Des nanocomposites polyuréthane-argent (PU-Ag) ont été élaborés à l'aide de deux procédés respectueux de l'environnement et du manipulateur, dans le but de prévenir la colonisation microbienne de ces matériaux. Le premier consiste à incorporer une dispersion aqueuse de nanoparticules d'argent, réalisée ex situ, au cours du procédé de synthèse d'un PU en dispersion aqueuse. Une dispersion de nanoparticules d'argent obtenue par réduction chimique, sous micro-ondes, d'ions d'argent en présence de polyéthylèneglycol a été développée dans l'objectif d'intégrer chimiquement le PEG dans les chaînes de PU. Le second procédé réside dans la réduction photochimique, in situ, d'ions argent dans une matrice PU, en l'absence de tout autre composé chimique.La caractérisation des matériaux obtenus montre une dispersion homogène des nanoparticules d'argent avec des tailles de particules faibles (5 à 50 nm] et une activité biocide des surfaces vis-à-vis de deux souches bactériennes (Pseudomonas aeruginosa et Enterococcus faecalis) sans modification notable des propriétés physicochimiques intrinsèques du PU. / Two environment and human-friendly processes were developed to synthesize polyurethane-silver (PU-Ag) nanocomposites having biocide surfaces able preventing the microbial colonization.The first one, called ex-situ process, consists in incorporating a silver nanoparticles aqueous dispersion during the synthesis process of polyurethane, which is itself carried out in aqueous dispersion. In this case, the chemical reduction of silver ions under microwaves and in the presence of polyethyleneglycol was particularly developed with the aim to chemically incorporate the PEG in the PUchains. For the second process, silver ions dispersed inside a PU matrix were photochemically reduced in situ.The obtained materials exhibit a homogeneous dispersion of silver nanoparticles with small diameter (from 5 to 50 nm) without marked modification of the intrisic physomchemical properties of the PU. Lastly, the antibacterial properties of the surfaces aginst Pseudomonas aeruginosa and Enterococcus faecalis were confirmed.

Gels are a special class of materials which are composed of 3D networks of crosslinked polymer chains that encapsulate liquid/air in the matrix. They can be classified into organogels or hydrogels (organic solvent for organogel and water for hydrogel). For hydrogels that contain metallic elements in the form of ions, the term of metallo-supramolecular polymer hydrogel (MSPHG) is often used. The aim of this project is to develop a kind of new MSPHG and investigate its properties and possible applications. The commercial polymeric anhydride poly(methyl vinyl ether-alt-maleic anhydride) (PVM/MA) is converted by reaction with NaOH to give poly(methyl vinyl ether-alt-monosodium maleate) (PVM/Na-MA). By addition of AgNO3-solution, the formation of the silver(I) supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]∙AgNO3 is obtained. Freeze-dried samples of the hydrogel show a mesoporous network of polycarboxylate ligands that are crosslinked by silver(I) cations. The supercritical CO2 dried silver(I) hydrogel was characterized by FT-IR, SEM-EDAX, TEM, TGA and Physical adsorption (BET) measurements. The intact silver(I) hydrogel was characterized by cryo-SEM. In the intact hydrogel, ion-exchange studies are reported and it is shown that Ag+ ions can be exchanged by copper(II) cations without disintegration of the hydrogel. The silver(I) hydrogel shows effective antibacterial activity and potential application as burn wound dressing.

Dans le cadre du Traité d’Interdiction Complète des Essais nucléaires, le Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA) développe des systèmes de détection des essais nucléaires en se basant sur la mesure des isotopes radioactifs du xénon, tels que le Système de Prélèvement d’Air en Ligne avec l’Analyse des radioXénons. L’adsorption est un procédé adapté pour ce type d’applications mais nécessite l’utilisation de matériaux adsorbants très performants pour piéger et séparer les gaz rares d’intérêt présents dans l’air à l’état de traces. Ce travail doctoral a tout d’abord permis de poser un cadre méthodologique permettant de comparer les matériaux adsorbants disponibles pour séparer le xénon aux faibles pressions partielles et de sélectionner la zéolithe Ag@ZSM-5. De nombreuses techniques ont été employées dont la microscopie électronique à transmission et la simulation ab initio afin d’étudier le vieillissement de ce matériau en conditions procédés, lié aux étapes d’élution en température et aux conditions environnementales, et d’approfondir la connaissance de cet adsorbant. L’influence du support zéolithique sur la formation et la stabilité des particules métalliques, ainsi que l’interaction entre les nanoparticules et le xénon ont en effet été investigués. Finalement la zéolithe Ag@ZSM-5 a été mise en application dans un pilote de laboratoire automatisé. Ce procédé compact de séparation des gaz rares basé uniquement sur des étapes d’adsorption présente des performances encourageantes et permet d’envisager l’utilisation de ce matériau dans des applications variées, de la dépollution de l’air en radon jusqu’à la production industrielle de xénon / In the context of the Comprehensive Nuclear Test Ban Treaty, the Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA) is developing systems to detect nuclear tests based on the xenon radioactive isotopes measurement, such as the Système de Prélèvement d’Air en Ligne avec l’Analyse des radioXénons. Adsorption is a suitable process for this type of application but requires the use of high performance adsorbent materials to trap and separate the rare gases of interest present in the air in trace amounts.In the first instance, this PhD thesis has set a methodological framework to compare the adsorbent materials available to separate xenon at low partial pressures and to select the Ag@ZSM-5 zeolite. Numerous techniques ranging from transmission electron microscopy to ab initio calculation have been employed to study the aging of this material under process conditions, related to the thermal elution steps and environmental conditions. The knowledge of the material has been deepened by studying the influence of zeolite support on the formation and stability of metal particles, as well as the interaction between nanoparticles and xenon. Finally, the Ag@ZSM-5 zeolite was applied in an automated pilot. This compact process for the separation of noble gases based only on adsorption steps shows encouraging performances and allow considering the use of this material in various applications, ranging from decontamination of air polluted by radon to the industrial production of xenon

Silver nanoparticles (AgNPs) are the most common nanomaterials incorporated in commercial products due to their antimicrobial activity. Recently, AgNPs were detected in surface waters suggesting the potential for bioavailability in the aquatic receptor organisms. This dissertation research attempts to understand the potential toxicity of AgNPs on water quality indicators, focusing on the microbial community and amphipods. This study evaluated whether: (1) the antimicrobial properties of AgNPs pose potential risks to microbial communities in pathogen impaired streams; (2) AgNPs can cause a shift in functional diversity and metabolic fingerprinting of microbial communities; (3) survival and growth of Hyalella azteca (amphipods) could be affected by AgNPs; and (4) surface coating agents influence AgNP toxicity in H. azteca. Microbial community responses to AgNPs were assessed using standard plate count, microbial enzyme assays, and carbon substrate utilization with Biolog EcoPlates™. Ten-day and 28-d toxicity tests were conducted in a static system to assess AgNP effects on H. azteca. AgNPs caused a 69% decrease in microbial concentration and a 77% decrease in β-glucosidase activity at 0.32 mg Ag kg-1 dry sediment. The substrate utilization pattern of the microbial community was altered by AgNPs at 0.33 mg Ag kg-1 dry sediment. Ten-day LC50s for the survival of H. azteca were 3.3, 9.2, and 230.0 µg Ag L-1 for AgNO3, citrate-AgNP, and PVP-AgNP, respectively, whereas the 28-d LC50s were 3.0, 3.5, and 66.0 µg Ag L-1 for AgNO3, citrate-AgNP, and PVP-AgNP, respectively. The EC20s for growth (calculated as biomass) for the 10-d test were 1.6, 4.7, and 188.1 µg Ag L-1 for AgNO3, citrate-AgNP, and PVP-AgNPs; while the 28-d EC20s for AgNO3, citrate-AgNP and PVP-AgNP were 3.2, 0.5, and < 50 µg Ag L-1. The NOECS for dry weight were 4 and 1, and 100 µg Ag L-1, while those for biomass were 2, 0.5, and < 50 µg Ag L-1 for AgNO3, citrate-AgNP, and PVP-AgNP, respectively. The overall toxicity followed the trend: AgNO3 > citrate-AgNP > PVP-AgNP. The studies suggest that AgNPs pose potential risks to microbial communities and epibenthic macroinvertebrates used as bioindicators of water quality to protect public health and ecosystem health.

Magister Scientiae (Biodiversity and Conservation Biology) / Combating antimicrobial resistant infections caused by nosocomial pathogens poses a major public health problem globally. The widespread use of broad-spectrum antibiotics for the treatment of wound infections has led to the appearance of multidrug-resistant (MDR) microbes which further exacerbates the growth of microbes amongst patients. It may result in prolonged debility of the patient and an increase in healthcare costs due to prolonged hospital stays and expensive treatment regimens to avoid patient-patient transmission. Therefore, it is imperative that alternative sources of treatment to antimicrobial use in wound infections needs to be developed in order to inhibit or kill resistant microbes and to provide point of care medical treatment to the less fortunate at an affordable cost.

No description available.

Despite the growing applications of silver nanoparticles, toxicity information on this nanomaterial is still deficient. Conclusions on the toxicity of silver nanoparticles vary and atomic level toxicity mechanisms are not yet achieved. Consequently, our group conducted combined computational and experimental toxicity studies of silver nanoparticles (AgNPs). Toxicity of 10 nm citrate stabilized AgNPs on HepG2 cells were investigated. Experimental results show that the 10 nm citrate stabilized AgNPs begin to be toxic to HepG2 cells at a dosage that exceeds 1 ppm and LD50 was observed at 3 ppm. Elevated reactive oxygen species levels were seen upon exposure to AgNPs with the maximum at the LD50 concentration of 3 ppm. Normal protein regulation of HepG2 cells were affected by exposure to AgNPs. TEM images of HepG2 cells exposed to AgNPs reveal that AgNPs can penetrate and agglomerate inside the cells. Our preliminary computational study was guided by one of the widely accepted toxicity mechanism of AgNPs in which the nanoparticles dissolute to Ag+. The computational model was composed of a 1:1 ratio of silver and phospholipid head. The silver employed are in atomic and anionic form while the phospholipid head are the phosphocholine (PC) and phosphoethanolamine (PE), which are abundant in HepG2 cells. Computational study shows that the presence of Ag+ results in partial oxidation of both the phospholipid heads. Our preliminary experimental and computational studies lead us to develop new computational methods that can accurately predict oxidation potentials (HOMO), reduction potentials (LUMO), and absorption spectra that can be used in studying toxicity mechanism of AgNPs through the oxidation pathway. Thus, computational methods for cyclic voltammetry and absorption spectroscopy that use DFT and TD-DFT, respectively, were improved to provide more accurate electronic and optical properties. Cyclopenta-fused polycyclic hydrocarbons (CP-PAHs) with available experimental data for HOMO, LUMO, ΔEgap and absorption spectra and have potential application as AgNP stabilizers were used in developing the improved computational methods for cyclic voltammetry and absorption spectroscopy. The improved computational method for cyclic voltammetry was developed by accounting for the anion species that occur experimentally and by using B3LYP the best density functional in predicting the HOMO, LUMO and ΔEgap of CP-PAHs with overall MAE of 014 eV. The best absorption spectra otef CP-PAHs were predicted using B3LYP for geometry optimizations followed by TD-CAMB3LYP with MAE of 29 nm. All calculations of CP-PAHs were implemented using the 6-311g (d,p) basis set and tetrahydrofuran (THF) as solvent. These two developed computational methods were tested on a group of methyl triphenyl amine (MTPA) derivatives with available experimental data for HOMO, LUMO, ΔEgap and absorption spectra and have potential application as AgNP stabilizers. The new computational methods for cyclic voltammetry and absorption spectroscopy also provided the most accurate predicted electronic and optical properties of MTPA derivatives. Among the ten density functionals employed, prediction of HOMO, LUMO and ΔEgap were most accurate using B3LYP and B3PW91 with overall MAE of 0.31 eV and 0.27 eV, respectively. Absorption spectra of MTPA derivatives were still best predicted using the B3LYP/TD-CAMB3LYP method with MAE of 13 nm. All calculations of MTPA were implemented using the 6-31+g (d,p) basis set and dichloromethane as solvent.

In this work, we use optical approaches to study and provide mechanistic insight into electrochemical reactions occurring at the surface of single nanoparticles. Correlated optical-electrochemical studies offer several advantages over single nanoparticle electrochemical studies including, higher spatial resolution, the ability to interrogate many nanoparticles at the same time and identify populations of inactive nanoparticles. Throughout this dissertation, two optical techniques are discussed in detail, dark-field scattering and super-localization imaging. In the first set of experiments, we describe calcite-assisted localization and kinetics (CLocK) microscopy, a multiparameter super-localization imaging technique. By placing a rotating birefringent calcite crystal in the infinity space of an optical microscope, CLocK provides immediate polarization and orientation information while still maintaining the ability to localize a single nanoparticle with < 10 nm resolution. Additionally, we demonstrate that the CLocK point spread function encodes kinetic information that we quantified to be an order of magnitude shorter than the integration time of the camera. In this work, CLocK provides new mechanistic insight into dynamic processes such as the dissolution of single gold nanorods as well as single-molecule surface-enhanced Raman scattering. In the second work, dark-field scattering was employed to monitor a proposed post-synthesis silver nanoparticle surface cleaning strategy to improve homogeneity across a population. Here, a sacrificial silver-sulfide sulfide shell is chemically grown on single silver nanoparticles to outcompete surface impurities. We demonstrate that upon electrochemical removal of the shell, a more reactive and reproducible silver surface can be achieved as revealed by enhanced electrodissoluion of the freshly cleaned silver nanoparticles. In these experiments, we additionally found a sulfide-dependent formation of multiple sulfide-species as well as mixed character sulfide shells on single nanoparticles themselves, thus demonstrating the sensitivity provided by optical microscopy at identifying multiple surface chemistries. Overall, the work in this dissertation highlights the ability of optical tools at revealing heterogeneity in single particle studies providing insight into structure-function relationships. / Physiology

Microbial community functional diversity enhances the degradation of organic matter and pollutants in the environment, but there is a growing concern that these ecosystem services may be altered by the introduction of emerging environmental contaminants including silver nanoparticles (AgNPs) into aquatic systems. We added 0, 25, 50, 75, 100, and 125 mg L−1 (nominal concentrations) of citrate-AgNP and polyvinylpyrrolidone-AgNP (PVP-AgNP) each to freshwater sediment and examined their antimicrobial effects on microbial communities using community-level physiological profiling. The results showed that citrate-AgNP decreased the overall microbial catabolic activity by 80% from 1.16 ± 0.02 to 0.23 ± 08 while PVP-AgNP decreased the catabolic activity by 51% from 1.25 ± 0.07 to 0.61 ± 0.19 at 125 mg L−1. Citrate-AgNP and PVP-AgNP caused a statistically significant reduction in substrate richness and substrate diversity that decreased microbial functional diversity. AgNPs decreased microbial catabolic capability and functional diversity at concentrations ranging from 0.12 ± 0.04 to 0.43 ± 0.07 mg Ag kg-1 which are lower than the predicted concentrations in freshwater sediment. To our knowledge, this is the first study to demonstrate inhibition of microbial functional diversity by citrate-AgNP and PVP-AgNP in a pathogen impaired stream. Citrate-AgNP caused greater inhibition of carbon substrate utilization but amino acids, carbohydrates, and carboxylic acids were the most affected carbon groups which led to a shift in the metabolic fingerprint pattern of the microbial community. AgNPs decreased the catabolic capability and the ability of the microbial community to degrade organic matter and a variety of pollutants in the environment.

No description available.