DERIVATIZACIÓN Y CARACTERIZACIÓN ESPECTROSCÓPICA DE UN BIOPOLÍMERO A BASE DE L -LISINA CON ANÁLOGOS DE LA D-BIOTINA: CO -POLI(L-LISINA)-GRAFT -(ε-N-[X-D -BIOTINIL]-L-LISINA)

We report the single-step derivatization reaction of a biopolymer based onL -lysine with D -biotin analogs:Co -poly(L -lysine)-graft-(ε-N -[X-D-biotinyl]-L -lysine) (PLL-X-Biotin). The valeric acid carboxylate of D -biotin is activated to an NHS ester for direct modification of amine groups in proteins and other macromolecules. NHS esters react by nucleophilic attack of an amine in the carbonyl group, releasing the NHS group, and forming a stable amide linkage. NHS-X-Biotin is the simplest biotinylation reagent commercially available. In contrast withD -biotin, it has a longer spacer arm off the valeric acid side chain allowing better binding potential for avidin or streptavidin probes. Derivatization of poly(L -lysine) (PLL) with NHS-X-Biotin led to a copolymer PLL-X-Biotin. UV-Visible, IR-FT and 1H NMR characteristics derived from synthesis are briefly discussed.

DESENVOLVIMENTO DE ENSAIO PARA ANÁLISE QUALITATIVA DE BIODIESEL EM MISTURAS DIESEL-BIODIESEL PARA APLICAÇÃO EM POSTOS REVENDEDORES DE COMBUSTÍVEIS

In this study, we developed a method for the visual detection of biodiesel in petrodiesel-biodiesel (BX) blends through the aminolysis of the methyl or ethyl esters of fatty acids that are found in biodiesel and that are absent from diesel and vegetable oils. This method is based on three reactional stages, which produce a dark red and easily visualized complex in the presence of biodiesel. In the absence of biodiesel, there is no dark red coloring, whereas in the presence of diesel or vegetable oil, there is a light red to yellow coloring. This simple, practical, inexpensive, and effective procedure may be applied by petrol stations to guarantee to consumers and resellers the presence of biodiesel in diesel blends, regardless of the BX blend's initial coloring or of the sulfur found in the diesel. In short, it ensures a safe fuel tank fill-up with BX blend.

FAST GC-FID METHOD FOR MONITORING ACIDIC AND BASIC CATALYTIC TRANSESTERIFICATION REACTIONS IN VEGETABLE OILS TO METHYL ESTER BIODIESEL PREPARATION

A fast gas chromatography with a flame ionisation detector (GC-FID) method for the simultaneous analysis of methyl palmitate (C16:0), stearate (C18:0), oleate (C18:1), linoleate (C18:2) and linolenate (C18:3) in biodiesel samples was proposed. The analysis was conducted in a customised ionic-liquid stationary-phase capillary, SLB-IL 111, with a length of 14 m, an internal diameter of 0.10 mm, a film thickness of 0.08 µm and operated isothermally at 160 °C using hydrogen as the carrier gas at a rate of 50 cm s-1 in run time about 3 min. Once methyl myristate (C14:0) is present lower than 0.5% m/m in real samples it was used as an internal standard. The method was successful applied to monitoring basic and acidic catalysis transesterification reactions of vegetable oils such as soybean, canola, corn, sunflower and those used in frying process.

Hemiselluloosien erotus ja in situ -modifiointi

Hemiselluloosat kuuluvat selluloosan ja ligniinin ohella puun ja muiden kasvimateriaalien päärakenneaineksiin. Hemiselluloosan kemiallisessa koostumuksessa on eroja kasvilajien välillä, mikä tekee ryhmästä hyvin monimuotoisen. Lehtipuiden pääasiallinen hemiselluloosa on glukuroniksylaani. Ksylaaneja esiintyy laajasti myös muissa kasveissa erilaisina rakenteina. Havupuiden yleisin hemiselluloosa on puolestaan galaktoglukomannaani. Arabinogalaktaani on erityisesti lehtikuusesta runsaana löytyvä hemiselluloosa, jota muissa puulajeissa on vain vähän. Luonnon polymeerejä tutkitaan jatkuvasti muun muassa vaihtoehtojen löytämiseksi raakaöljypohjaisille tuotteille. Aiemmin hemiselluloosia on pääosin hyödynnetty sellaisenaan tai jalostettu esimerkiksi sokereiksi. Selluloosan ja tärkkelyksen tavoin ne voivat kuitenkin toimia myös kemiallisen, fysikaalisen tai entsymaattisen muokkauksen lähtöaineena. Hemiselluloosien käyttöä rajoittaa usein se, että niiden eristäminen kasvimateriaalista hyvällä saannolla on vaikeaa. Useimmiten hemiselluloosa erotetaan biomassasta ligniinin poiston jälkeen uuttamalla erilaisilla reagensseilla, kuten emäksillä. Arabinogalaktaanin erottamiseen ei kuitenkaan vaadita ankaria olosuhteita, vaan yleisimmin siihen riittää uutto vedellä. Kalvosuodatus puolestaan on hyvä keino hemiselluloosan talteenottoon uuttoliuoksista. Tässä työssä tarkasteltiin arabinogalaktaanin erotusta siperianlehtikuusesta uuttokokein. Saadut uuttoliuokset konsentrointiin ja puhdistettiin kalvosuodatusmenetelmillä. Lisäksi tutkittiin eristetyn arabinogalaktaanin käyttöä kemiallisen muokkauksen lähtöaineena, missä pyrkimyksenä oli etenkin in situ -modifiointi suoraan uuttoliuoksessa oleville yhdisteille. Uuttokokeilla saatiin kuitenkin vain pieni osa lehtikuusen arabinogalaktaanista erotetuksi. Myös kalvosuodatusvaiheen aikana menetettiin osa uuttoliuosten arabinogalaktaanista. Koska arabinogalaktaanipitoisuus uuttoliuoksissa jäi hyvin alhaiseksi, in situ -modifiointeja oli vaikea saada onnistumaan. Uutto-olosuhteiden lisätutkimuksella sekä kiinnittämällä erityistä huomiota suodatuskalvojen valintaan voitaneen pitoisuutta nostaa ja saada lisämateriaalia kemiallista muokkausta varten.

Dewatering of hard-to-dewater pulps

Nanocellulose has much potential for enhancing the tensile strength of paper but it slows down significantly drainage, restricting its use in industrial scale. Main objective of the work was to find ways to improve the dewatering of nanocellulose-containing papers. The effects of cationic potato starch, microparticle system and filler addition on dewatering and such key properties as formation, tensile strength and air permeance of manufactured paper were studied. Test points had 0, 4 or 8 % CNF and 0, 15 or 30 % PCC content. Based on earlier studies, 25 mg/g starch dosage was added to some test points. Modern microparticle system, consisted of cationic polyacrylamide and amorphous silica, was used in few test points. Dosages for both components were 0.3 and 0.6 mg/g, following the recommendations of the supplier. Also, the influences of CNF and filler on drying behaviour after different stages (drainage, wet pressing and cylinder drying) were estimated. Following trends were observed. Starch does not have unambiguous influence on dewatering. In some cases, it improved drainage slightly but effects on the properties of end product were discovered small. Filler quickened dewatering but large proportions were noticed to be detrimental for the drainage, air permeance and tensile strength. Microparticle system improved drainage notably, especially if CNF dosage was high. In addition, microparticle system increased tensile strength and decreased air permeance. However, its effects on formation were detrimental. Dewatering of nanocellulose-containing furnishes is treatable up to a certain point. In the end, such drainage times that were measured from test points which consisted only of pure kraft pulps are awkward to reach.

Potentiometric determination of captopril in pharmaceutical formulations

A simple, precise, rapid and low-cost potentiometric method for captopril determination in pure form and in pharmaceutical preparations is proposed. Captopril present in tablets containing known quantity of drug was potentiometrically titrated in aqueous solution with NaOH using a glass pH electrode, coupled to an autotitrator. No interferences were observed in the presence of common components of the tablets as lactose, microcrystalline cellulose, croscarmellose sodium, starch and magnesium stearate. The analytical results obtained by applying the proposed method compared very favorably with those obtained by the United States Pharmacopoeia Standard procedure. Recovery of captopril from various tablet dosage formulations range from 98.0 to 102.0%.

Lability of Cd, Cr, Cu, Mn and Pb complexed by aquatic humic substances

The lability of Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) complexed by humic substances (HSs) was investigated by means of ion exchange on cellulose modified with p-aminobenzoic groups (Cell-PAB), using a batch procedure. The HSs were extracted from water samples using adsorption in a column packed with XAD 8 resin. The metal-HS complexes were prepared by adding solutions containing all the aforementioned metal ions ( Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) ). The results indicated that the distribution coefficients (Kd) of Cell-PAB decreased with the presence of HSs, and that the lability of metal fractions complexed by HSs decreases in pH values > 4.0, complexation time > 10 h and HS concentration > 500 mg L-1. The metal exchange between HSs and Cell-PAB exhibited the following order of metal ion lability: Cd < Pb < Mn @ Cr < Cu.

Natural and synthetic fibres improving tensile strength and elongation of paper products

The theory part of the Master’s thesis introduces fibres with high tensile strength and elongation used in the production of paper or board. Strong speciality papers are made of bleached softwood long fibre pulp. The aim of the thesis is to find new fibres suitable for paper making to increase either tensile strength, elongation or both properties. The study introduces how fibres bond and what kind of fibres give the strongest bonds into fibre matrix. The fibres that are used the in manufacturing of non-wovens are long and elastic. They are longer than softwood cellulose fibres. The end applications of non-wovens and speciality papers are often the same, for instance, wet napkins or filter media. The study finds out which fibres are used in non-wovens and whether the same fibres could be added to cellulose pulp as armature fibres, what it would require for these fibres to be blended in cellulose, how they would bind with cellulose and whether some binding agents or thermal bonding, such as hot calendaring would be necessary. The following fibres are presented: viscose, polyester, nylon, polyethylene, polypropylene and bicomponent fibres. In the empiric part of the study the most suitable new fibres are selected for making hand sheets in laboratory. Test fibres are blended with long fibre cellulose. The test fibres are viscose (Tencel), polypropylene and polyethylene. Based on the technical values measured in the sheets, the study proposes how to continue trials on paper machine with viscose, polyester, bicomponent and polypropylene fibres.

Lipase-catalyzed Approaches towards Secondary Alcohols: Intermediates for Enantiopure Drugs

The use of enantiopure intermediates for drug synthesis is a trend in pharmaceutical industry. Different physiological effects are associated with the enantiomers of chiral molecules. Thus, the safety profile of a drug based on an enantiopure active pharmaceutical ingredient is more reliable. Biocatalysis is an important tool to access enantiopure molecules. In biocatalysis, the advantage of selectivity (chemo-, regio- and stereoselectivity) is combined with the benefits of a green synthesis strategy. Chemoenzymatic syntheses of drug molecules, obtained by combining biocatalysis with modern chemical synthesis steps usually consists of fewer reaction steps, reduced waste production and improved overall synthetic efficiency both in yields and enantio- and/or diastereoselectivities compared with classical chemical synthesis. The experimental work together with the literature review clearly indicates that lipase catalysis is highly applicable in the synthesis of enantiopure intermediates of drug molecules as the basis to infer the correct stereochemistry. By lipase catalysis, enantiopure secondary alcohols used as intermediates in the synthesis of Dorzolamide, an antiglaucoma drug, were obtained. Enantiopure _-hydroxy nitriles as potential intermediates for the synthesis of antidepressant drugs with 1-aryl-3- methylaminopropan-1-ol structure were also obtained with lipases. Kinetic resolution of racemates was the main biocatalytic approach applied. Candida Antarctica lipase B, Burkholderia cepacia lipase and Thermomyces lanuginosus lipase were applied for the acylation of alcohols and the alcoholysis of their esters in organic solvents, such as in diisopropyl ether and tert-butyl methyl ether. Candida Antarctica lipase B was used under solvent free conditions for the acylation of ethyl 3-hydroxybutanoate.

Production of biodiesel from babassu oil using methanol-ethanol blends

Maranhão state in Brazil presents a big potential for the cultivation of several oleaginous species, such as babassu, soybean, castor oil plant, etc... These vegetable oils can be transformed into biodiesel by the transesterification reaction in an alkaline medium, using methanol or ethanol. The biodiesel production from a blend of these alcohols is a way of adding the technical and economical advantages of methanol to the environmental advantages of ethanol. The optimized alcohol blend was observed to be a methanol/ethanol volume ratio of 80 % MeOH: 20 % EtOH. The ester content was of 98.70 %, a value higher than the target of the ANP, 96.5 % (m/m), and the biodiesel mass yield was of 95.32 %. This biodiesel fulfills the specifications of moisture, specific gravity, kinematic viscosity and percentages of free alcohols (methanol plus ethanol) and free glycerin.

Formation of polyelectrolyte multilayers and polyelectrolyte complexes in dual polymer treatment of papermaking pulp

The goal of this study was to find a new approach to modify chemically the properties of paper by improving fiber quality. This Master’s thesis includes the multiple polymer treatment in general and themeasurement methods with which the formation of multilayers and complexes can be noticed. The treatment by an oppositely charged dual polymer system is a good approach to increase paper strength. In this work, starch, a cationic polymer, and carboxymethyl cellulose (CMC), an anionic polymer, were used step-by-step to improve paper strength. The adsorption of cationic starch and CMC on cellulose fibers were analyzed via polyelectrolyte titration. The results showed that paper strength was enhanced slightly with a layer-by-layer assembly of the polymers. However, if the washing stage, which was required for layer-by-layer assembly, was eliminated, the starch/CMC complex was deposited on fibers more efficiently, and the paper strength was improved more significantly.

Biokaasu-, bioetanoli- ja yhdistelmäprosessin energia- ja hiilidioksiditase vertailu

Biojäte soveltuu erinomaisesti biokaasuprosessin raaka-aineeksi sisältämänsä runsaan or-gaanisen aineksen vuoksi. Bioetanoliprosessin raaka-aineeksi se soveltuu, koska biojäte sisäl-tää runsaasti tärkkelystä sekä selluloosaa. Tässä työssä tutkittiin laskennallisesti bioetanoli-, biokaasu- sekä näiden yhdistelmäprosessin energia- ja hiilidioksiditaseita kirjallisuuden tietoihin pohjautuen. Biokaasuprosessista lopputuotteena saatavan biometaanin käyttäminen bensiiniä korvaavana liikennepolttoaineena tuottaa jo pelkästään palamistuotteena syntyvän hiilidioksidin säästöinä 62 kg/tbiojätettä. Energian suhteen biokaasuprosessi on selvästi yliomavaraisin kaikista kolmesta prosessista, vaikka energiankulutukseen huomioidaan myös jalostuksen tarvitsema sähkönku-lutus. Biokaasuprosessissa oma käyttö on alle 20 % lopputuotteen lämpöarvosta, yhdistelmä-prosessin osalta luku on 4 %-yks alhaisempi.

Nematicidal effect of volatile organic compounds (VOCs) on the plant-parasitic nematode Meloidogyne javanica

Previous studies have demonstrated that volatile organic compounds (VOCs), produced by the yeast Saccharomyces cerevisiae, were able to inhibit the development of phytopathogenic fungi. In this context, the nematicidal potential of the synthetic mixture of VOCs, constituted of alcohols and esters, was evaluated for the control of the root-knot nematode Meloidogyne javanica, which causes losses to crops of high economic value. The fumigation of substrate containing second-stage juveniles with VOCs exhibited nematicidal effect higher than 30% for the lowest concentration tested (33.3 µL g-1 substrate), whereas at 66.6 and 133.3 µL g-1 substrate, the nematode mortality was 100%. The present results stimulate other studies on VOCs for nematode management.

Kiintoaineen ja nesteen erotusprosessit lignoselluloosaetanolin tuotannossa

Työn tarkoituksena on tehdä kirjallisuuskatsaus kiintoaine-neste-erotusprosesseihin lignoselluloosaetanolin tuotannossa. Työssä keskitytään hydrolysoidun ligniinipitoisen lignoselluloosamateriaalin kiintoaine-neste-erotukseen. Tarkoituksena on tutkia lignoselluloosamateriaalin suodatus- ja sentrifugointiprosesseja sekä niiden vaikutusta lignoselluloosaetanolin tuotantoon.

Mapping of QTLs related with wood quality and developmental characteristics in hybrids (Eucalyptus grandis x Eucalyptus urophylla)

The present work aimed to characterize and identify QTLs for wood quality and growth traits in E. grandis x E. urophylla hybrids. For this purpose a RAPD linkage map was developed for the hybrids (LOD=3 and r=0.40) containing 52 markers and 12 linkage groups. Traits related to wood quality and growth were evaluated in the QTL analyses. QTL analyses were performed using chi-square tests, single-marker, interval mapping and composite interval mapping analyses. All approaches led to the identification of similar QTLs associated with wood density, cellulose pulp yield and percentage of extractives, which were detected and confirmed by both the interval mapping and composite interval mapping methodologies. Some QTLs regions were confirmed only by the composite interval mapping methodology: percentage of soluble lignin, percentage of insoluble lignin, CBH and total height. Overlapping QTLs regions were detected, and these, can be the result of major genes involved in the regulation and control of the growth traits by epistatic interactions. In order to evaluate the effect of early selection using RAPD molecular data, molecular markers adjacent to QTLs were used genotype selection. The analysis of selection differential values suggests that for all the traits the phenotypic selection at seven years should generate larger genetic gains than early selection assisted by molecular markers and the combination of the strategies should elevate the selection efficiency.