Study of interaction between Si(O,C) nanowires and the biological system

Nanomedicine is a new branch of medicine, based on the potentiality and intrinsic properties of nanomaterials. Indeed, the nanomaterials ( i.e. the materials with nano and under micron size) can be suitable to different applications in biomedicine. The nanostructures can be used by taking advantage of their properties (for example superparamagnetic nanoparticles) or functionalized to deliver the drug in a specific target, thanks the ability to cross biological barriers. The size and the shape of 1D-nanostructures (nanotubes and nanowires) have an important role on the cell fate: their morphology plays a key role on the interaction between nanostructure and the biological system. For this reason the 1D nanostructure are interesting for their ability to mime the biological system. An implantable material or device must therefore integrate with the surrounding extracellular matrix (ECM), a complex network of proteins with structural and signaling properties. Innovative techniques allow the generation of complex surface patterns that can resemble the structure of the ECM, such as 1D nanostructures. NWs based on cubic silicon carbide (3C-SiC), either bare (3C-SiC NWs) or surrounded by an amorphous shell (3C-SiC/SiO2 core/shell NWs), and silicon oxycarbide nanowires (SiOxCy NWs) can meet the chemical, mechanical and electrical requirements for tissue engineering and have a strong potential to pave the way for the development of a novel generation of implantable nano-devices. Silicon oxycarbide shows promising physical and chemical properties as elastic modulus, bending strength and hardness, chemical durability superior to conventional silicate glasses in aggressive environments and high temperature stability up to 1300 °C. Moreover, it can easily be engineered through functionalization and decoration with macro-molecules and nanoparticles. Silicon carbide has been extensively studied for applications in harsh conditions, as chemical environment, high electric field and high and low temperature, owing to its high hardness, high thermal conductivity, chemical inertness and high electron mobility. Also, its cubic polytype (3C) is highly biocompatible and hemocompatible, and some prototypes of biomedical applications and biomedical devices have been already realized starting from 3C-SiC thin films. Cubic SiC-based NWs can be used as a biomimetic biomaterial, providing a robust and novel biocompatible biological interface . We cultured in vitro A549 human lung adenocarcinoma epithelial cells and L929 murine fibroblast cells over core/shell SiC/SiO2, SiOxCy and bare 3C-SiC nanowire platforms, and analysed the cytotoxicity, by indirect and direct contact tests, the cell adhesion, and the cell proliferation. These studies showed that all the nanowires are biocompatible according to ISO 10993 standards. We evaluated the blood compatibility through the interaction of the nanowires with platelet rich plasma. The adhesion and activation of platelets on the nanowire bundles, assessed via SEM imaging and soluble P-selectin quantification, indicated that a higher platelet activation is induced by the core/shell structures compared to the bare ones. Further, platelet activation is higher with 3C-SiC/SiO2 NWs and SiOxCyNWs, which therefore appear suitable in view of possible tissue regeneration. On the contrary, bare 3C-SiC NWs show a lower platelet activation and are therefore promising in view of implantable bioelectronics devices, as cardiovascular implantable devices. The NWs properties are suitable to allow the design of a novel subretinal Micro Device (MD). This devices is based on Si NWs and PEDOT:PSS, though the well know principle of the hybrid ordered bulk heterojunction (OBHJ). The aim is to develop a device based on a well-established photovoltaic technology and to adapt this know-how to the prosthetic field. The hybrid OBHJ allows to form a radial p–n junction on a nanowire/organic structure. In addition, the nanowires increase the light absorption by means of light scattering effects: a nanowires based p-n junction increases the light absorption up to the 80%, as previously demonstrated, overcoming the Shockley-Queisser limit of 30 % of a bulk p-n junction. Another interesting employment of these NWs is to design of a SiC based epicardial-interacting patch based on teflon that include SiC nanowires. . Such contact patch can bridge the electric conduction across the cardiac infarct as nanowires can ‘sense’ the direction of the wavefront propagation on the survival cardiac tissue and transmit it to the downstream surivived regions without discontinuity. The SiC NWs are tested in terms of toxicology, biocompatibility and conductance among cardiomyocytes and myofibroblasts.

Estudo de propriedades de resinas compostas bulk fill

Diante da evolução da composição das resinas compostas e do lançamento de compósitos do tipo bulk fill, faz-se necessário o estudo do desempenho dessa nova classe de materiais. Para isso, o presente estudo teve como objetivo avaliar propriedades como grau de conversão (GC) , dureza Knoop (KHN), resistência à flexão (RF) e tenacidade à fratura (KIC) de sete compósitos bulk fill (EverX Posterior, EXP; Filtek Bulk Fill Flow, FBFF; Fill-Up!, FU; SonicFill, SF; Surefil SDR, SDR; Tetric EvoCeram Bulk Fill, TECBF; Venus Bulk Fill, VBF) e um compósito nanohíbrido convencional (Charisma Diamond, CD). De forma complementar, foi realizado tratamento térmico a 170 °C por 10 minutos para melhor compreensão do comportamento desses materiais quanto ao potencial de conversão e à indução de tensões na interface carga/matriz. A avaliação do GC (n=3) foi realizada através de espectroscopia FTIR, a leitura da dureza Knoop foi realizada nas superfícies do topo e da base (n=3), e os ensaios de RF de três pontos (n=10) e KIC (n=10) em máquina de ensaios universais. Os resultados obtidos foram submetidos à analise de variância (complementados pelo teste de Tukey) ou teste Kruskal-Wallis, com nível de significância de 5%. A análise do GC (%) revelou diferença entre os materiais testados, sendo que todas as resinas bulk fill apresentaram valores maiores que a resina convencional: SF (75,7) > VBF (66,7) = EXP (66,4) = SDR (62,8), sendo esta também semelhante a FU (60,0); FU, TECBF (56,6), FBFF (56,6) e CD (54,5) apresentaram conversão semelhante. Os valores de KHN variaram de acordo com o material e com a superfície: apenas SF apresentou KHN semelhante (na superfície do topo) a CD, entretanto não foi possível realizar a leitura da superfície da base deste último material; SF, TECBF e FBFF apresentaram valores de KHN diferentes nas superfícies topo e base; EXP, FU, SDR e VBF mantiveram os valores de dureza do topo semelhantes à superfície da base. Para a RF (MPa), os resultados variaram de acordo com o material: EXP (122,54) = SF (101,09) = CD (99,15), sendo estes dois últimos semelhantes a FU (83,86) e TECBF (82,71), os quais não diferiram da resina SDR (65,18); esta última também mostrou comportamento semelhante a FBFF (60,85) e VBF (59,90). Quanto ao KIC (MPa.mm0,5), EXP (3,35) apresentou o maior valor, semelhante a SF (2,42), que por sua vez também foi igual ao compósito convencional CD (2,01); CD apresentou KIC semelhante a SDR (1,74); SDR = VBF (1,59) = TECBF (1,57); TECBF, FU (1,54) e FBFF (1,37) apresentaram valores semelhantes. Na dependência do material, o tratamento térmico aumentou os valores dos parâmetros estudados, apontando limitações da reação de polimerização dos compósitos estudados. Com base nos resultados obtidos, podese concluir que: resinas bulk fill apresentam elevado GC, superior à resina convencional estudada; a nova classe de materiais restauradores é capaz de polimerizar em profundidade e alguns materiais apresentam KHN semelhantes no topo e na base de espécimes de 4 mm de profundidade; RF e KIC variaram de acordo com o material, e o compósito EXP apresentou os maiores valores para ambos os testes.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Hydrogen storage in CO2-activated amorphous nanofibers and their monoliths

Amorphous carbon nanofibers (CNFs), produced by the polymer blend technique, are activated by CO2 (ACNFs). Monoliths are synthesized from the precursor and from some ACNFs. Morphology and textural properties of these materials are studied. When compared with other activating agents (steam and alkaline hydroxides), CO2 activation renders suitable yields and, contrarily to most other precursors, turns out to be advantageous for developing and controlling their narrow microporosity (< 0.7 nm), VDR(CO2). The obtained ACNFs have a high compressibility and, consequently, a high packing density under mechanical pressure which can also be maintained upon monolith synthesis. H2 adsorption is measured at two different conditions (77 K / 0.11 MPa, and 298 K / 20 MPa) and compared with other activated carbons. Under both conditions, H2 uptake depends on the narrow microporosity of the prepared ACNFs. Interestingly, at room temperature these ACNFs perform better than other activated carbons, despite their lower porosity developments. At 298 K they reach a H2 adsorption capacity as high as 1.3 wt.%, and a remarkable value of 1 wt.% in its mechanically resistant monolith form.

Structure, gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.

Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes

The electrochemical reactions of dopamine, catechol and methylcatechol were investigated at tetrahedral amorphous carbon (ta-C) thin film electrodes. In order to better understand the reaction mechanisms of these molecules, cyclic voltammetry with varying scan rates was carried out at different pH values in H2SO4 and PBS solutions. The results were compared to the same redox reactions taking place at glassy carbon (GC) electrodes. All three catechols exhibited quasi-reversible behavior with sluggish electron transfer kinetics at the ta-C electrode. At neutral and alkaline pH, rapid coupled homogeneous reactions followed the oxidation of the catechols to the corresponding o-quinones and led to significant deterioration of the electrode response. At acidic pH, the extent of deterioration was considerably lower. All the redox reactions showed significantly faster electron transfer kinetics at the GC electrode and it was less susceptible toward surface passivation. An EC mechanism was observed for the oxidation of dopamine at both ta-C and GC electrodes and the formation of polydopamine was suspected to cause the passivation of the electrodes.

James Otis research materials,

Includes copies of correspondence from James Otis, and copies of historical summaries of the Stamp Act and extracts from the annual register, circa 1760s.

James Otis research materials,

Includes extracts from Benjamin Franklin’s works.

James Otis research materials,

Includes notes on activities of the Stamp Act Congress in 1765.

James Otis research materials,

Includes copies of correspondence from James Otis, notes on the American Revolution, and an extract from the Journal of Congress, approximately 1760s-1780s.

James Otis research materials,

Draft of Tudor’s manuscript, interfiled with loose notes and extracts from John Reeves’ work on English law, and a copy of Otis’ supposed work, "An Appeal to the World, or, a Vindication of the Town of Boston," approximately 1760s-1820s.

James Otis research materials,

Draft of Tudor's manuscript, interfiled with loose notes and copies of various documents regarding the Boston Tea Party and the Charter Oak tree.

James Otis research materials,

Notes for a chapter that included the history of two pieces of artillery, the "Adams" and the "Hancock," used in Revolutionary War; epitaph in Latin on William Bollan, and agent for the province of Massachusetts, and Governor William Shirley; clippings regarding the death of General James Warren.

James Otis research materials,

Undated copied and original correspondence and remembrances of James Otis.

Properties of granular analogue model materials: A community wide survey

We report the material properties of 26 granular analogue materials used in 14 analogue modelling laboratories. We determined physical characteristics such as bulk density, grain size distribution, and grain shape, and performed ring shear tests to determine friction angles and cohesion, and uniaxial compression tests to evaluate the compaction behaviour. Mean grain size of the materials varied between c. 100 and 400 μm. Analysis of grain shape factors shows that the four different classes of granular materials (14 quartz sands, 5 dyed quartz sands, 4 heavy mineral sands and 3 size fractions of glass beads) can be broadly divided into two groups consisting of 12 angular and 14 rounded materials. Grain shape has an influence on friction angles, with most angular materials having higher internal friction angles (between c. 35° and 40°) than rounded materials, whereas well-rounded glass beads have the lowest internal friction angles (between c. 25° and 30°). We interpret this as an effect of intergranular sliding versus rolling. Most angular materials have also higher basal friction angles (tested for a specific foil) than more rounded materials, suggesting that angular grains scratch and wear the foil. Most materials have an internal cohesion in the order of 20–100 Pa except for well-rounded glass beads, which show a trend towards a quasi-cohesionless (C < 20 Pa) Coulomb-type material. The uniaxial confined compression tests reveal that rounded grains generally show less compaction than angular grains. We interpret this to be related to the initial packing density after sifting, which is higher for rounded grains than for angular grains. Ring-shear test data show that angular grains undergo a longer strain-hardening phase than more rounded materials. This might explain why analogue models consisting of angular grains accommodate deformation in a more distributed manner prior to strain localisation than models consisting of rounded grains.