Kinetics of the photocatalysed oxidation of NO in the ISO 22197 reactor

The photocatalytic reactor described in the NOx removal ISO 22197-1:2007 is used to study the kinetics of the process, using a film of P25 TiO2 which has either been conventionally pre-irradiated in a stream of air, or unconventionally in a stream of NO (1 ppmv). In the former case it is shown that the system does not achieve steady state exit levels of NO, probably due to the gradual accumulation of HNO3 on the surface of the photocatalyst. The NO-preconditioned TiO2 film demonstrated excellent steady-state levels when monitored as a function of NO concentration, [NO] and UV irradiance, ρ. However, in this case the photocatalytic reaction under study is NOT NOx removal, but the conversion of NO to NO2. It is shown that the kinetics of this steady state process fit very well to a kinetic expression based on a disrupted adsorption reaction mechanism, which has also been used by others to fit their observed (non-steady state) kinetics for NOx removal on conventionally-(air) preconditioned films of P25. The appropriateness of this model for either system is questioned, since in both systems the kinetics appear to have a significant mass transport element. These findings suggest that mass transport and non-steady-state kinetics are likely to be significant features for most active photocatalytic samples, where the %NO conversion is >7%, and so limits the usefulness of the NOx removal ISO 22197-1:2007.

Modelling the nonlinear behaviour and fracture process of AS4/PEKK thermoplastic composite under shear loading

The accurate determination of non-linear shear behaviour and fracture toughness of continuous carbon-fibre/polymer composites remains a considerable challenge. These measurements are often necessary to generate material parameters for advanced computational damage models. In particular, there is a dearth of detailed shear fracture toughness characterisation for thermoplastic composites which are increasingly generating renewed interest within the aerospace and automotive sectors. In this work, carbon fibre (AS4)/ thermoplastic Polyetherketoneketone (PEKK) composite V-notched cross-ply specimens were manufactured to investigate their non-linear response under pure shear loading. Both monotonic and cyclic loading were applied to study the shear modulus degradation and progressive failure. For the first time in the reported literature, we use the essential work of fracture approach to measure the shear fracture toughness of continuous fibre reinforced composite laminates. Excellent geometric similarity in the load-displacement curves was observed for ligament-scaled specimens. The laminate fracture toughness was determined by linear regression, of the specific work of fracture values, to zero ligament thickness, and verified with computational models. The matrix intralaminar fracture toughness (ply level fracture toughness), associated with shear loading was determined by the area method. This paper also details the numerical implementation of a new three-dimensional phenomenological model for carbon fibre thermoplastic composites using the measured values, which is able to accurately represent the full non-linear mechanical response and fracture process. The constitutive model includes a new non-linear shear profile, shear modulus degradation and load reversal. It is combined with a smeared crack model for representing ply-level damage initiation and propagation. The model is shown to accurately predict the constitutive response in terms of permanent plastic strain, degraded modulus as well as load reversal. Predictions are also shown to compare favourably with the evolution of damage leading to final fracture.

“CAPACITAR O DOENTE ONCOLÓGICO COM DOENÇA AVANÇADA E/OU O CUIDADOR PARA A GESTÃO DA DOR EM DOMICÍLIO” “EMPOWER THE ONCOLOGIC PATIENT WITH ADVANCED DISEASE AT HOME AND/OR THE CAREGIVER FOR THE MANAGEMENT OF PAIN”

RESUMO ABSTRACT Comunicações orais e Posters Oral communications and posters Este formulário, após preenchido, e aceites as condições descritas no regulamento das Comunicações orais e Posters deve ser enviado para isnr@porto.ucp.pt After complete this form and accept the conditions described in the oral communications and posters regulation, please sent to isnr@porto.ucp.pt Tipo de comunicação (comunicação oral ou poster): Comunicação oral Type of communication: (oral communication or poster): Oral comunication Título (Title): “CAPACITAR O DOENTE ONCOLÓGICO COM DOENÇA AVANÇADA E/OU O CUIDADOR PARA A GESTÃO DA DOR EM DOMICÍLIO” “EMPOWER THE ONCOLOGIC PATIENT WITH ADVANCED DISEASE AT HOME AND/OR THE CAREGIVER FOR THE MANAGEMENT OF PAIN” Autoria (Authors): CORREIA, Isabel* (doutoranda em Enfermagem na Universidade de Lisboa) LOPES, Manuel (orientador do projeto) Afiliação dos autores (Authors affiliation): – Professora adjunta na Universidade de Évora, Escola Superior de Enfermagem de São João de Deus de Évora, doutoranda em enfermagem Universidade de Lisboa - – Professor Doutor em Enfermagem, Diretor da Escola Superior de Enfermagem de São João de Deus de Évora, Universidade de Évora E-mail: icorreia@uevora.pt - 964078445 mjl@uevora.pt Resumo (3000 caracteres com espaços) INTRODUÇÃO Um dos sintomas mais frequentes no doente oncológico com doença avançada é a dor. Segundo Palliative Care in European, a dor oncológica, tem uma importância especial porque o cancro é a segunda causa de morte em Portugal e por existir dor moderada a intensa em mais de 90% dos doentes em situação oncológica terminal. O desenvolvimento de um programa estruturado de intervenção de enfermagem que vá de encontro às necessidades do doente oncológico com doença avançada e/ou cuidador, relativamente à gestão da dor, poderá ter um impacto muito significativo no controlo da dor e de outros sintomas. OBJETIVOS Avaliar o efeito de um programa de Intervenção de Enfermagem na capacidade de gestão da dor por parte do doente oncológico com doença avançada e/ou o cuidador em domicílio. MATERIAIS E MÉTODOS A implementação do programa tem a duração prevista para 6 semanas. Compreende duas sessões educativas, três telefonemas e uma sessão de avaliação final. O programa foi elaborado, após uma Revisão sistemática de Literatura, com base no programa “ THE PRO-SELF”, nas Orientações Genéricas preconizadas pelo Plano Nacional de Luta Contra a dor e na Intervenção de enfermagem “Controle da Dor” da Nursing Intervention Classification (NIC). RESULTADOS O projeto encontra-se na fase de implementação e avaliação do programa educativo. No início os doentes não apresentam informação relativamente à gestão da dor, no final demonstram capacidade para a monitorização da dor e de outros sintomas e para a gestão da terapêutica, realizando os registos num diário de bordo. A literacia, a situação clínica e a disponibilidade interferem na capacidade de gestão. A proximidade da morte e a alteração do estado de consciência interferem na autonomia e na tomada de decisão. CONCLUSÃO Em fase de colheita e análise de dados. REFERÊNCIAS BIBLIOGRÁFICAS 1. FREIXO, Manuel. Metodologia Cientifica - Fundamentos, Metodos e Tecnicas. s.l. : Piaget, 2011. 2. Bulechek, Gloria M. e etal. Classificaçaõ das Intervenções de Enfermagem (NIC). Rio de Janeiro : elsevier, 2010. 3. Tsigaroppoulos, T. e etal. Problems faced by relatives caring for cancer patients at home. International Journal Of Nursing Practice. 15, 2009, Vol. 1, Nursing Pratice. 4. west, C.:Dodd,M., et al. Pain Control Program-an effective approach for cancer pain management. Oncology Nursing Forum. 1, 2003, Vol. 30, Oncology Nursing. 5. NR/rdonlyres/6861126B-C57A-46E1-B065-316C0CF8DACD/0/ControlodaDor.pdf, . (2008). . Consultado em 30 de Novembro de 2012 a partir de. Direcção-Geral da Saúde . http://www.portaldasaude.pt. [Online] 2008. [Citação: 30 de Novembro de 2012.] http://www.portaldasaude.pt/NR/rdonlyres/6861126B-C57A-46E1-B065-316COCF8DACD/0/Controlodador.pdf . Abstract (3000 characters with spaces) INTRODUCTION One of the most frequent symptoms in oncological patient with advanced disease is pain. According to Palliative Care in European, oncological pain, has a special importance because the cancer is the second most common cause of death in Portugal and there is moderate to severe pain in more than 90 % of patients in oncological terminal situation. The development of a structured program of nursing intervention that will meet the needs of the oncological patient with advanced disease and/or caregiver at home on pain management, will be able to provide for the management of pain, increasing knowledge for the control of pain while minimizing the associated symptoms that influence the quality of life of the patient and the caregiver's anxiety. PURPOSE/GOAL/AIM To evaluate the effect of an educational program of Nursing Intervention on pain management by the oncological patient with advanced disease and/or caregiver. RESEARCH/PROBLEM What is the effect of a structured program of nursing intervention directed to the patient and/or oncological patient caregiver with advanced disease at home, in the management of pain? METHODOLOGY Almost experimental study, with assessment of the management capacity of the oncological patient pain with advanced disease at home and/or informal caregiver, before and after the intervention of nursing (educational program) and transverse evaluation throughout the study. Population: oncological patients with advanced disease at home, with more than 18 years, and or family caregiver, attending an Oncology Unit – Hospital during the day. RESULTS Made an application in an Oncology service in oncological patients with advanced disease at home, it was found that at the beginning the patients did not present information regarding pain management, at the end demonstrated capacity for monitoring of pain and other symptoms and therapeutic management, performing a logbook records. CONCLUSION In the process of collection and analysis of data. KEYWORDS Educational Program; oncological patient; oncological pain.

Advanced optical modulation and format conversion

Over the years, the increased search and exchange of information lead to an increase of traffic intensity in todays optical communication networks. Coherent communications, using the amplitude and phase of the signal, reappears as one of the transmission techniques to increase the spectral efficiency and throughput of optical channels. In this context, this work present a study on format conversion of modulated signals using MZI-SOAs, based exclusively on all- optical techniques through wavelength conversion. This approach, when applied in interconnection nodes between optical networks with different bit rates and modulation formats, allow a better efficiency and scalability of the network. We start with an experimental characterization of the static and dynamic properties of the MZI-SOA. Then, we propose a semi-analytical model to describe the evolution of phase and amplitude at the output of the MZI-SOA. The model’s coefficients are obtained using a multi-objective genetic algorithm. We validate the model experimentally, by exploring the dependency of the optical signal with the operational parameters of the MZI-SOA. We also propose an all-optical technique for the conversion of amplitude modulation signals to a continuous phase modulation format. Finally, we study the potential of MZI-SOAs for the conversion of amplitude signals to QPSK and QAM signals. We show the dependency of the conversion process with the operational parameters deviation from the optimal values. The technique is experimentally validated for QPSK modulation.

Advanced monitoring of South Portugal water bodies towards WFD

The challenge on implementation of the EU Water Framework Directive (WFD) fosters the development of new monitoring methods and approaches. It is now commonly accepted that the use of classical monitoring campaigns in discrete point is not sufficient to fully assess and describe a water body. Due to this the WFD promote the use of modelling techniques in surface waters to assist all phases of the process, from characterisation and establishment of reference conditions to identification of pressures and assessment of impact. The work presented in this communication is based on these principles. A classical monitoring of the water status of the main transitional water bodies of Algarve (south of Portugal) is combined with advanced in situ water profiling and hydrodynamic, water quality and ecological modelling of the systems to build a complete description of its state. This approach extends spatially and temporally the resolution of the classical point sampling. The methodology was applied during a 12 month program in Ria Formosa coastal lagoon, the Guadiana estuary and the Arade estuary. The synoptic profiling uses an YSI 6600 EDS multi-parameter system attached to a boat and a GPS receiver to produce monthly synoptic maps of the systems. This data extends the discrete point sampling with laboratory analysis performed monthly in several points of each water body. The point sampling is used to calibrate the profiling system and to include variables, such as nutrients, not measured by the sensors. A total of 1427 samplings were performed for physical and chemical parameters, chlorophyll and microbiologic contamination in the water column. This data is used to drive the hydrodynamic, transport and ecological modules of the MOHID water modelling system (www.mohid.com), enabling an integrate description of the water column.

Analysis of chromium behaviour and speciation during the electrodialytic process

The interest in chromium (Cr) arises from the widespread use of this heavy metal in various industrial processes that cause its release as liquid, solid and gaseous waste into the environment. The impact of Cr on the environment and living organisms primarily depends on its chemical form, since Cr(III) is an essential micronutrient for humans, other animals and plants, and Cr(VI) is highly toxic and a known human carcinogen. This study aimed to evaluate if the electrodialytic process (ED) is an appropriate treatment for Cr removal, through a critical overview of Cr speciation, before and after the ED experiments, to assess possible Cr(III)-Cr(VI) interconversions during the treatment. ED was the treatment technique applied to two types of matrices containing Cr: chromate copper arsenate (CCA) contaminated soil and municipal solid waste incineration (MSWI) fly ash. In order to study Cr remediation, three EDR set-ups were used: a new set-up, the combined cell (2/3C or 3/2C), with three compartments, alternating current between two anodes and different initial experimental conditions, one set-up with three compartments (3C cell) and the other set-up with two compartments (2C cell). The Cr removal rates obtained in this study were between 10-36% for the soil, and 1-13% for the fly ash. The highest Cr removal rates were achieved in the 26 days experiments: 36% for the soil, 13% for the fly ash. Regarding the 13 days experiments, the highest Cr removal rates were attained with the 2/3C set-up: 24% for the soil, 5% for the fly ash. The analysis of Cr(VI) was performed before and after ED experiments to evaluate eventual changes in Cr speciation during the treatment. This analysis was conducted by two methods: USEPA Method 3060A, for the extraction of Cr(VI); and Hach Company Method 8023, for the detection of Cr(VI). Despite the differences in Cr total concentration, both matrices presented a similar speciation, with Cr(III) being the main species found and Cr(VI) less than 3% of Cr total, before and after the treatment. For fly ash, Cr(VI) was initially below the detection limit of the method and remained that way after the treatment. For soil, Cr(VI) decreased after the treatment. Oxidation of Cr(III) to Cr(VI) did not occur during the ED process since there was no increase in Cr(VI) in the matrices after the treatment. Hence, the results of this study indicate that ED is an appropriate technique to remediate matrices containing Cr because it contributes to Cr removal, without causing Cr(III)-Cr(VI) interconversions.

Removal of organic contaminants from wastewater using the electrodialytic process

Pharmaceuticals and personal care products (PPCPs) are widely used on a daily basis. After their usage they reach the wastewater treatment plants (WWTPs). These compounds have different physico-chemical characteristics, which makes them difficult to completely remove in the WWTPs, througth conventional treatments. Currently, there is no legislation regarding PPCPs thresholds in effluent discharge. But, even at vestigial concentrations, these compounds enclose environmental risks due to, e.g., endocrine disruption potential. There is a need of alternative techniques for their removal in WWTPs. The main goal of this work was to assess the use of electrodialytic (ED) process to remove PPCPs from the effluent to be discharged. A two-compartment ED cell was used testing (i) the effluent position in the cell (anode and cathode compartment); (ii) the use of anion (AEM) and cation exchange membrane (CEM); (iii) the treatment period (6, 12 and 24 hours); (iv) effluent recirculation and current steps; (v) the feasibility of sequential treatments. Phosphorus (P) removal from effluent and energetic costs associated to the process were also evaluated. Five PPCPs were studied – caffeine (CAF), bisphenol A (BPA), 17 β-estradiol (E2), ethinyl estradiol (EE2) and oxybenzone (MBPh). The ED process showed to be effective in the removal when effluent is in the anode compartment. Oxidation is suggested to be the main removal process, which was between 88 and 96%, for all the compounds, in 6 hours. Nevertheless, the presence of intermediates and/or by-products was also observed in some cases. Effluent recirculation should have a retention time in the ED cell big enough to promote removal whereas the current steps (effluent in anode compartment) slightly increased removal efficiencies (higher than 80% for all PPCPs). The sequential set of ED treatment (effluent in anode compartment) showed to be effective during both periods with a removal percentage between 80 and 95% and 73 to 88% in the case of AEM and CEM, respectively. Again, the main removal process is strongly suggested to be oxidation in the anode compartment. However, there was an increase of BOD5 and COD, which might be explained by effluent spiking, these parameters limiting the effluent discharge. From these treatments, the use of AEM, enhanced the P removal from effluent to minimize risk of eutrophication. Energetic costs of the best set-up (6 hours) are approximately 0,8€/m3 of wastewater, a value considered low, attending to the prices of other treatment processes.

Peroxisomal beta-oxidation--a metabolic pathway with multiple functions.

Fatty acid degradation in most organisms occurs primarily via the beta-oxidation cycle. In mammals, beta-oxidation occurs in both mitochondria and peroxisomes, whereas plants and most fungi harbor the beta-oxidation cycle only in the peroxisomes. Although several of the enzymes participating in this pathway in both organelles are similar, some distinct physiological roles have been uncovered. Recent advances in the structural elucidation of numerous mammalian and yeast enzymes involved in beta-oxidation have shed light on the basis of the substrate specificity for several of them. Of particular interest is the structural organization and function of the type 1 and 2 multifunctional enzyme (MFE-1 and MFE-2), two enzymes evolutionarily distant yet catalyzing the same overall enzymatic reactions but via opposite stereochemistry. New data on the physiological roles of the various enzymes participating in beta-oxidation have been gathered through the analysis of knockout mutants in plants, yeast and animals, as well as by the use of polyhydroxyalkanoate synthesis from beta-oxidation intermediates as a tool to study carbon flux through the pathway. In plants, both forward and reverse genetics performed on the model plant Arabidopsis thaliana have revealed novel roles for beta-oxidation in the germination process that is independent of the generation of carbohydrates for growth, as well as in embryo and flower development, and the generation of the phytohormone indole-3-acetic acid and the signal molecule jasmonic acid.

Enhancement of ultrafiltration process by pretreatment in recovery of hemicelluloses from wood extracts

Hemicelluloses are potential raw material for several items produced in future wood-based biorefineries. One possible method for recovering hemicelluloses from wood extracts is ultrafiltration (UF). However, low filtration capacities and severe fouling restrict the use of tight UF membranes in the treatment of wood extracts. The lack of suitable commercial membranes creates a need for pretreatment which would decrease fouling and increase the filtration capacity. This thesis focuses on the evaluation of the possibility to improve the filtration capacity and decrease fouling with the pretreatment of wood extracts. Methods which remove harmful compounds and methods which degrade them are studied, as well as combinations of the methods. The tested pretreatments have an influence on both the concentration of different compounds and the molecular mass distribution of the compounds in the extract. This study revealed that in addition to which kind of compounds were removed, also the change in molecular size distribution affected the filtration capacity significantly. It was shown that the most harmful compounds for the filtration capacity of the hydrophobic 5 kDa membrane were the ones capable of permeating the membrane and fouling also the inner membrane structure. Naturally, the size of the most harmful compounds depends on the used UF membrane and is thus case-specific. However, in the choice of the pretreatment method, the focus should be on the removal of harmful compound sizes rather than merely on the total amount of removed foulants. The results proved that filtration capacity can be increased with both adsorptive and oxidative pretreatments even by hundreds of per cents. For instance, the use of XAD7 and XAD16 adsorbents increased the average flux in the UF of a birch extract from nearly zero to 107 kg/(m2h) and 175 kg/(m2h), respectively. In the treatment of a spruce extract, oxidation by pulsed corona discharge (PCD) increased the flux in UF from 46 kg/(m2h) to 158 kg/(m2h). Moreover, when a birch extract batch was treated with laccase enzyme, the flux in UF increased from 15 kg/(m2h) to 36 kg/(m2h). However, fouling was decreased only by adsorptive pretreatment while oxidative methods had a negligible or even negative impact on it. This demonstrates that filtration capacity and fouling are affected by different compounds and mechanisms. The results of this thesis show that filtration capacity can be improved and fouling decreased through appropriate pretreatment. However, the choice of the best possible pretreatment is case-specific and depends on the wood extract and the membrane used. Finding the best option requires information on the extract content and membrane characteristics as well as on the filtration performance of the membrane in the prevailing conditions and a multivariate approach. On the basis of this study, it can be roughly concluded that adsorptive pretreatment improves the filtration capacity and decreases fouling rather reliably, but it may lead to significant hemicellulose losses. Oxidation reduces the loss of valuable hemicelluloses and could improve the filtration capacity, but fouling challenges may remain. Combining oxidation with adsorptive pretreatment was not a solution for avoiding hemicellulose losses in the tested cases.

The adoption of advanced feed-in tariffs in Ontario : a case of institutional layering

En mai 2009, l’Ontario a adopté la Loi sur l’énergie verte et devint ainsi la première juridiction en Amérique du Nord à promouvoir l’énergie renouvelable par le biais de tarifs de rachat garantis. En novembre 2010, dans son Plan énergétique à long terme, la province s’est engagée à déployer 10,700 MW en capacité de production d’énergie renouvelable non-hydroélectrique par 2018. Il s’agit de la cible de déploiement la plus élevée dans ce secteur au Canada. Les infrastructures de production et de distribution d’électricité comprennent des coûts d’installation élevés, une faible rotation des investissements et de longs cycles de vie, facteurs qui servent habituellement à ancrer les politiques énergétiques dans une dynamique de dépendance au sentier. Depuis le début des années 2000, cependant, l’Ontario a commencé à diverger de sa traditionnelle dépendance aux grandes centrales hydroélectriques, aux centrales à charbon et aux centrales nucléaires par une série de petits changements graduels qui feront grimper la part d’énergie renouvelable dans le mix énergétique provincial à 15% par 2018. Le but de ce mémoire est d’élucider le mécanisme de causalité qui a sous-tendu l’évolution graduelle de l’Ontario vers la promotion de l’énergie renouvelable par le biais de tarifs de rachat garantis et d’une cible de déploiement élevée. Ce mémoire applique la théorie du changement institutionnel graduel de Mahoney et Thelen au cas du développement de politiques d’énergie renouvelable en Ontario afin de mieux comprendre les causes, les modes et les effets du changement institutionnel. Nous découvrons que le contexte canadien de la politique énergétique favorise la sédimentation institutionnelle, c’est-à-dire un mode changement caractérisé par de petits gains favorisant l’énergie renouvelable. Ces gains s’accumulent pourtant en transformation politique importante. En Ontario, la mise sur pied d’une vaste coalition pour l’énergie renouvelable fut à l’origine du changement. Les premiers revendicateurs de politiques favorisant l’énergie renouvelable – les environnementalistes et les premières entreprises d’approvisionnement et de service en technologies d’énergie renouvelable – ont dû mettre sur pied un vaste réseau d’appui, représentant la quasi-totalité de la société ontarienne, pour faire avancer leur cause. Ce réseau a fait pression sur le gouvernement provincial et, en tant que front commun, a revendiqué l’énergie renouvelable non seulement comme solution aux changements climatiques, mais aussi comme solution à maints autres défis pressants de santé publique et de développement économique. La convergence favorable d’un nombre de facteurs contextuels a certes contribué à la réussite du réseau ontarien pour l’énergie renouvelable. Cependant, le fait que ce réseau ait trouvé des alliés au sein de l’exécutif du gouvernement provincial s’est révélé d’importance cruciale quant à l’obtention de politiques favorisant l’énergie renouvelable. Au Canada, les gouvernements provinciaux détiennent l’ultime droit de veto sur la politique énergétique. Ce n’est qu’en trouvant des alliés aux plus hauts échelons du gouvernement que le réseau ontarien pour l’énergie renouvelable a pu réussir.

Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds

Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involves catalysis.Solid acid catalysts are appealing since the nature of acid sites is known and their chemical behavior in acid catalyzed reactions can be rationalized by means of existing theories and models. Mixed oxides crystallizing in spinel structure are of special interest because the spinel lattice imparts extra stability to the catalyst under various reaction conditions so that theses systems have sustained activities for longer periods. The thesis entitled" Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds " presents the preparation ,characterization ,and activity studies of the prepared spinels were modified by incorporating other ions and by changing the stoichiometry.The prepared spinels exhibiting better catalytic activity towards the studied reactions with good product selectivity.Acid-base properties and cation distribution of the spinels were found to control the catalytic activity.

Low density lipoprotein undergoes oxidation within lysosomes in cells

The oxidised low density lipoprotein (LDL) hypothesis of atherosclerosis proposes that LDL undergoes oxidation in the interstitial fluid of the arterial wall. We have shown that aggregated (vortexed) nonoxidised LDL was taken up by J774 mouse macrophages and human monocyte-derived macrophages and oxidised intracellularly, as assessed by the microscopic detection of ceroid, an advanced lipid oxidation product. Confocal microscopy showed that the ceroid was located in the lysosomes. To confirm these findings, J774 macrophages were incubated with acetylated LDL, which is internalised rapidly to lysosomes, and then incubated (chase incubation) in the absence of any LDL. The intracellular levels of oxysterols, measured by HPLC, increased during the chase incubation period, showing that LDL must have been oxidised inside the cells. Furthermore, we found that this oxidative modification was inhibited by lipid-soluble antioxidants, an iron chelator taken up by fluid-phase pinocytosis and the lysosomotropic drug chloroquine, which increases the pH of lysosomes. The results indicate that LDL oxidation can occur intracellularly, most probably within lysosomes.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Low density lipoprotein undergoes oxidation within lysosomes in cells

The oxidized low density lipoprotein (LDL) hypothesis of atherosclerosis proposes that LDL undergoes oxidation in the interstitial fluid of the arterial wall. We have shown that aggregated (vortexed) nonoxidized LDL was taken up by J774 mouse macrophages and human monocyte-derived macrophages and oxidized intracellularly, as assessed by the microscopic detection of ceroid, an advanced lipid oxidation product. Confocal microscopy showed that the ceroid was located in the lysosomes. To confirm these findings, J774 macrophages were incubated with acetylated LDL, which is internalized rapidly to lysosomes, and then incubated (chase incubation) in the absence of any LDL. The intracellular levels of oxysterols, measured by HPLC, increased during the chase incubation period, showing that LDL must have been oxidized inside the cells. Furthermore, we found that this oxidative modification was inhibited by lipid-soluble antioxidants, an iron chelator taken up by fluid-phase pinocytosis and the lysosomotropic drug chloroquine, which increases the pH of lysosomes. The results indicate that LDL oxidation can occur intracellularly, most probably within lysosomes.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.