1,4-Diamino-2-butanone, a wide-spectrum microbicide, yields reactive species by metal-catalyzed oxidation

The alpha-aminoketone 1,4-diamino-2-butanone (DAB), a putrescine analogue, is highly toxic to various microorganisms, including Trypanosoma cruzi. However, little is known about the molecular mechanisms underlying DAB`s cytotoxic properties. We report here that DAB (pK(a) 7.5 and 9.5) undergoes aerobic oxidation in phosphate buffer, pH 7.4, at 37 degrees C, catalyzed by Fe(II) and Cu(II) ions yielding NH(4)(+) ion, H(2)O(2), and 4-amino-2-oxobutanal (oxoDAB). OxoDAB, like methylglyoxal and other alpha-oxoaldehydes, is expected to cause protein aggregation and nucleobase lesions. Propagation of DAB oxidation by superoxide radical was confirmed by the inhibitory effect of added SOD (50 U ml(-1)) and stimulatory effect of xanthine/xanthine oxidase, a source of superoxide radical. EPR spin trapping studies with 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) revealed an adduct attributable to DMPO-HO(center dot), and those with alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone or 3,5-dibromo-4-nitrosobenzenesulfonic acid, a six-line adduct assignable to a DAB(center dot) resonant enoyl radical adduct. Added horse spleen ferritin (HoSF) and bovine apo-transferrin underwent oxidative changes in tryptophan residues in the presence of 1.0-10 mM DAB. Iron release from HoSF was observed as well. Assays performed with fluorescein-encapsulated liposomes of cardiolipin and phosphatidylcholine (20:80) incubated with DAB resulted in extensive lipid peroxidation and consequent vesicle permeabilization. DAB (0-10 mM) administration to cultured LLC-MK2 epithelial cells caused a decline in cell viability, which was inhibited by preaddition of either catalase (4.5 mu M) or aminoguanidine (25 mM). Our findings support the hypothesis that DAB toxicity to several pathogenic microorganisms previously described may involve not only reported inhibition of polyamine metabolism but also DAB pro-oxidant activity. (C) 2011 Elsevier Inc. All rights reserved.

Horseradish peroxidase compound I as a tool to investigate reactive protein-cysteine residues: from quantification to kinetics

Proteins containing reactive cysteine residues (protein-Cys) are receiving increased attention as mediators of hydrogen peroxide signaling. These proteins are mainly identified by mining the thiol proteomes of oxidized protein-Cys in cells and tissues. However, it is difficult to determine if oxidation occurs through a direct reaction with hydrogen peroxide or by thiol-disulfide exchange reactions. Kinetic studies with purified proteins provide invaluable information about the reactivity of protein-Cys residues with hydrogen peroxide. Previously, we showed that the characteristic UV-Vis spectrum of horseradish peroxidase compound I, produced from the oxidation of horseradish peroxidase by hydrogen peroxide, is a simple, reliable, and useful tool to determine the second-order rate constant of the reaction of reactive protein-Cys with hydrogen peroxide and peroxynitrite. Here, the method is fully described and extended to quantify reactive protein-Cys residues and micromolar concentrations of hydrogen peroxide. Members of the peroxiredoxin family were selected for the demonstration and validation of this methodology. In particular, we determined the pK(a) of the peroxidatic thiol of rPrx6 (5.2) and the second-order rate constant of its reactions with hydrogen peroxide ((3.4 +/- 0.2) x 10(7) M(-1) s(-1)) and peroxynitrite ((3.7 +/- 0.4) x 10(5) M(-1) s(-1)) at pH 7.4 and 25 degrees C. (C) 2011 Elsevier Inc. All rights reserved.

Serum amyloid A induces reactive oxygen species (ROS) production and proliferation of fibroblast

Serum amyloid A (SAA) levels are elevated highly in acute phase response and elevated slightly and persistently in chronic diseases such as rheumatoid arthritis and diabetes. Given that fibroblasts exert profound effects on progression of inflammatory chronic diseases, the aim of this study was to investigate the response of fibroblasts to SAA. A dose-dependent increase in O(2)(-) levels was observed by treatment of fibroblasts with SAA (r = 0.99 and P <= 0.001). In addition, the expression of p47-phox was up-regulated by SAA (P < 0.001) and diphenyliodonium (DPI), a nicotinamide adenine dinucleotide phosphate (NADPH) oxidase inhibitor, reduced the release of O(2)(-) by 50%. Also, SAA raised fibroblast proliferation (P < 0.001) and this effect was completely abolished by the addition of anti-oxidants (P < 0.001). These findings support the notion that, in chronic inflammatory sites, SAA activated fibroblast proliferation and ROS production.

The role of mitochondrial DNA damage in the citotoxicity of reactive oxygen species

Mitochondria contain their own genome, a small circular molecule of around 16.5 kbases. The mitochondrial DNA (mtDNA) encodes for only 13 polypeptides, but its integrity is essential for mitochondrial function, as all 13 proteins are regulatory subunits of the oxidative phosphorylation complexes. Nonetheless, the mtDNA is physically associated with the inner mitochondrial membrane, where the majority of the cellular reactive oxygen species are generated. In fact, the mitochondrial DNA accumulates high levels of oxidized lesions, which have been associated with several pathological and degenerative processes. The cellular responses to nuclear DNA damage have been extensively studied, but so far little is known about the functional outcome and cellular responses to mtDNA damage. In this review we will discuss the mechanisms that lead to damage accumulation and the in vitro models we are establishing to dissect the cellular responses to oxidative damage in the mtDNA and to sort out the differential cellular consequences of accumulation of damage in each cellular genome, the nuclear and the mitochondrial genome.

Organotellurides as precursors of reactive organometallics

Reaction of organotellurides with easily available organometallics leads to a fast and clean tellurium/metal exchange reaction, allowing the preparation of a range of functionalized organometallics with C-sp(3), C-sp(2), and C-sp hybridization carbanionic centers. Some synthetic applications of the tellurium/metal exchange reactions are discussed.

Effects of a high fat diet on liver mitochondria: increased ATP-sensitive K(+) channel activity and reactive oxygen species generation

High fat diets are extensively associated with health complications within the spectrum of the metabolic syndrome. Some of the most prevalent of these pathologies, often observed early in the development of high-fat dietary complications, are non-alcoholic fatty liver diseases. Mitochondrial bioenergetics and redox state changes are also widely associated with alterations within the metabolic syndrome. We investigated the mitochondrial effects of a high fat diet leading to non-alcoholic fatty liver disease in mice. We found that the diet does not substantially alter respiratory rates, ADP/O ratios or membrane potentials of isolated liver mitochondria. However, H(2)O(2) release using different substrates and ATP-sensitive K(+) transport activities are increased in mitochondria from animals on high fat diets. The increase in H(2)O(2) release rates was observed with different respiratory substrates and was not altered by modulators of mitochondrial ATP-sensitive K(+) channels, indicating it was not related to an observed increase in K(+) transport. Altogether, we demonstrate that mitochondria from animals with diet-induced steatosis do not present significant bioenergetic changes, but display altered ion transport and increased oxidant generation. This is the first evidence, to our knowledge, that ATP-sensitive K(+) transport in mitochondria can be modulated by diet.

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (lambda = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L(-1) NaCl + 0.5 mol L(-1) H(2)SO(4) solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L(-1) NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min(-1) and 0.069 min(-1), for Pt and Pt/Ti electrodes, respectively.

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Heterogeneous photocatalytic degradation of reactive dyes in aqueous TiO(2) suspensions: Decolorization kinetics

This work assesses the photocatalytic (TiO(2)/UV) degradation of a simulated reactive dye bath (Black 5, Red 239, Yellow 17, and auxiliary chemicals). Color removal was monitored by spectrophotometry. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 30 min of irradiation, it was achieved 97% and 40% of color removal with photocatalysis and photolysis, respectively. No mineralization occurred within 30 min. A kinetic model composed of two, first-order in-series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 2.6 min(-1) and the second k(2) = 0.011 min(-1). The fast decolorization of Reactive Black 5 dye is an indication that the number of azo and vinylsulfone groups in the dye molecule maybe a determining factor for the increased photolytic and photocatalytic color removal and degradation rates. (C) 2008 Elsevier B.V. All rights reserved.

Modeling Information Diffusion in University Libraries: Assessing Peer Interaction Patterns as a Complex Dynamic System

This presentation was offered as part of the CUNY Library Assessment Conference, Reinventing Libraries: Reinventing Assessment, held at the City University of New York in June 2014.

PERFORMANCE EVOLUTION OF PEER TO PEER NETWORKS

This thesis work concerns about the Performance evolution of peer to peer networks, where we used different distribution technique’s of peer distribution like Weibull, Lognormal and Pareto distribution process. Then we used a network simulator to evaluate the performance of these three distribution techniques.During the last decade the Internet has expanded into a world-wide network connecting millions of hosts and users and providing services for everyone. Many emerging applications are bandwidth-intensive in their nature; the size of downloaded files including music and videos can be huge, from ten megabits to many gigabits. The efficient use of network resources is thus crucial for the survivability of the Internet. Traffic engineering (TE) covers a range of mechanisms for optimizing operational networks from the traffic perspective. The time scale in traffic engineering varies from the short-term network control to network planning over a longer time period.Here in this thesis work we considered the peer distribution technique in-order to minimise the peer arrival and service process with three different techniques, where we calculated the congestion parameters like blocking time for each peer before entering into the service process, waiting time for a peers while the other peer has been served in the service block and the delay time for each peer. Then calculated the average of each process and graphs have been plotted using Matlab to analyse the results

En utvärdering av Android och Iphone : För utveckling av webbtjänstunderstödda applikationer ämnade för intern distribution

Tack vare bättre och bättre förutsättningar för utveckling av mobila applikationer, samt utbredning av internetbaserade tjänster, presenteras här ett underlag inför val av mobil utvecklingsplattform. De undersökta plattformarna är Android och Iphone på grund av deras växande utbredning på smartphonemarknaden. Studien presenterar förutsättningar för att utveckla webbtjänst-understödda applikationer för intern distribuering. Ett visuellt tilltalande användargränssnitt är också i fokus för den typen av applikation studien riktar sig mot.Vi har kommit fram till att Android är lättare att lära sig om man kommer ifrån en Java- eller .Netmiljö samt lättare att distribuera. Iphone har däremot bättre stöd för att utveckla grafiskt tilltalande applikationer. Båda plattformarna har dock bristfälligt stöd för kommunikation via webbtjänster. Detta resultat uppnåddes genom litteraturstudier, samt en fallstudie där vi utvecklade applikationer med fokus på just webbtjänstkommunikation, intern distribuering samt ett tilltalande användargränssnitt.

IT­-Forensisk undersökning av flyktigt minne : På Linux och Android enheter

Att kunna gör en effektiv undersökning av det flyktiga minnet är något som blir viktigare ochviktigare i IT-forensiska utredningar. Dels under Linux och Windows baserade PC installationermen också för mobila enheter i form av Android och enheter baserade andra mobila opperativsy-stem.Android använder sig av en modifierad Linux-kärna var modifikationer är för att anpassa kärnantill de speciella krav som gäller för ett mobilt operativsystem. Dessa modifikationer innefattardels meddelandehantering mellan processer men även ändringar till hur internminnet hanteras ochövervakas.Då dessa två kärnor är så pass nära besläktade kan samma grundläggande principer användas föratt dumpa och undersöka minne. Dumpningen sker via en kärn-modul vilket i den här rapportenutgörs av en programvara vid namn LiME vilken kan hantera bägge kärnorna.Analys av minnet kräver att verktygen som används har en förståelse för minneslayouten i fråga.Beroende på vilken metod verktyget använder så kan det även behövas information om olika sym-boler. Verktyget som används i det här examensarbetet heter Volatility och klarar på papperet avatt extrahera all den information som behövs för att kunna göra en korrekt undersökning.Arbetet avsåg att vidareutveckla existerande metoder för analys av det flyktiga minnet på Linux-baserade maskiner (PC) och inbyggda system(Android). Problem uppstod då undersökning avflyktigt minne på Android och satta mål kunde inte uppnås fullt ut. Det visade sig att minnesanalysriktat emot PC-plattformen är både enklare och smidigare än vad det är mot Android.

Passive MVC och MVVM designmönster i Android : En jämförelse av kodkomplexitet mellan Passive MVC och MVVM

Det mobila operativsystemet Android är idag ett ganska dominerande operativsystem på den mobila marknaden dels på grund av sin öppenhet men också på grund av att tillgängligheten är stor i och med både billiga och dyra telefoner finns att tillgå. Men idag har Android inget fördefinierat designmönster vilket leder till att varje utvecklare får bestämma själv vad som ska användas, vilket ibland kan leda till onödigt komplex kod i applikationerna som sen blir svårtestad och svårhanterlig. Detta arbete ämnar jämföra två designmönster, Passive Model View Controller (PMVC) och Model View View-Model (MVVM), för att se vilket designmönster som blir minst komplext med hjälp av att räkna fram mätvärden med hjälp av Cyclomatic Complexity Number (CCN). Studien är gjord utifrån arbetssättet Design & Creation och ämnar bidra med: kunskap om vilket mönster man bör välja, samt om CCN kan peka ut vilka delar i en applikation som kommer att ta mer eller mindre lång tid att testa. Under studiens gång tog vi även fram skillnader på om man anväder sig av den så kallade Single Responsibilyt Principle (SRP) eller inte. Detta för att se om separerade vyer gör någon skillnad i applikationernas komplexitet. I slutändan så visar studien på att komplexiteten i små applikationer är väldigt likvärdig, men att man även på små applikationer kan se skillnad på hur komplex koden är men också att kodkomplexitet på metodnivå kan ge riktlinjer för testfall.