xx, 204 p. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Efforts toward developing improved methods of synthesizing acrylamides are ongoing. Several homogeneous organometallic and coordination complexes have proven useful in catalytic acrylonitrile hydration; however, none of these complexes have been tested in the hydration of cyanohydrins used to synthesize substituted acrylamides. This dissertation describes the reactivity of molybdocene and Pt phosphinito nitrile hydration catalysts toward cyanohydrin substrates and the effect of Cp ring substituents on aqueous molybdocene chemistry. Chapter I identifies the motivation for developing a transition metal-catalyzed process for cyanohydrin hydration and the strategy used to improve on the reactivity of molybdocene catalysts. Chapter II reports the effect of cyclopentadienyl ring substituents on the electronic and geometric structure, solution behavior, and hydrolytic activity of molybdocenes. To examine the effect of Cp ring substituents, ansa -molybdocenes containing the fragment {C 2 Me 4 (C 5 H 4 ) 2 }Mo 2+ were compared to non-bridged molybdocenes containing (C 5 H 5 ) 2 Mo 2+ and (C 5 H 4 Me) 2 Mo 2+ . Addition of a tetramethylethylene-bridge decreases the electron density on the Mo center and exerts a small effect on the structure of the metallocene. However, the catalytic activity of the molybdocene catalysts is unchanged or slowed because of counteractive effects on the bound nucleophile and electrophile. Although adding substituents to the Cp rings did not change the catalytic activity of the molybdocene, the substituents led to significant changes in the equilibrium behavior. The equilibria have practical consequences that warrant investigation. Chapters III and IV chronicle the effect of Cp ring substituents on the monomer-dimer equilibria and the acidity of the molybdocene complexes, respectively. Interestingly, the monomer-dimer equilibrium established by ansa -{C 2 Me 4 (C 5 H 4 ) 2 }Mo(OH)(OH 2 ) + exhibits a strong solvent dependence. New equilibrium schemes are reported for the ansa and non- ansa complexes. Chapter V describes the reactivity of the molybdocene and Pt phosphinito catalysts toward cyanohydrins. Both catalysts gave unsatisfactory results; however, the à à à à à ±-hydroxy substituent of cyanohydrins facilitates nitrile hydration. The low reactivity exhibited by these systems was due to liberation of hydrogen cyanide from the cyanohydrin leading to acute poisoning of either catalyst. As discussed in Chapter VI, this study will expedite the innovation of new catalysts that are better suited to overcome the challenges associated with cyanohydrin hydration. This dissertation includes previously published and unpublished co-authored material. / Adviser: David R. Tyler

xviii, 242 p. : ill. (some col.) / Fuel purification is an extremely active area of research in today's green world. Specifically, desulfurization of fuels is an important area of research for two reasons. First, any sulfur present in fuels generates SOx pollutants that are hazardous to human health and also contribute to acid rain. Secondly, even trace sulfur contaminants prohibit the use of fuel streams in fuel cells. However, achieving near-zero sulfur levels with existing technology is impractical. The work in this thesis investigates a new process for the removal of sulfur from fuel streams using a film-shear reactor (based on a process known as oxidative desulfurization), and goes on to investigate the mode of activation for the process within the reactor through a study of the reactor conditions. Additionally, other applications of the film-shear reactor, including mechanical activation of molecules and controlled nanoparticle synthesis are explored. Chapter I outlines the current status of oxidative desulfurization research, highlighting the strengths of the method, innovative approaches and drawbacks to the various approaches. Chapters II and III go on to discuss the enhancement of the process in the film-shear reactor using model fuels and a variety of substrates. This method was found to significantly enhance the oxidative desulfurization process, reducing both the time and temperature required to achieve considerable sulfur removal. Levels of desulfurization that require hours at elevated temperatures by conventional stirring methods were obtainable on the scale of seconds at or below room temperature. Chapter IV offers investigations into the conditions within the film-shear reactor, and also presents studies of the ability of the high shear rates obtained in the reactor to mechanically activate molecules. Chapter V extends the applicability of the film-shear reactor to nanoparticle synthesis through investigation of two titania synthesis methods utilizing the film-shear reactor. Appendices A and B offer supplementary information to enhance the studies presented in Chapters II and III, while Appendices C, D, and E highlight work done investigating the ability of platinum complexes to hydrate nitriles and cyanohydrins. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Victoria J. DeRose, Chairperson; David R. Tyler, Advisor; Kenneth M. Doxsee, Member; Catherine J. Page, Member; Mark H. Reed, Outside Member

Introdução: Apesar da falta de evidência cientifica, costuma-se pensar que crianças obesas apresentam desvantagens e são menos tolerantes ao se exercitarem no calor. Objetivo: Comparar a sudorese, balanço hidro-eletrolítico e a tolerância ao exercício no calor entre meninos pré-púberes obesos e eutróficos que pedalam no calor. Métodos: Trinta meninos pré-púberes foram alocados para o grupo de obesos (GO, n=15) e eutróficos (GE, n=15). Após uma sessão de avaliação, os meninos vieram ao laboratório para a sessão de exercício no calor (35C, 40-45%UR). Eles pedalavam por 30 minutos a 50-60% do seu VO2pico pré determinado. Para coletar o suor, adesivos foram fixados sobre 4 regiões da pele (costas, peito, antebraço e coxa) e as amostras foram analisadas para eletrólitos (AVL, 9180). Após o exercício, amostras de urina foram coletadas para análise de volume e eletrólitos para coleta regional de suor (AVL, 9180). Após a pedalada, os meninos descansaram por 10 min e pedalaram a 90% do VO2pico até a exaustão e o tempo de desempenho foi registrado. Durante a sessão, a ingestão “ad libitum” de uma bebida esportiva foi avaliada. Sensação subjetiva de calor foi avaliada durante toda a sessão. Resultados: A taxa de sudorese relativa a área de superfície corporal foi similar entre eutróficos e obesos (488  232 e 417  89.6 ml.m2.min-1, respectively; p=0,004) e as [Na+] e [Cl-] no suor foram maiores nos meninos obesos (p=0,005), enquanto a [K+] foi similar entre os grupos (p = 0,004). Ambos os grupos apresentaram um balanço hidroeletrolítico negativo, mas não existiu diferença entre os grupos. O tempo de desempenho foi maior no GE (89.6  64.1) que o GO (41.2  29.6 seg; p=0,005). A sensação subjetiva de calor foi maior no GO que no GE em todos os momentos (p = 0,005). Conclusão: Meninos pré-púberes obesos apresentaram uma similar taxa de sudorese relativa à área de superfície corporal, menor tolerância ao exercício no calor, e maior [Na+] e [Cl-] no suor comparado aos eutróficos. Crianças obesas não diferem das eutróficas em relação ao balanço hidroeletrolítico. / Introduction: Despite the lack of scientific evidence, it is generally thought that obese children have disadvantages and are less tolerant to exercise in the heat when compared to lean children. Purpose: To compare sweating, water and electrolyte balance, and exercise tolerance heat between obese and lean boys who cycled in the heat. Methods: Thirty prepubertal boys formed an obese (OG, n=15) and a lean (LG, n=15) group. After a screening session and evaluation of physical characteristics and VO2peak, the boys came to the laboratory for the exercise session in the heat (35C, 40-45%RU). They cycled for 30 minutes at 50-60% of their pre-determined VO2peak. To collect sweat, patches were attached on 4 regions of the skin (back, chest, forearm and thigh) and samples were analyzed for electrolytes (AVL 9180). After exercise, urine samples were collected for volume and electrolyte analyses (AVL 9180). After this cycling, the boys rested 10 min and cycled at 90% VO2peak until exhaustion and the performance time was registered. During the whole session, a sports drink was available to drink “ad libitum” and the intake was registered. Heat subject sensation (HSS) was evaluated during the whole session. Results: Sweat rate relative to body surface area was similar between lean and obesity boys (488  232 and 417  89.6 ml.m2.min-1, respectively; p=0.004) and sweat [Na+] and [Cl-] were higher in the obese boys (p=0.005), whereas [K+] was similar between groups (p = 0.004). Both groups showed a negative water and electrolyte balance, but there was no difference between groups. The performance time was longer in the LG (89.6  64.1) than OG (41.2  29.6 sec; p=0.005). The heat subjective sensation was higher in GO than in GE at all times (p = 0.005). Conclusion: Obese prepubescent boys showed similar sweat rate relative to body surface area, lower exercise heat tolerance, and increased [Na+] and [Cl-] sweat loss compared to lean children. Obese children did not differ from lean children related to water and electrolyte balance.

Introdução: Apesar da falta de evidência cientifica, costuma-se pensar que crianças obesas apresentam desvantagens e são menos tolerantes ao se exercitarem no calor. Objetivo: Comparar a sudorese, balanço hidro-eletrolítico e a tolerância ao exercício no calor entre meninos pré-púberes obesos e eutróficos que pedalam no calor. Métodos: Trinta meninos pré-púberes foram alocados para o grupo de obesos (GO, n=15) e eutróficos (GE, n=15). Após uma sessão de avaliação, os meninos vieram ao laboratório para a sessão de exercício no calor (35C, 40-45%UR). Eles pedalavam por 30 minutos a 50-60% do seu VO2pico pré determinado. Para coletar o suor, adesivos foram fixados sobre 4 regiões da pele (costas, peito, antebraço e coxa) e as amostras foram analisadas para eletrólitos (AVL, 9180). Após o exercício, amostras de urina foram coletadas para análise de volume e eletrólitos para coleta regional de suor (AVL, 9180). Após a pedalada, os meninos descansaram por 10 min e pedalaram a 90% do VO2pico até a exaustão e o tempo de desempenho foi registrado. Durante a sessão, a ingestão “ad libitum” de uma bebida esportiva foi avaliada. Sensação subjetiva de calor foi avaliada durante toda a sessão. Resultados: A taxa de sudorese relativa a área de superfície corporal foi similar entre eutróficos e obesos (488  232 e 417  89.6 ml.m2.min-1, respectively; p=0,004) e as [Na+] e [Cl-] no suor foram maiores nos meninos obesos (p=0,005), enquanto a [K+] foi similar entre os grupos (p = 0,004). Ambos os grupos apresentaram um balanço hidroeletrolítico negativo, mas não existiu diferença entre os grupos. O tempo de desempenho foi maior no GE (89.6  64.1) que o GO (41.2  29.6 seg; p=0,005). A sensação subjetiva de calor foi maior no GO que no GE em todos os momentos (p = 0,005). Conclusão: Meninos pré-púberes obesos apresentaram uma similar taxa de sudorese relativa à área de superfície corporal, menor tolerância ao exercício no calor, e maior [Na+] e [Cl-] no suor comparado aos eutróficos. Crianças obesas não diferem das eutróficas em relação ao balanço hidroeletrolítico. / Introduction: Despite the lack of scientific evidence, it is generally thought that obese children have disadvantages and are less tolerant to exercise in the heat when compared to lean children. Purpose: To compare sweating, water and electrolyte balance, and exercise tolerance heat between obese and lean boys who cycled in the heat. Methods: Thirty prepubertal boys formed an obese (OG, n=15) and a lean (LG, n=15) group. After a screening session and evaluation of physical characteristics and VO2peak, the boys came to the laboratory for the exercise session in the heat (35C, 40-45%RU). They cycled for 30 minutes at 50-60% of their pre-determined VO2peak. To collect sweat, patches were attached on 4 regions of the skin (back, chest, forearm and thigh) and samples were analyzed for electrolytes (AVL 9180). After exercise, urine samples were collected for volume and electrolyte analyses (AVL 9180). After this cycling, the boys rested 10 min and cycled at 90% VO2peak until exhaustion and the performance time was registered. During the whole session, a sports drink was available to drink “ad libitum” and the intake was registered. Heat subject sensation (HSS) was evaluated during the whole session. Results: Sweat rate relative to body surface area was similar between lean and obesity boys (488  232 and 417  89.6 ml.m2.min-1, respectively; p=0.004) and sweat [Na+] and [Cl-] were higher in the obese boys (p=0.005), whereas [K+] was similar between groups (p = 0.004). Both groups showed a negative water and electrolyte balance, but there was no difference between groups. The performance time was longer in the LG (89.6  64.1) than OG (41.2  29.6 sec; p=0.005). The heat subjective sensation was higher in GO than in GE at all times (p = 0.005). Conclusion: Obese prepubescent boys showed similar sweat rate relative to body surface area, lower exercise heat tolerance, and increased [Na+] and [Cl-] sweat loss compared to lean children. Obese children did not differ from lean children related to water and electrolyte balance.

abstract: There is considerable recent interest in the dynamic nature of immune function in the context of an animal’s internal and external environment. An important focus within this field of ecoimmunology is on how availability of resources such as energy can alter immune function. Water is an additional resource that drives animal development, physiology, and behavior, yet the influence hydration has on immunity has received limited attention. In particular, hydration state may have the greatest potential to drive fluctuations in immunity and other physiological functions in species that live in water-limited environments where they may experience periods of dehydration. To shed light on the sensitivity of immune function to hydration state, I first tested the effect of hydration states (hydrated, dehydrated, and rehydrated) and digestive states on innate immunity in the Gila monster, a desert-dwelling lizard. Though dehydration is often thought to be stressful and, if experienced chronically, likely to decrease immune function, dehydration elicited an increase in immune response in this species, while digestive state had no effect. Next, I tested whether dehydration was indeed stressful, and tested a broader range of immune measures. My findings validated the enhanced innate immunity across additional measures and revealed that Gila monsters lacked a significant stress hormone response during dehydration (though results were suggestive). I next sought to test if life history (in terms of environmental stability) drives these differences in dehydration responses using a comparative approach. I compared four confamilial pairs of squamate species that varied in habitat type within each pair—four species that are adapted to xeric environments and four that are adapted to more mesic environments. No effect of life history was detected between groups, but hydration was a driver of some measures of innate immunity and of stress hormone concentrations in multiple species. Additionally, species that exhibited a stress response to dehydration did not have decreased innate immunity, suggesting these physiological responses may often be decoupled. My dissertation work provides new insight into the relationship between hydration, stress, and immunity, and it may inform future work exploring disease transmission or organismal responses to climate change. / Dissertation/Thesis / Doctoral Dissertation Biology 2016

abstract: Water makes up about 45-70% of a human body's total weight. It is estimated that 80% of the human brain's tissue is composed of water. Cognitive productivity is altered when the body is in a mere 2% dehydrated state. Several cognitive functions impacted by dehydration include: visual motor tracing, short-term recall, attentiveness, and mathematic efficiency. It is estimated that 80% of the U.S. adult population endures the majority of their day in a mildly dehydrated state. Participants were employees working full-time jobs with Arizona State University or Tri Star Motor Company. Employees had to be 18 or older were invited to join the study. Employees participating in the study lived within the the greater Phoenix area. Participants of all races, genders, activity statuses, and BMIs were encouraged to join. A one-arm, pre-test, post-test study design was utilized. We examined whether the hydration status of participants in the intervention improved or worsened during the course of the intervention, and then attributed any such improvement or deterioration to the intervention. Urine collections from an afternoon sample were gathered before and after the one-week intervention. For the intervention, the participating offices received a water dispensing system in close proximity to employee desk spaces. A reusable water bottle was also given to each participant. Urine specific gravity (USG) was assessed in all urine samples to indicate hydration status, and all participants completed water intake surveys before and after the intervention. From this study, the overall change in water intake over the course of the one-week intervention was 143 ounces/day. This is an average of adding two and a half 8 oz glasses of water each day of the week per participant. USG also decreased significantly at the end of the intervention in comparison to the baseline value. In the greater body of research, this study strengthens the viability of inputting a hydration station and offering reusable water bottles to employees. This cost-effective method is an easy way to incorporate employee wellness in the workplace. The benefit of employees to drink more water is numerous, including increased focus, mental reactivity, and overall mood and wellness. / Dissertation/Thesis / Masters Thesis Nutrition 2018

No presente trabalho, realizado com hemoproteínas na forma de pó, o efeito da hidratação foi observado através de espectroscopia fotoacústica. Amostras de carboxi-hemoglobina e carboxi-mioglobina mantidas em diferentes ambientes de umidade relativa (UR), mostraram variações em seus espectros na região da banda de Soret. Para amostras mantidas em baixa hidratação característico do derivado carboxi, em alta hidratação (acima de aproximadamente 90% UR) o espectro era característico do derivado carboxi e na região intermediária o espectro era de uma mistura dos dois derivados. Essa mudança de ligante observada em alta hidratação pode ser explicada supondo que a proteína tem flexibilidade e atinge um estado conformacional que possibilita a entrada e saída do ligante. Em baixa hidratação a estrutura da proteína é rígida e tal que o acesso ao grupo heme está fechado, impossibilitando a troca do ligante. Essa explicação é coerente com vários resultados experimentais que indicam a existência de duas estruturas para essas hemoproteínas em solução / At the present work accomplished with powder of hemoproteins, the hydration effect was observed through photoacoustic spectroscopy. Samples of caroxyhemoglobin and carboxymyglobin kept at different relative humidity (RH) environments, showed variations in their spectra in the Soret bad region. For the samples which were kept at low hydration (Bellow about 33% RH) the spectrum was characteristic of carboxy derivative, whereas at high hydration (above about 93% RH) the spectrum was characteristic of oxy derivative, and in the the intermediate region the spectrum was a mixture of both derivatives. This ligand change observed at high hydration, may be explained assuming that the protein has flexibility, and reach a conformational state which enables the ligand to GO in and out. At low hydrations the protein structure is rigid and such that the access to the heme group is closed becoming impossible the ligand change. This explanation agrees with several experimental results that point to the existence of two structures to these hemoproteins in solution

Introdução: a água é componente vital para o desempenho das funções corporais e fundamental para a produção vocal. Sabe-se ainda que exercícios de aquecimento vocal preparam a voz para o canto. O propósito deste estudo foi investigar a influência da hidratação sistêmica na voz de coristas sem e com aquecimento vocal. Material e métodos: esta pesquisa teve a aprovação do CEP-FOB/USP, protocolo: 085/2011. Participaram 16 coristas, com média de idade de 49,38 anos, DP 14,74, sendo 12 do sexo feminino (75%) e quatro do sexo masculino (25%). Todos os coristas eram integrantes de coros há no mínimo um ano, saudáveis, sem queixas vocais e auditivas nos dias das avaliações e sem histórico de cirurgias laríngeas. Procedimentos: os participantes tiveram suas vozes avaliadas em dois dias não consecutivos, o primeiro na condição desidratado (D) e o segundo na condição hidratado (H). Em ambos os dias tiveram suas vozes gravadas antes (D1 e H1) e após a realização do aquecimento vocal (D2 e H2). Para a condição desidratado os coristas ficaram sem ingerir água durante as 12 horas que antecederam a primeira avaliação. Para a condição de hidratado houve a ingestão fracionada de três litros de água para os homens e dois litros para as mulheres no dia anterior ao dia da segunda avaliação. As condições hidratado e desidratado foram avaliadas por meio da coloração e gravidade específica da urina. Foi realizada a avaliação acústica dos parâmetros F0, jitter, shimmer e NHR, por meio do Multi Dimensional Voice Program (MDVP). A análise perceptivo-auditiva considerou o grau geral, a rugosidade, a soprosidade, a tensão, o pitch e o loudness da vogal /a/ sustentada por meio da escala visual analógica (EVA). As vozes foram analisadas pela fonoaudióloga que apresentou melhor análise intra-juiz (p=0,000 e r=0,77). Resultados: houve forte correlação entre os métodos da coloração e a gravidade específica da urina (r=0,807 e p<0,05). Na avaliação acústica houve redução da F0 e melhora do shimmer e na avaliação perceptivo-auditiva foi identificada melhora dos parâmetros da rugosidade, soprosidade, tensão e redução do pitch, nas vozes hidratadas sem aquecimento vocal. Nas vozes com aquecimento vocal a avaliação acústica revelou estabilidade da F0 e melhora do shimmer e na perceptivo-auditiva redução da rugosidade e do pitch. Conclusão: a hidratação sistêmica agiu positivamente na voz sem aquecimento vocal revelando na avaliação acústica redução da F0 e melhora do shimmer e na avaliação perceptivo-auditiva melhora dos parâmetros da rugosidade, soprosidade, tensão e redução do pitch. A hidratação sistêmica agiu positivamente na voz com aquecimento vocal revelando na avaliação acústica estabilidade da F0 e melhora do shimmer e na perceptivo-auditiva redução da rugosidade e do pitch. / Introduction: Water is a vital component for bodily functions and is fundamental for voice production. It is known that vocal warming exercises prepare the voice for singing. The purpose of this study was to investigate the influence of systemic hydration on choristers voices whilst warmed and unwarmed. Material and Methods: This research had the approval from CEP-FOB/USP protocol 085 2011. 16 choristers took part on the research, whose average age is 49.38 years (standard deviation 14,74), being 12 female (75%) and 4 male (25%). All choristers are healthy, do not present complaint on vocal or hearing issues during test days and do not possess history of laryngeal surgery. Procedure: the participants had their voices evaluated in two non-consecutive days, with hydrated voice (H) on the first day and with dehydrated voice (D) on the second. In both days, their voices were recorded before vocal warming (D1 and H1) and after vocal warming (D2 and H2.) For the dehydration condition, the choristers drank no water during the 12 preceding hours relative to the first test. For the hydration condition, fractioned water intake(3 liters for men and 2 liters for women) was held on the day before the second test. Hydrated and dehydrated conditions were determined by means of urine coloration and specific gravity. The acoustic evaluation was performed focusing in parameters F0, jitter, shimmer and NHR using the multidimensional voice program. The perceptual-auditory analysis considered the overall degree, rugosity, breathiness, tension, pitch and loudness of the sustained vowel a by visual analog scale. The voices were analyzed by the speech therapist who presented best intra-judge analysis (P = 0.000, R = 0.77). Results: The urine coloration and specific gravity have held strong correlation, with R = 0.807 and P < 0.05. On the acoustic evaluation, there has been reduction of F0 and shimmer improvement; and in the perceptive-auditory evaluation it was identified improvement on rugosity, breathiness, tension and reduction of pitch on hydrated unwarmed voices. On warmed voices, the acoustic evaluation revealed stability on F0 and improvement on shimmer; on the perceptive-auditory evaluation, rugosity and pitch have reduced. Conclusion: The systemic hydration acted positively on unwarmed voice revealing F0 reduction and shimmer improvement on the acoustic evaluation; and improvement on rugosity, breathiness, tension and pitch on the perceptive-auditory evaluation. Also, systemic hydration acted positively on the warmed voice, revealing F0 stability and shimmer improvement on the acoustic evaluation; and rugosity and pitch reduction on the perceptive-auditory evaluation.

A água é o principal componente do ser humano, a falta desse elemento pode resultar em consequências negativas, como o comprometimento do funcionamento de órgãos e sistemas ou até a morte. Considerando a hidratação um hábito essencial para a saúde do corpo, qual a sua relação com a saúde vocal? O objetivo do presente estudo foi verificar se as mudanças no estado de hidratação sistêmica dos indivíduos influenciam na qualidade vocal antes e após o uso contínuo da voz. Participaram desse estudo 13 indivíduos do sexo masculino, estudantes da Escola de Engenharia de São Carlos da Universidade de São Paulo USP, com média de idade de 21,31 ± 2,10 anos e IMC de 22,44 ± 2,04 kg/\'M POT.2\'. Os participantes foram submetidos a três avaliações não consecutivas em diferentes estados de hidratação sistêmica. Avaliação 1, hidratados, para tanto, os indivíduos foram orientados a ingerir a quantidade de 3,0 litros de água no dia anterior a avaliação e 1,5 litros na manhã do dia da avaliação. Avaliação 2, desidratados, os indivíduos foram orientados a não ingerir água ou líquidos das 22:00 horas do dia anterior até a manhã do dia da avaliação. Avaliação 3, desidratação por exercício físico, a orientação de ingestão de água foi igual a Avaliação 2 e para induzir ainda mais a desidratação, os indivíduos foram submetidos a exercício em esteira por 40 minutos. Nas 3 avaliações os procedimentos foram: gravação da voz em computador, para posteriores avaliações acústica e perceptivo-auditiva da voz; e coleta de urina, para verificação dos estados de hidratação. Para a análise da urina foram utilizados dois métodos: a gravidade específica e coloração da urina. Para a análise acústica da voz foi utilizado o programa MDVP com as medidas da frequência fundamental, jitter, shimmer e proporção harmônico ruído utilizando-se a vogal /a/ sustentada. A avaliação perceptivo-auditiva da voz foi realizada por uma fonoaudióloga especialista em voz, por meio das gravações da contagem de números. Os resultados da análise da urina confirmaram os diferentes estados de hidratação sistêmica e apresentaram forte correlação entre os métodos da gravidade e da coloração da urina. Os resultados da análise acústica indicaram valores de jitter acima da referência na desidratação tanto antes como após o uso contínuo de fala; maior valor médio de jitter antes da leitura no 9 estado de desidratação; aumento da frequência fundamental após leitura no estado de desidratação. Não foram observadas alterações significativas nas medidas de shimmer e na proporção harmônico ruído. A avaliação perceptivo-auditiva apontou melhora da qualidade vocal após leitura no estado de hidratação. As mudanças vocais observadas nos diferentes estados de hidratação sistêmica confirmaram que a hidratação traz benefícios para a voz. / Water is the main component of the human being, the lack of this element can result in negative consequences such as impaired functioning of organs and systems or even death. Considering hydration as an essential habit to the health of body, which is its relationship with vocal health? The aim of this study was to determine whether changes in systemic hydration status of individuals can influence the voice quality before and after continuous use of voice. In this study, 13 male students of the School of Engineering of the University of São Paulo-USP, with a average age of 21.31 ± 2.10 years and BMI 22.44 ± 2.04 kg/\'M POT.2\'. The participants were subject to three, nonconsecutive assessments, at different status of systemic hydration: Evaluation 1, hydrated, the subjects were instructed to drink 3 liters of water the day before the evaluation and 1.5 liters in the morning of the evaluation. Evaluation 2, dehydrated, subjects were instructed not to drink water or liquids from 10pm the day before until the morning of the evaluation. Evaluation 3, dehydration by physical exercise, the orientation of water intake was equal to evaluation 2 and to induce further dehydration, the subjects were subjected to a treadmill exercise during 40 minutes. At the 3 evaluations, the procedures were: voice recording on computer for subsequent acoustic and auditive-perceptual evaluations and urine collect to verify the hydration levels. For the urine analysis were used two methods: the specific gravity of the urine and its color. For the acoustic voice analysis the program MDVP was used to measures of fundamental frequency, jitter, shimmer and harmonic noise using the sustained vowel /a/. The auditive-perceptual evaluation of voice was performed by a Speech Therapist specialized in voice studies, through the recordings of the counting numbers. The results of urine analysis confirmed the different levels of hydration and both specific gravity and color of the urine showed a strong correlation. The results of acoustic analysis indicated jitter values above the reference in the dehydration both before and after reading, higher average jitter value before reading in the state of dehydration, also increasing fundamental frequency. There were no significant changes in measures of shimmer and harmonic noise. 11 The perceptual assessment of voice quality showed a improvement after reading during the state of hydration. Vocal changes observed in the different states of systemic hydration confirmed that hydration is beneficial to the voice.

The use of supplementary cementitious materials (SCMs) in commercial construction have been increasing over the last several decades as climate change and sustainability has been gaining global attention. Incorporation of SCMs into concrete mixtures provides several environmental benefits. Since most SCMs are waste by-products of other industries, their use in concrete reduces waste disposal. Additionally, cements substitution with SCMs reduces the carbon footprint of the construction industry. Cement production generates large amounts of CO2 emissions; the use of SCMs reduces the amount of cement in a concrete mixture thereby reducing emissions from its production. In addition to SCMs, modern concretes typically incorporate a combination of chemical admixtures. Adverse interaction of admixtures with cement, with or without the SCMs, or with each other is one of the most common reasons for early-age concrete issues. Since the possible combinations of admixtures are numerous and there is a variety of cements on the market, testing all possible chemical/mineral/cement admixture combinations is impractical. The aim of this research was to cover a broad base of admixture-related issues, each addressing a specific need of the construction industry. There is currently no explanation for why calcium chloride-based accelerator is not always effective when used with high tricalcium aluminate (C3A) cements. It was determined that increasing C3A or gypsum content alone did not appear to significantly affect acceleration; however, the presence of alkalis reduced the effectiveness of CaCl2 accelerator. When CaCl2-based accelerators are used in concrete, they are typically used in combination with other chemical admixtures, such as water-reducing and retarding admixtures (WRRA) to allow for the use of a low water-cementitious material ratio. In order to avoid premature hardening, CaCl2 accelerator is most often added onsite, rather than at the concrete batching plant. Onsite addition can lead to accidental overdose of accelerator. It was found that increasing dosages of calcium chloride-containing accelerating admixtures in the presence of WRRA has a non-linear effect on the pore size distribution and consequently a non-linear increase on the autogenous shrinkage, which can contribute to early-age concrete cracking. Water-reducing admixtures and superplasticizers are added to concrete to improve workability, which decreases not only with a decrease in water-cementitious material ratio, but also with addition of some SCMs. Silica fume and metakaolin are known to decrease workability; fly ash and slag addition improve it. The effect of SCM combinations on workability is typically assumed to be additive. However, this investigation revealed that combining SCMs does not have an additive effect on workability, measured in terms of apparent yield stress and plastic viscosity; consequently, these parameters cannot be estimated from their respective values. Cement replacement with SCMs affects not only workability, but also heat of hydration, and is commonly used to reduce concrete temperature rise in concrete. Prediction and control of concrete temperature rise due to cement hydration is of great significance for mass concrete structures since large temperature gradients between the surface and the core of the structure can lead to cracking thus reducing durability of the structure. A number of equations have been proposed to predict the heat of hydration of cement and cement/SCM blends. However, these equations do not include metakaolin, which is a relatively new mineral admixture. Based on statistical experimental design, an equation was developed to predict the reduction of total hydration heat at 24, 48 and 72 hours with addition of SCMs compared to a plain ordinary portland cement (OPC)-water mixture. The developed equation allows the evaluation of the contribution of Class F fly ash (FA), blast furnace slag (BFS), silica fume (SF) and metakaolin (MK) as well as their combinations. Since metakaolin has been on the market for only about 10 years, the current knowledge on its effect on hydration products and paste microstructure remains incomplete. The effect of MK on the nature of hydration products was evaluated through x-ray diffraction. Its effect on the microstructure was assessed by measuring porosity with nitrogen adsorption and determining nanoindentation modulus as well as the volume fraction of calcium silicate hydrates (C-S-H) with variable packing densities. No significant effect was observed on the nature of hydration products with MK or BFS addition. However, nitrogen-accessible porosity increased with MK and BFS addition, the increase being larger with BFS. The average indentation modulus for the hydration products decreased with addition of MK and BFS, which corresponded to increasing nitrogen accessible pores. The results of this study indicate that phase quantification by quantitative x-ray diffraction (QXRD) of the hydrated paste may not be sufficient to assess the impact of metakaolin or BFS addition on the hydrating cementitious systems, and a multi-technique approach that provides information not only on the amount of hydration products, but also their morphology is preferable.