HYDROLYTIC DEGRADATION BEHAVIOR OF PLLA NANOCOMPOSITES REINFORCED WITH MODIFIED CELLULOSE NANOCRYSTALS

Bionanocomposites derived from poly(L-Lactide) (PLLA) were reinforced with chemically modified cellulose nanocrystals (m-CNCs). The effects of these modified cellulose nanoparticles on the mechanical and hydrolytic degradation behavior of polylactide were studied. The m-CNCs were prepared by a method in which hydrolysis of cellulose chains is performed simultaneously with the esterification of hydroxyl groups to produce modified nanocrystals with ester groups. FTIR, elemental analysis, TEM, XRD and contact angle measurements were used to confirm and characterize the chemical modifications of the m-CNCs. These bionanocomposites gave considerably better mechanical properties than neat PLLA based on an approximately 100% increase in tensile strength. Due to the hydrophobic properties of the esterified nanocrystals incorporated into a polymer matrix, it was also demonstrated that a small amount of m-CNCs could lead to a remarkable decrease in the hydrolytic degradation rate of the biopolymer. In addition, the m-CNCs considerably delay the degradation of the nanocomposite by providing a physical barrier that prevents the permeation of water, which thus hinders the overall absorption of water into the matrix. The results obtained in this study show the nanocrystals can be used to reinforce polylactides and fine-tune their degradation rates in moist or physiological environments.

DIRECT INFUSION ESI-MS APPLIED IN THE DETECTION OF BYPRODUCTS DUE TO REDUCTIVE DEGRADATION OF ACETAMIPRID BY ZERO-VALENT IRON

This study investigated the reductive degradation of acetamiprid (5 mg L-1) in aqueous medium (at pH 2.0) induced by zero-valent iron (50 mg). The process was monitored using high-performance liquid chromatography (HPLC) to determine the degradation rate as a function of reaction time, and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) to search for (and potentially characterize) any possible byproducts formed during degradation. The results obtained via HPLC showed that after 60 min, the degradation of the substrate reached nearly 100% in an acidic medium, whereas the mineralization rate (as determined by total organic carbon measurements) was as low as 3%. Data obtained by DI-ESI-MS showed that byproducts were formed mainly by insertions of hydrogen atoms into the nitrile, imine, and pyridine ring moieties, in addition to the observation of chlorine substitution by hydrogen replacement (hydrodechlorination) reactions.

CHARACTERIZING THE MECHANISM OF QUETIAPINE DISTRIBUTION IN LIPID-CORE NANOCAPSULES PSEUDO-PHASES USING A VALIDATED LC/UV METHOD

Quetiapine is an atypical antipsychotic used to treat schizophrenia. However, despite great interest for its chronic therapeutic use, quetiapine has some important side effects such as weight gain induction. The development of a quetiapine nanocarrier can potentially target the drug into central nervous system, resulting in a reduction of systemic side effects and improved patient treatment. In the present work, a simple liquid chromatography/ultraviolet detection (LC/UV) analytical method was developed and validated for quantification of total quetiapine content in lipid core nanocapsules as well as for determination of incorporation efficiency. An algorithm proposed by Oliveira et al. (2012) was applied to characterize the distribution of quetiapine in the pseudo-phases of the nanocarrier, leading to a better understanding of the quetiapine nanoparticles produced. The analytical methodology developed was specific, linear in the range of 0.5 to 100 µg mL−1 (r2 > 0,99), and accurate and precise (R.S.D < ±5%). The absolute recovery of quetiapine from the nanoparticles was approximately 98% with an incorporation efficiency of approximately 96%. The results indicated that quetiapine was present in a type III distribution according to the algorithm, and was mainly located in the core of the nanoparticle because of its logD in the formulation pH (6.86 ± 0.4).

OBTAINING ZnO IMMOBILIZED OVER DIFFERENT SUBSTRATES BY HYDROTHERMAL TREATMENT FOR PHOTOCATALYSIS APPLICATION

The aim of this work is to systematically explore the effect of the synthesis conditions of ZnO structures, immobilized on different substrates by hydrothermal treatment, in its photocatalytic activity. A circumscribed central composite design of experiments was used to analyze the effects of reagents stoichiometry, reaction time and temperature, covering a wide range of these variables. The substrates used were etched glass, copper and zinc foils. The photocatalytic activity of the as-obtained ZnO samples was evaluated through photocatalytic degradation of rhodamine B (RhB) in aqueous solution under UV irradiation. Zinc foils presented the best immobilized film quality and the maximum dye removal was 80% in one hour of UV exposure.

Efeito da irradiação UV-C no controle da podridão parda (Monilinia fructicola) e da podridão mole (Rhizopus stolonifer) em pós-colheita de pêssegos

Este trabalho teve por objetivo avaliar o efeito da irradiação UV-C no controle in vitro de Monilinia fructicola e Rhizopus stolonifer e no controle das doenças causadas por estes fungos em pêssegos inoculados com ferimento. No experimento in vitro, avaliou-se o crescimento micelial dos fungos em meio BDA após a exposição nas doses de UV-C de 0, 0,26, 0,52, 1,04, 3,13, 5,22, 10,44, 15,66, e 31,32 kJ.m-2 num equipamento com quatro lâmpadas com taxa de fluência de 1,74 mW.cm-2. Nos experimentos in vivo, os frutos foram tratados com irradiação UV-C de forma protetora e curativa. No tratamento protetor, os frutos foram expostos a 1,04 kJ.m-2 por 1 min. e foram inoculados imediatamente após e 16, 24 e 40 h após. No tratamento curativo, os frutos foram inoculados, incubados e irradiados com doses de UV-C de 0, 1,04, 5,22, 10,44, 15,66 e 31,32 kJ.m². Avaliou-se a incidência das doenças e a severidade da podridão parda. No experimento in vitro, apenas as doses aplicadas durante 1 e 10 min. de exposição reduziram o crescimento micelial de M. fructicola enquanto que a aplicação da luz UV-C entre 10-15 minutos reduziu o crescimento micelial de R. stolonifer e a dose aplicada durante 30 minutos inibiu completamente o crescimento micelial deste fungo. Não houve efeito protetor da luz UV-C no controle das doenças. Não houve controle curativo da podridão parda. A irradiação UV-C foi eficiente no controle curativo da podridão mole e o tempo de exposição de 10 min. foi o que apresentou melhor resultado.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Thermal degradation behaviour of some polydithiooxamide metal complexes

The thermal decomposition behavior of the Fe(II), Co(II), Ni(II) and Zn(II) complexes of polydithiooxamide has been investigated by thermogravimetric analysis (TGA) at a heating rate of 20°C min-1 under nitrogen. The Coats-Redfern integral method is used to evaluate the kinetic parameters for the successive steps in the decomposition sequence observed in the TGA curves. The processes of thermal decomposition taking place in the four complexes are studied comparatively as the TGA curves indicate the difference in the thermal decomposition behavior of these complexes. The thermal stabilities of these complexes are discussed in terms of repulsion among electron pairs in the valence shell of the central ion and electronegativity effects.

Puulevystä valmistettujen kalusteosien pintakäsittelyn kehittäminen UV-telalinjalla

Diplomityö tehtiin Kidex Oy:lle, joka on Kiteellä sijaitseva Martela-konsernin tytäryhtiö. Kidex Oy toimii sopimusvalmistajana Martelalle sekä muille valituille levykalusteasiakkaille, ja tuotteet ovat pääasiassa toimisto- ja keittiökalusteita. Kevättalvella 2008 yritykseen siirrettiin Nummelasta pintakäsittelyosasto, jolla on tehty petsaus- ja lakkaustöitä. Näiden lisäksi tehtaalla on pohdittu mahdollisuuksia maalaustöihin, jotta UV-telalinjan kapasiteetti saataisiin paremmin käyttöön Työssä selvitettiin, mitä muutoksia UV-kovettuvilla aineilla maalaaminen vaatii linjaan ja luotiin edellytykset maalaustoiminnan aloittamiselle. Muutokset pyrittiin pitämään niin vähäisinä kuin mahdollista. Lisäksi määritettiin maalattavien tuotteiden laadun kriteerit ja todennusmenetelmät, jotka voidaan viestiä asiakkaille väärinkäsitysten välttämiseksi. Laadun todentamista varten valmistettiin sarja koekappaleita, joista mitattiin asiakkaan kannalta tärkeimmät maalikalvon ominaisuudet. Työssä tarkasteltiin myös pintakäsittelylaitoksia koskevaa VOC-asetusta ja verrattiin liuottimien kulutusta asetuksen määrittämiin rajoihin. Puulevystä valmistettujen kalusteosien pintakäsittely UV-telalinjalla eroaa oleellisesti perinteisistä menetelmistä esimerkiksi tuotantonopeuden osalta, joka johtuu pääasiassa pinnoitekalvon hetkessä tapahtuvasta kovettumisesta UV-valon vaikutuksesta. UV-aineet ovat käytännössä täysin kiinteistä aineista koostuvia, eivätkä näin sisällä vaarallisia haihtuvia liuottimia. UV-kovettuvilla tuotteilla maalaaminen on viime vuosina runsaasti tutkittu alue, joka eroaa tietyiltä osin myös pintakäsittelystä UV-kirkaslakoilla. Pigmentoitujen kalvojen kovettuminen vaatii erilaista UV-säteilyä ja levitysmäärien seuranta on huomattavasti tarkempaa.

Análise do teor de cocaína em amostras apreendidas pela polícia utilizando-se a técnica de cromatografia liquida de alta eficiência com detector UV-Vis

A técnica de CLAE com detecção UV-Vis foi empregada na análise do teor de cocaína em amostras apreendidas de cocaína e crack. Uma fase móvel de acetonitrila/água (95:5v/v) possibilitou um sinal de pico para a cocaína em 3,5 minutos. O sinal espectrofotométrico otimizado foi obtido em um comprimento de onda de 224 nm. A curva analítica de 1,0 a 40,0 ppm para cocaína foi obtida, exibindo um coeficiente de correlação linear de 0,9989, com limites de detecção e quantificação de 0,75 e 3,78 ppm, respectivamente. Esta metodologia foi aplicada na dosagem de amostras confiscadas de cocaína e crack no Laboratório de Polícia Científica de Ribeirão Preto-SP.

Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Hidrotermia e radiação UV-C no controle de patógenos de manga e melão

As doenças de pós-colheita são, em geral, de difícil controle e são responsáveis por perdas significativas de manga (Mangifera indica L.) e melão (Cucumis melo L.) no Brasil. Os principais patógenos pós-colheita do melão são Alternaria alternata, Fusarium pallidoroseum e Myrothecium roridum, enquanto que na manga são Colletotrichum gloeosporioides e Lasiodiplodia theobromae. O objetivo deste trabalho foi avaliar a sensibilidade dos propágulos destes patógenos aos tratamentos de hidrotermia e de radiação UV-C. Suspensões de conídios e discos de micélio de cada patógeno foram submetidos aos tratamentos de hidrotermia a 50, 55 e 58 ºC por 15 e 30 s e de radiação UV-C nas doses de 0,330 kJ m-2, 0,660 kJ m-2 e 1,320 kJ m-2. Após os tratamentos e incubação por 72 e 48 h, foram avaliados o número de unidades formadoras de colônias (UFCs) e o crescimento micelial dos patógenos, respectivamente. Os tratamentos apresentaram eficiência distinta entre os propágulos e os patógenos. O controle de UFCs e do crescimento micelial de C. gloeosporioides e L. theobromae foi superior a 88 % com água aquecida a 55 ºC ou 58 ºC, independente do tempo de tratamento. Para os mesmos patógenos, a maior dose de radiação, 1,320 kJ m-2, controlou acima de 96 % das UFCs. Entretanto, o controle do crescimento micelial destes patógenos com radiação UV-C foi inferior quando comparado ao uso de água aquecida a 55 ºC ou 58 ºC. O controle de UFCs de A. alternata, M. roridum e F. pallidoroseum foi superior com os tratamentos de água aquecida a 55 ºC por 30 s, 58 ºC por 15 s e 30 s e com as doses de radiação de 0,660 kJ m-2 e 1,320 kJ m-2. O controle do crescimento micelial de A. alternata e de M. roridum foi inferior com as doses de radiação e com a temperatura de 50 ºC quando comparados aos demais tratamentos. Na redução do crescimento micelial de F. pallidoroseum, os tratamentos a 58 ºC ou as doses de 0,660 kJ m-2 e 1,320 kJ m-2 foram mais eficiêntes, com controle superior a 88 %. Água aquecida a 58 ºC por 15 s controlou UFCs e o crescimento micelial dos patógenos testados.

Uv. Lilla slafvinnan ("Ali Baba") : alkusoitto

Soitinnus: orkesteri.

Kloorifenoleja sisältävien jätevesien AOP-käsittely

Kirjallisuustyössä tutkittiin tehostetun hapetuksen menetelmiä (engl. Advanced Oxidation Processes, AOPs) kloorifenolien käsittelyssä. Tutkittava aine valittiin US EPA:n (United States Environmental Protection Agency) ympäristölle haitallisten aineiden listalta. Työssä tutkitut AOP-menetelmät olivat otsonointi kasvatetussa pH:ssa, O3/H2O2-prosessi, fotolyyttinen otsonointi (O3/UV), H2O2/UV-prosessi ja Fenton-prosessi (H2O2+Fe2+). AOP-käsittelyssä OH-radikaalien oletetaan pääosin aiheuttavan epäpuhtauksien hapettumisen. Kirjallisuustyössä tutkittiin OH-radikaaleihin vaikuttavien parametrien, kuten pH:n, lämpötilan sekä hapettimien ja hapetettavan aineen konsentraatioiden vaikutusta kloorifenolien hapetusprosessissa. Työn tarkoituksena oli selvittää tehokkain AOP-käsittely kloorifenoleja sisältävien jätevesien käsittelylle. AOP-käsittelyjen tehokkuutta verrattiin hajoamisnopeusvakioiden, puoliintumisaikojen sekä hapettimen kemikaalikulutuksen ja kustannuksen perusteella. Fenton-prosessin ja otsonoinnin pH:ssa 9 todettiin olevan tehokkaimpia menetelmiä kloorifenolien hapetuksessa. Fenton-prosessin hapetusnopeus oli tehokkaampaa 4-CP:n ja 2,4-DCP:n hapetuksessa, kun taas otsonointi pH:ssa 9 hapetti nopeammin 2,3,4,6-TeCP:n ja 2,4,6-TCP:n. Kustannustehokkuuden perusteella Fenton-prosessi oli otsonointia tehokkaampi. Parhaan menetelmän valinta kloorifenoleiden poistamiseksi oli vaikeaa, sillä useissa tutkimuksissa oli tutkittu vain yhtä menetelmää. Lisäksi eri tutkimuksissa käytetyt prosessiolosuhteet olivat erilaiset, joka hankaloitti tutkimusten vertailua. Lopullinen AOP-menetelmän valinta tulisikin suorittaa vasta laboratoriotutkimusten jälkeen.

Application of capillary electrophoretic methods for determining carbohydrates and aliphatic carboxylic acids formed during wood processing

Knowledge of the behaviour of cellulose, hemicelluloses, and lignin during wood and pulp processing is essential for understanding and controlling the processes. Determination of monosaccharide composition gives information about the structural polysaccharide composition of wood material and helps when determining the quality of fibrous products. In addition, monitoring of the acidic degradation products gives information of the extent of degradation of lignin and polysaccharides. This work describes two capillary electrophoretic methods developed for the analysis of monosaccharides and for the determination of aliphatic carboxylic acids from alkaline oxidation solutions of lignin and wood. Capillary electrophoresis (CE), in its many variants is an alternative separation technique to chromatographic methods. In capillary zone electrophoresis (CZE) the fused silica capillary is filled with an electrolyte solution. An applied voltage generates a field across the capillary. The movement of the ions under electric field is based on the charge and hydrodynamic radius of ions. Carbohydrates contain hydroxyl groups that are ionised only in strongly alkaline conditions. After ionisation, the structures are suitable for electrophoretic analysis and identification through either indirect UV detection or electrochemical detection. The current work presents a new capillary zone electrophoretic method, relying on in-capillary reaction and direct UV detection at the wavelength of 270 nm. The method has been used for the simultaneous separation of neutral carbohydrates, including mono- and disaccharides and sugar alcohols. The in-capillary reaction produces negatively charged and UV-absorbing compounds. The optimised method was applied to real samples. The methodology is fast since no other sample preparation, except dilution, is required. A new method for aliphatic carboxylic acids in highly alkaline process liquids was developed. The goal was to develop a method for the simultaneous analysis of the dicarboxylic acids, hydroxy acids and volatile acids that are oxidation and degradation products of lignin and wood polysaccharides. The CZE method was applied to three process cases. First, the fate of lignin under alkaline oxidation conditions was monitored by determining the level of carboxylic acids from process solutions. In the second application, the degradation of spruce wood using alkaline and catalysed alkaline oxidation were compared by determining carboxylic acids from the process solutions. In addition, the effectiveness of membrane filtration and preparative liquid chromatography in the enrichment of hydroxy acids from black liquor was evaluated, by analysing the effluents with capillary electrophoresis.