Photoacoustic evaluation of the thermal effusivity in the isotropic phase of certain comb-shaped polymers

The thermal effusivity values in the isotropic phase of certain comb-shaped polymers have been evaluated for the first time using an open photoacoustic cell configuration. The compounds investigated have siloxane and acrylate backbone and they carry mesogenic groups in their side chain. The results indicate that the polymer chain length as well as the side chain length have pronounced influence on the thermal effusivity values in liquid crystalline polymers

Nanostructure des particules polymériques : aspects physiques, chimiques et biologiques

Les nanotechnologies appliquées aux sciences pharmaceutiques ont pour but d’améliorer l’administration de molécules actives par l’intermédiaire de transporteurs nanométriques. Parmi les différents types de véhicules proposés pour atteindre ce but, on retrouve les nanoparticules polymériques (NP) constituées de copolymères “en bloc”. Ces copolymères permettent à la fois l’encapsulation de molécules actives et confèrent à la particule certaines propriétés de surface (dont l’hydrophilicité) nécessaires à ses interactions avec les milieux biologiques. L’architecture retenue pour ces copolymères est une structure constituée le plus fréquemment de blocs hydrophiles de poly(éthylène glycol) (PEG) associés de façon linéaire à des blocs hydrophobes de type polyesters. Le PEG est le polymère de choix pour conférer une couronne hydrophile aux NPs et son l’efficacité est directement liée à son organisation et sa densité de surface. Néanmoins, malgré les succès limités en clinique de ces copolymères linéaires, peu de travaux se sont attardés à explorer les effets sur la structure des NPs d’architectures alternatives, tels que les copolymères en peigne ou en brosse. Durant ce travail, plusieurs stratégies ont été mises au point pour la synthèse de copolymères en peigne, possédant un squelette polymérique polyesters-co-éther et des chaines de PEG liées sur les groupes pendants disponibles (groupement hydroxyle ou alcyne). Dans la première partie de ce travail, des réactions d’estérification par acylation et de couplage sur des groupes pendants alcool ont permis le greffage de chaîne de PEG. Cette méthode génère des copolymères en peigne (PEG-g-PLA) possédant de 5 à 50% en poids de PEG, en faisant varier le nombre de chaînes branchées sur un squelette de poly(lactique) (PLA). Les propriétés structurales des NPs produites ont été étudiées par DLS, mesure de charge et MET. Une transition critique se situant autour de 15% de PEG (poids/poids) est observée avec un changement de morphologie, d’une particule solide à une particule molle (“nanoagrégat polymére”). La méthode de greffage ainsi que l’addition probable de chaine de PEG en bout de chaîne principale semblent également avoir un rôle dans les changements observés. L’organisation des chaînes de PEG-g-PLA à la surface a été étudiée par RMN et XPS, méthodes permettant de quantifier la densité de surface en chaînes de PEG. Ainsi deux propriétés clés que sont la résistance à l’agrégation en conditions saline ainsi que la résistance à la liaison aux protéines (étudiée par isothermes d’adsorption et microcalorimétrie) ont été reliées à la densité de surface de PEG et à l’architecture des polymères. Dans une seconde partie de ce travail, le greffage des chaînes de PEG a été réalisé de façon directe par cyclo-adition catalysée par le cuivre de mPEG-N3 sur les groupes pendants alcyne. Cette nouvelle stratégie a été pensée dans le but de comprendre la contribution possible des chaines de PEG greffées à l’extrémité de la chaine de PLA. Cette librairie de PEG-g-PLA, en plus d’être composée de PEG-g-PLA avec différentes densités de greffage, comporte des PEG-g-PLA avec des PEG de différent poids moléculaire (750, 2000 et 5000). Les chaines de PEG sont seulement greffées sur les groupes pendants. Les NPs ont été produites par différentes méthodes de nanoprécipitation, incluant la nanoprécipitation « flash » et une méthode en microfluidique. Plusieurs variables de formulation telles que la concentration du polymère et la vitesse de mélange ont été étudiées afin d’observer leur effet sur les caractéristiques structurales et de surface des NPs. Les tailles et les potentiels de charges sont peu affectés par le contenu en PEG (% poids/poids) et la longueur des chaînes de PEG. Les images de MET montrent des objets sphériques solides et l'on n’observe pas d’objets de type agrégat polymériques, malgré des contenus en PEG comparable à la première bibliothèque de polymère. Une explication possible est l’absence sur ces copolymères en peigne de chaine de PEG greffée en bout de la chaîne principale. Comme attendu, les tailles diminuent avec la concentration du polymère dans la phase organique et avec la diminution du temps de mélange des deux phases, pour les différentes méthodes de préparation. Finalement, la densité de surface des chaînes de PEG a été quantifiée par RMN du proton et XPS et ne dépendent pas de la méthode de préparation. Dans la troisième partie de ce travail, nous avons étudié le rôle de l’architecture du polymère sur les propriétés d’encapsulation et de libération de la curcumine. La curcumine a été choisie comme modèle dans le but de développer une plateforme de livraison de molécules actives pour traiter les maladies du système nerveux central impliquant le stress oxydatif. Les NPs chargées en curcumine, montrent la même transition de taille et de morphologie lorsque le contenu en PEG dépasse 15% (poids/poids). Le taux de chargement en molécule active, l’efficacité de changement et les cinétiques de libérations ainsi que les coefficients de diffusion de la curcumine montrent une dépendance à l’architecture des polymères. Les NPs ne présentent pas de toxicité et n’induisent pas de stress oxydatif lorsque testés in vitro sur une lignée cellulaire neuronale. En revanche, les NPs chargées en curcumine préviennent le stress oxydatif induit dans ces cellules neuronales. La magnitude de cet effet est reliée à l’architecture du polymère et à l’organisation de la NP. En résumé, ce travail a permis de mettre en évidence quelques propriétés intéressantes des copolymères en peigne et la relation intime entre l’architecture des polymères et les propriétés physico-chimiques des NPs. De plus les résultats obtenus permettent de proposer de nouvelles approches pour le design des nanotransporteurs polymériques de molécules actives.

Lightly branched comb polyesters: application in fast drying solvent-borne coating formulations

Novel oxazoline-based comb-polymers possessing linoleyl or oleic side chains have been synthesized and used to produce low viscosity coatings. Inclusion of the polymers in model paint formulations results in coatings that exhibit faster drying times than commercially available alkyd resin formulations. The comb polymers were produced from diol substituted oxazoline monomers that were synthesized through a scalable, solvent free protocol and purified by simple recrystallisation. Co-polymerisation of the oxazolines with adipic acid at 160 °C in the bulk resulted in the targeted polyester comb type polymers. The polymers were soluble in a range of organic solvents and compatible with commercial alkyd resins. Model paint formulations containing up to 40 wt% of the linoleyl-based comb polymers exhibited a dramatic reduction in viscosity (from 35 to 13 Poise at 25 °C) with increasing quantities of polymer added. Dynamic mechanical analysis (DMA) studies revealed that the drying rate of the model paint formulations containing the comb polymers was enhanced when compared with that of commercial alkyd resins.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.

Effect of polymer architecture on Curcumin 1 encapsulation and release from PEGylated polymer nanoparticles: toward a drug delivery nano-platform to the CNS

We developed a nanoparticles (NPs) library from poly(ethylene glycol)–poly lactic acid comb-like polymers with variable amount of PEG. Curcumin was encapsulated in the NPs with a view to develop a delivery platform to treat diseases involving oxidative stress affecting the CNS. We observed a sharp decrease in size between 15 and 20% w/w of PEG which corresponds to a transition from a large solid particle structure to a “micelle-like” or “polymer nano-aggregate” structure. Drug loading, loading efficacy and release kinetics were determined. The diffusion coefficients of curcumin in NPs were determined using a mathematical modeling. The higher diffusion was observed for solid particles compared to “polymer nano-aggregate” particles. NPs did not present any significant toxicity when tested in vitro on a neuronal cell line. Moreover, the ability of NPs carrying curcumin to prevent oxidative stress was evidenced and linked to polymer architecture and NPs organization. Our study showed the intimate relationship between the polymer architecture and the biophysical properties of the resulting NPs and sheds light on new approaches to design efficient NP-based drug carriers.

Darstellung und Charakterisierung perlenkettenartiger und zylindrischer Polyelektrolyte

Zusammenfassung: Es sollten zum einen strukturell fixierte, perlenkettenartige Polyelektrolyte dargestellt werden. Dazu wurde lineares Poly-2-vinylpyridin(PVP) mit vinylfunktionalisierten, hydrophoben Quaternisierungsagentien zu einer Polyseife umgesetzt. Bei der Quaternisierungsreaktion ließ sich der Gehalt an hydrophoben Gruppen variieren, wodurch Polyseifen mit unterschiedlichen Ladungsdichten zugänglich wurden. Trotz vielfältiger Versuche war es dennoch nicht möglich, eine polymerisationsfähige Polyseife herzustellen, welche in wäßriger Lösung intramolekular micellisiert und die Überstruktur einer Perlenkette annimmt. Durch die Herstellung hochreiner PVP-Makromonomere konnten zylindrische Bürsten hergestellt werden. Durch Umsetzung der PVP-Bürsten mit Methyltosylat sind unter milden Reaktionsbedingungen nahezu vollständig umgesetzte positiv geladene Polyelektrolyte zugänglich. Durch eine Sulfonierung von Polystyrol-Polymakromonomeren wurden negativ geladene zylindrische Polyelektrolyte erhalten.Das Verhalten dieser Polyelektrolyte in verdünnter wäßriger Lösung wurde mit der statischen und der dynamischen Lichtstreuung untersucht. Dabei deuten die statischen Messungen darauf hin, daß deren Verhalten in verdünnter wäßriger Lösung maßgeblich durch die osmotische Aktivität der Gegenionen bestimmt wird.Durch eine Quaternisierung der PVP-Bürsten mit langkettigen Reagentien konnten hochverzweigte Polyelektrolytarchitekturen hergestellt werden. Dabei läßt sich die Tatsache, daß eine Quaternisierung mit solchen Reagentien einen nur unwesentlichen Einfluß auf die Struktur der Bürste hat, nicht durch einfache Überlegungen erklären. Dennoch scheinen die langkettigen Seitenketten die Ausbildung geordneter Strukturen innerhalb von Domänen an der Oberfläche zu induzieren.

Amphiphile Kammpolymere von Poly(2,7-carbazol)

Die vorliegende Dissertation beschreibt die Verschmelzung der Konzepte von konjugierten Polyelektrolyten und amphiphilen Kammpolymeren in Form von konjugierten, Poly(2,7-carbazol)-basierenden Polyelektrolytkammpolymeren mit Poly(L-lysin)seitenketten sowie Alkyl- oder Polyethylenglykolsubstituenten. Die Synthese wurde durch die Suzuki-Polykondensation von monodispersen Makromonomeren erreicht. Hierbei fand die Precursor-Synthesestrategie Anwendung. In diesem Ansatz war die ε-Aminofunktion des Lysins mit einer Benzoyloxycarbonylschutzgruppe geschützt. Der Aufbau der benötigten monodispersen Makromonomere erfolgte durch die Kupplung von Poly(L-lysin)ketten an den Carbazolbaustein mittels eines aktivierten Esters. Eine Besonderheit der hergestellten Kammpolymere lag in den konformativen Eigenschaften seiner einzelnen Komponenten. Dabei konnte die Konformation der Poly(L-lysin)seitenketten infolge ihres Polyelektrolyt- und Peptidcharakters gezielt mit Hilfe des pH-Wertes und der Ionenstärke variiert werden, wohingegen das konjugierte Rückgrat seine steife Konformation beibehielt. Infolge des Polyelektrolytcharakters zeigte sich zudem, dass die Polymere in sauren und neutralen, wässrigen Lösungen zu großen Teilen in Form von Domänenstrukturen auftraten, während im Basischen eine sofortige Aggregation eintrat. Ein weiteres Merkmal der vorgestellten Polyelektrolytkammpolymere war ihr amphiphiler Charakter. Diese Amphiphilie der in dieser Arbeit vorgestellten Polyelektrolytkammpolymere beeinflusste dabei maßgeblich ihre unstrukturierte Anordnung in Lösung, in der festen Phase sowie an Oberflächen.

Sulfur-containing polymers for surface attachment

Different concepts for the synthesis of sulfur-containing polymers as well as their adsorption onto gold surfaces were studied. The present work is divided into three parts. The main part focuses on the synthesis of poly(1,2-alkylene sulfides) (“polysulfides”) with complex architectures on the basis of polyether-based macroinitiators by the anionic ring-opening polymerization of ethylene sulfide and propylene sulfide. This synthetic tool kit allowed the synthesis of star-shaped, brush-like, comb-like and pom-pom-like polysulfides, the latter two with an additional poly(ethylene glycol) chain. Additionally, the number of polysulfide arms as well as the monomer composition could be varied over a wide range to obtain copolymers with multiple thioether functionalities.rnThe second section deals with the synthesis of a novel lipoic acid-based initiator for ring-opening polymerizations for lactones and epoxides. A straightforward approach was selected to accomplish the ability to obtain tailored polymers with a common used disulfide-anchoring group, without the drawbacks of post-polymerization functionalization. rnIn the third part, a new class of block-copolymers consisting of polysulfides and polyesters were investigated. For the first time this approach enabled the use of hydroxyl-terminated poly(propylene sulfide) as macroinitiator for the synthesis of a second block.rnThe adsorption efficiency of those different polymer classes onto gold nanoparticles as well as gold rnsupports was studied via different methods.rn

Thermal diffusivity of polymers by modified angstrom method

The nature of the molecular structure of plastics makes the properties of such materials markedly temperature dependent. In addition, the continuous increase in the utilization of polymeric materials in many specific applications has demanded knowledge of their physical properties, both during their processing as raw material, as well as over the working temperature range of the final polymer product. Thermal conductivity, thermal diffusivity and specific heat, namely the thermal properties, are the three most important physical properties of a material that are needed for heat transfer calculations. Recently, among several different methods for the determination of the thermal diffusivity and thermal conductivity, transient techniques have become the preferable way for measuring thermal properties of materials. In this work, a very simple and low cost variation of the well known Angstrom method is employed in the experimental determination of the thermal diffusivity of some selected polymers. Cylindrical shaped samples 3 cm diameter and 7 cm high were prepared by cutting from long cylindrical commercial bars. The reproducibility is very good, and the results obtained were checked against results obtained by the hot wire technique, laser flash technique, and when possible, they were also compared with data found in the literature. Thermal conductivity may be then derived from the thermal diffusivity with the knowledge of the bulk density and the specific heat, easily obtained by differential scanning calorimetry. (C) 2009 Elsevier Ltd. All rights reserved.

The ultrastructure of Amylovorax dehorityi comb. nov and erection of the Amylovoracidae fam. nov (Ciliophora : Trichostomatia)

The ultrastructural features of the holotrichous ciliates inhabiting macropodid maruspials were investigated to resolve their morphological similarity to other trichostome ciliates with observed differences in their small subunit rRNA gene sequences. The ultrastructure of Amylovorax dehorityi nov. comb. (formerly Dasytricha dehorityi) was determined by transmission electron microscopy. The somatic kineties are composed of monokinetids whose microtubules show a typical litostome pattern. The somatic cortex is composed of ridges which separate kinety rows, granular ectoplasm and a basal layer of hydrogenosomes lining the tela corticalis. The vestibulum is an invagination of the pellicle lined down one side with kineties (invaginated extensions of the somatic kineties); transverse tubules line the surface of the vestibulum and small nematodesmata surround it forming a cone-like network of struts. Cytoplasmic organelles include hydrogenosomes, irregularly shaped contractile vacuoles surrounded by a sparse spongioplasm, food vacuoles containing bacteria and large numbers of starch granules. This set of characteristics differs sufficiently from those of isotrichids and members of the genus Dasytricha to justify the erection of a new genus (Amylovorax) and a new family (Amylovoracidae). Dasytricha dehorityi, D. dogieli and D. mundayi are reassigned to the new genus Amylovorax and a new species A. quokka is erected. While the gross morphological similarities between Amylovorax and Dasytricha may be explained by convergent evolution, ultrastructural features indicate that these two genera have probably diverged independently from haptorian ancestors by successive reduction of the cortical and vestibular support structures.

Cooperative effects in the detection of a nitroaliphatic liquid explosive and na explosive taggant in the vapor phase by calix[4]arene-based carbazole-containing conjugated polymers

Two fluorescent molecular receptor based conjugated polymers were used in the detection of a nitroaliphatic liquid explosive (nitromethane) and an explosive taggant (2,3-dimethyl-2,3-dinitrobutane) in the vapor phase. Results have shown that thin films of both polymers display remarkably high sensitivity and selectivity toward these analytes. Very fast, reproducible, and reversible responses were found. The unique behavior of these supramolecular host systems is ascribed to cooperativity effects developed between the calix[4] arene hosts and the phenylene ethynylene-carbazolylene main chains. The calix[4]-arene hosts create a plethora of host-guest binding sites along the polymer backbone, either in their bowl-shaped cavities or between the outer walls of the cavity, to direct guests to the area of the transduction centers (main chain) at which favorable photoinduced electron transfer to the guest molecules occurs and leads to the observed fluorescence quenching. The high tridimensional porous nature of the polymers imparted by the bis-calixarene moieties concomitantly allows fast diffusion of guest molecules into the polymer thin films.

Preparation, characterization, and rheological properties of star-shaped poly(ethylene glycol) with a cholane core and study of its effect on red blood cell aggregation

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Template-assisted patterning of functional polymers

In this thesis, anodic aluminum oxide (AAO) membranes, which provide well-aligned uniform mesoscopic pores with adjustable pore parameters, were fabricated and successfully utilized as templates for the fabrication of functional organic nanowires, nanorods and the respective well-ordered arrays. The template-assisted patterning technique was successfully applied for the realization of different objectives:rnHigh-density and well-ordered arrays of hole-conducting nanorods composed of cross-linked triphenylamine (TPA) and tetraphenylbenzidine (TPD) derivatives on conductive substrates like ITO/glass have been successfully fabricated. By applying a freeze-drying technique to remove the aqueous medium after the wet-chemical etching of the template, aggregation and collapsing of the rods was prevented and macroscopic areas of perfectly freestanding nanorods were feasible. Based on the hole-conducting nanorod arrays and their subsequent embedding into an electron-conducting polymer matrix via spin-coating, a novel routine concept for the fabrication of well-ordered all-organic bulk heterojunction for organic photovoltaic applications was successfully demonstrated. The increased donor/acceptor interface of the fabricated devices resulted in a remarkable increase of the photoluminescence quenching compared to a planar bilayer morphology. Further, the fundamental working principle of the templating approach for the solution-based all-organic photovoltaic device was demonstrated for the first time.rnFurthermore, in order to broaden the applicability of patterned surfaces, which are feasible via the template-based patterning of functional materials, AAO with hierarchically branched pores were fabricated and utilized as templates. By pursuing the common templating process hierarchically polymeric replicas, which show remarkable similarities with interesting biostructures, like the surface of the lotus leaf and the feet of a gecko, were successfully prepared.rnIn contrast to the direct infiltration of organic functional materials, a novel route for the fabrication of functional nanowires via post-modification of reactive nanowires was established. Therefore, reactive nanowires based on cross-linked pentafluorophenylesters were fabricated by utilizing AAO templates. The post-modification with fluorescent dyes was demonstrated. Furthermore, reactive wires were converted into well-dispersed poly(N-isopropylacrylamide) (PNIPAM) hydrogels, which exhibit a thermal-responsive reversible phase transition. The reversible thermal-responsible swelling of the PNIPAM nanowires exhibited a more than 50 % extended length than in the collapsed PNIPAM state. rnLast but not least, the shape-anisotropic pores of AAO were utilized to uniformly align the mesogens of a nematic liquid crystalline elastomer. Liquid crystalline nanowires with a narrow size distribution and uniform orientation of the liquid crystalline material were fabricated. It was shown that during the transition from the nematic to the isotropic phase the rod’s length shortened by roughly 40 percent. As such these liquid crystalline elastomeric nanowires may find application, as wire-shaped nanoactuators in various fields of research, like lab-on-chip systems, micro fluidics and biomimetics.rn

Eliminating Adhesion Errors in Nanoindentation of Compliant Polymers and Hydrogels

Nanoindentation is a valuable tool for characterization of biomaterials due to its ability to measure local properties in heterogeneous, small or irregularly shaped samples. However, applying nanoindentation to compliant, hydrated biomaterials leads to many challenges including adhesion between the nanoindenter tip and the sample. Although adhesion leads to overestimation of the modulus of compliant samples when analyzing nanoindentation data using traditional analysis techniques, most studies of biomaterials have ignored its effects. This paper demonstrates two methods for managing adhesion in nanoindentation analysis, the nano-JKR force curve method and the surfactant method, through application to two biomedically-relevant compliant materials, poly(dimethyl siloxane) (PDMS) elastomers and poly(ethylene glycol) (PEG) hydrogels. The nano-JKR force curve method accounts for adhesion during data analysis using equations based on the Johnson-Kendall-Roberts (JKR) adhesion model, while the surfactant method eliminates adhesion during data collection, allowing data analysis using traditional techniques. In this study, indents performed in air or water resulted in adhesion between the tip and the sample, while testing the same materials submerged in Optifree Express() contact lens solution eliminated tip-sample adhesion in most samples. Modulus values from the two methods were within 7% of each other, despite different hydration conditions and evidence of adhesion. Using surfactant also did not significantly alter the properties of the tested material, allowed accurate modulus measurements using commercial software, and facilitated nanoindentation testing in fluids. This technique shows promise for more accurate and faster determination of modulus values from nanoindentation of compliant, hydrated biological samples. Copyright 2013 Elsevier Ltd. All rights reserved.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.