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The primary objective of this study was to find out if changes in chemistry could be used to quantify Pinus radiata compression wood severity or degree of compression wood development. Basic chemical composition and the lignin structure was assessed for a range of different compression wood samples sourced from juvenile wood, mature wood, earlywood, latewood, branches, knots, 2-year and 1-year old Pinus radiata. Fluorescence microscopy was used as the reference method to assess the degree of compression wood development. Lignin structure of compression wood was studied by thioacidolysis, size exclusion chromatography, and thioacidolysis/31P NMR spectroscopy. Variation in the basic chemical composition and lignin structure with compression wood severity was ascertained. Results showed that, as the severity of compression wood changed, progressively from normal through mild to severe, all chemical parameters commonly associated with compression wood changed concurrently. With increasing severity lignin and galactose levels increased while glucose and mannose levels decreased. Lignin structural changes were also associated with changing severity of compression wood. Levels of p-hydroxyphenyl (H) releasable β-ethers increased and guaiacyl (G) releasable β-ethers decreased. Similarly, levels of uncondensed p-hydroxyphenyl units increased, while uncondensed guaiacyl units decreased. Similar proportions of condensed guaiacyl units were present in compression wood and normal wood. Similar trends in chemical composition were observed between the compression wood and related opposite wood in branches, knots and young wood of Pinus radiata. A number of chemical parameters changed linearly with compression wood severity. They were: the amount of lignin and galactose, the galactose/glucose ratio and p-hydroxyphenyl content in lignin. Parameters based on the p-hydroxyphenyl unit content in lignin, the H/G releasable β-ether ratio, releasable p-hydroxyphenyl β-ether units and uncondensed p-hydroxyphenyl C9 units are most suitable indicators of compression wood severity as they spanned a larger range relative to the normal wood levels and were not influenced by the morphological origin of wood samples. Chemical methods for quantifying compression wood severity should focus on the detection and measurement of these parameters. Galactan present in Pinus radiata compression wood was isolated and characterised. Structural investigation by methylation analysis and NMR spectroscopy revealed that this galactan was largely composed of (1→4)-linked β-D-galactopyranose residues. No evidence was found to indicate the presence of any branches. Characterisation of lignin in cell wall fractions of Pinus radiata normal wood revealed that middle lamella lignin has a higher lignin content, a lower amount of releasable β-ethers and a more condensed lignin than the secondary wall lignin. Levels of releasable p-hydroxyphenyl units were not higher in middle lamella lignin. A new method based on thioacidolysis and 31P quantitative NMR spectroscopy for estimation of the degree of lignin condensation of the phenolic and etherified C9 units in in situ wood lignin is described. Using this method it was found that phenolic C9 units in in situ lignin were considerably less condensed than etherified C9 units in both compression wood and normal wood.

Made available in DSpace on 2014-12-17T14:13:34Z (GMT). No. of bitstreams: 1 PauloDPS_DISSERT_partes_autorizadas.pdf: 366490 bytes, checksum: 3e5abdd24789d0e82844edffadbb1a3e (MD5) Previous issue date: 2010-06-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The acidic galactan (AG) was obtained by extraction and proteolysis by acetone precipitation of the eggs of the mollusc Pomacea lineata. Its structure was elucidated by a combination of chemical analysis, the intrinsic viscosity and NMR spectroscopy 1D and 2D. Biological aspects of AG were evaluated by in vivo testing of healing and peritonitis induced (anti-inflammatory activity) and in vitro assays of cytotoxicity (MTT). This polymer showed a simple structure without the presence of sulfate and uronic acids in its structure. Its intrinsic viscosity and relative were evaluated at 0.44 ? 0.05 and 1.744? 0.07 dl.g-1. Spectroscopy showed that the AG has a constitution composed predominantly of β-D-galactosis, and β-D-glucosamine-NAcetil that comes in a smaller proportion in chain. The character of this acidic polysaccharide is given by the presence of pyruvate in the molecule, forming a cyclic acetal of six states, located in β-D-galactosis. The involvement of AG in the healing process was evaluated and the histological analysis revealed that there was so early in the process of healing, a great stimulation of macrophages with granuloma formation. Suggesting that AG may have promoted the advance of biological events required for tissue healing. In the trial of the GA-induced peritonitis showed dose dependent, demonstrating the anti-inflammatory effect at concentrations above 20 mg/kg, and confirming its inflammatory character and the concentration of 1mg/kg. In vitro tests used in the GA concentration of 1000 μg/mL showed proliferative activity by stimulating the growth of 3T3 cells, corroborating the findings in vivo and demonstrating the absence of cytotoxic activity / O Galactano ac?dico (GA) foi obtido atrav?s de extra??o por prote?lise e precipita??o com acetona das ovas do molusco Pomacea lineata. Sua estrutura foi elucidada atrav?s de uma combina??o de an?lises qu?micas, da viscosidade intr?nseca e de espectroscopia de Resson?ncia Magn?tica Nuclear, mono e bidimensionais. Os aspectos biol?gicos do GA foram avaliados atrav?s de ensaios in vivo de cicatriza??o e de peritonite induzida (atividade antiinflamat?ria); e ensaios in vitro da atividade citot?xica (MTT). Este polissacar?deo apresentou uma estrutura simples, sem presen?a de sulfato e ?cidos ur?nicos. Suas viscosidades intr?nseca e relativa foram avaliadas em 0,44 ? 0,05 e 1,744 ? 0,07 dL.g-1. A espectroscopia mostrou que o GA possui uma constitui??o formada predominantemente por β-D-galactoses, al?m de β- D-NAcetil-glucosamina que surge em menor propor??o na cadeia. O car?ter ac?dico deste polissacar?deo ? dado pela presen?a de piruvato na mol?cula, formando um acetal c?clico de 6-membros, localizados nas β-D-galactoses. A participa??o do GA na cicatriza??o foi avaliada e as an?lises histol?gicas revelaram que houve, de forma precoce ao processo de cicatriza??o, uma grande estimula??o de macr?fagos, com forma??o de granulomas. Sugerindo que o GA pode ter promovido a antecipa??o de eventos biol?gicos necess?rios ? cicatriza??o do tecido. No ensaio de peritonite induzida o GA se mostrou dose dependente, demonstrando uma a??o antiinflamat?ria em concentra??es acima de 20mg/kg, e comprovando seu car?ter inflamat?rio na concentra??o de 1mg/Kg. Em ensaios in vitro o GA utilizado na concentra??o de 1000 μg/mL apresentou atividade proliferativa estimulando o crescimento de c?lulas 3T3, corroborando os achados in vivo e demonstrando aus?ncia de atividade citot?xica

In this thesis, carbohydrate mimicry is investigated through the syntheses of carbohydrate analogues and evaluation of their inhibitory effects on carbohydrate-processing enzymes. Galactofuranosides are interesting structures because they are common motifs in pathogenic microorganisms but not found in mammals. M.tuberculosis, responsible for the disease tuberculosis, has a cell wall containing a repeating unit of alternating (1→5)- and (1→6)-linked β-D-galactofuranosyl residues. Synthetic inhibitors of the enzymes involved in the biosynthesis of the cell wall could find great therapeutic use. The first part of this thesis describes the first synthesis of the hydrolytically stable carbasugar analogue of galactofuranose, 4a-carba-β-D-Galf, and the synthetic work of synthesising β-linked pseudodisaccharides containing carba-Galf, which were tested for glycosyltransferease inhibitory activity. The pseudodisaccharide carba-Galf-(β1→5)-carba-Galf was found to be a moderate inhibitor of the glycosyltransferase GlfT2 of M.tuberculosis. The thesis also describes how a general method towards biologically relevant α-linked carba-Galf ethers was developed. The final part of this thesis is focussed on the formation of nitrogen-linked monosaccharides without the participation of the anomeric centre. Such a mode of coupling is called tail-to-tail neodisaccharide formation. The couplings of carbohydrate derivatives via the Mitsunobu reaction are successfully reported herein. The method describes the key introduction of an allylic alcohol in the electrophile and the subsequent functionalisation of the alkene to obtain the neodisaccharide. Two synthesised neodisaccharides presented in this thesis have been sent to be tested for glycosidase inhibitory activity. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript. Paper 6: Manuscript.