Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.

Growth and Melting of Metallic Nanoclusters in Glass: A Review of Recent Investigations

The mechanisms of nucleation and growth and the solid-to-liquid transition of metallic nanoclusters embedded in sodium borate glass were recently studied in situ via small-angle X-ray scattering (SAXS) and wide-an-le X-ray scattering (WAXS). SAXS results indicate that, under isothermal annealing conditions, the formation and growth of Bi or Ag nanoclusters embedded in sodium borate glass occurs through two successive stages after a short incubation period. The first stage is characterized by the nucleation and growth of spherical metal clusters promoted by the diffusion of Bi or Ag atoms through the initially supersaturated glass phase. The second stage is named the coarsening stage and occurs when the (Bi- or Ag-) doping level of the vitreous matrix is close to the equilibrium value. The experimental results demonstrated that, at advanced stages of the growth process, the time dependence of the average radius and density number of the clusters is in agreement with the classical Lifshitz-Slyozov-Waoner (LSW) theory. However, the radius distribution function is better described by a lognormal function than by the function derived from the theoretical LSW model. From the results of SAXS measurements at different temperatures, the activation energies for the diffusion of Ag and Bi through sodium borate glass were determined. In addition, via combination of the results of simultaneous WAXS and SAXS measurements at different temperatures, the crystallographic structure and the dependence of melting temperature T(m) on crystal radius R of Bi nanocrystals were established. The experimental results indicate that T(m) is a linear and decreasing function of nanocrystal reciprocal radius 1/R, in agreement with the Couchman and Jesser theoretical model. Finally, a weak contraction in the lattice parameters of Bi nanocrystals with respect to bulk crystals was established.

Chemical and physical effects of ultrasound: sonoluminescence and materials

When a liquid is irradiated with ultrasound, acoustic cavitation (the formation, growth, and implosive collapse of bubbles in liquids irradiated with ultrasound) generally occurs. This is the phenomenon responsible for the driving of chemical reactions (sonochemistry) and the emission of light (sonoluminescence). The implosive collapse of bubbles in liquids results in an enormous concentration of sound energy into compressional heating of the bubble contents. Therefore, extreme chemical and physical conditions are generated during cavitation. The study of multibubble sonoluminescence (MBSL) and single-bubble sonoluminescence (SBSL) in exotic liquids such as sulfuric acid (H2SO4) and phosphoric acid (H3PO4) leads to useful information regarding the intracavity conditions during bubble collapse. Distinct sonoluminescing bubble populations were observed from the intense orange and blue-white emissions by doping H2SO4 and H3PO4 with sodium salts, which provides the first experimental evidence for the injected droplet model over the heated-shell model for cavitation. Effective emission temperatures measured based on excited OH• and PO• emission indicate that there is a temperature inhomogeneity during MBSL in 85% H3PO4. The formation of a temperature inhomogeneity is due to the existence of different cavitating bubble populations: asymmetric collapsing bubbles contain liquid droplets and spherical collapsing bubbles do not contain liquid droplets. Strong molecular emission from SBSL in 65% H3PO4 have been obtained and used as a spectroscopic probe to determine the cavitation temperatures. It is found that the intracavity temperatures are dependent on the applied acoustic pressures and the thermal conductivities of the dissolved noble gases. The chemical and physical effects of ultrasound can be used for materials synthesis. Highly reactive species, including HO2•, H•, and OH• (or R• after additives react with OH•), are formed during aqueous sonolysis as a consequence of the chemical effects of ultrasound. Reductive species can be applied to synthesis of water-soluble fluorescent silver nanoclusters in the presence of a suitable stabilizer or capping agent. The optical and fluorescent properties of the Ag nanoclusters can be easily controlled by the synthetic conditions such as the sonication time, the stoichiometry of the carboxylate groups to Ag+, and the polymer molecular weight. The chemical and physical effects of ultrasound can be combined to prepare polymer functionalized graphenes from graphites and a reactive solvent, styrene. The physical effects of ultrasound are used to exfoliate graphites to graphenes while the chemical effects of ultrasound are used to induce the polymerization of styrene which can then functionalize graphene sheets via radical coupling. The prepared polymer functionalized graphenes are highly stable in common organic solvents like THF, CHCl3, and DMF. Ultrasonic spray pyrolysis (USP) is used to prepare porous carbon spheres using energetic alkali propiolates as the carbon precursors. In this synthesis, metal salts are generated in situ, introducing porous structures into the carbon spheres. When different alkali salts or their mixtures are used as the precursor, carbon spheres with different morphologies and structures are obtained. The different precursor decomposition pathways are responsible for the observed structural difference. Such prepared carbon materials have high surface area and are thermally stable, making them potentially useful for catalytic supports, adsorbents, or for other applications by integrating other functional materials into their pores.

Homoleptic and Heteroleptic Metal Carbonyl Clusters and Nanoclusters

This Thesis aims at presenting the general results achieved during my PhD, that was focused on the study and characterisation of new homoleptic and heteroleptic metal carbonyl clusters. From a dimensional point of view, the nuclearity of such species ranges from 2 to 44 metal atoms. Lower nuclearity compounds may be viewed as polymetallic complexes, whereas higher nuclearity species can reach the nanocluster size, by resembling to ultrasmall nanoparticles (USNPs). Initially, my research was focused on the investigation of small MCCs stabilised by N-Heterocyclic carbene (NHCs) ligands. At this regard, a general strategy for the synthesis of mono-anionic [Fe(CO)4(MNHC)]− and neutral Fe(CO)4(MNHC)2, Co(CO)4(MNHC) (M = Cu, Ag, Au; NHC = IMes, IPr) species has been developed. Furthermore, during this investigation, neutral trimetallic Fe(CO)4(MNHC)(M’NHC) (M, M’ = Cu, Ag, Au; M ≠ M'; NHC = IPr) and neutral heteroleptic Fe(CO)4(MNHC)(MNHC’) (M = Au; NHC = IMes, IPr) compounds have been isolated. Thermal treatment turned out to be an efficient method for the growth of the dimension of MCCs. Indeed, species of the type [M3Fe3(CO)12]3– and [M4Fe4(CO)16]4– (M = Ag, Au) as well as larger clusters were formed during the thermal treatment of the new Fe-M (M = Ag, Cu, Au) carbonyl compounds. These species inspired the investigation of promising reaction paths for the synthesis of Fe-M (M = Ag, Cu, Au) carbonyl compounds devoid of ancillary ligands and alloy MCCs, such as the heterometallic [MxM’5-xFe4(CO)16]3− (M, M' = Cu, Ag, Au; M ≠ M'; x = 0-5) carbonyl clusters. The second part of this Thesis regards high nuclearity MCCs. In particular, new strategies for the growth of platinum carbonyl clusters involving, for instance, the employment of bidentate phosphines are described, as well as the syntheses and the thermal decomposition of new Ni-M (Pd, Pt) carbonyl clusters.

Compact Ag@fe3o4 Core-shell Nanoparticles By Means Of Single-step Thermal Decomposition Reaction.

A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine.

Biogenic Silver Nanoparticles Associated With Silver Chloride Nanoparticles (ag@agcl) Produced By Laccase From Trametes Versicolor.

In the present study, semi-purified laccase from Trametes versicolor was applied for the synthesis of silver nanoparticles, and the properties of the produced nanoparticles were characterized. All of the analyses of the spectra indicated silver nanoparticle formation. A complete characterization of the silver nanoparticles showed that a complex of silver nanoparticles and silver ions was produced, with the majority of the particles having a Ag(2+) chemical structure. A hypothetical mechanistic scheme was proposed, suggesting that the main pathway that was used was the interaction of silver ions with the T1 site of laccase, producing silver nanoparticles with the concomitant inactivation of laccase activity and posterior complexing with silver ions.

The role of quantum confinement and crystalline structure on excitonic lifetimes in silicon nanoclusters

The emission energy dependence of the photoluminescence (PL) decay rate at room temperature has been studied in Si nanoclusters (Si-ncl) embedded in Si oxide matrices obtained by thermal annealing of substoichiometric Si oxide layers Si(y)O(1-y), y=(0.36,0.39,0.42), at various annealing temperatures (T(a)) and gas atmospheres. Raman scattering measurements give evidence for the formation of amorphous Si-ncl at T(a)=900 degrees C and of crystalline Si-ncl for T(a)=1000 degrees C and 1100 degrees C. For T(a)=1100 degrees C, the energy dispersion of the PL decay rate does not depend on sample fabrication conditions and follows previously reported behavior. For lower T(a), the rate becomes dependent on fabrication conditions and less energy dispersive. The effects are attributed to exciton localization and decoherence leading to the suppression of quantum confinement and the enhancement of nonradiative recombination in disordered and amorphous Si-ncl. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3457900]

Quantitative determination of optical transmission through subwavelength slit arrays in Ag films: Role of surface wave interference and local coupling between adjacent slits

Measurement of the transmitted intensity from a coherent monomode light source through a series of subwavelength slit arrays in Ag films, with varying array pitch and number of slits, demonstrates enhancement (suppression) by factors of as much as 6 (9) when normalized to the transmission efficiency of an isolated slit. Pronounced minima in the transmitted intensity are observed at array pitches corresponding to lambda(SPP), 2 lambda(SPP), and 3 lambda(SPP), where lambda(SPP) is the wavelength of the surface plasmon polariton (SPP). The position of these minima arises from destructive interference between incident propagating waves and pi-phase-shifted SPP waves. Increasing the number of slits to four or more does not increase appreciably the per-slit transmission intensity. A simple interference model fits well the measured transmitted intensity profile.

Isotopically resolved (B)over-tilde<-(X)over-tilde electronic spectrum of Ag-3 and calculation of its Jahn-Teller effects

Ag-3 was produced by pulsed-nozzle laser vaporisation and jet-cooled in a Ne supersonic expansion. One-color resonant two-photon ionisation (R2PI) spectra of the (B) over tilde(2) E '' <-- (X) over tilde(2) E' transition of Ag-3 were separately measured for all four isotopic combinations. Long vibrational progressions are observed, involving clearly resolved bands at low energy, merging into a dense but resolvable spectrum up to 1000 cm(-1) above the origin. Both the ground (X) over tilde(2) E' and excited (B) over tilde(2) E '' states of Ag-3 are susceptible to Jahn-Teller distortion along the degenerate e' bending coordinate. The Jahn-Teller analysis includes both linear and quadratic terms, simultaneously with the spin-orbit coupling. Following extensive parameter fitting, the absorption spectrum is calculated, and bands assigned. The spin-orbit splitting is quenched below the localization energy, but becomes observable approximate to 300 cm(-1) above the origin.

Human GC-AG alternative intron isoforms with weak donor sites show enhanced consensus at acceptor exon positions

It has been previously observed that the intrinsically weak variant GC donor sites, in order to be recognized by the U2-type spliceosome, possess strong consensus sequences maximized for base pair formation with U1 and U5/U6 snRNAs. However, variability in signal strength is a fundamental mechanism for splice site selection in alternative splicing. Here we report human alternative GC-AG introns (for the first time from any species), and show that while constitutive GC-AG introns do possess strong signals at their donor sites, a large subset of alternative GC-AG introns possess weak consensus sequences at their donor sites. Surprisingly, this subset of alternative isoforms shows strong consensus at acceptor exon positions 1 and 2. The improved consensus at the acceptor exon can facilitate a strong interaction with U5 snRNA, which tethers the two exons for ligation during the second step of splicing. Further, these isoforms nearly always possess alternative acceptor sites and always possess alternative acceptor sites and exhibit particularly weak polypyrimidine tracts characteristic of AG-dependent introns. The acceptor exon nucleotides are part of the consensus required for the U2AF(35)-mediated recognition of AG in such introns. Such improved consensus at acceptor exons is not found in either normal or alternative GT-AG introns having weak donor sites or weak polypyrimidine,tracts. The changes probably reflect mechanisms that allow GC-AG alternative intron isoforms to cope with two conflicting requirements, namely an apparent need for differential splice strength to direct the choice of alternative sites and a need for improved donor signals to compensate for the central mismatch base pair (C-A) in the RNA duplex of U1 snRNA and the pre-mRNA. The other important findings include (i) one in every twenty alternative introns is a GC-AG intron, and (ii) three of every five observed GC-AG introns are alternative isoforms.

Implanta????o do pr??-atendimento na ag??ncia dos correios Adolfina de Pinheiros em S??o Paulo

A experi??ncia da Diretoria Regional de S??o Paulo Metropolitana dos Correios objetiva implementar melhoria em um dos seus principais processos: o atendimento nas ag??ncias. Dentro do contexto de gest??o pela qualidade total, destacamos o programa de ger??ncia da rotina e gerenciamento de melhorias (revis??o de processos), cujas ferramentas nortearam o nosso projeto. Nas ag??ncias, em decorr??ncia dos diversos produtos e servi??os que a ECT comercializa, faz-se necess??ria a gest??o das filas para que o tempo de espera excessivo n??o ocasione a insatisfa????o dos clientes. Com a implanta????o do pr??-atendimento em guich?? espec??fico, na ag??ncia Adolfina de Pinheiros, houve uma redu????o significativa do tempo de espera na fila, servindo como modelo para implanta????o em outras ag??ncias dos Correios. Al??m de atender ?? necessidade do cliente, estabelecida na matriz do QFD (Desdobramento da Fun????o Qualidade) do sistema de gest??o da qualidade da ECT, o projeto objetiva tornar a rotina de trabalho dos atendentes de guich?? mais f??cil, racional e produtiva

Avalia????o das pr??ticas de gest??o do conhecimento na ag??ncia nacional de telecomunica????es

A Gest??o do Conhecimento ?? de suma import??ncia para as organiza????es em que o conhecimento desempenha papel essencial. Nesses casos, o conhecimento afeta o trabalho e determina mudan??as irrevers??veis, tanto na vida das organiza????es como das pessoas que l?? trabalham. Este estudo analisa o processo de planejamento, implementa????o e desenvolvimento de pr??ticas de gest??o do conhecimento na Anatel, Ag??ncia Nacional de Telecomunica????es. ?? orientado por uma abordagem te??rica que foca, particularmente, na sociedade em rede (Castells, 1999) e nas dimens??es da Gest??o do Conhecimento (Angeloni, 2008). Um grupo de servidores da Anatel foi entrevistado e responderam a um question??rio com o objetivo de se avaliar sua familiaridade com pr??ticas de Gest??o do Conhecimento. A inclus??o da Gest??o do Conhecimento como t??pico da nova vers??o do Regimento Interno da Ag??ncia foi examinada, para verificar se representa passo estrat??gico para sua ado????o pela Ag??ncia. O estudo avalia a motiva????o para a ado????o da Gest??o do Conhecimento, investiga a ocorr??ncia de pr??ticas de Gest??o do Conhecimento na Anatel, bem como o est??gio de sua implementa????o e o alcance de sua ado????o entre os usu??rios da Ag??ncia e pela sociedade em geral. Finalmente, o estudo analisa se as iniciativas j?? tomadas para implementar a Gest??o do Conhecimento s??o consistentes com as diretrizes estabelecidas no novo Regimento Interno e se tais a????es s??o coordenadas de forma a promover a efic??cia da Gest??o do Conhecimento na Anatel

An??lise da estrutura organizacional da fiscaliza????o do transporte rodovi??rio na ag??ncia nacional de transportes terrestres

Fiscalizar a presta????o dos servi??os de transporte interestadual e internacional de passageiros e de transporte rodovi??rio de cargas ?? atribui????o da Superintend??ncia de Fiscaliza????o da Ag??ncia Nacional de Transportes Terrestres ??? ANTT. Esta pesquisa visa analisar a efici??ncia e efic??cia desta estrutura organizacional