O presente trabalho enfoca o desenvolvimento de procedimentos analíticos limpos através da extração e pré-concentração de íons metálicos em ponto nuvem para aumento de sensibilidade, melhoria de seletividade e substituição de solventes tóxicos. Cobre(II), ferro(II) e níquel(II) foram extraídos simultaneamente em digeridos de materiais vegetais, utilizando como agente extrator o Triton X-114, após formarem complexos hidrofóbicos com o 1,2-tiazolilazo-2-naftol (TAN). Os analitos foram determinados por espectrometria de absorção atômica com chama (Cu, Fe e Ni) ou por espectrofotometria de absorção molecular (Fe). A determinação de Cu e Ni por espectrofotometria de absorção molecular foi inviabilizada por interferências espectrais causadas pela formação de complexos com diversos íons metálicos encontrados nos digeridos dos materiais vegetais. Nas medidas por FAAS, os limites de detecção (99,7 % de confiança) foram estimados em 1,10 e 5 µg L-1 para cobre, ferro e níquel, respectivamente. Respostas lineares foram observadas para cobre e ferro na faixa de concentração de 25-200 µg L-1 e para o níquel entre 5 e 80 µg L-1 . O fator de enriquecimento foi estimado em 30 e a extração dos analitos foi quantitativa, de acordo com medidas efetuadas no sobrenadante após extração. Na determinação de ferro por espectrofotometria de absorção molecular, o limite de detecção foi estimado em 1 µg L-1 , com resposta linear entre 6 e 60 µg L-1 e fator de enriquecimento estimado em 20. Após digestão com ácidos diluídos em forno de microondas, o procedimento proposto foi aplicado à determinação dos analitos em digeridos de materiais de referência certificados, sendo os resultados concordantes com os valores certificados a nível de confiança de 95 %. O consumo de reagentes foi estimado em 50 mg Triton X-114 e 150 µg TAN por determinação. / This work is focused on the development of green analytical procedures for cloud-point extraction and concentration of metal ions, aiming increasing sensitivity, improving selectivity and avoiding the use of toxic solvents. Copper(II), iron(II) and nickel(II) were simultaneously extracted from plant materials digests, by using Triton X-114 as extracting agent, after formation of hydrophobic complexes with 1,2- tiazolylazo-2-naphthol (TAN). The analytes were determined by flame atomic absorption spectrometry (Cu, Fe and Ni) or by molecular absorption spectrophotometry (Fe). The determination of Cu and Ni by UV-vis spectrophotometry was hindered by spectral interferences caused by the formation of complexes with several metal ions in the sample digests. In the measurements by FAAS, the detection limits (99.7 % confidence level) were estimated as 1, 10 and 5 µg L-1 for copper, iron and nickel, respectively. Linear responses were observed in the 25-200 µg L-1 range for copper and iron and 5-80 µg L-1 for nickel. The enrichment factor was estimated as 30 and the extraction was quantitative, as evaluated by measurements in the supernatant solution after extraction. For iron determination by UV-vis spectrophotometry, the detection limit was estimated as 1 µg L-1 , with linear response within 6 and 60 µg L-1 and enrichment factor of 20. After digestion with diluted acids in microwave oven, the procedure was applied to the determination of the metals in reference materials and the results agreed with the certified values at the 95 % confidence level. The reagent consumption was estimated as 50 mg Triton X-114 and 150 µg TAN per determination.

A autoxidação dos complexos de Ni(II) e Co(II) com tetra, penta e hexaglicina, em meio de tampão borato, é acelerada por espécies de enxofre (IV) (H2S0<SUB3, HS03-e SO32-). A formação dos complexos de Ni(III) e Co(III) foi acompanhada espectrofotometricamente em 325 e 265 nm, respectivamente. A velocidade da reação de autoxidação do complexo de Ni(II)/Gn aumenta com a concentração de S(IV) e é máxima em pH &#926;8,5. O processo é autocatalítico com Ni(III)ou Co(III)atuando como iniciadores, forma~os pela oxidação espontânea de Ni(II) ou Co(II) pelo oxigênio molecular. A dependência da constante de velocidade observada com a oncentração de S(IV) evidenciou possíveis reações paralelas com formação de um complexo com ligantes mistos antes da etapa da oxidação. A autoxidação dos complexos de Cu(II)com penta e hexaglicina em pH =9 é muito lenta, na presença e na ausência de S(IV).A presença de S(IV) e de traços de Ni(II)ou Co(II) aumenta significativamente a velocidade e a eficiência da reação (período de indução de 0,5 s). O mecanismo envolve uma cadeia de reações e um ciclo redox dos complexos. Acetaldeído e formaldeído inibem parcialmente a reação de autoxidação de Ni(II)/G4 na presença de S(IV) e luminol.O método quimiluminescente desenvolvido pode ser empregado para determinação de formaldeído [(5,0.10-5 - 1,0.10-2) mol L-1] e acetaldeído [(1,0.10-4 - 0,10) mol L-1], não sendo possível detectar separadamente cada um desses aldeídos. Na autoxidação de Ni(OH)2 induzida por S(IV) na presença de luminol ocorre emissão de radiação, possibilitando a detecção de S(IV) na faixa de 5,0.10-8 a 1,0.10-5 mol L-1, com limite de detecção estimado de 1,3.10-8 mol L-1. / The autoxidation of Ni(lI) and Co(lI) complexes with tetra, penta and hexaglycine, in borate medium, is accelerated by sulfur (IV) species (H2S03, HS03- and SO32-). The formation of Ni(llI) and Co(lIl) complexes was followed spectrophotometrically at 325 and 265 nm, respectively. The autoxidation rate of Ni(II)/Gn complex increases with S(IV) concentration and is maximum at pH ~ 8.5. The process is autocatalytic with Ni(lIl) or Co(llI) acting as initiators, formed by spontaneous oxidation by oxygen. The dependence of the observed rate constant with S(IV) concentration showed evidences of back or parallel reactions with formation of mixed ligand complex prior to the oxidation step. The autoxidation of Cu(II)/penta and hexaglycine complexes at pH = 9, in the presence and absence of S(IV), is very slow. The presence of S(IV) and of small amounts of Ni(lI) or Co(lI) increases significantly the effectiveness and reaction rate (induction period = 0.5 s). The mechanism involves a radical chain and redox cycling of the metal íon complexes. Acetaldehyde and formaldehyde partially inhibit the autoxidation reaction of Ni(II)/G4 in the presence of S(IV) and luminol. The developed chemiluminescent method can be used for determination of formaldehyde [(5.0.10-5 - 1.0.10-2) mol L-1] and acetaldehyde [(1.0.10-4 - 0.10) mol L-1), being not possible their isolated detection. The S(IV) induced autoxidation of Ni(OH)2 in the presence of luminol, occurs with radiation emission, allowing S(IV) detection in the range 5.0.10-8 to 1.0.10,-5 mol L-1, with detection limit of 1.3.10-8 mol L-1.

This work provides improved procedures for spectrophotometric carbon system measurements. Indicator dyes used for routine spectrophotometric pH measurements in seawater suffer from impurity issues, which introduce vendor-specific systematic errors in pH determinations. The magnitude of these errors for several vendors was investigated for meta Cresol Purple (mCP) and Cresol Red (CR). Flash chromatography procedures were developed to obtain purified mCP and CR on a bulk scale in order to supply the oceanographic research community with the indicators. Easy access to the purified indicators ensures global intercomparability of spectrophotometric pH determinations. Internal consistency of marine inorganic carbon system measurements was studied using datasets obtained on two large coastal ocean acidification research cruises. In both cases, purified mCP was used to obtain the pH measurements, thereby improving accuracy relative to previous studies in which measurements were obtained with unrefined mCP. Based on this internal consistency study, recommendations are made for selecting the parameter pairs used for saturation state calculations. Direct spectrophotometric methods for measuring carbonate ion concentrations in seawater were improved by (a) using a higher concentration of lead as the carbonate indicator and (b) altering the carbonate computational algorithm based on high quality field data. Measurements of DIC and pH (using purified mCP) were used to calculate carbonate ion concentrations for comparison with spectrophotometrically measured carbonate ion concentrations (i.e., via spectrophotometric measurements of Pb(II) spectra in the ultraviolet). Minor changes in the computational algorithm substantially improved agreement between measured and calculated carbonate ion concentrations.

<p> </p><p>Correlation between production method and mineral-, cadmium- and protein content were sought for Swedish winter wheat. The wheat was grown according to conventional, organic or biodynamic principles. The minerals; iron, zinc, magnesium, copper and the heavy metal cadmium were analyzed with atomic absorption spectroscopy. Protein was analyzed with elemental combustion analysis. All together, 17 samples were analyzed; nine from the still ongoing Bollerup field trial in Skåne and eight from four different farm pairs in the midst of Sweden.</p><p>The Bollerup field trials showed that organic wheat had a higher concentration of iron than conventional. Both organic and biodynamic wheat had a higher concentration of zinc than conventional. Magnesium concentration was higher in biodynamic wheat than in conventional grown wheat. Differences between production methods were in the range of 7.5 and 17%.</p><p>No unmistakable connections were found between any of the parameters and production method for the farm pairs. However, a tendency for more minerals in organic/biodynamic wheat was seen for all minerals but iron.</p><p>Due to unclean equipment, analyzing of cadmium contents could not be completed.</p>

White cement has currently received increasing attention due to potential for use in sustainable concrete structures. Based on the U.S. Green Building Council certification practice, the LEED Green Building Rating System for New Construction and Major Renovation (LEED-NC) considers that the reflective quality of white surfaces may help to improve lighting efficiency and reduce temperature fluctuations, resulting in lower heating and cooling with reduction of related energy costs. In addition to the environmental impact, white concrete represents a valuable tool for the aesthetic acceptability of a structure, and can also offer important practical benefits in terms of safety (i.e., light reflection in the dark). In this thesis white concrete was combined with off-white rice husk ash and with a glass fibers reinforced polymer to obtain an innovative composite system able to: a) reduce the energy used for the production of the primary materials, b) decrease the temperature fluctuation in the building resulting in less energy needed for heating and cooling, and c) increase the life of the structure and thereby reduce energy usage for material disposal. It is evident that in applications where aesthetics is the driver, a great deal of attention needs to be devoted to the concrete mixture, but also to durability properties. To further improve the durability of white concrete, novel methodologies were introduced to study the corrosion mechanism of steel embedded in concrete and its effect on the color degradation of white surface. This study demonstrates the validity of the sustainable system made by white cement, OWRHA, and GFRP, and of the methodology introduce to evaluate corrosion and color degradation of reinforced concrete.

This thesis describes and evaluates an optical method utilizing ultra violet (UV) absorbance for on-line monitoring of haemodialysis treatment. Increased efficiency of haemodialysis treatment is considered to correlate to decreased morbidity and mortality when urea clearance (Kt/V) is elevated. However, further improvements have not been achieved at a higher Kt/V. The mortally rate in the haemodialysis population is still high (27% in Sweden). Urea as the clinical marker is under discussion, partly due to urea being non-toxic, but also that the uraemic syndrom is the result of a cumulative retention of innumerable involved compounds. On-line monitoring systems based on urea determination for improved dialysis efficiency have been suggested and developed in different settings over the last two decades, but have not achieved worldwide utilisation as routine clinical equipment. This thesis demonstrates that the UV-technique utilising 280, 285 and 297 nm is capable of estimating dialysis efficiency in therms of Kt/V, nutritional status in terms of protein catabolic rate (PCR), with the same characteristics as existing methods. One novel finding using UV-absorbance with high sampling rates is the on-line visualisation of the clearance process for following variations in clearance caused by clinical events and disturbances as well as during and after adjustments. The fact that the UV-absorbance technique does not measure urea directly but has high correlation to several other both UV-absorbing and not-absorbing solutes makes it suitable to reflect a more overall solute retention process. Finally, a new efficiency parameter based on the calculation of the area under UV- curve (clearance curve), is suggested to reflect the total removal of some solutes. In summary the UV-technique has the potential to be an additional tool to evaluate improvements of dialysis efficiency, which may result in decreased morbidity, longer life span and enhanced quality of life for the haemodialysis patients.

Correlation between production method and mineral-, cadmium- and protein content were sought for Swedish winter wheat. The wheat was grown according to conventional, organic or biodynamic principles. The minerals; iron, zinc, magnesium, copper and the heavy metal cadmium were analyzed with atomic absorption spectroscopy. Protein was analyzed with elemental combustion analysis. All together, 17 samples were analyzed; nine from the still ongoing Bollerup field trial in Skåne and eight from four different farm pairs in the midst of Sweden. The Bollerup field trials showed that organic wheat had a higher concentration of iron than conventional. Both organic and biodynamic wheat had a higher concentration of zinc than conventional. Magnesium concentration was higher in biodynamic wheat than in conventional grown wheat. Differences between production methods were in the range of 7.5 and 17%. No unmistakable connections were found between any of the parameters and production method for the farm pairs. However, a tendency for more minerals in organic/biodynamic wheat was seen for all minerals but iron. Due to unclean equipment, analyzing of cadmium contents could not be completed.

Vaistinės arbatos mišiniai vertingi dėl jose esančių komponentų, kaip fenoliniai junginiai (atsakingi už antimikrobinį veikimą) ir flavonoidai (natūralūs antioksidantai, surišantys laisvuosius radikalus). Flavonoidų cheminės savybės apžvelgtos darbe. Šio darbo tikslas - atlikti flavonoidų ir fenolinių junginių kiekybinę ir kokybinę analizę bei nustatyti bendrą antioksidacinį aktyvumą vaistinių arbatų mišinių ekstraktuose. Paruošti metanoliniai vaistinių arbatų mišinių ekstraktai po kietafazės ekstrakcijos buvo analizuojami spektrofotometru, kapiliarine elektroforeze ir efektyviąja skysčių chromatografija su reakcijos detektoriumi. Spektrofotometru išmatuotas bendras fenolinių junginių, flavonoidų kiekis vaistinėse arbatose. Įvertintos metanolinių ekstraktų laikymo sąlygos šaldytuve bei sausos žaliavos laikymo sąlygos sausoje, vėsioje vietoje. Efektyviąja skysčių chromatografija įvertintas fenolinių junginių kiekis ir jų antioksidacinis aktyvumas su 2,2 - difenil – 1 - pikrilhidrazilo (DPPH ) laisvuoju radikalu. Blukinimo reakcija matuota UV detektoriumi ties 517 nm. Efektyviaja skysčių chromatografija išskirstyti fenoliniai junginiai, taikant gradientą. Atliktas kapiliarinės elektroforezės metodo optimizavimas: įvertintas buferio pH, organinio tirpiklio priedo, įtampos įtaka skirstymo efektyvumui, skiriamajai gebai. Atlikti įteisinimo žingsniai: įvertintos aptikimo ir nustatymo ribos, matavimų glaudumas, stabilumas ir atrankumas. Priedo metodu buvo identifikuoti flavonoidų... [toliau žr. visą tekstą] / Previous studies refer mostly to the HPLC analysis of the flavonoids, for oxidative product deterioration and radicals scavenging action. Methanolic extracts after solid phase extraction of 6 different functional teas were analyzed by means of capillary zone electrophoresis (CZE) and high performence liquid chromatography (HPLC) with reaction detector. A rapid on-line method for screening components was developed using methanolic solution 2,2 – diphenyl – picrylhydrazyl (DPPH) as stable free radical. Bleaching reaction is detected as a negative peak by an absorbance detector at 517 nm. HPLC gradient runs with mobile phase composition ranging from 33 to 90% organic solvent (methanol) in water with 0.1% TFA. The activity of compounds in functional teas (complex mixtures) was determined. Development and validation of the CZE method was carried out.. Limits of detection and quantification were determined. The results obtained using CZE are comparable to the spectrophotometric and HPLC analysis results. The influence of the extraction conditions (with solid phase extraction (SPE) and without SPE extraction), amount of flavonoids and phenolic compounds in the various functional teas was studied. The highest content of flavonoids was obtained in Choleretic herbs mixture 2,08 mg/g and the highest content of phenolic compounds was determined in Diaphoretic functional tea 3,53mg/g in raw dry medicinal functional tea herbs. The total amount of flavonoids did not directly correlate... [to full text]

Ištirti Lietuvoje auginamų obelų veislių skirtingų poskiepių ir kultivavimo sistemų obuolių fenolinių junginių kiekinės sudėties įvairovę bei įvertinti antioksidantinį aktyvumą. / To evaluate quantitative composition and antioxidant activity of phenolic compounds in Lithuania grown apples from different rootstocks and cultivation systems.

Tyrimo objektas ir metodai: Sorbus L. genties augalo S. aucuparia L. lapų ir žiedų tyrimas. Bendras fenolinių junginių kiekis paprastojo šermukšnio augalinėse žaliavose nustatytas UV spektrofotometriniu metodu, fenolinės rūgštys ir flavonoidai nustatyti ESC metodu. Darbo tikslas: nustatyti S. aucuparia L. lapuose ir žieduose esančius fenolinius junginius, jų kiekinės sudėties įvairavimą augalo vegetacijos metu ir augalinių žaliavų (lapų ir žiedų) laikymo metu. Darbo uždaviniai: Surinkti ir susisteminti literatūros duomenis apie Sorbus aucuparia L., paprastojo šermukšnio augalinių žaliavų cheminę sudėtį, fenolinių junginių analizės metodus, poveikį ir panaudojimą medicinos praktikoje; Ištirti S. aucuparia L. lapų ir žiedų kiekybinę fenolinių junginių sudėtį ir nustatyti bendro fenolinių junginių kiekio įvairavimą augalo vegetacijos metu; Ištirti S. aucuparia L. lapų ir žiedų kokybinę ir kiekybinę fenolinių rūgščių ir flavonoidų sudėtį ir nustatyti jų kiekinės sudėties kitimą augalų vegetacijos periodo metu; Nustatyti S. aucuparia L. lapuose ir žieduose esančių fenolinių junginių kiekybinės sudėties kitimus augalinių žaliavų laikymo metu. Išvados: S. aucuparia L. augalinės žaliavos gali būti kaip šaltinis išskiriant biologiškai aktyvius junginius, kurie gali būti naudojami medicinos praktikoje. S. aucuparia L. lapuose ir žieduose esančių junginių kiekis kinta augalo vegetacijos metu; lapuose daugiausia fenolinių junginių sukaupiama gegužės - birželio mėn., žieduose – žydėjimo... [toliau žr. visą tekstą] / Object and methods: Sorbus aucuparia L. leaves and flowers study. Total amaunt of phenolic compounds in mountain ash leaves and flowers were evaluated using UV spectrophotometry, phenolic acids and flavonoids were identified and evaluated using HPLC. Aim: to identify and evaluate the content of phenolic compounds in rowan leaves and flowers during mountain ash vegetation and during plant materials (leaves and flowers) storage. Objective: to collect and organise the information about the use of Sorbus aucuparia L., S. aucuparia L. leaves and flowers acumulated compounds, phenolic compounds analysis methods and the impact of the use in medical practice; to perform quantitative analysis of S. aucuparia L. leaves and flowers phenolic compounds and to determine the total phenolics content during rowan growing season; to perform qualitative and quantitative analysis of S. aucuparia L. leaves and flowers phenolic acids and flavonoids and to determine the variation of the phenolics content during rowan growing season; to determine phenolic compounds content changes in Sorbus aucuparia L. plant materials (flowers and leaves) during them storage. Conclusions: S. aucuparia L. leaves and flower is a source of biological active substances which can be used in medicinal practice. Phenolic compounds content in S. aucuparia L. leaves and flowers change during vegetation; mainly phenolic compounds in leaves was accumulated in May - June, in flowers - in the beginning of flowering and massive... [to full text]