Relationship between homocysteine and cardiorespiratory fitness is sex-dependent

Elevated plasma homocysteine is recognized as an independent risk factor for cardiovascular disease. Recently, there have been conflicting reports of the relationship between physical activity and homocysteine. A more objective measure of physical activity is cardiorespiratory fitness; however, its relationship with homocysteine has yet to be investigated. The aim of this study was to determine the relationship between cardiorespiratory fitness and plasma homocysteine. Cross-sectional associations between cardiorespiratory fitness (VO(2)max) and plasma homocysteine were examined in 49 men and 11 women. A submaximal bicycle test was used to determine VO(2)max and plasma homocysteine was measured using high performance liquid chromatography with fluorescence detection. Dietary analysis determined B vitamin intake. There was a significant inverse relationship between plasma homocysteine concentration and VO(2)max in women (r = -0.81, P = 0.003) but not in men (r = -0.09, P = 0.95). There were no significant relationships between plasma homocysteine and age, BMI, body fat, total cholesterol, and LDL cholesterol. In summary, elevated cardiorespiratory fitness is associated with decreased plasma homocysteine concentrations in women. (C) 2004 Elsevier Inc. All rights reserved.

Shortcomings of protein removal prior to high performance liquid chromatographic analysis - A case study using method development for BAY 11-7082

During the analytical method development for BAY 11-7082 ((E)-3-[4-methylphenylsulfonyl]-2-propenenitrile), using HPLC-MS-MS and HPLC-UV, we observed that the protein removal process (both ultrafiltration and precipitation method using organic solvents) prior to HPLC brought about a significant reduction in the concentration of this compound. The use of a structurally similar internal standard, BAY 11-7085 ((E)-3-[4-t-butylphenylsulfonyl]-2-propenenitrile), was not effective in compensating for the loss of analyte as the extent of reduction was different to that of the analyte. We present here a systematic investigation of this problem and a new validated method for the determination of BAY 11-7082. (c) 2006 Elsevier B.V. All rights reserved.

Analysis of organomercurials in environmental and biological samples by capillary column gas chromatography with atomic fluorescence detection

The general method for determining organomercurials in environmental and biological samples is gas chromatography with electron capture detection (GC-ECD). However, tedious sample work up protocols and poor chromatographic response show the need for the development of new methods. Here, Atomic Fluorescence-based methods are described, free from these deficiencies. The organomercurials in soil, sediment and tissue samples are first released from the matrices with acidic KBr and cupric ions and extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean up and the organomercury species are isolated as their chloride derivatives by cupric chloride and subsequent extraction into a small volume of dichloromethane. In water samples the organomercurials are pre-concentrated using a sulfhydryl cotton fiber adsorbent, followed by elution with acidic KBr and CuSO 4 and extraction into dichloromethane. Analysis of the organomercurials is accomplished by capillary column chromatography with atomic fluorescence detection.

Distribution, occurrence and biotoxin composition of the main shellfish toxin producing microalgae within European waters: A comparison of methods of analysis.

Harmful algal blooms (HABs) are a natural global phenomena emerging in severity and extent. Incidents have many economic, ecological and human health impacts. Monitoring and providing early warning of toxic HABs are critical for protecting public health. Current monitoring programmes include measuring the number of toxic phytoplankton cells in the water and biotoxin levels in shellfish tissue. As these efforts are demanding and labour intensive, methods which improve the efficiency are essential. This study compares the utilisation of a multitoxin surface plasmon resonance (multitoxin SPR) biosensor with enzyme-linked immunosorbent assay (ELISA) and analytical methods such as high performance liquid chromatography with fluorescence detection (HPLC-FLD) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) for toxic HAB monitoring efforts in Europe. Seawater samples (n = 256) from European waters, collected 2009–2011, were analysed for biotoxins: saxitoxin and analogues, okadaic acid and dinophysistoxins 1/2 (DTX1/DTX2) and domoic acid responsible for paralytic shellfish poisoning (PSP), diarrheic shellfish poisoning (DSP) and amnesic shellfish poisoning (ASP), respectively. Biotoxins were detected mainly in samples from Spain and Ireland. France and Norway appeared to have the lowest number of toxic samples. Both the multitoxin SPR biosensor and the RNA microarray were more sensitive at detecting toxic HABs than standard light microscopy phytoplankton monitoring. Correlations between each of the detection methods were performed with the overall agreement, based on statistical 2 × 2 comparison tables, between each testing platform ranging between 32% and 74% for all three toxin families illustrating that one individual testing method may not be an ideal solution. An efficient early warning monitoring system for the detection of toxic HABs could therefore be achieved by combining both the multitoxin SPR biosensor and RNA microarray.

Distribution, occurrence and biotoxin composition of the main shellfish toxin producing microalgae within European waters: A comparison of methods of analysis.

Harmful algal blooms (HABs) are a natural global phenomena emerging in severity and extent. Incidents have many economic, ecological and human health impacts. Monitoring and providing early warning of toxic HABs are critical for protecting public health. Current monitoring programmes include measuring the number of toxic phytoplankton cells in the water and biotoxin levels in shellfish tissue. As these efforts are demanding and labour intensive, methods which improve the efficiency are essential. This study compares the utilisation of a multitoxin surface plasmon resonance (multitoxin SPR) biosensor with enzyme-linked immunosorbent assay (ELISA) and analytical methods such as high performance liquid chromatography with fluorescence detection (HPLC-FLD) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) for toxic HAB monitoring efforts in Europe. Seawater samples (n = 256) from European waters, collected 2009–2011, were analysed for biotoxins: saxitoxin and analogues, okadaic acid and dinophysistoxins 1/2 (DTX1/DTX2) and domoic acid responsible for paralytic shellfish poisoning (PSP), diarrheic shellfish poisoning (DSP) and amnesic shellfish poisoning (ASP), respectively. Biotoxins were detected mainly in samples from Spain and Ireland. France and Norway appeared to have the lowest number of toxic samples. Both the multitoxin SPR biosensor and the RNA microarray were more sensitive at detecting toxic HABs than standard light microscopy phytoplankton monitoring. Correlations between each of the detection methods were performed with the overall agreement, based on statistical 2 × 2 comparison tables, between each testing platform ranging between 32% and 74% for all three toxin families illustrating that one individual testing method may not be an ideal solution. An efficient early warning monitoring system for the detection of toxic HABs could therefore be achieved by combining both the multitoxin SPR biosensor and RNA microarray.

Herbicide distribution in soils of a riparian forest and neighboring sugar cane field

Riparian forests are protected by Brazilian law to preserve rivers and their margins. A sugar cane field adjacent to a strip of young riparian forest bordering an older riparian forest along a stream was used to study the riparian forest as a buffer zone to prevent pesticides pollution. Concentrations of the herbicides diuron, hexazinone and tebuthiuron were determined in different soil layers of a Red Yellow Oxisol during 2003 and 2004. The determination was done by High Performance Liquid Chromatography with reverse phase C-18 column, through two mobile phases. Diuron and hexazinone concentration diminished between the sugar cane and riparian forest as buffer strip demonstrating a protective effect. However, tebuthiuron had about four times higher concentrations in the old riparian forest compared to the other areas. Concentrations were higher in the surface and decreased in deeper soil layers in the old riparian forest suggesting that this herbicide probably was introduced by air pollution. This pesticide concentrated in the canopy could be washed by rain to the soil adjacent to the stream. Our data suggest that climate conditions were responsible for enhanced volatilization exposing the old riparian forest to more air pollution that was captured by the higher canopy. (C) 2010 Elsevier B.V. All rights reserved.

Marjojen antosyaanien erottaminen ja väkevöinti

Antosyaanit ovat luonnossa esiintyvien flavonoidien suurin ryhmä. Niitä on tunnistettu yli 600 erilaista, mutta kuitenkin vain kuusi on luonnossa yleisesti esiintyviä. Eniten antosyaaneja on tummissa marjoissa kuten mustikassa, marja-aroniassa sekä variksenmarjassa. Antosyaaneilla on havaittu monia positiivisiaterveysvaikutuksia kuten antioksidatiivisia, antikarsinogeenisia, sekä antimikrobiaalisia vaikutuksia. Tässä työssä tutkittiin marjojen antosyaanien talteenottoa uuttamalla sekä niiden väkevöintiä. Tavoitteena oli saada mahdollisimman korkea antosyaanien saanto ja hyvä säilyvyys. Antosyaanien analysointi tehtiin nestekromatografisesti käyttäen ODS-2 kolonnia sekä nopeampaa spektrofotometristä pH-eromenetelmää. Tulokset laskettiin syanidiini-3-glukosidina. Antosyaanien väkevöintiä tutkittiin käyttäen erityyppisiä polymeerisiä makrohuokoisia adsorptiohartseja. Väkevöintiä kokeiltiin myös erottamalla epäpuhtauksia antosyaaniuutteesta sekä esikäsittelemällä puristejäännös eri olosuhteissa ennen antosyaanien uuttoa. Kuiva antosyaaniuute sisälsi ennen väkevöintiä noin 50 mg/g antosyaaneja ja väkevöinnin jälkeen yli 300 mg/g. Antosyaanien säilyvyyttä tutkittiin eri lämpötiloissa sekä kuivana että uutteena. Riippumatta säilytysolosuhteista kuivan puhdistetun antosyaanin havaittiin säilyvän hyvin.

Päällystetyn graafisen kartongin hajuominaisuudet

Diplomityön tavoitteena oli selvittää elintarvikepakkauksiin soveltuvan graafisen kartongin potentiaalinen hajun aiheuttaja. Lisäksi tavoitteena oli vähentää päällystetyn tasakoosteisen (SBS) kolmikerroskartongin hajutasoa keskittyen päällystyspastakomponentteihin sekä massaosaston jälkeen annosteltaviin kemikaaleihin. Kirjallisuusosassa tarkasteltiin eri kartonkilajeja, päällystyspastoja ja sen sisältämiä komponentteja, pääpainon ollessa kuitenkin kartongin hajuominaisuuksiin vaikuttavien tekijöiden selvittämisessä. Lisäksi luotiin katsaus kartonkien aistinvaraisiin ja instrumentaalisiin määritysmenetelmiin. Instrumentaalisista määritysmenetelmistä käsiteltiin headspace –kaasukromatografia (HSGC) sekä korkeanerotuskyvyn nestekromatografia yhdistettynä massaspektrometriin (HPLC/MS). Kokeellisen osan alussa kartoitettiin päällystyskemikaalien sekä liima- ja retentioaineiden haihtuvat yhdisteet HSGC- ja HPLC/MS –tekniikoiden avulla. Kaasukromatografisesti analysoidut kokonaishaihtuvien tasot eivät poikenneet normaaleista tasoista, joten jouduttiin siirtymään HPLC/MS –menetelmään. HPLC/MS –tekniikalla on päästy tutkimaan herkästi haihtuvien typpiyhdisteiden amiinipitoisuuksia. Kemikaalimittausten perusteella vaihdettiin potentiaaliset hajua aiheuttavat kemikaalit, kovete ja synteettinen paksuntaja, markkinoilla oleviin vaihtoehtoisiin kemikaaleihin ja suoritettiin pilot -koeajo sekä tehdasmittakaavaiset koeajot. Työssä perehdyttiin myös varastoinnin aiheuttamiin vaikutuksiin eri kartonkilaatujen aistinvaraisissa ominaisuuksissa. Päällystyspastan kemikaaleista suuren hajukuorman aiheuttavat kovete, dispergointiaine, päällystyspigmentit ja lateksit sekä synteettinen paksuntaja. Kovetteen annostelumäärä päällystyspastoihin on alhainen, mutta sen sisältämä ammoniakkipitoisuus on kuitenkin huomattavan suuri. Kovete ohjaakin lopputuotteen ammoniakkipitoisuutta. Merkittävän metyyliamiinikuorman sisältää dispergointiaine. Sen vaikutus lopputuotteeseen voidaan olettaa vähäiseksi johtuen kemikaalin pienestä määrästä pastassa. Päällystyspigmenttien ja lateksien korkea metyyliamiinikuorma voi puolestaan aiheuttaa lopputuotteeseen huomattavan hajukuorman johtuen niiden suurista annostelumääristä. Eri synteettisille paksuntajille tehtyjen tutkimusten mukaan niiden hajukuormat olivat hyvin samankaltaisia ja vaikutus lopputuotteen kokonaishajutasoon jäi pieneksi. Aistinvaraisesti tarkasteltuna eri kartonkilaaduille saadaan eri hajutasoja. Elintarvikepakkauksiin soveltuvan graafisen kartongin hajutasot olivat korkeita muihin kartonkilaatuihin nähden niin tuoreena kuin varastoinnin jälkeen. Erityisesti tuoreen kartonkinäytteen metyyliamiinipitoisuus ylitti hajukynnyksen. Käytetty lateksi, kovete ja synteettinen paksuntaja näyttävät muodostavan niin tiiviin hajua koteloivan päällystekerroksen kartongin pinnalle, että hajua vapautuu pitkällä aikavälillä. Myös varastointi tiiviinä pakkauksena estää amiinien haihtumisen. Tutkimusten mukaan ammoniakkivapaalla PZC –kovetteella saadaan alennettua graafisen kartongin ammoniakkikuormaa huomattavasti. Tämä on vaikuttamassa myös lopputuotteen hajutasoon, jota on mahdollisuus alentaa käyttämällä ammoniakkivapaata kovetetta.

MONITORING OF ORGANOPHOSPHOROUS PESTICIDE RESDUES IN SAMPLES OF BANANA, PAPAYA, AND BELL PEPPER

The objective of this study was to monitor 11 organophosphorus pesticides in samples of papaya, bell pepper, and banana, commercialized in the metropolitan area of Vitória (ES, Brazil). The pesticides were determined by an optimized and validated method using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). All three samples exhibited a matrix effect for most of the pesticides, mainly with signal suppression, and therefore the calibration curves were produced in matrices. Linearity revealed coefficients of determination (r2) greater than 0.9895 for all pesticides and recovery results ranged from between 76% and 118% with standard deviation no greater than 16%. Precision showed relative standard deviation values lower than 19% and HorRat values lower than 0.7, considering all pesticides. Limits of quantification were less than 0.01 mg/kg for all pesticides. Regarding analysis of the samples (50 of each), none of the pesticides exceeded the maximum residue limit determined by Brazilian legislation.

Experimental poisoning by Baccharis megapotamica var. weirii in buffalo

Five male 6-8 month-old Murrah buffalo calves were orally dosed with the fresh aerial parts of Baccharis megapotamica var. weirii at doses of 1, 3, 4, 5 and 10g/kg body weight (bw) (~1-10mg macrocyclic trichothecenes/kg/bw). The B. megapotamica used for the experiment was harvested on a farm where a recent spontaneous outbreak of poisoning caused by such plant had occurred. Clinical signs appeared 4-20 hours and 4 buffaloes died 18-49 hours after the ingestion of the plant. Clinical signs were apathy, anorexia, and watery diarrhea, fever, colic, drooling, muscle tremors, restlessness, laborious breathing and ruminal atony, and dehydration. The most consistent gross findings were restricted to the gastrointestinal (GI) tract consisted of varying degrees of edema and reddening of the mucosa of the forestomach. Histopathological findings consisted of varying degrees of necrosis of the epithelial lining of the forestomach and of lymphocytes within lymphoid organs and aggregates. Fibrin thrombi were consistently found in sub-mucosal vessels of the forestomach and in the lumen of hepatic sinusoids. It is suggested that dehydration, septicemia and disseminated intravascular coagulation participate in the pathogenesis of the intoxication and play a role as a cause of death. A subsample of B. megapotamica var. weirii was frozen-dried and ground and analyzed using UHPLC (Ultra High Performance Liquid Chromatography) with high resolution Time of Flight mass spectrometry and tandem mass spectrometry, it was shown that the plant material contained at least 51 different macrocyclic trichothecenes at a total level of 1.1-1.2mg/g. About 15-20% of the total trichothecenes contents was found to be monosaccharide conjugates, with two thirds of these being glucose conjugates and one third constituted by six aldopentose conjugates (probably xylose), which has never been reported in the literature.

Endogenous carotenoid concentrations in cancerous and non-cancerous tissues of gastric cancer patients in Korea

Carotenoid concentrations were measured in serum and in both non-cancerous and cancerous gastric mucosal tissues of Korean patients with gastric cancer (n = 18). Carotenoids in serum and gastric tissue were extracted with chloroform/methanol (2:1), and measured using reverse-phase high-performance liquid chromatography with a C30 column. Cryptoxanthin and β-carotene were the major carotenoids in the Korean blood and they had a median ratio of non-cancerous tissue/serum levels which was less than 1.0. No significant differences of Cryptoxanthin and β-carotene levels were found between non-cancerous and cancerous tissues. After incubation of β-carotene with gastric tissue, significantly higher levels of β-carotene breakdown products were produced in the homogenates of cancerous tissue when compared with non-cancerous tissue. Lutein, zeaxanthin and α-carotene were the minor carotenoid constituents in the blood and their median ratio of non-cancerous tissue/serum levels was greater than 1.0. Cancerous tissue had significantly lower levels of lutein, zeaxanthin and α-carotene than did non-cancerous tissue. It appears that the increased breakdown of β-carotene and cryptoxanthin in cancerous tissue can be compensated for by an increased uptake of circulating carotenoids by cancerous tissue, whereas lutein, zeaxanthin and α-carotene levels in cancerous tissue are not able to be maintained.

Caracterização de hidrocarbonetos policíclicos aromáticos (HPA) em rios da bacia hidrográfica do Turvo/Grande

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

O papel das substâncias húmicas na disponibilidade de metais e benzo[a]pireno e indução de metalotioneínas em peixes

Pós-graduação em Química - IBILCE

Avaliação sobre o comportamento de antimicrobianos veterinários em solo e em cama de frango: estudos de adsorção e previsão do potencial de contaminação de águas superficiais e subterrâneas

Pós-graduação em Química - IQ