(Bio)funcionalização de superfícies nanoestruturadas para eletrocatálise e desenvolvimento de biossensores eletroquímicos e óticos

Tese de doutoramento, Química (Química Física), Universidade de Lisboa, Faculdade de Ciências, 2016

Low generation triazine-based dendrimers-synthesis, characterzation and in vitro biological activity

In the present study, two low generation triazine-based dendrimers, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer, were synthesized and their cytotoxicity were tested by using the NIH 3T3 and the A2780 cell lines. In the synthesis process of the G1.0(Cl)4 dendrimer, cyanuric chloride (CAC) which has high reactivity chlorine atom was connected to the terminal of triethylene glycol (TEG) via nucleophilic substitution by controlling temperature. The prepared G1.0(Cl)4 dendrimer was purified by silica gel column chromatography. Then the four chlorine atoms in the G1.0(Cl)4 dendrimer were substituted by diethanolamine (DEA) to give dendrimer with the hydroxyl terminal group G1.5(OH)8. The starting materials, CAC, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer were analyzed by one-dimensional NMR, FTIR and MS techniques. The two dendrimers, G1.0(Cl)4 and G1.5(OH)8, showed perfect stability in the air environment at room temperature. However, G1.0(Cl)4 is not soluble in water while the G1.5(OH)8 dendrimer is a water soluble compound. Furthermore, cell biological evaluation at the studied concentrations showed that the CAC, as well as the prepared G1.0(Cl)4 and G1.5(OH)8 dendrimers, have no cytotoxicity towards the NIH 3T3 and A2780 cell lines.

Argamassas de auto-limpeza : da formulação às aplicações

Atualmente assiste-se a um grave problema de salubridade visual das cidades, designadamente no espaço edificado/ construído. A sujidade é uma ameaça que, junto com os graffitis, tem contribuído para a degradação precoce dos espaços urbanos. A fim de se enfrentar este problema, que tem vindo a proliferar nas cidades, um pouco por todo o mundo, a presente dissertação de mestrado ambiciona contribuir para a sistematização da informação existente sobre a produção e caracterização de argamassas de auto-limpeza. As argamassas de auto-limpeza são produzidas por uma de duas formas: com a adição de nanopartículas de dióxido de titânio (TiO2) na sua matriz ou com a aplicação de um filme fino à base de TiO2 na sua superfície. Esta segunda é apontada como a técnica mais eficaz e económica. Salienta-se o facto do TiO2 ser um dos nanomateriais mais utilizados na construção pelas suas propriedades fotocatalíticas que o capacitam como um dos mais exímios fotocatalisadores, aquando da fotocatálise heterogénea. É graças ao processo de fotodegradação química da fotocatálise, que na presença de luz solar e da ação da água, que o TiO2 é ativado, desencadeando reações químicas que aumentam a eficácia e eficiência fotocatalítica. Analisou-se um conjunto de trabalhos de investigação recentes que comprovam que o uso das argamassas de auto-limpeza é adequado e benéfico em intervenções em edifícios novos como em obras de conservação e reabilitação de edifícios antigos. Além de reduzirem os investimentos em obras de limpeza, manutenção/conservação e reabilitação, prolongam a conservação das fachadas e melhoram os níveis da qualidade do ar. Apesar do crescente número de patentes pedidas e concedidas nesta área, as normas aplicáveis ainda não se encontram uniformizadas. Nesse sentido, a experiência do Japão deve ser tida como exemplo para que os restantes países desenvolvam de forma consensual as suas próprias normas e patentes, permitindo, futuramente, conferir maior credibilidade, segurança no uso dos nanomateriais e uma maior permeabilidade no setor da construção. Elencam-se alguns nano-produtos à base de nano TiO2 comercializados que têm vindo a ser aplicados sobretudo na China, Japão e na Alemanha.

Controlling Long-Range Ordered Self-assembly of Solid-Binding Peptide Monolayers on Atomically Flat Layered Materials

Thesis (Master's)--University of Washington, 2016-06

Fractal effects on the measurement of the specific surface areas of single-walled carbon nanotubes

The specific surface area (SSA) of single-walled carbon nanotubes (SWNTs) has been measured by different groups. Fujiwara et al. measured the SSA of SWNT bundles by using nitrogen and oxygen as adsorbates, and found that the SSA from O2-adsorption was 6.6% larger than that from N2-adsorption for the same SWNT sample [1]. Also Wei et al. [2] measured the SSA of HiPco SWNTs by using O2, N2 and Ar, and found that, for the same samples, Vm(Ar) > Vm(O2) > Vm(N2), here Vm is the monolayer adsorption capacity at the standard conditions of temperature and pressure (STP). Those research results indicate that, for the same SWNT sample, its measured surface area depends on the employed adsorbate.

Packing-dependent pore structure in single-walled carbon nanotube arrays

Based on a self-similar array model of single-walled carbon nanotubes (SWNTs), the pore structure of SWNT bundles is analyzed and compared with that obtained from the conventional triangular model and adsorption experimental results. In addition to the well known cylindrical endo-cavities and interstitial pores, two types of newly defined pores with diameters of 2-10 and 8-100 nm are proposed, inter-bundle pores and inter-array pores. In particular, the relationship between the packing configuration of SWNTs and their pore structures is systematically investigated. (c) 2005 American Institute of Physics.

Crisis management and risk communication: Why the food industry must get it right

There is public unease about food-related issues including food additives, food poisoning bacteria and GM ingredients. The public wants evidence of no risks, but all regulators can ever offer is no evidence of risk or evidence of a very small risk. The situation is complex because experts and non-experts can perceive the same risk in vastly different ways. The way in which the food industry manages crises and communicates risks will determine the public acceptance and success of new technologies such as GM foods and nanomaterials. There is a need for the food industry (including regulators and scientific experts) to sharpen up their risk communication skills to ensure that technical innovations are accepted by consumers, and crises such as food recalls do not undermine the public's confidence in the food industry. The AIFST has a key role to play in driving the risk communication process and allaying public unease about food-related issues.

Nanoscale tubular vessels for storage of methane at ambient temperatures

Novel carbon nanostructures can serve as effective storage media for methane, a source of clean energy for the future. We have used Grand Canonical Monte Carlo Simulation for the modeling of methane storage at 293 K and pressures up to 80 MPa in idealized bundles of (10,10) armchair-type single-walled carbon nanotubes and wormlike carbon pores. We have found that these carbon nanomaterials can be treated as the world's smallest high-capacity methane storage vessels. Our simulation results indicate that such novel carbon nanostructures can reach a high volumetric energy storage, exceeding the US FreedomCAR Partnership target of 2010 (5.4 MJ dm(-3)), at low to moderate pressures ranging from 1 to 7 MPa at 293 K. On the contrary, in the absence of these nanomaterials, methane needs to be compressed to approximately 13 MPa at 293 K to achieve the same target. The light carbon membranes composed of bundles of single-walled carbon nanotubes or wormlike pores efficiently physisorb methane at low to moderate pressures at 293 K, which we believe should be particularly important for automobiles and stationary devices. However, above 15-20 MPa at 293 K, all investigated samples of novel carbon nanomaterials are not as effective when compared with compression alone since the stored volumetric energy and power saturate at values below those of the bulk, compressed fluid.

Optimization of slitlike carbon nanopores for storage of hythane fuel at ambient temperatures

Carbons with slitlike pores can serve as effective host materials for storage of hythane fuel, a bridge between the petrol combustion and hydrogen fuel cells. We have used grand canonical Monte Carlo simulation for the modeling of the hydrogen and methane mixture storage at 293 K and pressure of methane and hydrogen mixture up to 2 MPa. We have found that these pores serve as efficient vessels for the storage of hythane fuel near ambient temperatures and low pressures. We find that, for carbons having optimized slitlike pores of size H congruent to 7 angstrom ( pore width that can accommodate one adsorbed methane layer), and bulk hydrogen mole fraction >= 0.9, the volumetric stored energy exceeds the 2010 target of 5.4 MJ dm(-3) established by the U. S. FreedomCAR Partnership. At the same condition, the content of hydrogen in slitlike carbon pores is congruent to 7% by energy. Thus, we have obtained the composition corresponding to hythane fuel in carbon nanospaces with greatly enhanced volumetric energy in comparison to the traditional compression method. We proposed the simple system with added extra container filled with pure free/adsorbed methane for adjusting the composition of the desorbed mixture as needed during delivery. Our simulation results indicate that light slit pore carbon nanomaterials with optimized parameters are suitable filling vessels for storage of hythane fuel. The proposed simple system consisting of main vessel with physisorbed hythane fuel, and an extra container filled with pure free/adsorbed methane will be particularly suitable for combustion of hythane fuel in buses and passenger cars near ambient temperatures and low pressures.

Strong and weak lifespan extension: What is most feasible and likely?

Recent advances in biomedical science indicate that it may eventually be possible to intervene in the biological process of human ageing. This paper overviews the current state of the science of lifespan extension and promising future directions. It is uncertain whether 'strong' lifespan extension - the extension of human life beyond the maximum 122 years so far observed - will become a reality. It is more likely that cumulative effects of numerous scientific and biomedical advances in the treatment of common disease will produce 'weak' lifespan extension - the extension of average life expectancy. The practical application of molecular, genetic and nanomaterials research may also lead to advances in life expectancy. It is not too early to begin to consider the policy implications of either form of lifespan extension.

Proceedings of the ARCCFN Annual Conference

Proceedings of the ARCCFN Annual Conference

Nanotossicologia dei quantum dot di CdS in linee cellulari umane

Le nanotecnologie sono un settore emergente in rapida crescita, come dimostra l'esplosione del mercato dei prodotti ad esso collegati. I quantum dot di cadmio solfuro (CdS QD) sono ampiamente utilizzati per la produzione di materiali semiconduttori e dispositivi optoelettronici; tuttavia, non sono ancora completamente chiari gli effetti di questi nanomateriali sulla salute umana. Questo lavoro di dottorato si pone l'obbiettivo di definire il potenziale citotossico e genotossico dei CdS QD in linee cellulari umane e definirne il meccanismo implicato. A questo scopo, essendo il fegato uno dei principali organi di accumulo del cadmio e dei nanomateriali a base di cadmio, è stata utilizzata la linea cellulare HepG2 derivante da un epatocarcinoma umano. È stato evidenziato, in seguito all'assorbimento, da parte delle cellule, dei CdS QD, un effetto citotossico, con conseguente modulazione dell'espressione genica di una serie di geni coinvolti sia nei processi di rescue (autofagia, risposta allo stress) sia in quelli di morte cellulare programmata. È stato, inoltre, dimostrata l'assenza di un rilevante effetto genotossico dipendente da questi nanomateriali. Infine, è stato osservato che cellule esposte ai CdS QD presentano mitocondri con un potenziale di membrana alterato, con conseguente alterazione della funzionalità di tale organello, pur conservando l'integrità del DNA mitocondriale.

Bottom-up risk regulation? How nanotechnology risk knowledge gaps challenge federal and state environmental agencies

Nanotechnologies have been called the "Next Industrial Revolution." At the same time, scientists are raising concerns about the potential health and environmental risks related to the nano-sized materials used in nanotechnologies. Analyses suggest that current U.S. federal regulatory structures are not likely to adequately address these risks in a proactive manner. Given these trends, the premise of this paper is that state and local-level agencies will likely deal with many "end-of-pipe" issues as nanomaterials enter environmental media without prior toxicity testing, federal standards, or emissions controls. In this paper we (1) briefly describe potential environmental risks and benefits related to emerging nanotechnologies; (2) outline the capacities of the Toxic Substances Control Act, the Clean Air Act, the Clean Water Act, and the Resources Conservation and Recovery Act to address potential nanotechnology risks, and how risk data gaps challenge these regulations; (3) outline some of the key data gaps that challenge state-level regulatory capacities to address nanotechnologies' potential risks, using Wisconsin as a case study; and (4) discuss advantages and disadvantages of state versus federal approaches to nanotechnology risk regulation. In summary, we suggest some ways government agencies can be better prepared to address nanotechnology risk knowledge gaps and risk management.

Defects in ZnO nanoparticles laser-ablated in water-ethanol mixtures at different pressures

The effect of liquid medium and its pressure on the photoluminescence of ZnO nanoparticles prepared via laser ablation of Zn targets in various water-ethanol mixtures is studied. As the ethanol content increases, the photoluminescence of the product changes, while metallic zinc is observed to emerge in nanomaterials prepared in ethanol-rich environments. The applied pressure had a less profound effect, mainly affecting materials produced in water or water-ethanol, and much less those generated in pressurized ethanol. Tuning the reactivity of the liquid and pressurizing it during laser ablation is demonstrated to be promising for tailoring the emission properties of the product.