Thesis (Ph.D.)--McMaster University, 2003. / Advisor: N. Werstiuk. Includes bibliographical references (leaves 148-156). Also available via World Wide Web.

Purpose - The purpose of this master thesis is to identify critical factors and create guidelines for traditional consultant brokerage firms to stay competitive in a digital economy. Methodology - This qualitative study with an abductive approach, gathered data primary from semi-structured interviews. A total 18 interviews were conducted with travel agency executives as well as buyers, sellers, and matchmakers of consultant services. Collected data were analyzed using thematic coding. Findings - The main findings of this show that traditional matchmakers can take actions to stay competitive if a digital platform enters the market. In addition, the study suggests proactive and reactive measures that organizations can take to address these disruptive forces. Theoretical implications - The study will provide an understanding of consultant brokerage and their function as a matchmaker in the marketplace. Besides, it will provide an insight into how some traditional matchmakers can survive in a digital economy. Practical implications - This thesis will provide managers with concrete guidelines on how to react in the event of disintermediation of a matchmaker market. Keywords - Disintermediation, Business strategy, Reintermediation, Matchmakers, Intermediates, Consultants, Brokers Paper type - Master thesis

O sistema quimiluminescente peróxi-oxalato vem sendo estudado por diversos grupos de pesquisa ao redor do mundo desde os anos 60. Esse interesse em especial se deve ao fato de que em comparação com a maioria dos sistemas quimiluminescentes, que apresentam rendimentos quânticos da ordem de 1%, esse sistema apresenta rendimentos quânticos de emissão consideravelmente maiores, cerca de 30%. O sistema peróxi-oxalato consiste na reação de ésteres fenólicos substituídos derivados do ácido oxálico com peróxido de hidrogênio, catalisada por uma base e em presença de compostos aromáticos policondensados fluorescentes com baixo potencial de oxidação, chamados de ativadores (ACT). O mecanismo desta reação, apesar de intensamente estudado, ainda não se encontra completamente esclarecido. Especificamente, a estrutura do intermediário formado durante a reação, que é responsável pela quimiexcitação do ativador, não é conhecida ainda. No presente trabalho, foram completados estudos previamente efetuados no nosso grupo com derivados perácidos, intermediários na reação peróxi-oxalato. Foram sintetizados e caracterizados dois novos derivados perácido, o O,Ohidrogênio monoperóxi-oxalato de 3-clorofenila e o O,O-hidrogênio monoperóxioxalato de 3-nitrofenila. Dos estudos cinéticos da reação destes perácidos com imidazol, na presença de 9,10-difenilantraceno como ativador, foram obtidos constantes de velocidade de ciclização e rendimentos quânticos singlete. As constantes de velocidade determinadas, junto com os dados obtidos anteriormente no grupo, mostram correlação linear de energia livre com as constantes de substituintes de Hammett, obtendo-se um valor de = 2,18 ± 0,16, o que indica a formação de alta densidade de carga negativa no estado de transição do passo lento. A correlação linear entre as constantes de velocidade e os valores de pKa dos grupos de partida fenólicos levou à determinação do valor de βGP = -1,07 ± 0,08, indicando que a quebra da ligação para o grupo de partida é muito avançada no estado de transição no passo lento da reação. Os rendimentos quânticos singlete mostram dependência com as propriedades eletrônicas dos substituintes, aumentando inicialmente com o aumento das propriedades de atração de elétron do substituinte, porém, com substituintes mais atraentes que hidrogênio, observa-se uma leve diminuição no rendimento quântico. O conjunto de dados apresentados neste trabalho, junto com os resultados obtidos anteriormente pelo grupo, demonstra claramente que a reação de ciclização dos perácidos, catalisada por imidazol, deve ocorrer de maneira concertada, ou seja, a saída do grupo de partida fenólico ocorre em conjunto com o ataque nucleofílico do íon percarboxilato à função éster no passo lento da reação. Conseqüentemente, foram obtidas neste trabalho evidências experimentais fundamentadas para a ocorrência da 1,2- dioxetanodiona como intermediário de alta energia na reação peróxi-oxalato. / The peroxyoxalate chemiluminescence has been intensely studied since the sixties by several research groups all around the world. This interest is mainly due to the fact that the peroxyoxalate system is highly efficient, showing quantum yields of around 30 %, much higher than other well known chemiluminescence reactions which commonly show quantum yields of around 1% or less. The peroxyoxalate system consists in the base catalyzed reaction of activated oxalate esters with hydrogen peroxide in the presence of highly fluorescent polycondensed aromatic hydrocarbons with low oxidation potentials, called activators (ACT). Although intensely investigated, the mechanism of this complex transformation is still not yet completely clarified. This is true specifically for the structure of the high-energy intermediate, formed during the reaction sequence, which is responsible for chemiexcitation, not known at all up to now. In the present work, former studies of our group on peracid derivatives, intermediates in the peroxyoxalate reaction, were completed. Two new peracid derivatives, 3-chlorophenyl O,O-hydrogen monoperoxyoxalate and 3- nitrophenyl O,O-hydrogen monoperoxyoxalate were synthesized and characterized. Kinetic studies on the reaction of these peracid derivatives with imidazole, in the presence of 9,10-diphenylanthracene as activator, led to the determination of cyclization rate constants and singlet quantum yields. These rate constants, together with data formerly obtained by our group, show linear free-energy correlation with the Hammett substituent constants, resulting in a reaction constant of = 2,18 ± 0,16, that indicates the formation of a high negative charge density in the transition state of the rate-limiting step. Similarly, the linear correlation of the rate constants with the pKa values of the phenolic leaving groups leads to the determination of a value βGP = -1,07 ± 0,08, indicating a high degree of leaving group bond cleavage in the transition state of the rate-limiting step. The singlet quantum yields also show dependence on the electronic properties of the substituents, initially increasing with the increase in the electron withdrawing nature of the substituent, however, a slight decrease in the quantum yields is observed with substituents more electron withdrawing than hydrogen. The data accumulated in this work, together with results earlier obtained in our group, clearly demonstrate that the cyclization reaction of the peracid derivatives, catalyzed by imidazole, proceeds in a concerted manner, i.e. the phenolic leaving group departure occurs together with the nucleophilic percarboxylate attach to the ester function in the rate-limiting reaction step. Consequently, it was possible to obtain in this work solid experimental evidence for the occurrence of 1,2-dioxetandione as the high-energy intermediate in the peroxyoxalate reaction.

Background The Red proteins of lambda phage mediate probably the simplest and most efficient homologous recombination reactions yet described. However the mechanism of dsDNA recombination remains undefined. Results Here we show that the Red proteins can act via full length single stranded intermediates to establish single stranded heteroduplexes at the replication fork. We created asymmetrically digestible dsDNA substrates by exploiting the fact that Redα exonuclease activity requires a 5' phosphorylated end, or is blocked by phosphothioates. Using these substrates, we found that the most efficient configuration for dsDNA recombination occurred when the strand that can prime Okazaki-like synthesis contained both homology regions on the same ssDNA molecule. Furthermore, we show that Red recombination requires replication of the target molecule. Conclusions Hence we propose a new model for dsDNA recombination, termed 'beta' recombination, based on the formation of ssDNA heteroduplexes at the replication fork. Implications of the model were tested using (i) an in situ assay for recombination, which showed that recombination generated mixed wild type and recombinant colonies; and (ii) the predicted asymmetries of the homology arms, which showed that recombination is more sensitive to non-homologies attached to 5' than 3' ends. Whereas beta recombination can generate deletions in target BACs of at least 50 kb at about the same efficiency as small deletions, the converse event of insertion is very sensitive to increasing size. Insertions up to 3 kb are most efficiently achieved using beta recombination, however at greater sizes, an alternative Red-mediated mechanism(s) appears to be equally efficient. These findings define a new intermediate in homologous recombination, which also has practical implications for recombineering with the Red proteins.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19895号 / 工博第4211号 / 新制||工||1651(附属図書館) / 32972 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 吉田 潤一, 教授 松田 建児, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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<p>This dissertation presents several examples of diverse applications of mass spectrometry. For example, high-resolution mass spectrometry was utilized for qualitative and quantitative chemical characterization of ionized compounds in petrochemical samples, specifically, in condensate-like oil samples. Further, the ability to use tandem mass spectrometry to rapidly detect trace amounts of short-lived reaction intermediates in solution reactions is demonstrated. Finally, selective tandem mass spectrometry methods based on diagnostic gas-phase ion-molecule reactions were developed for the identification of carboxylic acid functionalities in protonated analytes.</p>

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Defining and measuring the quality of customer service has been a major challenge for business-to-business marketers. This research addresses the question whether an established instrument for consumer markets (SERVQUAL) can be used for understanding the role of customer service in the European nylon intermediates industry. To accomplish this objective, an in-depth literature review is accomplished followed by several expert panels adopting the instrument slightly. Based on a survey sample of 110 industry members collected with the ¿drop and collect technique¿ the appropriateness of the tool to verify the anticipated structure is examined using reliability tests as well as exploratory and confirmatory factor analysis. The findings suggest that even though various criteria for reliability and validity are met, the five-dimensional structure of the instrument cannot be recovered. The research questions the usefulness of the instrument for the European nylon intermediates industry despite it being originally anticipated to be applicable. However, the research emphasises that the instrument is a useful indicator for understanding the role of customer service based on individual items rather than on the instrument¿s dimensionality. It is demonstrated how the implementation in the nylon intermediates industry enables an organization to develop a greater awareness of customer service quality and how an enterprise gains an initial instrument to comprehend and improve this element of the offering. The thesis concludes by linking the results of the research with the discussion on service-dominant logic.

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