全文获取类型
收费全文 | 561篇 |
免费 | 24篇 |
国内免费 | 1篇 |
专业分类
化学 | 413篇 |
晶体学 | 2篇 |
力学 | 92篇 |
数学 | 49篇 |
物理学 | 30篇 |
出版年
2023年 | 6篇 |
2022年 | 1篇 |
2021年 | 12篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 24篇 |
2014年 | 25篇 |
2013年 | 30篇 |
2012年 | 34篇 |
2011年 | 47篇 |
2010年 | 33篇 |
2009年 | 24篇 |
2008年 | 48篇 |
2007年 | 36篇 |
2006年 | 26篇 |
2005年 | 27篇 |
2004年 | 24篇 |
2003年 | 22篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1993年 | 11篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 7篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1921年 | 1篇 |
排序方式: 共有586条查询结果,搜索用时 531 毫秒
101.
Mothi Mohamed Ebrahim Antonia Neels Helen Stoeckli-Evans Krishnaswamy Panchanatheswaran 《Polyhedron》2007
The reaction of mercury(II) halides with 1,2-bis(diphenylphosphino)ethane monoxide (dppeO) in 1:1 molar ratio yielded P,O-coordinated polymers having the empirical formula [HgX2(dppeO)]n [X = Cl (1), Br (2), I (3)]. In contrast, the reaction between the same reactants in a 1:2 molar ratio yielded the P, P-coordinated monomeric complexes, HgX2(dppeO)2[X = Cl (4), Br (5), I (6)]. The structures of 2, 3, 4 and 5 have been characterized crystallographically. The results indicate that the geometry around the mercury atom in each of these molecules is tetrahedral with considerable distortion. The 31P NMR spectra of the 1:1 complexes indicate the dissociation of the Hg–O bond in solution. 相似文献
102.
Martínez Vidal JL Fernández Moreno JL Arrebola Liébanas FJ Garrido Frenich A 《Journal of AOAC International》2007,90(4):1146-1164
A multiresidue method has been developed for determining pesticide residues in the tropical fruits kiwi, custard apple, and mango. The intended purpose of the method is for regulatory analyses of commodities for pesticides that have established maximum residue limits. A fast and simple extraction method with cyclohexane-ethyl acetate (1 + 1, v/v) and a high-speed homogenizer was optimized. Pressurized liquid extraction was evaluated as an alternative automated extraction technique. The pesticide residues were determined by using low-pressure gas chromatography coupled to tandem mass spectrometry. The proposed methodology was validated for each matrix. Pesticide recoveries ranged from 70 to 110%, with repeatability relative standard deviations of < or = 18% at spiking levels of 12 and 50 microg/kg. The limits of quantitation were in the range of 0.03-6.17 microg/kg, and the limits of detection were between 0.01 and 3.75 microg/kg. Mango can be selected as a representative matrix for calibration on the basis of the results of a potential matrix effect study. The method was successfully applied to the determination of pesticide residues in real samples in Spain. 相似文献
103.
Victoria F. Samanidou Dimitrios E. Giannakis Antonia Papadaki 《Journal of separation science》2009,32(9):1302-1311
Herein a quantitative method for the determination of seven penicillins in bovine plasma and veterinary drugs has been developed. Amoxicillin (AMO), ampicillin (AMP), penicillin G (PENG), penicillin V (PENV), oxacillin (OXA), cloxacillin (CLO) and dicloxacillin (DICLO) were separated on a Perfectsil ODS‐2 (250×4 mm, 5 μm) column, using gradient elution, with a mobile phase of 0.1% v/v TFA and ACN–methanol (90:10 v/v). PDA detection was used at 240 nm. Penicillins were isolated from bovine plasma by SPE on Lichrolut RP‐18 cartridges with mean recoveries from 85.7 to 113.5%. Colchicine (3 ng/μL) was used as an internal standard. The developed method was validated in terms of selectivity, linearity, accuracy, precision, stability and sensitivity. Repeatability (n = 5) and between‐day precision (n = 5) revealed RSD < 12%. The detection limits in the bovine plasma were estimated as 18 ng for AMO and AMP, 25 for PENG, PENV and OXA, 3 ng for CLO and 12 ng for DICLO. Spiked plasma samples were stable for 1 wk, except for AMP and CLO, which were stable for 3 wk and OXA for 4 wk. AMO, PENG and PENV were stable for two freeze–thaw cycles, OXA, CLO and DICLO for four, while AMP only for one. 相似文献
104.
Percolation theory is a multidisciplinary theory that studies chaotic systems. It has been applied in the pharmaceutical field since 1987. The application of this theory to study the release and hydration rate of hydrophilic matrices allowed for first time to explain the changes in release and hydration kinetic of swellable matrices type controlled delivery systems. The objective of the present paper is to estimate the percolation threshold of HPMC K4M in matrices of lobenzarit disodium and to apply the obtained result to the design of hydrophilic matrices for the controlled delivery of this drug. The materials used to prepare the tablets were Lobenzarit disodium (LBD) and HPMC of viscosity grade K4M. The drug mean particle size was 42+/-0.61 mum and the polymer was sieved and 150-200 microm granulometric fraction was selected. The formulations studied were prepared with different excipient contents in the range of 10-80% w/w. Dissolution studies were carried out using the paddle method and the water uptake measurements were performed using a modified Enslin apparatus. In order to estimate the percolation threshold, the behaviour of the kinetic parameters with respect to the volumetric fraction of each component at time zero, was studied. According to percolation theory, the critical points observed in dissolution and water uptake studies are attributed to the existence of an excipient percolation threshold. This threshold was situated between (18.58 to 24.33% v/v of HPMC). Therefore, the LBD-HPMC K4M matrices with a relative HPMC particle size of should be formulated with an excipient content above 24.33% v/v of HPMC, to obtain a control of the drug release from these systems. 相似文献
105.
We present an empirical but simple and practical spectral chart method for determining the mean turbulent kinetic energy dissipation rate $ \left\langle \varepsilon \right\rangle $ in a variety of turbulent flows. The method relies on the validity of the first similarity hypothesis of Kolmogorov (C R (Doklady) Acad Sci R R SS, NS 30:301–305, 1941) (or K41) which implies that spectra of velocity fluctuations scale on the kinematic viscosity ν and $ \left\langle \varepsilon \right\rangle $ at large Reynolds numbers. However, the evidence, based on the DNS spectra, points to this scaling being also valid at small Reynolds numbers, provided effects due to inhomogeneities in the flow are negligible. The methods avoid the difficulty associated with estimating time or spatial derivatives of the velocity fluctuations. It also avoids using the second hypothesis of K41, which implies the existence of a ?5/3 inertial subrange only when the Taylor microscale Reynods number R λ is sufficiently large. The method is in fact applied to the lower wavenumber end of the dissipative range thus avoiding most of the problems due to inadequate spatial resolution of the velocity sensors and noise associated with the higher wavenumber end of this range.The use of spectral data (30?≤?R λ?≤?400) in both passive and active grid turbulence, a turbulent mixing layer and the turbulent wake of a circular cylinder indicates that the method is robust and should lead to reliable estimates of $ \left\langle \varepsilon \right\rangle $ in flows or flow regions where the first similarity hypothesis should hold; this would exclude, for example, the region near a wall. 相似文献
106.
Nostro A Filocamo A Giovannini A Catania S Costa C Marino A Bisignano G 《Natural product research》2012,26(22):2132-2136
This study reported the antimicrobial activity and phenolic content of natural site and micropropagated Limonium avei (De Not.) Brullo & Erben inflorescences. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of ethanolic extracts were determined according to the Clinical Laboratory Standards Institute guidelines. Individual phenolic acids and flavonoids were detected by a high performance liquid chromatography (HPLC-DAD) method. The samples showed a comparable antimicrobial activity, although the natural site extract possessed the lower MIC values. The best activity was detected against Gram-positive bacteria, such as Staphylococcus aureus including methicillin resistant strains (MIC and MBC values ranging from 7.81 to 62.50?μg?mL(-1) and from 500 to 2000?μg?mL(-1) respectively). In contrast, a low activity was found on Gram-negative bacteria and Candida albicans. The HPLC-DAD analysis revealed ten phenolic acids and four flavonoids with a major amount of m-coumaric acid, naringin and quercetin in the natural site extract. 相似文献
107.
Photooxygenations of 2-(γ,ε-dihydroxyalkyl) furans in H(2)O followed by in situ reduction and ketalization affords, in one synthetic operation, DE-bicyclic ketals of the pectenotoxins. 相似文献
108.
Antonia M. Carro Diego García‐Rodríguez Paula Gonzalez‐Siso Rosa A. Lorenzo 《Journal of separation science》2012,35(21):2866-2874
Chemicals are widely used in aquaculture and one of the main recipients of these analytes is the aquatic environment. The aim of this work was to develop and validate a simple and sensitive method for the determination of multiclass chemotherapeutic agents in farmed fish and shellfish using matrix solid‐phase dispersion and liquid chromatography‐tandem mass spectrometry. Residues of azamethiphos, three avermectins, two carbamates, and two benzoylureas were extracted from samples using silica gel as clean‐up adsorbent and 0.5% acetic acid in acetonitrile as elution solvent. The extraction conditions were investigated and optimized using an experimental design. Mass spectrometry detection was carried out in positive electrospray ionization mode with multiple‐reaction monitoring scan (except for benzoylurea family). Matrix‐matched standards were used for the drugs quantification. Good linearity (R2 ≥ 0.996) was observed in the range of 5–500 μg kg?1. Limits of detection were in the range of 1.5–3.7 μg kg?1. Recoveries from salmon samples spiked with veterinary drugs were in the range 84.9–118%. Precision was satisfactory since relative standard deviations were lower than 10.6%. The method can be successfully applied for the analysis of fish and shellfish from aquaculture. 相似文献
109.
Maria J. Ortiz Antonia R. Agarrabeitia Gonzalo Duran-Sampedro Jorge Bañuelos Prieto Teresa Arbeloa Lopez Walter A. Massad Hernán A. Montejano Norman A. García Iñigo Lopez Arbeloa 《Tetrahedron》2012,68(4):1153-1162
A theoretical and experimental study on the iodination of BODIPY dyes with different degrees of substitution has been developed. Polyhalogenated BODIPYs synthesized in this work are the first examples of this type of dyes with more than two halogen atoms in the BODIPY core and they can be selectively functionalized. Surprisingly, the position in which halogen is attached has a marked effect in the photophysical properties and modulates the fluorescence capacity of the resulting BODIPY. These iodinated BODIPYs are efficient singlet oxygen generators. 相似文献
110.
Energy transfer between vibrational, rotational, and translational degrees of freedom of a molecule during a collision process is enhanced when the classical frequencies associated with the initial state are in the proximity of nonlinear resonance conditions. We present an analysis of the classical resonant effects in the collisions of light diatoms with periodic surfaces, and discuss the initial conditions in which these effects can be observed. In particular, we find that for grazing incidence and resonant initial values of the classical frequencies, corresponding to specific vibro-rotational molecular states and translational energies, an efficient energy transfer between the intramolecular vibro-rotational degrees of freedom and the translational degree of freedom along a symmetry direction on the surface can be found. This efficient energy transfer manifests itself in the emergence of specific peaks in the molecular diffraction patterns. The predictions of the resonance analysis are contrasted with the results of classical trajectory calculations obtained in a diatom-rigid surface collision model. 相似文献