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排序方式: 共有173条查询结果,搜索用时 15 毫秒
1.
2.
Christer Albano William Dunn Ulf Edlund Erik Johansson Bo Nordén Michael Sjöström Svante Wold 《Analytica chimica acta》1978,103(4):429-443
Problems of pattern recognition in chemistry and other subjects can be divided conveniently into four different types depending on the level of scope of the problem.(1) Classification into one of a number of defined classes. As an example blood samples taken from persons known to be either controls or welders are considered. The problem is whether trace element concentrations in these samples contain information on whether or not a person is a welder.(2) Level 1 plus the possibility that an object is an outlier, i.e. does not belong to any of the defined classes. As an example, the üse of 13C-n.m.r. data to decide whether 2-substituted norbornanes have the exo or endo structure is discussed. (2A) Level 2, asymmetric. This situation occurs when one class does not have a systematic structure, but another class is homogeneous and can be described by a level 2 model. This occurs in the classification of materials or compounds as good or bad, active or inactive, and in binary classifications. As an example the use of trace element data to classify steel samples as having good or poor properties of strength is discussed.(3) Level 2 plus the ability to relate the variables measured to external properties of continuous character. As an example, the classification of a series of chemical compounds as β -receptor blockers, β -receptor stimulants, or neither, on the basis of their structural variables is discussed. In addition, relations between these structural variables and the measured biological activity are sought within each of the two classes.(4) Level 3 with the difference that several external property variables in the objects are measured. It may be desirable to use variables of the objects both for classification and for relations to several property variables: such examples are numerous in analytical chemistry. 相似文献
3.
Three-dimensional model binary glasses produced by quenching from a range of liquid temperatures were tested in shear over a range of strain rates using molecular-dynamics techniques. Tests were performed under constant volume and constant pressure constraints. The simulations revealed a systematic change in short-range order as a function of the thermal and strain history of the glass. While subtle signs of differences in short-range order were evident in the pair distribution function, three-body correlations were observed to be markedly more sensitive to the changes in structure. One particular structural parameter, the number of aligned three-atom clusters, was analyzed as a function of the degree of supercooling, the strain and the strain rate. The glasses quenched from the supercooled liquid regime were observed to contain an initially higher number of such clusters, and this number decreased under shear. Those quenched from high-temperature equilibrium liquids contained lower numbers of such clusters and these increased or remained constant under shear. The glasses quenched from the supercooled liquid regime showed higher strength, more marked shear softening, and an increased propensity toward shear localization. The evolution of this structural parameter depended both on its initial value and on the imposed shear rate. These results were observed to hold for simulations performed under both constant density and constant pressure boundary conditions. 相似文献
4.
Ezequiel V. Albano 《Journal of statistical physics》1995,78(3-4):1147-1155
The spreading of a globally distributed damage, created in the stationary regime, is studied in a single-component irreversible reaction process, i.e., the BK model [Browne and Kleban,Phys. Rev. A
40, 1615 (1989)]. The BK model describes one variant of the A+AA2 reaction process on a lattice in contact with a reservoir of A species. The BK model has a single parameter, namely the rate of arrival of A species to the lattice (Y). The model, exhibits an irreversible phase transition between a stationary reactive state with production of A2 species and a poisoned state with the lattice fully covered by A species. The transition takes place at critical points (Y
C
) which solely depend on the Euclidean dimensiond. It is found that the system is immune ford=1 andd=2, in the sense that even 100% of initial damage is healed within a finite healing period (T
H
). Within the reactive regime,T
H
diverges when approachingY
C
according toT
H
(Y
C
–Y)–, with 1.62 and 1.08 ford=1 andd=2, respectively. Ford=3 a frozen-chaotic transition is found close toY
s
0.4125, i.e., well inside the reactive regime 0YY
C
0.4985. Just atY
S
the damageD(t) heals according toD(t) t
–, with 0.71. For the frozen-chaotic transition atd=3 the order parameter critical exponent 0.997 is determined. 相似文献
5.
6.
Albano VG Di Serio M Monari M Orabona I Panunzi A Ruffo F 《Inorganic chemistry》2002,41(10):2672-2677
The silver-assisted ligand metathesis reaction involving a platinum(II) complex of formula [PtClMe(N,N-chelate)] with acetonitrile has been investigated. By using a suitably hindered N,N-chelate, an otherwise hardly detectable trinuclear species has been isolated and characterized through X-ray diffractometry. The trinuclear cation consists of two nearly orthogonal [PtCl(Me)(N,N-chelate)] square-planar units entrapping an Ag(+) cation through the chloride ligands that, acting as bidentate, form a linear AgCl(2) unit with two nonequivalent Ag-Cl bonds. The residual acidity of the silver cation is satisfied by one secondary Ag-Pt interaction [Ag-Pt(1) = 2.82 A] in which the platinum atom acts as a donor. Kinetic studies have demonstrated that the silver assistance operates both through a simple associative step and through a pathway in which the above trinuclear complex is an active intermediate. In a noncoordinating solvent the latter species evolves with AgCl loss and formation of a dinuclear Pt,Pt complex showing a rare single chloride bridge. 相似文献
7.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
8.
Relevant aspects of the critical behavior of the site percolation model in aL×M geometry (LM) are studied. It is shown that this geometry favors the growth of percolating clusters in theL-direction with respect to those growing in theM-direction, causing pronounced finite-size effects on the percolation probabilities. Scaling functions have an additional parameter, namelyM, which introduces a dependence of these functions on the aspect ratioL/M. At criticality, the probability of a site belonging to the percolation clusters (P
L,M
) behaves likeP
L,M
L
/v
(L/M) with =5/36 andv=4/3, where is a suitable scaling function. Using scaling arguments it is conjectured and then tested by means of Monte Carlo simulations, the following asymptotic behavior (L/M)(L/M), (L,M, =1), for the leading term. Systematic deviations of the Monte Carlo data from the conjectured behavior are due to second order corrections to the leading term which can also be under-stood on the basis of scaling ideas. Finite-size dependent critical probabilities are also functions ofL/M as it follows from scaling arguments which are corroborated by the simulations.Financially supported by the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) de la República Argentina 相似文献
9.
Vincenzo G. Albano Carlo Castellari Cristina Femoni M. Carmela Iapalucci Giuliano Longoni Magda Monari Stefano Zacchini 《Journal of Cluster Science》2001,12(1):75-87
The new Au8{Fe(CO)4}4(P^P)2 and Au6Cu2{Fe(CO)4}4(P^P)2 (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au3{Fe(CO)4}2(P^P)]- anions with Au(SEt2)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2 have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis. 相似文献
10.
Lucilena Rebelo Monteiro Daniela Graffitti Filipe Albano Darilena Porfírio Laercio Pires Fernandes Junior Marycel E. B. Cotrim Maria Aparecida Faustino Pires 《Accreditation and quality assurance》2013,18(3):207-215
This paper describes a Brazilian interlaboratory program study on anion measurement in synthetic water. The program described is promoted regularly since 2007 and recommended the use of ion chromatography as analytical technique for all participant laboratories. Two samples (X and Y) with different anion (fluoride, chloride, nitrite-N, nitrate-N, sulfate and phosphate-P) concentration levels were twice distributed in 2011. Each sample on each round had the homogeneity, and the stability tested for a period of 15 days. Upon ensuring the homogeneity and stability, the samples were distributed to 39 laboratories located around the country. The aim of this study was to verify the laboratories’ precision and to establish the measurement comparability among Brazilian laboratories that routinely use ion chromatography for water sample analysis. It was also possible to identify the most frequent sources of systematic and random errors for each measured anion, related to the ion chromatography technique. Some specific metrological issues related to the geographical region are discussed. 相似文献