Inaug.-Diss.--Göttingen. / Vita.

As part of CSIR Biosciences’ interest in aroma chemicals, the processing of crude sulphated turpentine (CST) into high value aroma products was investigated. The primary target product, linalool, was obtained from a mixture of α- and β-pinene in four steps. It can be transformed into a wide range of high value added aroma chemicals. Isomerisation of linalool in the presence of a transition metal catalyst furnishes geraniol and nerol. The scientific work described in this report was part of a bigger project aimed at developing innovative processes to manufacture aroma, flavour & fragrance chemicals through beneficiation of industrial waste streams and other raw materials, available locally from the Forestry, Paper & Pulp industries. The evaluation of a process for the preparation of precursor aroma, flavour & fragrance compounds, in particular geraniol and nerol, from locally available raw materials and industrial waste streams, was investigated. Preparation of geraniol and nerol from linalool (ex α-pinene stream) was investigated using acids or organometallic complexes as catalysts for the corresponding isomerisation reaction. The investigation was conducted in an effort to find a less costly process utilising milder conditions than via the conventional cleavage of β-pinene to myrcene under extreme pyrolysis conditions (>650°C). The transformation of linalool to geraniol/nerol using mineral acids was found to be dominated by secondary reactions such as dehydration and cyclisation, resulting in poor product selectivities and yields. On the other hand, organometallic complexes, in particular vanadium-based complexes (e.g. (OV(OBu)3) produced satisfactory results in the preliminary assessment (conversion of 79.8 percent and selectivity of 98.3 percent). A set of statistically designed experiments was carried out on the (VO(BuO)3 + [(Bu)4N+]OH¯) catalyst system where three variables were tested, i.e. substrate concentration, temperature, and catalyst loading. The selected model for conversion was significant with the “Probability > F” being < 0.0001. The most important contributing variable to the model for conversion was temperature i.e. 83.9 percent. Temperature was still the most important variable for the selectivity response at 65.0 percent contribution level. The response surface generated for the selectivity response was flat indicating a robust method within the parameter range selected.

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The extraction and distillation of pine sap for the naval stores industry reached its apex of production in the early decades of the twentieth century. Post-emancipation, the industry employed African American labor in the long leaf pine forests of the southeastern United States under a system of debt peonage that replaced the master-slave dynamic with a similar circumscriptive construct. Laborers rented company housing and were paid in scrip, a monetary system that limited their purchase of the basic goods of subsistence to the company commissary at inflated prices, resulting in an endless cycle of debt. Despite the oppressive circumstances of debt peonage labor, African Americans developed venues known as “jook joints” for the expression of agency through leisure. The jook was a structure where laborers congregated on weekends to socialize, dance, drink, gamble, and fight. The Polk County, Florida turpentine camp of Nalaka was in operation from 1919 until 1928. In 1942, the Nalaka site, and thousands of surrounding acreage, were purchased by the United States Government for use as an Air Force training range in anticipation of US involvement in World War Two. Although no structures survive, artifact scatters from the 1920s remain in situ. No known records exist to document the spatial arrangement of the structures at Nalaka. This study reconstructs the layout of the camp based upon artifact provenience, secondary iii ethnographic sources, and historical documents, to determine whether or not Nalaka supported a jook joint, and if so, where was its location.

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>

La chimie des résines est née en France à Bordeaux au début du XXe siècle. Son émergence est inextricablement liée à la création de l’Institut du Pin. Cet établissement est une entité complexe dont les origines remontent à 1900, moment où Maurice Vèzes, professeur de chimie, établit à Bordeaux le Laboratoire de chimie appliquée à l’industrie des résines afin d’aider l’industrie locale à résoudre une crise sociale et économique. La place des produits résineux sur le marché est menacée à l’époque par l’émergence de l’industrie pétrolière. Sous la direction des grandes figures de la chimie française Georges Dupont et Georges Brus, l’Institut du Pin contribue à la valorisation de la résine de pin. Non seulement il développe de nouveaux débouchés, mais il s’implique dans la normalisation de dérivés résineux en France et à l’international. Les travaux de l’Institut suscitent aussi l’intérêt outre-Atlantique. L’industrie américaine des résines profite amplement de l’expertise française et essaie d’établir ses propres institutions scientifiques à l’image de celles en France. L’Institut du Pin devient le véritable centre mondial de la chimie des résines et remplit ce rôle jusqu’au déclin de l’industrie régionale à la fin des années 1960. / Pine resin chemistry was born in France in the beginning of the 20th century. Its birth is intimately linked to the establishment of the Pine Institute. It was a complex entity whose origins go back to 1900 when Maurice Vèzes, professor of chemistry at the Faculty of Sciences in Bordeaux, created the Laboratory of Chemistry Applied to the Resin Industry in order to help the regional resin industry to fight the social and economic crisis. The market position of resinous products was threatened by the rise of the petroleum industry offering low quality but cheap alternatives. Under the direction of great French chemists, Georges Dupont and Georges Brus, the Pine Institute helped the resin producers to face the threat of petroleum. Not only it elaborated new products but it actively contributed to the development of national and international standards on resin. The Institute’s works aroused interest also in the United States of America. The American resin industry greatly profited from the French expertise and it tried to establish its own scientific institutions following the French example. The Pine Institute became the global centre of resin chemistry and it fulfilled this role until the decline of the regional industry in the end of the 1960s.

Medicinal turpentine has been used extensively in the eastern Free State and KwaZulu-Natal in the belief that it is able to prevent and treat redwater in cattle. A number of commercial beef farmers have been using it for many years and the information has been passed down through generations. Redwater is often a fatal disease in cattle and results in losses of large numbers every year in South Africa. In this study redwater is used to describe both Babesia bigemina (African redwater) and Babesia bovis (Asiatic redwater). Redwater is also known as babesiosis. Medicinal turpentine is obtained by the distillation of resin obtained from numerous pine tree species as a by-product during the production of chemical wood pulp9,72. The use of turpentine for the treatment of redwater is, however, yet to be scientifically validated. This study was initiated in an attempt to investigate the validity in the use of the turpentine as a medicinal agent. For this study the use of turpentine was evaluated in three parts. The first component of the study involved a detailed survey with ten commercial farmers from KwaZulu-Natal and the eastern Free State who were known to be proponents for the use of turpentine. The second part of the study made use of a screening assay of Babesia caballi in a red cell culture which was exposed to various concentrations of turpentine in comparison to Diminazene and Imidocarb. Both of these drugs are used on a large scale in the conventional treatment of redwater and are at this point in time the most effective treatments available in South Africa. In the third part a tolerance study was undertaken. Twenty four cattle were treated with turpentine. Three different volumes were used and a control group was treated with saline. Blood was then drawn from these animals at specified intervals and pre-determined parameters were measured. These included obtaining serum for Babesia bovis and Babesia bigemina serology to determine whether the animals used had ever been exposed to either one of these parasites. Temperatures, weights, pregnancy status and injection site reactions were also monitored. From the information gathered farmers are using turpentine in a fairly consistent manner so it was relatively straight forward to design a treatment protocol for the tolerance study that could be representative of what was being done in the field. The cultures indicated that turpentine may have a delayed static effect on parasite growth or it may have an indirectly cidal effect. This effect was most obvious at certain concentrations. It was not seen with all the concentrations used in the cultures. The tolerance study revealed that a significant effect was seen in the protein levels and no deleterious effects were noted either in liver or kidney function. Further studies will need to be undertaken to determine the exact effect turpentine has on the immune response and whether this response is in fact adequate to protect animals from redwater. AFRIKAANS : Die gebruik van medisinale terpentyn is ekstensief in KwaZulu-Natal en die oos Vrystaat gebruik vir die voorkoming van beide Afrika en Asiatiese rooiwaterstamme. Hierdie gebruik is reeds geslagte lank vir die behandeling en voorkoming van rooiwater deur boere gebruik. Rooiwater is n toenemende probleem vir kommersiële boere en daar kom jaarliks groot veeverliese voor. Medisinale terpentyn is die byproduk van sekere denneboomspesies. Die harpuis verkry tydens die vervaardiging van houtpulp met die Kraftproses, word gedistilleer9,72. Tydens die ondersoek na die gebruik van terpentyn deur sekere boere is eerstens tien boere van KwaZulu-Natal en die oos Vrystaat betrek. ‘n Vraelys is opgestel waarin die betrokke boere oor die gebruik van terpentyn gevra is. Tweedens is kulture van Babesia caballi in die laboratorium gekweek en met verskillende konsentrasies van terpentyn behandel. Diminazene en Imidocarb is as die positiewe kontroles gebruik. Beide hierdie produkte word op groot skaal met sukses deur boere gebruik om beide rooiwaterspesies te bestry. Huidiglik is dit die mees effektiewe behandeling van rooiwater in Suid Afrika. Derdens is die verdraagsaamheidstudie onderneem en vier en twintig beeste is in die proef gebruik. Terpentyn is teen drie verskillende konsentrasies gebruik. Die kontrole groep is met soutwater behandel. Bloed is met verskillende intervalle van die beeste getrek en vooraf bepaalde parameters is vir meting gebruik. Dié oefening het ingesluit die verkryging van serum om te bepaal of die diere voorheen blootgestel was aan enige van die rooiwaterspesies. Temperatuur, gewigte, dragtigheidstatus en reaksie op die inspuitplekke is gemonitor. Die gegewens ingewin by die boere wat terpentyn gebruik, was voor die handliggend om toleransie daarvan in die praktyk te bepaal. Die kweking van die parasiete dui daarop dat verskillende konsentrasies van terpentyn die groei daarvan vertraag en moontlik vernietig. Hierdie effek is nie by al die konsentrasies waargeneem nie. Die toleransie studie het aan die lig gebring dat dit ‘n effek op die proteïenvlakke gehad het maar geen newe-effekte op die lewer en nierfunksie gehad het nie. Verdere studies sal onderneem moet word om te bepaal watter effek terpentyn op die immuunstelsel het en of dit genoegsaam is om diere teen rooiwater te beskerm. Copyright / Die gebruik van medisinale terpentyn is ekstensief in KwaZulu-Natal en die oos Vrystaat gebruik vir die voorkoming van beide Afrika en Asiatiese rooiwaterstamme. Hierdie gebruik is reeds geslagte lank vir die behandeling en voorkoming van rooiwater deur boere gebruik. Rooiwater is n toenemende probleem vir kommersiële boere en daar kom jaarliks groot veeverliese voor. Medisinale terpentyn is die byproduk van sekere denneboomspesies. Die harpuis verkry tydens die vervaardiging van houtpulp met die Kraftproses, word gedistilleer9,72. Tydens die ondersoek na die gebruik van terpentyn deur sekere boere is eerstens tien boere van KwaZulu-Natal en die oos Vrystaat betrek. ‘n Vraelys is opgestel waarin die betrokke boere oor die gebruik van terpentyn gevra is. Tweedens is kulture van Babesia caballi in die laboratorium gekweek en met verskillende konsentrasies van terpentyn behandel. Diminazene en Imidocarb is as die positiewe kontroles gebruik. Beide hierdie produkte word op groot skaal met sukses deur boere gebruik om beide rooiwaterspesies te bestry. Huidiglik is dit die mees effektiewe behandeling van rooiwater in Suid Afrika. Derdens is die verdraagsaamheidstudie onderneem en vier en twintig beeste is in die proef gebruik. Terpentyn is teen drie verskillende konsentrasies gebruik. Die kontrole groep is met soutwater behandel. Bloed is met verskillende intervalle van die beeste getrek en vooraf bepaalde parameters is vir meting gebruik. Dié oefening het ingesluit die verkryging van serum om te bepaal of die diere voorheen blootgestel was aan enige van die rooiwaterspesies. Temperatuur, gewigte, dragtigheidstatus en reaksie op die inspuitplekke is gemonitor. Die gegewens ingewin by die boere wat terpentyn gebruik, was voor die handliggend om toleransie daarvan in die praktyk te bepaal. Die kweking van die parasiete dui daarop dat verskillende konsentrasies van terpentyn die groei daarvan vertraag en moontlik vernietig. Hierdie effek is nie by al die konsentrasies waargeneem nie. Die toleransie studie het aan die lig gebring dat dit ‘n effek op die proteïenvlakke gehad het maar geen newe-effekte op die lewer en nierfunksie gehad het nie. Verdere studies sal onderneem moet word om te bepaal watter effek terpentyn op die immuunstelsel het en of dit genoegsaam is om diere teen rooiwater te beskerm. / Dissertation (MMedVet)--University of Pretoria, 2011. / Production Animal Studies / unrestricted

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