The first step of the synthesis of the hydrocarbon-based chiral surfactant (2) involved the methylation of (S)-leucinol to give (2S)-N-hexadecyl-N,N-dimethyl-(1-hydroxy-4-methyl-1-pentyl)-2-ammonium bromide (2.92g, 67%). The chiral surfactant was synthesized by reacting (2S)-N,N-dimethyl-2-amino-4-methyl-1-pentanol (1) with bromohexadecane (2.06g, 71%). The functionalized styrene for the polymer supported chiral catalyst (6) was synthesized by reacting (1) with 4-vinylbenzyl chloride. The polymerization was carried out with 10% of the functionalized monomer (5) (1.26g, 70.2%), 5% cross-linking agent divinylbenzene, and 85% of styrene with AIBN as the initiator. The structure of each of the products was confirmed by using FTIR and NMR spectroscopy. The activity of the hydrocarbon surfactant and polymeric catalyst were examined by using them as additives in a standard reduction of 2-pentanone with sodium borohydride to yield (R)- and (S)-2-pentanol (3) (4gm, 25%). The resulting alcohol was then esterified with (2S)-methylbutyric acid with iodine as the catalyst and the ester was characterized.

No description available.

No description available.

Thesis (MScEng)-- Stellenbosch University, 2013. / ENGLISH ABSTRACT: The simplified Perturbed-Chain Statistical Associating Fluid Theory (sPC-SAFT) is characterised by the dual advantages of decreased computational intensity, while remaining accurate for a variety of systems. Vapour-liquid equilibrium data are used to generate equation of state parameters. However, incorporating monomer fraction data into the parameter regression has long been advocated as a good, or even preferred, practice. Therefore, the monomer fraction data of dilute alcohol-acetone systems were analysed in this study. A small stainless steel sample vessel was constructed with temperature control, manual pressure control and a mechanism for liquid phase analysis via infrared spectroscopy. The performance of the spectrometer was verified by comparison with the ethanol – n-hexane data of von Solms et al. (2007), after which new monomer fraction data were obtained for dilute solutions (between 0.01 and 1.5 mol%) of methanol, ethanol, 1-propanol and 2-propanol in acetone near 23 °C. For dilute alcohol-acetone systems it was found that the propanols had the highest monomer fractions, and methanol the lowest. With increasing alcohol concentration, the monomer fractions decreased exponentially to values of 0.4 and 0.1 for methanol and the other alcohols respectively. The excess availability of hydrogen bond acceptors in the mixtures explains the equivalency observed for ethanol, 1-propanol and 2-propanol. For dilute acetone-alcohol systems it was found that, especially for methanol and ethanol, there was a pronounced trend towards acetone monomer fractions of 1 at infinite dilution. For the acetone – 2-propanol system, a previously unrecorded monomer peak was observed and quantified. Acetone monomer fractions tended to decrease as alcohol chain-length increased, showing that acetone could more easily penetrate the hydrogen bond network of the solvent when the solvent-solvent bonds were weaker. Monomer fraction data were compared to predictions for the sPC-SAFT scheme and parameters combinations published in the literature. The experimental data were accurately modelled using modified association parameters such that the solute associates strongly (εAB≈103 κ≈1), while the solvent parameters were decreased (εAB≈102 κ≈10˗3) to give a weakened solvent association effect. The difficulty for the dilute solute in penetrating the solvent bonding network appeared to be similar to the hydrophobic effect. Two new association schemes were proposed for acetone, assigning a single (N) or two (2N) negative association sites to represent the oxygen valence electron pairs. These schemes showed relative success in modelling acetone as the solvent in the mixture, while not being able to predict acetone monomer fractions when acetone was the solute. For dilute acetone-alcohol systems, the data were best described using the 2B model for acetone, while the best choice of scheme for the alcohol varied from system to system. For dilute alcohol-acetone mixtures it was generally found that a 2B-N model (with modified association parameters) provided the best fit to those experimental data. Accurate modelling below 0.1 mol% was difficult to attain with average errors decreasing to the order of 10% when this area was excluded. In this highly dilute region, not one of the models could describe the rapid change in (monomer fraction) gradient sufficiently while simultaneously offering accurate predictions over the entire experimental range. / AFRIKAANSE OPSOMMING: Die sPC-SAFT of simplified Perturbed-Chain Statistical Associating Fluid Theory toestandsvergelykings word wyd gebruik as gevolg van sy goeie akkuraatheid vir ‘n wye reeks sisteme, ten spyte van verminderde berekeningsintensiteit. Die parameters vir dié toestandsvergelyk word afgelei van faseewewig data, maar monomeer fraksie data word voorgestel vir die verbetering van (veral) die assosiasie parameters. Ten opsigte hiervan, was alkohol-asetoon sisteme bestudeer en hul monomeer fraksies gemeet. ‘n Staal reaktor was ontwerp (met ‘n temperatuurbeheerstelsel sowel as drukbeheer) om vloeistof monsters voor te berei vir analise d.m.v. infrarooi-spektroskopie. Die akkuraatheid van die eksperimentele apparaat is bewys deur nabootsing van etanol – n-heksaan data van von Solms et al. (2007), waarna nuwe monomeer fraksie data gegenereer is vir verdunde mengsels (0.01 tot 1.5 mol%) van metanol, etanol, 1- en 2-propanol met asetoon by 23 °C. Metanol monomeer fraksies het eksponensieël afgeneem na 0.4, terwyl etanol en propanol fraksies afgeneem het na ‘n gemene waarde van ongeveer 0.1. Hierdie tendens word toegeskryf aan ‘n oormaat van toeganklike waterstofbindingontvangers in hierdie mengsels. Vir verdunde asetoon-alkohol sisteme is daar ‘n tendens, (veral vir verdunnings met metanol en etanol) vir die monomer fraksies om te neig na 1 by oneindige verdunning. ‘n Monomeer piek is ook waargeneem vir die asetoon – 2-propanol sisteem. Hierdie piek is nie voorheen gesien in ander studies nie en dit is ook die eerste keer wat sulke data gekwantifiseer is. Daar is bevind dat asetoon monomeer fraksies afneem soos alkohol kettinglengte toeneem. Die gegenereerde monomeer fraksie data word vergelyk met verskeie sPC-SAFT parameterstelle vanuit die literatuur. Oor die algemeen, is die beraamde fraksie veel hoër as die eksperimentele data wanneer die 2B/3B/2C skemas met ‘n nie-assosiërende asetoon molekuul gemodelleer word. Wanneer die 2B parameters van von Solms et al. (2004) gebruik word, toon die beraming ‘n drastiese onderskatting van die data. Om ‘n akkurate beraming van die monomeer fraksie data te kry, moet die assosiasie parameters van die opgeloste stof vermeerder word (met εAB≈103 κ≈1) terwyl die oplosmiddel s’n drasties verswak moet word (met εAB≈102 κ≈10-3). Hierdie patroon kan vergelyk word met die hidrofobiese effek waar die kragte binne die oplosmiddel ‘n netwerk vorm wat die opgeloste stof uitstoot. Twee nuwe assosiasie skemas word ook voorgestel vir asetoon waar onderskeidelik een (N) en twee (2N) negatiewe sones, wat die valenselektroonpare op die suurstofatoom voorstel, aan asetoon geheg word. Hierdie twee skemas het relatiewe sukses getoon in die modellering van verdunde alkohol-asetoon sisteme terwyl dit ‘n swak beskrywing van die verdunde asetoon-alkohol mengsels voorspel het. ‘n Gewysigde 2B asetoon skema gee ‘n goeie beskrywing van die eksperimentele data. In hierdie geval, is die keuse van alkohol skema minder belangrik, terwyl die waardes van die assosiasie parameters verminder moet word. Vir verdunde alkohol-asetoon mengels word daar bevind dat ‘n 2B-N model met nuwe assosiasie parameters die beste passing van die eksperimentele data gee. Daar was ook bevind dat die modelle se akkuraatheid drasties afneem (met fout vermeerdering in die orde van 10%) wanneer die konsentrasie van die opgeloste stof minder as 0.1 mol% is.

Neste trabalho, estudos da copolimerização em emulsão de estireno e butadieno foram realizados em duas etapas. A primeira etapa consistiu na obtenção de um modelo matemático que representasse os processos em batelada e em semicontínuo através das principais variáveis do processo. Na segunda etapa, o efeito de diversas variáveis importantes ao processo foi avaliado, dentre elas: o tempo de adição dos reagentes, o tipo de alimentação empregado e a temperatura da reação. O modelo matemático se baseia em um trabalho previamente publicado que foi adaptado para simular o processo de copolimerização de estireno e butadieno em emulsão. Foram simulados processos em batelada e em semicontínuo. Em conjunto com os resultados experimentais, foi realizada a estimação de parâmetros não obtidos na literatura utilizando o método de Marquardt. As características do processo e as propriedades do polímero, tais como, conversão, diâmetro de partícula, taxa de polimerização e pressão interna do reator também foram obtidas, fornecendo condições para otimização e avaliação do processo de polimerização em batelada e em semicontínuo. Adicionalmente, também foi proposto um modelo de equilíbrio líquido-vapor dos monômeros. Os ensaios experimentais foram realizados em reator encamisado semicontínuo de mistura com 3 litros, nos quais foram utilizados persulfato de sódio como iniciador, lauril sulfato de sódio como emulsificante e tercdodecil mercaptana como agente de transferência de cadeia. Foram estudados os efeitos da temperatura, do tipo e do tempo de alimentação utilizada. A velocidade de polimerização, os diâmetros médios de partículas, o teor de monômero residual, o teor de insolúveis e o teor de resíduos foram avaliados. A cromatografia gasosa foi aplicada com sucesso em análises de látex e monômeros com finalidades diversas, destacando-se a obtenção de coeficientes de atividade necessários ao modelo de equilíbrio líquido-vapor, análise da concentração de monômeros ao longo da reação e análise da concentração de monômero residual. / In this work, studies of the styrene butadiene emulsion copolymerization had been performed in two stages. The first stage composed of a mathematical model that represented the batch and semi continuous process. In the second stage, the effects of diverse process variables were evaluated, among them: the time of addition of the reagents, feeding type and temperature reaction. The mathematical model was based on previously published work that it was adapted to simulate the styrene butadiene emulsion copolymerization process. Batch and semi continuous processes were simulated. In assembly with the experimental results, Marquardt method was applied to estimate some parameters that wasn’t found in literature. The variable process and the properties of polymer, such as, conversion, particle diameter, rate of polymerization and pressure of the reactor had been also simulated to batch and semicontinous process. A liquid-vapor balance of monomers model was proposed. The experimental stage had been carried through in a semi continuous stirring jacket tank reactor with 3 liters. Sodium persulfate as initiating, sodium lauryl sulfate as surfactant and Tert dodecyl mercaptan as chain transference agent had been used. The effect of temperature, type and time feeding had been studied. Polymerization rate, particles diameter, residual monomer had been evaluated. The gaseous chromatography was successfully applied in analyses of latex with diverse purposes: activity coefficient estimation, adjustment of liquid-vapor model, analysis of residual monomer of the reaction and volatiles organic components concentration in final latex.

O objetivo do trabalho foi investigar múltiplos aspectos relacionados ao pré-aquecimento da resina composta anterior à fotoativação: o grau de conversão e a cinética da polimerização em função da temperatura de polimerização, tempo de fotoativação e profundidade; o desempenho da fonte aquecedora (temperatura máxima, estabilidade térmica do aparelho e variações de temperatura ao pré-aquecer compules) e aspectos clínicos (o efeito de ciclos de pré-aquecimento repetidos e prolongados sobre o grau de conversão, a variação da temperatura intrapulpar in vitro e a variação da temperatura in vivo ao usar resina composta pré-aquecida ou a temperatura ambiente. A conversão de monômeros e os parâmetros de cinética foram determinados através de FTIR-ATR. Os espécimes foram fotoativados por 5, 10, 20 ou 40s entre 3 o e 60 o C. Foram calculados o grau de conversão em tempo real, a taxa máxima de conversão, o tempo em que ocorreu a taxa máxima, e a conversão na taxa máxima. Os dados foram tratados por análise de variância, teste-t e análise de regressão (p ≤0,05). O desempenho do dispositivo aquecedor foi medido monitorando-se a mudança de temperatura em tempo real com o auxílio de um termopar tipo-k conectado a um conversor analógico-digital. Os termopares foram colocados no aquecedor e dentro de compules de compósito. Os dados foram analisados com teste t (p ≤0,05). Compules (n=5) foram submetidos a um dos ciclos térmicos: Pré-aquecimento repetido (da temperatura ambiente a 60 o C, por 10 vezes) ou Prolongado (24h a 60 o C). O grau de conversão foi medido 24h após os ciclos, com o compósito à temperatura ambiente, seguindo o protocolo descrito acima. Os dados foram tratados por análise de variância e teste de Tukey (p≤0,05). O aumento da temperatura intrapulpar foi medido por um termopar colocado na câmara pulpar de um prémolar contendo uma cavidade de Classe V (com 1mm de espessura de dentina remanescente). O preparo foi preenchido com compósito à temperatura ambiente ou pré-aquecido enquanto a temperatura intrapulpar era continuamente monitorada (n=5). Os dados foram comparados por análise de variância e teste de Tukey (p ≤0,05). Para a medida da variação de temperatura in vivo, foram feitos preparos cavitários de 2mm de profundidade em dentes posteriores de um indivíduo (n=3). Uma sonda que mensurava a temperatura foi introduzida no dente preparado em cada procedimento restaurador e durante a inserção da resina composta à temperatura ambiente ou pré-aquecida a 60°C. Os dados foram comparados com análise de variância e teste de Tukey (p ≤0,05). Os resultados indicaram que: 1) o pré-aquecimento da resina composta anterior à fotoativação aumenta o grau de conversão, reduz o tempo de fotoativação e resulta em maior taxa de conversão, sem alterar o tempo em que a taxa máxima ocorre; 2) tanto o dispositivo aquecedor quanto os compules atingiram temperaturas inferiores das determinadas pelo fabricante; ao remover o compósito do aquecedor a perda de calor é acentuada ; 3) o grau de conversão não foi afetado por ciclos repetidos e prolongados de pré-aquecimento da resina composta; 4) não houve aumento da temperatura intrapulpar ao serem comparadas as resinas composta à temperatura ambiente e pré-aquecida; 5) a medida da temperatura in vivo revelou que o compósito pré-aquecido a 60 o C fica somente 8 o C acima da temperatura intrabucal; a técnica de pré-aquecimento deve ser usada com cautela. / This work examined multiple aspects of pre-heating dental resin composite prior to light-curing: the monomer conversion and polymerization kinetics as a function of cure temperature, light-exposure duration and depth; the performance of the heating device (maximum temperature, thermal stability of device and temperature change when pre-heating compules); and clinically relevant issues (the effect of repeated and extended pre-heating cycles on conversion; in vitro intrapulpal temperature change and in vivo temperature change when using either room-temperature or pre-heated composite). Monomer conversion and kinetic parameters were determined using FTIR-ATR. Specimens were cured for 5, 10, 20 or 40s between 3 o and 60 o C. Real-time monomer conversion, maximum conversion rate, time into exposure when maximum rate occurred, and conversion at maximum rate were calculated. Data were analyzed using regression analysis, Student's t-tests, and ANOVA with appropriate post-hoc tests (alpha = 0.05). Performance of the heating device was measured by monitoring the real-time temperature change with a K-type thermocouple connected to an analog-to-digital converter. Thermocouples were placed both in the heater and inside composite compules. Data were analyzed using Student t-test (alpha = 0.05). Compules (n=5) were submitted to one of the temperatures cycles: Repeated (from room temperature to 60 o C, 10 times) or Extended pre-heating (24h at 60 o C). Monomer conversion was measured 24h after cycling, with composite at room temperature, following the protocol described above. Data were analyzed using ANOVA and the Tukey-Kramer post-hoc test (alpha = 0.05). Intrapulpal temperature rise was measured by placing a K-type thermocouple in the pulp chamber of a extracted, human premolar, which had a Class V preparation (1mm remaining dentin thickness). The preparation was filled using composite either at room-temperature, or pre-heated while continuously monitoring intrapulpal temperature (n=5). Data were compared using ANOVA and the Tukey-Kramer post-hoc test (α =0.05). For measurement of temperature change in vivo, 2mm deep preparations were made on posterior teeth of a live human subject (n=3). Temperature values were recorded by placing a custom-made probe on the tooth preparation after each restorative procedure and during insertion of resin-composite at room temperature or pre-heated to 60°C. Data were compared using a 2-way ANOVA, and Tukey-Kramer post-hoc test (α =0.05). Results indicated that: 1) pre-warming composite prior to polymerization results in greater conversion, requires shorter exposure duration, and enhances maximal rate of conversion without changing the time into the exposure when the maximum rate occurs; 2) either the heating device or the compules achieved lower temperatures than those stated by the manufacturer; composite temperature loss upon removal from the heater was dramatic; 3) neither repeated nor extended pre-heating of composites significantly affected monomer conversion values; 4) no increase in intrapulpal temperature values was observed when comparing room temperature and pre-heated composite; 5) temperature measurement in vivo revealed that composite pre-heated to 60°C attains only 8 o C above intraoral temperature upon delivery; thus, the composite pre-heating technique should be used with caution.

As reações de metatese assim como o desenvolvimento de complexos metal-carbeno (W, Mo, Ru) se tornaram amplamente conhecidos na química graças aos avanços que trouxeram. Na química orgânica, possibilitou a síntese de macrocíclos por meio da RCM e na química de polímeros a ROMP permitiu um alto grau de controle da polimerização além da alta reatividade dos catalisadores. Isso fez desta reação uma poderosa ferramenta no desenvolvimento de novos materias. A tentativa de combinar a processabilidade dos polímeros com as propriedades luminescentes de determinandos compostos tem sido tema de muitas pesquisas.O objetivo deste trabalho é derivatizar compostos luminescentes , como o complexo metálico [Ru(bpy)3] (PF6)2e a porfirina tetrakis-(pentafluorfenil)porfirina (TPPF20), com o monômero norborneno (NBE) para obtenção de monômeros lumiscentes passíveis de serem polimerizados via ROMP. Aqui será apresentado e discutido a síntese e a caracterização desses compostos partindo-se dos reagentes: ácido-5-norborneno-2carboxílico; etilenodiamina e o ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, cis-[RuCl2(bpy)2] e a porfirina TPPF20. Os compostos foram sintetizados com rendimentos superiores a 60%, com exceção da obtenção da porfirina, e caracterizados por RMN - 1H e 13C; FTIR; UV-vis. Os estudos de copolimerização entre NEN (norborneno-etilenodiamina-norborneno), NBE-TPPF e [Ru(bpy)2(NBbpy)](PF6)2 foram feitos usando o catalisador de Grubbs segunda gereação. Os polímeros gerados foram caracterizados usando TG-FTIR e RMN-1H, as massas moleculares não puderam ser calculadas por GPC porém os estudos indicam obtenção de baixo peso molelcular. O material obtido foi testado como sensibilizador em vidro condutor ITO, porém não houve adsorção do composto necessitam algumas modificações no metalomonômero. / The metathesis reactions as well as the development of metal-carbene complexes (W, Mo, Ru) became widely known in chemistry thanks to advancements brought. In organic chemistry, it enabled the synthesis of macrocycle by RCM. Useful for the synthesis of natural products. In polymer chemistry, ROMP, allow a high degree of polymerization control. This made the ROMP reaction a powerful tool in the development of new materials. In attempt to combine the processability of polymers with luminescent properties of such compounds has been the subject of several researchs. The aim of this work is to synthesize luminescent compounds based on [Ru(bpy)3] (PF6)2 metal complex and on the porphyrin tetrakis-(pentafluorphenyl)porphyrin (TPPF20), funcionalized with pendant norbornene monomer (NBE) to obtain lumiscentes monomers which can undergo ROMP polymerization. Here will be discussed the synthesis and characterization of these compounds using as starting materials: 5-norbornene-2-carboxylic acid; ethylenediamine; 2,2\'-bipyridine-4,4\'dicarboxylic acid, cis-[RuCl2(bpy)2] and the porphyrin TPPF20. The compounds were synthesized with yields higher than 60%, with the exception of the porphyrin, and characterized by 1H and 13C-NMR; FTIR; UV-vis. Copolymerization reaction between NEN (Norbornene-Ethylenediamine-Norbornene), NBE-TPPFe [Ru(bpy)2(NBbpy)] (PF6)2 were performed using Grubbs second generation catalyst. Resultinf polymers were characterized by TG-FTIR and 1H-NMR, molecular weight could not be measured by GPC, since polymers were insoluble, but studies indicate low molelcular weight. The material obtained was tested as sensitizer in conductive glass ITO. The polymer didn\'t adsorb in to the ITO surface. Some changes in the compound molecular structure are required to improve adsorption.

As reações de metatese assim como o desenvolvimento de complexos metal-carbeno (W, Mo, Ru) se tornaram amplamente conhecidos na química graças aos avanços que trouxeram. Na química orgânica, possibilitou a síntese de macrocíclos por meio da RCM e na química de polímeros a ROMP permitiu um alto grau de controle da polimerização além da alta reatividade dos catalisadores. Isso fez desta reação uma poderosa ferramenta no desenvolvimento de novos materias. A tentativa de combinar a processabilidade dos polímeros com as propriedades luminescentes de determinandos compostos tem sido tema de muitas pesquisas.O objetivo deste trabalho é derivatizar compostos luminescentes , como o complexo metálico [Ru(bpy)3] (PF6)2e a porfirina tetrakis-(pentafluorfenil)porfirina (TPPF20), com o monômero norborneno (NBE) para obtenção de monômeros lumiscentes passíveis de serem polimerizados via ROMP. Aqui será apresentado e discutido a síntese e a caracterização desses compostos partindo-se dos reagentes: ácido-5-norborneno-2carboxílico; etilenodiamina e o ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, cis-[RuCl2(bpy)2] e a porfirina TPPF20. Os compostos foram sintetizados com rendimentos superiores a 60%, com exceção da obtenção da porfirina, e caracterizados por RMN - 1H e 13C; FTIR; UV-vis. Os estudos de copolimerização entre NEN (norborneno-etilenodiamina-norborneno), NBE-TPPF e [Ru(bpy)2(NBbpy)](PF6)2 foram feitos usando o catalisador de Grubbs segunda gereação. Os polímeros gerados foram caracterizados usando TG-FTIR e RMN-1H, as massas moleculares não puderam ser calculadas por GPC porém os estudos indicam obtenção de baixo peso molelcular. O material obtido foi testado como sensibilizador em vidro condutor ITO, porém não houve adsorção do composto necessitam algumas modificações no metalomonômero. / The metathesis reactions as well as the development of metal-carbene complexes (W, Mo, Ru) became widely known in chemistry thanks to advancements brought. In organic chemistry, it enabled the synthesis of macrocycle by RCM. Useful for the synthesis of natural products. In polymer chemistry, ROMP, allow a high degree of polymerization control. This made the ROMP reaction a powerful tool in the development of new materials. In attempt to combine the processability of polymers with luminescent properties of such compounds has been the subject of several researchs. The aim of this work is to synthesize luminescent compounds based on [Ru(bpy)3] (PF6)2 metal complex and on the porphyrin tetrakis-(pentafluorphenyl)porphyrin (TPPF20), funcionalized with pendant norbornene monomer (NBE) to obtain lumiscentes monomers which can undergo ROMP polymerization. Here will be discussed the synthesis and characterization of these compounds using as starting materials: 5-norbornene-2-carboxylic acid; ethylenediamine; 2,2\'-bipyridine-4,4\'dicarboxylic acid, cis-[RuCl2(bpy)2] and the porphyrin TPPF20. The compounds were synthesized with yields higher than 60%, with the exception of the porphyrin, and characterized by 1H and 13C-NMR; FTIR; UV-vis. Copolymerization reaction between NEN (Norbornene-Ethylenediamine-Norbornene), NBE-TPPFe [Ru(bpy)2(NBbpy)] (PF6)2 were performed using Grubbs second generation catalyst. Resultinf polymers were characterized by TG-FTIR and 1H-NMR, molecular weight could not be measured by GPC, since polymers were insoluble, but studies indicate low molelcular weight. The material obtained was tested as sensitizer in conductive glass ITO. The polymer didn\'t adsorb in to the ITO surface. Some changes in the compound molecular structure are required to improve adsorption.

<p>This thesis describes the current status and novel aspects of the analysis of the molecules of life, i.e. peptides and proteins, using capillary electrophoresis (CE) coupled to mass spectrometry (MS) via (sheathless) electrospray ionization (ESI). Early reports of sheathless CE-ESI-MS were plagued by limited lifetimes of the electrospray emitter. In this thesis, two new approaches, the Black Dust and the Black Jack methods, utilizing polymer-embedded graphite instead of noble metals are presented. These emitters have shown improved long-term stability and proven excellent for sheathless electrospray operation. Failure of an emitter is often caused by electrochemical reactions occurring at the emitter-liquid interface. The electrochemical properties of the graphite coated emitters were therefore evaluated by classical electrochemical methods, such as cyclic voltammetry and chronoamperometry. The graphite coated emitters showed excellent electrochemical stability and properties compared to noble metal and polymer configurations.</p><p>Analyte-wall interactions have long been known to cause problems in the CE analysis of biomolecules. This can be circumvented by internal modification of the capillary walls. Additionally, it is of outermost importance to have a stable and sufficiently high electroosmotic flow (EOF) to sustain the electrospray, when using a sheathless approach. New monomer and polymer coatings are presented for rapid and high-efficient CE-ESI-MS separations of peptides and proteins.</p><p>Furthermore, the use of CE-ESI coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) shows great potential for rapid proteomic probing of human cerebrospinal fluid. The results are comparable with more established techniques, such as liquid chromatography and two-dimensional gel electrophoresis coupled to MS. However, the CE-ESI-FTICRMS analysis has significantly lower sample consumption and faster analysis time compared to the other techniques. The applications and use of CE-ESI-MS is expected to have a bright future with continued growth as current trends of multidimensional hyphenation and microfabricated devices are further developed and explored.</p>

This thesis describes the current status and novel aspects of the analysis of the molecules of life, i.e. peptides and proteins, using capillary electrophoresis (CE) coupled to mass spectrometry (MS) via (sheathless) electrospray ionization (ESI). Early reports of sheathless CE-ESI-MS were plagued by limited lifetimes of the electrospray emitter. In this thesis, two new approaches, the Black Dust and the Black Jack methods, utilizing polymer-embedded graphite instead of noble metals are presented. These emitters have shown improved long-term stability and proven excellent for sheathless electrospray operation. Failure of an emitter is often caused by electrochemical reactions occurring at the emitter-liquid interface. The electrochemical properties of the graphite coated emitters were therefore evaluated by classical electrochemical methods, such as cyclic voltammetry and chronoamperometry. The graphite coated emitters showed excellent electrochemical stability and properties compared to noble metal and polymer configurations. Analyte-wall interactions have long been known to cause problems in the CE analysis of biomolecules. This can be circumvented by internal modification of the capillary walls. Additionally, it is of outermost importance to have a stable and sufficiently high electroosmotic flow (EOF) to sustain the electrospray, when using a sheathless approach. New monomer and polymer coatings are presented for rapid and high-efficient CE-ESI-MS separations of peptides and proteins. Furthermore, the use of CE-ESI coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) shows great potential for rapid proteomic probing of human cerebrospinal fluid. The results are comparable with more established techniques, such as liquid chromatography and two-dimensional gel electrophoresis coupled to MS. However, the CE-ESI-FTICRMS analysis has significantly lower sample consumption and faster analysis time compared to the other techniques. The applications and use of CE-ESI-MS is expected to have a bright future with continued growth as current trends of multidimensional hyphenation and microfabricated devices are further developed and explored.