Neste trabalho foi realizada a síntese e caracterização de um derivado de S,S-dioxidotioxantona, 7,8-benzotioxanton-9-ona-10,10-dióxido (TX-Np-SO2). A TX-Np-SO2 foi caracterizada estruturalmente por espectros eletrônico e vibracional (UV-vis e fluorescência, Infravermelho) e também por ressonância magnética nuclear (RMN) de 1H e 13C. As propriedades fotofísicas, espectros de emissão de fluorescência e fosforescência e o rendimento quântico de fluorescência da TX-Np-SO2 foram determinadas, assim como os tempos de vida de fluorescência (τF = 3,62 ns) e fosforescência (τPh = 800 ms). Os espectros de absorção triplete-triplete dos transientes da TX-Np-SO2, em soluções desoxigenadas de metanol, acetonitrila e metilciclohexano, foram determinados por Fotólise por Pulso de Laser, bem como as constantes de velocidade de supressão bimoleculares do derivado pelos supressores trans-estilbeno, trietilamina, p-dimetilamina benzoato de etila e 2-propanol. A fotopolimerização do metacrilato de metila (MMA) iniciada por TX-Np-SO2 foi estudada por dilatometria. A reação de polimerização do iniciador (TX-Np-SO2) na presença de amina e o monômero MMA foi estudada de modo a determinar a taxa de polimerização (Rp) a diferentes concentrações de trietilamina (TEA) e p-dimetilamina benzoato de etila (EDB). / The aim of this work was the synthesis and characterization of a S,S-dioxidethioxanthone derivative, 7,8-benzo-thioxanthen-9-one-10,10-dioxide (TX-Np-SO2). The TX-Np-SO2 was structurally characterized by its electronic and vibrational spectra (UV-vis and fluorescence, IR) and also by 1H and 13C RMN methods. The photophysical properties, fluorescence and phosphorescence emission spectra, and fluorescence quantum yield of TX-Np-SO2 were determined, as well as the fluorescence lifetime (τF = 3,62 ns) and the phosphorescence lifetime (τPh = 800 ms). The transient absorption spectra of TX-Np-SO2 in degassed solutions of methanol, acetonitrile and methylcyclohexane were determined by Laser Flash Photolysis, as well as the bimolecular triplet quenching rate constants for of the derivative by various compounds. The photopolymerization of methyl methacrylate (MMA) initiated by TX-Np-SO2 was studied by dilatometry. The polymerization reaction of the initiator (TX-Np-SO2) in the presence of amine and MMA monomer was studied in order to determine the polymerization rate (Rp) at different loadings of triethylamine (TEA) and ethyl-4-dimethylaminobenzoate (EDB).

Neste trabalho foi realizada a síntese e caracterização de um derivado de S,S-dioxidotioxantona, 7,8-benzotioxanton-9-ona-10,10-dióxido (TX-Np-SO2). A TX-Np-SO2 foi caracterizada estruturalmente por espectros eletrônico e vibracional (UV-vis e fluorescência, Infravermelho) e também por ressonância magnética nuclear (RMN) de 1H e 13C. As propriedades fotofísicas, espectros de emissão de fluorescência e fosforescência e o rendimento quântico de fluorescência da TX-Np-SO2 foram determinadas, assim como os tempos de vida de fluorescência (τF = 3,62 ns) e fosforescência (τPh = 800 ms). Os espectros de absorção triplete-triplete dos transientes da TX-Np-SO2, em soluções desoxigenadas de metanol, acetonitrila e metilciclohexano, foram determinados por Fotólise por Pulso de Laser, bem como as constantes de velocidade de supressão bimoleculares do derivado pelos supressores trans-estilbeno, trietilamina, p-dimetilamina benzoato de etila e 2-propanol. A fotopolimerização do metacrilato de metila (MMA) iniciada por TX-Np-SO2 foi estudada por dilatometria. A reação de polimerização do iniciador (TX-Np-SO2) na presença de amina e o monômero MMA foi estudada de modo a determinar a taxa de polimerização (Rp) a diferentes concentrações de trietilamina (TEA) e p-dimetilamina benzoato de etila (EDB). / The aim of this work was the synthesis and characterization of a S,S-dioxidethioxanthone derivative, 7,8-benzo-thioxanthen-9-one-10,10-dioxide (TX-Np-SO2). The TX-Np-SO2 was structurally characterized by its electronic and vibrational spectra (UV-vis and fluorescence, IR) and also by 1H and 13C RMN methods. The photophysical properties, fluorescence and phosphorescence emission spectra, and fluorescence quantum yield of TX-Np-SO2 were determined, as well as the fluorescence lifetime (τF = 3,62 ns) and the phosphorescence lifetime (τPh = 800 ms). The transient absorption spectra of TX-Np-SO2 in degassed solutions of methanol, acetonitrile and methylcyclohexane were determined by Laser Flash Photolysis, as well as the bimolecular triplet quenching rate constants for of the derivative by various compounds. The photopolymerization of methyl methacrylate (MMA) initiated by TX-Np-SO2 was studied by dilatometry. The polymerization reaction of the initiator (TX-Np-SO2) in the presence of amine and MMA monomer was studied in order to determine the polymerization rate (Rp) at different loadings of triethylamine (TEA) and ethyl-4-dimethylaminobenzoate (EDB).

Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets. To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP). The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP. The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR). The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility. In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures. Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP. / QC 20101019

<p>Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets.</p><p>To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP).</p><p>The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP.</p><p>The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR).</p><p>The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility.</p><p>In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures.</p><p>Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP.</p>

Liquid chromatography is an analytical technique that is constantly facing new challenges in the separation of small molecules and large biomacromolecules. Recently the development of ultra high pressure liquid chromatography has increased the demand on sturdy particles as stationary phase. At the same time the particle size has decreased to sub-2 µm and packed into shorter analytical columns. This thesis deals with the development of new ways of preparing particulate polymer materials using divinylbenzene (DVB) as crosslinker. It includes a novel procedure for synthesizing monodisperse polymer particles by photoinitiated precipitation polymerization. A 150 W short arc xenon lamp was used to initiate the polymerizations. The synthesized particles are monodisperse and have an average particle size ranging from 1.5 to 4 μm depending on reaction conditions and have subsequently been used as grafting templates. The surface of DVB particles contains residual vinyl groups that serve as anchoring points for further functionalization via a variety of grafting schemes. Copolymerization with incorporation of 2,3-epoxypropyl methacrylate yielded pendant oxirane groups on the particle surface. Atom transfer radical polymerization (ATRP) was used to graft methacrylates from the surface resulting in a core-shell type material. A “grafting to” scheme was used to attach pre-made sulfopropyl methacrylate telomers onto particles containing oxirane rings. / Populärvetenskaplig sammanfattning på svenska: Vätskekromatografi är en analytisk kemisk teknik som ständigt står inför nya utmaningar när det gäller att separera allt från små organiska föreningar till stora makro¬molekyler. Denna avhandling beskriver tillverkning av polymera partiklar med exceptionellt jämn storleksfördelning och ytmodifiering av dessa, för användning som stationärfas i kromatografi¬kolonner. Polymeriserings¬tekniken som används är utfällnings¬polymerisering där lösningen UV-bestrålas av en 150 W xenonlampa. Monomeren (byggstenen) löses tillsammans med en intiator i ett lösningsmedel och efterhand som polymeriseringen fortskrider faller polymerpartiklarna ut. Polymerpartiklarna är gjorda av monomeren divinylbensen som fungerar som en tvärbindare, dvs att den länkar ihop flera kedjor till ett hårt litet nystan. Partiklarna växte till en storlek på 1,5 till 4 µm under två till fyra dygn. Efter tillverkningen är partiklarnas yta täckta av vinylgrupper som kan användas för att fästa funktionella polymerkedjor. Genom att tillföra monomeren 2,3-epoxipropyl¬metakrylat i polymeriseringen kunde man desutom få en partikelyta som innehöll epoxigrupper. Epoxigrupperna användes för att fästa positivt laddade polymerkedjor av bestämd längd. Materialet packades i en kromatografikolonn och användes för att separera en testlösning bestående av fyra proteiner. Partiklarna användes även som bas för ymppolymerisering där den vinyltäckta ytan fått reagera med vätebromid. Detta gör att partiklarna blir stora makroinitiatorer som kan användas för att på ett kontrollerat sätt låta polymerkedjor växa från ytan. I en undersökning ympades 2,3-epoxypropylmetakrylat från ytan på partiklarna och resultatet blev ett tjockt ytskikt. Epoxigrupperna kunde sedan hydrolyseras till dioler vilket gjorde partiklarna mer hydrofila.

Indiana University-Purdue University Indianapolis (IUPUI) / Objectives: A new technology has been introduced into the field of dental resin composites that professes to enhance light-curing efficiency. Rapid amplified photopolymerization (RAP) initiator technology has not yet been fully compared with resin composites with conventional initiators such as camphorquinone (CQ). The purpose of this study was to compare and contrast the effects of this novel technology (RAP) on properties of two light-cured resin composites. Flowable (EFQ) and microfilled (ESQ) experimental composites were fabricated and supplied from Tokuyama Dental with (w/RAP) and without RAP (w/o RAP). The flexural strength (MPa) and flexural modulus (MPa) were obtained using a three-point bending apparatus (Sintech Renew 1123, Instron Engineering Corp., Canton, MA). Polymerization stress curves were created using a tensometer (American Dental Association Health Foundation, NIST, Gaithersburg, MD) which were then used to calculate the maximum stress rate. Finally, the degree of conversion was measured using infrared spectroscopy (Jassco FT-IR spectrometer, Model: 4100, Jasco Corporation, Tokyo, Japan). When evaluating the flexural strength, the peak stress for EFQ w/RAP was significantly higher than EFQ w/o RAP (p = 0.0001). This was statistically not significant for the ESQ group, even though ESQ w/RAP did have a higher peak stress then ESQ w/o RAP (p = 0.28). The interaction between resin type and RAP was not significant when evaluating the flexural modulus (p = 0.21). Formulations with RAP had a significantly higher flexural modulus then w/o RAP (p = 0.0001). Experimental resins with RAP had significantly higher maximum stress rates than those w/o RAP when evaluating polymerization stress (p = 0.0001). Finally, groups w/ RAP appeared to have a higher degree of conversion than groups without (p = 0.0057). This study showed that the experimental composites with RAP had greater mechanical properties than those without. Unfortunately, the increase in polymerization stress causes concern clinically due to the chance of leakage at the restoration/tooth interface. One of the main potential disadvantages of this new RAP technology is an increase in the polymerization stress. Deciding if this amount of polymerization stress is clinically acceptable is yet to be accomplished.

Made available in DSpace on 2014-08-20T14:30:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-07-10 / The objective of this study was to evaluate the effectiveness of benzodioxole derivatives as co-initiators of radical polymerization of experimental self-etching adhesive systems. To compose the experimental self-etching adhesive systems a primer, containing methacrylate monomers and solvents, was developed. A monomer mixture, based on 50 wt % of Bisphenol A glicidyl dimethacrylate (Bis-GMA), 25 wt% of triethyleneglycol dimethacrylate (TEGDMA) and 25 wt% of 2-hydroxyethyl methacrylate(HEMA), was used as a model dental adhesive resin. Camphorquinone (CQ) 1 mol % was used as a photoinitiator to initiate polymerization. Different co-initiators (1,3- benzodioxole and piperonyl alcohol) and concentrations (0.25, 0.50, 1, 2, 4, 8, 16 mol %) were used in a model dental adhesive resin, to compose the experimental groups. Additionally, tertiary amine (EDAB) was used as co-initiator in the control group. The physical, chemical and mechanical properties and characteristics of the polymer obtained for the experimental adhesives (ABDO, APA, AEDAB) were evaluated using polymerization kinetics, sorption and solubility, flexural strength and elastic modulus. The microtensile bond strength (µTBS) to enamel and dentin, and fracture mode were investigated. Adicionalmente morphological analysis of the dentin bonding Interface were evaluated. The results indicated that the BDO and PA were effective co-initiators for the photoinitiator system based on CQ. Comparisons between the benzodioxole derivative co-initiators and traditionally used amine EDAB, showed similar performance in the kinetics of polymerization, flexural strength, water sorption and solubility of the model dental adhesive resin evaluated. In the microtensile bond strength dentin means were higher than enamel and mixed failures were predominant. APA showed higher bond strengths than AEDAB, while ABDO showed intermediate data. The hybrid layer for all groups was shown to be shallow (1-2 µm thick). No appreciable differences in homogeneity were detected along the bonded interface. BDO and PA were feasible alternatives to conventional amine as co-initiator of radical polymerization, moreover, as these benzodioxoles are found in the human diet, this characteristic made them more promising and advantageous to use in dental adhesive resin formulations than amine. / O objetivo deste estudo foi avaliar a efetividade de componentes derivados de benzodioxolas, como co-iniciadores da polimerização radicalar de um adesivo autocondicionante experimental. Para compor sistemas adesivos autocondicionantes experimentais foi desenvolvido um primer, composto por monômeros metacrilatos e solventes. O adesivo foi formulado utilizando uma resina adesiva modelo, composta por 50% de bisfenol A glicidil dimetacrilato (Bis-GMA), 25% de 2-hidroxietil metacrilato (HEMA) e 25% de trietilenoglicol dimetacrilato (TEGDMA), em massa. Canforoquinona (CQ) na concentração 1% molar foi utilizada como fotoiniciador da polimerização da resina modelo. Os grupos experimentais foram formulados com diferentes coiniciadores na resina adesiva: 1,3-benzodioxola (BDO) e álcool piperonílico (AP), em diferentes concentrações molares (0.25, 0.50, 1, 2, 4, 8, 16 %). Adicionalmente um grupo com amina terciária, etil,4-dimetilamino benzoato (EDAB) como co-iniciador, foi formulado como controle. Características e propriedades físicas, químicas e mecânicas do polímero obtido pelos adesivos experimentais foram avaliadas utilizando as metodologias de cinética de polimerização, sorção e solubilidade, resistência à flexão e módulo de elasticidade. A resistência de união à microtração (MPa) ao esmalte e à dentina, com a caracterização do tipo de fratura foi investigada. Adicionalmente, análise morfológica da interface adesiva em dentina foi avaliada. Os resultados indicaram que o BDO e PA foram co-iniciadores efetivos para sistemas fotoiniciadores à base de canforoquinona (CQ). Comparações entre os adesivos experimentais com co-iniciadores derivados de benzodioxolas (ABDO e AAP) e amina (AEDAB), mostraram performance similar na avaliação da cinética de polimerização, resistência à flexão, sorção e solubilidade da resina adesiva modelo avaliada. Na avaliação da resistência de união ao esmalte e à dentina, foi detectada diferença estatística e houve predominância de falhas mistas. APA apresentou maior resistência de união que AEDAB, enquanto ABDO mostrou resultados intermediários. A camada híbrida para todos os grupos apresentou uma espessura entre 1 e 2 Vm. Não foi observada diferença na homogeneidade da interface adesiva em dentina. BDO e PA se revelaram alternativas viáveis à amina como co-iniciadores para a polimerização radicalar. Ademais, estas benzodioxolas são mais promissoras e vantajosas que as aminas, por sua biocompatibilidade e presença na dieta humana