Microbial colonization on the surface of silicone rubber high voltage outdoor insulators often results in the formation of highly hydrated biofilm that influence the surface properties, such as surface hydrophobicity. The loss of hydrophobicity might lead to dry band formation, and, in the worst cases, flashover and failure of the insulator. In this work, the biocidal effects of various antimicrobial compounds in silicone rubber materials were determined. These materials were evaluated according to an ISO standard for the antimicrobial activity against the growth of aggressive fungal strains, and microorganisms that have been found colonizing the surfaces of outdoor insulators in several areas in the world. Several compounds suppressed microbial growth on the surfaces of the materials without compromising the material properties of the silicone rubber. A commercial biocide and thymol were very effective against fungal growth, and sodium benzoate could suppress the fungal growth to some extent. Thymol could also inhibit algal growth. However, methods for preservation of the antimicrobial agents in the bulk of the material need to be further developed to prevent the loss of the compounds during manufacturing. Biofilm formation affected the surface hydrophobicity and complete removal of the biofilm was not achieved through cleaning. Surface analysis confirmed that traces of microorganisms were still present after cleaning. Further, surface modification of the silicone rubber was carried out to study how the texture and roughness of the surface affect biofilm formation. Silicone rubber surfaces with regular geometrical patterns were evaluated to determine the influence of the surface texture on the extent of microbial growth in comparison with plane silicone rubber surfaces. Silicone rubber nanocomposite surfaces, prepared using a spray-deposition method that applied hydrophilic and hydrophobic nanoparticles to obtain hierarchical structures, were studied to determine the effects of the surface roughness and improved hydrophobicity on the microbial attachment. Microenvironment chambers were used for the determination of microbial growth on different modified surfaces under conditions that mimic those of the insulators in their outdoor environments. Different parts of the insulators were represented by placing the samples vertically and inclined. The microbial growth on the surfaces of the textured samples was evenly distributed throughout the surfaces because of the uniform distribution of the water between the gaps of the regular structures on the surfaces. Microbial growth was not observed on the inclined and vertical nanocomposite surfaces due to the higher surface roughness and improved surface hydrophobicity, whereas non-coated samples were colonized by microorganisms. / <p>QC 20151002</p>

Dans le cadre de ce travail, l'objectif était d'élaborer des surfaces PVC antibactériennes. Deux types de surfaces ont été élaborés, des surfaces bactéricides visant à tuer les bactéries au contact et des surfaces antiadhésives (bactériophobes) empêchant ou limitant l'adhésion bactérienne.Pour ce faire, des copolymères porteurs de groupements cationiques bactéricides ainsi que des copolymères renfermant des structures à effets antiadhésifs de type polysaccharides ou PEG ont été synthétisés et caractérisés. Ces composés ont été ensuite greffés chimiquement par click addition sur des surfaces PVC porteuses de fonctions azoture (PVC-N3). Les propriétés physico-chimiques des nouvelles surfaces obtenues ont été caractérisées par diverses techniques (IRTF, XPS, angle de contact, AFM, microscopie confocale à fluorescence, ATG etDSC). Les propriétés bactéricides ou antiadhésives ont été évaluées à l'égard de Escherichia coli et Staphylococcus epidermidis. La microscopie confocale à fluorescence a mis en évidence le caractère hautement bactéricide des surfaces PVC cationiques via le test Live and Dead.Cette technique a aussi permis de démontrer l'effet antiadhésif de la méthyl cellulose, del'hydroxyéthyl cellulose et du PEG greffés en surface, diminuant d'au moins 10⁴ fois le nombre de bactéries adhérées par rapport aux surfaces témoins.

Using seawater in cooling systems is a common practice in many parts of the world where there is a shortage of freshwater. However, biofouling is one of the major operational problems associated with the usage of seawater in cooling systems. Microfouling is caused by the activities of microorganisms, such as bacteria and algae, producing a very thin layer that sticks to the inside surface of the tubes in heat exchangers. This thin layer has a tremendously negative impact on heat transferred across the heat exchanger tubes in the system. In some instances, even a 250 micrometer thickness of fouling film can reduce the heat exchanger's heat transfer coefficient by 50 percent. On the other hand, macrofouling is the blockage caused by relatively large marine organisms, such as oysters, mussels, clams, and barnacles. A biocide is typically added to eliminate, or at least reduce, biofouling. Typically, microfouling can be controlled by intermittent dosages, and macrofouling can be controlled by continuous dosages of biocide. The aim of this research work is to develop a systematic approach to the optimal operating and design alternatives for integrated seawater cooling systems in industrial facilities. A process integration framework is used to provide a holistic approach to optimizing the design and operation of the seawater cooling system, along with the dosage and discharge systems. Optimization formulations are employed to systematize the decision-making and to reconcile the various economic, technical, and environmental aspects of the problem. Building blocks of the approach include the biocide water chemistry and kinetics, process cooling requirements, dosage scenarios and dynamic profiles, biofilm growth, seawater discharge, and environmental regulations. Seawater chemistry is studied with emphasis on the usage of biocide for seawater cooling. A multi-period optimization formulation is developed and solved to determine: * The optimal levels of dosing and dechlorination chemicals * The timing of maintenance to clean the heat-exchange * The dynamic dependence of the biofilm growth on the applied doses, the seawater-biocide chemistry, the process conditions, and seawater characteristics for each time period. The technical, economic, and environmental considerations of the system are accounted for and discussed through case studies.

Bacterial infection in burn wounds can jeopardize healing and can even lead to a patient’s death. Recently using a topical wound dressing with antimicrobial ability has been increasing. An ideal dressing for a burn wound is required to be antimicrobial, pain free and able to control the wound moisture to facilitate healing. In this research, a UV-radiation grafting method for depositing polyacrylamide (PAM) layer was used to improve the non-adherence properties of two commercially available silver based wound dressings. The dressing adherence, evaluated via an in vitro gelatine model, dramatically decreases after the deposition of PAM. This deposition did not negatively affect the antibacterial ability and cytotoxicity of the dressings. Furthermore, a poly(amidoamine) dendrimer based biocide was incorporated into PET dressings coated with poly(acrylic acid-co-acrylamide ) hydrogel. The resulting dressing was able to release a therapeutic dose of the antimicrobial agent in a sustained manner. / February 2016

Os sistemas de armazenamento de combustível podem apresentar vulnerabilidade á contaminação tanto química quanto microbiana, comprometendo a qualidade final do produto. Este trabalho teve como objetivo selecionar antimicrobianos para utilização no controle da contaminação microbiana de misturas diesel/biodiesel armazenadas e monitorar a degradação química deste combustível. Foram estudados dezoito diferentes produtos antimicrobianos indicados para utilização em combustíveis, quanto ao seu espectro de ação e dosagens contra diferentes grupos microbianos em diferentes tipos de misturas diesel/biodiesel, através de testes em laboratório e em campo. A degradação química da fase oleosa foi monitorada através de testes específicos para algumas características indicativas de qualidade e a análise da degradação microbiana foi acompanhada com espectrometria de infravermelho. Foi realizada a avaliação de um KIT comercial para a detecção de ATP por bioluminescência com a bactéria Pseudomonas e um inóculo não caracterizado ( ASTM1259-10) em fase aquosa (meio mineral e água de drenagem de tanques de estocagem). A toxicidade da fase aquosa que esteve em contato com a mistura B10 e um aditivo selecionado foi avaliada com o uso das espécies Lactuca sativa L. (alface) e Artemia salina Leach (micro-crustáceo), durante 30 dias. Um aditivo contendo 50% de oxazolidina como ativo antimicrobiano em sua formulação foi considerado efetivo para o controle preventivo da contaminação microbiana em misturas B10. Porém outras formulações contendo, isotiazolonas ou morfolinas podem constituir uma boa opção para tratamentos corretivos. O kit para determinação do ATP por bioluminescência testado neste estudo, na forma como está projetado, não é adequado para estimar o grau de contaminação microbiana da fase aquosa proveniente de tanques de combustíveis. Os resultados de toxicidade mostram que tanto a água que esteve em contato com o combustível tratado (com o aditivo) e não tratado apresentaram toxicidade para os organismos estudados. Porém, a água que esteve em contato com o combustível tratado com o biocida mostrou alta toxicidade aguda para ambos os organismos-teste utilizados. / The fuel storage systems may present vulnerability to chemical as well as microbial contamination, compromising final product quality. This goal was to select antimicrobials for use in the control of microbial contamination of diesel/biodiesel blends stored and monitor aspects of chemical degradation of the fuel. 18 different antimicrobial products suitable for use in fuels, as their spectrum of activity against different microbial groups and dosages, in different types of diesel/biodiesel blends by means of laboratory tests and field were studied. The chemical degradation of the oil phase was monitored using specific tests for certain characteristics indicative of quality and analysis of microbial degradation was monitored with infrared spectrometry. The evaluation of a commercial kit for the ATP bioluminescence detection in aqueous phase with Pseudomonas and a uncharacterized inoculum (ASTM1259 -10) (mineral medium and natural bottom water from storage tanks) was performed. The toxicity of aqueous phase which was in contact with the B10 blend and selected additive was evaluated with the use of the species Lactuca sativa L. (Lettuce) and Artemia salina Leach (microcrustacean) for 30 days. An additive containing 50% oxazolidine as antimicrobial agent in its formulation was considered effective for preventive control of microbial mixtures B10. But other formulations containing isothiazolones or morpholines could be a good option for corrective treatment. The kit for determination of ATP bioluminescence tested in this study as designed it’s unappropriate to estimate the degree of microbial contamination of the aqueous phase from the fuel tank. The toxicity results show that both the water that was in contact with the treated fuel (with additive) and untreated showed toxicity to studied organisms. However, the water that was in contact with the biocide treated fuel showed high acute toxicity to both test organisms used.

Submitted by Claudia Rocha (claudia.rocha@udesc.br) on 2018-02-21T13:32:57Z No. of bitstreams: 1 PGPV16MA184.pdf: 606917 bytes, checksum: 366469520943d142992388dc8f04df93 (MD5) / Made available in DSpace on 2018-02-21T13:32:57Z (GMT). No. of bitstreams: 1 PGPV16MA184.pdf: 606917 bytes, checksum: 366469520943d142992388dc8f04df93 (MD5) Previous issue date: 2015-11-23 / Capes / The post-harvest longevity of cut roses is short, although it can vary according to various factors such as cultivar, harvest stage and time of day when the sample is taken and applied treatments. Many studies have been published with the aim to prolong this period. The use and research on preservatives solutions with the addition of biocides and substances inhibitory to the ethylene effect with low environmental impact are incipient. Therefore the aim of this study was to evaluate the effects of different concentrations of methanol and ethanol in the quality and longevity of Rosa hybrida cv. Vega. Concentrations tested were 0; 0.5; 1.0 and 2.0% methanol and ethanol maintenance solution. The stems were obtained from a commercial producer, located in Sao Sebastiao do Cai, RS. After put the flowers on the treatments, they were stored for seven days in cold chamber with temperature of 0.5 ° C ± 1 and relative humidity of 95 ± 4%, followed by another five days at ambient conditions (21 ° C ± 4 ° C / 80% ± 5% RH). The experimental design was completely randomized with four replications and experimental units composed of two rods standardized in 33 cm and four leaves. The variables studied were respiratory activity, color of leaves and petals (L, C and hº) Spad index of leaves, relative fresh weight of stems (g) , daily rate of flower opening (% day-1) and longevity of flowers. The variables were evaluated at the end of cold storage and after five days at ambient conditions. The use of ethanol reduces respiratory activity to CO² 34.89 mL kg-1 h-1 on cold storage and to 32.65 mL kg-1 h-1 of CO² after five days at room conditions, while the witness value was approximately 58 ml CO² kg-1 h-1, also increased the value hº of leaves out of the cold storage, demonstrating efficiency in maintaining the chlorophyll content of the leaves, also resulted in increase of MF about 7.1% of the PFi at cold storage time and 2.1% of PFI after five days at room conditions, the TDAF was reduced compared to the control treatment the and had no effect on longevity. Methanol reduces the respiratory activity at concentrations above 0.5% in the end of cold storage and decrease the CO² production evaluated after five days at room conditions to 37.76 mL kg-1 h-1 compared with approximately 62 mL CO² kg-1 h-1, witness was also effective in keeping the hº value of the leaves and the MF of the rods in both the storage period in cold storage and in shelf period, its reduced the opening of flowers until the concentration 1.0%, and increased the longevity of the flowers at a concentration of 1.49% in about 47% compared with the control. It is concluded that ethanol had no effect on longevity, but had positive results in other variables and methanol was effective in increasing longevity in concentration close to 1.5% with positive results in other variables / A longevidade pós-colheita de rosas é curta, apesar de variar em função de diversos fatores, tais como, cultivares, ponto de colheita, período do dia em que se realiza a colheita e tratamentos utilizados. Muitos trabalhos têm sido publicados com o objetivo de prolongar esse período. O uso e as pesquisas sobre soluções conservantes com adição de substâncias biocidas e inibidoras do efeito de etileno, que possuam baixo impacto ambiental, são incipientes. Diante disto o objetivo deste trabalho foi avaliar os efeitos de diferentes concentrações de metanol e etanol na qualidade e longevidade de Rosa hybrida cv. Vega. Foram testadas as concentrações de 0; 0,5; 1,0 e 2,0% de metanol e etanol em solução de manutenção. As hastes foram obtidas de um produtor comercial, localizado no município de São Sebastião do Cai, RS. Após a aplicação dos tratamentos as flores foram armazenadas durante sete dias em câmara fria com temperatura de 1±0,5 ºC e umidade relativa de 95±4%, seguido por mais cinco dias em condições ambiente (21ºC ± 4ºC/80% ± 5% de UR). O delineamento experimental utilizado foi completamente casualizado com quatro repetições e unidades experimentais compostas por duas hastes padronizadas em 33 cm e quatro folhas. As avaliações foram realizadas na saída da câmara fria e após cinco dias em condições ambiente e as variáveis avaliadas foram a atividade respiratória, coloração de folhas e pétalas (L, C e hº), índice Spad das folhas, massa fresca relativa (g), taxa diária de abertura floral (% dia-1) e longevidade das flores. O uso de etanol reduziu a atividade respiratória para 34,89 mL CO² kg-1 h-1 na saída do armazenamento refrigerado e para 32,65 mL CO² kg-1 h-1 após mais cinco dias, enquanto na testemunha o valor foi aproximadamente 58 mL CO² kg-1 h-1, também aumentou o valor do hº da cor das folhas na saída da câmara fria demonstrando eficiência na manutenção do teor de clorofila das folhas, resultou no ganho de MF de 7,1% do PFi no período de armazenamento em câmara fria e de 2,1% do PFi após cinco dias em condição ambiente, reduziu a TDAF em comparação com as hastes do tratamento testemunha e não apresentou efeito na longevidade. O metanol reduziu a atividade respiratória em concentrações superiores a 0,5% na saída do armazenamento refrigerado e redução para 37,76 mL CO² kg-1 h-1 em comparação com, aproximadamente, 62 mL CO² kg-1 h-1 da testemunha avaliado após cinco dias em ambiente, também foi eficiente em manter o valor hº da cor das folhas e a massa fresca das hastes, tanto no período de armazenamento em câmara fria quanto no período de prateleira, seu uso reduziu a abertura das flores até a concentração de 1,0%, e aumentou a longevidade das hastes em 47%, em comparação com a testemunha, na concentração de 1,49%. Conclui-se que o etanol não teve efeito na longevidade, mas que teve resultados positivos nas demais variáveis e que o metanol foi eficiente no aumento da longevidade na concentração próxima a 1,5% com resultados positivos nas demais variáveis

Nesta dissertação, duas resinas reticuladas comerciais (denominadas, AmberliteGT73 e AmberliteIRC748) foram empregadas para suportar partículas de prata. Os grupos tiol da GT73 e ácido iminodiacético da IRC748 presentes nessas resinas foram empregados para a fixação de íons Ag+ a partir de solução aquosa. Posteriormente, os íons Ag+ foram reduzidos pelo emprego de três redutores diferentes em pH alcalino, denominados hidrazina, hidroxilamina e formaldeído (pH &#61504; 12). A morfologia e a impregnação de prata dos materiais binários assim obtidos foram avaliadas por meio de microscópio eletrônico de varredura equipado com detector de elétrons retro-espalhados (SEM-BSE). O detector de espectrometria de energia dispersiva de raios-X (EDAX) acoplado ao SEM permitiu a observação de partículas de prata. Os espectros de raios-X revelaram a presença do metal nas superfícies interna e externa das microesferas dos compósitos. A quantidade de prata incorporada foi determinada pelo método titulométrico, empregando solução padrão de tiocianato de potássio. As características antibactericidas dos compósitos foram avaliadas em colunas contendo pérolas de resina por onde foram percoladas suspensões da bactéria Escherichia coli auxotrópica AB1157 (tipo selvagem) nas concentrações de 103 a 107 células/mL. A avaliação biocida mostrou que estes materiais foram completamente bactericidas, sendo efetivos na eliminação da bactéria em poucos minutos. Esta ação biocida foi atribuída à combinação da atuação da prata e dos grupos funcionais das resinas / In this work, two different commercial cross-linked resins (namely, Amberlite&#61666; GT73 and Amberlite&#61666;IRC748) were employed for anchoring silver. The SH and the N(CH2COOH)2 groups, respectively present on these resins, were used for the Ag+ chelation from aqueous solution. The Ag+ ions were reduced by employing three different reductants, namely hydrazine, hydroxylamine and formaldehyde (under alkaline pH). The produced composites were characterized by thermogravimetry (TG-DTG) and scanning electron microscopy equipped with backscattered scanning electron detector (SEM-BSE). Energy dispersive X-ray spectroscopy (EDS) coupled to SEM allowed the observation of submicron particles of silver and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites were determined towards 103 to 107 cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain, showing that the networks containing anchored submicron silver particles were completely bactericidal within a few minutes due to the combined action of silver and functional groups of the resins

Os sistemas de armazenamento de combustível podem apresentar vulnerabilidade á contaminação tanto química quanto microbiana, comprometendo a qualidade final do produto. Este trabalho teve como objetivo selecionar antimicrobianos para utilização no controle da contaminação microbiana de misturas diesel/biodiesel armazenadas e monitorar a degradação química deste combustível. Foram estudados dezoito diferentes produtos antimicrobianos indicados para utilização em combustíveis, quanto ao seu espectro de ação e dosagens contra diferentes grupos microbianos em diferentes tipos de misturas diesel/biodiesel, através de testes em laboratório e em campo. A degradação química da fase oleosa foi monitorada através de testes específicos para algumas características indicativas de qualidade e a análise da degradação microbiana foi acompanhada com espectrometria de infravermelho. Foi realizada a avaliação de um KIT comercial para a detecção de ATP por bioluminescência com a bactéria Pseudomonas e um inóculo não caracterizado ( ASTM1259-10) em fase aquosa (meio mineral e água de drenagem de tanques de estocagem). A toxicidade da fase aquosa que esteve em contato com a mistura B10 e um aditivo selecionado foi avaliada com o uso das espécies Lactuca sativa L. (alface) e Artemia salina Leach (micro-crustáceo), durante 30 dias. Um aditivo contendo 50% de oxazolidina como ativo antimicrobiano em sua formulação foi considerado efetivo para o controle preventivo da contaminação microbiana em misturas B10. Porém outras formulações contendo, isotiazolonas ou morfolinas podem constituir uma boa opção para tratamentos corretivos. O kit para determinação do ATP por bioluminescência testado neste estudo, na forma como está projetado, não é adequado para estimar o grau de contaminação microbiana da fase aquosa proveniente de tanques de combustíveis. Os resultados de toxicidade mostram que tanto a água que esteve em contato com o combustível tratado (com o aditivo) e não tratado apresentaram toxicidade para os organismos estudados. Porém, a água que esteve em contato com o combustível tratado com o biocida mostrou alta toxicidade aguda para ambos os organismos-teste utilizados. / The fuel storage systems may present vulnerability to chemical as well as microbial contamination, compromising final product quality. This goal was to select antimicrobials for use in the control of microbial contamination of diesel/biodiesel blends stored and monitor aspects of chemical degradation of the fuel. 18 different antimicrobial products suitable for use in fuels, as their spectrum of activity against different microbial groups and dosages, in different types of diesel/biodiesel blends by means of laboratory tests and field were studied. The chemical degradation of the oil phase was monitored using specific tests for certain characteristics indicative of quality and analysis of microbial degradation was monitored with infrared spectrometry. The evaluation of a commercial kit for the ATP bioluminescence detection in aqueous phase with Pseudomonas and a uncharacterized inoculum (ASTM1259 -10) (mineral medium and natural bottom water from storage tanks) was performed. The toxicity of aqueous phase which was in contact with the B10 blend and selected additive was evaluated with the use of the species Lactuca sativa L. (Lettuce) and Artemia salina Leach (microcrustacean) for 30 days. An additive containing 50% oxazolidine as antimicrobial agent in its formulation was considered effective for preventive control of microbial mixtures B10. But other formulations containing isothiazolones or morpholines could be a good option for corrective treatment. The kit for determination of ATP bioluminescence tested in this study as designed it’s unappropriate to estimate the degree of microbial contamination of the aqueous phase from the fuel tank. The toxicity results show that both the water that was in contact with the treated fuel (with additive) and untreated showed toxicity to studied organisms. However, the water that was in contact with the biocide treated fuel showed high acute toxicity to both test organisms used.

Os sistemas de armazenamento de combustível podem apresentar vulnerabilidade á contaminação tanto química quanto microbiana, comprometendo a qualidade final do produto. Este trabalho teve como objetivo selecionar antimicrobianos para utilização no controle da contaminação microbiana de misturas diesel/biodiesel armazenadas e monitorar a degradação química deste combustível. Foram estudados dezoito diferentes produtos antimicrobianos indicados para utilização em combustíveis, quanto ao seu espectro de ação e dosagens contra diferentes grupos microbianos em diferentes tipos de misturas diesel/biodiesel, através de testes em laboratório e em campo. A degradação química da fase oleosa foi monitorada através de testes específicos para algumas características indicativas de qualidade e a análise da degradação microbiana foi acompanhada com espectrometria de infravermelho. Foi realizada a avaliação de um KIT comercial para a detecção de ATP por bioluminescência com a bactéria Pseudomonas e um inóculo não caracterizado ( ASTM1259-10) em fase aquosa (meio mineral e água de drenagem de tanques de estocagem). A toxicidade da fase aquosa que esteve em contato com a mistura B10 e um aditivo selecionado foi avaliada com o uso das espécies Lactuca sativa L. (alface) e Artemia salina Leach (micro-crustáceo), durante 30 dias. Um aditivo contendo 50% de oxazolidina como ativo antimicrobiano em sua formulação foi considerado efetivo para o controle preventivo da contaminação microbiana em misturas B10. Porém outras formulações contendo, isotiazolonas ou morfolinas podem constituir uma boa opção para tratamentos corretivos. O kit para determinação do ATP por bioluminescência testado neste estudo, na forma como está projetado, não é adequado para estimar o grau de contaminação microbiana da fase aquosa proveniente de tanques de combustíveis. Os resultados de toxicidade mostram que tanto a água que esteve em contato com o combustível tratado (com o aditivo) e não tratado apresentaram toxicidade para os organismos estudados. Porém, a água que esteve em contato com o combustível tratado com o biocida mostrou alta toxicidade aguda para ambos os organismos-teste utilizados. / The fuel storage systems may present vulnerability to chemical as well as microbial contamination, compromising final product quality. This goal was to select antimicrobials for use in the control of microbial contamination of diesel/biodiesel blends stored and monitor aspects of chemical degradation of the fuel. 18 different antimicrobial products suitable for use in fuels, as their spectrum of activity against different microbial groups and dosages, in different types of diesel/biodiesel blends by means of laboratory tests and field were studied. The chemical degradation of the oil phase was monitored using specific tests for certain characteristics indicative of quality and analysis of microbial degradation was monitored with infrared spectrometry. The evaluation of a commercial kit for the ATP bioluminescence detection in aqueous phase with Pseudomonas and a uncharacterized inoculum (ASTM1259 -10) (mineral medium and natural bottom water from storage tanks) was performed. The toxicity of aqueous phase which was in contact with the B10 blend and selected additive was evaluated with the use of the species Lactuca sativa L. (Lettuce) and Artemia salina Leach (microcrustacean) for 30 days. An additive containing 50% oxazolidine as antimicrobial agent in its formulation was considered effective for preventive control of microbial mixtures B10. But other formulations containing isothiazolones or morpholines could be a good option for corrective treatment. The kit for determination of ATP bioluminescence tested in this study as designed it’s unappropriate to estimate the degree of microbial contamination of the aqueous phase from the fuel tank. The toxicity results show that both the water that was in contact with the treated fuel (with additive) and untreated showed toxicity to studied organisms. However, the water that was in contact with the biocide treated fuel showed high acute toxicity to both test organisms used.

Les nanoparticules d'argent sont de plus en plus utilisées dans les objets de consommation courante ainsi que dans les dispositifs médicaux pour leur activité biocide, qui est due au relargage d'ions Ag(I) au cours du temps. Le recul sur ces nano-objets et en particulier sur leur innocuité n'est toujours pas suffisant et les études sur leur transformation et leur impact in vivo sont sujets à d’intenses recherches. En effet, le devenir dans l’organisme des macro- et micro-matériaux étudiés classiquement n’est pas le même que celles des nanomatériaux. Les nanoparticules d’argent illustrent bien cette problématique : l’argent soluble injecté par voie intraveineuse est éliminé plus rapidement que la même quantité d’argent injectée sous forme nanoparticulaire. De plus, la concentration en argent retrouvée dans le sang et les organes est dix fois supérieure lorsque les nanoparticules d’argent sont injectées plutôt qu’ingérées. C'est pourquoi le développement de produits implantatoires qui se retrouvent donc en contact direct avec l’organisme, et qui contiennent des nanoparticules d’argent doit prendre en compte les risques associés, ce qui peut se faire par une approche Safer-by-design.Une des composantes principales du développement Safer-by-design concerne la fonctionnalisation des nano-objets. L’affinité des thiolates pour l’ion Ag(I) étant très forte, des ligands thiolés pourraient donc constituer une piste pour la fonctionnalisation des nanoparticules d’argent. Néanmoins, il est connu que les molécules thiolées conduisent à différents comportements allant de la dissolution de la nanoparticule d’argent en ions Ag(I) à la simple passivation de la surface de la nanoparticule ce qui peut entrainer la perte de son activité biocide.Ainsi, l’Ecoconception de Nouveaux Agents Biocides à base de Nanoparticules d’Argent à Enrobage Bio-inspiré avait pour objectif principal de poser les bases conceptuelles du développement d’un agent biocide Safer-by-design constitué de nanoparticules d’argent et de molécules thiolées en se positionnant à l’interface de plusieurs disciplines.Le développement de ce projet a nécessité d’étudier la réactivité de diverses molécules biologiques ou bio-inspirées thiolées avec les nanoparticules d’argent. Ainsi, nous avons mis en évidence l’importance de la pré-organisation architecturale des biomolécules dans la cinétique de dissolution, ainsi que le nombre de thiols libres dans la molécule. Dans le cas de composés induisant la dissolution des nanoparticules, sa cinétique augmente avec le nombre de thiols libres présents sur la molécule, et avec la pré-organisation du site de liaison du métal. Le projet principal de cette thèse a ensuite mené à la preuve de concept recherchée, avec le développement d’un nouvel agent biocide composé de nanoparticules d’argents pontées entre elles par un ligand thiolé tripode symétrique qui est le mime chimique d’un site de liaison d’une métallothionéine. Ces assemblages de nanoparticules se sont montrés actifs contre les bactéries (E. coli) et moins toxiques sur les cellules eucaryotes (HepG2), malgré une entrée dans les cellules similaire. Enfin, un criblage a également été réalisé avec des polyéthylèneglycols possédant un à huit thiols et des longueurs de polymères variables dans le but d’essayer de rationaliser les différences de comportement des nanoparticules d’argent en présence des molécules thiolées. Ce travail, a conduit à l’observation des comportements très variés qui vont permettre d’explorer de nouvelles voies de développements de biocides à base d’assemblages de nanoparticules médiés par des liaisons thiol – Ag(I).L’ensemble de ce travail de thèse a donc permis à la fois un travail très fondamental sur la réactivité des thiols vis-à-vis des atomes d’argent à la surface des nanoparticules et au développement de produits à potentiel applicatif, les assemblages de nanoparticules d’argent qui sont des biocides Safer-by-design. / Silver nanoparticles are increasingly used in everyday consumer goods as well as in medical devices for their biocidal activity, which is due to the release of Ag(I) ions over time. The hindsight on these nano-objects and, in particular, on their safety is still not sufficient and studies on their transformation and their impact in vivo is currently an intense research field. Indeed, the fate in the body of macro- and micro-materials studied classically is not the same as for nanomaterials. The case of the silver nanoparticles illustrates this problem: the soluble silver injected intravenously is eliminated faster than the same amount of silver injected in nanoparticular form. Moreover, the concentration of silver found in the bloodstream and organs is ten times higher when silver nanoparticles are injected rather than ingested. The development of silver nanoparticle-containing implanted devices, that get in direct contact with the body, must thus take into account the related risks. A Safer-by-design approach could be a way to solve this issue.One of the main components of Safer-by-design development is the functionalization of nano-objects. The affinity of the thiolates for Ag(I) ions is very high, which would make thiolated ligands a good tool for silver nanoparticle functionalization. However, it is known that the thiolated molecules lead to different behaviors, ranging from the dissolution of silver nanoparticles into Ag(I) ions to the simple passivation of the surface of the nanoparticles, which leads to the loss of their biocidal activity.The Ecodesign of New Biocidal Agents based on Silver Nanoparticles and Bio-inspired Coating is therefore at the interface of several research areas and its main objective was to lay the conceptual foundations for the development of a Safer-by-design biocidal agent based on the interaction between silver nanoparticles and thiolated molecules.The development of this project required to study the reactivity of various biological or bio-inspired thiolated molecules with silver nanoparticles. First of all, we have highlighted the importance of the architectural pre-organization of biomolecules in the dissolution kinetics, as well as the role of the number of free thiols in the molecule. In the case of molecules inducing the dissolution of the nanoparticles, its kinetics increases with the number of free thiols present on the molecule and with the pre-organization of the metal binding site. In a second time, the main project of this thesis was the development of a proof of concept of a new biocidal agent composed of silver nanoparticles bridged together via a thiolated ligand, which is the chemical mimic of one binding site of a metallothionein. These nanoparticle assemblies were active against bacteria (E. coli) and less toxic than silver nanoparticles on eukaryote cells (HepG2), despite a similar cellular entry. Finally, a screening was performed with polyethylene glycols having two to eight thiols and varying polymer lengths in an attempt to rationalize the differences in the behavior of silver nanoparticles in the presence of the thiolated molecules. This ongoing work leads to various behaviors that will enable to explore novel ways for the development of biocidal based on nanoparticles assemblies mediated by thiol – Ag(I) bonds.Therefore, this overall PhD work allows performing both very fundamental researches concerning the reactivity of thiols with surface silver atoms of the nanoparticles and the development of products with application potential, silver nanoparticle assemblies that are Safer-by-design biocide.