemical study of a series of novel phenolate bound complexes, of general formulas [M(L-L)(2)(box)](PF(6)), where M is Os and Ru, L-L is 2,2-bipyridine or 2,2-biquinoline, and box is 2-(2-hydroxyphenyl)benzoxazole, is presented. The objectives of this study were to probe the origin of the LUMOs and HOMOs in these complexes, to elucidate the impact of metal and counter ligand on the electronic properties of the complex, and to identify the extent of orbital mixing in comparison with considerably more frequently studied quinoid complexes. [M(L-L)(2)(box)](PF(6)) complexes exhibit a rich electronic spectroscopy extending into the near infrared region and good photostability, making them potentially useful as solar sensitizers. Electrochemistry and spectroscopy indicate that the first oxidation is metal based and is associated with the M(II)/(III) redox states. A second oxidative wave, which is irreversible at slow scan rates, is associated with the phenolate ligand. The stabilities of the oxidized complexes are assessed using dynamic electrochemistry and discussed from the perspective of metal and counter ligand (LL) identity and follow the order of increasing stability [Ru(biq)(2)(box)](+) < [Ru(bpy)(2)(box)](+) < [Os(bpy)(2)(box)](+). Electronic and resonance Raman spectroscopy indicate that the lowest energy optical transition for the ruthenium complexes is a phenolate (pi) to L-L (pi) interligand charge-transfer transition (ILCT) suggesting the HOMO is phenolate based whereas electrochemical data suggest that the HOMO is metal based. This unusual lack of correlation between redox and spectroscopically assigned orbitals is discussed in terms of metal-ligand orbital mixing which appears to be most significant in the biquinoline based complex. 相似文献