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1.
Phys Rev E ; 109(3-1): 034305, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38632742

RESUMO

While classical in many theoretical settings-and in particular in statistical physics-inspired works-the assumption of Gaussian i.i.d. input data is often perceived as a strong limitation in the context of statistics and machine learning. In this study, we redeem this line of work in the case of generalized linear classification, also known as the perceptron model, with random labels. We argue that there is a large universality class of high-dimensional input data for which we obtain the same minimum training loss as for Gaussian data with corresponding data covariance. In the limit of vanishing regularization, we further demonstrate that the training loss is independent of the data covariance. On the theoretical side, we prove this universality for an arbitrary mixture of homogeneous Gaussian clouds. Empirically, we show that the universality holds also for a broad range of real data sets.

2.
Anal Bioanal Chem ; 401(9): 3011-7, 2011 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-21904798

RESUMO

Classical photo-induced fluorescence methods are conducted in two steps: a UV irradiation step in order to form a photo-induced compound followed by its fluorimetric determination. Automated flow injection methods are frequently used for these analyses. In this work, we propose a new method of direct laser photo-induced fluorescence analysis. This new method is based on direct irradiation of the analyte in a fluorimetric cell in order to form a photo-induced fluorescent compound and its direct fluorimetric detection during a short irradiation time. Irradiation is performed with a tuneable Nd:YAG laser to select the optimal excitation wavelength and to improve the specificity. It has been applied to the determination of bisphenol A, an endocrine disrupter compound that may be a potential contaminant for food. Irradiation of bisphenol A at 230 nm produces a photo-induced compound with a much higher fluorescence quantum yield and specific excitation/emission wavelengths. In tap water, the fluorescence of bisphenol A increases linearly versus its concentration and, its determination by direct laser photo-induced fluorescence permits to obtain a low limit of detection of 17 µg L(-1).

3.
J Fluoresc ; 21(3): 843-50, 2011 May.
Artigo em Inglês | MEDLINE | ID: mdl-20084436

RESUMO

This work presents spectroscopic properties of some Endocrine Disrupting Compounds (EDCs), frequently found in food and in natural water. Studied molecules belong to the groups of phenolic and phthalate EDCs. In a first part, we have examined their absorption and fluorescence properties. Fluorescence emission wavelengths are about 300 nm for phenolic compounds and 360 nm for phtalate compounds; main excitation wavelengths being comprised between 210 nm and 230 nm. Fluorescence lifetimes measured are short (about 4 ns) and the fluorescence quantum yield has been determined. In a second part, to avoid the time consuming solvent extraction step, an analytical application to evaluate the performance of a direct analysis by laser induced fluorescence spectroscopy of ECDs traces in tap water and in raw water is presented. Good detection limits have been obtained, i.e.: 0.35 µg.L(-1) of chlorophenol in tap water, which are always lower than the reported Predictive Non Efficient Concentration (PNEC).


Assuntos
Disruptores Endócrinos/análise , Monitoramento Ambiental/métodos , Espectrometria de Fluorescência/métodos , Contaminação de Alimentos/análise , Lasers , Limite de Detecção , Fenóis , Ácidos Ftálicos , Poluentes Químicos da Água/análise
4.
J Colloid Interface Sci ; 345(2): 496-504, 2010 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-20181355

RESUMO

This laboratory study mimicked the pollution of a suspension of silica beads, used as a crude model of sand, by naphthalene in mixture with carbofuran at first, and then by this mixture in association with a metal salt, Pb(NO(3))(2). The silica properties and the working conditions were such that they allowed us to only observe physisorption, which is the first and essential step of any adsorption mechanism. Naphthalene and carbofuran were, respectively, chosen as hydrocarbon and pesticide. Naphthalene adsorption from simple solutions is rather large compared to other organic adsorptions, and carbofuran seems to adsorb on a layer of naphthalene when the latter is mixed in solution with carbofuran. Like other organics, naphthalene favours the adsorption of lead ions, but ionic adsorption is considerably increased by the combination of naphthalene and carbofuran. The Wagner-Onsager-Samaras theory shows that the result implies a special organization of organic molecules at the interface. Conclusions about some environmental mechanisms of fixation, or release, of ions on sands in the case of simple physisorption are drawn from the study.

5.
Mar Pollut Bull ; 54(12): 1932-9, 2007 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-17964611

RESUMO

Coal is currently becoming an increasingly interesting fossil energy resource and that is the reason why its maritime transport, and hence the risk of collier accidents, increase. In this work, the environmental impact of an accidental coal immersion at sea is studied: the physicochemical effects are estimated using innovative experimental setups--a laboratory seawater canal called "polludrome" is used to evaluate the behaviour of coal particles submitted to a seawater flow, and a specifically designed tub is used to study the physicochemical consequences induced when coal is introduced into continuously renewed seawater. When coal is introduced into seawater, the most easily visible consequences are physical: fine coal particles reduce the daylight penetration up to 100% and move along with the flow, and coal chunks accumulate on the floor. Chemical effects are also measured: humic matters are dissolved from coal into seawater (up to 2 mg L(-1)), but no release of polycyclic aromatic hydrocarbons is evidenced. Some inorganic compounds are dissolved, among which manganese, whose concentrations can reach 1 microg L(-1). Fortunately, the results show that the environmental impact of this type of accident would remain limited.


Assuntos
Carvão Mineral/análise , Monitoramento Ambiental , Água do Mar/análise , Poluentes Químicos da Água/análise , Acidentes de Trabalho , Substâncias Húmicas/análise , Luz , Magnésio/análise , Tamanho da Partícula , Medição de Risco , Navios , Fatores de Tempo , Movimentos da Água
6.
J Fluoresc ; 16(2): 177-83, 2006 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-16544201

RESUMO

The absorption and fluorescence spectra of carbaryl (CB), carbofuran (CF) and carbendazim (MBC) have been studied. Fluorescence lifetime and fluorescence quantum yields are also reported as well as the influence of pH, solvent and presence of humic acids on fluorescence. The limit of detection (LD) of the three compounds has been measured by direct analysis by laser-induced fluorescence (LIF) using a pulsed YAG laser with an Optical Parametric Oscillator (OPO) as excitation source and an Intensified Charged Coupled Device (ICCD) camera for the fluorescence detection. Instrumental LD found for CB, for MBC and for CF are respectively 4, 50 and 1000 ng L(-1). In tap water, the LD obtained is 800 ng L(-1) for MBC and 20,000 ng L(-1) for CF. For CB, the use of a time shift between excitation and emission allows to reach a LD of 20 ng L(-1) in tap water.

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