This thesis describes methods to obtain value–addedcompounds from TMP-turpentine obtained from the spruce, Piceaabies. The methodology focuses on biotransformations using twoapproaches: an oxygenation approach (i.e. oxygenation ofterpene hydrocarbons by cell cultures) and an esterificationapproach (i.e. lipase-catalysed transesterification of vinylacetate with terpene alcohols, and a further fractionation ofthe TMP-turpentine). The main constituents of the turpentine, a-pinene, b-pineneand limonene, were subjected to a P. abies suspension culture.Allylic oxidation formed the major products for α-pineneand β-pinene, which were further oxidised to theirrespective aldehyde or ketone. One of the minor products froma-pinene, cis-verbenol, was not only transformed into verbenonebut also isomerised to trans-verbenol. Limonene gavelimonene-(1,2)-epoxide as the major product. Fractionation of monoterpenes is accomplished throughphysical separation methods, chromatography and distillation,and lipase-catalysed transesterification of vinyl acetate withterpene alcohols. The esters of myrtenol and trans-pinocarveolwere separated from the more slowly reacting alcohols such asborneol and carveol by use of a combination of the Mucor mieheilipase and Candida antarctica lipase A as catalysts.Furthermore, the non-reacting tertiary terpene alcohols wereseparated from the reacting alcohols in a single step byCandida antarctica lipase A. Lipase-catalysed (Candida antarctica lipase B andPseudomonas cepacia lipase) transesterification of vinylacetate with sterically hindered secondary alcoholsunexpectedly yielded hemiacetals or hemiacetal esters. Thereaction conditions required to obtain these side products havebeen studied. <b>Keywords:</b>Picea abies, Pinaceae, Essential oilscomposition; Terpene alcohol; Hemiacetal; Hemiacetal ester,TMP-turpentine; Monoterpene; α-Pinene; β-Pinene;Limonene; Verbenol; Pinocarveol; Borneol; Myrtenol; Suspensioncell culture; Biotransformation; Lipase-catalysed; Oxidation;Allylic oxidation; Transesterification; Autoxidation;Separation.

<p>This thesis describes methods to obtain value–addedcompounds from TMP-turpentine obtained from the spruce, Piceaabies. The methodology focuses on biotransformations using twoapproaches: an oxygenation approach (i.e. oxygenation ofterpene hydrocarbons by cell cultures) and an esterificationapproach (i.e. lipase-catalysed transesterification of vinylacetate with terpene alcohols, and a further fractionation ofthe TMP-turpentine).</p><p>The main constituents of the turpentine, a-pinene, b-pineneand limonene, were subjected to a P. abies suspension culture.Allylic oxidation formed the major products for α-pineneand β-pinene, which were further oxidised to theirrespective aldehyde or ketone. One of the minor products froma-pinene, cis-verbenol, was not only transformed into verbenonebut also isomerised to trans-verbenol. Limonene gavelimonene-(1,2)-epoxide as the major product.</p><p>Fractionation of monoterpenes is accomplished throughphysical separation methods, chromatography and distillation,and lipase-catalysed transesterification of vinyl acetate withterpene alcohols. The esters of myrtenol and trans-pinocarveolwere separated from the more slowly reacting alcohols such asborneol and carveol by use of a combination of the Mucor mieheilipase and Candida antarctica lipase A as catalysts.Furthermore, the non-reacting tertiary terpene alcohols wereseparated from the reacting alcohols in a single step byCandida antarctica lipase A.</p><p>Lipase-catalysed (Candida antarctica lipase B andPseudomonas cepacia lipase) transesterification of vinylacetate with sterically hindered secondary alcoholsunexpectedly yielded hemiacetals or hemiacetal esters. Thereaction conditions required to obtain these side products havebeen studied.</p><p><b>Keywords:</b>Picea abies, Pinaceae, Essential oilscomposition; Terpene alcohol; Hemiacetal; Hemiacetal ester,TMP-turpentine; Monoterpene; α-Pinene; β-Pinene;Limonene; Verbenol; Pinocarveol; Borneol; Myrtenol; Suspensioncell culture; Biotransformation; Lipase-catalysed; Oxidation;Allylic oxidation; Transesterification; Autoxidation;Separation.</p>

CAPES / Neste trabalho foi investigado a composição química de metabólitos voláteis extraídos de quatro plantas Pimenta pseudocaryophyllus (Myrtaceae), Psidium cattleyanum (Myrtaceae), Hedychium coronarium (Zingiberaceae) e Costus spiralis (Zingiberaceae) através da cromatografia gasosa acoplada à espectrometria de massas (CG/MS). São apresentados resultados relativos à composição química sazonal do óleo essencial obtido das folhas de Pimenta pseudocaryophyllus, em amostras coletadas bimestralmente de janeiro a novembro de 2009. Em novembro foram observadas as maiores concentrações relativas aos constituintes majoritários do óleo essencial das folhas dessa espécie, sendo o chavibetol (70,90%) e metileugenol (20,70%). Além disso, foram avaliadas as atividades antimicrobianas do óleo essencial das folhas de P. pseudocaryophyllus através de técnicas de difusão com discos e microdiluição em caldo. O chavibetol, composto majoritário mostrou-se o responsável pela maior atividade antifúngica. São apresentados também a sazonalidade do óleo essencial obtido do rizoma de Hedychium coronarium, em amostras coletadas bimestralmente de março a janeiro de 2012 a 2013. Em março foram observadas as maiores concentrações relativas aos constituintes majoritários do óleo essencial do rizoma dessa espécie, sendo β- pineno (31,82%) e 1,8 cineol (28,30%). O estudo populacional dos metabólitos voláteis das folhas do Psidium cattleyanum coletados em Curitiba-PR identificou vinte e oito componentes sendo majoritário o lavander lactona (12,26%). Por outro lado, trinta e um compostos foram identificados no óleo essencial dessa mesma espécie em ecossistema de restinga, sendo majoritário o α-tujeno (25,20%). A extração de metabólitos voláteis das flores H. coronarium e brácteas da C. spiralis foi efetuada através do processo de aeração, fornecendo o linalol (43,58%) e o β- pineno (23,25%), respectivamente como os compostos majoritários. / In this work we investigated the chemical composition of volatile metabolites extracted from four plants Pepper pseudocaryophyllus (Myrtaceae), Psidium cattleyanum (Myrtaceae), Hedychium coronarium (Zingiberaceae) and Costus spiralis (Zingiberaceae) by gas chromatography-mass spectrometry (GC / MS). Results are presented relative to seasonal chemical composition of the essential oil obtained from the leaves of Pepper pseudocaryophyllus in samples collected bimonthly from January to November 2009. In November showed the highest concentrations on the major constituents of the essential oil from the leaves of this species, being chavibetol (70.90%) and methyleugenol (20.70%). Furthermore, we evaluated the antimicrobial activity of essential oil from the leaves of P. pseudocaryophyllus through techniques of diffusion disk and broth microdilution. The chavibetol, major compound was shown to be responsible for the greatest antifungal activity. We present also the seasonality of the essential oil obtained from the rhizome of Hedychium coronarium in samples collected bimonthly from March to January 2012-2013. In March the highest concentrations were observed on the major constituents of the essential oil of the rhizome of this species, and β-pinene (31.82%) and 1,8 cineole (28,30%). The population study of volatile metabolites from the leaves of Psidium cattleyanum collected in Curitiba identified twenty-eight components, the majority being lavander lactone (12.26%). Conversely, thirty-one compounds were identified in the essential oil of the species ecosystem in restinga provided the major constituent being the α-tujeno (25.20%). The extraction of volatile metabolites of flowers H. coronarium and bracts of C. spiralis was effected through the aeration process, providing linalool (43.58%) and β-pinene (23.25%), respectively as the major compounds.

CAPES / Neste trabalho foi investigado a composição química de metabólitos voláteis extraídos de quatro plantas Pimenta pseudocaryophyllus (Myrtaceae), Psidium cattleyanum (Myrtaceae), Hedychium coronarium (Zingiberaceae) e Costus spiralis (Zingiberaceae) através da cromatografia gasosa acoplada à espectrometria de massas (CG/MS). São apresentados resultados relativos à composição química sazonal do óleo essencial obtido das folhas de Pimenta pseudocaryophyllus, em amostras coletadas bimestralmente de janeiro a novembro de 2009. Em novembro foram observadas as maiores concentrações relativas aos constituintes majoritários do óleo essencial das folhas dessa espécie, sendo o chavibetol (70,90%) e metileugenol (20,70%). Além disso, foram avaliadas as atividades antimicrobianas do óleo essencial das folhas de P. pseudocaryophyllus através de técnicas de difusão com discos e microdiluição em caldo. O chavibetol, composto majoritário mostrou-se o responsável pela maior atividade antifúngica. São apresentados também a sazonalidade do óleo essencial obtido do rizoma de Hedychium coronarium, em amostras coletadas bimestralmente de março a janeiro de 2012 a 2013. Em março foram observadas as maiores concentrações relativas aos constituintes majoritários do óleo essencial do rizoma dessa espécie, sendo β- pineno (31,82%) e 1,8 cineol (28,30%). O estudo populacional dos metabólitos voláteis das folhas do Psidium cattleyanum coletados em Curitiba-PR identificou vinte e oito componentes sendo majoritário o lavander lactona (12,26%). Por outro lado, trinta e um compostos foram identificados no óleo essencial dessa mesma espécie em ecossistema de restinga, sendo majoritário o α-tujeno (25,20%). A extração de metabólitos voláteis das flores H. coronarium e brácteas da C. spiralis foi efetuada através do processo de aeração, fornecendo o linalol (43,58%) e o β- pineno (23,25%), respectivamente como os compostos majoritários. / In this work we investigated the chemical composition of volatile metabolites extracted from four plants Pepper pseudocaryophyllus (Myrtaceae), Psidium cattleyanum (Myrtaceae), Hedychium coronarium (Zingiberaceae) and Costus spiralis (Zingiberaceae) by gas chromatography-mass spectrometry (GC / MS). Results are presented relative to seasonal chemical composition of the essential oil obtained from the leaves of Pepper pseudocaryophyllus in samples collected bimonthly from January to November 2009. In November showed the highest concentrations on the major constituents of the essential oil from the leaves of this species, being chavibetol (70.90%) and methyleugenol (20.70%). Furthermore, we evaluated the antimicrobial activity of essential oil from the leaves of P. pseudocaryophyllus through techniques of diffusion disk and broth microdilution. The chavibetol, major compound was shown to be responsible for the greatest antifungal activity. We present also the seasonality of the essential oil obtained from the rhizome of Hedychium coronarium in samples collected bimonthly from March to January 2012-2013. In March the highest concentrations were observed on the major constituents of the essential oil of the rhizome of this species, and β-pinene (31.82%) and 1,8 cineole (28,30%). The population study of volatile metabolites from the leaves of Psidium cattleyanum collected in Curitiba identified twenty-eight components, the majority being lavander lactone (12.26%). Conversely, thirty-one compounds were identified in the essential oil of the species ecosystem in restinga provided the major constituent being the α-tujeno (25.20%). The extraction of volatile metabolites of flowers H. coronarium and bracts of C. spiralis was effected through the aeration process, providing linalool (43.58%) and β-pinene (23.25%), respectively as the major compounds.