Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Cianobactérias de diferentes tipos de lagoas ("salina", "salitrada" e "baía") representativas do Pantanal da Nhecolândia, MS, Brasil

Diante da importância ecológica das cianobactérias e da escassez de informações mais detalhadas sobre estes organismos nos diversos sistemas aquáticos do Pantanal brasileiro, o objetivo deste trabalho foi estudar a flora de cianobactérias de três lagoas do Pantanal da Nhecolândia. As lagoas estudadas são corpos d'água naturais, rasos (profundidade máxima 1,1 m), aproximadamente circulares e apresentam características limnológicas distintas. As amostras foram coletadas em períodos de seca e de cheia, entre 2004 e 2007. Foram identificadas 21 espécies de cianobactérias, com predominância da ordem Oscillatoriales (24% do total de espécies), seguida das ordens Synechococcales, Pseudanabaenales, Chroococcales e Nostocales, cada uma contribuindo com 19%. A lagoa Salina do Meio, de condições ambientais extremas, apresentou maior número de espécies de cianobactérias, 13 (62%). Nesta lagoa, florações de Anabaenopsis elenkinii Miller foram observadas principalmente nos períodos de seca. As lagoas Salitrada Campo Dora (9 espécies) e Baía da Sede Nhumirim (9) apresentaram riqueza de espécies iguais entre si, porém com composição distinta, provavelmente relacionada às diferentes condições ambientais das lagoas. Todas as espécies são citadas pela primeira vez para o Pantanal brasileiro.

Aspectos estruturais da comunidade arbórea em remanescentes de floresta estacional decidual, em Corumbá, MS, Brasil

(Aspectos estruturais da comunidade arbórea em remanescentes de floresta estacional decidual, em Corumbá, MS, Brasil). Um estudo comparativo da estrutura da comunidade arbórea entre dois remanescentes de floresta decídua foi conduzido em diferentes altitudes: florestas deciduais de terras baixas (FEDTB) e submontana (FEDSM), localizados em Corumbá, MS, Centro Oeste brasileiro. Amostraram-se indivíduos arbóreos com CAP ³ 15 cm, utilizando-se método de quadrantes. Foram demarcados 80 pontos em FEDTB e em FEDSM 78 pontos foram distribuídos por altitude: 180 m (18 pontos), 220, 260 e 300 m de altitude (20 pontos cada). Em FEDTB foram amostradas 34 espécies, sendo que Calycophyllum multiflorum Griseb., Ceiba pubiflora (A. St.-Hil.) K. Schum. e Anadenanthera colubrina (Vell.) Brenan apresentaram os maiores valores de importância. Na área de FEDSM foram amostradas 33 espécies, sendo que Anandenanthera colubrina, Ceiba pubiflora e Acosmium cardenasii H. S. Irwin & Arroyo foram as mais importantes. O padrão de distribuição das espécies variou ao longo do gradiente altitudinal. Em ambas as áreas, o índice de diversidade de Shannon foi de 2,9 e a Equitabilidade de 0,8, onde as famílias mais representativas foram Fabaceae (8 spp.) e Rubiaceae (4 spp). As florestas estudadas apresentaram baixa densidade de indivíduos por hectare em relação a outros estudos, exceto na área a 300 m. A comunidade arbórea apresentou 22,46% de indivíduos perfilhados e em fases iniciais de sucessão. O dossel variou de 6 a 12 m, com indivíduos emergentes de até 18 m. Estes remanescentes representam fonte de diversidade biológica para a região do Pantanal sendo importantes componentes dos corredores naturais da região.

Breviarium Fratrum Praedicatorum (MS C.IV.10)

Two probably originally distinct but roughly contemporary books (I-II, copied by three scribes, A-C): A psalter and a Dominican breviary. Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Contents: I: Psalter: Fols. 7r–76va, Psalter, with additional hymns, concluding with Te Deum; Fols. 76vb–77vb, the Athanasian Creed; Fols. 77vb–80v, litany and other prayers. II: Dominican breviary: Fols. 1r–6v, English Dominican calendar (Jan.–Dec.); Fols. 81r–242v, 276r–312r, proprium de tempore (defect), from the First Advent to the First Sunday after Trinity, and from septuagesima in mensis Augusti to the 25th Sunday after Trinity; Fols. 313ra–318v, Office for the dedication of a church; Fols. 243r–275v, 319r–334v, 353r–v, 335r–352v, 354r–371r, proprium de sanctis (defect), from the beginning up to the office of Mary Magdalene, with a misplaced leaf, fol. 353, at translatio B. Dominici, and, after several missing gatherings, the end of commune sanctorum; Fol. 371v, originally empty, with office for St Ursula added in a saec. XIV hand.

Codex Westh (MS C.III.19, kirkollinen käsinkirjoitettu kokoomanide)

Koodeksiin sisältyy kolme tekstikokonaisuutta. Ydinosan muodostavat suomalainen kirkkokäsikirja ja messu eli jumalanpalvelusjärjestys, joilla on oma, alkuperäinen sivunumerointinsa. Kolmas kokonaisuus on suomennos saksalaisen Urbanus Rhegiuksen laatimasta sielunhoidon opaskirjasta Sieluin vahvistus, lohutos ja lääkitys.

Identification of the divergent calmodulin binding motif in yeast Ssb1/Hsp75 protein and in other HSP70 family members

Yeast soluble proteins were fractionated by calmodulin-agarose affinity chromatography and the Ca2+/calmodulin-binding proteins were analyzed by SDS-PAGE. One prominent protein of 66 kDa was excised from the gel, digested with trypsin and the masses of the resultant fragments were determined by MALDI/MS. Twenty-one of 38 monoisotopic peptide masses obtained after tryptic digestion were matched to the heat shock protein Ssb1/Hsp75, covering 37% of its sequence. Computational analysis of the primary structure of Ssb1/Hsp75 identified a unique potential amphipathic alpha-helix in its N-terminal ATPase domain with features of target regions for Ca2+/calmodulin binding. This region, which shares 89% similarity to the experimentally determined calmodulin-binding domain from mouse, Hsc70, is conserved in near half of the 113 members of the HSP70 family investigated, from yeast to plant and animals. Based on the sequence of this region, phylogenetic analysis grouped the HSP70s in three distinct branches. Two of them comprise the non-calmodulin binding Hsp70s BIP/GR78, a subfamily of eukaryotic HSP70 localized in the endoplasmic reticulum, and DnaK, a subfamily of prokaryotic HSP70. A third heterogeneous group is formed by eukaryotic cytosolic HSP70s containing the new calmodulin-binding motif and other cytosolic HSP70s whose sequences do not conform to those conserved motif, indicating that not all eukaryotic cytosolic Hsp70s are target for calmodulin regulation. Furthermore, the calmodulin-binding domain found in eukaryotic HSP70s is also the target for binding of Bag-1 - an enhancer of ADP/ATP exchange activity of Hsp70s. A model in which calmodulin displaces Bag-1 and modulates Ssb1/Hsp75 chaperone activity is discussed.

Avaliação do teor de cobre e zinco em carnes cruas, processadas termicamente, resfriadas e congeladas no período de um mês

Para que elementos químicos, como o cobre e o zinco, sejam utilizados pelos sistemas biológicos, é necessário que estejam disponíveis para absorção, sendo assim, apenas a sua abundância na natureza não é fator que garanta a sua absorção. As carnes bovinas e de aves são de grande importância na alimentação, justamente por serem alimentos fonte de proteínas de alto valor biológico e lipídios. Processos de conservação através de refrigeração e congelamento, bem como processamento térmico, podem alterar fisicamente as carnes. Este trabalho tem como objetivo avaliar o comportamento de cobre e zinco em carnes resfriadas e conservadas em temperatura de congelamento por um período de 1 mês, processadas termicamente e in natura. Os teores de cobre e zinco foram determinados através da espectroscopia de absorção atômica. Os dados foram tratados estatisticamente através do teste de Grubs e t de Student. Mesmo com perdas no processamento térmico, e com a conservação em temperatura de congelamento durante o período de 4 semanas, o teor de cobre na maioria das amostras estudadas foi superior a 0,025mg%, e o do zinco superior a 0,3mg% para as amostras de carnes de aves e 0,6mg% para as amostras de carnes bovinas.

Brazilian roasted coffee oil obtained by mechanical expelling: compositional analysis by GC-MS

A preliminary analysis by GC-MS comparing the mass spectrum of the compounds with the Wiley 275 L mass spectral data base was used to identify the fatty acids and mainly, some volatile compounds responsible for the flavor of the roasted coffee oil. The oil was obtained by mechanical expelling of Brazilian beans (Coffea arabica) roasted at 238ºC for 10 minutes. Different sample preparation methodologies such as headspace, adsorbent suction trapping and esterification were used. It was possible to identify pyrazines, pyridines, furan derivatives and other compounds not reported in the literature.

Graduale (MS C.III.36, "Ilmajoen Graduale II")

A very small gradual and hymnary, for the most part copied in the last years of the sixteenth century or in the first quarter of the seventeenth. Assuming that Henricus Jacobi indeed signed his name in the sixteenth century (as Kurvinen reports), some of the manuscript was copied in that century: in lieu of a more accurate indicator the date of the manuscript appears to fall between 1589 and Mathias Benedicti's additions in 1635. The book was kept, perhaps even copied but certainly used, at Ilmajoki from the seventeenth century, and came from there to the University Library.

Antiphonarium (MS A.ö.II.29, Ilmajoen antifonarium)

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Psalterium Davidicum (MS C.IV.24)

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Graduale (MS A.ö.II.55, Ilmajoen graduale)

A graduale (defect) from Ilmajoki. Written in three parts, part I (fols. 1-134) dating probably from the 1540's, part II (fols. 135-140) probably from the 1550's and part III (fols. 141-194) from the 1530's.

Graduale (MS Coll. 762.3)

A Lutheran gradual copied apparently by one scribe at the end of the sixteenth century and probably repaired (fol. 29) in the beginning of the seventeenth century.

Graduale (MS C.ö.III.17)

A Lutheran gradual from Kalanti. As covers used a fragment of the Liturgical calendar of the Diocese of Turku, Saec. XIV 2/2, Diocese of Turku.