Yes / Antibacterial hydrogels have been intensively studied due to their wide practical potential in wound healing. However, developing an antibacterial hydrogel that is able to integrate with exceptional mechanical properties, cell affinity, and adhesiveness will remain a major challenge. Herein, a novel hydrogel with antibacterial and superior biocompatibility properties was developed using aluminum ions (Al3+) and alginate− dopamine (Alg-DA) chains to cross-link with the copolymer chains of acrylamide and acrylic acid (PAM) via triple dynamic noncovalent interactions, including coordination, electrostatic interaction, and hydrogen bonding. The cationized nanofibrillated cellulose (CATNFC), which was synthesized by the grafting of long-chain quaternary ammonium salts onto nanofibrillated cellulose (NFC), was utilized innovatively in the preparation of antibacterial hydrogels. Meanwhile, alginate-modified dopamine (Alg-DA) was prepared from dopamine (DA) and alginate. Within the hydrogel, the catechol groups of Alg-DA provided a decent fibroblast cell adhesion to the hydrogel. Additionally, the multitype cross-linking structure within the hydrogel rendered the outstanding mechanical properties, self-healing ability, and recycling in pollution-free ways. The antibacterial test in vitro, cell affinity, and wound healing proved that the as-prepared hydrogel was a potential material with all-around performances in both preventing bacterial infection and promoting tissue regeneration during wound healing processes. / This work was supported by the National Natural Science Foundation of China (32070826 and 51861165203), the Chinese Postdoctoral Science Foundation (2019M650239, 2020T130762), the Sichuan Science and Technology Program (2019YJ0125), the State Key Laboratory of Polymer Materials Engineering (sklpme2019-2-19), the Chongqing Research Program of Basic Research and Frontier Technology (cstc2018jcyjAX0807), Chongqing Medical Joint Research Project of Chongqing Science and Technology Committee & Health Agency (2020GDRC017), and the RCUK China-UK Science Bridges Program through the Medical Research Council, and the Fundamental Research Funds for the Central Universities.

No description available.

No description available.

No description available.

No description available.

<p>A series of bismaleimide and bisfuran monomers were synthesized and then combined to produce thermally reversible polymers. Reversibility was demonstrated through multiple heating and cooling cycles, and verified using ¹H NMR spectroscopy. Variation of the spacer chemistry in the monomers was found to profoundly influence the physical properties of the resulting polymers. A tripodal maleimide and furan system was then synthesized, but it was found that the incorporation of cross-linking into the polymer network did not significantly alter the mechanical properties of the resulting polymers.</p> <p>Dilute solutions of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends containing PS- or PMMA-functionalized single-walled carbon nanotubes (SWNT) were spin cast and annealed at 180°C for 12 h. Characterization of the annealed films by scanning Raman spectroscopy confirmed that the migration of the nanotubes in the films could be controlled using the appropriate functionality on the nanotubes, thus the PS-functionalized nanotubes were found to migrate to the PS domains, while the PMMA-functionalized nanotubes migrated to the PMMA domains.</p> <p>SWNTs were then functionalized using linear reversible polymers, resulting in significant solubilization of the nanotubes. Heating of this solution resulted in the collapse of the DA polymer, and precipitation of the dissolved nanotubes, illustrating the reversible nature of the polymers, and their influence on carbon nanotube solubilization.</p> / Doctor of Philosophy (PhD)

Yes / Shape memory polymer (SMP) products have been developed for application as crack closure de-vices in concrete. They have been made from PET in the form of both fibres and hollow tubes. Here, manufacturing methods using die-drawing and mandrel-drawing to induce shape memory are reported. The fibre-based devices are incorporated into concrete and, upon triggering, exert shrinkage restraint forces that close cracks in the concrete. The evolution of shrinkage restraint force in the fibres as manufactured was measured as a function of temperature, showing stresses in excess of 35 MPa. Tendons consisting of fibre bundles are incorporated into concreate beams subjected to controlled cracking. When activated, the tendons reduce the crack widths by 80%. The same fibres are used to produce another class of device known as knotted fibres, which have knotted ends that act as anchor points when they incorporated directly into concrete. Upon acti-vation within the cracked concrete, these devices are shown to completely close cracks. The tubes are used to enclose and restrain prestressed Kevlar fibres. When the tubes are triggered, they shrink and release the prestress force in the Kevlar, which is transferred to the surrounding con-crete in the form of a compressive force, thereby closing cracks. The Kevlar fibres also provide substantial reinforcement after activation. The devices are shown to be able to partially and fully close cracks that have been opened to 0.3 mm and achieve post-activation flexural strengths com-parable to those of conventional reinforced and prestressed structural elements. Finally, a pre-liminary life cycle assessment study was used to assess the carbon footprint a nominal unit of concrete made with SMPs fibres compared to conventional concrete. / This research was funded by the UKRI-EPSRC Resilient Materials 4 Life (RM4L), grant number EP/P02081X/1 and the support of ARUP via the UKIMEA research funding.

Polysaccharides are known as among the most abundant natural polymers on the Earth. As this class of material is usually renewable, biodegradable, biocompatible in many contexts and environmentally friendly, it is of great interest to use these benign polymers to design and prepare materials, especially for applications with green and biomedical purposes. In this dissertation we will discuss novel pathways to two different types of polysaccharide-based materials: block copolymers and hydrogels. Block copolymers are composed of two or even more covalent bonded polymer blocks that have quite distinct properties. Synthesis of polysaccharide-based block copolymers is an attractive and challenging research topic, opening up promising application potential and requiring advances in polysaccharide regio- and chemoselectivity. Herein, we report two independent approaches to prepare these interesting and potential useful materials. In one approach, trimethyl cellulose was modified regiospecifically at the reducing end anomeric carbon to create an ω-unsaturated alkyl acetal by solvolysis with an ω-unsaturated alcohol. Then, olefin cross-metathesis, a known versatile and mild tool for polysaccharide chemical modification, was used to couple the trimethyl cellulose block with various polymer blocks containing acrylates. To demonstrate the method, trimethyl cellulose-b-poly(tetrahydrofuran), cellulose-b-poly(ethylene glycol), and cellulose-b-poly(lactic acid) were synthesized by this coupling strategy. In another approach, we introduced a simple and novel method to prepare dextran-based block copolymers. In this strategy, N-bromosuccinimide (NBS)/triphenyl phosphine (PPh3) was chosen to regioselectively brominate the only primary alcohol of linear unbranched dextran. The resulting dextran, bearing a terminal C-6 bromide, was coupled with several amine terminated polymers via SN2 substitution to obtain block copolymers, including dextran-b-polystyrene, dextran-b-poly(N-isopropylacrylamide) and dextran-b-poly(ethylene glycol). Dextran-b-poly(N-isopropylacrylamide) exhibits thermally-induced micellization as revealed by dynamic light scattering, forming micelles with 155 nm diameter at 40 °C. Dextran-b-polystyrene film was analyzed by small angle X-ray scattering, suggesting the existence of microphase separation. This dissertation also introduces a novel, simple and effective strategy to prepare polysaccharide-based hydrogels. Hydrogels are typically crosslinked hydrophilic polymers that have high water affinity and no longer dissolve in water. Polysaccharide-based hydrogels are of great interest to for biomedical applications due to their benefits including biocompatibility, polyfunctionality, and biodegradability. Recently the Edgar group has discovered that chemoselective oxidation of oligo(hydroxypropyl)-substituted polysaccharides impairs ketone groups at the termini of the oligo(hydroxypropyl) side chains. These ketones can condense with amines to form imines, leading hydrogel formation., Based on this concept, we prepared oxidized hydroxypropyl polysaccharide/chitosan hydrogels. This class of all-polysaccharide hydrogels exhibits a series of interesting properties such as tunable moduli (300 Pa to 13 kPa), self-healing, injectability, and high swelling ratios. To further explore imine-crosslinked hydrogels, we designed thermally responsive hydrogels by using a Jeffamine, a polyethylene oxide-b-polypropylene oxide-b-polyethylene oxide triblock copolymer with two terminal amines. As the Jeffamine has a lower critical solution temperature, oxidized hydroxypropyl cellulose/Jeffamine hydrogels display moduli that are tunable by controlling the temperature. / Doctor of Philosophy / Polysaccharide are natural polymers that are among the most abundant polymers on Earth. It is greatly in society's interest to extend the scope of their applications, due to the benign nature of polysaccharides. This dissertation mainly focuses on two polysaccharides: cellulose and dextran. Cellulose is a long linear polymer of linked glucose molecules. As cellulose is sustainable, biodegradable, non-toxic, affordable and accessable for chemical modification, it is a suitable polymer for biomedical and environmentally friendly application. Dextran is also a polymer chain made up only of glucose but connected with each other differently from cellulose by, bacterial fermentation, and it may be lightly branched. It is biocompatible in many situations and is biodegradable both in vivo and in the environment, thus it has been investigated for drug delivery and many other medical applications. Using these two polysaccharides, we designed and prepared two quite different classes of materials: block copolymers and hydrogels. Block copolymers consist of two or more different types of polymer blocks connected by strong covalent bonds. As block copolymerization enables construction of a single polymer comprising segments with distinct properties, it is appealing to synthesize a block copolymer which preserves the properties of natural polymers coupled to very different polymers, such as polyolefins (e.g. the polyethylene that is used for milk bottles). In order to prepare polysaccharide-based block copolymers, we developed two different synthetic routes to end-functionalize methyl cellulose and dextran , and these resulting products were used to prepare two independent series of polysaccharide-based block copolymers via combination (in other words, sticking the polysaccharide and, e.g., the polyethylene together end to end). This study confirms the feasibility of this method to make methyl cellulose-based and dextran-based block copolymers. We expect these classes of materials will have significant potential in applications including drug delivery, as compatibilizers for polymer blends of materials that otherwise cannot be mixed (polyolefin/polysaccharide), membrane and adhesive. Hydrogels are crosslinked polymer networks with high water affinity, and they have been heavily investigated in the field of tissue engineering, drug delivery, agriculture and 3D printing. Polysaccharide-based hydrogels are attractive materials for these applications because they are biocompatible, biodegradable and have polyfunctionality. However, any use of toxic small molecules to crosslink the hydrogels diminishes their usefulness in biomedical applications. In this work, we demonstrate a simple, green and efficient method for preparation of all-polysaccharide-based hydrogels. The starting materials, oxidized hydroxypropylpolysaccharide, were simply prepared by using household bleach (NaOCl) as the oxidation reagent. We discovered that oxidized hydroxypropyl polysaccharides readily form hydrogels with hydrophilic amine-containing polymers like chitosan (a natural polysaccharide that comes from shells of crustaceans like crabs or shrimp) and Jeffamines, affording interesting properties including tunable stiffness, self-healing, injectability, and responsiveness to acidity and temperature. We expect that this new class of hydrogel will be very promising for biomedical-related applications.

A self-sensing and self-healing bolted joint has been developed. This concept encompasses the areas of health monitoring, joint dynamics and smart materials. In order to detect looseness in a joint the impedance health monitoring method is used. A new method of making impedance measurements for health monitoring that greatly reduces the equipment cost and equipment size was developed. This facilitates implementation of the impedance technique in real-life field applications. Several proof of concept experiments are presented and compared to the traditional method of making impedance measurements. Investigations of bolted joint dynamics were conducted. A literature review of bolted joints and their diagnostics is presented. The application of the transfer impedance method is compared to standard modal tests on various bolt tensions. An investigation of damping in bolted joints was also made comparing a bolted and monolithic beam. Practical issues in adaptive bolted joints are investigated. This includes issues on activating/heating SMA actuators, connecting the actuators to the power source, size selection of SMA actuators and insulations. These issues are examined both experimentally and theoretically. / Master of Science

Poly(ethylene-co-methacrylic acid) (EMAA) ionomer polymers carry great potential for use in a wide variety of unique applications due to their property of “self-healing” following projectile impact. Following puncture, certain films based on these materials are observed to “heal”, with the penetration opening recovering to an air-tight condition. Specifically, four polymers of this class were examined, including DuPont™ Surlyn® 8920, Surlyn® 8940, Nucrel® 925, and Nucrel® 960. Though these differ in their amount of ionic content, all expressed a certain degree of self-healing. Thin films were prepared by a compression molding process and punctured at temperatures ranging from room up to that of the melt using a pellet gun. Samples were then assessed for self-healing. A quantitative post-puncture burst-test method examined the strength or quality of the healed site in the four examples. A comparison of this data provided an understanding of the importance of ionic content and the mechanism of puncture healing. Additional damage modes were also examined to determine other cases where healing occurs and the requirements necessary to elicit the healing response. In addition, interesting composite materials consisting of carbon nanotube filled ionomers were fabricated by a melt-mixing process which produced potentially self-healing composites with superior mechanical properties. By comparing peel testing, projectile testing, the quantitative healed strength, and other characteristics, it was determined that healing is not a function of the ionic content of the materials involved. Further, healing was determined to occur due to a synergy of thermomechanical properties facilitated by the addition of the methacrylic acid groups to the polymer backbone. / Master of Science