With the recent development of nanotechnology, there has been increased production of engineered nanomaterials but limited containment strategies, resulting in inevitable release of a large amount of engineered nanoparticles (ENPs) in the environment. Many ENPs have potential adverse impacts on the environment, and one of the most commonly used ENPs, silver nanoparticle (AgNP), has attracted increased global concern. The current study focused on phytotoxicity of AgNPs to a model plant, Arabidopsis thaliana. Silver nanoparticles were introduced into the growth medium for the wild type A. thaliana plants and root uptake and translocation of AgNPs were examined in hydroponic growth condition. We also conducted growth stage based phenotypic analysis by growing A. thaliana throughout its life cycle in soil. The result indicated that: (1) wild type seeds germination was not affected by either AgNPs or their dissolved Ag+ ions; (2) AgNPs exposure resulted in a concentration- and size- dependent inhibition effect to the root elongation; (3) confocal and electron microscopy indicated that AgNPs could be taken up by seedling roots, yet most of AgNPs attached to the surface of seedling root cap; (4) AgNPs and their dissolved Ag+ ions at tested concentrations had little influence on the vegetative growth of A. thaliana, but they accelerated the floral development; and (5) the effect on the floral development stage reduced the quality of second-generation (F1) seeds, as indicated by their lower germination rate. In conclusion, AgNPs displayed both acute and chronic phytotoxicity to A. thaliana.

The most common type of adverse events in healthcare in Canada reported by the Canadian Institute for Health Information (CIHI) are nosocomial infections. Amongst nosocomial infections, implant associated infections have been reported to be most common. Despite having the implantation surgeries carefully performed, a small, but still considerable number of devices gets colonized by bacteria resulting in implant associated infections and/or surgical site infections. The patients are then started on high dose antibiotics, which if ineffective, is followed by reimplantation surgeries that leads to long hospital stays and detrimental effects in their lives. Due to this, an alternative to antibiotics is required which could prevent and/or treat bacterial colonization on implants. The main objective of this thesis was to demonstrate the effectiveness of an antimicrobial based CLKRS peptide capped silver nanoparticle coating on a metallic and polymeric based biomaterial used in various implantable medical devices. The CLKRS peptide capped silver nanoparticle formulation was specifically engineered and tested for its antibacterial and antibiofilm properties. Silver nanoparticles were synthesised by photochemical reduction of silver ions upon photocleavage of the photoinitiator I-2959. The metal nanostructure surfaces were protected with the CLKRS peptide and tested on planktonic and biofilms of P. aeruginosa, S. aureus and S. epidermidis. The bacterial quantification was done by survival colony counting. The cytotoxicity of the silver nanoparticle formulation was also tested on human dermal fibroblast, mouse bone marrow derived macrophages, and human epithelial cells by cell proliferation assay. Results show the formation of a nanometric layer of nanosilver on the surface of the material inhibiting the growth of bacteria and eradicating pre-existing biofilms with no significant cell toxicity suggesting the prepared formulation could be a useful tool in preventing and controlling infections on implants during surgery and post implantation. This technology thus could serve as an alternative therapy for surgical site infections and/or implant associated infections.

A study was done to examine the effect of surface orientation as well as heterogeneous epitaxy at an interface between two materials with a large lattice mismatch. Silver nanoparticles of different diameters were grown in an effort to study methods of preferentially orienting the geometry of metal nanoparticles. Arrays of calcium fluoride nanorods were grown on silicon substrates using oblique angle thermal vapor deposition. The chamber operated at an ultra high vacuum pressure of 10^-10 Torr during the deposition of the rods and an oblique angle of 75° was kept between the silicon substrate normal and the direction of incident flux. A method was then developed to grow silver nanoparticles exclusively on the (111) facet of the calcium fluoride tips. This was accomplished by once again using oblique angle deposition with an angle of 75° along with the larger size of the (111) calcium fluoride tip facet. Cross sectional scanning electron microscopy and transmission electron microscopy imaging was used to verify that the nanoparticles adhered exclusively to the desired facet of the tip. Using selected area diffraction, (SAED) and dark field in the TEM, it was shown that the nanoparticles did grow at a (111) orientation at the interface between them and the calcium fluoride rods. Different thicknesses and diameters of nanoparticles were then grown to determine what an ideal size was to achieve the most (111) orientation of the nanoparticles. Thicknesses of the particles varied between 5 nanometers and 15 nanometers. Through characterization it was shown that all three of the different thicknesses grown exhibited (111) orientation of the silver nanoparticles, both at the interface and in the overall nanoparticle as well with the 10 nanometer sample being the most ideal in terms of the desired result. Lattice straining of the silver nanoparticles was also observed by characterization through diffraction and SAED.

Os cateteres intravasculares são aliados indispensáveis na prática da medicina moderna, particularmente em unidades de terapia intensiva (UTIs). Pelo Cateter Venoso Central (CVC) pacientes que ficam muito tempo internados recebem medicação e alimentação sendo, no entanto, importante fonte de infecção da corrente sanguínea primária. Os CVC\'s de poliuretano podem ter sua superfície modificada pela incorporação de titânio e prata (Ti/Ag) que possuem características antimicrobianas conhecidas desde a antiguidade. A incorporação das nanopartículas de prata sobre o polímero pode ser feita com o uso da radiação ionizante, que também irá esterilizar o material. Assim, este trabalho tem por objetivo utilizar a radiação ionizante para incorporação de nanopartículas de prata em Cateter Venoso Central (CVC) a fim de adquirir propriedades antibactericidas. Para isto utilizou-se o CVC Pellethane 2363-65D, termoplástico de poliuretano elastômero (TPU), óxido de titânio puro, sintetizado pelo processo sol-gel e nanopartículas de prata (NpAg_925). A irradiação para incorporação da prata foi com dose de 25 kGy e com taxa de dose de 1,03 kGy/h em um irradiador \"Gammacel 220\" de 60Co. Posteriormente, os cateteres foram esterelizados com dose de 25 kGy. Pode-se concluir que a incorporação da prata pelo processo de irradiação foi possível e que este processo não afeta a estrutura do polímero, o que é importante para a correta inserção do cateter venoso central no corpo do paciente. Observou-se que o método sol-gel, para deposição do titânio na superfície do CVC, não foi homogênea, dificultando a incorporação da prata que depende do titânio neste processo. Os testes de análise antimicrobiana não indicaram atividade antimicrobiana nos cateteres revestido com titânio e prata, acredita-se que a metodologia escolhida seja inadequada para o tipo de análise. / Intravascular catheters are indispensable allies in the practice of modern medicine, particularly in intensive care units (ICUs). Central Venous Catheter (CVC) patients who are hospitalized for a long time receive medication and feeding, however, being an important source of infection of the primary bloodstream. Polyurethane CVCs may have their surface modified by the incorporation of titanium and silver (Ti/Ag) which have antimicrobial characteristics known from antiquity. The incorporation of the silver nanoparticles on the polymer can be done with the use of ionizing radiation, which will also sterilize the material. Thus, this work aims to use ionizing radiation to incorporate silver nanoparticles in Central Venous Catheter (CVC) in order to acquire antibacterial properties. For this purpose CVC Pellethane 2363-65D, thermoplastic elastomer polyurethane (TPU), pure titanium oxide, synthesized by the sol-gel process and silver nanoparticles (NpAg_925) were used. Irradiation for incorporation of silver was at a dose of 25 kGy and at a dose rate of 1.03 kGy/h in a \"Gammacell 220\" irradiator of 60Co. Subsequently, the catheters were sterilized at a dose of 25 kGy. It can be concluded that the incorporation of silver by the irradiation process was possible and that this process does not affect the structure of the polymer, which is important for the correct insertion of the central venous catheter into the patient\'s body. It was observed that the sol-gel method, for deposition of the titanium on the surface of the CVC, was not homogeneous, making difficult the incorporation of the silver that depends on the titanium in this process. The antimicrobial analysis tests did not indicate antimicrobial activity in catheters coated with titanium and silver, it is believed that the chosen methodology is inadequate for the type of analysis.

Os cateteres intravasculares são aliados indispensáveis na prática da medicina moderna, particularmente em unidades de terapia intensiva (UTIs). Pelo Cateter Venoso Central (CVC) pacientes que ficam muito tempo internados recebem medicação e alimentação sendo, no entanto, importante fonte de infecção da corrente sanguínea primária. Os CVC\'s de poliuretano podem ter sua superfície modificada pela incorporação de titânio e prata (Ti/Ag) que possuem características antimicrobianas conhecidas desde a antiguidade. A incorporação das nanopartículas de prata sobre o polímero pode ser feita com o uso da radiação ionizante, que também irá esterilizar o material. Assim, este trabalho tem por objetivo utilizar a radiação ionizante para incorporação de nanopartículas de prata em Cateter Venoso Central (CVC) a fim de adquirir propriedades antibactericidas. Para isto utilizou-se o CVC Pellethane 2363-65D, termoplástico de poliuretano elastômero (TPU), óxido de titânio puro, sintetizado pelo processo sol-gel e nanopartículas de prata (NpAg_925). A irradiação para incorporação da prata foi com dose de 25 kGy e com taxa de dose de 1,03 kGy/h em um irradiador \"Gammacel 220\" de 60Co. Posteriormente, os cateteres foram esterelizados com dose de 25 kGy. Pode-se concluir que a incorporação da prata pelo processo de irradiação foi possível e que este processo não afeta a estrutura do polímero, o que é importante para a correta inserção do cateter venoso central no corpo do paciente. Observou-se que o método sol-gel, para deposição do titânio na superfície do CVC, não foi homogênea, dificultando a incorporação da prata que depende do titânio neste processo. Os testes de análise antimicrobiana não indicaram atividade antimicrobiana nos cateteres revestido com titânio e prata, acredita-se que a metodologia escolhida seja inadequada para o tipo de análise. / Intravascular catheters are indispensable allies in the practice of modern medicine, particularly in intensive care units (ICUs). Central Venous Catheter (CVC) patients who are hospitalized for a long time receive medication and feeding, however, being an important source of infection of the primary bloodstream. Polyurethane CVCs may have their surface modified by the incorporation of titanium and silver (Ti/Ag) which have antimicrobial characteristics known from antiquity. The incorporation of the silver nanoparticles on the polymer can be done with the use of ionizing radiation, which will also sterilize the material. Thus, this work aims to use ionizing radiation to incorporate silver nanoparticles in Central Venous Catheter (CVC) in order to acquire antibacterial properties. For this purpose CVC Pellethane 2363-65D, thermoplastic elastomer polyurethane (TPU), pure titanium oxide, synthesized by the sol-gel process and silver nanoparticles (NpAg_925) were used. Irradiation for incorporation of silver was at a dose of 25 kGy and at a dose rate of 1.03 kGy/h in a \"Gammacell 220\" irradiator of 60Co. Subsequently, the catheters were sterilized at a dose of 25 kGy. It can be concluded that the incorporation of silver by the irradiation process was possible and that this process does not affect the structure of the polymer, which is important for the correct insertion of the central venous catheter into the patient\'s body. It was observed that the sol-gel method, for deposition of the titanium on the surface of the CVC, was not homogeneous, making difficult the incorporation of the silver that depends on the titanium in this process. The antimicrobial analysis tests did not indicate antimicrobial activity in catheters coated with titanium and silver, it is believed that the chosen methodology is inadequate for the type of analysis.

This thesis studies the interaction between free radical species and supported noble metal nanoparticles (silver and gold) in the context of oxidation reactions. The peroxidation of cumene is the first reaction to be discussed and the difference in peroxidation product distribution using silver nanoparticles (AgNP) versus gold nanoparticles (AuNP) is examined. Specifically, cumyl alcohol is obtained as the major product obtained when using supported AuNP, whereas cumene hydroperoxide is favoured for AgNP. Such variations in product distribution are partially explained by the differences in the nanoparticle Fenton activity, where the TiO2 support was proposed to enhance such activity due to possible electron shuttling capabilities with the nanoparticle surface. Use of hydrotalcite as a support was found to minimize this characteristic, due to its insulator properties. The stability of hydroperoxide was tested in the presence of various others supports (activated carbon, Al2O3, ZnO, SiO2 and clays) with little success, with hydroperoxide exhibiting stability in the presence of HT. Using an oxygen uptake apparatus, the interaction of the cumyl peroxyl radical with the AuNP surface was demonstrated. Furthermore, this interaction promotes decomposition leading to the corresponding alkoxyl radical and subsequent hydrogen abstraction to form the observed cumyl alcohol product. The radical interaction with supported nanoparticles, and its reversibility appear different for gold and silver and accounts for a large part of the product distribution differences observed between AuNP and AgNP, as illustrated below. The peroxidation of ethylbenzene and propylbenzene was studied and revealed the participation of a reactive surface oxygen species due to the decomposition of peroxyl radicals on the nanoparticle surface. The reactive oxygen species was found to be transient in nature in the case of AuNP . Furthermore, this surface species was found to be an important participant in hydrogen abstraction leading to peroxide product formation. Finally, supported nanoparticle catalyzed tetralin peroxidation was investigated to determine the influence of temperature on the peroxidation product distribution and how changes in the reaction temperature can effect the radical-nanoparticle surface interactions.

Accurate determination of the surface enhanced Raman scattering (SERS) enhancement factor (EF) is critically important for a fundamental understanding of the SERS phenomenon. Experimental quantification of SERS EFs is challenging. A series of instrument-, analyte-, and SERS-substrate related issues can affect the SERS intensity and thus compromise the reliability of the measured SERS EFs. This dissertation presents a series of computational and experimental studies that enhance the quantitative understanding of the SERS signal variation and identify ways to enhance the reliability of the SERS EF determination. Chapter I presents an overview of works described in this dissertation. The gold nanoparticle (AuNP) inner filter effect on SERS measurements is demonstrated in Chapter II. Using dithiopurine and ethanol as model analytes, we demonstrate that the nanoparticle will modify the analytes’ Raman signal through two competitive mechanisms: enhancing the Raman signal of the analyte on the nanoparticle surface through electromagnetic enhancement, and attenuating the analyte Raman signal through photon extinction. The significance of the AuNP inner filter effect is quantitatively evaluated using ethanol as the internal reference. A solvent internal reference method is presented in Chapter III for quantifying the SERS EFs of analytes adsorbed onto AuNPs and AgNPs. One of the key findings is that while an analyte’s SERS EF varies significantly as a function of nanoparticle aggregation, its peak SERS EF depends only on the types and sizes of nanoparticles, but not on experimental conditions including concentrations of analyte, nanoparticle, and aggregation reagent. Chapter IV presents a SERS internal reference method for the determination of the resonance Raman EFs in the SERS study of rhodamine 6G (R6G) adsorbed onto AuNPs and AgNPs. The most striking finding is that the AgNP binding reduces, instead of enhancing, the R6G resonance enhancement. Finally, the wavelength-dependent correlation between UV-vis intensities and SERS EFs of aggregated AuNPs and AgNPs were investigated under three fixed excitation wavelengths (532, 632, and 785 nm). The nanoparticle UV-vis intensity is an excellent indicator for identifying the optimal aggregation state for AgNP-based SERS acquisitions under each of the three excitation wavelengths and for the AuNP-based SERS under a 632 nm excitation.

No description available.

Plasmonic nanoparticles, specifically gold and silver nanoparticles, exhibit unique optical, physical, and chemical properties that are exploited in many biomedical applications. Due to their nanometer size, facile surface functionalization and enhanced optical performance, gold and silver nanoparticles can be used to investigate cellular biology. The work herein highlights a new methodology that has exploited these remarkable properties in order to probe various aspect of cancer cell biology, such as cell cycle progression, drug delivery, and cell death. Cell death mechanisms due to localized gold and silver nanoparticle exposure were also elucidated in this work. Chapter 1 introduces the reader to the synthesis and functionalization of gold and silver nanoparticles as well as reviews their implementation in biodiagnostic and therapeutic applications to provide a foundation for Chapters 3 and 4, where their use in spectroscopic and cytotoxic studies are presented. Chapter 2 provides the reader with detailed explanations of experimental protocols for nanoparticle synthesis and functionalization, in vitro cellular biology experiments, and live-cell Raman spectroscopy experiments that were utilized throughout Chapters 3 and 4. Chapter 3 presents the use of nuclear-targeted gold nanoparticles in conjunction with a Raman microscope modified to contain a live-cell imaging chamber to probe cancer cell cycle progression (Chapter 3.1), examine drug efficacy (Chapter 3.2), monitor drug delivery (Chapter 3.3), and detect apoptotic molecular events in real-time (Chapter 3.4). In Chapter 4, the intracellular effects of gold and silver nanoparticles are explored through live-cell Rayleigh imaging, cell cycle analysis and DNA damage (Chapter 4.1), as well as through the elucidation of cytotoxic cell death mechanisms after nanoparticle exposure (Chapter 4.2) and live cell imaging of silver nanoparticle treated cancer cell communities (Chapter 4.3).

Neste trabalho de mestrado foram desenvolvidos nanobiocompósitos contendo quitosana (QS) e nanopartículas de prata (AgNPs) para aplicação em matrizes poliméricas com propriedades bactericidas. O trabalho foi conduzido em 4 etapas, sendo: i) a primeira referente ao estudo e escolha do melhor modo de estabilização dos colóides de prata em solução, sendo escolhido o modo de estabilização estérica com a quitosana (QS); ii) a segunda parte está relacionada com um estudo detalhado da interação entre a QS e as nanopartículas de prata (AgNPs) além da otimização da relação QS:AgNPs no nanocompósito para se obter maior ação bactericida; iii) foi também proposta uma rota de síntese na qual não se utiliza-se o Boro Hidreto de Sódio (NaBH4) como redutor, composto altamente reativo, sendo utilizados o citrato de sódio e QS conjuntamente como redutores; iv) inserção do nanocompósito QS:AgNPs em uma matriz de polivinil álcool (PVA). Foram utilizadas as técnicas de espectroscopia UV-vis e FT IR, DLS, Potencial Zeta, MET, DR-X, ensaios microbiológicos de MIC, OD595 e teste de halo de inibição, TGA, DSC e ensaios mecânicos. Concluímos que o uso da QS como agente estabilizante em comparação ao PVA é a mais indicada, devido ao maior número de grupos funcionais interagindo com as nanopartículas de prata. O poder de ação bactericida do nanocompósito QS:AgNPs pode ser aumentado numa certa relação entre ambos, a saber 4:1 em massa. A síntese utilizando citrato de sódio e QS como redutores mostrou a possibilidade da obtenção de nanopartículas de prata pequenas, com tamanho de 2 - 5 nm com estrutura esférica ou maiores. com tamanho de 300 nm, apresentando estruturas dendríticas, dependendo apenas do tempo de reação e concentração de citrato de sódio. A última etapa revelou a possibilidade da inserção do nanocompósito no polímero PVA sem perda significativa das características térmicas e mecânicas do polímero. / The work reported here was aimed at developing chitosan/AgNPs based nanobiocomposits for bactericidal applications. The studies were divided into four main steps, viz.,: i) optimization of the silver colloids stabilition process, in which the use of chitosan resulted in the best stability, ii) a detailed investigation on the interactions between chitosan and AgNPs, as well as the optimization of the chitosan :AgNPs ratio to promote the best bactericidal effect, iii) development of a new synthetic route without using NaBH4, in a search for an environmentally-friendly route, and iv) incorporation of the chitosan:AgNps nanobiocomposites in a PVA matrix for application as smart food packaging. The nanobiocomposites were characterizaed via UV-vis and FT IR spectroscopies, DLS, Zeta potential, TEM and DR-X. Biological essays had also been carried out, as well as tensilestress and thermo analyses (DSC and TGA). The best bactericidal effect was observed for a nanobiocompostie comprising chitosan:AgNPs at a ratio of 4:1 (wt/wt). The synthetic route employing sodium citrate as reducing agent resulted in AgNPs with average diameters of 2 5 nm, as well as bigger nanoparticles with diameters of ca. 300 nm, depending on the reaction time and citrate concentration. The incorporation of the chitosan:AgNPs composites in the PVA matrix resulted in the formation of a bactericidal composite with good mechanical and thermal properties, suitable for applications as smart food packing.