CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Existe um consenso de que a instabilidade da interface de uniÃo resina-dentina està relacionada com a quantidade de monÃmeros hidrofÃlicos presentes no sistema adesivo. Dessa forma, interfaces adesivas mais duradouras seriam alcanÃadas com a utilizaÃÃo de sistemas adesivos mais hidrofÃbicos. Uma maneira de unir monÃmeros hidrÃfobos à dentina à atravÃs da saturaÃÃo da matriz dentinÃria desmineralizada por etanol ao invÃs de Ãgua (ethanol-wet bonding technique). O objetivo deste trabalho in vitro foi avaliar o efeito do protocolo de saturaÃÃo dentinÃria, utilizando alcoÃis, na estabilidade da interface de uniÃo produzida por sistemas adesivos convencionais de dois passos. Para isso, foram utilizados 20 terceiros molares humanos, que tiveram a dentina coronÃria exposta e foram distribuÃdos aleatoriamente em quatro grupos experimentais (n=5): Adper Single Bond 2 (SB) aplicado sobre dentina saturada com Ãgua ou etanol; e XP Bond (XP) aplicado sobre dentina saturada com Ãgua ou tert-butanol. O protocolo de saturaÃÃo da dentina foi realizado atravÃs da aplicaÃÃo de 2 &#956;l de etanol 100% ou tert-butanol 99,5% diretamente sobre a dentina por um perÃodo de 60 s. Um platà de resina composta foi confeccionado sobre superfÃcie dentinÃria apÃs a aplicaÃÃo do sistema adesivo e os espÃcimes foram cortados pela tÃcnica non-trimming de obtenÃÃo de palitos para o teste de microtraÃÃo. Os palitos de cada dente foram igualmente divididos em dois subgrupos: imediatamente testado ou envelhecido em soluÃÃo de NaOCl a 10% por 1 hora. Os espÃcimes foram tracionados atà a ruptura da uniÃo a uma velocidade de 1 mm/min e sua forÃa de uniÃo mensurada. Os palitos fraturados foram analisados e classificados de acordo com o modo de fratura em mista, adesiva, coesiva em dentina e coesiva em compÃsito, e os valores expressos em porcentagem. Os valores de resistÃncia de uniÃo foram estatisticamente analisados usando os testes ANOVA a trÃs critÃrios e Tukey (&#945;=0.05). Discos extras de dentina foram submetidos aos procedimentos adesivos de cada grupo testado e utilizados para investigar as caracterÃsticas morfolÃgicas da interface de uniÃo atravÃs de microscopia Ãptica apÃs imersÃo em soluÃÃo amonical de nitrato de prata. Os resultados do teste de microtraÃÃo mostraram que a imersÃo em soluÃÃo de NaOCl reduziu significativamente a forÃa de uniÃo em comparaÃÃo aos grupos controle (p<0.05) e aumentou a nanoinfiltraÃÃo das interfaces adesivas de todos os sistemas adesivos testados. A saturaÃÃo da dentina com etanol 100% reduziu os valores de resistÃncia adesiva para SB quando comparado ao grupo controle, e esta mesma tendÃncia foi observada na infiltraÃÃo de prata. O uso do tert-butanol 99,5% nÃo afetou os valores de resistÃncia adesiva para o XP, assim como a deposiÃÃo de nitrato de prata na interface adesiva. ConclusÃo: Os protocolos simplificados de saturaÃÃo da dentina com alcoÃis utilizados no presente estudo nÃo foram capazes de melhorar a estabilidade da interface de uniÃo para sistemas adesivos convencionais de dois passos. / There is a consensus that the resin-dentin bond instability is correlated with increased hydrophilic resin monomer content in dentin adhesive. Thus, more durable bonds could be created when more hydrophobic resins were used. One way to bond hydrophobic monomers to acid-etched dentin is saturating the demineralized dentin with ethanol instead of water (ethanol-wet bonding technique). The objective of this in vitro study was to evaluate the effect of âalcohol wet bondingâ technique on the stability of adhesive interface produced by two-step etch-and-rinse adhesives systems. For this, it was used 20 human third molars that had superficial dentin exposed and were randomly divided into four experimental groups (n=5): Adper Single Bond 2 (SB) bonded to acid-etched dentin saturated with water or ethanol; and XP Bond (XP) bonded acid-etched dentin saturated with water or 99.5% tert-butanol. The simplified dentin dehydration protocol was performed using 2 &#956;l 100% ethanol or 99.5% tert-butanol directly applied in dentin for 60 s. Composite build-ups were built on dentin surface and specimens were cut into non-trimming dentin-composite beams to microtensile testing. Beams from each tooth were divided equally in two subgroups: immediately tested and aged by immersion in 10% NaOCl solution for 1 h. Specimens were pulled until failure at crosshead speed of 1 mm/min and bond strength was calculated. Fractured sticks were analyzed and classified according to the failure mode as mixed, adhesive, cohesive in dentin and cohesive in composite; and expressed in percentage. Data from &#956;TBS test were statistically analyzed using three-way ANOVA and Tukey tests (&#945;=0.05). Additional dentin disks were bonded using the same groups tested and the morphological characteristics of adhesive interface were investigated by light microscopy after immersion in ammoniacal silver nitrate solution. &#956;TBS results showed that NaOCl solution reduced significantly bond strength comparing with the control groups (p<0.05) and increased the silver nitrate interfacial deposit for all adhesives tested. SB used in ethanol saturated-dentin showed significant lower bond strength values in comparison with SB control group, and this same tendency was observed in the silver nitrate deposition. The use of tert-butanol did not influence XP bond strengths values and silver nitrate deposits. Conclusion: The âalcohol wet bondingâ simplified technique used in the present study was not able to improve resin-dentin bond stability for simplified etch-and-rinse adhesive systems.

This thesis explored whether youth mentoring could be used as a crime prevention strategy for Ontario. It examined risk factors for youth crime and social bonding theory, the effectiveness of selected programs to prevent crime and best practices, and Ontario government reports on effective crime prevention. It also explored youth mentoring in practice with some mentors from Big Brothers Big Sisters of Ottawa and Sudbury Ontario. The analysis of the literature on risk factors for youth crime identified a number of individual, relationship, community, and societal level factors that correlate with the likelihood of a young person engaging in crime. Travis Hirschi’s social bonding theory provided a lens to understand the contribution mentoring can have on preventing crime through attachment, commitment, involvement, and belief with parents and schools. The evidence-based research on the effectiveness of selected programs that had a mentoring component showed that the likelihood of offending could be reduced with other well-being indicators. Research on mentoring relationships showed that when mentors focused on the assets of the youth and were committed to the relationship, they could foster a lasting emotional bond. Best practices of an effective youth mentoring program included outreaching to vulnerable youth, involving parents, screening and training mentors, matching mentors and mentees based on background, having mentoring connected to a larger strategy, following a developmental approach, and developing standards for implementation. The recent reports from the Province of Ontario on crime prevention and community safety use much of the same evidence on risk factors and social development programs to confirm that prevention is an effective way to reduce crime. These reports also point to strong public support for government investment in prevention and education over punishment. The semi-structured interviews with mentoring practitioners in Sudbury and Ottawa, Ontario analyzed the methods used by mentors volunteering with high-risk youth in the Big Brothers Big Sisters community-based program. Results showed the organizational procedure, youth and risk factors, the bonding process between mentors and mentees, and challenges of mentoring at-risk youth were important. Mentors had positive beliefs on the impacts mentoring had on preventing crime and violence. Therefore, youth mentoring is a crime prevention strategy consistent with evidence and government reports and so is viable, but will require political support and investment upstream to make a difference across the province.

Weak intermolecular interactions have very strong impact on the structures and properties of life giving molecules like H2O, DNA, RNA etc. These interactions are responsible for many biological phenomena. The directional preference of some of these interactions is used for designing different synthetic approaches in the supramolecular chemistry. The work reported in this Thesis comprises of investigations of weak intermolecular interactions in gas phase using home-built Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer as an experimental tool and ab-initio and Atoms in Molecules (AIM) theory as theoretical tools. The spectrometer which is coupled with a pulsed nozzle is used to record pure rotational spectra of the molecular clusters in a jet cooled molecular beam. In the molecular beam molecules/complexes are free from interactions with other molecules/complexes and thus, spectroscopy in the molecular beams provides information about the 'isolated' molecule/complex under investigation. The rotational spectra of the molecules/complexes in the molecular beam provide their geometry in the ground vibrational states. These experimental geometries can be used to test the performance and accuracy of theoretical models like ab-initio theory, when applied to the weakly bound complexes. Further the AIM theory can be used to gain insights into the nature and strength of the intermolecular interactions present in the system under investigation. Chapter I of this Thesis gives a brief introduction of intermolecular interactions. Other than hydrogen bonding, which is considered as the most important intermolecular interaction, many other intermolecular interactions involving different atoms have been observed in past few decades. The chapter summarizes all these interactions. The chapter also gives a brief introduction to the experimental and theoretical methods used to probe these interactions. In Chapter II, the experimental and theoretical methods used in this work are summarized. Details of our home-built PN-FTMW spectrometer are given in this chapter. The chapter also discusses briefly the theoretical methods like ab-initio, AIM and Natural bond orbital (NBO) analysis. We have made few changes in the mode of control of one of our delay generators which have also been described. Chapter III and Chapter V of this Thesis are dedicated to the propargyl alcohol complexes. Propargyl alcohol (PA) is a molecule of astrophysical interest. It is also important in combustion chemistry since propargyl radical is considered as the precursor in soot formation. Moreover, PA is a multifunctional molecule, having a hydroxyl (-OH) and an acetylenic (-C≡C-H) group. Both of the groups can individually act as hydrogen bond acceptor as well as donor and thus PA provides an exciting possibility of studying many different types of weak interactions. Due to internal motion of -OH group, PA monomer can exist in gauche as well as trans form. However, rotational spectra of PA-monomer show the presence of only gauche conformer. In Chapter III, rotational spectra of Ar•••PA complex are discussed. The pure rotational spectra of the parent Ar•••PA complex and its two deuterated isotopologues, Ar•••PA-D (OD species) and Ar•••PA-D (CD species), could be observed and fitted within experimental uncertainty. The structural fitting confirmed a structure in which PA is present as gauche conformer and argon interacts with both the O-H group and the acetylenic group leading to Ar•••H-O and Ar•••π interactions respectively. Presence of these interactions was further confirmed by AIM theoretical analysis. In all the three isotopologues c-type rotational transitions showed significant splitting. Splitting patterns in the three isotopologues suggest that it originates mainly due to the large amplitude motion of the hydroxyl group and the motion is weakly coupled with the carbon chain bending motion. No evidence for the complex with trans conformer of PA was found. Although, we could not observe Ar•••trans-PA complex experimentally, we decided to perform ab-initio and AIM theoretical calculations on this complex as well. AIM calculations suggested the presence of Ar•••H-O and a unique Ar•••C interaction in this complex which was later found to be present in the Ar•••methanol complex as well. This prompted us to explore different possible interactions in methanol, other than the well known O-H•••O hydrogen bonding interactions, and eventually led us to an interesting interaction which we termed as carbon bond. Chapter IV discusses carbon bonding interaction in different complexes. Electrostatic potential (ESP) calculations show that tetrahedral face of methane is electron-rich and thus can act as hydrogen/halogen bond acceptor. This has already been observed in many complexes, e.g. CH4•••H2O/HF/HCl/ClF etc., both experimentally and theoretically. However, substitution of one of the hydrogens of methane with -OH leads to complete reversal of the properties of the CH3 tetrahedral face and this face in methanol is electron-deficient. We found that CH3 face in methanol interacts with electron rich sites of HnY molecules and leads to the formation of complexes stabilized by Y•••C-X interactions. This interaction was also found to be present in the complexes of many different CH3X (X=OH/F/Cl/Br/NO2/NF2 etc.) molecules. AIM, NBO and C-X frequency shift analyses suggest that this interaction could be termed as "carbon bond". The carbon bonding interactions could be important in understanding hydrophobic interactions and thus could play an important role in biological phenomena like protein folding. The carbon bonding interaction could also play a significant role in the stabilization of the transition state in SN2 reactions. In Chapter V of this Thesis rotational spectra of propargyl alcohol dimer are discussed. Rotational spectra of the parent dimer and its three deuterated (O-D) isotopologues (two mono-substituted and one bi-substituted) could be recorded and fitted within experimental uncertainty. The fitted rotational constants are close to one of the ab-initio predicted structure. In the dimer also propargyl alcohol exists in the gauche form. Atoms in molecules analysis suggests that the experimentally observed dimer is bound by O-H•••O, O-H•••π and C-H•••π interactions. Chapter VI of the thesis explores the 'electrophore concept'. To observe the rotational spectra of any species and determine its rotational constant by microwave spectroscopy, the species should have a permanent dipole moment. Can we obtain rotational constants of a species having no dipole moment via microwave spectroscopy? Electrophore concept can be used for this purpose. An electrophore is an atom or molecule which could combine with another molecule having no dipole moment thereby forming a complex with a dipole moment, e.g. Argon atom is an electrophore in Ar•••C6H6 complex. The microwave spectra of Ar•••13CC5H6 and Ar•••C6H5D complexes were recorded and fitted. The A rotational constant of these complexes was found to be equal to the C rotational constant of 13CC5H6 and C6H5D molecules respectively and thus we could determine the C rotational constant of microwave 'inactive' 13CC5H6. This concept could be used to obtain the rotational spectra of parallel displaced benzene-dimer if it exists. We recently showed that the square pyramidal Fe(CO)5 can act as hydrogen bond acceptor. Appendix I summarizes the extension of this work and discusses interactions of trigonal bipyramidal Fe(CO)5 with HF, HCl, HBr and ClF. Our initial attempts on generating a chirped pulse to be used in a new broadband spectrometer are summarized in Appendix II. Preliminary investigations on the propargyl•••water complex are summarized in Appendix III.

Kyoto University (京都大学) / 0048 / 新制・論文博士 / 博士(工学) / 乙第12493号 / 論工博第4047号 / 新制||工||1503(附属図書館) / 28243 / (主査)教授 平尾 一之, 教授 横尾 俊信, 教授 田中 勝久 / 学位規則第4条第2項該当

This thesis describes the synthesis of interlocked anion host systems which exploit hydrogen bonding, halogen bonding, and lanthanide-coordination for anion recognition and sensing in aqueous solution. Chapter 1 introduces the field of anion supramolecular chemistry, with particular focus on areas of particular relevance to this thesis, namely anion recognition and sensing, anion templation and the synthesis of interlocked structures. Chapter 2 describes the synthesis of hydrogen bonding rotaxane and catenane hosts for recognising and sensing oxoanions in aqueous solvent media. The novel use of nitrate anion templation for the synthesis of interlocked molecules is reported, and the unprecedented selective recognition of nitrate in aqueous solvent media is demonstrated. Chapter 3 details the preparation of water soluble permethylated β-cyclodextrin-stoppered rotaxane hosts that utilise halogen bonding and hydrogen bonding interactions to bind anions in pure water. The first thermodynamic investigation into halogen bonding in water is reported, and the relative capabilities of halogen and hydrogen bonding for anion recognition in water are compared. Chapter 4 investigates the incorporation of lanthanide cations into rotaxane hosts for optical anion sensing. The seminal use of lanthanide cation templation for interlocked molecule synthesis is described, before anion templation approaches towards the synthesis of lanthanide-based rotaxanes are discussed. The luminescence anion sensing capabilities of these interlocked hosts are investigated. Chapter 5 describes the experimental procedures used in this work, and details the characterisation of compounds presented in Chapters 2–4. Chapter 6 summarises the conclusions of this thesis.

(i) Hydrogen Bonding Studies - The nature of hydrogen bonding in solutions of alcohols, ROH, in various solvents has been studied using nuclear resonance techniques. Data obtained from dilution-shift curves for the OH protons in alcohols have been combined with information derived from infra-red investigations of the OH stretching regions in these compounds. The information obtained has been interpreted in terms of three effects, (i) The electronic effects of the group R. (ii) The steric effects of the group R. (iii) Effects due to other forms of molecular association. On this basis, deductions have been made concerning the degree and type of association in these compounds. The relative hydrogen bonding strengths have been predicted in some instances. The importance of steric inhibition of hydrogen bonding by bulky substituent groups has also been demonstrated. Some dilution-shift studies of acrylic acid in various solvents have been carried out. Studies of the effect of temperature on the OH proton resonances of alcohols have led, amongst other things, to a value for the average hydrogen bond energy in a methanol / carbon tetrachloride solution. The temperature-shift curves for a variety of ortho-substituted phenols have also been obtained and discussed in the light of existing infra-red spectral evidence concerning the nature of hydrogen bonding in these substances. The relation between the association shifts and the integrated absorption intensities of alcohols has been discussed. A correlation between these two quantities was found for alcohols of a similar type. (ii) Studies of Unstable Positive Ions. (a) Triphenyl Carbonium Ions. The NMR spectra of a variety of substituted triphenyl carbonium ions in a trifluoroacetic acid trifluoroacetic anhydride solvent have been obtained at 40 Mc and 60 Mc. No unequivocal evidence as to the structures of these compounds has been obtained, i.e. no distinction between 'symmetrical propeller’ and assymetric forms was possible, due to the presence of exchange effects. The data have given information about the changes in electron density in the aromatic rings due to the various substituent groups. Partial assignments of the aromatic proton spectra have been given. The importance of hyperconjugative electron release by aliphatic substituents is indicated. Some preliminary investigations of the protonated form of 1,1-Di-p-anisylethylene have also been carried out. (b) The l⁺ Ion. The NMR spectra of solutions of iodine in oleum have been investigated to try and shed light on the possibility of the existence of the l⁺ ion in such systems. The measured broadenings and shifts of the oleum proton resonances at various iodine concentrations have been interpreted in terms of the presence of this species, which should be paramagnetic. A value for the magnetic moment of this ion has been obtained. Other evidence for the existence of the l⁺ ion has been fully discussed. / Science, Faculty of / Chemistry, Department of / Graduate

The water molecules in inorganic hydrate salts adopt different geometries and are involved in different hydrogen bond interactions. In this work, magic-angle spinning (MAS) and static 17O solid-state NMR experiments are performed to characterize the 17O electric field gradient (EFG) and chemical shift (CS) tensors of the water molecules in a series of inorganic salt hydrates which include: oxalic acid hydrate, barium chlorate hydrate, sodium perchlorate hydrate, lithium sulphate hydrate, and potassium oxalate hydrate, which were all enriched with 17O water. Data were acquired at magnetic field strengths of 9.4, 11.75, and 21.1 T. Gauge-including projector-augmented-wave density functional theory (GIPAW DFT) calculations are performed on barium chlorate hydrate and oxalic acid hydrate where structural changes including the Ow-H•••O distance, H-O-H angle, and O-H distance are employed to understand their impact on the NMR parameters. Furthermore, simplified molecular models consisting of a metal cation and a water molecule were built to establish the effect the M-Ow distance has on the parameters. The computational studies are then used to understand the experimental results. The 17O quadrupolar coupling constant ranged from 6.75 MHz in K2C2O4•H2O to 7.39 MHz in NaClO4•H2O while the asymmetry parameter ranged from 0.75 in NaClO4•H2O to 1.0 in K2C2O4•H2O and the isotropic chemical shift ranged from -15.0 ppm in NaClO4•H2O to 19.6 ppm in BaClO3•H2O. The computational results revealed the trends for each parameter, where there is an increasing trend for quadrupolar coupling constant and span as a function of increasing hydrogen bond distance, decreasing trend for the three chemical shift tensors as a function of increasing M-Ow distance and unclear trends for asymmetry parameter and skew due to competing electronic factors. Overall, this study provides benchmark 17O NMR data for water molecules in crystalline hydrates, including the first measurement of 17O chemical shift anisotropy for such materials.

Orientador: Sérgio Eduardo de Paiva Gonçalves / Banca: Sérgio Eduardo de Paiva Gonçalves / Banca: Carlos Alberto Adde / Banca: Andréa Anido Anido / Banca: Clovis Pagani / Banca: Ana Paula Martins Gomes / Resumo: O objetivo desta pesquisa foi avaliar em MEV a influência da irradiação com laser Nd:YAG na qualidade da hibridização da dentina bovina, empregando-se sistema adesivo convencional Adper Single Bond - 3M ESPE (SB) ou autocondicionante Clearfil SE Bond - Kuraray (CSEB). Para tanto, foram utilizados 12 incisivos bovinos, extraídos e congelados. Os dentes foram seccionados em duas hemicoroas e incluídos em resina acrílica. Em seguida, a superfície vestibular foi desgastada até a obtenção da dentina de profundidade média. Cada hemi-coroa do mesmo dente, foi submetida em sua porção incisal ao SB e em sua porção cervical ao CSEB, sendo divididas em 3 grupos, de 6 hemi-coroas cada: Controle - após a aplicação dos sistemas adesivos foi realizada a fotopolimerização ; G1 - após a aplicação dos sistemas adesivos a amostra foi irradiada com laser Nd:YAG com 60mJ de energia/pulso previamente à fotopolimerização e G2 - após a aplicação dos sistemas adesivos a amostra foi irradiada com laser Nd:YAG com 140mJ de energia/pulso previamente à fotopolimerização. Todas as amostras receberam a aplicação de dois incrementos de resina composta Filtek Z350 - 3M ESPE e fotopolimerização de acordo com as orientações do fabricante. Após 24h de armazenagem em água destilada a 37ºC, os perfis de adesão foram polidos, submetidos a um desafio ácido-base, e processados para análise em MEV da espessura da camada híbrida, presença de falhas e de tags e microtags. Foram obtidas quatro medidas e a média para cada amostra. Os resultados foram submetidos aos testes estatísticos de Análise de Variância (ANOVA) e de Tukey (p<0,05), segundo os quais, independente do sistema adesivo o G2 apresentou a maior média de espessura da camada híbrida (1,89±0,15) e o Controle com o Clearfil SE Bond apresentou a menor média de espessura de camada híbrida, diferindo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this study was to assess through analyses in scanning electronic microscopy (SEM), the Nd:YAG laser influence on the hybridization quality of bovine dentine, using conventional adhesive system Adper Single Bond - 3M ESPE (SB) or self-etching adhesive system - Clearfil SE Bond - Kuraray (CSEB). Twelve extracted and frozen bovine incisors were used. The teeth were sectioned and divided in half mesio-distal section built-in acrylic resin. The buccal dentinal surface was worn out until the dentin medium depth was reached. Each specimen of the same tooth was treated on its incisal portion with SB and with CSEB in its cervical portion. The samples were divided into 3 groups with 6 specimens in each: Control group - after the application of the adhesive systems the polymerization was done; G1 - after the application of the adhesive systems the samples were lased with 60mJ /pulse and polymerized and G2 - after the application of the adhesive systems the samples were lased with with 140mJ /pulse and also polymerized. All the samples received the composite resin (Filtek Z350 - 3M ESPE) increments. After 24h storage in distilled water at 37ºC, the adhesion profiles were polished, submitted to the acid-base challenge, and the presence of imperfections and tags or microtags in the hybrid layer analysed using the SEM. Four measures and the mean value of each sample were obtained. The results were submitted to Analysis of Variance (ANOVA) and Tukey statistical tests (p 0,05). Independent of the adhesive system used the G2 presented the higher average of hybrid layer thickness (1,89±0,15) and the Control group with the Clearfil SE Bond presented the smaller hybrid layer thickness presenting significant statistical difference from the other groups. Different scores were attributed for the degree of imperfections (0-3) and for the degree of presence of tags and microtags (0-2)... (Complete abstract, click electronic access below) / Doutor

The use of thin-film techniques for the fabrication of microfluidic devices has gained attention over the last decade, particularly for three-dimensional channel structures. The reasons for this include effective use of chip volume, mechanical flexibility, dead volume reduction, enhanced design capabilities, integration of passive elements, and scalability. Several fabrication techniques have been adapted for use on thin films: laser ablation and hot embossing are popular for channel fabrication, and lamination is widely used for channel enclosure. However, none of the previous studies have been able to achieve a strong bond that is reliable under moderate positive pressures. The present work aims to develop a thin-film process that provides design versatility, speed, channel profile homogeneity, and the reliability that others fail to achieve. The three building blocks of the proposed baseline were fifty-micron poly(methyl methacrylate) thin films as substrates, channel patterning by laser ablation, and device assembly by thermal-fusion bonding. Channel fabrication was characterized and tuned to produce the desired dimensions and surface roughness. Thermal bonding was performed using an adapted mechanical testing device and optimized to produce the maximum bonding strength without significant channel deformation. Bonding multilayered devices, incorporating conduction lines, and integrating various types of membranes as passive elements demonstrated the versatility of the process. Finally, this baseline was used to fabricate a droplet generator and a DNA detection chip based on micro-bead agglomeration. It was found that a combination of low laser power and scanning speed produced channel surfaces with better uniformity than those obtained with higher values. In addition, the implemented bonding technique provided the process with the most reliable bond strength reported, so far, for thin-film microfluidics. Overall, the present work proved to be versatile, reliable, and fast, making it a good candidate to reproduce several on-chip functions. Future work includes implementing thick-substrate bonding techniques to further improve the process and decrease energy requirements.

Repellents play a key role in preventing mosquito-borne diseases such as malaria by reducing human-vector contact. The general mechanism of action relies on providing a repelling vapour around the applied area on the skin. Thus, the proper evaporation rate and consistency of the composition of the released vapour are factors determining the performance of repellent formulations. The formulation should evaporate fast enough to provide a sufficient level of repellence during its life time. However, if evaporation proceeds too fast, then it will be depleted rapidly so that activity is lost within a short period of time, which makes the repellent inefficient. Several controlled-release approaches have been developed to improve both the protection time and level. However, these techniques have inherent drawbacks from the industrial point of view. Moreover, these techniques mostly focus only on reducing the release rate, while the consistency of the vapour composition has not been addressed. In the present study, a novel approach towards controlling the evaporation behaviour of repellents is proposed. It is based on engineering the molecular interactions in order to design negative pseudo-azeotrope formulations. Negative pseudo-azeotrope mixtures are less volatile than the pure parent components and they do not undergo separation during evaporation. The feasibility of the idea was investigated by studying the molecular structure of generally available repellents. Among known molecular interactions, hydrogen bonding has the most likely impact on the formation of azeotropes and in particular pseudo-azeotropes. Thus, established repellents were classified based on their chemical structures and their capability to take part in hydrogen bonding. Next, a simple spectroscopic method for anticipating pseudoazeotropes formation was developed. Binary compositions of nonanoic acid and ethyl butylacetylaminopropionate (IR3535) showed a potential for forming pseudo-azeotrope mixtures. Hence R3535 and nonanoic acid were selected as model compounds to test the hypothesis. An experimental technique to confirm pseudo-azeotrope formation and to locate the composition of the probable pseudo-azeotrope point was required. To this end, an oven test was designed. The temporal mass loss, under an isothermal program, of a series of evaporating mixtures was measured. Simultaneously, the Fourier transform infrared (FTIR) spectra of the liquid remaining was recorded. Inverse analysis techniques were used to determine the composition of remaining liquid mixtures from the recorded FTIR spectra. The oven tests revealed that, as vaporisation progressed, the composition of the liquid remaining and the emitted vapour converged to a fixed IR3535 content of ca. 75 mol%. Mixtures close to this composition also featured the lowest volatility. Oven test also showed that the composition of the liquid mixtures diverged from the fixed IR3535 content of ca. 10 mol%. Mixtures close to this composition featured the highest volatility. These observations showed that IR3535 and nonanoic acid forms two pseudo-azeotrope compositions, i.e. a negative pseudo-azeotrope at an IR3535 content of ca. 75 mol%, and a positive pseudo-azeotrope at IR3535 content of ca. 10 mol%. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied to check these results. TGA confirmed that the negative pseudo-azeotrope mixture is less volatile while the positive pseudo-azeotrope is more volatile than the parent compounds. The DSC results revealed that in comparison with the pure compounds, negative pseudo-azeotrope had a lower boiling point onset while the positive pseudo-azeotrope had a higher boiling point. Although negative pseudo-azeotrope repellent formulations have the desired lower constant release rate, their repellent activity needed to be tested. This is due to the fact that mixing the ingredients to formulate a negative pseudo-azeotrope results in interactions among the components. As a consequence, the inherent repellence effect of the compounds might have been impaired in the mixture. The modified arm-in-cage test was used to test the repellence of the controlled-release repellent formulation i.e. the negative pseudo-azeotrope of the IR3535 + nonanoic acid system. Results showed that the mixture featured improved performance with respect to both repellence efficacy and persistence. Moreover, the negative pseudo-azeotrope also exhibited a knock down effect, even resulting in mortality of most of the test mosquitoes. The presence of two pseudo-azeotrope points at different composition in the IR3535 + nonanoic acid system is a rare occurrence, analogous to double azeotropy. Thus, molecular simulation techniques were used to explore the nature of system and the interactions responsible for this unique behaviour. Gibbs-Monte Carlo simulation results suggest that variations in the sizes of the molecular clusters present in the liquid at various compositions might be responsible. They revealed that IR3535 and nonanoic acid in neat form are both highly structured liquids. The break-down in the structure of IR3535 at high concentrations of the acid may be the origin of increased evaporation rate and formation of the positive pseudo-azeotrope. On the other hand, negative pseudo-azeotrope may be resulted from formation of bulkier clusters at the ration of 3:1 (IR3535: nonanoic acid). / Thesis (PhD (Chemical Technology))--University of Pretoria, 2016. / English / PhD (Chemical Technology) / Unrestricted