Hydraulic fracturing is a well-established technology of generating highly conductive flow path inside the rock by injecting massive amount of fracturing fluid and proppant with sufficient pressure to break the formation apart. But as the concern for environment and health effects of hydraulic fracturing becomes intense, many efforts are made to replace the conventional fracturing fluid with more environment-friendly materials. The degradable biopolymer is one of the novel materials that is injected in the form of solid pellets containing proppant, degrades in the presence of water to form a viscous gel fluid, leaving no gel residue or harmful material. This work develops a methodology and computer program to determine the best candidate wells for the field test of degradable biopolymer as fracturing fluid. The unique properties of degradable biopolymer is captured in the selection of decision criteria such as bottomhole temperature and treatment volume as well as traditional hydraulic fracturing candidate well selection criteria such as formation permeability, productivity index.

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Therapeutic angiogenesis is a promising technique to treat ischemia by creating new blood vessels. The aim of this thesis was to develop and characterize biodegradable elastomers for localized delivery of growth factors and to investigate the ability of released growth factors to induce angiogenesis. An osmotic delivery mechanism using photo-cross-linked elastomers based on trimethylene carbonate (TMC) was used to deliver vascular endothelial growth factor (VEGF165) and hepatocyte growth factor (HGF) alone or in combination at two different doses. It was hypothesized that elastomers made of TMC can provide an effective osmotic release using trehalose as a main osmotigen and that the use of TMC would eliminate the microenvironmental pH drop implicated in denaturing acid sensitive growth factors. To obtain an insight into the degrading zone in which growth factors will be released, the in vivo degradation mechanism and tissue response were investigated. The in vivo degradation of D,L-lactide/ε-caprolactone (DLLACL) elastomers that degrade by hydrolysis was investigated for comparison. Cross-link-density played a significant role in the degradation pattern of DLLACL elastomers. TMC and TMCCL elastomers degraded by surface erosion and oxidation played a significant role in their in vivo degradation. To obtain an efficient release, the mechanical properties of TMC elastomers were tailored by copolymerizing TMC with CL and DLLA and/or by controlling the cross-link density. The delivery device was able to provide a sustained release of growth factors for longer than two weeks with no initial burst. Cell based bioactivity assays indicated that released growth factors were highly bioactive over the entire release period. Microenvironmental pH studies using FITC-BSA indicated no significant drop in pH in TMC elastomers that contained small amounts of DLLA. Using 125I-VEGF165, it was found that the osmotic delivery can provide a direct in vivo-in vitro release correlation. Released growth factors were able to induce angiogenesis in rats when tested by subcutaneous implantation. Angiogenesis was dose dependent for both VEGF165 and HGF. Combined release of VEGF and HGF achieved the best results. The formed blood vessels were stable during the active release period, and they were normal looking and connected to the surrounding vasculature. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-09-03 14:54:28.709

Thesis advisor: Jeffery A. Byers / This dissertation discusses the development of a family of iron complexes and their role in the synthesis of degradable polymers. Chapter one will introduce the different areas of redox-switchable polymerization. In chapter two the synthesis of block copolymers containing a polyester and polyether block is presented. The application redox-switchable polymerization to form a copolymer with two fundamentally distinct backbone functionalities and their characterization is discussed. In chapter three the synthesis of a degradable cross-linked polymer through a novel redox-triggered cross linking event is summarized. In chapter four, a detailed mechanistic study of iron-complex catalyzed epoxide polymerization is examined and a unique mechanistic scheme is proposed. Lastly, in chapter five the synthesis and characterization of a formally iron(I) complex is presented. This complex shows remarkable catalytic activity towards ring-opening polymerization. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The functionalization of renewable and abundant carbon dioxide as a building block for industrial polymer production leads to safer designs in manufacturing of materials, decreases the dependence of fossil fuel feedstocks, and diminishes plastic waste generation due to engineered biodegradability. Through judicious catalyst design, the copolymerization of carbon dioxide and oxiranyl small molecules has not only opened new synthetic routes towards the manufacturing of novel polycarbonate architectures, but in addition, allows for the mass production of commodity plastics via raw materials derived entirely from biomass. This environmentally friendly methodology pioneered by Shohei Inoue not only accommodates polymer product with an eco-design, but in tandem serves as a means of carbon capture, mitigating the effects of global climate change. With a global market value anticipated to reach 2 billion dollars by 2026, polyacrylate resins are ubiquitous in the paint, automotive, and adhesive industries. However, the production of these non-degradable polymers compounds the rising concern of plastic pollution in the environment. Herein, the design and synthesis of polyacrylate mimetics bearing a degradable carbonate moiety in the backbone is described. The synthetic methodology utilizes a green pathway through the use of carbon dioxide as the C1 source. The thermal, chemical, and rheological properties of the materials are evaluated and compared to commercial acrylates and adhesives. Additional modification of the materials through terpolyermization is conducted, and their ability to perform as smart adhesive surfaces as well as clinical use in lung resection surgery is covered. / 2020-11-12T00:00:00Z

Thesis advisor: Jeffery A. Byers / This dissertation covers the development of redox-switchable ring-opening polymerizations for the synthesis of copolymers of underutilized monomers. In Chapter one, the progress in the development of switchable methods for ring-opening polymerization and ring-opening copolymerizations. Chapter two describes a method for the redox-switchable copolymerization of L-lactide, propylene oxide and carbon dioxide. The benefits of this method are demonstrated through the facile synthesis of blocky and statistical copolymers of the three monomers. In Chapter three, a method for the redox-switchable polymerization of N-carboxyanhydrides is presented. A mechanistic analysis and copolymerizations of N-carboxyanhydrides and either lactones or epoxides follow the initial findings. Chapter four further expands the uses of N-carboxyanhydride redox-switchable polymerizations by immobilizing the catalysts onto semiconductor surfaces for the synthesis of surface bound polyamides. / Thesis (PhD) — Boston College, 2021. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Lactating dairy cows convert 25 to 35% of intake N to milk N, and a part of the remaining N ends up in the environment, causing pollution. Dairy cows absorb amino acids available in the small intestine supplied mainly by digestion of microbial protein and ruminally undegraded feed protein (RUP). Ruminally degradable feed protein (RDP) is the major supplier of N for microbial protein synthesis. Most of the excess RDP will be degraded to ammonia and eliminated as urea in urine. Thus, avoiding excess RDP in dairy cattle diets is important in reducing environmental N pollution. The objectives of the work in this dissertation were to test the hypothesis that lactating dairy cows, when fed varying dietary RDP, can maintain feed intake, milk and milk protein yield, ruminal metabolism, passage of nutrients out of the rumen, and N excretion. The first study investigated the effects of decreasing RDP in lactating dairy cow diets on feed intake, milk production and apparent N efficiency. Forty mid-lactation cows (36 Holstein and 4 Jersey × Holstein cross-breds) were fed a diet containing 11.3% of diet dry matter (DM) as RDP for the first 28 d (covariate period). From d 29 to 47 (treatment period) cows were randomly assigned to 1 of 4 diets containing constant RUP (7.1% of DM) but 11.3, 10.1, 8.8, or 7.6% of DM as RDP. Reducing RDP in diets linearly decreased DM intake and tended to decrease milk yield. Milk protein, fat and lactose contents, milk protein yield, body weight, and plasma essential amino acids were unaffected by reduced dietary RDP. However, milk urea-N concentration and milk fat yield decreased linearly with reduced dietary RDP. The apparent efficiency of N utilization for milk N production increased linearly as dietary RDP was reduced. As RDP declined in diets, linear reductions in DM intake and milk production suggested that these cannot be maintained below NRC recommendations of RDP for cows in this study. The aim of the second study was to test the hypothesis that decreasing dietary RDP in lactating dairy cow diets can maintain ruminal metabolism and flow of nutrients out of the rumen and reduce nitrogen excretion. This study was designed as a replicated Latin square with 4 periods of 21 d each. Four treatment diets containing decreasing RDP and constant RUP similar to the first study were used. Three ruminally and duodenally cannulated and 4 ruminally cannulated lactating Holstein cows were randomly assigned to one of the four dietary treatments. A double marker system with Co-EDTA and Yb-labeled forage as markers was used to determine ruminal outflows of nutrients from omasal samples and nutrients reaching the intestine from duodenal samples. Ruminal microbial protein flow was observed using ¹⁵N as an external microbial marker. Feed intake, milk yield, milk composition, and urine and feces output were determined in the last week of each period. Ruminal fluid samples were taken 2 and 4 h after feeding to determine ruminal NH₃-N and volatile fatty acid concentrations. Outflows of nutrients from the rumen were determined by analyzing omasal samples collected over a 24 h feeding cycle in the last week of each period. Reducing dietary RDP decreased protein intakes while DM and fiber intakes were unaffected. Ruminal NH₃-N concentrations linearly declined and peptides and amino acids were unaffected with reduced dietary RDP. A trend for a linear decline in ruminal outflows of microbial N and total N was observed with decreasing dietary RDP. Ruminal volatile fatty acids concentrations were unaltered by feeding treatment diets. Ruminal outflows of DM and acid detergent and neutral detergent fibers were unaffected by treatments. Treatment diets did not have any effect on milk yield and milk composition. However, milk urea-N and milk fat yield decreased linearly with decreasing dietary RDP. Reducing dietary RDP did not affect milk and milk protein yields but did result in greater body protein mobilization. Fecal N output was unaffected however, urine volume and urine N output decreased linearly suggesting reduced environmental N pollution. There was a trend for a linear decrease in total body N balance, but no significant effects on calculated ruminal N balance as dietary RDP decreased. Linear reductions in microbial N leaving the rumen were due to decreased ruminal NH₃-N as peptides plus amino acids and energy supply were unaffected. The linear reduction in milk production and microbial N flow in the first and second studies, respectively, did not support our hypothesis that lactating dairy cows can be fed dietary RDP below current NRC (2001) recommendations without affecting animal performance. The need to raise 15% more cows to alleviate the loss in production may nullify the advantage in reduced N output into the environment by cows fed lower dietary RDP. / Ph. D.

Yes / Biomaterials capable of precisely controlling the delivery of agrochemicals/biologics/drugs/fragrances have significant markets in the agriscience/healthcare industries. Here, we report the development of degradable electroactive polymers and their application for the controlled delivery of a clinically relevant drug (the anti-inflammatory dexamethasone phosphate, DMP). Electroactive copolymers composed of blocks of polycaprolactone (PCL) and naturally occurring electroactive pyrrole oligomers (e.g., bilirubin, biliverdin, and hemin) were prepared and solution-processed to produce films (optionally doped with DMP). A combination of in silico/in vitro/in vivo studies demonstrated the cytocompatibility of the polymers. The release of DMP in response to the application of an electrical stimulus was observed to be enhanced by ca. 10-30% relative to the passive release from nonstimulated samples in vitro. Such stimuli-responsive biomaterials have the potential for integration devices capable of delivering a variety of molecules for technical/medical applications. / This research was funded by a variety of sources, and the authors acknowledge the UK Engineering and Physical Sciences Research Council (EPSRC) National Productivity Investment Fund (NPIF) for a PhD Studentship for M.D.A. (Grant references: EP/R512564/1, 2065445), in support of the EPSRC First Grant for J.G.H. (Grant reference: EP/ R003823/1); the UK Royal Society for support of J.G.H. (Grant reference: RG160449); and the UK Royal Society and CONICET (Argentina) for supporting M.D.A., S.M., M.F.D., and J.G.H. (Grant Reference: A103355).

The commercial field of radical polymerized polymers, such as polyvinyl alcohol, is very broad partly because they are easy to polymerize and cheap. One aspect that could improve their commercial range is to enhance their degradation rate. As the environmental aspect of polymers grows bigger an enhancement of biological degradation is a great improvement. This thesis deals with the prospect of polymerizing polyvinyl alcohol with degradable linkages in the main chain. In order to achieve the aim the monomer 2-methylene-1,3-dioxepane is successfully synthesized and characterized. The synthesis is followed by copolymerization of 2-methylene-1,3-dioxepane with vinylacetate at the feed compositions; 30/70, 50/50, 70/30 mol% respectively. The copolymerization was successful and reached over 90% conversion at the reaction time 3-4 hours with the conditions 60°C and 5mol% 2,2-Azobis(2-methylpropionitrile) as initiator. The copolymerization is followed by hydrolysis with potassium hydroxide or Candida Rugosa Lipase. The results show that chain scission occurs when the polymer is hydrolyzed by potassium hydroxide but not by lipase. There is also a tendency toward hydrolysis of the chain with lipase.