全文获取类型
收费全文 | 99篇 |
免费 | 0篇 |
专业分类
化学 | 85篇 |
数学 | 3篇 |
物理学 | 11篇 |
出版年
2022年 | 2篇 |
2020年 | 1篇 |
2018年 | 2篇 |
2016年 | 2篇 |
2015年 | 3篇 |
2014年 | 2篇 |
2013年 | 4篇 |
2012年 | 3篇 |
2011年 | 10篇 |
2010年 | 7篇 |
2009年 | 5篇 |
2008年 | 5篇 |
2007年 | 8篇 |
2006年 | 7篇 |
2005年 | 7篇 |
2004年 | 6篇 |
2003年 | 6篇 |
2002年 | 7篇 |
2001年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1972年 | 1篇 |
1935年 | 1篇 |
1912年 | 1篇 |
排序方式: 共有99条查询结果,搜索用时 31 毫秒
1.
Toluene adsorption reactions on the (1 1 0) surface of VSbO4 have been analyzed following the changes in the electronic structure of the hydrocarbon molecule and metal cation sites of the oxide using the Just Another Extended Hückel Molecular Orbital Program (JAEHMOP) code. The bonding character of these interactions has also been studied in the same theoretical framework. The calculations indicate that the exothermic hydrocarbon parallel interaction on Sb-V sites results in the weakening of one of the C-H bonds of the methyl fragment. This leads to a H-abstraction that involves the participation of a Sb-cation. Both methyl and phenyl fragments decrease their electronic population and so does the V-cation site. Most of these electrons are transferred to other V atoms in the bulk solid. As a result the LUMO of the toluene-oxide system fully populates. The analysis reveals that methyl-Sb bonding interactions mainly involve C2px and H1s orbitals with Sb5s orbital, while non-bonding phenyl-V interactions involve C2px orbitals with V3dx2−y2 orbital. This last interaction facilitates the desorption of the benzyl species after H-abstraction. 相似文献
2.
Robert J. Maxwell Alan R. Lightfield Alida A. M. Stolker 《Journal of separation science》1995,18(4):231-234
An in-line collector assembly designed for use in supercritical fluid extraction (SFE) vessels is described. This assembly enables solutes extracted by supercritical fluids (SF) to be retained in-line on standard solid phase extraction (SPE) columns. The assembly consists of a standard 1 mL or 3 mL SPE column fitted into a specially fabricated Teflon© sleeve. The SPE column-Teflon sleeve assembly is inserted into the SFE vessel followed by the sample matrix. This unit forms a leak-tight seal with the vessel's end-cap up to pressures of 680 bar. The choice of sorbents used in the in-line SPE columns is dependent upon the properties of the solute in the supercritical state. After SFE is completed, the SPE column is removed and the solutes are recovered in 1–2 mL of the eluting solvent. No further clean-up is normally required prior to chromatographic analysis of the analyte. A comparison was made of recoveries by in-line and off-line (after SF decompression) techniques for the SFE of three anabolic steroids in fortified chicken liver. The HPLC chromatograms of the steroids from the off-line SPE columns were too complex for quantitation, because of coeluting artifacts, whereas chromatograms obtained from in-line SPE columns were free from UV-absorbing interferences and were easily quantified. 相似文献
3.
Traditionally, the screening of unknown pesticides in food has been accomplished by GC/MS methods using conventional library searching routines. However, many of the new polar and thermally labile pesticides and their degradates are more readily and easily analyzed by LC/MS methods and no searchable libraries currently exist (with the exception of some user libraries, which are limited). Therefore, there is a need for LC/MS approaches to detect unknown non-target pesticides in food. This report develops an identification scheme using a combination of LC/MS time-of-flight (accurate mass) and LC/MS ion trap MS (MS/MS) with searching of empirical formulas generated through accurate mass and a ChemIndex database or Merck Index database. The approach is different than conventional library searching of fragment ions. The concept here consists of four parts. First is the initial detection of a possible unknown pesticide in actual market-place vegetable extracts (tomato skins) using accurate mass and generating empirical formulas. Second is searching either the Merck Index database on CD (10,000 compounds) or the ChemIndex (77,000 compounds) for possible structures. Third is MS/MS of the unknown pesticide in the tomato-skin extract followed by fragment ion identification using chemical drawing software and comparison with accurate-mass ion fragments. Fourth is the verification with authentic standards, if available. Three examples of unknown, non-target pesticides are shown using a tomato-skin extract from an actual market place sample. Limitations of the approach are discussed including the use of A + 2 isotope signatures, extended databases, lack of authentic standards, and natural product unknowns in food extracts. 相似文献
4.
Amadeo Murase 《Ambix》2020,67(1):47-61
As William R. Newman has already shown, the alchemical homunculus described in the pseudo-Paracelsian writing De natura rerum was not the only kind of “homunculus” present in the works of (or attributed to) Paracelsus. Two other important kinds of “homunculi” indeed appeared in other treatises: one in De homunculis et monstris and the other in both Vom langen Leben and the Liber de imaginibus. This article focuses on the latter tract and its relationships with De natura rerum. After discussing the authenticity of the Liber de imaginibus, I will provide a brief analysis of its content and discuss the major topics common to the two treatises: the “signatures of things” and the homunculus. By studying the reception of the latter, I will show how the alchemical conception of the homunculus, as explained in De natura rerum, quickly established itself as the most prominent notion despite the fact that the golem-like version of Vom langen Leben and De imaginibus had nearly as much success at first among Paracelsians. 相似文献
5.
6.
7.
8.
José Barluenga Prof. Dr. Amadeo Fernández Alejandro Diéguez Dr. Félix Rodríguez Dr. Francisco J. Fañanás Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(43):11660-11667
An efficient method for the synthesis of [3.3.1]bicyclic compounds from easily available alkynol derivatives has been developed. The reaction is based on a gold‐ or platinum‐catalyzed tandem process that involves an intramolecular hydroalkoxylation of a triple bond followed by a Prins‐type cyclization. The reaction has been carried out with differently substituted alkynol derivatives and oxygen‐, nitrogen‐, and carbon‐centered nucleophiles. The incorporation of halogen atoms as nucleophiles and elimination reactions has also been studied. Enantiomerically pure [3.3.1]bicyclic systems were easily synthesized from the chiral pool. 相似文献
9.
Irene Gouvinhas Nelson Machado Amadeo Girons‐Vilaplana Snia Gomes Teresa Carvalho Raúl Domínguez‐Perles Ana I. R. N. A. Barros 《Journal of Chemometrics》2016,30(9):548-558
The olive tree (Olea europaea L.) can be affected by Colletotrichum acutatum, causing a loss of yield and quality of the final products, whilst the incidence of this fungal infection depends on several factors, including cultivar susceptibility. Thus, the effect of C. acutatum infection in cultivars displaying different susceptibilities to this fungal disease (‘Galega Vulgar’ ‐ susceptible, ‘Cobrançosa’ ‐ moderately susceptible, ‘Picual’ ‐ tolerant) has been assessed through spectrophotometric methods and HPLC, while the FTIR spectra of the cuticles have been concomitantly registered, resorting to the ATR accessory. With the support of multivariate analysis, these spectra allowed to discriminate olives with distinct infection times, besides retrieving evidences concerning the different susceptibility of each cultivar, while these observations were reinforced by the spectrophotometric and chromatographic methods. Furthermore, the assessment of the phenolic profile evidenced individual compounds in the distinct cultivars, so as their variations in response to the fungal infection. 相似文献
10.
We analyze the influence of residual two-photon excitation (2PE) in two-color (two-photon) optical beam induced current (2CE-OBIC) generation in wide band gap semiconductor samples. 2CE-OBIC generation is accomplished with two confocal excitation beams of separation angle θ and wavelengths λ1 and λ2 where , λe = hc/Eb, h is the Planck’s constant, c is speed of light in vacuum, and Eb is the energy band gap. Because the conduction band of the sample is a continuum, at least one excitation beam would also contribute an undesirable 2PE-OBIC signal that degrades the signal-to-noise ratio of the measured 2CE-OBIC response and broadens the effective OBIC distribution in the sample particularly when θ ≠ 0 or π. We show that the deleterious effects of crosstalk are reduced by a careful selection of λ1 and λ2 and the relative excitation beam intensities. λ1 and λ2 should be chosen to minimize the ratio of the two-photon absorption coefficients (β1, β2) to the 2CE absorption coefficient β12 or at least satisfy the constraint: β1 + β2 β12. Keeping the two excitation intensities equal is beneficial only when β1 = β2. Otherwise, it is advantageous to bias the intensity ratio towards the wavelength with a lower 2PE absorption coefficient. 相似文献