Additional revenue opportunities in pulp mills and their impacts on the kraft process

Although the concept of multi-products biorefinery provides an opportunity to meet the future demands for biofuels, biomaterials or chemicals, it is not assured that its implementation would improve the profitability of kraft pulp mills. The attractiveness will depend on several factors such as mill age and location, government incentives, economy of scale, end user requirements, and how much value can be added to the new products. In addition, the effective integration of alternative technologies is not straightforward and has to be carefully studied. In this work, detailed balances were performed to evaluate possible impacts that lignin removal, hemicelluloses recovery prior to pulping, torrefaction and pyrolysis of wood residues cause on the conventional mill operation. The development of mill balances was based on theoretical fundamentals, practical experience, literature review, personal communication with technology suppliers and analysis of mill process data. Hemicelluloses recovery through pre-hydrolysis of chips leads to impacts in several stages of the kraft process. Effects can be observed on the pulping process, wood consumption, black liquor properties and, inevitably, on the pulp quality. When lignin is removed from black liquor, it will affect mostly the chemical recovery operation and steam generation rate. Since mineral acid is used to precipitate the lignin, impacts on the mill chemical balance are also expected. A great advantage of processing the wood residues for additional income results from the fact that the pulping process, pulp quality and sales are not harmfully affected. For pulp mills interested in implementing the concept of multi-products biorefinery, this work has indicated possible impacts to be considered in a technical feasibility study.

Polysulfidiprosessi sulfaattisellutehtaassa

Kandidaatintyön tavoitteena on kartoittaa merkittävimmät muutokset sellutehtaalla siirryttäessä sulfaattimassan valmistuksesta polysulfidiselluprosessiin. Työssä esitellään sulfaattisellun valmistusprosessi ja polysulfidin vaatimat muutokset selluprosessissa erityisesti höyrynkulutuksen kannalta. Sellutehtaan höyrynkulutusta ja sen mahdollisia muutoksia tarkastellaan suhteessa tehtaan selluntuotantoon. Tutkimus tehdään tutustuen dokumenttilähteisiin sekä erityisesti hankkimalla lisätietoa ja käytännön näkemystä asiantuntijahaastatteluista. Työssä käytetään esimerkkinä tyypillistä modernia sellutehdasta, jonka perusteella tarkasteltavat osaprosessit ovat valikoituneet. Sulfaattiprosessiin tehtävät muutokset käsittävät keittolipeän muuttamisen polysulfidipitoiseksi, polysulfidin valmistusprosessin (MOXY) sekä keiton muuttamisen siten, että polysulfidin vaikutus voidaan maksimoida. Polysulfidiprosessi vaikuttaa merkittävästi lipeäkiertoon, keittämöön sekä kuivauskoneeseen. Muilla osastoilla ominaishöyrynkulutuksen odotetaan pysyvän tavanomaista sulfaattiprosessia vastaavalla tasolla. Höyrynkulutuksella on huomattava merkitys modernin sellutehtaan tuotanto- ja kustannustehokkuuteen, sillä säästetyllä ylijäämähöyryllä voidaan tuottaa myyntisähköä. Uusiutuvan energian tuottajana ja ympäristövastuullisena toimijana sellutehtaiden on järkevää pyrkiä vähentämään omaa höyrynkulutustaan ja lisäämään sitä kautta sähköntuotantoaan.

Polysulfidiprosessin vaikutukset höyrynkulutukseen sulfaattisellutehtaassa

Diplomityön tavoitteena on kartoittaa höyrynkulutuksen merkittävimmät muutokset sellutehtaalla siirryttäessä sulfaattimassan valmistuksesta polysulfidiselluprosessiin. Työssä esitellään sulfaattisellun valmistusprosessi ja polysulfidin vaatimat muutokset selluprosessissa erityisesti höyrynkulutuksen kannalta. Sellutehtaan höyrynkulutusta ja sen mahdollisia sekä todennettuja muutoksia tarkastellaan suhteessa tehtaan selluntuotantoon. Diplomityössä analysoidaan muutoksiin johtaneita syitä ja erityisesti peilataan niitä ennalta odotettuihin muutoksiin, joita kandidaatintyö ”Polysulfidiprosessi sulfaattisellutehtaassa” (Szepaniak 2014) esitti kirjallisuuden pohjalta. Tutkimus tehdään tutustuen dokumenttilähteisiin sekä erityisesti hankkimalla lisätietoa ja käytännön näkemystä asiantuntijahaastatteluista. Työssä käytetään esimerkkinä tyypillistä modernia sellutehdasta, jonka perusteella tarkasteltavat osaprosessit ovat valikoituneet. Tutkimustulosten perusteella esitetään jatkotutkimus- ja kehityskohteita. Sulfaattiprosessiin tehtävät muutokset käsittävät keittolipeän muuttamisen polysulfidipitoiseksi, polysulfidin valmistusprosessin (MOXY) sekä keiton muuttamisen siten, että polysulfidin vaikutus voidaan maksimoida. Polysulfidiprosessi vaikuttaa merkittävästi lipeäkiertoon ja keittämöön. Keittämön höyrynkulutus kasvaa, haihduttamon kuorma vähenee ja soodakattilan lämmöntuotanto heikkenee. Muilla osastoilla ominaishöyrynkulutuksen muutokset ovat tilastollisesti merkityksettömiä. Höyrynkulutuksella on huomattava merkitys modernin sellutehtaan tuotanto- ja kustannustehokkuuteen, sillä säästetyllä ylijäämähöyryllä voidaan tuottaa myyntisähköä. Uusiutuvan energian tuottajana ja ympäristövastuullisena toimijana sellutehtaiden on järkevää pyrkiä vähentämään omaa höyrynkulutustaan ja lisäämään sitä kautta sähköntuotantoaan.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Effects of the partial removal of wood hemicelluloses on the properties of kraft pulp

The objective of this work was to study the effects of partial removal of wood hemicelluloses on the properties of kraft pulp.The work was conducted by extracting hemicelluloses (1) by a softwood chip pretreatment process prior to kraft pulping, (2) by alkaline extraction from bleached birch kraft pulp, and (3) by enzymatic treatment, xylanase treatment in particular, of bleached birch kraft pulp. The qualitative and quantitative changes in fibers and paper properties were evaluated. In addition, the applicability of the extraction concepts and hemicellulose-extracted birch kraft pulp as a raw material in papermaking was evaluated in a pilot-scale papermaking environment. The results showed that each examined hemicellulose extraction method has its characteristic effects on fiber properties, seen as differences in both the physical and chemical nature of the fibers. A prehydrolysis process prior to the kraft pulping process offered reductions in cooking time, bleaching chemical consumption and produced fibers with low hemicellulose content that are more susceptible to mechanically induced damages and dislocations. Softwood chip pretreatment for hemicellulose recovery prior to cooking, whether acidic or alkaline, had an impact on the physical properties of the non-refined and refined pulp. In addition, all the pretreated pulps exhibited slower beating response than the unhydrolyzed reference pulp. Both alkaline extraction and enzymatic (xylanase) treatment of bleached birch kraft pulp fibers indicated very selective hemicellulose removal, particularly xylan removal. Furthermore, these two hemicellulose-extracted birch kraft pulps were utilized in a pilot-scale papermaking environment in order to evaluate the upscalability of the extraction concepts. Investigations made using pilot paper machine trials revealed that some amount of alkalineextracted birch kraft pulp, with a 24.9% reduction in the total amount of xylan, could be used in the papermaking stock as a mixture with non-extracted pulp when producing 75 g/m2 paper. For xylanase-treated fibers there were no reductions in the mechanical properties of the 180 g/m2 paper produced compared to paper made from the control pulp, although there was a 14.2% reduction in the total amount of xylan in the xylanase-treated pulp compared to the control birch kraft pulp. This work emphasized the importance of the hemicellulose extraction method in providing new solutions to create functional fibers and in providing a valuable hemicellulose co-product stream. The hemicellulose removal concept therefore plays an important role in the integrated forest biorefinery scenario, where the target is to the co-production of hemicellulose-extracted pulp and hemicellulose-based chemicals or fuels.

Intensification of hemicellulose hot-water extraction from spruce wood by parameter tuning

The growing population on earth along with diminishing fossil deposits and the climate change debate calls out for a better utilization of renewable, bio-based materials. In a biorefinery perspective, the renewable biomass is converted into many different products such as fuels, chemicals, and materials, quite similar to the petroleum refinery industry. Since forests cover about one third of the land surface on earth, ligno-cellulosic biomass is the most abundant renewable resource available. The natural first step in a biorefinery is separation and isolation of the different compounds the biomass is comprised of. The major components in wood are cellulose, hemicellulose, and lignin, all of which can be made into various end-products. Today, focus normally lies on utilizing only one component, e.g., the cellulose in the Kraft pulping process. It would be highly desirable to utilize all the different compounds, both from an economical and environmental point of view. The separation process should therefore be optimized. Hemicelluloses can partly be extracted with hot-water prior to pulping. Depending in the severity of the extraction, the hemicelluloses are degraded to various degrees. In order to be able to choose from a variety of different end-products, the hemicelluloses should be as intact as possible after the extraction. The main focus of this work has been on preserving the hemicellulose molar mass throughout the extraction at a high yield by actively controlling the extraction pH at the high temperatures used. Since it has not been possible to measure pH during an extraction due to the high temperatures, the extraction pH has remained a “black box”. Therefore, a high-temperature in-line pH measuring system was developed, validated, and tested for hot-water wood extractions. One crucial step in the measurements is calibration, therefore extensive efforts was put on developing a reliable calibration procedure. Initial extractions with wood showed that the actual extraction pH was ~0.35 pH units higher than previously believed. The measuring system was also equipped with a controller connected to a pump. With this addition it was possible to control the extraction to any desired pH set point. When the pH dropped below the set point, the controller started pumping in alkali and by that the desired set point was maintained very accurately. Analyses of the extracted hemicelluloses showed that less hemicelluloses were extracted at higher pH but with a higher molar-mass. Monomer formation could, at a certain pH level, be completely inhibited. Increasing the temperature, but maintaining a specific pH set point, would speed up the extraction without degrading the molar-mass of the hemicelluloses and thereby intensifying the extraction. The diffusion of the dissolved hemicelluloses from the wood particle is a major part of the extraction process. Therefore, a particle size study ranging from 0.5 mm wood particles to industrial size wood chips was conducted to investigate the internal mass transfer of the hemicelluloses. Unsurprisingly, it showed that hemicelluloses were extracted faster from smaller wood particles than larger although it did not seem to have a substantial effect on the average molar mass of the extracted hemicelluloses. However, smaller particle sizes require more energy to manufacture and thus increases the economic cost. Since bark comprises 10 – 15 % of a tree, it is important to also consider it in a biorefinery concept. Spruce inner and outer bark was hot-water extracted separately to investigate the possibility to isolate the bark hemicelluloses. It was showed that the bark hemicelluloses comprised mostly of pectic material and differed considerably from the wood hemicelluloses. The bark hemicelluloses, or pectins, could be extracted at lower temperatures than the wood hemicelluloses. A chemical characterization, done separately on inner and outer bark, showed that inner bark contained over 10 % stilbene glucosides that could be extracted already at 100 °C with aqueous acetone.

Recovery boilers - history and future

Recovery boilers are built all over the world. The roots of recovery technology are longer than the roots of recovery boilers. But it wasn’t until the invention of recovery boilers before the Second World War that the pulping technology was revolutionalized. This led to long development of essentially the same type of equipment, culminating into units that are largest biofuel boilers in the world. Early recovery technology concentrated on chemical recovery as chemicals cost money and if one could recycle these chemicals then the profitability of pulp manufacture would improve. For pulp mills the significance of electricity generation from the recovery boiler was for long secondary. The most important design criterion for the recovery boiler was a high availability. The electricity generation in recovery boiler process can be increased by elevated main steam pressure and temperature or by higher black liquor dry solids as well as improving its steam cycle. This has been done in the modern Scandinavian units.

Karboksyylihappojen kromatografinen fraktiointi

Suurin osa alifaattisista karboksyylihapoista tuotetaan nykyään synteettisesti, mutta öljyn hinnan nousu ja ekologisempi ajattelutapa on aiheuttanut kiinnostusta tuottaa näitä karboksyyli- ja hydroksihappoja jatkossa fermentoimalla tai sellun valmistuksen sivuvirtana syntyvästä mustalipeästä. Nykyään mustalipeä poltetaan sellaisenaan soodakattiloissa keittokemikaalien regeneroimiseksi, energiaksi ja sähköksi. Jatkossa mustalipeästä voisi erottaa arvokkaat orgaaniset hapot ennen polttamista. Saadusta happoseoksesta tulisi erottaa yksittäiset alifaattiset karboksyylihapot toisistaan jatkojalostusta varten. Tämän kandidaatintyön tavoitteena oli selvittää, millä kromatografisella erotusmenetelmällä fermentointituotteina ja teollisuuden sivuvirtoina syntyvistä karboksyylihapposeoksista saadaan yksittäiset alifaattiset karboksyylihapot erotettua toisistaan. Mittaukset suoritettiin kolonnilla, jossa hartsipedin halkaisija oli 1,5 cm ja korkeus 15 cm. Kolonnin erototusmateriaaleina kokeiltiin vahvoja ja heikkoja kationinvaihtohartseja, vahvaa anioninvaihtohartsia ja polymeerisiä adsorbentteja. Erotettavaksi happoseokseksi valittiin sitruuna-, viini-, glykoli-, maito- ja etikkahapon seos. Tehokkain erotus saatiin Puroliten valmistamalla Macronet 270:lla, joka on mikrohuokoinen polymeerinen adsorbentti. Macronet 270:lla saatiin erotettua erityisesti viini- ja glykolihappo sitruuna-, maito- ja etikkahaposta. Yksittäisiä happoja ei saatu kuitenkaan kunnolla erotettua. Parhaat koeolosuhteet erotustehokkuuden ja retentioaikojen kannalta saatiin vesieluentin virtausnopeudella 2 mL/min, syöttöpulssin tilavuudella 5 mL ja kolonnin lämpötilassa 75 °C.

Selvitys erilaisten mäntyöljynkeittoprosessien toiminnasta

Työn tavoitteena oli tutustua eri mäntyöljyprosessien toimintaan. Sulfaattisellun valmistuksessa syntyy sivutuotteena mäntyöljyä. Se tuo lisätuottoa sellutehtaalle. Nykypäivänä mäntyöljyn valmistukseen on kiinnitetty yhä enemmän huomiota uusien jalostusmahdollisuuksien vuoksi. Mäntyöljyä syntyy, kun mustalipeän pinnalta kuorittu suopa palstoitetaan sopivalla hapolla. Suopa koostuu puun uuteaineista eli hartsi- ja rasvahapoista sekä saippuattomista aineista. Suopa pitää erottaa mustalipeästä mahdollisimman hyvin, jotta se ei aiheuttaisi ongelmia sellutehtaan eri prosessin vaiheissa. Suopaa voidaan erottaa mustalipeästä säiliöerotuksena, sentrifugeilla tai hydrosykloneilla. Suovan palstoitusprosessi voi olla erä- tai jatkuvatoiminen prosessi. Jatkuvatoimisia prosesseja ovat: sentrifugi-, säiliödekantointi- ja HDS-prosessi. Mäntyöljyä voidaan käyttää kemianteollisuuden raaka-aineena tai siitä voidaan jalostaa biodieseliä. Tämä biodiesel on niin sanottua toisen polven biopolttoainetta eli se ei sisällä ravinnoksi kelpaavaa raaka-ainetta. Nykypäivänä markkinoilla on sekä eräkeitto- sekä jatkuvatoimisia prosesseja. Suovan erotussäiliöiden rinnalle on tullut uusi sentrifugeilla tapahtuva suovan erotussysteemi.

Placental hydroxymethylation vsmethylation at the imprinting control region 2 on chromosome 11p15.5

In addition to methylated cytosines (5-mCs), hydroxymethylcytosines (5-hmCs) are present in CpG dinucleotide-enriched regions and some transcription regulator binding sites. Unlike methylation, hydroxymethylation does not result in silencing of gene expression, and the most commonly used methods to study methylation, such as techniques based on restriction enzymatic digestion and/or bisulfite modification, are unable to distinguish between them. Genomic imprinting is a process of gene regulation where only one member of an allelic pair is expressed depending on the parental origin. Chromosome 11p15.5 has an imprinting control region (ICR2) that includes a differentially methylated region (KvDMR1) that guarantees parent-specific gene expression. The objective of the present study was to determine the presence of 5-hmC at the KvDMR1 in human placentas. We analyzed 16 third-trimester normal human placentas (chorionic villi). We compared two different methods based on real-time PCR after enzymatic digestion. The first method distinguished methylation from hydroxymethylation, while the other method did not. Unlike other methylation studies, subtle variations of methylation in ICRs could represent a drastic deregulation of the expression of imprinted genes, leading to important phenotypic consequences, and the presence of hydroxymethylation could interfere with the results of many studies. We observed agreement between the results of both methods, indicating the absence of hydroxymethylation at the KvDMR1 in third-trimester placentas. To the best of our knowledge, this is the first study describing the investigation of hydroxymethylation in human placenta using a genomic imprinting model.

DNA methylation regulates expression of VEGF-C, and S-adenosylmethionine is effective for VEGF-C methylation and for inhibiting cancer growth

DNA hypomethylation may activate oncogene transcription, thus promoting carcinogenesis and tumor development. S-adenosylmethionine (SAM) is a methyl donor in numerous methylation reactions and acts as an inhibitor of intracellular demethylase activity, which results in hypermethylation of DNA. The main objectives of this study were to determine whether DNA hypomethylation correlated with vascular endothelial growth factor-C (VEGF-C) expression, and the effect of SAM on VEGF-C methylation and gastric cancer growth inhibition. VEGF-C expression was assayed by Western blotting and RT-qPCR in gastric cancer cells, and by immunohistochemistry in tumor xenografts. VEGF-C methylation was assayed by bisulfite DNA sequencing. The effect of SAM on cell apoptosis was assayed by flow cytometry analyses and its effect on cancer growth was assessed in nude mice. The VEGF-C promoters of MGC-803, BGC-823, and SGC-7901 gastric cancer cells, which normally express VEGF-C, were nearly unmethylated. After SAM treatment, the VEGF-C promoters in these cells were highly methylated and VEGF-C expression was downregulated. SAM also significantly inhibited tumor growthin vitro and in vivo. DNA methylation regulates expression of VEGF-C. SAM can effectively induce VEGF-C methylation, reduce the expression of VEGF-C, and inhibit tumor growth. SAM has potential as a drug therapy to silence oncogenes and block the progression of gastric cancer.

Separation of lignin in Pulp Mill process and its effect on sodium sulphur balance

The aim of this thesis is to define effects of lignin separation process on Pulp mill chemical balance especially on sodium/sulphur-balance. The objective is to develop a simulation model with WinGEMS Process Simulator and use that model to simulate the chemical balances and process changes. The literature part explains what lignin is and how kraft pulp is produced. It also introduces to the methods that can be used to extract lignin from black liquor stream and how those methods affect the pulping process. In experimental part seven different cases are simulated with the created simulation model. The simulations are based on selected reference mill that produces 500 000 tons of bleached air-dried (90 %) pulp per year. The simulations include the chemical balance calculation and the estimated production increase. Based on the simulations the heat load of the recovery boiler can be reduced and the pulp production increased when lignin is extracted. The simulations showed that decreasing the waste acid stream intake from the chlorine dioxide plant is an effective method to control the sulphidity level when about 10 % of lignin is extracted. With higher lignin removal rates the in-mill sulphuric acid production has been discovered to be a better alternative to the sulphidity control.

Hemiselluloosien talteenotto paineistetulla kuumavesiuutolla tuotetuista puu-uutteista

Puunjalostusteollisuus keskittyy tällä hetkellä lähinnä sellun ja paperin tuotantoon. Sellun tuotannossa käytetään puun komponenteista vain selluloosa. Puun muita pääkomponentteja ovat hemiselluloosa ja ligniini. Nämä yhdisteet ovat mahdollisia tulevaisuuden biomateriaalien lähtöaineita, mutta tähän mennessä ne on jätetty käyttämättä hyödyksi. Paineistettu kuumavesiuutto on menetelmä, jolla hemiselluloosat ja ligniinit olisi mahdollista erottaa puumateriaalista ennen sellunkeittoa, ja sen jälkeen fraktioida uutteesta erilleen jatkojalostusta varten. Fraktioinnista on tehty tutkimusta monella erilaisella menetelmällä ja eri menetelmiä yhdistelemällä. Tämä kandidaatin työ on kirjallinen työ, jossa käsitellään paineistettua kuumavesiuuttoa, sekä eri yksikköoperaatioita ja niiden mahdollisuuksia hemiselluloosan erotukseen puu-uutteista. Membraanisuodatus on menetelmä, jolla puu-uutteesta saadaan erotettua konsentroitu hemiselluloosafraktio. Membraanisuodatuksessa on kuitenkin puu-uutteiden tapauksessa havaittu ongelmia muun muassa kalvon likaantumisen kanssa. Yhdistämällä muutamia eri yksikköoperaatioita, saadaan parannettua membraanisuodatuksen tehoa, sekä hemiselluloosan puhtautta ja saantoa. Näitä mahdollisia yksikköoperaatioita ovat adsorptio, hapetus, saostus, kromatografiset menetelmät ja neste-nesteuutto.

O6-Methylguanine-DNA-Methyltransferase methylation: prevalence and predictive value in head and neck squamous cell carcinoma

Introduction: Le gène O6-méthylguanine-ADN méthyltransferase (MGMT) code pour une enzyme spécifique réparatrice de l’ADN qui protège les cellules de la toxicité des agents alkylants. Ainsi, l’activité du MGMT est un mécanisme majeur de résistance aux agents alkylants. Il a été démontré qu’une diminution de l’expression du gène MGMT par une hyperméthylation du promoteur résulte en une amélioration de la survie chez les patients avec certains types de tumeurs qui sont traitées avec des agents chimiothérapeuthique alkylants. Objectifs: Déterminer la prévalence de la méthylation du gène MGMT chez des patients avec des cancers épidermoïdes localement avancés de la sphère ORL traités avec chimioradiothérapie et évaluer l’impact de cette méthylation sur la survie. Méthodes: Sur 428 patients consécutifs, traités avec chimioradiothérapie à notre institution et suivis pour un période médiane de 37 mois, 199 spécimens chirurgicaux paraffinés ont été récupérés. L’ADN était extrait et modifié par le traitement au bisulfite. Une réaction en chaîne de la polymérase, spécifique à la méthylation était entreprise pour évaluer l’état de méthylation du promoteur du gène du MGMT. Les résultats de laboratoire étaient corrélés avec la réponse clinique. L’analyse statistique était exécutée à l’aide du test de Fisher pour les données catégoriques et à l’aide des courbes de Kaplan-Meier pour les échecs au traitement. Résultats : Des 199 extraits d’ADN initiaux, 173 (87%) étaient modifiés au bisulfite avec succès. Des ces spécimens modifiés, 71 (41%) ont démontré une hyperméthylation du MGMT. Pour les cas de méthylation et nonméthylation du MGMT, les caractéristiques des patients n’étaient pas significativement différentes. Les taux de réponse étaient 71 et 73% (p=NS) respectivement. Le contrôle locorégional était respectivement 87 et 77% (p=0.26), la survie sans maladie était 80 et 60% (p=0.38), la survie sans métastase à distance était 92 et 78% (p=0.08) et la survie globale était 64 et 62% (p=0.99) à 3 ans. Conclusions : L’état de méthylation du MGMT est fortement prévalent (41%) et semble avoir un possible impact bénéfique sur la survie quand la chimioradiothérapie est administrée aux patients avec des stades avancés de cancers tête et cou.

L'épigénétique, moteur de l'évolution d'un vertébré asexué

L’objectif de cette thèse est de déterminer l’étendue de la variabilité épigénétique, plus particulièrement du polymorphisme de méthylation de l’ADN, non liée à la variabilité génétique dans les populations asexuées en milieu naturel. Cette évaluation nous a permis de mieux cerner l’importance que peuvent avoir les processus épigénétiques en écologie et en évolution. Le modèle biologique utilisé est l’hybride clonal du complexe gynogénétique Chrosomus eos-neogaeus. Malgré une homogénéité génétique, une importante variabilité phénotypique est observée entre les hybrides d’une même lignée clonale mais retrouvés dans des environnements différents. L’influence des processus épigénétiques apporte une explication sur ce paradoxe. L’épigénétique se définit comme une modification de l’expression des gènes sans changement de la séquence d’ADN. La diversité des phénotypes peut entre autre s’expliquer par des patrons de méthylation différentiels des gènes et/ou des allèles des gènes entre les hybrides génétiquement identiques. La diversité des lignées épiclonales peut quant à elle s’expliquer par la colonisation de plusieurs lignées épiclonales, s’établir en réponse à l’environnement ou de façon aléatoire. Plusieurs méthodes seront utilisées afin de survoler le génome des hybrides clonaux pour mettre en évidence le polymorphisme de méthylation de l’ADN à l’échelle de l’individu et entre les individus de différentes populations.