No description available.

Poly ethylene glycol (PEG) based microgels were synthesized and investigated. The PEG microgel has the same phase transition as the traditional poly N-isopropylacrylamide (PNIPAM). As a good substitute of PNIPAM, PEG microgel exhibits many advantages: it is easier to control the lower critical solution temperature (LCST) of the microgel by changing the component of copolymers; it has a more solid spherical core-shell structure to have a double thermo sensitivity; it is straightforward to add other sensitivities such as pH, magnetic field or organic functional groups; it readily forms a photonic crystal structure exhibiting Bragg diffraction; and, most importantly, the PEG microgel is biocompatible with human body and has been approved by FDA while PNIPAM has not. PEG microgels with core-shell structure are synthesized with a two-step free radical polymerization and characterized with DLS, SLS and UV–Vis. The dynamic mechanics of melting and recrystallizing of the PEG core-shell microgel are presented and discussed. Photonic crystals of PEG microgels were synthesized and characterized. The crystal can be isolated in a thin film or a bulk column. The phase transition of PEG microgel was simulated with the mean field theory. The enthalpy and entropy of phase transition can be estimated from the best fit to theoretical calculation with experimental data.

No description available.

Hydrogels are promising materials for a number of biomedical applications, including tissue engineering, controlled drug delivery, and wound healing. Due to the semi-permeable nature of the water-swollen crosslinked polymer network, hydrogels have the unique ability to encapsulate materials, while allowing passage of any necessary resources, such as the import of oxygen or nutrients and the export of waste or therapeutic agents. Hydrogel properties vary greatly depending on the polymer material and crosslinking chemistry chosen, all of which can be tuned for a particular application. Current hydrogel systems typically involve either natural or synthetic polymers. Synthetic polymers afford more structural control to the resulting hydrogel, however the employed crosslinking chemistry is often non-ideal, due to the high temperatures required or the presence of cytotoxic catalysts. Click chemistry, particularly the strain-promoted alkyne-azide cycloaddition (SPAAC), is ideal for hydrogel crosslinking as it is fast at physiological temperatures, bio-orthogonal, doesn’t produce any byproducts, and doesn’t require a catalyst or external stimuli. For the hydrogel material, synthetic poly(ethylene glycol) (PEG) is most appealing since it is non-toxic, easy to functionalize, and physiologically stable. At the time of this thesis, there were few examples of PEG hydrogels prepared via SPAAC, with limited characterization of the physical properties of these gels and the parameters that dictate their gelation behavior. The work presented in this thesis involved the optimized synthesis of a cyclooctyne derivative, aza-dibenzocyclooctyne (DIBAC), which was subsequently used for the preparation and characterization of a series of PEG hydrogels crosslinked via SPAAC. We showed that the PEG chain length and number of crosslinking groups had a significant effect on the swelling, degradation time and stiffness of the resulting hydrogels. Additionally, there was very little protein adsorption on the surface of the hydrogels, and the polymer components proved non-cytotoxic. A second objective of this work was to investigate reproducible hydrogels. We created novel, SPAAC crosslinked PEG hydrogels that contained well-defined dendritic crosslinking groups, making them more reproducible than the previous linear analogs. These hydrogels have short gelation times at low polymer concentration, minimal swelling at physiological temperatures, and kept human mesenchymal stem cells (hMSCs) viable for over 15 days. / Thesis / Doctor of Philosophy (PhD)

In this work, we created shear thinning block copolymers that could be potentially utilized as an artificial vitreous replacement. The materials were created using poly(ethylene glycol) (PEG) and silicone polymers, respectively, due to their high biocompatibility. Both the ABA and BAB geometry triblock copolymers were created and were characterized using parallel plate and cone-and plate rheometers. It was observed that the materials from both geometries exhibited a decrease in viscosity with increasing shear rates, thus fulfilling the criteria of being a shear thinning material. The materials were also characterized under different aqueous conditions. It was observed that the materials with a higher PEG composition were better able to retain their physical structure – did not disperse into aqueous solutions – at higher water content levels. The materials that retained their structure were also shown to retain their shear thinning properties. In the absence of solvent, the opacity of the materials increased with increasing PEG composition ratio per copolymer chain. When exposed to different aqueous conditions, the opacity of the materials was found to decrease at specific water concentrations. Materials with larger PEG blocks required a greater water content to exhibit optimal light transmission. / Thesis / Master of Science (MSc)

Os polietilenoglicóis (PEGs) são polímeros sintéticos não iônicos, solúveis em água, que possuem diferentes propriedades físico-químicas devido ao efeito de sua cadeia longa, conferindo assim uma vasta disposição na aplicação industrial do PEG. Como exemplos de aplicação destacam-se o uso como lubrificante solúvel em água para moldes de borracha, fibras têxteis e operações de formação de metais, sendo também usado em tintas à base de água, revestimento de papéis, polimento, na indústria cerâmica, na confecção de fases estacionárias para cromatografia, entre inúmeras outras. O PEG também pode ser adicionado às dietas de ruminantes baseadas em foragem com alto teor de taninos, onde ele se insere como um agente complexante do tanino. Contudo, devido à ampla aplicação do PEG, mostra-se uma maior preocupação com seu uso e disposição no meio ambiente, uma vez que sua concentração, seja no solo ou água, possa ser grande. No entanto, pouco se sabe acerca do seu destino no ambiente, principalmente em condições tropicais, sendo que não foram encontrados na literatura estudos de monitoramento de águas subterrâneas e superficiais, e nem mesmo estudos de impacto ambiental. Neste contexto, este projeto se insere na busca sobre o destino do PEG-4000 no ambiente, buscando informações sobre sua mobilidade, degradação e sorção em solos, utilizando técnicas radiométricas (14C-PEG). Complementando o estudo do PEG, foi avaliado o transporte de pesticidas na presença do PEG, uma vez que ele possui uma alta solubilidade, podendo atuar como co-solvente, avaliando assim o papel do PEG na presença de contaminantes / Polyethylene glycols (PEGs) are non-ionic synthetic polymer, soluble in water, which have different physical and chemical properties because of its long chain, thereby providing a broad industrial application of PEG. Examples of application are the use as water-soluble lubricant for rubber molds, textile fibers and metallurgy, also used in water-based paints, paper coating, polishing, ceramic industry, in construction of stationary phases for chromatography, and numerous others. PEG can also be added to the diets of ruminants based on forage with a high content of tannins, where it comes as a complexing agent of tannin. However, due to the wide application of PEG, it is a greater concern about its use and disposal in the environment, since their concentration, either in soil or water, can be large. However, little is known about their fate in the environment, especially in tropical conditions, which were not found in the literature studies for monitoring underground and surface water, and even environmental impact studies. In this context, this project falls in the search on the fate of PEG-4000 in the environment, seeking information on their mobility, degradation and sorption in soils, using radiometric techniques (14C-PEG). Complementing the study of PEG, was evaluated the pesticides transport in the presence of PEG, since it has a high solubility and can act as co-solvent, thereby assessing the role of PEG in the presence of contaminants

This research project entails analyses of both alcoholic route C8S3 J-aggregate bundles and the interactions of a polyethylene glycol additive with alcoholic route C8S3 J-aggregates. First, the C8S3 J-aggregate bundles are characterized by both polarized and non-polarized spectroscopy methods. Orientation of the tubular bundled molecular complex was achieved, depending on the experiment, through a combination of flow cell experiments and cover slip deposited sample analysis. Next, isolated alcoholic route C8S3 J-aggregates were investigated using a polyethylene glycol (PEG) additive which has been shown, through absorbance and fluorescence emission spectroscopy, to selectively and reversibly remove the outer wall of the J-aggregate tubule. Spectroscopic analyses have indicated that the addition of a PEG additive left behind an in-tact inner wall tubule without the use of oxidizing agents, a feat never before accomplished with the C8S3 monomer. / text

Les composés polymacrocycliques présentent un grand intérêt grâce à leurs caractéristiques remarquables de coordination. Pour la première fois, l’approche synthétique fonctionnelle aux diverses composés bi- et polycycliques contenant plusieurs fragments d’éthers aza-couronnes, aux cryptands et aux supercryptands à base d’éthers aza-couronnes a été élaborée par Krakowiak et ses collaborateurs au début des années 1990, par l’usage de simples réactions de substitution nucléophile. Actuellement, les composés hétéropolymorphes polymacrocycliques, capables de former des complexes polynucléaires avec différents métaux présentent le plus grand intérêt. Dans la grande majorité des travaux la synthèse de presque toutes les composés polymacrocycliques a été réalisée à l’aide des méthodes non orthodoxes, à l’exception des molécules, composées de plusieurs macrocycles porphyriques (de la diade et de la triade), pour l’obtention desquelles ont été appliquées les réaction de Suzuki, le couplage de Sonogashira et la réaction de Heck. Le laboratoire de synthèse organominérale de la Faculté de chimie de l’Université d’Etat de Moscou a accumulé une riche expérience dans l’utilisation de l’amination pallado-catalysée pour la synthèse de diverses composés macrocycliques et polymacrocycliques, et, actuellement, on étudie activement l’arylation cupro-catalysée des di- et polyamines. À cet égard, l’étude de l’amination cupro-catalysée pour la synthèse de composés polymacrocycliques qui contiennent comme connecteurs des diamines et des polyamines a permis développer des méthodes de catalyse métallique et d’obtenir de nouveaux types de conjugués polytopiques et polymacrocycliques, qui comprennent dans leur composition structurelle des fragments éthers aza-couronnes, porphyrines et calixarènes, étudiés pour leur capacité à détecter des cations des métalliques.Le but de ces recherches est de développer des méthodes catalytiques de synthèse de conjugués polymacrocycliques qui contiennent dans leur composition structurale des fragments éthers aza-couronnes, des porphyrines et des calix[4]arènes et d’étudier leurs capacités à détecter des cations métalliques. Pour atteindre cet objectif, il est nécessaire de résoudre les problèmes suivants: 1) établir la généralité de l’amination catalysée par le Cu(I) des dérivés éthers aza-couronnes et des porphyrines contenant des halogènes et de synthétiser les dérivés aminés; 2) développer des méthodes de la macrocyclisation catalytique pour obtenir des composés macrobicycliques et macrotricycliques qui contiennent dans leur structure des fragments éthers diaza-couronnes, des tétraazamacrocycles ( cyclènes et cyclames) et des calix[4]arènes; 3) modifier les composés macrocycliques et macrobicycliques par des substituants fluorophores, y compris des porphyrines; 4) à l’aide de la spectroscopie UV et de la fluorescence, étudier la liaison cations métalliques-polymacrocycles et identifier les détecteurs potentiels moléculaires fluorescents et colorimétriques. / Polymacrocyclic compounds are of great interest due to their unique coordination properties. The first convenient synthetic approach to various polycyclic compounds containing several azacrown-ether moieties, to cryptands and supercryptands, based on azacrown-ethers, has been developed by Krakowiak and coworkers in the beginning of 1990s using simple nucleophilic substitution reactions. At present time heteropolytopic polymacrocyclic compounds, capable of forming polynuclear complexes with various metals, attract the utmost interest. In the majority of publications dealing with the synthesis of polymacrocyclic compounds non-catalytic approaches were applied, except for several porphyrin dyads and triads, which were obtained using Suzuki, Sonogashira and Heck reactions. The laboratory of organoelement compounds of Chemistry Department of Lomonosov Moscow State University has a great experience of the application of Pd-catalyzed amination reactions for the synthesis of polymacrocyclic compounds, nowadays Cu-catalyzed arylation of di- and polyamines is under investigation. Bearing it in mind we have found the research for Cu-catalyzed amination to be important in synthesis of polymacrocyclic compounds containing di- and polyamine linkers; as well as the synthesis of new types of polytopic polymacrocyclic conjugates, bearing azacrown-ether, porphyrin and calixarene moieties, by means of Pd- and Cu-catalyzed reactions; and studying their properties as metal cations detectors.The aim of the research is to develop catalytic synthetic approaches to polymacrocyclic conjugates, bearing azacrown-ether, porphyrin and calix[4]arene moieties, and to study their abilities as detectors for metal cations. For this purpose it is necessary to carry out the following investigations: 1) to study the regularities of Cu(I)-catalyzed amination of halogen derivatives of azacrown-ethers and porphyrins and to synthesize corresponding amino derivatives; 2) to develop the methods for the catalytic macrocyclization aimed at the synthesis of macrobicyclic and macrotricyclic compounds, containing diazacrown-ether, cyclen, cyclam and calix[4]arene moieties; 3) to introduce fluorophoric fragments (including porphyrins) into macrocyclic and macrobicyclic compounds; 4) to investigate metal cations binding by thus synthesized polymacrocycles using UV and fluorescent spectroscopy, and to find possible fluorescent and colorimetric detectors among them.

Os polietilenoglicóis (PEGs) são polímeros sintéticos não iônicos, solúveis em água, que possuem diferentes propriedades físico-químicas devido ao efeito de sua cadeia longa, conferindo assim uma vasta disposição na aplicação industrial do PEG. Como exemplos de aplicação destacam-se o uso como lubrificante solúvel em água para moldes de borracha, fibras têxteis e operações de formação de metais, sendo também usado em tintas à base de água, revestimento de papéis, polimento, na indústria cerâmica, na confecção de fases estacionárias para cromatografia, entre inúmeras outras. O PEG também pode ser adicionado às dietas de ruminantes baseadas em foragem com alto teor de taninos, onde ele se insere como um agente complexante do tanino. Contudo, devido à ampla aplicação do PEG, mostra-se uma maior preocupação com seu uso e disposição no meio ambiente, uma vez que sua concentração, seja no solo ou água, possa ser grande. No entanto, pouco se sabe acerca do seu destino no ambiente, principalmente em condições tropicais, sendo que não foram encontrados na literatura estudos de monitoramento de águas subterrâneas e superficiais, e nem mesmo estudos de impacto ambiental. Neste contexto, este projeto se insere na busca sobre o destino do PEG-4000 no ambiente, buscando informações sobre sua mobilidade, degradação e sorção em solos, utilizando técnicas radiométricas (14C-PEG). Complementando o estudo do PEG, foi avaliado o transporte de pesticidas na presença do PEG, uma vez que ele possui uma alta solubilidade, podendo atuar como co-solvente, avaliando assim o papel do PEG na presença de contaminantes / Polyethylene glycols (PEGs) are non-ionic synthetic polymer, soluble in water, which have different physical and chemical properties because of its long chain, thereby providing a broad industrial application of PEG. Examples of application are the use as water-soluble lubricant for rubber molds, textile fibers and metallurgy, also used in water-based paints, paper coating, polishing, ceramic industry, in construction of stationary phases for chromatography, and numerous others. PEG can also be added to the diets of ruminants based on forage with a high content of tannins, where it comes as a complexing agent of tannin. However, due to the wide application of PEG, it is a greater concern about its use and disposal in the environment, since their concentration, either in soil or water, can be large. However, little is known about their fate in the environment, especially in tropical conditions, which were not found in the literature studies for monitoring underground and surface water, and even environmental impact studies. In this context, this project falls in the search on the fate of PEG-4000 in the environment, seeking information on their mobility, degradation and sorption in soils, using radiometric techniques (14C-PEG). Complementing the study of PEG, was evaluated the pesticides transport in the presence of PEG, since it has a high solubility and can act as co-solvent, thereby assessing the role of PEG in the presence of contaminants

Peg solitaire is a game in which pegs are placed in every hole but one and the player jumps over pegs along rows or columns to remove them. Usually, the goal of the player is to leave only one peg. In a 2011 paper, this game is generalized to graphs. In this thesis, we consider a variation of peg solitaire on graphs in which pegs can be removed either by jumping them or merging them together. To motivate this, we survey some of the previous papers in the literature. We then determine the solvability of several classes of graphs including stars and double stars, caterpillars, trees of small diameter, particularly four and five, and articulated caterpillars. We conclude this thesis with several open problems related to this study.