Face à l’apparition croissante de troubles pigmentaires liés à l’exposition aux UV, le développement de nouveaux actifs blanchissants représente un enjeu majeur pour l’industrie cosmétique. De plus en plus de consommateurs s’orientent vers des produits eco-responsables, il devient urgent de développer de nouvelles méthodes de biocatalyse pour accéder à des antipigmentants. Certains glycosides, comme l’arbutine présentent des propriétés blanchissantes qui restent toutefois limitées face à l’hydrolyse rapide de la liaison O-glycosidique. L’enjeu du projet consiste à synthétiser des analogues de cette molécule en série thioglycosidique. En effet, cette liaison permet une plus grande stabilité vis à vis de l’hydrolyse. La mutation d’une glycosidase native issue de dictyoglomus thermophilum a permis d’accéder à une thioglycoligase. Cette dernière permet d’obtenir par catalyse enzymatique des analogues de l’arbutine. Six composés en série S- et O-glycosidique ont pu être synthétisés et testés en tant qu’agents dépigmentants. La méthodologie de synthèse a ensuite été appliquée pour l’obtention de thioglycolipides. Ces molécules sont connues pour leurs propriétés hydrogélifiantes permettant d’accéder à des matériaux thermoreversibles. Cinq molécules ont été identifiées en tant qu’agents hydrogélifiants. Les propriétés rhéologiques, thermiques et structurales ont été caractérisées mettant en évidence des différences significatives parmi les composés. Enfin les résultats préliminaires sur la formulation d’un produit à la fois antipigmentant et texturant s’avèrent prometteurs pour la validation d’un concept de matériau intelligent pour l’industrie cosmétique. / Considering the increasing appearance of pigmentation disorders caused by UV exposure, the development of new whitening agents is a major challenge for the cosmetics industry. Consumers are turning to ecoresponsible products, it is urgent to develop new methods of biocatalysis for the access to new depigmenting agents. Some glycosides, such as arbutin, have whitening properties which are still limited because of therapid hydrolysis of the O-glycosidic bond. The challenge of this project is synthesize analogues of this molecule in thioglycoside series. Endeed, this bond allows a greater stability against the hydrolysis. The mutation of anative glycosidase to dictyoglomus thermophilum gives access to a thioglycoligase. This makes possible the enzymatic synthesis of arbutine analogues. Six molécules were synthesized and tested as depigmenting agents. The synthesis methodology was then applied to the preparation of thioglycolipids. These moleculesare known for their hydrogellating properties allowing access to thermoreversible materials. Five molecules have been identified as hydrogellating agents. The rheological, thermal and structural properties have been characterized and showed significant differences depending of the compound structure. Lastly, the preliminary results on the formulation of a product that is both antipigmenting and texturizing are promising for the validation of an smart material concept for the cosmetic industry.

A dual wavelength method was developed for the field detection of optical brighteners (OBs), fluorescent laundry additives used as indicators of anthropogenic wastes. The method was quantitative for OBs under variable levels of fluorescent colored dissolved organic matter (CDOM). Based on excitation at 300-400 nm and 440 and 550 nm emission, the method assumed a constant ratio of fluorescence due to CDOM alone, even if absolute amplitude varied. Concentrations of OBs were computed as the difference between the observed 440 nm emission and the expected CDOM fluorescence at 440 nm, as extrapolated from the 550 nm fluorescence and established CDOM fluorescence ratio. Real-time inner filter corrections were based on absorption modeled from 550 nm fluorescence and from exponential relationships at alternate wavelengths. The effects of temperature and dissolved oxygen on CDOM fluorescence and computed OB were quantified but were minimal because effects were comparable between the two fluorescence regions. Assumptions on the locally conservative behavior of CDOM were supported in field surveys of sewered and non-sewered areas. Varying water masses were detected, but OB quantities were detected that did not co-vary with fluorescence alone. Eleven geographic regions of peninsular Florida and sources of OBs were sampled to evaluate the method under a broader range of CDOM and to conduct an extensive detergent spike analysis. Fluorescence data were collected as EEMs and subjected to PARAFAC modeling, isolating eight spectral factors that could sufficiently describe all samples. There were no visible regions of the spectra that were unique to detergents or OBs, but a previously unreported peak in the UV (<230 / 284 ex / em) was tentatively identified as a detergent surfactant and should be pursued as a potential complementary indicator of anthropogenic wastes. Limits on EEM fluorescence measurements were identified: maximum linear range, maximum turbidity, and sensitivity to assumptions. A sub-sampling technique of EEM data approximated the filter fluorometer readings, was used to optimize the dual wavelength method, validated the method with spike recoveries, and presented alternative approaches.

This thesis is about modelling and predicting the perceived whiteness of plain paper from the paper composition, including fluorescent whitening agents. This includes psycho-physical modelling of perceived whiteness from measurable light reflectance properties, and physical modelling of light scattering and fluorescence from the paper composition. Existing models are first tested and improvements are suggested and evaluated. The standardised and widely used CIE whiteness equation is first tested on commercial office papers with visual evaluations by different panels of observers, and improved models are validated. Simultaneous contrast effects, known to affect the appearance of coloured surfaces depending on the surrounding colour, are shown to significantly affect the perceived whiteness. A colour appearance model including simultaneous contrast effects  (CIECAM02-m2), earlier tested on coloured surfaces, is successfully applied to perceived whiteness. A recently proposed extension of the Kubelka-Munk light scattering model including fluorescence for turbid media of finite thickness is successfully tested for the first time on real papers. It is shown that the linear CIE whiteness equation fails to predict the perceived whiteness of highly white papers with distinct bluish tint. This equation is applicable only in a defined region of the colour space, a condition that is shown to be not fulfilled by many commercial office papers, although they appear white to most observers. The proposed non-linear whiteness equations give to these papers a whiteness value that correlates with their perceived whiteness, while application of the CIE whiteness equation outside its region of validity overestimates perceived whiteness. It is shown that the quantum efficiency of two different fluorescent whitening agents (FWA) in plain paper is rather constant with FWA type, FWA concentration, filler content, and fibre type. Hence, the fluorescence efficiency is essentially dependent only on the ability of the FWA to absorb light in its absorption band.  Increased FWA concentration leads accordingly to increased whiteness. However, since FWA absorbs light in the violet-blue region of the electromagnetic spectrum, the reflectance factor decreases in that region with increasing FWA amount. This violet-blue absorption tends to give a greener shade to the paper and explains most of the observed greening and whiteness saturation at larger FWA concentrations. A red-ward shift of the quantum efficiency is observed with increasing FWA concentration, but this is shown to have a negligible effect on the whiteness value. The results are directly applicable to industrial applications for better instrumental measurement of whiteness and thereby optimising the use of FWA with the goal to improve the perceived whiteness. In addition, a modular Monte Carlo simulation tool, Open PaperOpt, is developed to allow future spatial- and angle-resolved particle level light scattering simulation. / PaperOpt

[pt] A avaliação de artigos brancos tratados com alvejantes ópticos, como eles são comuns em substratos têxteis, plásticos e de papel, é uma tarefa que tradicionalmente resulta em muitas divergências entre avaliações visuais realizadas em uma cabine padronizada e avaliações instrumentais realizadas com espectrofotômetros de refletância. Mesmo entre as avaliações visuais ou entre as avaliações instrumentais são encontradas diferenças muito além do aceitável. Uma das principais causas é a fluorescência dos alvejantes ópticos que é influenciada pela quantidade de radiação UV em relação com a radiação na faixa visível do espectro. O trabalho apresentado analisa as diferentes formas de avaliação, principalmente do ponto de vista da qualidade da distribuição espectral de potência do simulador de luz do dia. No caso das avaliações visuais, são testadas diferentes lâmpadas fluorescentes. Para as avaliações instrumentais, a calibração e o ajuste de UV em conjunto com as diferentes aberturas de medição são analisados. O objetivo é aprimorar os aspectos metrológicos da avaliação e contribuir para a sua padronização a fim de garantir a maior reprodutibilidade de resultados, um procedimento importante e almejado por todos os segmentos industriais que utilizam os alvejantes ópticos. / [en] The evaluation of white objects treated with fluorescent whitening agents, such as they are commonly found on substrates like textiles, plastics and paper, is a task that traditionally leads to frequent controversy between the visual evaluations performed in a standardized light booth and the instrumental evaluations performed on reflectance spectrophotometers. Even between visual or instrumental evaluations the differences encountered are far beyond the acceptable. One of the main reasons is the fluorescence of the optical brightening agents that is influenced by the amount of UV radiation in relation to the amount of radiation in the visible range of the spectrum. The work presented analyses the different forms of evaluation, mainly from the point of view of the quality of the daylight simulators´ spectral power distribution. In the case of the visual evaluations, different fluorescent lamps are tested. For the instrumental evaluations, the UV calibration and adjustment are analyzed together with the different measurement apertures. The objective is to improve the metrological aspects of the evaluation and contribute to its standardization with the aim to guarantee better reproducibility of results, an important procedure that is desired by all the industrial segments that use optical brighteners.