Ce travail de thèse a porté sur l’étude des propriétés d’adsorption et de séparation en milieu humide par des polymères de coordination poreux. Nous avons utilisé les techniques de volumétrie d’adsorption, de séparation par chromatographie en phase gaz, de spectroscopie de fluorescence ainsi que et de la modélisation Monte Carlo afin de comprendre les mécanismes qui gouvernent l’adsorption de ces matériaux. Les molécules adsorbables étudiées sont l’eau et des vapeurs d’hydrocarbures linéaires (pentane et n-hexane), cycliques (cyclohexane et cyclohexène) et polycycliques (anthracène). Les adsorbants étudiés sont les Analogues de Bleu de Prusse (ABP) ainsi que deux matériaux organométalliques poreux de référence, le ZIF8 et le CuBTC. Parmi les résultats principaux apportés par ce travail, nous avons montré que les Analogues de Bleu de Prusse ont une stabilité hydrothermale remarquable leur conférant des propriétés d’adsorption en milieu humide très prometteuses. Parmi les ABP étudiés, le Co[CoIII(CN)6]0.66 ⊡0.33 .5.2H2O a montré des propriétés d’adsorption et de séparation très supérieures à celles d’autres ABPs. Par exemple, il a été possible de moduler sa balance hydrophobe/hydrophile par le contrôle de la coordination de l’eau sur le centre métallique insaturé, tout en préservant son caractère lipophile. Nous avons aussi montré que cet analogue de bleu de Prusse est capable de séparer des mélanges d’hydrocarbures secs ou très humides de façon répétée. Sur un aspect plus fondamental, nous avons montré que le confinement d’anthracène par le ZIF-8, qui est un composé organométallique poreux possédant des cavités de taille ajustée à celle du fluorophore, pouvait induire une extinction complète de certaines bandes d’absorption de celui-ci. / This PhD thesis is focused on the study of wet adsorption and separation properties by porous coordination polymers. We used adsorption volumetry, gas chromatography separation techniques, fluorescence spectroscopy techniques and Monte Carlo modeling to understand the mechanisms governing the adsorption of these materials. The adsorbable molecules studied are water and hydrocarbon vapors linear (pentane and n-hexane), cyclic (cyclohexane and cyclohexene) and polycyclic (anthracene). The adsorbents studied are the Prussian Blue Analogues (ABP) as well as two reference porous organometallic materials, ZIF8 and CuBTC. Among the main results provided by this work, we have shown that Prussian Blue Analogues have remarkable hydrothermal stability conferring them very promising wet adsorption properties. Among the ABPs studied, Co [CoIII (CN)6] 0.66 ⊡0.33 .5.2H2O showed adsorption and separation properties far superior to those of other ABPs. For example, it has been possible to modulate its hydrophobic / hydrophilic balance by controlling the coordination of water on the unsaturated metal center, while preserving its lipophilic character. We have also shown that this Prussian blue analogue is capable of separating mixtures of dry or very wet hydrocarbons repeatedly. On a more fundamental aspect, we have shown that the confinement of anthracene by ZIF-8, which is a porous organometallic compound with cavities of size adjusted to that of the fluorophore, could induce a complete extinction of certain absorption bands of this one.

Le travail de la thèse est focalisé sur l’ élaboration plasma d’un revêtement multicouches avec une couche supérieure anti-brouillard et une couche inférieure dite barrière sur un polycarbonate. L’ensemble des travaux est divisé en 3 parties: élaborations des deux monocouches barrière ou antibuée puis dépôt de la multicouche barrière - antibuée. La polymérisation plasma de la couche barrière est effectuée à partir d’un mélange de dioxygène et d’un précurseur organosilicié : l’hexaméthyledisiloxane ou le 2,4,6,8-tétraméthylcyclotétrasiloxane ou bien encore le triéthoxyfluorosilane. La caractérisation des couches minces obtenues repose sur la spectroscopie Infrarouge à Transformée de Fourier , la spectroscopie de photoélectrons X et la microscopie à force atomique. L’influence des conditions de dépôt plasma comme la puissance, la proportion monomère/dioxygène, le temps du dépôt sur la structure chimique et l’hydrophobicité de la surface des différents types de couches organosiliciées est étudiée. Les résultats de la perméation avec l’eau liquide ou le dioxygène montrent que la propriété barrière des couches organosiliciées non fluorées est meilleure que pour la couche fluorée. L’élaboration de copolymères anti-buée repose sur l’utilisation de combinaisons entre deux précurseurs hydrophile et hydrophobe en voie plasma pulsé. Les précurseurs tels que le 2-(diméthylamino)éthyl méthacrylate ou l’acide acrylique sont choisis pour leur hydrophile alors que le 1H,1H,2H-perfluoro-1-décène représente la partie oléophobe. La propriété anti-brouillard et sa stabilité à long terme après un vieillissement thermique ou en milieu humide est dépendante de leurs structure et morphologie. / The PhD work is focused on the deposition of a multilayer coating with an anti-fog top layer obtained thanks to the plasma copolymerization of hydrophilic and hydrophobic monomers and an intermediate barrier layer, also obtained by plasma deposition on polycarbonate. The work is divided into 3 parts: the independently preparations of the two monolayers, barrier and anti-fogging ones, then the barrier-antifog multilayer deposition. The characterization of the thin films obtained is based on Fourier Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy.The barrier plasma-layer is issued from by the mixture of dioxygen and one of these three organosilicon precursors : hexamethyledisiloxane ; 2,4,6,8-tetramethylcyclotetrasiloxane ; triethoxyfluorosilane. The influence of the plasma conditions such as discharge power, monomer/dioxygen ratio, deposition duration on the chemical structure and the hydrophobicity of the different types of the organosilicon layers was studied. The results of permeation with liquid water or dioxygen show that the barrier property of the organosilicon layer is more efficient than that of the fluorinated layer. Anti-fog plasma-copolymer is synthetized from two hydrophilic and hydrophobic precursors deposited by pulsed plasma mode. The precursors such as 2-(dimethylamino) ethyl methacrylate and acrylic acid were selected for the hydrophilic part while the 1H, 1H, 2H-perfluoro-1-decene will be associated to the oleophobic part. The dependence of the chemical structure and the morphology of the anti-fog layers is studied according to the hydrophilic/oleophobic distribution and the deposition time.

<div><div><div><p>Lewis acid zeolites contain framework metal heteroatoms that catalyze sugar iso- merization reactions at different turnover rates depending on the local coordination around metal centers and the polarity of their confining secondary environments. Post-synthetic modification routes that react metal precursors with framework va- cancy defects in dealuminated Beta zeolites (Sn-Beta-PS-OH) are developed as an alternative synthetic strategy to the hydrothermal crystallization of Sn-Beta zeolites (Sn-Beta-HT-F). Post-synthetic routes provide the ability to systematically tailor the structural features of active and defect sites in Sn-zeolites, especially in composition ranges inaccessible to materials crystallized by hydrothermal routes (Si/Sn < 100; > 2 wt.% Sn), yet often result in incomplete or unselective Sn grafting within framework vacancy defects and form extraframework metal oxide domains and residual defect sites. The development of robust post-synthetic routes to prepare Sn-zeolites with intended active and defect structures has been limited by the dearth of characteri- zation techniques to unambiguously detect and quantify such structures present in stannosilicate materials, and of mechanistic links between such structures and the turnover rates of catalytic reactions.</p><p><br></p><p>The presence of framework Sn centers that can expand its coordination shell from four- to six-coordinate structures, and small extraframework tin oxide domains that cannot, were unambiguously detected from diffuse reflectance UV-Visible spectra of stannosilicate materials measured after dehydration treatments (523 K, 0.5 h) to discern ligand-to-metal charge transfer bands for tetrahedrally-coordinated Sn heteroatoms (< 220 nm, > 4.1 eV) and those for tin oxide domains (> 230 nm, < 4.1 eV). Liquid-phase grafting of stannic chloride in dichloromethane reflux (333 K) enables preparing Sn-Beta zeolites with higher framework Sn content (Si/Sn = 30– 144; 1.4–6.1 wt.% Sn) than grafting performed in isopropanol reflux (423 K, Si/Sn > 120; 1.6 wt.% Sn). This reflects competitive adsorption of isopropanol solvents with stannic chloride at framework vacancy defects during grafting procedures, consistent with infrared spectroscopy (IR) and temperature-programmed desorption (TPD) of dealuminated Beta samples after saturation with isopropanol at reflux temperatures (423 K), and not any limitations inherent to the structure of vacancy defects within dealuminated zeolite supports that would prevent reaction with metal precursors as often proposed.</p><p><br></p></div></div></div><div><div><div><p>This insight enabled preparing Sn-Beta zeolites with varying densities of residual defects, via dichloromethane-assisted grafting of stannic chloride to different extents, into dealuminated Beta supports of different initial Al content (Si/Al = 19–180) and mineralizing agent used for hydrothermal crystallization of the parent Al-Beta sam- ple (e.g., fluoride or hydroxide). Preparation of low-defect Sn-Beta zeolites using post-synthetic routes (Sn-Beta-PS-F) first required the synthesis of parent Al-Beta zeolites in fluoride media to minimize residual siloxy defects (OSi−) formed during crystallization, and dilute Al content (Si/Al > 100, < 0.6 Al (unit cell)−1), to min- imize the density of intrapore silanol groups formed after dealumination and high temperature oxidative treatment. The methanol packing density within microporous voids of Sn-Beta zeolites was assessed from relative volumetric uptakes at the point of micropore filling from single-component methanol (293 K) and nitrogen (77 K) adsorption isotherms, and decreased systematically among samples with increasing density of silanol groups. The total density of silanol groups within micropores and at external crystallite surface in Sn-Beta zeolites was quantified by H/D isotopic ex- change during temperature-programmed surface reactions (500–873 K), and within microporous voids from IR spectra measured after saturation of microporous binding sites with CD3CN (2275 cm−1, 303 K). In situ IR spectra collected at low methanol pressures (P/P0 < 0.2, 303 K) provide further evidence that methanol molecules ar- range in localized clusters within Sn-Beta-PS-F, but form extended hydrogen-bonded networks within Sn-Beta-PS-OH.</p><p><br></p></div></div></div><div><div><div><p>Glucose-fructose isomerization rate constants (373 K) were used to probe the lo- cal coordination of Sn heteroatoms and the polarity of the secondary environment as influenced by silanol defects within microporous cavities. Ex situ pyridine titration of Sn-Beta-HT-F samples suppressed isomerization rates (per total Sn, 373 K) after only a subset of Sn sites were poisoned, which correspond to the number of open Sn sites quantified ex situ via CD3CN IR (303 K), providing further evidence that open Sn sites are dominant active sites for glucose isomerization. First-order isomerization rate constants (373 K) decrease with increasing Sn content when normalized by total Sn density, and are invariant when normalized by the number of open Sn sites, be- cause open Sn sites are grafted preferentially within Sn-Beta-PS-OH (Si/Sn = 30–144; 1.4–6.1 wt.% Sn) at low Sn densities. Isomerization rate constants (per open Sn, 373 K), however, are lower by ∼4x and ∼15x on Sn-Beta-PS-F (Si/Sn = 284; 0.7 wt.% Sn) and Sn-Beta-PS-OH, respectively, than on Sn-Beta-HT-F. Open Sn sites catalyze aqueous-phase glucose isomerization at higher turnover rates (373 K) when their mi- croporous surroundings contain silanol defects present in low (hydrophobic) densities than high (hydrophilic) densities, which are characteristic of Sn-Beta-HT-F and Sn- Beta-PS-OH samples, respectively. This reflects reorganization of extended water networks, which are stabilized in high-defect, hydrophilic micropore environments, at kinetically relevant 1,2-hydride shift transition states that incurs entropic penal- ties that lower turnover rates. This thesis highlights the development of synthesis- structure-function relationships to guide the preparation of catalytic materials with intended active and defect site structures within confining reaction environments, the development of characterization techniques for the identification and quantification of such structures, and the influence of such structures on turnover rates of liquid-phase sugar isomerization.</p></div></div></div>

La voie orale suscite un intérêt pour l'administration des médicaments anticancéreux, qui sont encore administrés essentiellement par voie parentérale. En effet, la biodisponibilité des principes actifs est fortement limitée par leurs propriétés physico-chimiques et des facteurs physiologiques. L'utilisation de systèmes à base de lipides et de nanoparticules polymères peuvent se montrer très performants pour surmonter certaines limitations. L'objectif de ce travail a consisté à développer deux familles de systèmes dispersés pour la voie orale contenant dans leur phase interne de l'huile de copaïba servant de véhicules à des médicaments anticancéreux comme le paclitaxel. Dans la première partie du travail a été consacrée au développement et à la validation de méthodes d’analyses de l’huile de copaiba par chromatographie en phase gaseuse et de dosage du paclitaxel dans l'huile de copaïba. Dans la deuxième partie du travail, des microémulsions d'huile de copaïba/eau ont été formulée en proposant une approche originale basée sur la complémentarité chimique des composés de l'huile et des tensioactifs. Cette approche a permis l'obtention de microémulsion contenant des fractions volumiques importantes de l'huile essentielle de copaïba (19.6%) tout en maintenant les concentrations en tensioactifs faible (13.7%). Du paclitaxel a pu être incorporé dans les microémulsions sans perturber notablement les caractéristiques du system. La troisième partie du travail a été consacré au développement de nanocapsules mucoadhésives contenant de l'huile de copaïba. La mise en œuvre d’un plan d’expérience a contribué à la formulation de nanocapsules incorporant du paclitaxel pouvant être marquée par une sonde fluorescente. La stabilité des nanocapsules a été étudiée dans des milieux gastrique et intestinaux simulés. Leur mucoadhésion a été évaluée sur des fragments de muqueuse intestinale prélevés chez le rat. Les résultats de ces travaux ont conduit au développement de deux formulations de paclitaxel dans des nanosystèmes originaux qui pourront par la suite être évalués pour en étudier leur capacité à délivrer l'agent anticancéreux par voie orale. / Anticancer drug are still mainly administered by the parenteral route. Oral delivery is limited the physicochemical properties of drugs and physiological. Systems based on lipids and polymeric nanoparticles may overcome these limitations. The aim of our project was to develop dispersed systems containing copaiba oil in their internal phase as vehicle for oral administration of paclitaxel, an anticancer drug, paclitaxel. The work was carried on in three parts. At first, methods of analysis of copaiba oil and of dosage of paclitaxel in this oil were developed and validated based on gas chromatography and HPLC respectively. Then, copaiba oil/water microemulsion was formulated from a new approach based on the pairing of chemical properties of the oil components and the surfactants. Stable microemulsion containing remarkably high amount of copaiba essential oil (volume fraction 19.6%) and a low surfactant concentration (13.7%) were obtained and could incorporate paclitaxel. Finally, an experimental design approach was proposed to develop mucoadhesive nanocapsules encapsulating copaiba oil, paclitaxel and that can be labeled with a fluorescent. These systems were tested for their ability to concentrate paclitaxel on the gut mucosa by evaluating their mucoadhesion using a ex vivo model based on the Ussing chambers. The nanosystems proposed in this work are ready for an evaluation for their capacity to deliver this anticancer drug by the oral route.

Icing is an important problem, which often leads to emergency situations in northern countries. The reduction of icing requires a detailed understanding of this process. In this work, we report on a systematic investigation of the effects of geometry and chemical properties of surfaces on the formation of an ice layer, its properties, and thawing. We compare in detail icing and ice thawing on flat and rough hydrophilic and hydrophobic surfaces. We also show advantages and disadvantages of the surfaces of each kind. We demonstrate that water condenses in a liquid form, leading to the formation of a thin continuous water layer on a hydrophilic surface. Meanwhile, separated rounded water droplets are formed on hydrophobic surfaces. As a result of slower heat exchange, the freezing of rounded water droplets on a hydrophobic surface occurs later than the freezing of the continuous water layer on a hydrophilic one. Moreover, growth of ice on hydrophobic surfaces is slower than on the hydrophilic ones, because ice grows due to the condensation of water vapor on already formed ice crystals, and not due to the condensation on the polymer surface. Rough hydrophobic surfaces also demonstrate a very low ice adhesion value, which is because of the reduced contact area with ice. The main disadvantage of hydrophobic and superhydrophobic surfaces is the pinning of water droplets on them after thawing. Flat hydrophilic poly(ethylene glycol)-modified surfaces also exhibit very low ice adhesion, which is due to the very low freezing point of the water–poly(ethylene glycol) mixtures. Water easily leaves from flat hydrophilic poly(ethylene glycol)-modified surfaces, and they quickly become dry. However, the ice growth rate on poly(ethylene glycol)-modified hydrophilic surfaces is the highest. These results indicate that neither purely (super)hydrophobic polymeric surfaces, nor ‘‘antifreeze’’ hydrophilic ones provide an ideal solution to the problem of icing.

Biopharmaceuticals are becoming one of the most promising drugs on the market mainly due to their successful treatment of a vast array of serious diseases, such as cancers, immune disorders, and infections. Structurally, biopharmaceuticals are proteins and it is important to mention that more than 60 % of biopharmaceuticals are glycosylated. Glycosylation is one of the most common posttranslational modifications. It is also the most demanding and the most complex posttranslational modification. The research showed that glycosylation can significantly impact on the safety, efficiency, and quality of the therapeutic glycoproteins. In the first part of the introduction of the present thesis, the development of the therapeutic glycoproteins and their classification were reviewed. Glycosylation process and nomenclature were also discussed. The second part of the introduction revealed current issues in the field of the production and the characterization of the therapeutic glycoproteins. In the context of the doctoral thesis, we introduced new approach, namely hydrophilic interaction liquid chromatography coupled to a high-resolution mass spectrometer (HILIC-HR-MS) combined with Principal Component Analysis (PCA) and classification through Soft Independent Modelling by Class Analogy (SIMCA) data treatment. Accordingly, N-glycans were first enzymatically released using peptide-N-glycosidase F (PNGase F) and reduced using sodium borohydride. Then those N-glycans were separated by HILIC and detected by HR-MS. PCA and SIMCA simplified interpretation of the MS data collected in the huge tables. PCA was applied to test whether it is possible to visualize N-glycosylation differences between samples and to help identifying within which N-glycans changes occurred. SIMCA, which is a more complex data analysis technique, was applied to build and validate a classification models. SIMCA was also applied to verify whether it is possible to use built models to classify real samples. Described approach enabled us to detect small changes in N-glycosylation of the therapeutic glycoproteins (a change of only 1% in relative glycan abundance). It was applied to assess changes in N-glycosylation of therapeutic glycoproteins. Accordingly, we tested N-glycosylation consistency between batches of infliximab, trastuzumab, and bevacizumab and monitored the N-glycosylation of bevacizumab over storage time in plastic syringes.Furthermore, we worked on the faster sample preparation technique, where online-solid-phase extraction (SPE)-LC was combined to the previously mentioned HILIC-MS-PCA/SIMCA method. Online-SPE-LC allowed us to faster the sample preparation in terms of avoiding time-consuming cleaning steps. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

In this work, hydrophilic fluorene-based derivatives that contain ethylene oxide substituents, have been synthesized and characterized for potential use as new fluorophores for bioimaging applications and for fluorescence sensing of heavy metals. Symmetrical and unsymmetrical fluorene derivatives based on structural types of acceptor-pi-acceptor, acceptor-pi-donor, and donor-pi-donor were characterized by TGA, UV-vis absorption, fluorescence emission, lifetime, anisotropy, and two-photon absorption (2PA) cross section. They were found to possess high thermal stability, high photostability, high fluorescence quantum yields, and generally large two-photon absorption cross sections, making them quite suitable for new probes in single-photon absorption and two-photon absorption fluorescence microscopy imaging. Novel hydrophilic fluorene derivatives were synthesized from fluorene in multiple steps employing the metal-catalyzed Heck coupling reaction, the Stille reaction, the Sonogashira reaction, the Ullmann condensation reaction, and "click" chemistry. To increase the hydrophilicity of the new compounds, ethylene oxide substituents were utilized for to impart water solubility. An alternative alkylation methodology using ethyleneoxy tosylates was introduced for the synthesis of ethylene oxide-containing fluorene derivatives. Several of these hydrophilic derivatives were incubated into various cell lines as new probes for both conventional and two-photon absorption fluorescence bioimaging. These compounds were biocompatible, exhibiting low cytotoxicity as determined by cell viability studies, and displayed colocalization for selected cellular organelles. In addition, hydrophilic bis(1,2,3-triazolyl)fluorene derivatives were found to exhibit sensitive fluorescence responses in the presence of certain heavy metal, and were selective for sensing zinc and mercury over other a number of other metal ions relevant to living cells or other biological environments. The UV-vis absorption and fluorescence emission spectra of the complexes exhibited a blue-shifted absorption and emission for selective metal chelation upon binding to zinc and mercury(II) ions, resulting in an approximately two-fold enhanced fluorescence response. Fluorescence titration studies revealed that the complexes of 1:2 and 1:3 ligand to metal formed with binding constant values of 108 and 1014 for zinc and mercury ions, respectively. Finally, preliminary experiments were performed to explore the possibility of employing select hydrophilic fluorene-based derivatives in the synthesis of hydrophilic fluorescent gold nanoparticles. Although results are very preliminary, the aim is to use such materials for other biomedical applications, such as surface enhanced scattering resonance and noninvasive photothermal therapy to diagnose and to treat cancers. Thus, this research had led to the discovery of alternative methodologies for synthesis of hydrophilic fluorene derivatives by alkylation with alkyl tosylates and synthesis of hydrophilic fluorescent molecule capped gold nanoparticles. Furthermore, several novel hydrophilic fluorene-based derivatives were synthesized and characterized for their linear and nonlinear photophysical properties, and are now available for further examination of their bioimaging and sensing applications.

Return liquor from thermal hydrolysis process (THP) can significantly add to the nitrogen load of a wastewater treatment plant (WWTP) and introduce UV quenching substances to the wastewater stream when recycled. While there are mature technologies in place to handle the inorganic nitrogen produced due to the thermal pretreatment, organic nitrogen remains a parameter of concern for utilities employing THP pretreatment. The impact of operating conditions of the THP on dissolved organic nitrogen (DON) and UV absorbance in return liquor was investigated. Operating conditions studied were (1) operating temperature (2) solids retention time (SRT) in the anaerobic digester (3) THP flash pressure (4) the effect of co-digestion of sewage sludge with food waste and, (5) polymer conditioning. Operating temperature and polymer dose had the most significant impact on DON and UV quenching. It was found that an increase in operating temperature resulted in an increase in DON, which was primarily contributed by the hydrophilic fraction. An increase in temperature also resulted in increased UV254 absorbance. However, this trend was not linear and the increase was more pronounced when the temperature was increased from 150 C to 170 C. Increasing flash pressure from 25 psi to 45 psi did not have a significant impact on the return liquor. However, increasing the flash pressure to 75 psi increased the DON and UV254 absorbing compounds. Co-digesting the sludge with food waste resulted in a slight increase in DON and a decrease in dissolved organic carbon (DOC) and UV quenching compounds. Increasing the SRT from 10 days to 15 days resulted in a slight decrease in DON but did not have any impact on UV254 absorbance. Overall, it can be concluded that optimizing operating conditions of thermal hydrolysis process can result in decreased DON and UV quenching compounds in the recycle stream. / Master of Science

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