Orientador: Rodnei Bertazzoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-24T13:08:38Z (GMT). No. of bitstreams: 1 Marques_TamiresValim_M.pdf: 6834346 bytes, checksum: 5eb1bc6d88a438ca9002c92109a6c660 (MD5) Previous issue date: 2014 / Resumo: A crescente preocupação com a poluição das águas por novos poluentes denominados emergentes tem se intensificado, visto que aumentou o número destes compostos detectados em água. Dentre estes compostos encontram-se os fármacos e produtos de higiene pessoal, usados cotidianamente pela população. O presente trabalho teve como objetivo o desenvolvimento de um método simples, rápido e sensível utilizando a microextração líquido líquido (DLLME) combinada com a cromatografia líquida de ultra eficiência (HPLC) com detecção ultravioleta (UV) para a determinação de alguns benzodiazepínicos (bromazepam, clonazepam e diazepam) em amostras de água. A determinação foi realizada em uma coluna C18 de acordo com as condições cromatográficas ótimas (fase móvel acetonitrila:água (60:40, v/v); vazão 1,2 mL min-1; detecção 225 nm). No método de extração, uma mistura apropriada de solvente extrator e dispersor foi injetada rapidamente na amostra aquosa (10 mL) com auxílio de uma seringa. De modo que uma solução turva foi formada, esta solução é caracterizada por conter pequenas partículas do solvente extrator que se dispersa na fase aquosa. Os parâmetros da extração, tais como natureza e volume dos solventes extrator e dispersor, tempo de extração, pH da amostra, força iônica, velocidade e tempo de centrifugação, foram estudados para a otimização. Com as condições ótimas definidas (solvente extrator: clorofórmio, 200 ?L; solvente dispersor: metanol, 700 ?L; pH da amostra 9,0; velocidade e tempo de extração: 5000 rpm, 1 minuto; força iônica: adição de 1% (p/v) de (NH4)2SO4) o método proposto foi validado seguindo as figuras de método preconizadas pela ANVISA na Resolução N° 899 de 2003. A faixa linear para cada fármaco foram 8,0 - 96 ?g L-1 para bromazepam, 4,0 - 48 ?g L-1 para clonazepam e 1,0 - 12 ?g L-1 para diazepam. Todas as curvas obtiveram valores de (r) superiores a 0,999. Os limites de detecção e quantificação obtidos foram 2,4 e 8,0 ?g L-1 para bromazepam, 1,2 e 4,0 ?g L-1 para clonazepam, 0,2 e 1,0 ?g L-1 para diazepam, respectivamente. As recuperações variaram de 50 a 110% com RSD (Desvio Padrão Relativo) inferiores a 12,7 %. Finalmente, o método proposto foi aplicado em amostras coletadas na represa Billings localizada no município de Diadema-SP. / Abstract: The growing concern over water pollution caused by so-called new emerging pollutants has intensified since increased the number of these compounds detected in water. Among these compounds are pharmaceuticals and personal care products used daily by the population. This study aimed to develop a simple, rapid and sensitive liquid using liquid micro extraction (DLLME) combined with ultra-performance liquid chromatography (HPLC ) with ultraviolet detection (UV) for the determination of some benzodiazepines (bromazepam, clonazepam and diazepam) in water samples . The determination was performed on a C18 column in accordance with the optimal chromatographic conditions (mobile phase acetonitrile: water (60:40, v/v), flow rate 1.2 mL min-1, detection 225 nm). In the extraction method, a suitable mixture of extractant and dispersing solvent was injected rapidly into the aqueous sample (10 ml) with a syringe. So that a cloudy solution was formed, this solution is characterized by containing fine drops of the extractor solvent is dispersed in the aqueous phase. The parameters of the extraction, such as the nature and volume of the extractor and disperser solvents, extraction time, sample pH, ionic strength, speed and time of centrifugation, were studied for optimization. With the defined optimal conditions (extracting solvent: chloroform, 200 ?L; disperser solvent: methanol, 700 ?L, sample pH 9.0, extraction time and speed: 5000 rpm, 1 minute; ionic strength: adding 1% (p/v) (NH4)2SO4) the proposed method was validated following the figures of merit recommended by the ANVISA Resolution No. 899 of 2003. The linear ranges for each drug were 8.0 to 96 ?g L- 1 for bromazepam, 4.0 to 48 ?g L- 1 for clonazepam and 1.0 to 12 ?g L- 1 for diazepam. All curves obtained values (r) greater than 0.999. The limits of detection and quantification obtained were 2.4 and 8.0 ?g L- 1 to bromazepam, 1.2 and 4.0 ?g L- 1 to clonazepam, 0.2 and 1.0 ?g L- 1 for diazepam, respectively. Recoveries ranged from 50 to 110% with RSD (Relative Standard Deviation) of less than 12.7%. Finally, the proposed method was applied to samples collected in the Billings dam located in Diadema-SP. / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

No description available.

Thesis (MScFoodSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: In this study quality control tools were developed for the rooibos industry, primarily to determine the quality of rooibos infusions. A considerable variation between samples of the same quality grade has been noted. As there are no guidelines or procedures in place to help minimise this inconsistency it was important to develop quality control tools, which could confront this problem. Both the sensory characteristics and phenolic composition of rooibos infusions were analysed in order to create and validate these quality control tools. Descriptive sensory analysis was used for the development of a targeted sensory wheel and sensory lexicon, to be used as quality control tools by the rooibos industry, and to validate the major rooibos sensory profiles. In order to ensure all possible variation was taken into account, 230 fermented rooibos samples were sourced from the Northern Cape and Western Cape areas within South Africa over a 3-year period (2011-2013). The aroma, flavour, taste and mouthfeel attributes found to associate with rooibos sensory quality were validated and assembled into a rooibos sensory wheel, which included the average intensity, as well as the percentage occurrence of each attribute. Two major characteristic sensory profiles prevalent within rooibos, namely the primary and secondary profiles, were identified. Both profiles had a sweet taste and an astringent mouthfeel, however, the primary sensory profile is predominantly made up of “rooibos-woody”, “fynbos-floral” and “honey” aroma notes, while “fruity-sweet”, “caramel” and “apricot” aroma notes are the predominant sensory attributes of the secondary profile. The predictive value of the phenolic compounds of the infusions towards the taste and mouthfeel attributes (“sweet”, “sour”, “bitter” and “astringent”) was examined using different regression analyses, namely, Pearson’s correlation, partial least squares regression (PLS) and step-wise regression. Correlations between individual phenolic compounds and the taste and mouthfeel attributes were found to be significant, but low. Although a large sample set (N = 260) spanning 5 years (2009-2013) and two production areas (Western Cape and Northern Cape, South Africa) was used, no individual phenolic compounds could be singled out as being responsible for a specific taste or mouthfeel attribute. Furthermore, no difference was found between the phenolic compositions of the infusions based on production area, a trend that was also seen for the sensory characterisation of rooibos infusions. Sorting, a rapid sensory profiling method was evaluated for its potential use as a quality control tool for the rooibos industry. Instructed sorting was shown to successfully determine rooibos sensory quality, especially based on the aroma quality of the infusions. However, determining the quality of the infusion based on flavour quality was more difficult, possibly due to the low sensory attribute intensities. Categorisation of rooibos samples based on the two major aroma profiles i.e. the primary and secondary characteristic profiles, was achieved with uninstructed sorting. The potential of using sorting as a rapid technique to determine both quality and characteristic aroma profiles, was therefore demonstrated, indicating its relevance as another quality control tool to the rooibos industry. / AFRIKAANSE OPSOMMING: Gehaltebeheer hulpmiddels is as deel van hierdie studie vir die rooibosbedryf ontwikkel, hoofsaaklik om die sensoriese kwaliteit van rooibostee te bepaal. Aansienlike verskille is tussen monsters van dieselfde gehaltegraad opgemerk, primêr omdat daar in die wyer rooibosbedryf beperkte riglyne of prosedures in plek is om kwaliteitsverskille effektief te bepaal. Dit is as belangrik geag om gehaltebeheer hulpmiddels te ontwikkel om laasgenoemde probleem aan te spreek. Spesifieke gehaltebeheer hulpmiddels is dus vir hierdie studie ontwikkel en gevalideer deur die sensoriese eienskappe en fenoliese samestelling van rooibostee te analiseer. Beskrywende sensoriese analise (BSA) is gebruik om ‘n sensoriese wiel en leksikon vir die rooibosbedryf te ontwikkel en te valideer. Om alle moontlike produkvariasie te ondervang, is 230 gefermenteerde rooibos monsters afkomstig van die Noord-Kaap en Wes-Kaap areas in Suid-Afrika oor ‘n tydperk van drie jaar (2011-2013) verkry. Die aroma, geur, smaak en mondgevoel eienskappe wat met rooibos se sensoriese kwaliteit assosieer, is bevestig en uiteindelik gebruik om die sensoriese wiel te ontwikkel. Die gemiddelde intensiteit en persentasie voorkoms van elke eienskap is in die wiel ingesluit. Twee belangrike “karakteristieke” sensoriese profiele wat met rooibos geassosieer word, is geïdentifiseer, nl. die primêre en sekondêre sensoriese profiele. Tipies van beide sensoriese profiele is ‘n kenmerkende soet smaak en vrank mondgevoel, daarenteen bestaan die primêre sensoriese profiel hoofsaaklik uit "rooibos-houtagtige", "fynbos-blomagtige" en "heuning" aromas, terwyl "vrugtige-soet", "karamel" en "appelkoos" aromas die oorheersende sensoriese eienskappe van die sekondêre profiel is. Die korrelasie tussen die fenoliese verbindings en die smaak en mondgevoel eienskappe van rooibos ("soet", "suur", "bitter" en "vrankheid") is ondersoek met behulp van verskillende tipe regressieontledings, nl. Pearson se korrelasie, gedeeltelike kleinstekwadrate regressie (PLS) en stapsgewyse regressie. Korrelasies tussen individuele fenoliese verbindings en die smaak en mondgevoel eienskappe was laag, maar steeds betekenisvol. Alhoewel die uitgebreide stel monsters (N = 260) verteenwoordigend was van vyf oesjare (2009-2013) en twee produksiegebiede (Wes-Kaap en Noord-Kaap, Suid-Afrika), kon geen individuele fenoliese verbindings uitgesonder word as betekenisvolle voorspellers van spesifieke smaak of mondgevoel eienskappe nie. Verder is daar ook geen verskil tussen die verskillende produksie-areas wat betref fenoliese samestelling gevind nie. Soortgelyke resultate is bevind vir die sensoriese karakterisering van rooibostee. Sortering, 'n vinnige sensoriese profileringsmetode, is geëvalueer vir sy potensiële gebruik as 'n gehaltebeheer hulpmiddel vir die rooibosbedryf. Gestrukteerde sortering was suksesvol om rooibos se sensoriese kwaliteit, veral die algemene aroma kwaliteit van rooibos, te bepaal. Hierdie profileringsmetode was egter nie so suksesvol om rooibos se algemene geur, smaak en mondgevoeleienskappe te bepaal nie. Hierdie tendens kan moontlik toegeskryf word aan die betekenisvolle laer intensiteite van laasgenoemde sensoriese eienskappe. Die kategorisering van die rooibos monsters op grond van hul karakteristieke primêre en sekondêre sensoriese profiele is suksesvol deur middel van ongestrukteerde sortering bepaal. In die geheel gesien is die potensiaal van die sorteringstegniek as ‘n vinnige metode om die algemene sensoriese kwaliteit, asook die karakteristieke aroma profiele van rooibos te bepaal, dus bewys. Hierdie vinnige sensoriese profileringstegniek hou dus besliste voordele in vir die rooibosbedryf as dit kom by sensoriese gehaltebeheer.

Orientador: Delia B. Rodriguez-Amaya / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-10T05:46:01Z (GMT). No. of bitstreams: 1 Huber_LisiaSenger_D.pdf: 841058 bytes, checksum: 9612feac8503fceabd312029260ed6cf (MD5) Previous issue date: 2007 / Resumo: Devido a crescente importância atribuída aos flavonóides nos últimos anos, decorrente de suas ações relacionadas à prevenção de doenças degenerativas, e aliada à carência de dados destes compostos em alimentos brasileiros, este estudo teve como objetivo determinar os teores de flavonóis e flavonas em alimentos consumidos no Brasil e avaliar alguns fatores que influenciam seus níveis nestes alimentos. Uma revisão bibliográfica é apresentada no Capítulo 1, na qual são descritos os principais efeitos benéficos à saúde, aspectos analíticos e fatores que influenciam os teores de flavonóides em alimentos. Estes compostos com ação benéfica à saúde, atuam como antioxidantes, inibidores da proliferação celular, antiestrogênicos e mediadores intracelulares, exercendo proteção principalmente contra câncer e doenças cardiovasculares. A determinação desses compostos normalmente é feita utilizando-se cromatografia líquida de alta eficiência com detector de arranjo de diodos. Os níveis de flavonóides em alimentos podem ser influenciados por vários fatores, como estação do ano, preparo e processamento de alimentos. O Capítulo 2 descreve o desenvolvimento e validação da metodologia analítica para determinação de flavonóis e flavonas em hortaliças. Utilizando-se Delineamento Composto Central Rotacional, obtiveram-se as melhores condições para extração e hidrólise dos flavonóides encontrados na natureza na forma glicosídica, a suas respectivas agliconas. Essas condições foram: 1,0M de HCl por 6 horas para espinafre e couve, 1,6M de HCl por 5 horas para rúcula, 1,2M de HCl por 2 horas para alface, 1,7M de HCl por 4,3 horas para salsa e 0,8M de HCl por 2,5 horas para cebola. As condições cromatográficas utilizadas foram coluna Nova-Pak C18 (4ìm, 3,9x150mm), e fase móvel constituída de metanol e água, acidificados com 0,3% de ácido fórmico, em gradiente linear. Utilizando a metodologia analítica validada no Capítulo 2, no Capítulo 3 foram identificados e quantificados os flavonóides de alface lisa (6,73-9,77'g/g de quercetina), alface crespa (7,18-30,8'g/g de quercetina), cebola branca (323-362'g/g de quercetina), cebola roxa (390-423'g/g de quercetina), couve (256-399'g/g de quercetina e 333-339'g/g de kaempferol), espinafre (52,8-62,3'g/g de quercetina e 145-170'g/g de kaempferol), rúcula (137-143'g/g de quercetina e 402-501'g/g de kaempferol) e salsa (1521-1636'g/g de apigenina). Também foi avaliado o efeito sazonal nos teores destes compostos, sendo que estes tenderam a ser maiores no verão que no inverno, embora as diferenças não tenham sido estatisticamente significativas. No Capítulo 4, foram determinados os teores de flavonóides em sucos prontos para o consumo, sucos concentrados e polpas de caju, acerola e pitanga, e em amostras de cebola e salsa desidratadas. Os resultados indicaram perdas de flavonóides durante o processamento destes alimentos. Os teores nas amostras processadas foram nitidamente menores aos obtidos previamente nas amostras in natura. Os derivados de frutas apresentaram teores decrescentes na seguinte ordem: polpas, suco concentrado, suco pronto para consumo. Os teores de quercetina nas amostras de cebola desidratada foram bastante variados, indicando diferenças de variedades utilizadas como matéria-prima ou nas condições de processamento empregadas. Os resultados sugerem que estudos de monitoramento das perdas de flavonóides, da matéria-prima ao produto final, são altamente requeridos. O comportamento de flavonóis em couve, espinafre e rúcula minimamente processados, estocados em atmosfera modificada, em diferentes temperaturas, na presença e ausência de luz, foi avaliado e discutido no Capítulo 5. A qualidade sensorial dessas amostras também foi avaliada, para verificar a vida-de-prateleira. No geral, a vida útil foi negativamente influenciada pelo aumento na temperatura de estocagem na presença de luz. Não ocorreram perdas pronunciadas nos teores destes compostos durante a estocagem das três folhas minimamente processadas, podendo inclusive aumentar em certos períodos do armazenamento / Abstract: Had the increasing importance attributed to the flavonóides in the last years, decurrent of its action related to the prevention of degenerative illnesses, and allied to the lack of data of these composites in Brazilian foods, this study it had as objective to determine texts of flavonóis and flavonas in foods consumed in Brazil and to evaluate some factors that influence its levels in these foods. A bibliographical revision is presented in Chapter 1, in which the main beneficial effect to the health, analytical aspects and factors are described that influence texts of flavonóides in foods. These composites with beneficial action to the health, act as antirust, inhibiting of the proliferation cellular, antiestrogênicos and mediating intracellular, exerting protection mainly against cardiovascular cancer and illnesses. The determination of these composites normally is made using liquid chromatography of high efficiency with detector of arrangement of diodes. The levels of flavonóides in foods can be influenced by some factors, as station of the year, preparation and processing of foods. Chapter 2 describes the development and validation of the analytical methodology for determination of flavonóis and flavonas in hortaliças. Using Rotational Central Composed Delineation, the best conditions for extration and hydrolysis of the flavonóides found in the nature in the glicosídica form, its respective agliconas had been gotten. These conditions had been: 1,0M of HCl for 6 hours for spinach and borecole, 1,6M of HCl for 5 hours for rúcula, 1,2M of HCl for 2 hours for lettuce, 1,7M of HCl for 4,3 hours for parsley and 0,8M of HCl for 2,5 hours for onion. The used chromatographic conditions had been column Nova-Pak C18 (4ìm, 3,9x150mm), and mobile phase consisting of methanol and water, acidified with 0,3% of acid fórmico, in linear gradient. Using the validated analytical methodology in Chapter 2, in Chapter 3 they had been identified and quantified the flavonóides of smooth lettuce (6,73-9,77'g/g of quercetina), lettuce crespa (7,18-30,8'g/g of quercetina), white onion (323-362'g/g of quercetina), purple onion (390-423'g/g of quercetina), borecole (256-399'g/g of quercetina and 333-339'g/g of kaempferol), spinach (52,8-62,3'g/g of quercetina and 145-170'g/g of kaempferol), rúcula (137-143'g/g of quercetina and 402-501'g/g of kaempferol) and parsley (1521-1636'g/g of apigenina). Also the sazonal effect in texts of these composites was evaluated, being that these had tended to be bigger in the summer that in the winter, the differences have even so not been estatisticamente significant. In Chapter 4, the texts of flavonóides in ready juices for the consumption, intent juices and cashew pulps, acerola and pitanga had been determined, and in samples of dehydrated onion and parsley. The results had indicated losses of flavonóides during the processing of these foods. The texts in the processed samples had been nitidamente lesser to gotten previously in the samples in natura. The derivatives of fruits had presented decreasing texts in the following order: pulps, concentrated juice, ready juice for consumption. The texts of quercetina in the samples of dehydrated onion sufficiently had been varied, indicating differences of used varieties as raw material or in the employed conditions of processing. The results suggest that studies of monitoramento of the losses of flavonóides, of the raw material to the end item, highly are required. The behavior of flavonóis in borecole, spinach and rúcula minimamente processings, storaged in modified atmosphere, in different temperatures, na.presença and absence of light, was evaluated and argued in Chapter 5. The sensorial quality of these samples also was evaluated, to verify the life-of-shelf. In the generality, the useful life negative was influenced by the increase in the temperature of stockage na.presença of light. Sharp losses in texts of these composites had not occurred during the stockage of three minimamente processed leves, also being able to increase in certain periods of the storage / Doutorado / Doutor em Ciência de Alimentos

Orientadores: Carol Hollingworth Collins, Carla Beatriz Grespan Bottoli / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-16T14:14:29Z (GMT). No. of bitstreams: 1 Vigna_CamilaRosaMoraes_D.pdf: 1190348 bytes, checksum: ab228c805aba8ca12b954e0202343664 (MD5) Previous issue date: 2010 / Resumo: Neste trabalho verificou-se a potencialidade de uso de sorventes e fases estacionárias (FE), obtidos a partir da sorção e/ou imobilização do polímero poli(metiloctilsiloxano) (PMOS) sobre suportes de sílica Kromasil utilizando tamento térmico, na separação, quantificação e validação de uma metodologia para análise de agrotóxicos em amostras de água e caldo de cana-de-açúcar (garapa). Os materiais desenvolvidos foram caracterizados com testes químicos e físicos e aplicados nas etapas de concentração das amostras por extração em fase sólida nos modos off-line e on-line, com posterior separação, por Cromatografia Líquida de Alta Eficiência com detecção UV-Vis. Utilizou-se também o método QuEChERS como alternativa na etapa de extração das amostras de garapa. Os sorventes PMOS mostraram desempenho comparável aos sorventes comerciais, além de sua preparação ser simples, rápida e de menor custo. A FE Kromasil/PMOS utilizada propiciou uma boa separação entre os componentes das amostras de diversos agrotóxicos analisados, similar as fases comerciais, com boas eficiências, resolução e seletividade. A metodologia desenvolvida foi validada e mostrou bons resultados de recuperação para todos os agrotóxicos, além de precisão < 15% e coeficiente de correlaçã > 0,99. O limite de quantificação do método permitiu que os limites máximos de resíduos impostos pelas agências reguladoras para todos os compostos estudados fossem atingidos. Os métodos desenvolvidos e validados foram aplicados na análise de amostras de garapa do comércio local. Não foram observados níveis detectáveis dos agrotóxicos estudados nas amostras analisadas / Abstract: This work investigated the potentiality of use of sorbents and stationary phases (SP), obtained from the sorption and/or immobilization of poly(methyloctylsiloxane) (PMOS) onto the surface of a porous silica Kromasil support using heat, in the separation, quantification and validation of a methodology for analysis of agrochemicals in water and sugar cane samples. Physical-chemical characterization of the developed materials were carried out and applied in the concentration step of the samples in solid phase extraction (SPE) in off-line and on-line mode, with posterior separation, for High Performance Liquid Chromatography (HPLC) with UV-Vis detection. The QuEChERS method (Quick, Easy, Cheap, Effective and Safe) was also used as alternative in the extraction of the sugar cane samples. PMOS sorbents showed comparable performance to the commercial sorbents, with simple, fast and cheap preparation. The Kromasil/PMOS SP used demonstrated a good separation to the components of the samples of agrotoxics analyzed, similar to the commercial phases, with good efficiencies, resolution and selectivity. The developed methodology was validated and showed good results of recovery for the agrotoxics, with precision value < 15 % and correlation coefficient > 0,99. The limit of quantification (LQ) of the method allowed that the maximum residues limits (MRL) for the regulating agencies for all the studied compounds were reached. The developed and validated methods were applied in the analysis of sugar cane samples of the local commerce. Detectable levels of the agrochemicals studied in the analyzed samples were not detected / Doutorado / Quimica Analitica / Doutor em Ciências

High Pressure Liquid Chromatography (HPLC) is a well-known and widely used analytical technique which is prevalent throughout the pharmaceutical industry as a research tool. Despite its prominence HPLC possesses some disadvantages, most notably slow analysis time and large consumption of organic solvents. Ultra Pressure Liquid Chromatography (UPLC) is a relatively new technique which offers the same separation capabilities of HPLC with the added benefits of reduced run time and lower solvent consumption. One of the key developments which facilitate the new UPLC technology is sub 2-µm particles used as column packing material. These particles allow for higher operating pressures and increased flow rates while still providing strong separation. Although UPLC technology has been available since early 2000, few laboratories have embraced the new technology as an alternative to HPLC. Besides the resistance to investing in new capital, another major roadblock is converting existing HPLC methodology to UPLC without disruption. This research provides a framework for converting existing HPLC methods to UPLC. An existing HPLC method for analysis of Galantamine hydrobromide was converted to UPLC and validated according to ICH guidelines. A series of statistical evaluations on the validation data were performed to prove the equivalency between the original HPLC and the new UPLC method. This research presents this novel statistical strategy which can be applied to any two methodologies to determine parity. / Chemistry

A review of the main natural dyes (particularly yellow flavonoids and red anthraquinones) and proteinaceous substrates used in Historical Tapestries and North American porcupine quill work was undertaken, and is summarised in Chapter 1. The analysis of natural dyes which have been used on museum artefacts other than textiles has received little systematic study, particularly those of non-European origin. In this research, the use of Ultra Performance Liquid Chromatography (UPLC) for study of natural dyes found on historical textiles and ethnographical objects decorated with porcupine quill work is explored; this required a transfer of existing analytical protocols and methodology. The advantages of using Ultra Performance Liquid Chromatography (UPLC) was evaluated through a method development based on the separation and quantification of ten flavonoid and anthraquinone dyes as described in Chapter 2. These methods were then applied to the characterisation of the dye sources found on a group of sixteenth century historical tapestries which form an important part of the Burrell Collection in Glasgow and are believed to have been manufactured in an English workshop (Chapter 3) and also to the analysis of some late nineteenth century North American porcupine quill work from a collection owned by National Museums Scotland (Chapter 5); allowing exciting conclusions to be drawn in each case about the range of dyestuffs used in their manufacture. The second aim of this research was the development of methodology for the non-invasive quantification of metal ion residues on porcupine quill substrates. This was achieved through a comparative study of reference porcupine quills prepared in-house with dyebaths containing a range of metal ion concentrations (copper and tin). The concentration of metal ions sorbed by the porcupine quills was then quantified with Inductively Coupled Plasma (ICP) coupled to Optical Emission Spectrometry (OES) and non-invasive Particle Induced X-Ray Emission analysis (PIXE) coupled with Rutherford Backscattering Spectrometry (RBS) as described in Chapter 4. The responses provided by the different methods were compared and they were then applied to the study of micro-samples collected from mid-nineteenth century Northern Athapaskan porcupine quill work. Unexpectedly, the use of UPLC analysis and RBS-PIXE analysis allowed the characterisation of traded European natural dyes used with metallic mordants (copper and tin) on these samples, highlighting how European contact impacted on traditional Athapaskan porcupine quill work in the late nineteenth century (Chapter 5).

The general aim of this thesis was to evaluate a newly designed and constructed miniaturized rotating disk apparatus for in vitro dissolution rate measurements of different drug substances from all of the classes in the Biopharmaceutical Classification System (BCS). The new equipment is based on a low volume flow-through cell of Plexiglas, a gold plated magnetic bar and a special designed press. The disk of drug substance (approx. 5 mg) is placed eccentrically in the bar. Rotation speeds were set with a graded magnetic stirrer. An external HPLC pump delivered a continuous flow of aqueous medium to the flow-through cell during dissolution testing. A reversed phase high-performance liquid chromatography system using diode array detection (RP-HPLC-DAD) was coupled online to the new equipment. The injections from the miniaturized rotating disk outlet into the quantifying HPLC system were controlled by a six-position switching valve. The injection volumes from the valve and the autosampler, used for the external standards, were statistically evaluated to match each other volumetrically. No analyses were longer than three minutes, using isocratic mode. A traditional USP rotating disk apparatus was used as a reference system and the two instruments were shown to be statistically dissimilar in the numerical dissolution rate values probably due to different hydrodynamics, but had approximately the same precision/repeatability. When correlating the logarithmic values of the in vitro dissolution rate (G) with the apparent solubility (S), using shake-flask methodology in the solubility studies, the two apparatuses gave the same correlation patterns. Further correlation studies were done where the media components were altered by the use of different buffer species or additives into the buffers, such as inorganic salts. Chemometric tools, e.g. orthogonal partial least squares (OPLS), were used to better evaluate the most influential factors for G and S in different media. The most significant factor for a model basic drug substance (terfenadine) was pH, followed by the ionic strength (I) and added sodium chloride in one of the media. However, the surfactants in the Fasted State Simulated Intestinal Fluid (FaSSIF-V2) were found to be insignificant for G and S in this study (using a 95% confidence interval). The new miniaturized apparatus is a promising prototype for in vitro dissolution rate measurements both for early screening purposes and in dissolution testing during drug development, but needs further instrumental improvements.