Improving the stability of an oxime based electrochemical microsensor for organo-phosphate vapor detection

A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.

Holistic Design In High-Speed Optical Interconnects

Integrated circuit scaling has enabled a huge growth in processing capability, which necessitates a corresponding increase in inter-chip communication bandwidth. As bandwidth requirements for chip-to-chip interconnection scale, deficiencies of electrical channels become more apparent. Optical links present a viable alternative due to their low frequency-dependent loss and higher bandwidth density in the form of wavelength division multiplexing. As integrated photonics and bonding technologies are maturing, commercialization of hybrid-integrated optical links are becoming a reality. Increasing silicon integration leads to better performance in optical links but necessitates a corresponding co-design strategy in both electronics and photonics. In this light, holistic design of high-speed optical links with an in-depth understanding of photonics and state-of-the-art electronics brings their performance to unprecedented levels. This thesis presents developments in high-speed optical links by co-designing and co-integrating the primary elements of an optical link: receiver, transmitter, and clocking.

In the first part of this thesis a 3D-integrated CMOS/Silicon-photonic receiver will be presented. The electronic chip features a novel design that employs a low-bandwidth TIA front-end, double-sampling and equalization through dynamic offset modulation. Measured results show -14.9dBm of sensitivity and energy efficiency of 170fJ/b at 25Gb/s. The same receiver front-end is also used to implement source-synchronous 4-channel WDM-based parallel optical receiver. Quadrature ILO-based clocking is employed for synchronization and a novel frequency-tracking method that exploits the dynamics of IL in a quadrature ring oscillator to increase the effective locking range. An adaptive body-biasing circuit is designed to maintain the per-bit-energy consumption constant across wide data-rates. The prototype measurements indicate a record-low power consumption of 153fJ/b at 32Gb/s. The receiver sensitivity is measured to be -8.8dBm at 32Gb/s.

Next, on the optical transmitter side, three new techniques will be presented. First one is a differential ring modulator that breaks the optical bandwidth/quality factor trade-off known to limit the speed of high-Q ring modulators. This structure maintains a constant energy in the ring to avoid pattern-dependent power droop. As a first proof of concept, a prototype has been fabricated and measured up to 10Gb/s. The second technique is thermal stabilization of micro-ring resonator modulators through direct measurement of temperature using a monolithic PTAT temperature sensor. The measured temperature is used in a feedback loop to adjust the thermal tuner of the ring. A prototype is fabricated and a closed-loop feedback system is demonstrated to operate at 20Gb/s in the presence of temperature fluctuations. The third technique is a switched-capacitor based pre-emphasis technique designed to extend the inherently low bandwidth of carrier injection micro-ring modulators. A measured prototype of the optical transmitter achieves energy efficiency of 342fJ/bit at 10Gb/s and the wavelength stabilization circuit based on the monolithic PTAT sensor consumes 0.29mW.

Lastly, a first-order frequency synthesizer that is suitable for high-speed on-chip clock generation will be discussed. The proposed design features an architecture combining an LC quadrature VCO, two sample-and-holds, a PI, digital coarse-tuning, and rotational frequency detection for fine-tuning. In addition to an electrical reference clock, as an extra feature, the prototype chip is capable of receiving a low jitter optical reference clock generated by a high-repetition-rate mode-locked laser. The output clock at 8GHz has an integrated RMS jitter of 490fs, peak-to-peak periodic jitter of 2.06ps, and total RMS jitter of 680fs. The reference spurs are measured to be –64.3dB below the carrier frequency. At 8GHz the system consumes 2.49mW from a 1V supply.

Establishment of a protocol for the cryopreservation of cell sheets of adipose tissue stem cells

Dissertação de Mestrado, Ciências Biomédicas, Departamento de Ciências Biomédicas e Medicina, Universidade do Algarve, 2016

Global transcriptome analysis of Lactococcus garvieae strains in response to temperature

Lactococcus garvieae is an important fish and an opportunistic human pathogen. The genomic sequences of several L. garvieae strains have been recently published, opening the possibility of global studies on the biology of this pathogen. In this study, a whole genome DNA microarray of two strains of L. garvieae was designed and validated. This DNA microarray was used to investigate the effects of growth temperature (18°C and 37°C) on the transcriptome of two clinical strains of L. garvieae that were isolated from fish (Lg8831) and from a human case of septicemia (Lg21881). The transcriptome profiles evidenced a strain-specific response to temperature, which was more evident at 18°C. Among the most significant findings, Lg8831 was found to up-regulate at 18°C several genes encoding different cold-shock and cold-induced proteins involved in an efficient adaptive response of this strain to low-temperature conditions. Another relevant result was the description, for the first time, of respiratory metabolism in L. garvieae, whose gene expression regulation was temperature-dependent in Lg21881. This study provides new insights about how environmental factors such as temperature can affect L. garvieae gene expression. These data could improve our understanding of the regulatory networks and adaptive biology of this important pathogen.

A Mutational Hotspot and Strong Selection Contribute to the Order of Mutations Selected for during Escherichia coli Adaptation to the Gut

The relative role of drift versus selection underlying the evolution of bacterial species within the gut microbiota remains poorly understood. The large sizes of bacterial populations in this environment suggest that even adaptive mutations with weak effects, thought to be the most frequently occurring, could substantially contribute to a rapid pace of evolutionary change in the gut. We followed the emergence of intra-species diversity in a commensal Escherichia coli strain that previously acquired an adaptive mutation with strong effect during one week of colonization of the mouse gut. Following this first step, which consisted of inactivating a metabolic operon, one third of the subsequent adaptive mutations were found to have a selective effect as high as the first. Nevertheless, the order of the adaptive steps was strongly affected by a mutational hotspot with an exceptionally high mutation rate of 10-5. The pattern of polymorphism emerging in the populations evolving within different hosts was characterized by periodic selection, which reduced diversity, but also frequency-dependent selection, actively maintaining genetic diversity. Furthermore, the continuous emergence of similar phenotypes due to distinct mutations, known as clonal interference, was pervasive. Evolutionary change within the gut is therefore highly repeatable within and across hosts, with adaptive mutations of selection coefficients as strong as 12% accumulating without strong constraints on genetic background. In vivo competitive assays showed that one of the second steps (focA) exhibited positive epistasis with the first, while another (dcuB) exhibited negative epistasis. The data shows that strong effect adaptive mutations continuously recur in gut commensal bacterial species.

Modelação do cancro da mama na região do Alentejo

Estudos epidemiológicos são estudos estatísticos onde se procura relacionar ocorrências de eventos de saúde com uma ou várias causas específicas. A importância que os modelos epidemiológicos assumem hoje no estudo de doenças de foro oncológico, em particular no estabelecimento das suas etiologias, é incontornável. Segundo Ogden, J. (1999) o cancro é "um crescimento incontrolável de células anormais que produzem tumores chamados neoplasias". Estes tumores podem ter origem benigna (não se espalham pelo corpo) ou maligna (apresentam metastização de outros órgãos). Sendo uma doença actual, com uma elevada taxa de incidência em Portugal quando comparada com outras doenças (Instituto Nacional de Estatística- INE, 2009), aumentando esta taxa com a idade tal como refere Marques, L. (2003), podendo ocorrer o diagnóstico desta doença em qualquer idade. De acordo com INE (2000) pode dizer-se que o cancro está entre as três principais causas de morte em Portugal, registando-se um aumento progressivo do seu peso proporcional, sendo o cancro da mama o tipo de cancro mais comum entre as mulheres e uma das doenças com maior impacto na nossa sociedade. O objectivo principal deste trabalho é a estimação e modelação do risco de contrair uma doença de natureza não contagiosa e rara (neste caso, cancro da mama), usando dados da região do Alentejo. Pretende-se fazer um apanhado das metodologias mais empregues nesta área e aplicá-las na prática, com ênfase nos estudos caso-controlo e nos modelos lineares generalizados (GLM) - mais concretamente regressão logística. Os estudos caso-controlo são usados para identificar os factores que podem contribuir para uma condição médica, comparando indivíduos que têm essa condição (casos) com pacientes que não têm a condição, mas que de resto são semelhantes (controlos). Neste trabalho utilizou-se essa metodologia para estudar a associação entre o viver em ambiente rural/urbano e o cancro da mama. Tendo em conta que o objectivo principal deste estudo se prende com o estudo da relação entre variáveis, mais propriamente, análise de influência que uma ou mais variáveis (explicativas) têm sobre uma variável de interesse (resposta), para esse efeito são estudados os modelos lineares generalizados - GLM - unificados na mesma moldura teórica pela primeira vez por Nelder & Wedderburn (1972) - e, posteriormente aplicados ao conjunto de dados sobre cancro da mama na Região do Alentejo. O presente trabalho pretende assim, ser um contributo na identificação de factores de risco do cancro da mama na região do Alentejo. ABSTRACT: Epidemiological studies are statistical studies where attempts to relate occurrences of health events with one or more specific causes. The importance of epidemiological models that are far in the study of diseases of cancer forum, particularly in establishing their etiology, is inescapable. According to Ogden, J. (1999) cancer is "an incontrollable growth of abnormal cells that produce tumors called cancer". These tumors may be benign (not spread throughout the body) or malignant (show metastasis to other organs). Being a current illness with a high incidence rate in Portugal compared with the same respect to other diseases (National Statistics 1nstitute -1NE, 2009) having an increasing rate with age as mentioned Marques, L. (2003), and can possibly be diagnosed at any age. According to 1NE (2000) the cancer is among the top three causes of death in Portugal and there is a progressive increase of its proportional weight. Breast cancer is the most common form of cancer among women and the diseases with major impact in our society. The main objective of this work is to model and estimate the risk of contracting a non-contagious and rare disease (in this case, breast cancer), using data from the Alentejo region. It is intended to summarize some of the methodologies employed in this area and apply them in practice, with emphasis on case-control studies and generalized linear models (GLM) - more specifically the logistic regression. The case-control studies are used to identify factors that may contribute to a medical condition, comparing individuals who have this condition (cases) with patients who have not the condition but that are otherwise similar (controls). ln this work we used this methodology to study the association between living in a rural/urban and breast cancer. Given that the main objective of this study rather relates to the study of the relationship between variables to analyze the influence that one or more variables (explanatory) have on a variable (response), for this purpose we study the generalized linear models - GLM - first unified in the same theoretical framework by Nelder and Wedderburn (1972) and subsequently applied to the data set on breast cancer in the Alentejo region. This work intends to be a contribution in identifying risk factors for breast cancer in the Alentejo region.

Aging assessment of polyethylene-based insulated low-voltage cables for nuclear applications

This thesis aims at investigating the evolution of physico-chemical and electrical properties relevant to low-voltage power cables for nuclear application when subjected to typical nuclear power plant (NPP) environments i.e., to gamma radiation and high temperature. This research is part of the European Project Horizon 2020 TeaM Cables, which aims at providing a novel methodology for efficient and reliable NPP cable aging management to NPP operators. The analyzed samples consist of both coaxial and twisted pair cables with different polymeric compounds used as primary insulation. Insulating materials are based on the same silane cross-linked polyethylene matrix with different additives and fillers. In order to characterize the material response to the environmental stresses, various experimental techniques have been used. These characterizations range from the microscale chemical response e.g. by FTIR, OIT and DSC, to the macroscale electrical and mechanical behavior. A significant part of this Thesis is given to the correlation of the response to aging among the different measured properties. It has been shown that it could be possible to connect both the chemical and mechanical properties of the investigated XLPE cables with the electrical ones. In particular, the high-frequency dielectric response allows an effective monitoring of both the early periods of aging, controlled by the antioxidant consumption kinetics, and then the subsequent oxidation of the polymer matrix. Therefore, dielectric spectroscopy showed to be capable of assessing the LV cable aging state and, it might be used as an aging marker for cable diagnostic. The last part of the manuscript focuses on the building of a predictive modelling approach of LV cable conditions subjected to radio-chemical aging. It resulted into obtaining a lifetime curve which relates the aging factor to which the cable is subjected to, namely the dose rate, with the limit value of the considered electrical property (tanδ).

Exploring mediterranean durum wheat wild relatives and elite diversity panel for future breeding

Durum wheat (Triticum durum) is an important crop that has been used for millennia for human consumption, and modern breeding can take advantage of the wide variability useful for the adaptation to new challenges. Novel beneficial alleles can be found in wild relatives and landraces thus enhancing crop adaptation to many biotic and abiotic stresses. This dissertation considers the source of variability from both before and after wheat domestication, that caused a loss of potentially useful alleles. Chapter 1. is the thesis introduction, which outlines the importance of wheat in the world, providing an historical overview of the domestication, the evolution mechanisms that led to the current forms of durum wheat and the use of wild relatives as a source of germplasm for future breeding programs is crucial. Moreover, the emergence of Z. tritici has been considered as the main pathogen of wheat since it contains extremely high levels of genetic variability and is thus difficult to control. Chapter 2. Considers the contribution of the phenotypic diversity of 242 accessions of Aegilops tauschii from the Open Wild Wheat Consortium, involved in wheat domestication, provided with whole-genome resequencing. The accessions were phenotyped both in the field and in controlled conditions and A k-mer-based GWAS was performed to identify genomic regions involved in useful traits. Chapter 3. Describes the genetic basis of resistance to Z. tritici in a durum wheat elite diversity panel representative of the germplasm bred in Mediterranean. Quantitative trait loci (QTL) analysis results revealed several loci involved in the STB response that were found in several chromosome regions with a high infection rate. The genomic regions associated with STB resistance identified in this study could be of interest for marker assisted selection (MAS) in durum wheat breeding programs.

Management Of Severe Thoracic Impalement Trauma Against Two-wheeled Horse Carriage: A Case Report And Literature Review.

Thoracic injuries in general are of great importance due to their high incidence and high mortality. Thoracic impalement injuries are rare but severe due to the combination of cause, effect and result. This study's primary objective is to report the case of a young man who was impaled by a two-wheeled horse carriage shaft while crashing his motorcycle in a rural zone. An EMT-B ferry was called at the crash scene and a conscious patient was found, sustaining a severe impalement injury to the left hemithorax, suspended over the floor by the axial skeleton with the carriage shaft coming across his left chest. As a secondary objective, a literature review of thoracic impalement injuries is performed. Cases of thoracic impalement injury require unique and individualized care based on injury severity and affected organs. Reported protocols for managing impalement injuries are entirely anecdotal, with no uniformity on impaled patient's approach and management. In penetrating trauma, it is essential not to remove the impaled object, so that possible vascular lesions remain buffered by the object, avoiding major bleeding and exsanguination haemorrhage. Severed impaled thoracic patients should be transferred to a specialist centre for trauma care, as these lesions typically require complex multidisciplinary treatment. High-energy thoracic impalement injuries are rare and hold a high mortality rate, due to the complexity of trauma and associated injuries such as thoracic wall and lung lesions. Modern medicine still seems limited in cases of such seriousness, not always with satisfactory results.

A Feasibility Study Of Fricke Dosimetry As An Absorbed Dose To Water Standard For 192ir Hdr Sources.

High dose rate brachytherapy (HDR) using 192Ir sources is well accepted as an important treatment option and thus requires an accurate dosimetry standard. However, a dosimetry standard for the direct measurement of the absolute dose to water for this particular source type is currently not available. An improved standard for the absorbed dose to water based on Fricke dosimetry of HDR 192Ir brachytherapy sources is presented in this study. The main goal of this paper is to demonstrate the potential usefulness of the Fricke dosimetry technique for the standardization of the quantity absorbed dose to water for 192Ir sources. A molded, double-walled, spherical vessel for water containing the Fricke solution was constructed based on the Fricke system. The authors measured the absorbed dose to water and compared it with the doses calculated using the AAPM TG-43 report. The overall combined uncertainty associated with the measurements using Fricke dosimetry was 1.4% for k = 1, which is better than the uncertainties reported in previous studies. These results are promising; hence, the use of Fricke dosimetry to measure the absorbed dose to water as a standard for HDR 192Ir may be possible in the future.

Incontinencia urinaria e atividade fisica : uma revisão da literatura

Universidade Estadual de Campinas . Faculdade de Educação Física

Estudo da frequencia cardiaca de atletas de handebol segundo situação de jogo, durante 3 partidas oficiais dos 42º Jogos Regionais da Zona Leste do Estado de São Paulo

Universidade Estadual de Campinas . Faculdade de Educação Física

Fine needle aspiration biopsy in the oral cavity and head and neck region

The objective of the current study was to evaluate the sensitivity, specificity and accuracy of fine needle aspiration biopsy (FNAB) of submucous nodules from the oral cavity and head and neck region as an auxiliary diagnostic tool. Fifty patients with nodule lesions in the oral cavity and the head and neck region were selected. All of them were submitted to FNAB and to either incisional or excisional biopsy. The diagnoses from the FNABs were compared with the biopsy diagnosis as the gold standard. All the cases of FNAB were analyzed by a single oral pathologist prior to the biopsy diagnosis. The results showed that the sensitivity of FNAB was 75%, its specificity was 96% and its accuracy was 58.8%. The false positive and false negative rates were 6.7% and 13.3%, respectively. The positive predictive value was 86% and the negative predictive value was 93%. The inconclusive rate was 16/50. FNAB displayed a high success rate for identifying both malignant and benign lesions, but a low accuracy for making a final diagnosis.

Jogo patológico e suas conseqüências para a saúde pública

O artigo teve por objetivo caracterizar o jogo patológico, apresentando as principais conseqüências desse transtorno. Foi realizado levantamento bibliográfico sobre o tema, na literatura nacional e internacional. Foram selecionadas as publicações cujos principais achados enfatizavam prevalência, custos sociais e econômicos associados, legalização de jogos de azar e conseqüente impacto na saúde pública. Alto índice de suicídio, comorbidade com outros transtornos psiquiátricos, problemas familiares e no trabalho, e prática de atos ilícitos foram conseqüências relatadas. A prevalência desse transtorno é maior em países que legalizaram jogos de azar e no Brasil, há evidências do crescimento do número de jogadores patológicos. O desenvolvimento de pesquisas nacionais é imprescindível para a definição de políticas públicas adequadas à realidade brasileira.

Morte neonatal precoce segundo complexidade hospitalar e rede SUS e não-SUS na Região Metropolitana de São Paulo, Brasil

O objetivo foi analisar o perfil dos recém-nascidos, mães e mortalidade neonatal precoce, segundo complexidade do hospital e vínculo com o Sistema Único de Saúde (SUS), na Região Metropolitana de São Paulo, Brasil. Estudo baseado em dados de nascidos vivos, óbitos e cadastro de hospitais. Para obter a tipologia de complexidade e o perfil da clientela, empregaram-se análise fatorial e de clusters. O SUS atende mais recém-nascidos de risco e mães com baixa escolaridade, pré-natal insuficiente e adolescentes. A probabilidade de morte neonatal precoce foi 5,6‰ nascidos vivos (65% maior no SUS), sem diferenças por nível de complexidade do hospital, exceto nos de altíssima (SUS) e média (não-SUS) complexidade. O diferencial de mortalidade neonatal precoce entre as duas redes é menor no grupo de recém-nascidos < 1.500g (22%), entretanto, a taxa é 131% mais elevada no SUS para os recém-nascidos > 2.500g. Há uma concentração de nascimentos de alto risco na rede SUS, contudo a diferença de mortalidade neonatal precoce entre a rede SUS e não-SUS é menor nesse grupo de recém-nascidos. Novos estudos são necessários para compreender melhor a elevada mortalidade de recém-nascidos > 2.500g no SUS.