In collaboration with the United States Environmental Protection Agency (USEPA), the University of South Florida Health Risk Methodology Group has developed dose-time-response models to characterize neurobehavioral response to chemical exposure. The application of dose-time-response models to neurobehavioral screening tests on laboratory animals allows for benchmark dose estimation to establish exposure limits in environmental risk assessment. This thesis has advanced dose-time-response modeling by generalizing a published toxico diffusion model to allow for dose dependent time of peak effects. To accomplish this, a biphasic model was developed which adopted the effect compartment model paradigm used in pharmacokinetics/pharmacodynamics to estimate a distributional rate constant to account for dose related variation in the time of peak effect. The biphasic model was able to describe dose-dependent time of peak effects as observed in the data on acute exposure to parathion and adequately predicted the observed response. However, the experimental design appeared insufficient in statistical power to confirm statistical significance for each parameter of interest. Motivated by the question of what design requirement might be necessary to validate the biphasic model, Monte Carlo simulation was adopted. Simulations were performed to assess the efficacy and efficiency of various experimental designs for detecting and evaluating some critical characteristics of the biphasic model, including the TOPE. The results of simulation suggest that the location of measurement times around the TOPE have important implications for assessing the statistical significance of the parameter that describes dose-dependent TOPE and that the mean squared error of the parameter estimator was improved most when testing times were chosen to bracket the TOPE. While dose dependent time of peak effects has underlying physiological mechanisms such as synergistic or capacity limited kinetics, the biphasic model estimates these physiological properties through a mathematical function which may be physiologically relevant but does not necessarily define physiological mechanisms underlying the response. However, if verified through further testing, the biphasic model may contribute to the USEPA’s aim of developing physiologically relevant dose-response models for assessing risk of neurotoxicity with repeated measurements of response.

Um dos grandes desafios para o tratamento de defeitos ósseos extensos na região bucomaxilofacial têm sido o desenvolvimento de um biomaterial substituto ósseo ao enxerto autógeno. No presente trabalho avaliou-se a formação óssea e a biodegrabilidade do osso desproteinizado bovino Bio-Oss® e do seu similar GenOx Inorg® e da cerâmica bifásica GenPhos® XP no processo de reparo de defeitos ósseos cranianos em coelhos, comparativamente ao osso autógeno (controle positivo) e coágulo sanguíneo (controle negativo). Foram realizados cirurgicamente defeitos bilaterais de 8-mm de diâmetro nos ossos parietais de 39 coelhos. A seguir os defeitos foram preenchidos aleatoriamente com 0,1cm3 de material ou coágulo conforme cada grupo de tratamento. Após os períodos de 4, 8 e 24 semanas os crânios foram coletados, analisados no microtomógrafo e processados histologicamente. O percentual de volume do defeito ocupado pelo material e osso neoformado foi avaliado pela microtomografia e histomorfometria, enquanto que, para a medula óssea, tegumento e tecido conjuntivo, apenas pela análise histomorfométrica. Os resultados quantitativos obtidos foram comparados estatisticamente pela ANOVA a dois critérios (período e tratamento) e teste de Tukey com p<0,05. A intensidade da associação linear dos dados microtomográficos e histomorfométricos avaliada pelo coeficiente de correlação de Pearson, mostraram correlação moderada a forte. Nos períodos iniciais de reparo (30 e 60 dias), os defeitos tratados com Bio-Oss®, GenOx® Inorg e GenPhos® XP apresentaram manutenção do volume do material enxertado (Vvi médio de 34% ) e formação óssea menor e mais imatura em relação grupo autógeno (Vvi = 22% vs. 32% no grupo autógeno). No período mais tardio (180 dias) a quantidade de formação óssea foi estatisticamente similar nos grupos Bio-Oss® (Vvi = 27%), GenOx® Inorg (Vvi = 26%) e GenPhos® XP (Vvi = 20%) porém, o GenOx® Inorg promoveu a formação de um tecido ósseo mais organizado e com maior acúmulo de biomaterial+osso+medula óssea (Vvi = 67,9%) comparado ao GenPhos® XP (Vvi =58,9%) e Bio Oss (Vvi = 55,6%) mas, inferior ao do enxerto autógeno (Vvi = 78%). Os resultados aqui obtidos permitem concluir que o osso autógeno promove rápida formação e maturação óssea, porém não consegue promover o reestabelecimento completo da díploe removida cirurgicamente. Os materiais BioOss, GenOx® Inorg e GenPhos® XP são excelentes materiais osteocondutores levando a formação óssea em toda extensão do defeito, sendo o GenOx® Inorg o que apresenta menor grau de reabsorção e maior e melhor preenchimento do defeito. / One major challenge for treatment of critical size defects in maxillofacial region has been the development of a substitute biomaterial to the autogenous bone grafts. In present study we evaluated the bone formation and biodegradability of deproteinized bovine bone Bio-Oss® and GenOx® Inorg, and biphasic calcium phosphate GenPhos XP® during bone repair process in rabbits cranial defects compared to autogenous bone (positive control) and blood clot (negative control). In parietal bone of 39 rabbits were made bilateral 8-mm diameter defects, which were filled randomly with 0,1cm3 material or clot as each treatment group. After periods of 4, 8 and 24 weeks skulls of animals were collected, analyzed the MicroCT scanner and histologically processed. The percentage of defect volume occupied by biomaterial and new-formed bone were assessed by histomorphometry and microtomography, while the bone marrow, connective tissue and tegument only by first analysis. The quantitative data were compared by two-way ANOVA analysis (time and treatment) and Tukey\'s test at p <0.05. The intensity of the linear association of MicroCT and morphometric data evaluated by the Pearson correlation coefficient, showed moderate to strong correlation. In the early repair periods (30 and 60 days), the defects treated with Bio- Oss, GenOx® Inorg and GenPhos® XP showed maintenance of the graft material volume (average Vvi of 34%) and lower and more immature bone compared autograft group (Vvi = 22% vs. 32% in the autograft group). In the later period (180 days) the amount of bone formation was statistically similar to the groups Bio-Oss® (Vvi = 27 %), GenOx® Inorg (Vvi = 26%) and GenPhos® XP (Vvi = 20%) however, the bone formation in GenOx® Inorg was more organized and with greater accumulation of particles + bone tissue + bone marrow (Vvi = 67.9%), when compared to GenPhos® XP (Vvi = 58.9%) and Bio-Oss® (Vvi = 55.6%) but lower than the autograft (Vvi = 78%). It was concluded that the autogenous bone promotes rapid bone formation and maturation, but cannot promote the complete reestablishment of diploe surgically removed. The Bio-Oss®, GenOx® Inorg and GenPhos® XP are excellent osteoconductive materials leading to bone formation in the full extent of the defects, and the GenOx® Inorg showing less absorption promotes more and better defect filling.

No description available.

This thesis is concerned with the deposition of nanoparticle films onto boron-doped diamond and tin-doped indium oxide (lTO) surfaces and the characterisation of the films using electron microscopy, powder diffraction methods and quartz crystal microbalance (QCM) data. The redox behaviour of the porous films was examined using cyclic voltammetry in various media to investigate potential electroanalytical applications. TiOz (anatase) mono-layer films were immobilised onto an inert boron-doped diamond substrate. Cyclic voltammetry experiments allowed two distinct steps in the reduction - protonation processes to be identified that are consistent with the formation of Ti(III) surface sites accompanied by the adsorption of protons. Preliminary data for electron transfer processes at the reduced TiOz surface such as the dihydrogen evolution process and the 2 electron - 2 proton reduction of maleic acid to succinic acid are discussed. Novel multi-layer TiOz films were deposited with a variety of organic binder molecules onto ITO substrates. The redox reactivity of Cuz+ with 1,4,7,10- tetraazacyclododecane- 1,4,7, IO-tetrayl- tetrakis (methyl-phosphonic acid) in solution and immobilised on an electrode surface are investigated. The influences of film thickness, scan rate, and pH on the electrochemistry of immobilised pyrroloquinoline quinone was investigated with two possible electron transport processes observed. The thickness of TiOz phytate films was found to change the shape of the resulting cyclic voltammograms dramatically. Computer simulation and impedance spectroscopy allowed insights into the diffusion of electrons to be obtained. 1, 1 ~Ferrocenedimethanol was employed as an adsorbing redox system to study the voltammetric characteristics of carboxymethyl-y-cyclodextrin films and evidence for two distinct binding sites is considered. The apparent transport coefficients for dopamine and Ru(NHJ)6J+ are estimated for TiOz Nafion® films. The electrochemical processes in biphasic electrode systems for the oxidation of water-insoluble N,N-didodecyl-N;N~diethyl-benzene-diamine (DDPD) pure and dissolved in di-(2-ethyl-hexyl)phosphate (HDOP) immersed in aqueous electrolyte media are described. Transfer of the anion from the aqueous electrolyte phase into the organic phase accompanies the oxidation of pure DDPD. In the presence of HOOP, oxidation is accompanied by proton exchange. The electrochemically driven proton exchange process occurs over a wide pH range. Organic microdroplet deposits of OOPD in HDOP at basal plane pyrolytic graphite electrodes are studied using voltammetric techniques and compared to the behaviour of organic microphase deposits in mesoporous Ti02 thin films. Two types of Ti02 thin film electrodes were investigated, (i) a 300-400 nm film on ITa and (ii) a 300-400 nm film on ITa sputter-coated with a 20 nm porous gold layer. The latter biphasic design is superior. Titanium carbide (TiC) nanoparticies were deposited onto ITa electrodes. Partial anodic oxidation and formation of novel core-shell TiC-Ti02 nanoparticies was observed at applied potentials positive of 0.3 V vs. SCE. Significant thermal oxidation of TiC nanoparticies by heating in air occurs at 250 °c leading to coreshell TiC-Ti02 nanoparticies, then Ti02 (anatase) at ca. 350 °c, and Ti02 (rutile) at temperatures higher than 750 °c. The electrocatalytic properties of the core-shell TiC-Ti02 nanoparticulate films were surveyed for the oxidation of hydroquinone, ascorbic acid, dopamine and nitric oxide (NO) in aqueous buffer media. Mono- and multi-layer Ce02 deposits on ITa are shown to be electrochemically active. A reduction assigned to a Ce(IV/III) process has been observed and followup chemistry in the presence of phosphate discovered. The interfacial formation of CeP04 has been proven and effects of the deposit type, pH and phosphate concentration on the process analysed. The electrochemistry of multi-layer Ce02 nanoparticulate films in organic solvent is shown to be more stable.

Ce travail développe une nouvelle approche de la catalyse biphasique aqueuse qui repose sur la construction de micelles réticulées à partir de polymères de type cœur-coquille. Le catalyseur (Rh) doit être incorporé sur les ligands du polymère dans la couche interne lipophile et la coquille hydrophile externe permettra de le séparer aisément du milieu réactionnel organique (oct-1-ène, nonanal, pour la réaction modèle d'hydroformylation choisie). La première partie du projet a donc consisté à préparer ces polymères à couche périphérique hydrophile assurant leur confinement en phase aqueuse et une partie interne lipophile contenant les sites actifs pour la réaction. Deux stratégies ont été explorées avec succès pour aboutir à ces structures en s'appuyant sur la polymérisation radicalaire par transfert d'atome. La première, dite « convergente », met en jeu la réticulation des copolymères linéaires fonctionnalisés préformés en présence de monomères divinyliques. La préparation des macroamorceurs linéaires fonctionnalisés a permis d'effectuer en parallèle une optimisation des conditions d'introduction d'un monomère fonctionnalisé par une phosphine qui servira par la suite de ligand pour le métal. Cette voie d'assemblage s'est avérée inefficace car un résidu des chaines linéaires non-incorporées accompagnait les produit de réticulation. Sa contrepartie, l'approche dite « divergente », a été abordée à partir de l'extension de chaines provenant d'un cœur réticulé. Les structures cœur-coquille fonctionnalisées ainsi obtenues ont des distributions de taille très homogènes. Dans le but d'évaluer leur potentiel catalytique, les copolymères fonctionnalisés, linéaires et réticulés, ont été utilisés comme ligands pour l'hydroformylation de l'oct-1-ène catalysée par le rhodium en phase homogène. Le confinement du complexe au sein des polymères a entraîné une amélioration de la régiosélectivité ainsi qu'une diminution de l'activité avec les deux types de polymères utilisés par rapport au ligand PPh3. Grace au caractère vivant de la polymérisation qui permet l'association des étapes synthétiques en séquence, il a été possible d'introduire des blocs de type PtB(M)A comme précurseurs pour l'obtention d'un bloc externe hydrophile de type P(M)AA. Les résultats préliminaires d'hydrosolubilisation des nanoréacteurs sont aussi présentés. / The current project is focused on the development of a new tool for the rhodium-catalyzed aqueous biphasic hydroformylation based on the construction of crosslinked micelles from core-shell polymers. The first goal of the project was the preparation of polymers having an hydrophilic shell that insures solubility and total confinement in the aqueous phase and a lipophilic inner shell acting as a support of active catalytic sites. Two strategies were explored to achieve such structures based on atom transfer radical polymerization. The first one, known as “arm-first”, involved the crosslinking of preformed functionalized linear copolymers in the presence of divinyl monomers. The preparation of functionalized linear macroinitiators allowed at the same time the optimization of the conditions for the introduction of a functionalized phosphine monomer that will ultimately serve as a ligand for the metal. This assembly pathway was ineffective because some residual dead chains accompanied the crosslinking product of the reaction. Its counterpart, the approach called "core-first", is based on the extension of chains from a crosslinked core. From this second approach, functionalized core-shell structures with very uniform size distributions were obtained. Both linear and cross-linked copolymers were used as ligands for the rhodium catalyzed hydroformylation of 1-octene under homogeneous conditions in order to test their catalytic performance. Because of the confinement of the ligand inside the polymer coils, a selectivity improvement as well as the slowdown of the reaction rate was observed relative to PPh3 ligand. The living character of the synthesis technique allowed the introduction of external PtB(M)A blocks: precursors to obtain a hydrophilic outer shell P(M)AA. Preliminary hydrosolubilization results of the nanoreactors will be presented in the last part of the manuscript.

O amido de milho é uma importante fonte de energia para os seres humanos, além de ser um polímero natural utilizado nas indústrias químicas, farmacêuticas e de alimentos. O amido possui grande capacidade de retenção de água e gelatinizam na presença de água e em elevadas temperaturas. Nestas condições, suas propriedades reológicas e mecânicas se modificam e fazem com que seja interessante o uso na fabricação de diversos materiais. Os processos de aglomeração e recobrimento de partículas, em combinação com outros métodos, podem proporcionar o aprimoramento de ingredientes alimentícios em pó, por meio da alteração do tamanho e forma das partículas. Além disso, o processo de aglomeração também permite alterar o índice de compactação, incorporar aditivos às partículas e aplicar películas de revestimento. Assim, este trabalho teve como objetivo realizar o estudo do tamanho e forma de partículas de amido de milho aglomeradas com alginato de sódio, produzidas por meio de formação de gotas a partir de suspensão de amido-alginato de sódio, e posterior gelificação iônica em cloreto de cálcio. Os processos de aglomeração e recobrimento foram estudados por meio dos métodos de gotejamento e método de dispersão em óleo. O método de gotejamento, ou dripping, consistiu no gotejamento da suspensão de amido-alginato em solução de cloreto de cálcio. O método de agitação em líquidos imiscíveis consistiu na gelificação iônica da suspensão sob agitação continua, em que o óleo de soja é a fase contínua e a suspensão de amido-alginato é a fase dispersa. Após a secagem em estufa a 60 °C, as partículas foram caracterizadas pelas análises de tamanho e forma. As alterações na microestrutura dos grânulos e investigação da resistência foram observadas por ensaios de calorimetria diferencial de varredura. As partículas também foram caracterizadas por análises de imagem de tamanho e forma. Os grânulos de amido foram produzidos utilizando-se a partir de suspensões de amido-alginato, e resultaram em frações de amido iguais a (50, 60, 70, 80 e 90)%. O aumento da concentração de amido de milho na suspensão de alginato resultou no aumento da viscosidade e também grânulos secos com maior tamanho. Para o método de dispersão em óleo, o aumento da frequência de agitação de 4 Hz para 11 Hz produziu menores tamanho de gota e, consequentemente, em grânulos secos com menores tamanhos. A aplicação destas técnicas de aglomeração por formação de gotas pode ser uma ferramenta útil para a produção de microcápsulas ou agregação de sistemas particulados contento dois ou mais ingredientes com distribuições de tamanho distintas. / Cornstarch is an important source of energy for humans, as well as being a natural polymer seen in the chemical, pharmaceutical and food industries. Starch has a high retention capacity of water and gelatin in the presence of water and in heat. Under these conditions, its rheological and mechanical properties change and make it interesting to use as a material medium. Agglomeration and particle coating processes, in combination with other methods, can provide the enhancement of powdered food ingredients by altering the size and shape of the particles; agglomeration process can also replace, adopt applications and apply coating films. The aim of this work is to study the size and shape of particles of agglomerated particles with sodium alginate produced by the formation of droplets from the suspension of sodium starch alginate and subsequent ionic gelation in calcium chloride. The agglomeration and recoating processes were studied by means of the drip methods and oil dispersion method. The dripping method consisted of the drip of the starch-alginate suspension in to calcium chloride solution. The method of stirring in immiscible liquids consisted of ionic gelation of the suspension under continuous stirring, wherein the soybean oil is the continuous phase and the starch-alginate suspension is the dispersed phase. After oven drying at 60 ° C, the particles were characterized by size and shape analyzes. Changes in microstructure and resistance of the beads investigation were observed by differential scanning calorimetry assays. Particles were also characterized by size and shape image analyzes. The starch granules were produced using starch-alginate suspensions, and resulted in starch fractions equal to (50, 60, 70, 80 and 90%). Increasing the concentration of corn starch in the alginate suspension resulted in increased viscosity and also larger dried granules. For the oil dispersion method, increasing the stirring frequency from 4 Hz to 11 Hz produced smaller droplet size and consequently smaller dried granules. The application of these agglomeration techniques by droplet formation can be a useful tool for the production of microcapsules or aggregation of particulate systems containing two or more ingredients of different size distribution.

Developmental modularity may facilitate morphological evolution by allowing phenotypic change of a developing body component without negatively impacting other components. I examined foregut development in Amphissa columbiana, a predatory neogastropod with a highly derived foregut and in Crepidula fornicata, a phytoplankton-feeder with a less derived foregut, for evidence of developmental modules. Histological sections revealed that the post-metamorphic buccal cavity and radula of both species form as a ventral outpocketing (ventral module) from the larval esophagus (dorsal module). However, in Amphissa columbiana the ventral outpocketing is semi-isolated from the larval esophagus and also produces an “anterior esophagus” that is not developmentally homologous to the “anterior esophagus” of herbivorous caenogastropods. Semi-isolation of the ventral and dorsal modules of the developing neogastropod foregut allows precocious development of the post-metamorphic foregut during the larval stage without compromising larval feeding. Therefore, development of diverse variants of the post-metamorphic foregut are freed from larval constraints. / Graduate / 2020-08-03

[pt] As dispersões bifásicas (ex. espumas e emulsões), de grande relevância prática na química e na engenharia, são termodinamicamente instáveis devido à diminuição de energia livre no processo de coalescência. Esta limitação é comumente minimizada através de mecanismos de estabilização eletrostática e estérica. Recentemente, há um interesse crescente na estabilização de emulsões e espumas usando partículas sólidas (tipo Pickering), devido à forte adsorção das mesmas nas interfaces para formar uma película sólida. Dependendo do tamanho e do ângulo de contato, a adsorção das partículas pode tornar-se irreversível, melhorando a estabilidade em comparação com sistemas estabilizados por surfactante. Como nanopartículas de molhabilidade intermédia são relativamente raras, o ajuste deste parâmetro é o principal desafio para obter dispersões estáveis. No presente estudo, nanopartículas de sílica (SiNPs) foram modificadas superficialmente com 3-aminopropil trimetoxisilano e hexadeciltrimetoxisilano como agentes sililantes, para se obter três tipos diferentes de nanopartículas híbridas de maior hidrofobicidade, visando a formulação de dispersões bifásicas altamente estáveis usando um método de baixa energia (agitação manual). As SiNPs modificadas foram caracterizadas através de testes qualitativos, infravermelho, analise termogravimétrica, analise elementar e ressonância magnética nuclear de carbono treze e de silício vinte nove no estado sólido para confirmar o enxerto dos grupos funcionais. As propriedades das NPs em relação à sua dispersabilidade e comportamento em interfaces foram avaliadas por espalhamento de luz dinâmica e a tensão superficial crítica de molhabilidade. Finalmente, foram preparadas espumas líquidas e emulsões água-em-óleo (A/O) utilizando as partículas híbridas obtidas e pequenas quantidades de surfactantes, para facilitar o processo de dispersão. Os resultados mostraram que as NPs mais hidrofílicas estabilizam melhor a interface ar/água (espumas), enquanto a estabilização máxima em emulsões é obtida com as NPs mais hidrofóbicas, uma vez que a interação com a fase contínua é otimizada. Além disso, a presença de grupos funcionais na superfície das SiNPs oferece a possibilidade de obter efeitos de sinergia com os surfactantes, controlando a adsorção mista na interface. As aplicações potenciais destes resultados podem abranger diversas áreas, tais como biomedicina, ciência dos materiais, recuperação de petróleo, cosméticos e alimentos. / [en] Biphasic dispersions (e.g. foams and emulsions) are of practical relevance to many chemical and engineering fields. These dispersions are thermodynamically unstable, since their decay results in a decrease of the free energy. Different mechanisms can prevent the coalescence of the dispersion, such as electrostatic and steric stabilization. Recently, there has been an increased interest in the study of stabilization of emulsions and foams using solid particles (Pickering type), since particles can strongly adsorb at interfaces to form a solid film, replacing the incompatible water-oil(ar) interface by the more favorable oil(ar)-particle and particlewater interfaces. Depending on their size and contact angle of selective wetting, particle adsorption can become irreversible, with increased stability of particle-stabilized dispersions compared to surfactant-stabilized systems. Since particles of intermediate wettability by nature are relatively rare, tailoring particle wettability is the major challenge to obtain stable dispersions. In the present study, hybrid silica nanoparticles (SiNPs) were prepared by modification of their surface using 3 aminopropyltrimethoxysilane and hexadecyltrimethoxysilane as silanizing agents, to obtain three different nanoparticles with increased hydrophobicity, aiming to achieve highly stable biphasic dispersions using a low-energy method. The modified SiNPs were characterized using qualitative tests, FTIR, TGA, CHN and NMR (Si) to confirm grafting of functional groups. In addition, nanoparticle properties regarding aqueous dispersions and behavior at interfaces were evaluated by DLS and critical wetting surface tension. Liquid foams and water-in-oil (W/O) emulsions were prepared using the obtained hybrid particles and small amounts of different surfactants, to facilitate the dispersion process. The results showed that while more hydrophilic NPs stabilize better the air/water interface (foams), maximum stabilization in W/O emulsions is achieved with the most hydrophobic NPs, since interaction with continuous phase is optimized. In addition, the presence of different functional groups at the surface of the SiNPs offers the possibility for increased synergy with surfactants, controlling the mixed adsorption at the interface. The potential applications of these results can cover diverse fields such as biomedicine, materials science, oil recovery, cosmetics and food.

The social mole-rats have often been typecast as extreme examples of mammalian sociality. With their pronounced reproductive skew, status-related contrasts in lifespan and morphology, and the suggestion of a division of labour amongst helpers, mole-rat societies have repeatedly been likened to the structurally complex societies of some eusocial insects. However, because few studies of mole-rats have quantified individual variation in growth and behaviour across long periods of development, it has remained unclear the extent to which mole-rat societies, and the features of individuals within them, should be considered unique amongst social vertebrates. In this thesis, I examine life history variation in Damaraland mole-rats Fukomys damarensis from three perspectives- growth, behaviour, and ageing- to explore how individual developmental trajectories contribute to, and are influenced by, the structure of mole-rat societies. First, I use a large longitudinal dataset to test for the presence of behavioural specialisation in non-breeding mole-rat helpers. I find no indication of individual specialisation in cooperative activities. Instead, individual differences in helping behaviour are largely the result of age-related changes in the extent to which individuals commit to all forms of helping (Chapter 3); refuting the notion of helper castes. I then focus on the variation in growth across non-breeders, developing a novel biphasic model to accurately quantify sex differences in growth and explore the influence of social effects on growth trajectories (Chapter 4). Despite the proposition of intense intrasexual competition in mole-rat societies, there was no clear signature of sex-specific competition on helper growth trajectories. A more conspicuous form of socially-mediated growth in mole-rats is the secondary growth spurt displayed by females that have acquired the dominant breeding position, causing them to become larger and more elongated. By experimentally controlling reproduction in age-matched siblings, I show that rather than being stimulated by the removal from reproductive suppression, this adaptive morphological divergence is achieved through a lengthening of the lumbar vertebrae when breeding is commenced (Chapter 5). With contrasts in size and shape following the acquisition of the breeding role, this status-related growth pattern shares similarities with growth in naked mole-rats and other social vertebrates. Breeders also show a twofold greater lifespan than non-breeders in Fukomys mole-rats, prompting the suggestion that the transition to dominance also sets individuals onto a slower ageing trajectory. To date, there is little evidence to support a physiological basis to lifespan extension in breeders. This assertion is bolstered by the absence of longer telomeres or slower rates of telomere attrition in breeding females compared to non-breeding females residing in groups (Chapter 6), each of which might be expected if breeders age more slowly. I argue that previous studies exploring status-related ageing in captive Fukomys mole-rats have overlooked the importance of demographic processes (and associated behavioural influences) on mortality schedules. Irrespective of the proximate basis of the longer lifespan of breeders, at an interspecific level the social mole-rats are unusually long-lived for their size. A recent large-scale comparative analysis concluded that prolonged lifespan is a general characteristic of all mammalian cooperative breeders, but this conclusion is premature, as in most of the major clades containing both cooperative and non-cooperative species there is no consistent trend towards lifespan extension in cooperative species (Chapter 7). In the case of mole-rats, it seems more likely that their exceptional longevity arises principally from their subterranean habits and related reductions in extrinsic mortality. Overall, these findings demonstrate that cooperative breeding has important consequences for individual life histories, but there is no strong basis for the claim that Damaraland mole-rat societies are markedly different in form than other cooperative breeding societies.

Biocatalysis involves the use of enzymes to perform stereo- and enantio-specific reactions. One of the reactions where biocatalysis is a valuable technology is oxidation of naphthalene to 1-naphthol using Toluene ortho-Monooxygenase (TOM) variant TmoA3 V106A, also known as TOM-Green. Whole-cell biocatalysis in a water-organic solvent biphasic system was used to minimize naphthalene and 1-naphthol toxicity, and to increase substrate loading. Recombinant Escherichia coli TG1 cells expressing TOM-Green were used for biphasic biocatalysis and lauryl acetate gave best results among the solvents tested. On a constant volume basis, 8 - fold improvement in 1-naphthol production was achieved using biphasic systems compared to biotransformation in aqueous medium. The organic phase was optimized by studying the effects of organic phase ratio and naphthalene concentration in the organic phase. The efficiency of biocatalysis was further improved by application of a solvent tolerant strain Pseudomonas putida S12. P. putida S12 is solvent tolerant owing to its two adaptive mechanisms: outer membrane modification and solvent extrusion using solvent resistant pump srpABC. P. putida S12, in addition to its tolerance to various organic solvents, showed better tolerance to naphthalene compared to E. coli TG1 strain expressing TOM-Green. Application of solvent tolerant P. putida S12 further improved 1-naphthol productivity by approximately 42%. Solvent tolerance of P. putida S12 was further analyzed by transferring its tolerance to a solvent sensitive E. coli strain by transfer of solvent resistant pump srpABC genes. Engineered E. coli strain bearing srpABC genes either in low-copy number plasmid or high-copy number plasmid grew in the presence of a saturated toluene concentration. Engineered E. coli strains were also more tolerant to toxic solvents, e. g., decanol and hexane, compared to the control E. coli strain without srpABC genes. The expression of solvent resistant pump genes was confirmed by Reverse Transcriptase PCR analysis. The main drawbacks of biocatalysis for production of chemicals were addressed and approaches to minimize the drawbacks have been presented. The production of 1-naphthol was significantly improved using biocatalysis in liquid-liquid biphasic systems.