No description available.

During embryo development, extracellular matrix (ECM) remodeling by matrix metalloproteinases (MMPs) and promotes downstream cell specifications. Pluripotent stem cell (PSC) aggregates can recapitulate various aspects of embryogenesis in vitro, and incorporation of biomaterial microparticles also provides an ideal platform to study cell-biomaterial interactions. Stem cell interactions with ECM-based biomaterials can impact tissue remodeling and differentiation propensity via modulation of MMP activity. This work investigated the MMP activity and subsequent mesenchymal differentiation of embryonic stem cell (ESC) aggregates with incorporated gelatin methacrylate (GMA) MPs with either low (20%) or high (90%) cross-linking densities, corresponding to faster or slower degradation rate, respectively. GMA MP incorporation increased total MMP and MMP-2 levels within 3D ESC aggregates in a substrate-dependent manner. GMA MP-incorporated aggregates also expressed higher levels of epithelial-to-mesenchymal transition markers and displayed enhanced mesenchymal morphogenesis than aggregates without MPs, and the MP-mediated effects were completely abrogated with MMP inhibitor treatment. This work predicts that control of proteolytic responses via introducing ECM-based MPs may offer a novel avenue to engineer the ECM microenvironment to modulate stem cell differentiation.

No description available.

In this study, we develop a classification system for describing polymethyl methacrylate (PMMA) spread in vertebral bodies after kyphoplasty or vertebroplasty for vertebral compression fractures (VCFs) and for assessing whether PMMA spread varies between operators, VCF etiology, or vertebral level. Intraoperative fluoroscopic images of 198 vertebral levels were reviewed in 137 patients (women, 84; men, 53; mean age, 75.8 +/- 12.5; and those with a diagnosis of osteoporosis, 63%) treated with kyphoplasty between January 01, 2015 and May 31, 2015 at a single center to create a 5-class descriptive system. PMMA spread patterns in the same images were then classified by 2 board-certified radiologists, and a third board-certified radiologist resolved conflicts. A total of 2 primary PMMA spread patterns were identified, namely, acinar and globular, with subtypes of localized acinar, diffuse globular, and mixed, to describe an equal combination of patterns. Interrater reliability using the system was moderate (kappa = 0.47). After resolving conflicts, the most common spread class was globular (n = 63), followed by mixed (n = 58), diffuse globular (n = 30), acinar (n = 27), and localized acinar (n = 20). The spread class after treatment by the 2 most frequent operators differed significantly (n(1) = 63, n(2) = 70; P <.0001). There was no difference in the spread class between VCF etiologies or vertebral levels. PMMA spread may, therefore, be a modifiable parameter that affects kyphoplasty and vertebroplasty efficacy and adverse events.

Luminescent molecules and polymers are active component in light-emitting diodes; however, the aggregation and excimer formation in concentrated solution or in the solid film states had limited their applications. Therefore, this study used poly(methyl methacrylate) (PMMA) as separator to prevent the formations of aggregate and excimer and to enhance quantum efficiency. Basically, two systems are involved: (1) Inorganic phosphorescent irdium complex PMMA was doped with inorganic iridium complex IrQB by using THF as solvent. IrQB/PMMA films prepared from dilute solutions exhibit two emissions centered at 560 and 640 nm, respectively; in contrast, only 640-nm emission was observed for films from concentrated solutions. Experimentally, these two bands showed variations on the emission intensity with increasing temperature. Aggregation of IrQB is suggested to be responsible for the 560-nm emission. Chain conformation of PMMA in the solution state strongly affects the incorporated IrQBs and their emission properties. (2) Polybenzoxazines Polybenzoxazines with the built-in fluorenscent fluorine moiety are linear in nature; however, the inherent hydrogen-bond (H-bond) interactions in polybenzoxazines decrease the inter-chain distance and cause the chain aggregation. With the added PMMAs, new H-bonding from the carbonyl groups in PMMA and the hydroxyl groups in polybenzoxazine enhances the mutual miscibility between these two components and decreases the possibility of aggregate formation in polybenzoxazines. Quantum efficiency is therefore promoted by this approach.

A study of the atom transfer radical polymerisation (ATRP) of water-soluble, acidic, monomers was carried out in aqueous media. The ATRP of sodium methacrylate (MAANa) produced polymers with controlled molecular weights and narrow polydispersities (Me/M, - 1.3) at 90°C. This is the first reported example of direct polymerisation of an acidic monomer via ATRP. Previously, such acidic polymers were produced by polymerisation of protected monomers. In this thesis, copper(l) bromide and iron(II) bromide were investigated as ATRP catalysts. Both were found to be effective when solubilised by 2,2'-bipyridine (bipy). Monomer conversions between 75 and 85 % were obtained in the presence of Cu(l)Brlbipy, and conversions as high as 94 % were obtained in the presence of Fe(II)Br2Ibipy. Kinetic studies carried out on the ATRP of MAANa using the CuBrlbipy catalyst and an oligo(ethylene glycol)-based initiator indicated that polymerisation proceeded via first order kinetics with respect to monomer consumption, and that molecular weight increased linearly with conversion. This is as expected for a living polymerisation. At approximately 75 - 85 % conversion, however, premature termination occurred. Both bromine microanalyses and 'n and 13CNMR studies indicated that the halide-capped polymer chain-ends undergo HBr elimination. Low molecular weight « 10,000 g mol") MAANa homopolymers and oligo(ethylene glycol)-sodium methacrylate block copolymers (PEG-b-PMAANa) were examined as possible macro initiators for the ATRP of sodium 4-styrenesulfonate (SSNa), potassium 3- sulfopropyl methacrylate (SPMAK) and sodium allyl sulfonate (SAS). PEG-b-PMAANa was found to initiate the ATRP of SSNa, yielding a polymer with controlled molecular weight and a polydispersity of 1.23. Initiation of the ATRP of SPMAK and SAS was less successful. This was likely due to the loss of functionality of the MAANa-based polymers. Block copolymers were obtained, however, by macroinitiating the aqueous ATRP of MAANa using a monomethoxy-capped oligo(ethylene glycol) methacrylate homopolymer. Successful ATRP of MAANa was also achievable at ambient temperatures in the presence of a co-solvent, 2-(dimethylamino)ethanol, DMAE. DMAE appears to dramatically increase the rate of polymerisation whilst still maintaining control when used in equimolar quantities (relative to the monomer). Polymers with predetermined molecular weights and narrow polydispersities were produced in good yield (up to 86 % conversion) within five minutes at 20°C. The ATRP of other hydrophilic monomers was also investigated, albeit in less detail. These monomers included sodium acrylate, mono-2-(methacryloyloxy)ethyl succinate, 2- hydroxyethyl acrylate, itaconic acid, and 2-acrylamido-2-methyl-propanesulfonic acid. Generally less control was achieved for such syntheses than for the ATRP of MAANa.

No description available.

Reprints of 3 articles published by the author included in back of book / 1v. (various paging) : ill. ; 26 cm / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.1974) from the Dept. of Physical and Inorganic Chemistry, University of Adelaide

Thesis (M.S.)--Ohio University, November, 1985. / Title from PDF t.p.

Thesis (Ph.D. 1974) from the Dept. of Physical and Inorganic Chemistry, University of Adelaide. / Reprints of 3 articles published by the author included in back of book.