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Investigação ab initio dos mecanismos de formação de nanoligas core-shell com platina e metais de transição dos períodos 3d, 4d e 5d / Ab initio investigation of mechanisms of formation of core-shell nanoalloys with platinum and 3d, 4d, and 5d transition metalsJusto, Stella Granatto 06 December 2017 (has links)
Nanoligas bimetálicas têm atraído a atenção de pesquisadores nas últimas décadas devido a possibilidade de ajustar suas propriedades físico-químicas, tais como propriedades elétricas, ópticas, magnéticas e de reatividade, por meio da variação do número de átomos, da composição química e do formato geométrico. As nanoligas bimetálicas que combinam Pt com outros metais são especificamente interessantes na área de catálise heterogênea, devido a possibilidade de se obter materiais com propriedades distintas de seus respectivos sistemas unários no que se refere ao surgimento ou aumento da atividade catalítica, à seletividade e, muitas vezes, ao preço reduzido. Esse trabalho tem como objetivo investigar as propriedades estruturais, energéticas, eletrônicas e de estabilidade de nanoligas bimetálicas core-shell de 55 átomos que combinam Pt com metais de transição (MT) pertencentes às séries de transição 3d, 4d e 5d dos grupos de Fe a Zn. Esses sistemas foram estudados utilizando cálculos de primeiros princípios (ab initio) baseados na teoria do funcional da densidade, tal como implementada no código computacional VASP (Vienna Ab initio Simulation Package). As nanoligas putativas de mínimo global energético (pGMC) de composição Pt13MT42 e Pt42MT13 calculadas nesse estudo apresentaram características particulares quanto à geometria e ao arranjo das espécies metálicas na nanoliga. Ao que diz respeito aos arranjos core-shell, foram observados dois arranjos em que a fica Pt no caroço (Pt13Ag42 e Pt13 Au42) e sete arranjos em que a Pt fica na superfície (Pt42Fe13, Pt42Co13, Pt42Ni13, Pt42Cu13, Pt42Ru13, Pt42Rh13 e Pt42Os13). Os mecanismos que levam à formação destas e das demais nanoligas pGMC foram investigados com base em três fatores: raio atômico, energia de superfície e cargas de Bader. Verificou-se que raio e a energia de superfície competem como fator determinante pelas posições preferenciais de cada espécie metálica na nanoliga. Nos casos em que houve divergência, o raio apresentou-se como o fator de maior importância, entretanto, quando o raio das espécies são muitos próximos, a energia de superfície exerce um papel de maior importância. A partir da análise de cargas de Bader, observou-se ocorrência de transferência de carga da região do caroço para a região da superfície para a maioria das nanoligas. No mais, observou-se que as nanoligas core-shell contam com atração coulômbica de maior magnitude do que as demais nanoligas pGMC, como resultado de altas cargas de sinal oposto em cada uma das regiões. / Bimetallic nanoalloys have been attracting attention since the last decades due to the possibility of adjusting their physical-chemical properties, such as electrical, optical, magnetic and reactivity properties, by means of the variation of the number of atoms, chemical composition and geometry. Bimetallic nanoalloys that combine Pt with other metals are especially interesting for heterogeneous catalysis given the possibility of obtaining materials with properties that differ from their respective unary systems regarding the appearance or increase of catalytical activity, selectivity and, in many cases, reduced cost. The aim of this work is the evaluation of the stability and of structural, energetic and electronic properties of 55 atom core-shell bimetallic nanoalloys that combine Pt with transition metals (MT) from the 3d, 4d, and 5d transition periods from Fe to Zn groups. These systems were studied using first principle (ab initio) calculations based on density functional theory, as implemented in the VASP (Viena Ab initio Simulation Package) computer code. The nanoalloys with Pt13MT42 and Pt42MT13 compositions which were observed as putative global minimum configuration (pGMC) presented unique characteristics regarding their geommetry and the arrangement of the different metals within the nanoalloy. Considering the core-shell nanoalloys, two arrangements in which Pt is located in the core were observed (Pt13Ag42 e Pt13 Au42) as well as seven arrangements with Pt in the surface (Pt42Fe13, Pt42Co13, Pt42Ni13, Pt42Cu13, Pt42Ru13, Pt42Rh13 e Pt42Os13). The mechanisms that lead to the formation of these and of the remaining pGMC nanoalloys were investigated considering three factors: atomic radius, surface energy and Bader charges. It was verified that atomic radius and surface energy compete directly for the determination of preferential sites for the atoms in the nanoalloy. When these two factors diverge, the atomic radius is the most important factor. However, when the radii of the species involved are similar, the surface energy becomes the determining factor. In addition, Bader charges analysis showed that, for most nanoalloys, the core is positively charged and the shell accumulates negative charge, indicating that charge is transfered from the atoms in the core to the ones in the surface. Besides, the core-shell nanoalloys have a higher coulombic attraction in comparison with others pGMC, due to high quantities of charge with opposite sign in each region.
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Investigação ab initio dos mecanismos de formação de nanoligas core-shell com platina e metais de transição dos períodos 3d, 4d e 5d / Ab initio investigation of mechanisms of formation of core-shell nanoalloys with platinum and 3d, 4d, and 5d transition metalsStella Granatto Justo 06 December 2017 (has links)
Nanoligas bimetálicas têm atraído a atenção de pesquisadores nas últimas décadas devido a possibilidade de ajustar suas propriedades físico-químicas, tais como propriedades elétricas, ópticas, magnéticas e de reatividade, por meio da variação do número de átomos, da composição química e do formato geométrico. As nanoligas bimetálicas que combinam Pt com outros metais são especificamente interessantes na área de catálise heterogênea, devido a possibilidade de se obter materiais com propriedades distintas de seus respectivos sistemas unários no que se refere ao surgimento ou aumento da atividade catalítica, à seletividade e, muitas vezes, ao preço reduzido. Esse trabalho tem como objetivo investigar as propriedades estruturais, energéticas, eletrônicas e de estabilidade de nanoligas bimetálicas core-shell de 55 átomos que combinam Pt com metais de transição (MT) pertencentes às séries de transição 3d, 4d e 5d dos grupos de Fe a Zn. Esses sistemas foram estudados utilizando cálculos de primeiros princípios (ab initio) baseados na teoria do funcional da densidade, tal como implementada no código computacional VASP (Vienna Ab initio Simulation Package). As nanoligas putativas de mínimo global energético (pGMC) de composição Pt13MT42 e Pt42MT13 calculadas nesse estudo apresentaram características particulares quanto à geometria e ao arranjo das espécies metálicas na nanoliga. Ao que diz respeito aos arranjos core-shell, foram observados dois arranjos em que a fica Pt no caroço (Pt13Ag42 e Pt13 Au42) e sete arranjos em que a Pt fica na superfície (Pt42Fe13, Pt42Co13, Pt42Ni13, Pt42Cu13, Pt42Ru13, Pt42Rh13 e Pt42Os13). Os mecanismos que levam à formação destas e das demais nanoligas pGMC foram investigados com base em três fatores: raio atômico, energia de superfície e cargas de Bader. Verificou-se que raio e a energia de superfície competem como fator determinante pelas posições preferenciais de cada espécie metálica na nanoliga. Nos casos em que houve divergência, o raio apresentou-se como o fator de maior importância, entretanto, quando o raio das espécies são muitos próximos, a energia de superfície exerce um papel de maior importância. A partir da análise de cargas de Bader, observou-se ocorrência de transferência de carga da região do caroço para a região da superfície para a maioria das nanoligas. No mais, observou-se que as nanoligas core-shell contam com atração coulômbica de maior magnitude do que as demais nanoligas pGMC, como resultado de altas cargas de sinal oposto em cada uma das regiões. / Bimetallic nanoalloys have been attracting attention since the last decades due to the possibility of adjusting their physical-chemical properties, such as electrical, optical, magnetic and reactivity properties, by means of the variation of the number of atoms, chemical composition and geometry. Bimetallic nanoalloys that combine Pt with other metals are especially interesting for heterogeneous catalysis given the possibility of obtaining materials with properties that differ from their respective unary systems regarding the appearance or increase of catalytical activity, selectivity and, in many cases, reduced cost. The aim of this work is the evaluation of the stability and of structural, energetic and electronic properties of 55 atom core-shell bimetallic nanoalloys that combine Pt with transition metals (MT) from the 3d, 4d, and 5d transition periods from Fe to Zn groups. These systems were studied using first principle (ab initio) calculations based on density functional theory, as implemented in the VASP (Viena Ab initio Simulation Package) computer code. The nanoalloys with Pt13MT42 and Pt42MT13 compositions which were observed as putative global minimum configuration (pGMC) presented unique characteristics regarding their geommetry and the arrangement of the different metals within the nanoalloy. Considering the core-shell nanoalloys, two arrangements in which Pt is located in the core were observed (Pt13Ag42 e Pt13 Au42) as well as seven arrangements with Pt in the surface (Pt42Fe13, Pt42Co13, Pt42Ni13, Pt42Cu13, Pt42Ru13, Pt42Rh13 e Pt42Os13). The mechanisms that lead to the formation of these and of the remaining pGMC nanoalloys were investigated considering three factors: atomic radius, surface energy and Bader charges. It was verified that atomic radius and surface energy compete directly for the determination of preferential sites for the atoms in the nanoalloy. When these two factors diverge, the atomic radius is the most important factor. However, when the radii of the species involved are similar, the surface energy becomes the determining factor. In addition, Bader charges analysis showed that, for most nanoalloys, the core is positively charged and the shell accumulates negative charge, indicating that charge is transfered from the atoms in the core to the ones in the surface. Besides, the core-shell nanoalloys have a higher coulombic attraction in comparison with others pGMC, due to high quantities of charge with opposite sign in each region.
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Atividade fotocatalítica do TiO2 e do sistema core-shell CoFe2O4@TiO2 obtidos pelo método Pechini modificado / Photocatalytic activity of TiO2 and core-shell CoFe2O4@TiO2 system obtained by the modified Pechini methodNeris, Alex de Meireles 01 August 2014 (has links)
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Previous issue date: 2014-08-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The need to control textile effluents due to contamination of rivers has led CONAMA to regulate and require a more efficient treatment process. Among the methods of treatment, heterogeneous catalysis stands out due to its high efficiency. The most used photocatalyst is TiO2. The combination of this material with other ones has been employed to improve its activity and/or its performance. Several systems have been tested, including the core-shell that constitutes a complete coverage of one material by another. In this work, TiO2@CoFe2O4 was synthesized by the modified-Pechini method with the addition of CoFe2O4 nanoparticles into the polymeric resin containing titanium. A magnetic material was obtained, which was characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), ultraviolet - visible spectroscopy (UV-Vis), specific surface area by the BET method. The materials were applied in the photodiscoloration of an azo dye. The pure TiO2 calcined at 700 °C showed a mixture of phases anatase / rutile in the proportions 77/23%, which was the calcination temperature which led to the highest photocatalytic activity in the discoloration of the solution yellow gold remazol (RNL). A discoloration of 81% in color of the solution was attained after 6 h of exposure to UV light, while 94% was reached after 2 h of irradiation with sunlight. With the core@shell system CoFe2O4@TiO2 synthesized with 90 % of TiO2, a mixture of anatase and rutile of 92 : 8% was obtained for a calcination temperature of 500 °C. This material showed 76% discoloration after 16 h of exposure to UV light under the same conditions used for the test with pure TiO2 / A necessidade do controle de efluentes têxteis devido à contaminação de águas fluviais tem levado órgãos como o CONAMA a regulamentar e exigir um processo de tratamento mais eficiente. Dentre os métodos de tratamento estudados, os Processos Oxidativos Avançados (POA) têm demonstrado grande eficiência, como na fotocatálise heterogênea utilizando materiais semicondutores, sendo o TiO2 um dos mais empregados. A combinação deste material com outros tem sido estudada com o objetivo de melhorar a atividade e/ou performance do mesmo. Para isso vários sistemas têm sido utilizados, dentre eles o core@shell, que consiste na completa cobertura de um material por outro. Neste trabalho o CoFe2O4@TiO2 foi sintetizado pelo método Pechini modificado, com a adição do CoFe2O4 nanoparticulado à uma resina polimérica de titânio, sendo obtido um material magnético, o qual foi caracterizado por difração de raios X (DRX), espectroscopia infravermelho (IV), espectroscopia na região ultravioleta e visível (UV-Vis), análise de área superficial específica pelo método de BET. Os materiais foram testados na fotodegradação de um corante azo. O TiO2 puro calcinado a 700 ºC, apresentou mistura de fases anatase / rutilo com proporção 77 / 23 %, sendo a temperatura de calcinação que levou à maior atividade fotocatalítica na descoloração da solução de amarelo ouro remazol (RNL). Foi obtida 81 % de redução da cor da solução em 6 h de exposição a luz UV e 94 % após 2 h com irradiação de luz solar. Com o sistema core@shell CoFe2O4@TiO2 sintetizado com 90 % de TiO2 foi obtida uma mistura de 92 % de anatase e 8 % de rutilo, para uma temperatura de calcinação de 500 ºC. Este material levou a 76 % de descoloração em 16 h de exposição à luz UV com as mesmas condições utilizadas para o teste com o TiO2 puro
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Nanopartículas magnéticas de cobalto metálico e ferrita de cobalto recobertas com ouro como materiais biocompatíveis visando aplicações em biomedicina / Magnetic nanoparticles of gold-coated cobalt and cobalt ferrite as biocompatible materials for biomedical applicationsJoão Batista Souza Junior 24 May 2012 (has links)
Atualmente, as nanopartículas superparamagnéticas despertam enorme interesse científico devido sua grande variedade de aplicações em biomedicina, tanto na área de diagnóstico quanto no tratamento de enfermidades. Embora muitos materiais vem sendo estudados, os óxidos de ferro (magnetita e maghemita) apresentam maiores avanços nos estudos para aplicações em medicina. A preferência por óxidos de ferro se deve a baixa toxicidade destas partículas quando comparado as nanopartículas metálicas ou ligas. Entretanto, as nanopartículas destes óxidos possuem baixas magnetizações de saturação que diminuem ainda mais com as sucessivas etapas de recobrimento necessárias para conferir funcionalidade a estas partículas. Desse modo, há uma necessidade atual para o desenvolvimento de nanopartículas superparamagnéticas com elevada magnetização, baixa toxicidade e maior facilidade de funcionalização da sua superfície com biopolímeros e agentes funcionalizantes. Neste trabalho, nanopartículas superparamagnéticas de cobalto metálico e ferrita de cobalto foram sintetizadas e suas propriedades magnéticas foram comparadas com a magnetita. Nanopartículas de cobalto foram escolhidas, pois seu elevado comportamento ferromagnético é menor apenas que o ferro metálico, além do baixo custo de seus reagentes. As nanopartículas magnéticas foram sintetizadas pelos métodos de microemulsão e decomposição térmica (baseado no método poliol) e suas composições química, estrutural, tamanho e distribuição de tamanho foram devidamente determinadas. Além disso, as nanopartículas de cobalto metálico e ferrita de cobalto foram recobertas com ouro utilizando o método de crescimento mediado por semente. Os sistemas microemulsionados utilizados neste trabalho não foram eficientes nem na síntese de nanopartículas estáveis de cobalto metálico nem no seu esperado controle morfológico. Já o método de decomposição térmica resultou em um rigoroso controle de composição química, estrutural e morfológico para as diferentes nanopartículas sintetizadas. O recobrimento com ouro foi efetivo na proteção do núcleo magnético e adicionalmente conferiu estabilidade, baixa toxicidade e bifuncionalidade às nanopartículas magnéticas através do seu fenômeno de ressonância plasmônica de superfície o qual foi preservado na nanoestrutura core@shell. O comportamento superparamagnético das nanopartículas de cobalto metálico recobertas com ouro e sua elevada magnetização de saturação foram expressivamente intensificadas quando comparadas as nanopartículas de magnetita sem recobrimento. Portanto, as nanopartículas sintetizadas neste trabalho apresentam propriedades de superfície e magnéticas otimizadas demonstrando um bom potencial para aplicações em biomedicina como sensores bifuncionais óptico-magnético. / Superparamagnetic nanoparticles have been extensively studied because its wide range of biomedical applications in both diagnostic and therapy areas. Although different materials are currently investigated, superparamagnetic iron oxides nanoparticles (SPION), magnetite and maghemite, are the most extensively studied for applications in medicine. The lower toxicity profile of the SPION becomes the most attractive than metal or alloys nanoparticles. Nevertheless, iron oxides nanoparticles have low saturation magnetization, which further decreases due to successive coats to provide their functionality, leading the actual demand to develop superparamagnetic nanoparticles with high magnetization, low toxicity and easy surface functionalization with biocompatible agents. In this work, superparamagnetic nanoparticles of metallic cobalt and cobalt ferrite were synthesized and their magnetic properties were compared with the magnetite SPION. Cobalt nanoparticles were chosen because present high ferromagnetic behavior among chemical elements, second only to iron, besides their low cost. The magnetic nanoparticles were synthesized by both microemulsion and thermal decomposition (based on the polyol process) methods and their chemical composition, structure, size and size distribution were properly characterized. In addition, the ferrite and metallic cobalt nanoparticles were coated with gold by using the seed-mediated growth method. The used microemulsion systems were not efficient enough to synthesize stable metallic nanoparticles and to promote the expected morphological control even to ferrites. Instead, the thermal decomposition processes resulted in rigorous control of chemical compositional, structure and morphology in all different prepared samples. Au-coating process was effective to protect the magnetic nuclei also giving additional stability, low toxicity and a bifunctionality to the magnetic nanoparticle since their surface plasmon resonance phenomenon was preserved in the core@shell nanostructure. The superparamagnetic behavior of the Au-coated cobalt nanoparticle was preserved and their saturation magnetization was significantly increased compared with the naked magnetite SPION. In conclusion, the synthesized nanoparticles present enhanced magnetic and surface properties showing good potential to be used in biomedical application as bifunctional optical-magnetic sensor.
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Stanovení steviových glykosidů metodou HPLC / Determination of steviol glycosides by HPLCHollá, Marcela January 2017 (has links)
Charles University Faculty of Pharmacy in Hradec Králové Department of Biophysics and Physical Chemistry Candidate: Marcela Hollá Supervisor: Ing. Martin Drastík, Ph.D. Title of Diploma Thesis: Determination of steviol glycosides by HPLC A new HPLC method was developed and validated for simultaneous detemination of major steviol glycosides stevioside and rebaudioside A in food supplements. Separation took place in hydrophilic interaction chromatography mode on column with core-shell particles. The method was aplicated on analysis of steviol glycosides in products Valosun, SlaDIA, Solia and extract from dried stevia leaves. Isocratic separation was performed using Kinetex 2,6u HILIC 100A, (100 x 2,1 mm; 2,6 µm), Phenomenex analytical column with mobile phase consisted of acetonitrile/0,05 M ammonium formate adjusted with formic acid to pH=3 in ratio 90:10, with flow rate 0,7 ml/min, column temperature set at 30 řC, pressure 19,8 MPa, UV detection at 203 nm and injection volume 1 µl. We compared the results of the analyzes with content of stevioside glycosides declared by the manufacturer. The new developed method allows rapid analysis of food supplements and plant extract containig steviol glycosides. Key words: steviol glycosides, stevioside, rebaudioside A, Stevia rebaudiana Bertoni, high...
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Colloidal rods and spheres in partially miscible binary liquidsHijnen, Niek January 2013 (has links)
Different scenarios for assembling rod-like and spherical colloidal particles using binary mixtures of partially miscible liquids were investigated experimentally. Suitable rod-like colloids were developed first. The subsequent studies of colloids in binary liquids consisted, on one hand, of systems where particles were partially wetted by both phases and, on the other hand, of systems where particles were completely wetted by the minority phase. A simple method to prepare large quantities of micrometer-sized akagan eite-silica core-shell rods was developed. These were proven to be very versatile, with the possibility of modifying their properties on different levels. The aspect ratio is simply controlled by a gradual growth of the silica shells. From them, hollow silica rods and rods with an increased responsiveness to a magnetic field could be obtained in straightforward ways. Bijels were prepared by trapping rod-like particles on a percolating liquid-liquid interface. The familiar bicontinuous organization of liquid domains was observed after structural arrest. At a fixed volume per particle it is demonstrated that for rod-like particles the domain size decreases faster with increasing quantity of particles than in the case of spherical particles. Additionally, the packing of the rods at the interface was elucidated, revealing several characteristic features. In particle-stabilized droplet emulsions rapid evaporation of the continuous phase and eventual full mixing of the liquid phases can leave a cellular network of particles. The formation and eventual stability of these networks were investigated in detail with confocal microscopy. When colloids are completely wetted by the minority component of an asymmetric binary mixture there can be substantial temperature and composition regimes outside the binodal where shear-induced aggregation can take place. This happens as adsorbed layers present at the particle surfaces coalesce and bind particles through a liquid bridge. Depending on particle concentration, percolating networks can form of rods wetted by the minority phase after temperature quenching such a system just across the binodal.
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Surfactant Directed Encapsulation of Metal Nanocrystals in Metal-Organic FrameworksHu, Pan January 2015 (has links)
Thesis advisor: Dunwei Wang / Metal nanocrystals with size and shape control have great potential in heterogeneous catalysis. Controllable encapsulation of well-defined metal nanoparticles into the novel porous materials results in new multifunctional nanomaterials. The core-shell nanostructure can enhance the selectivity, durability, or reactivity of the catalysts and even provide additional functionalities. Metal-organic frameworks (MOFs) are a class of novel crystalline nanoporous materials, with well-defined pore structures and distinctive chemical properties. Using MOFs as the encapsulating porous materials has drawn great interest recently due to their tunable structures and properties. However, it could be challenging to grow another porous material layer on metal surface due to the unfavorable interfacial energy. In this work we develop a new concept of colloidal synthesis to synthesize the metal@MOF core-shell nanostructures, in which a layer of self-assembled molecules directed the growth and alignment between two materials. Surfactant cetyltrimethylammonium bromide (CTAB) is designated to facilitate the overgrowth of MOF onto metal surface, and an alignment between the {100} planes of the metal and {110} planes of the MOF can be observed. By utilizing the same concept, a third layer of mesoporous silica could also be coated on the MOF shell with assistance of CTAB. And our method could be a general strategy to fabricate multiple-layer MOF materials. / Thesis (MS) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
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Applications of Optical Properties from Nanomaterials for Enhanced Activity of a Titania Photocatalyst under Solar RadiationPickering, Jon W. 16 September 2015 (has links)
In recent years, employing advanced oxidation processes (AOPs) as a means of wastewater remediation has emerged as a promising route towards maintaining a sustainable global water management program. The heterogeneous photocatalytic oxidation process has been of particular interest due to the prospective of utilizing solar radiation as the driving force behind the degradation of pollutants. Of the photocatalyst studied to date, TiO2 remains the most attractive material for environmental applications due to its affordability, stability, biocompatibility and high quantum yield. A key draw back however is roughly only 5% of solar radiation incident on earth can provide the energy required (3.0-3.2 eV) to generate the electron-hole pairs necessary for photo-oxidation. As a means to improve the process under solar irradiance, optical properties such as surface plasmon resonance of metallic nanoparticles and upconversion luminescence of rare earth ions have been exploited for improved light harvesting as well as the generation of more usable UV light from lower energy photons. In order to explore these phenomena and their role in the enhancement of this AOP, the photocatalytic degradation of organic dyes was studied under various conditions employing Degussa P25 TiO2 as the photocatalyst. Ag nanocubes, Ag-Pd core-shell nanoparticles and YAG:Yb+3,Er+3 served as the dopants for the various studies which resulted in enhanced degradation rates, insight into the applicability of utilizing Yb+3 as sensitizing ion under solar radiation and a novel core-shell nanoparticle synthesis.
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Association Behavior of Poly(methacrylic acid)-block-Poly(methyl methacrylate) in Aqueous Medium: Potentiometric and Laser Light Scattering StudiesPalaniswamy, R., Wang, C, Tam, Michael K. C., Gan, L.H. 01 1900 (has links)
Atom transfer radical polymerisation (ATRP) technique was used to synthesize poly(methacrylic acid-block-methyl methacrylate) (P(MAA₁₀₂-b-MMA₁₀)) copolymer in order to study the aggregation behavior in aqueous solution over the course of neutralization. A combination of static and dynamic light scattering (SLS, DLS) and potentiometric titration techniques were used to investigate the size and shape of the micelle at various degrees of neutralization. The hydrodynamic radius (Rh) determined from dynamic light scattering increases from ~26nm (for unneutralized) to ~42nm (for completely neutralized sample). Both potentiometric and laser light scattering studies indicate the formation of a core shell micelle. The weighted average molecular weights of the polymer and micelle are 1.18x10⁴ and 2.25 x 10⁵ g/mol respectively, which suggests that the aggregation number of the micelle is ~20. / Singapore-MIT Alliance (SMA)
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Core-Shell Assisted Bimetallic Assembly of Pt and Ru Nanoparticles by DNA HybridizationLee, Jim Yang, Yang, Jun, Too, Heng-Phon, Chow, Gan-Moog, Gan, Leong M. 01 1900 (has links)
We have discovered that the current protocols to assemble Au nanoparticles based on DNA hybridization do not work well with the small metal nanoparticles (e.g. 5 nm Au, 3.6 nm Pt and 3.2 nm Ru particles). Further investigations revealed the presence of strong interaction between the oligonucleotide backbone and the surface of the small metal nanoparticles. The oligonucleotides in this case are recumbent on the particle surface and are therefore not optimally oriented for hybridization. The nonspecific adsorption of oligonucleotides on small metal nanoparticles must be overcome before DNA hybridization can be accepted as a general assembly method. Two methods have been suggested as possible solutions to this problem. One is based on the use of stabilizer molecules which compete with the oligonucleotides for adsorption on the metal nanoparticle surface. Unfortunately, the reported success of this approach in small Au nanoparticles (using K₂BSPP) and Au films (using 6-mercapto-1-hexanol) could not be extended to the assembly of Pt and Ru nanoparticles by DNA hybridization. The second approach is to simply use larger metal particles. Indeed most reports on the DNA hybridization induced assembly of Au nanoparticles have made use of relatively large particles (>10 nm), hinting at a weaker non-specific interaction between the oligonucleotides and large Au nanoparticles. However, most current methods of nanoparticle synthesis are optimized to produce metal nanoparticles only within a narrow size range. We find that core-shell nanoparticles formed by the seeded growth method may be used to artificially enlarge the size of the metal particles to reduce the nonspecific binding of oligonucleotides. We demonstrate herein a core-shell assisted growth method to assemble Pt and Ru nanoparticles by DNA hybridization. This method involves firstly synthesizing approximately 16 nm core-shell Ag-Pt and 21 nm core-shell Au-Ru nanoparticles from 9.6 nm Ag seeds and 17.2 nm Au seeds respectively by the seed-mediated growth method. The core-shell nanoparticles were then functionalized by complementary thiolated oligonucleotides followed by aging in 0.2 M PBS buffer for 6 hours. The DNA hybridization induced bimetallic assembly of Pt and Ru nanoparticles could then be carried out in 0.3 M PBS buffer for 10 hours. / Singapore-MIT Alliance (SMA)
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