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1.
The theory of tree-growing (RECPAM approach) is developed for outcome variables which are distributed as the canonical exponential family. The general RECPAM approach (consisting of three steps: recursive partition, pruning and amalgamation), is reviewed. This is seen as constructing a partition with maximal information content about a parameter to be predicted, followed by simplification by the elimination of ‘negligible’ information. The measure of information is defined for an exponential family outcome as a deviance difference, and appropriate modifications of pruning and amalgamation rules are discussed. It is further shown how the proposed approach makes it possible to develop tree-growing for situations usually treated by generalized linear models (GLIM). In particular, Poisson and logistic regression can be tree-structured. Moreover, censored survival data can be treated, as in GLIM, by observing a formal equivalence of the likelihood under random censoring and an appropriate Poisson model. Three examples are given of application to Poisson, binary and censored survival data. 相似文献
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The Pariser-Parr-Pople approximation was used to predict the properties of compounds I, 3-oxo-2H-1,2,3-triazolo[3,4-a]pyridine, and II, 3-oxoisoxazolo[2,3-a]pyridine, originated by joining a pyridine ring to two sydnone-like heterocyclic systems not yet reported in the literature. A parallel computation was carried out for two known compounds of similar structure, to give the predictions a better reliability through the comparison with observed spectral data and chemical behaviour. Compound I is expected to be stable, with an absorption spectrum similar to III, 2-oxo-1,3,4-oxadiazolo[4,5-a]pyridine, and chemical properties analogous to IV, 1-methyl-3-oxo-1,2,4-triazolo-[4,3-a]pyridine. A reaction path is suggested for obtaining from I the unknown isomeric structure V, 3-oxo-1H-1,2,3-triazolo[3,4-a]pyridine. Compound II is predicted as an unstable orange-red substance which should be handled and kept at low temperatures. 相似文献
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Summary Starting from energy and Navier-Stokes equations with temperature-dependent viscosity, we have obtained the Reynolds equations for the mean values of velocity, temperature and pressure. We have then applied these equations to the Couette flow; on the well-known hypothesis of mixing-length and Prandtl turbulent number, the above mentioned relations have been written in a more amenable form.Some general considerations concerning the reciprocal dependence between temperature and velocity gradients at wall have been deduced.Finally some solutions numerically obtained for several values of Reynolds number are given and discussed in some detail to point out the influence of the temperature-dependent viscosity.
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Sommario Introducendo nelle equazioni dell'energia e di Navier-Stokes le parti medie e fluttuanti della velocità, temperatura, pressione e viscosità, vengono ricavate le cosiddette equazioni di Reynolds, ossia le equazioni che descrivono i campi di velocità e temperatura medi. Dal confronto di quest'ultime, in cui la viscosità è considerata dipendente dalla temperatura, con quelle originarie di Reynolds si deduce la forma che nel caso in esame assumono gli sforzi apparenti.Successivamente le equazioni ottenute vengono applicate al moto a Couette e discusse, dopo aver introdotto in esse le ipotesi della lunghezza di miscelamento e del numero di Prandtl turbolento; da questa analisi vengono tratte alcune conclusioni di carattere generale riguardanti i legami tra il campo dinamico e quello termico. Infine vengono date alcune soluzioni ottenute per via numerica, le quali illustrano l'influenza che sulle distribuzioni di temperatura e velocità viene esercitata dalla dipendenza della viscosità dalla temperatura.
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The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references). 相似文献
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Ciampi S James M Michaels P Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(11):6940-6949
We demonstrate a simple method for coupling alkynes to alkynes. The method involves tandem azide-alkyne cycloaddition reactions ("click" chemistry) for the immobilization of 1-alkyne species onto an alkyne modified surface in a one-pot procedure. In the case presented, these reactions take place on a nonoxidized Si(100) surface although the approach is general for linking alkynes to alkynes. The applicability of the method in the preparation of electrically well-behaved functionalized surfaces is demonstrated by coupling an alkyne-tagged ferrocene species onto alkyne-terminated Si(100) surfaces. The utility of the approach in biotechnology is shown by constructing a DNA sensing interface by derivatization of the acetylenyl surface with commercially available alkyne-tagged oligonucleotides. Cyclic voltametry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and X-ray reflectometry are used to characterize the coupling reactions and performance of the final modified surfaces. These data show that this synthetic protocol gives chemically well-defined, electronically well-behaved, and robust (bio)functionalized monolayers on silicon semiconducting surfaces. 相似文献
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Summary We present a new, simple and cost effective scheme for the measure of the second-order correlation function of Nd-YAG laser
second-harmonic (532 nm) pulses. We measure the transmission of a probe beam in a cell containing 6G-Rhodamine solution bleached
by a counterpropagating pump beam. Under a convenient choice of experimental parameters, we can measure also the contribution
of third-order correlation function. 相似文献
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E. Ciampi G. De Luca J.W. Emsley 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1997,129(2):207-211
The proton NMR spectra of liquid crystalline samples can be simplified by selective, partial deuteration followed by deuterium decoupling. This leaves strong peaks from the protons at the undeuterated sites, but also weak resonances from the coupling of these protons to those at low abundance (2% in the present case) at the deuterated sites. The weak resonances can be separated from the strong by recording spectra while spinning the sample at a series of angles to the magnetic field. 相似文献
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Ng CC Magenau A Ngalim SH Ciampi S Chockalingham M Harper JB Gaus K Gooding JJ 《Angewandte Chemie (International ed. in English)》2012,51(31):7706-7710
Smart surfaces presenting both antifouling molecules with a charged functional group at their distal end, and molecules that are terminated by RGD peptides for cell adhesion, were fabricated and characterized (see picture). By applying potentials of +300 or -300?mV, the surfaces could be dynamically switched to make the peptide accessible or inaccessible to cells. 相似文献
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Simone Ciampi J. Justin Gooding Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(20):5961-5968
This paper demonstrates the direct electron transfer between the heme moiety of horse hearth cytochrome c and a pyridinyl group on self‐assembled‐monolayer‐modified Si(100) electrodes. Self‐assembled monolayers (SAMs) containing the putative receptor ligand were prepared by a step‐wise procedure using “click” reactions of acetylene‐terminated alkyl monolayers and isonicotinic acid azide derivatives. Unoxidized Si(100) electrodes, possessing either isonicotinate or isonicotinamide receptor ligands, were characterized using X‐ray photoelectron spectroscopy, contact‐angle goniometry, cyclic voltammetry, and electrochemical impedance spectroscopy. The ability of isonicotinic acid terminated layers to coordinatively bind the redox center of cytochrome c was found to be restricted to pyridinyl assemblies with a para‐ester linkage present. The protocol detailed here offers an experimentally simple modular approach to producing chemically well‐defined SAMs on silicon surfaces for direct electrochemistry of a well‐studied model redox protein. 相似文献