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No / Nanotechnology can offer new opportunities in the fight against infection. The aim of current work was to investigate an eco-friendly method for synthesis of silver nanoparticles (AgNP) which have the ability to load lipophilic compounds onto their surface. Pharmaceutically acceptable hydrophilic lipid (Gelucire® 50/13) has been used as a reducing agent for in situ reduction of silver nitrate so as to obtain silver nanoparticles. Propolis is used as model molecule for loading onto surface of AgNP owing to its well reported broad range of pharmacological activities including anti-inflammatory, antioxidant and antimicrobial activity. Propolis loaded silver nanoparticles (PLSN) were prepared and characterized for silver content, surface plasmon resonance, particle size, XRD, FTIR, TEM, antibacterial activity and burn wound healing in wistar rats. Propolis constituents were successfully loaded onto surface of AgNP using the proposed conceptual method. The formation of PLSN having size 24.3 ± 2.5 nm was confirmed using surface plasmon resonance, FTIR, XRD and TEM. The combination of propolis with AgNP significantly reduced minimum inhibitory concentration of AgNP alone when tested against Staphylococcus aureus. PLSN gel showed comparable burn wound healing in wistar rats when tested against marketed silver sulfadiazine gel. The use of Gelucire® as solubilizing agent for lipophillic drugs was effectively utilized for loading lipophillic constituents of propolis onto the AgNP. This potentially provides an effective method for the green synthesis of AgNP which can be used to load lipophillic molecules onto their surface whenever such combination is required.

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Supracrystals are highly symmetrical ordered superstructures built up from nanoparticles via self-assembly. While the NP assembly has been intensively investigated, the formation mechanism is still not understood. To shed some light onto the formation mechanism, we are using one of the most common supracrystal morphologies, the trigonal structures, as a model system to investigate the formation process in solution. To explain the formation of the trigonal structures and determining the size of the supracrystal seeds formed in solution, we introduce the concept of substrate-affected growth. Furthermore, we show the influence of the NP concentration on the seed size and extend our investigations from Ag towards Au. 1.

L’étude et la compréhension des interactions existantes entre semi-conducteur et nanoparticules métalliques sous irradiation est primordiale pour l’amélioration de leurs performances. Dans cette étude, trois composites oxydes semi-conducteur-métal ont été synthétisés : TiO2-Ag, Fe2O3-Ag et WO3-Ag. La synthèse des films mésoporeux de TiO2, Fe2O3 et WO3 a été effectuée par voie sol gel à l’aide de copolymères à bloc, avec la méthode d’auto-assemblage induit par évaporation (EISA). Les nanoparticules d’argent sont formées dans un deuxième temps par réduction chimique de sels dans la porosité des films. L’étude photo-électrochimique de ces composites a permis de mettre en évidence différents phénomènes : le potentiel d’électroréduction des ions Ag+ dans une matrice de TiO2 mésoporeuse peut être modulé par l’effet de la lumière. Ce phénomène semble résulter d’un effet de passivation des NP Ag par TiO2 qui dépend des conditions d’insolation. Des effets de rechargement de l’électrode poreuse en espèce Ag+ ont aussi été observés, sous l’action simultanée de la chrono-ampérométrie et de l’irradiation / The study and understanding of existing interactions between semiconductor and metal nanoparticles under irradiation is essential for improving their performance. In this study, three semiconductor-metal oxide composites were synthesized: TiO2-Ag, Fe2O3-Ag and WO3-Ag. The synthesis of the mesoporous films of TiO2, Fe2O3 and WO3 was carried out by gel sol method using block copolymers, with the method of self-assembly induced by evaporation (EISA). The silver nanoparticles are formed in a second time by chemical reduction of silver salts in the porosity of the films. The photo-electrochemical study of these composites made it possible to highlight various phenomena: the electroreduction potential of Ag+ ions in a mesoporous TiO2 matrix can be modulated by the effect of light. This phenomenon seems to result from a passivation effect of the NP Ag by TiO2, which depends on the insolation conditions. Charging effects of the porous electrode in Ag+ species have also been observed, under the simultaneous action of chrono-amperometry and irradiation

A prata metálica é um conhecido agente antimicrobiano, e a sua aplicação na forma de nanopartículas de prata vem sendo apontada como uma alternativa para aplicação em dispositivos médico hospitalares. Vários métodos foram sugeridos para a prevenção da infecção relacionada ao acesso vascular, entre eles, os cateteres revestidos com nanopartículas de prata têm recebido atenção mais recentemente, por oferecerem desempenho superior em aspectos onde outros métodos falharam. Este trabalho propôs avaliar a ação de nanopartículas de prata (AgNPs) em linhagens hospitalares e sua aplicabilidade em cateteres intraluminais. Na primeira fase, 12 linhagens (3 linhagens de referência e 8 linhagens hospitalares) foram testadas frente a diferentes concentrações de nanopartículas de prata de 10 nm; e na segunda fase, duas linhagens de referência foram escolhidas para os testes com os cateteres impregnados com uma solução polimérica contendo nanopartículas de prata. Os resultados obtidos atestam que as nanopartículas de prata funcionam como uma opção para controle bactericida. / In recent years, there has been increased concern regarding the use of antimicrobials (antibiotics) in general practices and in hospital-medicine devices, a factor that may contribute for the development and selection of antibiotic-resistant strains. The metallic silver is a known antimicrobial agent. Currently, its application in the form of nanoparticles (nanosilver) has been suggested as an alternative for use in hospital medical devices. Central venous catheters (CVCs) are commonly used in critically ill patients to administer fluids, blood products and parenteral nutrition. The contamination of catheters introduced into the bloodstream and subsequent infection, severe sepsis and septic shock are associated with high morbidity and mortality. This is one of the greater challenges of treating critically ill patients. Various methods have been suggested for prevention of infection related to the vascular access, including, catheters coated with silver nanoparticles which have received attention more recently, since they offer higher performance in aspects in that other methods have failed. This alternative consists in associating nanoparticles of metallic silver to a polymeric material that coats the catheter inner and externally. The main characteristics of the coating that can potentially be ajusted are the intensity and spectrum of bactericidal activity, the rate of bactericidal releasing and resistance to biofilm formation. This work proposes to evaluate the effects of silver nanoparticles (AgNPs) in hospital strains and their applicability in intraluminal catheter. In the first stage, 12 strains (3 reference strains and 9 hospital strains) were tested against different concentrations of silver nanoparticles of 10 nm (SIGMA-Aldrich); and in the second phase, two reference strain (a Gram-positive and Gram-negative) were selected for the tests with catheters impregnated with a polymer solution containing silver nanoparticles of 10 nm (SIGMA-Aldrich). The results obtained in the first stage showed a high efficiency of nanoparticles on three reference strains - S. aureus IPT 246, P. aeruginosa IPT 322 and K. pneumoniae IPT 412-, and moderate efficiency on hospital strains - S. aureus S.a. 1 and S.a. 2; P. aeruginosa P.a. 1 and P.a.2 ; and A. baumannii Acb. 2, Acb. 4 and Acb. 8, indicating that silver nanoparticles work as an option for bacterial control. A preliminary search of silver resistance genes in the strains indicates the possibility that 5 of these strains have genes related to silver resistance similar to those described in the literature. The results obtained in the second phase show that the process of impregnation of the intraluminal catheter has reached the desired goal in both the coating device, and in reducing bioburden according the tests carried with the reference strains S. aureus 246 IPT and P. aeruginosa IPT 322.

Devido às características especiais as nanopartículas (10-9m) estão sendo utilizadas em uma ampla gama de produtos, porém é conhecido que a utilização dessas partículas podem causar efeitos biológicos adversos, aumentando a preocupação em relação à saúde e ao meio ambiente. Recentemente, as nanopartículas de prata (AgNPs) têm sido alvo de estudos genotóxicos e citotóxicos, sendo que ainda não existe um consenso acerca da relação entre tamanho e toxicidade dessas partículas. Assim, este trabalho avaliou a citotoxicidade e a genotoxicidade das AgNPs de 10 e 100 nm nas linhagens celulares CHO-K1 e CHO-XRS5, por meio do Ensaios de Viabilidade Celular, Sobrevivência Clonogênica, Teste do Micronúcleo, o Ensaio Cometa e Cinética do Ciclo Celular por Citometria de Fluxo. Em todos os ensaios, as células foram expostas por 24 h à diferentes concentrações de AgNPs (0,025 a 5,0 g/ml) e, as células não tratadas foram utilizadas como controle negativo. A concentração de 5,0 g/ml foi citotóxica nos ensaios de Viabilidade Celular e Sobrevivência Clonogênica, sendo excluída dos ensaios de genotoxicidade. De maneira geral, as células CHO-XRS5 apresentaram menor viabilidade e maior quantidade de danos no DNA do que as células CHO-K1. As AgNPs de 10 nm causaram maiores níveis de danos no DNA em ambas as linhagens e um aumento de células em subG1 logo após o tratamento na linhagem CHO-K1. Entretanto, no tempos 24 e 72 h após o tratamento foi verificada a maior toxicidade (células em subG1) das AgNPs de 100 nm quando comparadas com suas homólogas menores (10 nm). Assim, foi observado que as AgNPs de 10 nm apresentam efeito tóxico a curto prazo similar ou maior do que a mesma concentração de partículas de 100 nm. No entanto, os efeitos genotóxicos e citotóxicos de longo prazo das AgNPs de 100 nm foram maiores do que os da partículas de 10 nm para ambas as linhagens celulares, comprovando que a exposição às AgNPs maiores (100 nm) pode causar mais efeitos biológicos adversos do que suas homólogas menores (10 nm). / Due to their particular characteristics, nanoparticles (10-9m) are being used in a range of products. However, these particles can cause adverse biological effects and because of that, there is a great concern about the health and environmental risks related to the use of these particles. Recently, silver nanoparticles (AgNPs) have been used in a variety of cytotoxicity and genotoxicity studies, but there are still controversies regarding the association between the size and the toxicity of these particles. Thus, in this study, we aimed to evaluate the cytotoxicity and genotoxicity of AgNPS (10 and 100 nm) in two different cell lines, CHO-K1 and CHO-XRS5, by performing Cell Viability assay (XTT), Clonogenic assay, Micronucleus test, Comet assay, as well as by investigating the Cell Cycle kinetics using the flow cytometry. For all the different assays, the cell cultures were exposed for 24 hours to different concentrations of AgNPs (0.025 to 5.0 g/ml) and the untreated cells were used as the negative controls. Since results from the Viability and Clonogenic assays indicated that the concentration of 5.0 g/ml was cytotoxic for both cell lines, this concentration was not included in the genotoxic assays. Our results indicated that the CHO-XRS5 cells presented a lower viability and higher levels of DNA damage compared to the CHO-K1 cells. The 10 nm-AgNPs induced greater levels of DNA damage than the 100 nm-particles in both cell lines and the former also led to a subG1 arrest soon after the treatment only in the CHO-K1 cell line. In contrast, results from all the other assays indicated that greater levels of toxicity were induced by the 100 nm-AgNPs when compared to the 10 nm-particles, both 24 and 72 h after the treatment. Thus, at the same concentration, the short-term effects of the 10 nm-AgNPs were equal to or more toxic than those of the 100 nm-particles. Nevertheless, both long-term genotoxicity and cytotoxicity induced by the 100 nm-AgNPs were greater than those induced by the 10 nm-particles for both cell lines, which suggests that the exposure to greater size particles (100 nm) can cause more adverse biological effects than the exposure to the smaller particles(10 nm).

O desenvolvimento de novos procedimentos e tecnologias tem proporcionado um grande avanço no tratamento de feridas e queimaduras, melhorando a qualidade de vida das vítimas e reduzindo as taxas de mortalidade de pessoas com queimaduras graves. Entretanto as complicações infecciosas continuam sendo um desafio e uma das principais causas de óbito de queimados. Por outro lado, em todo o mundo tem-se observado um crescente interesse no uso de hidrogéis para aplicação como curativos para queimaduras, ferimentos e úlceras de pele, tendo em vista que são capazes de absorver exsudatos, ajudam na cicatrização e proporcionam conforto ao paciente, uma vez que favorecem o alívio da dor. Além disso, os hidrogéis também podem ser aplicados como matrizes para sistemas de liberação controlada de princípios ativos e agentes antimicrobianos. O objetivo deste trabalho foi estudar as propriedades mecânicas e físico-químicas de hidrogéis compostos por blendas formadas por Poli(N-vinil-2-pirrolidona)/ Polietilenoglicol/ ágar (PVP/PEG/ágar), Poli(N-vinil-2-pirrolidona)/ glicerol/ ágar (PVP/glicerol/ágar); Poli(álcool vinílico)/ kappa-carragena/ ágar (PVA/KC/ágar), reticuladas por radiação ionizante. Para a preparação das blendas, utilizou-se planejamento de misturas como ferramenta, oferecendo assim subsídios a futuros desenvolvimentos de novos hidrogéis, que possam ser usados como curativos e como matrizes poliméricas para liberação de ativos hidrofílicos e lipofílicos. Foram otimizadas três formulações e sintetizadas seis, três das quais hidrogéis nanocompósitos de prata. As nanopartículas de prata (NPAg) foram sintetizadas, in situ, por radiação gama, sem uso de catalisadores ou outro reagente para obtenção de curativo mais puro e com ação antimicrobiana. A caracterização físico-química dos hidrogéis foi obtida por análises de fração gel, intumescimento, ensaios de tração e perfuração, microscopia eletrônica de varredura (MEV), espectroscopia na região do ultravioleta-visível (UV-vis). Também foi avaliada a atividade antimicrobiana dos hidrogéis e realizado estudo de citotoxicidade in vitro. O planejamento de misturas apresentou modelos confiáveis para os resultados de fração gel e intumescimento, porém, para as propriedades mecânicas, os resultados devem ser vistos com cautela. O uso da radiação se mostrou eficaz para a síntese de NPAg in situ nas blendas estudadas. Os resultados sugerem que os hidrogéis sintetizados não liberaram NPAg, porém os hidrogéis de PVP apresentaram atividade bactericida para S. aureus e P. Aeruginosa, enquanto que o hidrogel de PVA apresentou atividade bactericida para P. aeruginosa e atividade bacteriostática para S. aureus, sendo essa atividade pelo contato direto. / The development of new procedures and technologies have provided a major advance in the treatment of wounds and burns improving the quality of life of victims and reducing mortality rates of people with severe burns. However, infectious complications remain a challenge and a major cause death to burn. Furthermore, in the whole world, an increasing interest in the use of hydrogels as dressings for burns, wounds and skin ulcers has been observed, considering that they are capable of absorbing exudates, aid in healing and provide confort to the patient, since they favor the pain relief. In addition, hydrogels can also be applied as matrices for controlled release systems of active and antimicrobial agents. The aim of this study was to investigate the mechanical and physicochemical properties of hydrogels composed of blends formed by poly(N-vinyl-2-pyrrolidone)/ Polyethylene glycol/ agar (PVP/PEG/agar), poly(N-vinyl-2-pyrrolidone)/ glycerol/agar (PVP/ glycerol/agar) and poly(vinyl alcohol)/ kappa-carrageenan/ agar (PVA/KC/agar), crosslinked by ionizing radiation. In blends preparation, design of mixtures was utilized as a tool, thus offering information for future developments of new hydrogels, which can be used as dressings and as polymer matrices for the release of lipophilic and hydrophilic actives. Three formulations were optimized, and six synthesized, being three of these silver nanocomposite hydrogels. The silver nanoparticles (AgNPs) were synthesized, in situ, by gamma irradiation without using a catalyst or other reagent in order to obtain wound dressing with higher purity and antimicrobial activity. The physicochemical characterization of the hydrogels was obtained using assays of gel fraction, swelling, tensile and perforation, scanning electron microscopy (SEM), spectroscopy in the ultraviolet-visible (UV-vis) region. Antimicrobial activity of the hydrogels was evaluated, and cytotoxicity study in vitro also was performed. The mixture design offered reliable models for gel fraction and swelling, but for the mechanical properties the results must be seen with caution. The use of radiation has proven to be effective for synthesis of AgNPs in situ in the blends studied. The results suggest that hydrogels synthesized did not release AgNPs, but the PVP hydrogels showed bactericidal activity for S. aureus and P. aeruginosa, whereas the PVA hydrogel had bactericidal activity for P. Aeruginosa and bacteriostatic activity for S. aureus, being this activity by direct contact.

O presente trabalho teve a finalidade de estudar a utilização da radiação ionizante para revestimento de nanopartículas de prata em Cateteres Venosos Centrais de Poliuretano, proporcionando redução de infecções associadas à contaminação de cateteres introduzidos na corrente sanguínea. A espectroscopia de absorção no infravermelho por transformada de Fourier (FTIR) possibilitou a identificação de grupos funcionais na estrutura das macromoléculas, como o poli(eteruretano). Um estudo do comportamento térmico dos cateteres de poliuretano, antes e após a radiação ionizante, foi realizado com a finalidade de caracterização do material polimérico desses cateteres. A DSC e a TG, foram empregadas na observação das alterações das propriedades do material antes e depois da degradação. A curva DSC permitiu a caracterização das propriedades térmicas, como Tm e Tg dos copolímeros, assim como, evidenciar os principais eventos térmicos. As nanopartículas de prata possuem propriedades físicas, químicas e biológicas quando comparadas ao metal em escala macroscópica, e têm sido utilizadas na área médica, em razão de sua atividade antimicrobiana excelente. As nanopartículas de dióxido de titânio, obtidas pelo método sol-gel, foram utilizadas como revestimento dos cateteres para posterior impregnação de nanopartículas de prata por radiação ionizante na dose de 25 kGy. A espectrometria Raman foi utilizada na identificação do polimorfo de óxido de titânio, rutilo. Em ensaios com (ICP OES) foram avaliadas as quantidades de titânio e prata nos cateteres revestidos com óxido de titânio e de prata. A avaliação comparativa realizada entre os cateteres antes e após a irradiação, por FTIR, Raman e DSC, possibilitou a utilização da radiação ionizante como agente de esterilização e impregnação de nanopartículas de prata. / The present work aimed to study the use of ionizing radiation for coating of silver nanoparticles on Central Venous Polyurethane Catheters, providing reduction of infections associated with contamination of catheters introduced into the bloodstream. Fourier transform infrared spectroscopy (FTIR) enabled the identification of functional groups in the structure of macromolecules, such as poly(etherurethane). A study of the thermal behavior of central venous catheters before and after irradiation, was performed in order to characterize the polymeric material of these catheters. The DSC and TG were employed to observe the changes material properties before and after degradation. The DSC curve at the constant heating and cooling rate allowed the characterization of thermal properties, such as Tm and Tg of copolymers, as well as highlighting the main thermal events. Silver nanoparticles have physical, chemical and biological properties only when compared to metal on a macroscopic scale, and they have been used in the medical field because of its remarkable antimicrobial activity. Titanium dioxide nanoparticles obtained by the sol-gel method were used as the coating catheters for subsequent impregnation of silver nanoparticles with ionizing radiation, at 25 kGy. Raman spectrometry was used to identify the polymorph of titanium oxide, rutile. In trials with (ICP OES) were evaluated amounts of titanium and silver coated catheters in titanium oxide and silver. The comparative assessment conducted between the catheters before and after irradiation by FTIR, Raman and DSC enabled the use of ionizing radiation as an agent of sterilization and impregnating of silver nanoparticles.