Este trabalho teve como principal objetivo o desenvolvimento da técnica de cromatografia líquida de alta eficiência para a análise SARA de amostras de petróleo. As amostras de petróleo foram separadas em frações contendo saturados, aromáticos, resinas e asfaltenos. Para se obter êxito no desenvolvimento da técnica de cromatografia líquida em escala preparativa, o primeiro passo foi o desenvolvimento da técnica em escala analítica. Os parâmetros encontrados foram então extrapolados para escala preparativa. Através da técnica de cromatografia líquida de alta eficiência desenvolvida, foi possível obter uma separação eficaz das frações SARA de amostras de petróleo, resultado que não se mostra tão eficiente quando se trabalha com cromatografia líquida clássica. As comparações entre as metodologias por cromatografia clássica de coluna aberta e cromatografia líquida de alta eficiência desenvolvida no trabalho mostram que a cromatografia líquida possui enorme vantagem em relação à metodologia clássica. Dentre elas podemos destacar a grande reprodutibilidade já que os parâmetros de análise são altamente controlados o que não ocorre em cromatografia de coluna aberta, além da capacidade de automação e menor risco ocupacional. As frações separadas foram caracterizadas por espectrometria de massas, espectroscopia de fluorescência e infravermelho. Através da espectrometria de massas foi possível observar uma distribuição de massas entre o intervalo de massa que vai do ion de m/z 100 Da até o íon de m/z 800 Da, com esta distribuição centrada em 350 Da. A espectrometria de massa aliada a software de identificação de componentes de frações de petróleo através de massas moleculares permitiu determinar a fórmula molecular dos compostos presentes nas frações de asfaltenos das amostras de petróleo analisadas. A análise realizada pelo programa gerou os seguintes resultados: o programa encontrou estrutura molecular para aproximadamente 60% dos picos contidos no espectro de massas, destes, 6,05% dos compostos encontrados possuíam enxofre, 45,2% dos compostos possuem N e 32,1% possuem oxigênio em sua composição. A análise dos espectros de emissão de fluorescência mostrou que petróleos mais leves apresentam emissão de fluorescência mais intensas isso se deve ao fato de que petróleos mais pesados, de menor API, possuem mais espécies propensas a desativar o estado excitado, justificando assim a diminuição da emissão de fluorescência com aumento do API. / This work had as main objective the development of the technique of high performance liquid chromatography for SARA analysis of oil samples. The oil samples were separated into fractions containing saturates, aromatics, resins and asphaltenes. To achieve successful development of the technique for preparative scale liquid chromatography, the first step was the development of the technique in analytical scale. The parameters obtained were then extrapolated to preparative scale. Through the technique of high performance liquid chromatography developed, it was possible to obtain an effective separation of SARA fractions of oil samples, a result that does not show as efficient when working with classical liquid chromatography. Comparisons between both methodologies, classical and HPLC has showed that HPLC has huge advantage over classical methods. The separated fractions were characterized by mass spectrometry, fluorescence spectroscopy and infrared. Through mass spectrometry was possible to observe a distribution of masses between the mass range that goes from the ion m / z 100 Da to the ion m / z 800 Da, with this distribution centered at 350 Da. The analysis of the fluorescence emission spectra showed that lighter oils exhibit more intense fluorescence emission that is due to the fact that heavier oils, smaller API, have more likely species to disable the excited state, thus justifying the reduction of emissions fluorescence with an increased API.

O valor nutricional do milho é limitado devido ao seu alto conteúdo de proteínas de reserva (zeínas), que são deficientes em aminoácidos essenciais como lisina e triptofano. Por esse motivo, a Embrapa (Empresa Brasileira de Pesquisa Agropecuária) desenvolveu a variedade de milho BR473, que tem um excelente valor energético e um maior conteúdo protéico quando comparado ao milho comum. Tal variedade possui 0,9 e 4,0 g/kg de grão de triptofano e lisina, respectivamente, contra 0,6 e 2,6 do milho comum. O alto conteúdo de lisina em algumas variedades de milho como a opaco-2 (o2), por exemplo, é relacionado à presença de proteínas não-zeínas. Para identificar essas proteínas, o que poderia explicar o alto conteúdo protéico da variedade BR473, foi analisado o proteoma dos corpos protéicos dos grãos desse milho. Para tal, foram usadas e avaliadas as cromatografias uni e bidimensional, acopladas a espectrometria de massas (LC-MS/MS e LC/LC-MS/MS), uma vez que tais técnicas se tornaram ferramentas poderosas para seqüenciamento e identificação de proteínas. Neste trabalho, foram identificadas seis proteínas por LC-MS/MS e dezesseis proteínas por LC/LC-MS/MS. / The nutritional value of maize seed is limited due to its high content of zeins (storage proteins), which are deficient in essential amino acids as lysine and tryptophan. Because of this, Embrapa (Brazilian Agricultural Research Corporation) developed the BR 473 maize variety, which has excellent energetic value and higher proteic content than the normal maize. BR 473 maize variety has 0.9 and 4.0 g/kg of grain of tryptophan and lysine, respectively, against the 0.6 and 2.6 from normal maize. The high lysine content in some maize varieties as opaque-2 (o2), for example, has been related to the presence of non-zein proteins. In order to identify them, which could explain the high proteic content of BR 473 maize variety, the protein bodies proteome of these grains were analyzed. For this purpose, one and two-dimensional liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS and LC/LC-MS/MS) were used and evaluated, since these techniques have become a powerful tool for protein sequencing and identification. We have identified six proteins by LC-MS/MS and sixteen proteins by LC/LC-MS/MS.

by Chuen-shing Mok. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1993. / Includes bibliographical references (leaves 192-193). / Chapter Chapter 1 --- INTRODUCTION --- p.1 / Chapter Chapter 2 --- INSTRUMENTATION AND THEORY --- p.9 / Chapter Chapter 3 --- INDIRECT CONDUCTOMETRIC DETECTION OF AMINO ACIDS AFTER HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC SEPARATION --- p.17 / Chapter Chapter 4 --- DETERMINATION OF MONOSODIUM GLUTAMATE IN FOODS WITH HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY USING INDIRECT CONDUCTOMETRIC DETECTION --- p.52 / Chapter Chapter 5 --- HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC DETERMINATION OF ACTIVE INGREDIENTS IN COUGH-COLD SYRUPS WITH INDIRECT CONDUCTOMETRIC DETECTION --- p.83 / Chapter Chapter 6 --- HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC DETERMINATION OF ATROPINE AND ATROPINE- LIKE ALKALOIDS IN PHARMACEUTICAL PREPARATIONS WITH INDIRECT CONDUCTOMETRIC DETECTION --- p.144 / Chapter Chapter 7 --- CONCLUSION --- p.194

Sin Wai-Chu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / ABSTRACT --- p.i / 論文摘要 --- p.ii / ACKNOWLEDGEMENT --- p.iii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Electroplating history --- p.1 / Chapter 1.2 --- Electroplating bath --- p.7 / Chapter 1.3 --- Electroplating analytical methods --- p.8 / Chapter 1.3.1 --- Metal content and elemental impurities analysis --- p.10 / Chapter 1.3.2 --- "Metal complex, inorganic anion and cation analysis" --- p.11 / Chapter 1.3.3 --- Organic brighteners and levelers analysis --- p.12 / Chapter 1.4 --- HPLC literature review --- p.15 / Chapter 1.5 --- My research work --- p.16 / Chapter 1.6 --- References for Chapter 1 --- p.19 / Chapter Chapter 2 --- General Experimental --- p.23 / Chapter 2.1 --- The HPLC System --- p.23 / Chapter 2.2 --- The factors that affect the separation --- p.26 / Chapter 2.2.1 --- The composition of the solvent system --- p.27 / Chapter 2.2.2 --- The selection of column --- p.30 / Chapter 2.2.3 --- The most suitable analytical wavelength for UV detection --- p.34 / Chapter 2.3 --- Challenges in analyzing electroplating baths solution --- p.35 / Chapter 2.3.1 --- High metal content --- p.36 / Chapter 2.3.2 --- Strong ligand or complexing agent --- p.36 / Chapter 2.3.3 --- Interference --- p.37 / Chapter 2.3.4 --- Extreme pH --- p.37 / Chapter 2.3.5 --- Other difficulties --- p.38 / Chapter 2.3.6 --- Maintenance of HPLC instrument --- p.38 / Chapter 2.4 --- References for Chapter 2 --- p.38 / Chapter Chapter 3 --- Palladure 200 bath HPLC analysis --- p.41 / Chapter 3.1 --- Introduction --- p.41 / Chapter 3.2 --- Experimental --- p.43 / Chapter 3.3 --- Problems in the existing UV analysis for monitoring Palladure200 process --- p.45 / Chapter 3.4 --- HPLC method development for monitoring Palladure 200 process --- p.49 / Chapter 3.5 --- Analysis of aged Palladure 200 plating bath from production line --- p.55 / Chapter 3.6 --- Conclusion --- p.57 / Chapter 3.7 --- References for Chapter 3 --- p.58 / Chapter Chapter 4 --- Nickel PC3 bath HPLC analysis --- p.59 / Chapter 4.1 --- Introduction --- p.59 / Chapter 4.2 --- Experimental --- p.60 / Chapter 4.3 --- Problems in the existing Titration method for monitoring Nickel PC3 process --- p.62 / Chapter 4.4 --- HPLC method development for monitoring Nickel PC3 process --- p.63 / Chapter 4.4.1 --- Identify individual component of Nickel PC3 process --- p.63 / Chapter 4.4.2 --- Set up a calibration curve for the Nickel PC3 Additive --- p.67 / Chapter 4.4.3 --- Analysis of aged Nickel PC3 plating bath from production line --- p.68 / Chapter 4.5 --- Conclusion --- p.71 / Chapter 4.6 --- References for Chapter 4 --- p.72 / Chapter Chapter 5 --- Solderon SC bath HPLC analysis --- p.73 / Chapter 5.1 --- Introduction --- p.73 / Chapter 5.2 --- Experimental --- p.74 / Chapter 5.3 --- Instability in the existing Cyclic Voltammetric Stripping (CVS) method for monitoring Solderon SC process --- p.76 / Chapter 5.4 --- HPLC method development for monitoring Solderon SC process --- p.77 / Chapter 5.4.1 --- Identify the individual components --- p.77 / Chapter 5.4.2 --- Set up a calibration curve for the Solderon SC Primary --- p.82 / Chapter 5.4.3 --- Analysis of aged Solderon SC plating bath from production line --- p.84 / Chapter 5.5 --- Conclusion --- p.86 / Chapter 5.6 --- References for Chapter 5 --- p.86 / Chapter Chapter 6 --- Copper Gleam PPR bath HPLC analysis --- p.87 / Chapter 6.1 --- Introduction --- p.87 / Chapter 6.2 --- Experimental --- p.89 / Chapter 6.3 --- Problems in the existing Cyclic Voltammetric Stripping (CVS) method for monitoring Copper Gleam PPR process --- p.91 / Chapter 6.4 --- HPLC method development for monitoring Copper Gleam PPR process --- p.92 / Chapter 6.4.1 --- Identify Individual components and copper PPR additivein standard bath --- p.92 / Chapter 6.4.2 --- Set up a calibration curve for the Copper Gleam PPR Additive --- p.95 / Chapter 6.4.3 --- Analysis of aged Copper Gleam PPR plating bath from production line --- p.96 / Chapter 6.4.5 --- Study of H202 effect --- p.101 / Chapter 6.4.6 --- Study of air agitation effect --- p.104 / Chapter 6.4.7 --- Study of Copper anode effect --- p.105 / Chapter 6.5 --- Conclusion --- p.107 / Chapter 6.6 --- References for Chapter 6 --- p.107 / Chapter Chapter 7 --- Silverjet220 bath HPLC analysis --- p.109 / Chapter 7.1 --- Introduction --- p.109 / Chapter 7.2 --- Experimental --- p.110 / Chapter 7.3 --- HPLC method development for monitoring Silverjet 220 process --- p.112 / Chapter 7.3.1 --- Identify individual components and Silverjet 220 Additive in the plating bath --- p.112 / Chapter 7.3.2 --- Optimize the condition for HPLC analysis --- p.117 / Chapter 7.3.3 --- Analysis of aged Silverjet 220 plating bath from production line --- p.119 / Chapter 7.4 --- Conclusion --- p.122 / Chapter 7.5 --- References for Chapter 7 --- p.123 / Chapter Chapter 8 --- Conclusions and Further Studies --- p.124 / Chapter 8.1 --- Conclusions --- p.124 / Chapter 8.2 --- Further Studies --- p.126 / APPENDIX --- p.128 / The User guide for HPLC --- p.128 / HPLC System Calibration Maintenance --- p.135 / HPLC System Preventive Maintenance --- p.145

Orientador: Hérida Regina Nunes Salgado / Banca: Adriano Antunes de Souza Araújo / Banca: Anil Kumar Sing / Resumo: A cefalotina (CET) é um antimicrobiano β-lactâmico semi-sintético, bactericida e representa o protótipo das cefalosporinas, pertencente à classe da primeira geração. As cefalosporinas apresentam um espectro de atividade mais amplo do que as penicilinas e são amplamente prescritas. Poucos métodos analíticos são descritos na literatura para a análise de CET, e ao nosso conhecimento, nenhum método rápido e indicativo de estabilidade por cromatografia líquida para este composto foi publicado anteriormente. Foi desenvolvido um método indicativo de estabilidade por cromatografia líquida em fase reversa para determinação quantitativa de CET, na presença de impurezas e produtos de degradação gerados a partir dos estudos de degradação forçada em amostras de pó liofilizado para injeção. O método desenvolvido é também aplicável para a determinação de substâncias relacionadas em matéria-prima e em formas farmacêuticas. A separação cromatográfica foi obtida com a coluna Agilent Eclipse XDB-Phenyl, de 250 mm x 4,6 mm, 5 μm, em fase móvel composta por uma mistura das soluções A (tampão fosfato de amônio, pH 4,5) e B (acetonitrila), no modo de eluição gradiente. A vazão utilizada foi de 1,0 mL/min e o comprimento de onda 238 nm. O fármaco foi submetido a condições de estresse por hidrólise, oxidação, fotólise, umidade e degradação térmica. Obteve-se degradação considerável nas condições de hidrólise alcalina, ácida e estresse oxidativo. No método desenvolvido por cromatografia líquida de alta eficiência (CLAE), a resolução entre CET e os seus potenciais produtos de degradação foi maior que 2,4; além disso, a pureza de pico de CET em todas as condições foi maior que 99%, demonstrando o poder indicativo de estabilidade do método. A impureza B (desacetilcefalotina) que é um metabólito menos ativo da CET foi identificada e apresentou formação significativa, especialmente na condição... / Abstract: Cephalothin (CET) is a semi-synthetic β-lactam antimicrobial compound, bactericidal, and it represents the prototype of cephalosporins, which belongs to the first-generation class. Cephalosporins present a larger spectrum of activity than penicillins and they are widely prescribed. Few analytical methods are described in the literature for the analysis of CET and to our knowledge rapid stability-indicating liquid chromatography (LC) methods for this compound have not been published elsewhere. A stability-indicating gradient reversed phase liquid chromatography (RP-LC) method has been developed for the quantitative determination of CET, in the presence of its impurities and degradation products generated from forced degradation studies, in samples of lyophilized powder for injection. The developed method is also applicable for the related substances determination in bulk drugs and pharmaceutical forms. The chromatographic separation was achieved on an Agilent Eclipse XDB-Phenyl, 250 mm x 4.6 mm, 5 μm column with mobile phase containing a gradient mixture of solutions A (aqueous ammonium phosphate buffer, pH 4.5) and B (acetonitrile) as mobile phase. The flow rate was 1.0 mL/min and the detection wavelength was 238 nm. The drug substance was subjected to stress conditions of hydrolysis, oxidation, photolysis, humidity and thermal degradation. Considerable degradation was found to occur in base, acid and oxidative stress conditions. In the developed high performance liquid chromatography (HPLC) method, the resolution between CET and its potential degradation products was found to be greater than 2.4, further, the peak purity of CET in all conditions were more than 99% proving the stability-indicating power of method. The less active metabolite of CET, desacetylcephalothin (impurity B), was identified and is showed significant formation especially in alkaline condition. This method is able to detect the degradation products of CET at a ... / Mestre

Spurious, falsely-labeled, falsified or counterfeit (SFFC) pharmaceuticals are a health concern that claims hundreds of thousands of lives annually1, a violation of intellectual property rights which cost legitimate companies billions2, and a low-risk high yield revenue stream for organized crime2. While ports of entry and border control points are the primary access control points for SFFC3,4, advances in field portable detection and equipment offers an increasingly effective method for the assessment of pharmaceuticals at regional centers and points of distribution. This is particularly important for less developed countries (LDC) who do not maintain satellite or regional testing facilities. As part of a proposed protocol to assess field portable detection equipment, an ultrafast liquid chromatography, tandem mass spectrometry (UFLC-MS/MS) method for the quantification of liquid formulation Oxytocin was developed. The six minute method was found to have a within run %bias of +/-16%, a linear dynamic range of 150-1000 nanograms/milliliter (ng/ml), and an accuracy within acceptability criteria for all tested concentrations. The effectiveness of three identified transition ions, 723.1, 86.2 and 70.1 Daltons, for the analysis of oxytocin by mass spectrometry was assessed across several figures of merit to include signal to noise ratio, %CV, calibration sensitivity, and analytical sensitivity. The 723.1 ion fragment was recommended for quantification, while the 70.1 dalton ion was recommended as a qualifier ion, although 86.2 also performed within acceptability criteria. A method for the UFLC-MS/MS assessment of degradation products for oxytocin was proposed for specificity testing. Degradation of oxytocin by exposure to highly acidic, basic, and thermal conditions for one hour was attempted. Formation of degraded products was not observed. Additionally, existing High Performance Liquid Chromatography (HPLC) methods for the simultaneous assessment of Artesunate and Amodiaquine HCl were modified to assess compatibility with UFLC. No method assessed produced sufficient quality signal to continue with method development.

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Vitamin C occurs in relatively high concentrations in fresh and processed fruits and vegetables but is found to a lesser extent in animal tissues and animal-derived products. Nearly 90 % of vitamin C in the human diet is obtained from fruits and vegetables but this can be indirect by way of commercially prepared fruit juices. These juices are often enriched with vitamin C which has been synthetically prepared. There is a wide range of such juices on the New Zealand market, and they are a significant source of dietary vitamin C for many in the population. The focus of this research is on the Keri range of juice products.The present study monitors the fate of vitamin C during storage of Keri juices up to the best-before date, and under a range of other storage and consumption situations. Two methods were adopted for determining ascorbic acid (AA, the chemical identity of vitamin C). These were the titrimetric method, which is based upon the reduction of the dye 2,6-dichlorophenolindophenol by AA in acidic solution, and liquid chromatography, which is used to separate AA from its immediate oxidation product dehydroascorbic acid. In the latter method these two analytes can be measured independently. The liquid chromatography was less successful than the simpler titrimetric method, so most of the work was done by titration. However, the concentration of dehydroascorbic acid, which has vitamin C activity in vivo, remained uncertain. Moreover, the titrimetric method could not be applied to juices with high purple anthocyanin concentrations, like blackcurrant, because the colour change at the titration end point could not be detected. pH adjustment to change colour was ineffective, and decolourisation with charcoal led to the rapid and complete destruction of AA. The concentration of AA in Keri juices at the time of manufacture were always much higher than claimed on the labels. Storage for up to nine months at room temperature resulted in a loss in AA of between 37 and 68 %, depending on the juice and exposure to fluorescent light. However, the time of storage was a much more dominant factor than light exposure. The kinetics of loss, straight lines, were most easily explained by an aerobic model of AA degradation from oxygen diffusing across the polyethylene tetraphthalate bottle wall. Overall, the label claims made were defensible in terms of the best-before date, because it took at least 100 days of storage before the AA concentration in the most susceptible juices fell below the claimed value. This is because these drinks are fast moving consumer goods and storage beyond 100 days is unlikely. (Nonetheless, the supplier (Keri Juice Company) has since adopted its new unitised method of formulating juice. This has resulted in an initially higher concentration of vitamin C as compared to the juices under investigation.) In the nine months storage experiment there was some evidence for the presence of dehydroascorbic acid in blackcurrant drinks, but not in another three juices. Pasteurisation during preparation of these drinks resulted in up to 7 % loss of AA, probably due to oxygen dissolved in water, and accelerated by heat of pasteurisation. Higher temperatures in later storage also accelerated losses. Progressive exposure of juice to air during simulated consumption of 3 L bottles over a week also accelerated losses. Finally, exposure to sunlight in a diurnal temperature environment accelerated losses five-fold higher than in total darkness. Filtration of ultraviolet light approximately halved the loss due to sunlight. Overall however, it can be concluded that AA in the Keri range of juices is very resistant to degradation of AA.