全文获取类型
收费全文 | 131篇 |
免费 | 1篇 |
专业分类
化学 | 79篇 |
力学 | 4篇 |
数学 | 4篇 |
物理学 | 45篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2019年 | 1篇 |
2017年 | 1篇 |
2016年 | 3篇 |
2015年 | 1篇 |
2014年 | 1篇 |
2013年 | 8篇 |
2012年 | 5篇 |
2011年 | 5篇 |
2010年 | 3篇 |
2009年 | 4篇 |
2008年 | 10篇 |
2007年 | 6篇 |
2006年 | 7篇 |
2005年 | 9篇 |
2004年 | 11篇 |
2003年 | 4篇 |
2002年 | 6篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有132条查询结果,搜索用时 20 毫秒
31.
Nierengarten JF Zhang S Gégout A Urbani M Armaroli N Marconi G Rio Y 《The Journal of organic chemistry》2005,70(19):7550-7557
[structure: see text] Branched conjugated systems with a terminal alkyne function have been prepared starting from 4-(triisopropylsilylethynyl) phenylacetylene by applying the following iterative reaction sequence: (i) metal-catalyzed cross-coupling reaction of the terminal alkyne with 3,4-dibromobenzaldehyde or 2,5- dibromobenzaldehyde; (ii) Corey-Fuchs dibromoolefination and treatment with an excess of LDA. The building blocks thus prepared have been subjected to a Pd-catalyzed cross-coupling reaction with 1,4-diiodobenzene to yield isomeric branched pi-conjugated systems containing 7 (first generation) or 15 (second generation) phenyl units connected by ethynyl spacers. The different pi-conjugation patterns in those isomeric derivatives have a dramatic effect on their electronic properties, as attested by the differences observed in their absorption and emission spectra. Finally, theoretical calculations have been performed to rationalize the optical properties of these compounds. 相似文献
32.
The solution speciation of metals is a critical parameter controlling the bioavailability, solution-solid phase distribution and transport of metals in soils. The natural metal-complexing ligands that exist in soil solution include inorganic anions, inorganic colloids, organic humic substances, amino acids (notably phytosiderophores and bacterial siderophores) and low-molecular mass organic acids. The latter two groups are of particular significance in the soil surrounding plant roots (the rhizosphere). A number of analytical methodologies, encompassing computational, spectroscopic, physico-chemical and separation techniques, have been applied to the measurement of the solution speciation of metals in the environment. However, perhaps with the exception of the determination of the free metal cation, the majority of these techniques rarely provide species specific information. High-performance liquid chromatography (HPLC) coupled to a sensitive detection system, such as inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionisation mass spectrometry (ESI-MS), offers the possibility of separating and detecting metal-organic acid complexes at the very low concentrations normally found in the soil environment. This review, therefore, critically examines the literature reporting the HPLC separation of metal-organic acid complexes with reference to thermodynamic equilibrium and kinetic considerations. The limitations of HPLC techniques (and the use of thermodynamic equilibrium calculations to validate analytical results) are discussed and the metal complex characteristics necessary for chromatographic separation are described. 相似文献
33.
Bernd Mayer Giancarlo Marconi Christian Klein Gottfried Köhler Peter Wolschann 《Journal of inclusion phenomena and macrocyclic chemistry》1997,29(1):79-93
Complexation trajectories and the variation ofinduced circular dichroism are calculated for thedocking of phenol and 2,4,6-trimethyl-phenol with-cyclodextrin. The results are compared toexperimental chirality data to elucidate themechanism of nonspecific molecular recognitionprocesses in aqueous solution. Large geometricalchanges along nearly isoenergetic Dynamic Monte Carlotrajectories show the conformational flexibility ofsuch host–guest systems. This proves diffuseintermolecular interactions, van der Waals orelectrostatic in nature, as the main contributions to thebinding energy. The number and position of the methylsubstituents of the guest reduces the complexityof the conformational space as the guests positionbecomes fixed by steric constraints.The solvation free energy is calculated from thesolvent accessible surface area weighted byrespective atomic solvation parameters. Consideringthe solvation term in the dynamic simulationsrestricts the conformational flexibility of themacromolecular system. The relative importance ofvarious contributions to the solvation energy isdiscussed and it is shown that those terms arisingfrom the interaction of hydrophobic groups with theaqueous environment are essential for thedetermination of the complex structure. Consideringthese terms in the dynamic simulation model, the signand strength of the calculated rotatory strength isin perfect agreement with induced circular dichroismobtained from experimentally determined averagedspectra. The results demonstrate the accuracy of thegeometrical properties of host–guest systems obtainedfrom these simulations. 相似文献
34.
The photodecarboxylation of suprofen in the carboxylate form was studied in aqueous medium as a function of the temperature, the concentration and the presence of oxygen by steady-state and time-resolved photochemical techniques. The process is characterized by an activation energy of 9–10 kcal/mol, the precursor state being the lowest triplet which is of π,π* nature. The reactivity of the drug was also studied in the β-cyclodextrin inclusion complex and an additional photoreaction involving the macrocycle as reactive species was observed. Representative NMR and circular dichroism measurements were performed. Singlet molecular oxygen formation was also investigated. 相似文献
35.
The concentration levels of five metals, namely Cd, Cr, Fe, Ni and Pb, were investigated along the durum wheat processing chain, from grain to the final product. Cadmium and Pb are well-known toxic elements and their levels in wheat grain are regulated by the European legislation. Chromium, Fe and Ni were included in the study as markers of metal release from equipment during processing. Durum wheat grain, semolina and pasta were sampled at an industrial plant for milling and pasta making. Samples were taken at different stages along processing in order to elucidate the influence of each stage on the element content. Samples of the water used for grain tempering and dough preparation were also collected. The whole analytical procedure, from sampling to final analytical determinations, was carried out according to a pre-established quality assurance protocol. Analyses were performed by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES).Milling was the key process influencing the concentrations of the studied elements and reduced the metal levels according to a definite element-specific pattern. Purity of the water used as ingredient, element deposition from plant air and metal release from equipment were identified as critical issues in contamination control during processing. In the conditions of this study, it was found that a simple relationship can be established between the original concentrations in durum wheat grain and those in pasta for Cd and Fe, while for Pb, Cr and Ni, a greater uncertainty in the estimation of the levels in the final product is expected. 相似文献
36.
The vibronic coupling between quasidegenerate adiabatic Born—Oppenheimer states has been calculated by going beyond the Condon approximation. A simplified model in which accepting modes are distorted (non-totally symmetric) and of the same frequency, has been considered. The decay rate obtained with this approach is one order of magnitude larger than in the Condon scheme and seems to be practically independent of the symmetry of the accepting modes. 相似文献
37.
The problem of approximation in the space of bounded linear operators ? (E;G) between normed spaces E and G by compact operators has been extensively studied in the last few years. Recently Deutsch, Mach and Saatkamp ([2]) have considered the problem of approximating elements of ?(E;G) by the subset K N(E;G) of operators whose range is at most N dimensional. We consider in this paper the problem of approximating operators (not necessarily linear) beteen normed spaces E and G by continuous homogeneous polynomials, and in particular by such polynomials which have finite-dimensional range. 相似文献
38.
Silvia Canepari Elisabetta Marconi Maria Luisa Astolfi Cinzia Perrino 《Analytical and bioanalytical chemistry》2010,397(6):2533-2542
A quick and reliable analytical method for the separation and quantification of extractable Sb(III) and Sb(V) in atmospheric
particulate matter (PM) by ion chromatography(IC)-inductively coupled plasma-mass spectrometry (ICP-MS) has been optimized,
validated on pairs of real, equivalent PM10 samples and applied to a field monitoring campaign in a urban site. Both Sb(III) and Sb(V) forms were detected in real samples
with Sb(III)/Sb(V) ratios up to 1.5. These two Sb species accounts only for a portion, of variable magnitude, of the total
extractable Sb (10–70%); anyway, no other soluble Sb species were detected in the samples. The analysis of size-segregated
samples collected by a 13-stage impactor showed that the recovery of [Sb(III) + Sb(V)] versus total extractable Sb is almost
quantitative in the coarse fraction while it is below than 10% in the fine fraction. In the extracted solution from particles
below 1 μm we could highlight the presence of Sb-containing suspended solid nano-particles, which probably constitute the
missing fraction. The contribution of nano-particles can be estimated as the difference between ICP-MS and IC-ICP-MS data,
as small size solid bodies are able to pass through the nebulizer and reach the plasma torch, while they are retained by the
chromatographic column. The aggregation state of these nano-particles seems to be easily altered when they are suspended in
a water solution; a similar behavior could be hypothesized when in contact with biological fluids. It has been confirmed that
brake pad abrasion is the prevalent source of Sb(III) in PM and that Sb(V) may be formed by oxidation during the braking processes.
Differing from other environmental matrices, there is no evidence of any spontaneous oxidative conversion within the two species. 相似文献
39.
Pelillo M Iafelice G Marconi E Fiorenza Caboni M 《Rapid communications in mass spectrometry : RCM》2003,17(20):2245-2252
Free sterols from hexaploid and tetraploid free-threshing wheats (Triticum aestivum L. and T. durum Desf.) and from their respective hulled wheats (T. spelta L. and T. dicoccon Schrank) were analysed by gas chromatography with mass spectrometry. The qualitative analysis of sterols showed a similar pattern either between hexaploid (T. aestivum, T. spelta) and tetraploid (T. durum, T. dicoccon) wheats or between free-threshing (T. aestivum, T. durum) and hulled (T. spelta, T. dicoccon) wheats. However, quantitative differences were found between tetraploid and hexaploid wheats, in that free sterol amounts in tetraploid wheats were 40% higher than in hexaploid ones. The mass spectra of the sterols were classified into four groups, taking into account the structural features of rings A and B. Typical mass spectral fragmentations of the four classes, and additional evidence related to the side chain of each molecule, were investigated together with their chromatographic behaviour, allowing identification of all the detected sterols. 相似文献
40.
Salvatore Sortino Giancarlo Marconi Salvatore Giuffrida Guido De Guidi Sandra Monti 《Photochemistry and photobiology》1999,70(5):731-736
The photophysical properties of rufloxacin, 9-fluoro-2r3-dihydro-10-(4-methyl-l-pyrazinyl)-7-oxo-7-H-pyri-do[l,2,3-de]-l,4-benzothiazin-6-carboxylic acid, a fluoroquinolone antibacterial drug exhibiting photosensitizing action toward biological substrates, were studied in aqueous solutions at neutral pH. The lowest excited electronic states of the zwitterion were characterized by both experimental techniques and theoretical methods. Steady-state and time-resolved emission, triplet-state absorption and singlet oxygen production were investigated. The results indicate that the lowest excited singlet is a fluorescent, relatively long-lived state (φr= 0.075, Tr? 4.5 ns) with an efficient intersystem crossing to the triplet manifold (φisc? 0-7)- The lowest triplet is a long-lived state (TT? 10 μs at 295 K in 0.01 M phosphate buffer), with properties that make it a good candidate for being the precursor of the photodecarboxylation of the drug. It is quenched by oxygen at a rate of 1.7 times 109M-1 s-1 and singlet oxygen is formed with a quantum yield of 0.32 in air-saturated solutions. 相似文献