全文获取类型
收费全文 | 3704篇 |
免费 | 645篇 |
国内免费 | 391篇 |
专业分类
化学 | 2989篇 |
晶体学 | 46篇 |
力学 | 185篇 |
综合类 | 26篇 |
数学 | 341篇 |
物理学 | 1153篇 |
出版年
2024年 | 19篇 |
2023年 | 90篇 |
2022年 | 182篇 |
2021年 | 161篇 |
2020年 | 228篇 |
2019年 | 212篇 |
2018年 | 195篇 |
2017年 | 163篇 |
2016年 | 222篇 |
2015年 | 243篇 |
2014年 | 251篇 |
2013年 | 325篇 |
2012年 | 366篇 |
2011年 | 382篇 |
2010年 | 210篇 |
2009年 | 185篇 |
2008年 | 247篇 |
2007年 | 167篇 |
2006年 | 164篇 |
2005年 | 113篇 |
2004年 | 93篇 |
2003年 | 81篇 |
2002年 | 60篇 |
2001年 | 51篇 |
2000年 | 44篇 |
1999年 | 47篇 |
1998年 | 29篇 |
1997年 | 22篇 |
1996年 | 28篇 |
1995年 | 24篇 |
1994年 | 26篇 |
1993年 | 14篇 |
1992年 | 15篇 |
1991年 | 10篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1959年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有4740条查询结果,搜索用时 15 毫秒
81.
An improved method has been developed for the determination of acrylamide in infant powdered milk and baby foods in jars, a particular class of foodstuffs which represent an important source of nutrition for young infants and babies. This method uses isotope dilution liquid chromatography coupled to a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than previous published methods with a limit of quantification estimated at 1 microg kg(-1). The new method offers effective sample preparation procedures including defatting with petroleum ether, extraction with aqueous solution of sodium chloride, further liquid-liquid extraction with ethyl acetate and clean-up by solid-phase extraction (SPE) with HLB 200 mg cartridges. The analytical method was well validated and good results were obtained with respect to repeatability (RSD < 5%) and recovery (86-97%) which fulfilled the requirements defined by European Union (EU) legislation. The acrylamide level in infant powdered milk and baby foods in jars were 3.01-9.06 microg kg(-1) and 6.80-124.93 microg kg(-1), respectively. Especially, this new method is successfully applied to the trace quantification of acrylamide in infant/baby foods, the content of which is less than 10 microg kg(-1). 相似文献
82.
The electrochemical enzyme-linked immunoassay increases the sensitivity of the detection of cucumber mosaic virus (CMV) by 5-fold compared with the spectrophotometric o-phenylenediamine (OPD) enzyme-linked immunosorbent assay (ELISA). The detection limit for the purified CMV is 1.0 ng/mL and the highest dilution ratio of the infected leaf sap is 1:5.0 x 10(4). The method is based on coupling the oxidation reaction of o-aminophenol (OAP)-H2O2 catalyzed by HRP-IgG conjugate with the electro-reduction of the enzymatic product. The enzymatic product 2-aminophenoxazine-3-one exhibits a sensitive second order derivative linear-sweep voltammetric response at the potential of -0.65 V (vs. Ag/AgCl) in pH 8.0 Britton-Robinson (B-R) buffer solution. So it can be applied to the detection of the plant virus with highly improved sensitivity. 相似文献
83.
Electrochemical studies on the interaction of heparin with crystal violet and its analytical application 总被引:1,自引:0,他引:1
In this paper, crystal violet (CV) was used to determine heparin concentration by linear sweep voltammetry on a dropping mercury
electrode (DME). In Britton-Robinson (B-R) buffer solution, pH 3.0, CV had a well-defined second-order derivative linear sweep
voltammetric reductive wave at −0.74 V (vs. SCE). After the addition of heparin to the CV solution, the reductive peak current
decreased greatly with the positive movement of the peak potential and without appearance of new peaks in the scanning potential
range. Based on the decrease in the reductive peak current, a new voltammetric method for the determination of heparin was
established. The conditions for the interaction and the electrochemical detection were optimized, and interfering substances
were investigated. Under the optimal conditions, the decrease in reductive peak currents of CV was proportional to heparin
concentration in the range 0.1–8.0 mg/L with the linear regression equation Δip″(nA) = 400.42 + 1563.11c (mg/L), (n = 14, γ = 0.993). The detection limit was 0.092 mg/L. This new method was further successfully applied to the determination of heparin
content in heparin sodium injection samples with satisfactory results. The binding ratio and binding mechanism were also studied
by the electrochemical method.
The text was submitted by the authors in English. 相似文献
84.
Ab initio coupled cluster calculations with single and double substitutions and a perturbative treatment of connected triple excitations [CCSD(T)] with the augmented correlation-consistent polarized valence triple-zeta aug-cc-pVTZ basis at 51 816 geometries provide a six-dimensional potential-energy surface for the electronic ground state of NH3. At 3814 selected geometries, CBS+ energies are obtained by extrapolating the CCSD(T) results for the aug-cc-pVXZ(X=T,Q,5) basis sets to the complete basis set (CBS) limit and adding corrections for core-valence correlation and relativistic effects. CBS** ab initio energies are generated at 51,816 geometries by an empirical extrapolation of the CCSD(T)/aug-cc-pVTZ results to the CBS+ limit. They cover the energy region up to 20,000 cm-1 above equilibrium. Parametrized analytical functions are fitted through the ab initio points. For these analytical surfaces, vibrational term values and transition moments are calculated by means of a variational program employing a kinetic-energy operator expressed in the Eckart-Sayvetz frame. Comparisons against experiment are used to assess the quality of the generated potential-energy surfaces. A "spectroscopic" potential-energy surface of NH3 is determined by a slight empirical adjustment of the ab initio potential to the experimental vibrational term values. Variational calculations on this refined surface yield rms deviations from experiment of 0.8 cm-1 for 24 inversion splittings and 0.4 (3.0) cm-1 for 34 (51) vibrational term values up to 6100 (10,300) cm-1. 相似文献
85.
Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化 总被引:9,自引:0,他引:9
以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体,用它制备了甲醇阳极氧化的催化电极Pt/(nano-fibular PANI).研究结果表明, Pt/(nano-fibular PANI)电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下, Pt/(nano-fibular PANI)电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外, Pt的电沉积修饰方法同样影响Pt/(nano-fibular PANI)电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性. 相似文献
86.
A phosphate-based epoxy resin for flame retardance: synthesis, characterization, and cure properties 总被引:2,自引:0,他引:2
A phosphorus-containing oligomer, bis(3-hydroxyphenyl) phenyl phosphate (BHPP), was synthesized through the reaction of phenyl dichlorophosphate and 1,3-dihydroxybenzene, and characterized by elemental analysis, Fourier transform IR spectroscopy, and 1H NMR and 31P NMR spectroscopy. Consequently, the phosphate-based epoxy resins with a phosphorus content of 1 and 2 wt % were prepared via the reaction of diglycidyl ether of bisphenol-A with BHPP and bisphenol-A, and were confirmed with Fourier transform IR spectroscopy and gel permeation chromatography. Phenolic melamine, Novolak, and dicyanodiamide were used as curing agents to prepare the thermoset resins with the control and the phosphate-based epoxy resins. Thermal properties and thermal degradation behavior of these thermoset resins were investigated by using differential scanning calorimetry and thermogravimetric analysis. The thermoset resins cured with phenolic melamine exhibited higher glass-transition temperatures than the other cured resins owing to the high rigidity of their molecular chain. Thermogravimetric analysis studies demonstrated that the decomposition temperatures of the thermoset resins cured with Novolak were higher than those of the others. A synergistic effect from the combination of the phosphate-based epoxy resin and the nitrogen-containing curing agent can result in a great improvement of the flame retardance for their thermoset resins. 相似文献
87.
The synthesis of derivatives of 3-β-D-xylopyranosyl-1,2,4-oxadiazolesis accomplished by condensing protected β-D-xylopyranosyl amidoxime with acidanhydrides or various substituted benzoyl chlorides in good yield.Thestructures of now derivatives were identified by spectra and elemental analysis.The stability of 1,2,4-oxadiazole ring and mechanism of cyclization were.investigated. 相似文献
88.
Chen Z Heine T Jiao H Hirsch A Thiel W Schleyer Pv 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(4):963-970
Hybrid B3LYP and density-functional-based tight-binding (DFTB) computations on the solid-state structures and electronic properties of the C(20) fullerene monomer and oligomers are reported. C(20) cages with C(2), C(2h), C(i), D(3d), and D(2h) symmetries have similar energies and geometries. Release of the very high C(20) strain is, in theory, responsible for the ready oligomerization and the formation of different solid phases. Open [2+2] bonding is preferred both in the oligomers and in the infinite one-dimensional solids; the latter may exhibit metallic character. Two types of three-dimensional solids, the open [2+2] simple cubic and the body-centered cubic (bcc) forms, are proposed. The energy of the latter is lower due to the better oligomer bonding. The open [2+2] simple cubic solid should be a conductor, whereas the bcc solids are insulators. The most stable three-dimensional solid-state structure, an anisotropically compressed form of the bcc solid, has a HOMO-LUMO gap of approximately 2 eV and a larger binding energy than that of the proposed C(36) solid. 相似文献
89.
Xu J Jiao P Deng D Zhang Q Tsang CW Chan AS 《Rapid communications in mass spectrometry : RCM》2002,16(12):1174-1179
The mass spectrometric fragmentation behaviour of five pairs of (R,R)- and (S,S)-4,5-bis(benzoxazol-2-yl)-2,2-dimethyl-1,3-dioxolane derivatives, one pair of (R,R)- and (S,S)-4,5-bis(benzothiazol-2-yl)-2,2-dimethyl-1,3-dioxolanes, and three pairs of (R,R)- and (S,S)-N,N'-bis(2-hydroxyaryl)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbamides, all important compounds for asymmetric catalysis (P. Jiao et al., Tetrahedron Asymmetry 2001; 12: 3081), has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization conditions. The spectral observations have been rationalized in terms of fragment ion structures and fragmentation mechanisms that will provide an aid to spectral interpretation for new compounds of this type. 相似文献
90.
Lu C Wei F Wu N Huang L Zhao X Jiao X Luo C Cao W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):974-977
A kind of hybrid multilayer film based on mercaptobenzoic acid-capped Au nanoparticles (MBA-Au-NPs) and photoreactive nitrodiazoresin (NDR) has been fabricated via electrostatic self-assembly. Upon exposure to UV light, the initial ionic bonds between the layers of the film convert into covalent bonds and the film stability toward polar solvents, salt, or surfactant solutions increases significantly. The micropatterned NDR/MBA-Au-NP film with the covalently linked architecture was formed by selecting exposure of the film through a photomask and later developed in sodium dodecyl sulfate (SDS) aqueous solution. The metallic Au-NP micropatterns, furthermore, are produced by sintering the micropatterned NDR/MBA-Au-NP film at 550 degrees C, at which the organic components are removed completely. The well-defined micropatterns were characterized with atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), microscope with a charge-coupled device (CCD) camera, and X-ray photoelectron spectroscopy (XPS). 相似文献