Proof of Concept of the Electrochemical Sensing of 3-Iodothyronamine (T1AM) and Thyronamine (T0AM)

Recent studies have shown that, besides the well-recognized T3 and T4 hormones, there are other relevant thyroid hormones circulating in the human body. In particular, this is the case for 3-iodothyronamine (T1AM) and thyronamine (T0AM). One of the reasons for the lack of studies showing their precise importance is the absence of analytical methodologies available. Herein, for the first time, T1AM and T0AM are electrochemically characterized. T0AM was sensed by means of a glassy carbon electrode; furthermore, T1AM was sensed both with a graphitic surface (oxidatively) as well as with mercury (reductively). For both compounds, after oxidation, it was possible to observe the reversible redox reaction concerning the benzoquinone/hydroquinone couple, thus increasing the specificity of the electroanalysis. Therefore, this work provides the basis for an ‘at-point-of-use’ electrochemical strip test for T1AM and T0AM.

A disfunção redox espinhal na dor neuropática

As espécies reativas de oxigénio (ROS) estão envolvidas no desenvolvimento de dor neuropática. No entanto, a aplicação clínica de moléculas antioxidantes no tratamento desta patologia tem demonstrado pouca eficácia. A inibição da NADPH oxidase (NOX), uma das principais fontes de ROS, poderá ser uma boa estratégia terapêutica. O nosso grupo verificou que a apocinina (inibidor da NOX) melhora parcialmente os sintomas de dor neuropática e a disfunção redox espinhal no modelo SNI (spared nerve injury). De forma a melhorar este efeito terapêutico, o presente estudo insere-se num projeto maior, que visa identificar as isoformas da NOX envolvidas na fisiopatologia da doença e avaliar o efeito da administração de inibidores específicos para essas isoformas. Assim, propusemo-nos a avaliar a disfunção redox espinhal em fases precoces dador neuropática periférica induzida pelo modelo SNI no Rato, relacionando-a com os comportamentos de dor demonstrados pelos animais. Foram constituídos três grupos experimentais: SNI, sham e naïve, com subgrupos testados e sacrificados aos dias 1, 3, 7 e 14 após a cirurgia. Avaliou-se a sensibilidade mecânica (vonFrey e pinprick) e ao frio (acetona) dos animais, sacrificaram-se e recolheram-se as medulas espinhais para análise imunohistoquímica, com marcadores de dano oxidativo no DNA e de dano nitrosativo. Ao contrário dos animais sham, que demonstraram um comportamento muito próximo dos naïve, os animais SNI desenvolveram alodínia mecânica e ao frio e hiperalgesia mecânica na pata ipsilateral. No entanto, o dano oxidativo no corno dorsal ipsilateral da medula espinhal apresentou-se idêntico nos grupos SNI e sham ao longo dos 14 dias de estudo, não havendo também diferenças entre os cornos ipsi e contralateral à lesão nervosa. É possível que o desenvolvimento de dor neuropática nos animais SNI não se faça acompanhar de disfunção redox espinhal, pelo menos até aos 14 dias pós indução. O facto de a lesão nervosa no modelo SNI se localizar numa porção distal do ciático, ao contrário de outros modelos em que o stresse oxidativo espinhal foi já descrito, poderia explicar essas diferenças. Em todo o caso, considerando que os resultados comportamentais obtidos indicam que as cirurgias SNI e sham causam diferentes níveis de sensibilização nos animais, parece-nos fulcral prolongar os tempos de neuropatia, e executar uma avaliação do estado redox com outros marcadores, de forma a elucidar se, de facto, existem ROS envolvidas nesta sensibilização e, em caso positivo, poder identificar essas espécies, bem como as suas fontes.

Analysis of ground reaction force and electromyographic activity of the gastrocnemius muscle during double support

O documento em anexo encontra-se na versão post-print (versão corrigida pelo editor).

Comparative analysis of the ground reaction forces, during the support phase, in a group of pregnant women on their 3rd trimester of pregnancy and in a group of not pregnant women

PURPOSE: To analyze and compare the Ground Reaction Forces (GRF), during the stance phase of walking in pregnant women in the 3rd trimester of pregnancy, and non pregnant women. METHODS: 20 women, 10 pregnant and 10 non pregnant, voluntarily took part in this study. GRF were measured (1000 Hz) using a force platform (BERTEC 4060-15), an amplifier (BERTEC AM 6300) and an analogical-digital converter of 16 Bits (Biopac). RESULTS: The study showed that there were significant differences among the two groups concerning absolute values of time of the stance phase. In what concerns to the normalized values the most significant differences were verified in the maximums values of vertical force (Fz3, Fz1) and in the impulse of the antero-posterior force (Fy2), taxes of growth of the vertical force, and in the period of time for the antero-posterior force (Fy) be null. CONCLUSIONS: It is easier for the pregnant to continue forward movement (push-off phase). O smaller growth rates in what concerns to the maximum of the vertical force (Fz1) for the pregnant, can be associated with a slower speed of gait, as an adaptation strategy to maintain the balance, to compensate the alterations in the position of her center of gravity due to the load increase. The data related to the antero-posterior component of the force (Fy), shows that there is a significant difference between the pregnant woman’s left foot and right foot, which accuses a different functional behavior in each one of the feet, during the propulsion phase (TS).

Implementação de um sistema Kanban® na reposição de grandes volumes em dose unitária

Introdução. O sistema de distribuição em dose unitária tem por base a dispensa de medicação na dose prescrita, de forma individualizada. Este sistema de distribuição é vantajoso, pois torna a dispensa de medicamentos individualizada e dirigida ao doente, e diminui o stock existente nas enfermarias. Contudo, assume também desvantagens, sendo crucial que todos os medicamentos e produtos farmacêuticos estejam disponíveis e individualizados, sempre que necessários. De modo a assegurar uma adequada reposição de stocks no sector de Dose Unitária, o Centro Hospitalar de São João, EPE (CHSJ, EPE) implementou o sistema Kanban® como método de reposição. Assim, foi desenvolvido um conjunto de cartões-Kanban®, existindo diferentes cores que caracterizam diferentes grupos de produtos: [1] azul, produtos que necessitam de manipulação; [2] verde, produtos que se encontram na sua apresentação final; [3] roxo, produtos de grande volume que necessitam de manipulação. Deste modo, quando o stock de um produto está a terminar, compete aos Técnicos de Farmácia colocar o Kanban® no Quadro de Reposição, para que seja iniciado o processo de reposição. Face a algumas limitações associadas ao tamanho dos cartões anteriormente implementados, este trabalho visa desenvolver e implementar o Kanban® verde, através de um sistema de dupla identificação, utilizando duas etiquetas identificativas: uma verde, removível, que é colocada no Quadro de Reposição quando o stock termina, e uma amarela, fixa, alertando para a necessidade de repor o produto em causa. Material e Métodos. Efectuou-se um estudo do tipo investigação-acção no qual foram analisados todos os medicamentos e produtos farmacêuticos que não sofrem qualquer processo de manipulação entre a chegada aos Serviços Farmacêuticos e o seu envio para os Serviços Clínicos. Resultados. Da implementação deste sistema de dupla identificação, com base no modelo de rótulos pré-definido na instituição, resultaram um conjunto de rótulos identificativos dos vários produtos. Discussão/Conclusões. O stock do sector de Dose Unitária do CHSJ, EPE encontra-se organizado de duas formas: os medicamentos que necessitam de manipulação, que atendendo ao seu pequeno volume estão armazenados em gavetas, enquanto os restantes, pelo seu maior volume, são armazenados em estantes, com a devida identificação. Considerando que os novos Kanban® têm por base substituir os já existentes, acreditamos que alguma dificuldade existente será melhorada. A diferença na coloração das etiquetas designativas alertará para a necessidade de reposição, situação que poderia passar despercebida. Face à falta de literatura publicada, não existe qualquer informação que sustente os resultados esperados, porém acreditamos que este estudo pode servir de base ao desenvolvimento deste sistema noutras instituições, e como experiência do sucesso/insucesso da utilização do Sistema Kanban

PPO Reaction Scale-up

O óxido de polifenileno com a marca comercial PPO® é uma das resinas principais produzidas na SABIC IP e o ingrediente principal do plástico de engenharia com a marca registada, Noryl®. A equipa de tecnologia de processo de PPO® desenvolve uma série de novos produtos em reactores de pequena escala, tanto em Selkirk como em Bergen op Zoom. Para se efectuar uma transição rápida da escala laboratorial para a fábrica, é necessário um conhecimento completo do reactor. O objectivo deste projecto consiste em esboçar linhas gerais para o scale-up de novos produtos de PPO1, do laboratório para a escala industrial, baseado no estudo de um tipo de PPO, PPO 803. Este estudo pode ser dividido em duas fases. Numa primeira fase, as receitas e os perfis da reacção são comparados, de onde se retiram as primeiras conclusões. Posteriormente, com base nestas conclusões, é realizado um planeamento experimental. O estudo inicial sugeriu que a receita, a temperatura inicial do reactor e a velocidade do agitador poderiam influenciar o tempo da reacção bem como a queda da velocidade intrínseca do polímero (IV drop). As reacções experimentais mostraram que a receita é o principal factor que influencia, tanto o tempo de reacção, como a queda de viscosidade intrínseca. O tempo de reacção será tanto maior quanto menor a agitação devido à má dispersão do oxigénio na mistura. O uso de temperaturas iniciais elevadas conduz a uma queda maior da viscosidade intrínseca devido à desactivação do catalisador. O método experimental utilizado no laboratório de Bergen op Zoom é um bom exemplo, simulador, do procedimento utilizado na fábrica.

Electroanalytical determination of oxadiazon and characterization of its base-catalyzed ring-opening products

The electrochemical behavior of the hydrolysis products of oxadiazon was studied by cyclic and square-wave voltammetry using a glassy carbon electrode. Maximum currents were obtained at pH 12.8 in an aqueous electrolyte solution containing 30% ethanol and the current did not decrease with time showing that there was little adsorption of the reaction products on the electrode surface. The hydrolysis products of oxadiazon were identi®ed, after isolation and puri®cation, as 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl)-2-ethoxycarbonylhydrazine (Oxa1) and 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) with redox potentials 0.6Vand 70.1V (vs. Ag=AgCl), respectively. Based on the electrochemical behavior of 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) a simple electroanalytical procedure was developed for the determination of oxadiazon in commercial products used in the treatment of rice crops in Portugal that contain oxadiazon as the active ingredient. The detection limit was 161074 M, the mean content and relative standard deviation obtained for seven samples of two different commercial products by the electrochemical method were 28.4 0.8% (Ronstar) and 1.9 0.2% (Ronstar GR), and the recoveries were 100.3 5.4% and 101.1 5.3 %, respectively.

Determination of polyphenols in wines by reaction with 4-aminoantipyrine and photometric flow-injection analysis

A new flow-injection analytical procedure is proposed for the determination of the total amount of polyphenols in wines; the method is based on the formation of a colored complex between 4-aminoantipyrine and phenols, in the presence of an oxidizing reagent. The oxidizing agents hexacyanoferrate(III), peroxodisulfate, and tetroxoiodate(VII) were tested. Batch trials were first performed to select appropriate oxidizing agents, pH, and concentration ratios of reagents, on the basis of their effect on the stability of the colored complex. Conditions selected as a result of these trials were implemented in a flow-injection analytical system in which the influence of injection volume, flow rate, and reaction- coil length, was evaluated. Under the optimum conditions the total amount of polyphenols, expressed as gallic acid, could be determined within a concentration range of 36 to 544 mg L–1, and with a sensitivity of 344 L mol–1 cm–1 and an RSD <1.1%. The reproducibility of analytical readings was indicative of standard deviations <2%. Interference from sugars, tartaric acid, ascorbic acid, methanol, ammonium sulfate, and potassium chloride was negligible. The proposed system was applied to the determination of total polyphenols in red wines, and enabled analysis of approximately 55 samples h–1. Results were usually precise and accurate; the RSD was <3.9% and relative errors, by the Folin–Ciocalteu method, <5.1%.

Ground reaction forces and plantar pressure distribution during occasional loaded gait

This study compared the ground reaction forces (GRF) and plantar pressures between unloaded and occasional loaded gait. The GRF and plantar pressures of 60 participants were recorded during unloaded gait and occasional loaded gait (wearing a backpack that raised their body mass index to 30); this load criterion was adopted because is considered potentially harmful in permanent loaded gait (obese people). The results indicate an overall increase (absolute values) of GRF and plantar pressures during occasional loaded gait (p < 0.05); also, higher normalized (by total weight) values in the medial midfoot and toes, and lower values in the lateral rearfoot region were observed. During loaded gait the magnitude of the vertical GRF (impact and thrust maximum) decreased and the shear forces increased more than did the proportion of the load (normalized values). These data suggest a different pattern of GRF and plantar pressure distribution during occasional loaded compared to unloaded gait.

In-shoe plantar pressures and ground reaction forces during overweight adults' overground walking

Purpose: Because walking is highly recommended for prevention and treatment of obesity and some of its biomechanical aspects are not clearly understood for overweight people, we compared the absolute and normalized ground reaction forces (GRF), plantar pressures, and temporal parameters of normal-weight and overweight participants during overground walking. Method: A force plate and an in-shoe pressure system were used to record GRF, plantar pressures (foot divided in 10 regions), and temporal parameters of 17 overweight adults and 17 gender-matched normal-weight adults while walking. Results: With high effect sizes, the overweight participants showed higher absolute medial-lateral and vertical GRF and pressure peaks in the central rearfoot, lateral midfoot, and lateral and central forefoot. However, analyzing normalized (scaled to body weight) data, the overweight participants showed lower vertical and anterior-posterior GRF and lower pressure peaks in the medial rearfoot and hallux, but the lateral forefoot peaks continued to be greater compared with normal-weight participants. Time of occurrence of medial-lateral GRF and pressure peaks in the midfoot occurred later in overweight individuals. Conclusions: The overweight participants adapted their gait pattern to minimize the consequences of the higher vertical and propulsive GRF in their musculoskeletal system. However, they were not able to improve their balance as indicated by medial-lateral GRF. The overweight participants showed higher absolute pressure peaks in 4 out of 10 foot regions. Furthermore, the normalized data suggest that the lateral forefoot in overweight adults was loaded more than the proportion of their extra weight, while the hallux and medial rearfoot were seemingly protected.

Modulação do estado redox em bactérias por quinoxalinas

As quinoxalinas são compostos heterocíclicos que têm, entre outras, capacidades antimicrobianas, inclusivamente contra bactérias resistentes aos antimicrobianos convencionais. Os mecanismos pelos quais estes compostos exercem a sua atividade ainda não está completamente esclarecido. O objetivo do presente estudo é avaliar o efeito redox em sinergismo/antagonismo com as quinoxalinas em modelos de bactérias com e sem resistências a antimicrobianos. No que se refere aos compostos foram utilizados a quinoxalina 1,4-dióxido (QNX), 2-metil-3-benzilquinoxalina-1,4-dióxido (2M3BQNX), 2-metilquinoxalina-1,4-dióxido (2MQNX) e a 2-amino-3-cianoquinoxalina-1,4-dióxido (2A3CQNX). Quanto aos modelos procariotas, foram utilizados a Salmonella enterica, Klebsiella pneumoniae, Enterococcus faecalis, Staphylococcus saprophyticus, Enterobacter aerogenes, Enterobacter cloacae, Staphylococcus aureus ATCC 25923, Methicillin-resistant Staphylococcus aureus ATCC 43300, Escherichia coli TEM 201 e Escherichia coli TEM 180. Nos compostos químicos em que se verificou a Concentração Mínima Inibitória (CMI), realizou-se o estudo do comportamento do crescimento bacteriano. Relativamente ao estado redox, foi avaliado para cada estirpe sensível, através do rácio GSH/GSSG, nas doses inibitórias e não inibitórias de cada composto. Os resultados apresentam que todos os compostos testados, à exceção do 2M3BQNX, têm atividade antimicrobiana na maioria das estirpes, excetuando a E. faecalis e a S. saprophyticus. Os rácios GSH/GSSG apontam para o efeito oxidante em K. pneumoniae e S. enterica e antioxidante na E. aerogenes. A conclusão do estudo sugere que os compostos apresentam elevada capacidade antibacteriana e influência no equilíbrio redox das bactérias, podendo contribuir para o esclarecimento do mecanismo de ação dos derivados das quinoxalinas 1-4 dióxido, nas bactérias.

One-step preparation of optically transparent Ni-Fe oxide film electrocatalyst for oxygen evolution reaction

Optically transparent cocatalyst film materials is very desirable for improved photoelectrochemical (PEC)oxygen evolution reaction (OER) over light harvesting photoelectrodes which require the exciting light to irradiate through the cocatalyst side, i.e., front-side illumination. In view of the reaction overpotential at electrode/electrolyte interface, the OER electrocatalysts have been extensively used as cocatalysts for PEC water oxidation on photoanode. In this work, the feasibility of a one-step fabrication of the transparent thin film catalyst for efficient electrochemical OER is investigated. The Ni-Fe bimetal oxide films, 200 nm in thickness, are used for study. Using a reactive magnetron co-sputtering technique, transparent(> 50% in wavelength range 500-2000 nm) Ni-Fe oxide films with high electrocatalytic activities were successfully prepared at room temperature. Upon optimization, the as-prepared bimetal oxide film with atomic ratio of Fe/Ni = 3:7 demonstrates the lowest overpotential for the OER in aqueous KOH solution, as low as 329 mV at current density of 2 mA cm 2, which is 135 and 108 mV lower than that of as-sputtered FeOx and NiOx thin films, respectively. It appears that this fabrication strategy is very promising to deposit optically transparent cocatalyst films on photoabsorbers for efficient PEC water splitting.

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.

The influence of gait cadence on the ground reaction forces and plantar pressures during load carriage of young adults

Biomechanical gait parameters—ground reaction forces (GRFs) and plantar pressures—during load carriage of young adults were compared at a low gait cadence and a high gait cadence. Differences between load carriage and normal walking during both gait cadences were also assessed. A force plate and an in-shoe plantar pressure system were used to assess 60 adults while they were walking either normally (unloaded condition) or wearing a backpack (loaded condition) at low (70 steps per minute) and high gait cadences (120 steps per minute). GRF and plantar pressure peaks were scaled to body weight (or body weight plus backpack weight). With medium to high effect sizes we found greater anterior-posterior and vertical GRFs and greater plantar pressure peaks in the rearfoot, forefoot and hallux when the participants walked carrying a backpack at high gait cadences compared to walking at low gait cadences. Differences between loaded and unloaded conditions in both gait cadences were also observed.