RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Synthesis of molecular biomimetics

Biomimetics has paved the way toward new materials and technologies inspired in Nature. Biomolecules and their supramolecular organization have today a leading role in biomimetics, benefiting from the recent advances in nanotechnology. The production of biomimetic materials may be however a difficult task, because Nature does it very well. The use of several building blocks assembled in bottom-up arrangement is without doubt at the core of this process. Such building blocks include different molecules or molecular arrangements, of synthetic or natural origin, such as amino acids, lipids, carbohydrates, nucleic acids, carbon allotropes, dendrimers, or organosilanes, among others. The most common approaches to produce synthetic biomimetic materials are reported herein, with special emphasis to building blocks and their supramolecular arrangement.

Recycling old screen-printed electrodes with newly designed plastic antibodies on the wall of carbon nanotubes as sensory element for in situ detection of bacterial toxins in water

Using low cost portable devices that enable a single analytical step for screening environmental contaminants is today a demanding issue. This concept is here tried out by recycling screen-printed electrodes that were to be disposed of and by choosing as sensory element a low cost material offering specific response for an environmental contaminant. Microcystins (MCs) were used as target analyte, for being dangerous toxins produced by cyanobacteria released into water bodies. The sensory element was a plastic antibody designed by surface imprinting with carefully selected monomers to ensure a specific response. These were designed on the wall of carbon nanotubes, taking advantage of their exceptional electrical properties. The stereochemical ability of the sensory material to detect MCs was checked by preparing blank materials where the imprinting stage was made without the template molecule. The novel sensory material for MCs was introduced in a polymeric matrix and evaluated against potentiometric measurements. Nernstian response was observed from 7.24 × 10−10 to 1.28 × 10−9 M in buffer solution (10 mM HEPES, 150 mM NaCl, pH 6.6), with average slopes of −62 mVdecade−1 and detection capabilities below 1 nM. The blank materials were unable to provide a linear response against log(concentration), showing only a slight potential change towards more positive potentials with increasing concentrations (while that ofthe plastic antibodies moved to more negative values), with a maximum rate of +33 mVdecade−1. The sensors presented good selectivity towards sulphate, iron and ammonium ions, and also chloroform and tetrachloroethylene (TCE) and fast response (<20 s). This concept was successfully tested on the analysis of spiked environmental water samples. The sensors were further applied onto recycled chips, comprehending one site for the reference electrode and two sites for different selective membranes, in a biparametric approach for “in situ” analysis.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Artificial antibodies for troponin T by its imprinting on the surface of multiwalled carbon nanotubes: Its use as sensory surfaces

A novel artificial antibody for troponin T (TnT) was synthesized by molecular imprint (MI) on the surface of multiwalled carbon nanotubes (MWCNT). This was done by attaching TnT to the MWCNT surface, and filling the vacant spaces by polymerizing under mild conditions acrylamide (monomer) in N,N′-methylenebisacrylamide (cross-linker) and ammonium persulphate (initiator). After removing the template, the obtained biomaterial was able to rebind TnT and discriminate it among other interfering species. Stereochemical recognition of TnT was confirmed by the non-rebinding ability displayed by non-imprinted (NI) materials, obtained by imprinting without a template. SEM and FTIR analysis confirmed the surface modification of the MWCNT. The ability of this biomaterial to rebind TnT was confirmed by including it as electroactive compound in a PVC/plasticizer mixture coating a wire of silver, gold or titanium. Anionic slopes of 50 mV decade−1 were obtained for the gold wire coated with MI-based membranes dipped in HEPES buffer of pH 7. The limit of detection was 0.16 μg mL−1. Neither the NI-MWCNT nor the MWCNT showed the ability to recognize the template. Good selectivity was observed against creatinine, sucrose, fructose, myoglobin, sodium glutamate, thiamine and urea. The sensor was tested successfully on serum samples. It is expected that this work opens new horizons on the design of new artificial antibodies for complex protein structures.

Carbon key-properties for microcystin adsorption in drinking water treatment: structure or surface chemistry?

Dissertação para Obtenção de Grau de Mestre em Engenharia Química e Bioquímica

The effect of water inorganic matrix in ibuprofen adsorption onto activated carbon for water and wastewater treatment

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Effects of Soil Compaction and Organic Carbon Content on Preferential Flow in Loamy Field Soils

Abstract: Preferential flow and transport through macropores affect plant water use efficiency and enhance leaching of agrochemicals and the transport of colloids, thereby increasing the risk for contamination of groundwater resources. The effects of soil compaction, expressed in terms of bulk density (BD), and organic carbon (OC) content on preferential flow and transport were investigated using 150 undisturbed soil cores sampled from 15 × 15–m grids on two field sites. Both fields had loamy textures, but one site had significantly higher OC content. Leaching experiments were conducted in each core by applying a constant irrigation rate of 10 mm h−1 with a pulse application of tritium tracer. Five percent tritium mass arrival times and apparent dispersivities were derived from each of the tracer breakthrough curves and correlated with texture, OC content, and BD to assess the spatial distribution of preferential flow and transport across the investigated fields. Soils from both fields showed strong positive correlations between BD and preferential flow. Interestingly, the relationships between BD and tracer transport characteristics were markedly different for the two fields, although the relationship between BD and macroporosity was nearly identical. The difference was likely caused by the higher contents of fines and OC at one of the fields leading to stronger aggregation, smaller matrix permeability, and a more pronounced pipe-like pore system with well-aligned macropores.

Bartholin's Gland Cysts: Management with Carbon-Dioxide Laser Vaporization

OBJETIVO: Avaliar a eficácia, a taxa de recorrência e as complicações da vaporização laser com CO2 no tratamento dos cistos da glândula de Bartholin. MÉTODOS: Estudo retrospectivo com 127 pacientes que apresentavam cistos sintomáticos da glândula de Bartholin submetidas à vaporização laser CO2 na nossa instituição de janeiro de 2005 a junho de 2011. Foram excluídas todas as pacientes com abcessos da glândula de Bartholin ou com suspeita de câncer. Todos os procedimentos foram realizados em regime ambulatorial, sob anestesia local. A coleta dos dados foi feita com base na consulta do processo clínico, tendo-se procedido à análise das características demográficas, dos parâmetros anatômicos, das complicações intra e pós-operatórias e dos dados de acompanhamento. Os dados foram armazenados e analisados no software Microsoft Excel® 2007, e os resultados foram apresentados como frequência (porcentagem) ou média±desvio padrão. As taxas de complicações, recorrência e cura foram calculadas. RESULTADOS: A idade média das pacientes foi de 37,3±9,5 anos (variando entre 18 e 61 anos). Setenta por cento(n=85) delas eram multíparas. A queixa mais frequente foi dor e 47,2% (n=60) das pacientes tinham antecedentes de tratamento médico e/ou cirúrgico por abcesso da glândula de Bartholin. A dimensão média dos cistos foi de 2,7±0,9 cm. Foram verificados três (2,4%) casos de hemorragia intraoperatória ligeira e 17 (13,4%) recorrências durante um período médio de 14,6 meses (variando entre 1 e 56 meses): dez abscessos da glândula de Bartholin e sete cistos recorrentes, que precisavam de uma nova intervenção cirúrgica. A taxa de cura após um único tratamento à laser foi de 86,6%. Dentre as cinco pacientes com doença recorrente que foram submetidas a um segundo procedimento com laser, a taxa de cura foi de 100%. CONCLUSÕES: Na presente instituição, a vaporização laser com CO2 parece ser uma opção terapêutica segura e eficaz no tratamento dos cistos da glândula de Bartholin.

Development of regional spatial data infrastructure (SDI) case study in hearth of Borneo

Dissertation submitted in partial fulfillment of the requirements for the Degree of Master of Science in Geospatial Technologies.

Carbon monoxide, autophagy and cytoprotection in response to cerebral ischemia

Dissertação para obtenção do Grau de Mestre em Genética Molecular e Biomedicina

Catalytic hydrogenation of carbon dioxide to form methanol and methane

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Disclosing Carbon Monoxide Protection in Cerebral Ischemia: Insights into the cellular mechanisms

Dissertation presented to obtain the PhD degree in Biochemistry, Neurosciences

The role of electron transfer in DNA building blocks: evaluation of strand breaks and their implications

Dissertação para obtenção do Grau de Doutor em Engenharia Física

The building blocks of social entrepreneurship: empirical model and framework

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Management from the NOVA – School of Business and Economics