Publications

Scientific Reports doi: 10.1038/s41598-023-41947-z

Chem doi: 10.1016/j.chempr.2023.07.020

Journal of Chemical Information and Modeling. doi: 10.1021/acs.jcim.3c00835

AIP Conference Proceedings. doi: 10.1063/5.0145202

Journal of Medical Devices doi: 10.1115/1.4062492

Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy in Chemical Engineering.
DISSERTATION ABSTRACT:
In this dissertation, I developed and investigated gelatin-based microporous injectable hydrogels for the encapsulation of stem cells for multiple applications in cell delivery. Utilizing microgels composed from a mixture of gelatin and modified gelatin, I demonstrated the utility of a dual crosslinking mechanism, which enabled rapid gelation and tissue adhesion with improved cytocompatibility. Mesenchymal stem cells (MSCs) encapsulated in this hydrogel proliferated at a more rapid rate than in a nonporous counterpart, and showed increased immunomodulatory potential. Then, I investigated gelatin microporous hydrogel for the encapsulation of MSCs for bone tissue regeneration. Encapsulated cells more readily differentiated into osteoblasts (i.e. boneforming cells) in the microporous environment observed by morphological changes and quantitative assays. This is believed to be due to enhanced cell spreading and cell-cell communication in the unique 3D environment provided to the cells by the microporous hydrogel. Transcriptomic analysis was performed by mRNA sequencing (RNA-seq) of MSCs encapsulated in the differing 3D microenvironments. Results indicated that the 3D environment influenced the expression of genes that are related to cell adhesions, cell-cell interactions, cytoskeletal organization, and matrix remodeling, in addition to MSC differentiation. Because neuronal development is highly dependent on cell-cell communication, I encapsulated an established neural stem cell line (ReNcell) in gelatin microporous hydrogel to investigate neuronal differentiation in comparison to a nonporous analog. Laminin was chemically conjugated to microgel surfaces, which controlled the organization of encapsulated cells in the hydrogel environment. Cell differentiation was examined by immunofluorescence staining, and JC-1 assay was utilized to examine mitochondrial membrane polarization. The microporous hydrogel xii induced substantially greater cell spreading, morphological changes and cell-cell connections than nonporous hydrogel. The majority of the cells in the microporous hydrogel differentiated into neural lineages, evidenced by immunostaining by MAP2 and GFAP. In summary, this work demonstrates the utility of gelatin microporous injectable hydrogels for applications in in situ cell encapsulation and stem cell delivery for tissue regeneration.

Dissertation submitted to the Department of Chemistry and the University of Wyoming in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry.
DISSERTATION ABSTRACT:
Nanomaterials are a unique class of materials that exhibit unique chemical and physical properties due to their nanoscale dimensions. These properties make nanomaterials well-suited for use in sensing applications, particularly in the development of electrochemical sensors and biosensors. With a wide range of nanoparticle types available, differing in size, shape, and composition, the applications for nanomaterials in electroanalysis are broad and expanding. In particular, well-ordered nanoparticle arrays are attractive platforms for a variety of analytical applications. However, the fabrication of such arrays is generally challenging due to the difficulty of controlling individual nanoparticle nucleation and growth events. This is where Scanning Electrochemical Cell Microscopy (SECCM) comes in. SECCM is a versatile nanofabrication tool that enables the synthesis of individual nanoparticles of controlled size at precisely defined locations on a sample with high spatial resolution (<100 nm). SECCM allows for the fabrication of ordered nanoparticle arrays where individual nucleation and growth events can be detected and controlled, resulting in nanoparticles of controlled size. One application of this technology is developing electrochemical sensors and biosensors, where gold nanoparticles can be modified with biorecognition elements like thiol compounds to detect specific biomolecules. The ability to fabricate well-ordered nanoparticle arrays with controlled size and position using SECCM makes it an ideal tool for developing such sensing devices, providing a powerful and flexible platform for nanofabrication in electrochemical sensing applications.

Macromolecules doi: 10.1021/acs.macromol.2c02378

Chemical Society Reviews doi: 10.1039/D2CS01011A

Korean Journal of Chemical Engineering doi: 10.1007/s11814-022-1293-y

Materials  doi: 10.3390/ma16020572

Journal of the American Chemical Society doi: 10.1021/jacs.2c05510

Computer Methods in Applied Mechanics and Engineering. doi: 10.1016/j.cma.2022.115740

Biofabrication doi: 10.1088/1758-5090/ac94a1

Current Opinion in Electrochemistry, 37, 101164. doi: 10.1016/j.coelec.2022.101164

Book chapter in "Advanced Spectroscopic Methods to Study Biomolecular Structure and Dynamics" doi: 10.1016/B978-0-323-99127-8.00011-8

ASME 2022 17th International Manufacturing Science and Engineering Conference doi: 10.1115/MSEC2022-85595

Renewable and Sustainable Energy Reviews doi: 10.1016/j.rser.2022.112898

Proceedings of the ASEE 2022 Annual Conference. https://peer.asee.org/41107 

Journal of Medical Devices. doi: 10.1115/1.4055249

ACS Applied Materials & Interfaces, 14(37), 42374–42387. doi: 10.1021/acsami.2c07701

International Journal of Computational Materials Science and Engineering  doi: 10.1142/S2047684122500154

Frontiers in Physics doi: 10.3389/fphy.2022.936385
 

Journal of Dynamic Behavior of Materials. doi: 10.1007/s40870-022-00344-9

The Sustainability Institute

UNH Today

Journal of Micro and Nano-Manufacturing doi:10.1115/1.4055474

Proceedings of the IISE Annual Conference & Expo 2022.

Polymer Chemistry doi: 10.1039/D1PY01472B

International Journal of Mechanical Sciences doi: 10.1016/j.ijmecsci.2022.107663

DISSERTATION ABSTRACT:
Total joint devices that can survive more than 20 years in vivo require a bearing surface that can combine toughness, wear resistance, and chemical stability. Ultrahigh molecular weight polyethylene (UHMWPE) remains the gold standard for these bearings, having been utilized as a liner and bearing surface for over five decades. Well-documented material trade-offs lead to failure modes that suggest that hip liners and knee bearing surfaces without optimal processing may be prone to premature failure in the patient. Because the demographic of those receiving implants is changing and smart materials and devices are seeing increased use in medicine, implants may need to be more functional to allow optimization for the patient of the future. The present work explores material trade-offs by attempting to alter the microstructure of UHMWPE through the use of a severe plastic deformation technique known as equal channel angular pressing (ECAP). Work was performed to confirm the validity and reliability of dynamic mechanical analysis (DMA) as a rapid means to indicate and assess changes to the microstructure of UHMWPE in the form of entanglement density and chain interactions. ECAP was applied to both neat and conductive composites of UHMWPE in order to understand the microstructural and mechanical changes due to shearing. Two grades of UHMWPE were used to understand the impact of MW, a variety of temperatures were employed to better optimize shear strain, and consolidation and extrusion hydrostatic pressures were altered to determine if chain mobility and consolidation were hindered under large compressive forces. Preliminary modeling of the different thermal gradients that ECAP and compression molded (CM) controls are exposed to was carried out to aid in and inform future experiments. While ECAP did not reveal changes to the microstructure of neat materials as compared to compression molded (CM) controls, work-to-failure was decreased which is hypothesized to be due to residual stresses. Carbon composites, on the other hand, were shown to have increased work-to-failure after shearing which was coincident with a decline in conductivity as compared to CM controls.

Submitted to the University of New Hampshire In Partial fulfillment of The Requirements for the Degree of Doctor of Philosophy in Chemistry.
DISSERTATION ABSTRACT:
Certain organisms living in cold regions have adapted different strategies to survive in harshly cold temperatures. Some of them use freeze-avoiding strategies in which they can prevent freezing by controlling the concentration of sugars (et. sucrose, trehalose) or polyols (glycerol), regulation of the ice nucleator, and dehydration. Other organisms have adapted to this extremely cold condition by producing antifreeze (gly)proteins (AF(G)Ps) which exhibit ice recrystallization inhibition (IRI), thermal hysteresis activity (THA), and dynamic ice crystal shaping. These proteins discovered in Antarctic fish in 1960 for the first time have been reported in bacteria, fungi, insects, and plants. AF(G)Ps and their synthetic biomimetics have received increasing attention as potential candidates for various industrial and bio-medical applications. Promising results from vitrification and other protocols using antifreeze agents with ice recrystallization inhibition activity have widely been reported in biopreservation. Conversely, understanding of the antifreezing process caused by these macromolecules remains under challenge. This is due to the multifunctional nature of the freezing process and antifreeze macromolecule’s behavior which brings complexity in designing the synthetic antifreeze structures. In addition, the cost, low availability, toxicity at higher concentrations, and instability beside several other drawbacks make their large-scale production challenging. Although several synthetic attempts for the exploitation of AFPs have been studied in the past, challenges remain in the synthetic design of AFP analogs. On the other hand, poly (vinyl alcohol) (PVA) with simple structure has been reported with potent IRI activity as a good candidate for large-scale production and applications.

Our group has explored structural variations to polyol-based polymers to contrast with PVA as a control and identified several key structural elements for performance in IRI, THA, as well as in ice nucleation inhibition (INI). These structural features are bioinspired by the typical ice-binding plane of AFPs yet are surprisingly simple to produce with potency approaching that of typical AFPs. Key to the performance is positioning small organic functionalities with known antifreeze properties (glycerol) pendent to a host polymer chain with consideration of their conformational freedom. To build systematic variations into both the backbone and side-chain structures, we used poly (vinyl alcohol), poly (isopropenyl acetate), poly (acrylic acid), and poly(methacrylic acid) xvi parent polymers for such pendent modifications. One structure in particular, glycerol-grafted-PVA (G-g-PVA), shows potency rivaling that of AFPs at similar micromolar concentration. The findings in this study help guide the rational design of synthetic antifreeze polymers useful for applications such as anti-icing coatings through to cryopreservation methods for organ transport and cell preservation.

While AFPs are well-known for their ice nucleation and recrystallization inhibition activity along with controlling the ice crystal morphology, the contrasting behavior of ice nucleation promotion by AFPs and its key contribution to the whole antifreezing process also seems necessary to explore in this context. Here, silver iodide (AgI) has been used as an ice nucleator in different polymer solutions in ultra-pure water (UPW) to imitate the ice nucleation process by AFPs. PVA prepared by RAFT polymerization and our glycerol grafted derivative (G-g-PVA), now shown to be the most IRI active polymer to date, was investigated for its ice nucleation and recrystallization activity in AgI dispersion media. The results showed that the ice nucleation rate and temperature was significantly changed by adding the AgI dispersion in PVA and G-g-PVA solutions. The polymer solution in UPW containing AgI dispersion showed significant improvement in IRI activity compared the same polymer in PBS buffer solution. Our results demonstrate the considerable contribution of the ice nucleator in ice nucleation rate and temperature which enhances IRI activity of synthetic antifreeze polymers. These finding both aid our understanding of the ice nucleation promotion impact on synthetic polymers IRI activity along with engineering biomimetics for biomedical and industrial applications.

Next, we focused our efforts to transfer these functionalities and performance to the solid-state interface with water. Aqueous dispersions of polymeric colloidal particles served as this substrate and were functionalized with either PVA or G-g-PVA grafted to their surfaces to contrast with performance of the same polymers strictly in the solution state. These functionalized colloids also can be applied as a continuous coating through latex film formation to assess anti-icing and iceadhesion properties. While these systems also showed encouraging and potent activity, their performance was not enhanced compared to that of the solution state systems. This may have implications for fully solid-state anti-icing coatings, yet our attention then shifted from this scope of work to new funding which required again a solution state approach. 

In this final application, we explored PVA and G-g-PVA synthesized in our lab for their biopreservation aspects especially for red blood cell (RBC) cryopreservation at -80 °C. Our results again confirmed G-g-PVA to be an excellent candidate for cryopreservation and quite likely for organ cryopreservation. Using this polymer in solution as a cryoprotectant for RBCs showed significant improvement to controls, preventing hemolysis (cell rupture) along with eliminating other drawbacks that have been observed when using small molecule cryoprotective agents like glycerol, dimethyl sulfoxide (DMSO), etc.; especially with regard to the ability to fully remove all traces of the cryoprotectant after cryopreservation storage and thawing.

In summary, the studies in this dissertation provide critical insights and approaches for the understanding of the freezing process and ideas that can help understand relevant mechanisms of influencing key freezing steps that have not yet been fully understood. In addition, it provides guidelines to synthesize G-g-PVA, currently the most potent active polymer in terms of IRI and THA shown useful for several high impact applications. In particular, this research provides valuable data and experimental conditions to understand the IRI mechanism to use in engineering next generation highly efficient antifreeze systems. 
 

Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry.
THESIS ABSTRACT: 
Understanding the properties of bioconjugates and biomaterials has increasingly become the focus of pharmaceutical companies, material scientists, and academia due to their growing list of applications. Bioconjugates have found broad use in therapeutics, drug delivery, tissue engineering, and biosensing. Historically, interest in specific bioconjugates has depended on the cost-availability of the biomacromolecule, making proteins the most well studied, given their relatively low cost and ease of production. However, recent technological advances in plasmid DNA (pDNA) production from E. Coli allow for greater cost-efficiency, changing the landscape ofbiomaterial research. Employing alkylating agents with known chemo-selectivity to nucleophilic sites on DNA, a polymer or polymerization agent can be coupled to biologically derived pDNA. Subsequently, properties of the hybrid-DNA bioconjugate can be controlled via the location of alkylation, to tune degradation rate and stability of the DNA bioconjugate and graft-from polymerization to increase stability and solubility. 

Drones doi: 10.3390/drones6050100

Journal of Micro and Nano-Manufacturing doi: 10.1115/1.4055230

Cell Reports Physical Science doi: 10.1016/j.xcrp.2022.100786

UNH Today 

ACS Applied Polymer Materials. doi: 10.1021/acsapm.1c01312

Polymer Chemistry. doi: 10.1039/D1PY01005K

ACS Applied Materials & Interfaces. doi: 10.1021/acsami.1c14453

Chemical Society Reviews doi: 10.1039/d1cs00600b

Angewandte Chemie International Edition. doi: 10.1002/anie.202113569

Frontiers in Chemistry. doi: 10.3389/fchem.2021.753635

International Journal of Computational Materials Science and Engineering. doi: 10.1142/s2047684121500329

Proteins. doi: 10.1002/prot.26265

Sensors and Actuators Reports. doi: 10.1016/j.snr.2021.100051.

Journal of Alloys and Compounds. doi: 10.1016/j.jallcom.2021.161871.

Journal of Applied Ecology doi: 10.1111/1365-2664.14009

Canadian Journal of Fisheries and Aquatic Sciences doi: 10.1139/cjfas-2020-0402

Materials Science and Engineering: A. doi: 10.1016/j.msea.2021.141876

Volume 1: Additive Manufacturing; Advanced Materials Manufacturing; Biomanufacturing; Life Cycle Engineering; Manufacturing Equipment and Automation. doi: 10.1115/msec2021-63471

Proceedings of the 2021 IISE Annual Virtual Conference.

Forming the Future. doi: 10.1007/978-3-030-75381-8_155

Chem. doi: 10.1016/j.chempr.2021.06.004

JOM. doi: 10.1007/s11837-021-04715-w

CIRP Journal of Manufacturing Science and Technology. doi: 10.1016/j.cirpj.2021.04.006

Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Mechanical Engineering.
DISSERTATION ABSTRACT:
3D woven carbon/epoxy composites are high-performance materials with superior thermomechanical and physical properties making them an integral part of the aerospace, energy and automotive industries. However, under certain manufacturing conditions, these composites may accumulate severe intrinsic manufacturing-induced residual stresses which can even lead to microcracking. The complex reinforcement architecture makes analytical, numerical and experimental analysis of these composites challenging. This research has been focused on micromechanical analysis, computational modeling, and experimental characterization of 3D woven carbon/epoxy composites aiming to evaluate the manufacturing-induced residual stresses and enable mitigation of their negative impact on the resulting performance. A procedure to develop high-fidelity meso-scale finite element models with as-woven representation of the composite reinforcement informed by the μCT scanning was proposed. A set of meso-scale models for different reinforcement architectures was produced and utilized to predict the accumulation of intrinsic manufacturing-induced residual stresses in these composites. The models were correlated to the blind hole drilling experiments and used for interpretation of the experimental results providing full-field spatial distribution of the residual stresses accumulated in the composite specimens. A new simplified approach to account for nonlinear effects in the material due to severe residual stresses using linearly-elastic models was proposed. A set of parametric numerical studies was performed to improve correlation of the models with the experimental measurements. The developed meso-scale models were used to predict effective coefficients of thermal expansion for the composites with temperature-dependent properties of the constituents. Methods presented in this work provide valuable tools for the field of computational and experimental mechanics of textile composite materials.
 

The Journal of Physical Chemistry B. doi: 10.1021/acs.jpcb.0c11096

Environmental Development, 37, 100602. doi:10.1016/j.envdev.2020.100602

Sustainability Science doi:  10.1007/s11625-021-00904-3

Journal of Chemical Theory and Computation. doi: 10.1021/acs.jctc.0c01199

Journal of Materials Science & Technology, doi: 10.1016/j.jmst.2020.12.047

Biophysical Journal, doi: 10.1016/j.bpj.2020.12.010

Journal of the American Chemical Society, doi: 10.1021/jacs.0c07041

ProQuest Dissertation or Thesis  https://www.proquest.com/docview/2514738140

ACS Macro Letters, 9, 1836-1843. doi: 10.1021/acsmacrolett.0c00774

Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Master of Science in Mechanical Engineering.
THESIS ABSTRACT:
This work presents improvements to the methods used in crystal plasticity simulations. It shows how these improvements can be used to accurately predict the deformation behavior of two magnesium alloys, WE43, and AZ31. The first improvement to the methodology is guidance on the type of finite elements to use in explicit grain crystal plasticity simulations. This study found that quadratic tetrahedral and linear hexahedral elements are the most accurate element types included in the study. The study also concluded that tetrahedral elements are more desirable due to fast mesh generation and flexibility to describe geometries of grain structures. The second improvement made was the addition of a numerical scheme to enable the use of any rate sensitivity exponent in the fundamental power-law representation of the flow rule in crystal visco-plasticity. While allowing the use of even very large exponents that many materials exhibit, this numerical scheme adds little to no increase in computational time. This crystal plasticity model was used to accurately predict the deformation behavior of both WE43 and AZ31 under quasi-static and high rate deformation, predicting the stress-stain response and the evolution of texture, twinning and the relative activities of the various deformation modes.
 

Elementa: Science of the Anthropocene, 8(1). doi:10.1525/elementa.003

Energy Policy, 143, 111457. doi:10.1016/j.enpol.2020.111457

Environmental Research Letters, 15(10), 104054. doi:10.1088/1748-9326/abad58

ProQuest Dissertation or Thesis  https://www.proquest.com/docview/2445953572

Soft Matter, 16, 8101-8107. doi: 10.1039/d0sm00954g

 International Journal of Plasticity, 136, 102807. doi: 10.1016/j.ijplas.2020.102807

Nano Research. doi: 10.1007/s12274-020-2874-x

Restoration Ecology doi: 10.1111/rec.13228

Resources, Conservation and Recycling, 161, 104990. doi:10.1016/j.resconrec.2020.104990

Chemistry of Materials. doi: 10.1021/acs.chemmater.9b05289

Acta Materialia, 195, 59-70. doi: 10.1016/j.actamat.2020.04.036

Submitted to the University of New Hampshire In Partial Fulfillment of the Requirements for the Degree of Master of Science In Chemistry May 2020.
THESIS ABSTRACT:
This thesis explores the use of Diels-Alder functionalized particles to aide in the mechanical enhancement of additively manufactured objects. To date, materials generated via additive manufacturing lack isotropic properties due to the nature in which they are created – in a layer by layer fashion. This methodology often leads to poor interfacial adhesion at the junction between printed layers, lowering the stability of the part and thereby limiting its use in many applications. Dynamic covalent chemistry, such as the reversible Diels-Alder reaction, has the ability to alleviate this anisotropy to print stronger, more uniform objects. To do so, this work investigates crosslinked, Diels-Alder functionalized particles generated by two separate methods: polymerization via reversible addition fragmentation chain transfer (RAFT) followed by atom transfer radical coupling (ATRC) and free radical emulsion polymerization. These particles can be blended with a polymeric filament for 3D printing, where upon heating during the extrusion process of additive manufacturing, the retro-Diels-Alder reaction is initiated and releases the crosslinked particles exposing reactive diene and dienophile pairs. In subsequent xvii cooling after the printing process, these moieties undergo the forward Diels-Alder reaction and form chemical linkages between printed layers of the substrate to improve the mechanical integrity and uniformity of objects produced by means of additive manufacturing.

UNH Scholars Repository https://scholars.unh.edu/cgi/viewcontent.cgi?article=1012

Submitted to the Faculty in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry.
DISSERTATION ABSTRACT: 
Since the discovery of electrically conductive two-dimensional (2D) metal–organic frameworks (MOFs), the synthetically tunable properties and intrinsic porosity of these materials make them promising for multifunctional sensing devices. The focus of my work is on a class of 2D MOFs based on a triphenylene core (2,3,6,7,10,11- hexahydroxytriphenylene, HHTP and 2,3,6,7,10,11-hexaiminotriphenylene, HITP) coordinating to divalent Cu or Ni metal nodes forming M3HXTP2 MOF analogs (M = Ni, Cu; X = NH, HITP or O, HHTP). Chapter 2 describes a simple strategy for device fabrication, using mechanical abrasion, enabling the chemiresistive sensing of NH3, H2S, and NO. The value in this contribution is threefold. First, the technique may be applicable to a wide range of materials, both semiconductors and possibly insulators. Second, the rapid prototyping method enables direct deposition using mechanical abrasion on a wide range of substrates. Third, the integration of the MOF-based sensing material into devices is entirely solvent-free, which can preserve device substrates sensitive to harsh solvents. Chapter 3 describes a new strategy of MOF synthesis termed oxidative restructuring that feature several innovative characteristics that advance the field of MOF integration. First, oxidative restructuring enables the facile integration of Cu3HHTP2 and Cu-BTC onto prepatterned Cu layer on multiple substrates. Second, we detail spectroscopic evidence that provides insight into the interaction between Cu3HHTP2 and NO using diffuse reflectance infrared fourier transform spectroscopy and X-ray photoelectron spectroscopy. Third, Cu3HHTP2 MOF devices demonstrated the highest dynamic loading capacity of NO and functioned as chemiresistive sensors for the detection of NO and H2S. Chapter 4 describes the implementation of 2D MOF based electrodes to enable the voltammetric detection of biologically relevant analytes. First, strategic selection of redox active analytes combined with the electrochemical methods, allowed us to investigate the intrinsic electrochemical properties of M3HXTP2 MOF analogs (M = Ni, Cu; X = NH, HITP or O, HHTP). Second, this demonstrated one of the first uses of 2D MOFs in solution phase detection with nanomolar detection at 63 ± 11 nM for dopamine and 40 ± 17 nM for serotonin. Taken together, chapters 1-4 advance the field of conductive metal–organic frameworks by providing insight in molecular engineering of MOFs that guides the iii structure property relationships to enable precise function for chemical detection and provides strategies for the strategic integration of MOFs on substrates. 
 

Chemistry of Materials. doi: 10.1021/acs.chemmater.9b04092

Authorea doi: 10.1002/essoar.10502249.1

Environmental Sociology, 1–13. doi:10.1080/23251042.2019.1696008

Environmental Communication, 14(3), 416–429. doi:10.1080/17524032.2019.1686408 

Polymer Chemistry. doi:10.1039/c9py01510h

Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Master of Science in Mechanical Engineering September, 2019.
THESIS ABSTRACT:
The following research explores the continuous bending under tension (CBT) incremental forming process effects on four dual phase (DP) steels: DP 590, DP 780, DP 980, DP 1180. A parameter study was conducted, finding the ideal parameters for increased elongation to fracture compared to tension of over five times for DP 1180 and DP 980. These parameters were found to be a normalized bend depth of 3.5 and a crosshead pull speed of 1.35mm/s. Using these parameters, following tests were conducted on all four steels by stopping the CBT process before fracture at 2, 4, 6, 8, and some even at 10 and 12 CBT cycles. Smaller tensile specimens were machine from these CBT processed strips and uniaxial tension tests were performed to study the residual ductility of CBT testing. The strength of all steels increased with increased cycle count by 200-400 MPa, however the ductility decreased by over half. Using neutron diffraction, the texture evolution of the CBT process was explored. Results showed a preferred orientation in the {011} fiber in the pulling direction. This research also proves simulating the CBT process and matching to experimental data can be a method for extrapolating post-necking hardening behavior of DP 980 and DP 1180. The experimental data and results are further explained in the following chapters.

Nat Sustain 2, 647–649 (2019) doi:10.1038/s41893-019-0357-4

North American Journal of Fisheries Management, 39(5), 989–998. doi:10.1002/nafm.10330

Journal of the American Chemical Society 2019 141 (30), 11929-11937. doi: 10.1021/jacs.9b03441

Sustainability Science. doi:10.1007/s11625-019-00707-7

Chemistry – A European Journal, 25(46), 10768–10781. doi: 10.1002/chem.201900975

This dissertation has been examined and approved in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry.
DISSERTATION ABSTRACT:
Atom transfer radical coupling (ATRC) is gaining recognition for its utility in building complex polymeric architectures because it features efficiency, a wide range of compatible substrates, and a lack of byproducts. These qualities are especially desirable in applications requiring intramolecular cross-linking as in the synthesis single-chain nanoparticles (SCNP). This dissertation aims to (I) provide motivation and context for developing ATRC technology for intramolecular cross-linking, (II) provide guidance into the impact of catalyst selection and substrate on reaction efficiency and morphology, and (III) demonstrate the possibility to sequence intrachain ATRC with ATRP to create advanced SCNP architectures. Chapter II describes the preparation of SCNP from parent polymers containing alkyl or benzyl bromide ester pendants using ATRC catalyzed by copper halides complexes. Tri- or tetradentate alkyl or pyridyl amines (PMDETA, TPEN, and TPMA), which tune the redox potential of the Cu(I)/Cu(II) system, were directly compared. Coupling efficiency was positively correlated with the kATRP of the respective catalyst systems. However, PMDETA complexes afforded greater control as evidenced by lower polydispersity. In the case of alkyl halide pendants, selectivity for coupling over disproportionation systematically decreased under conditions designed to increase the concentration of CuI /L. Polymers with benzyl bromide pendants, which cannot disproportionate, tended to produce high molecular weight products, even in ultradilute solutions (0.25 –1.0 mg/mL). xvii Chapter III describes the preparation of SCNP from parent polymers capable of initiating intra-chain polymerization by ATRP under conditions favoring termination by coupling. Because of the wide variety of compatible monomers that have been well-established for ATRP systems, the ATRP/C framework both simplifies reaction procedures (one pot polymerization and coupling strategies are feasible) and imparts handles with which to control both architecture and functionality. To demonstrate this potential, model simple brushes and hyperbranched examples were prepared. SCNP with the hyperbranched motif were remarkably dense, a result which demonstrates the potential to facilitate more globular SCNP structures using modifications of intrachain polymerizations. Methacrylic brush arms, which are not non-ATRC active, could be induced to couple by adding 5 equivalents of styrene under the shared ATRP/C conditions. In addition, it was determined that hyperbranched SCNP retain “living” ω-ends which may be initiated to perform post-collapse polymerizations. A model styrene example is presented; despite occurring in an ultradilute solution, the polymerization maintains fidelity to pseudo-first order kinetics. In sum, there is currently a great impetus for pushing the boundaries of structural and functional complexity that can be designed using the single-chain nanoparticle motif. Atom transfer radical chemistry is a particularly versatile example and it is my hope that this work facilitates the creation of new creative and functional designs.

PLOS ONE, 14(2), e0212011. doi: 10.1371/journal.pone.0212011

Transactions of the American Fisheries Society. doi:10.1002/tafs.10126

Canadian Journal of Fisheries and Aquatic Sciences, 76(5), 762–779. doi: 10.1139/cjfas-2018-0008

Renewable and Sustainable Energy Reviews, 90, 945–956. doi: 10.1016/j.rser.2018.04.014

Transactions of the American Fisheries Society, 147(3), 525–540. doi: 10.1002/tafs.10053

Energy, Sustainability and Society, 8(1). doi: 10.1186/s13705-018-0152-5

Carsey Research National Fact Sheet, Carsey School of Public Policy, University of New Hampshire. National Fact Sheet No. 37

Springer International Publishing. doi: 10.1007/978-3-319-65711-0.

Agricultural and Forest Meteorology. doi: 10.1016/j.agrformet.2017.11.030

Ecology and Society 22(4):17. doi: 10.5751/es-09519-220417

Maine Policy Review, 26.2: 9-18.

Water Alternatives, 10(3): 724-743.

Resilience 2017 Conference Proceedings. Stockholm Waterfront Congress Centre, Sweden, August 20-23, 2017.

Geosciences, 7(3), 54. doi: 10.3390/geosciences7030054

Carsey Research Policy Brief, Carsey School of Public Policy, University of New Hampshire. National Issue Brief No. 123

Oxford Research Encyclopedia of Climate Science. doi: 10.1093/acrefore/9780190228620.013.563.

Society and Natural Resources, 1–16. doi:10.1080/08941920.2017.1315653

Carsey Research National Fact Sheet, Carsey School of Public Policy, University of New Hampshire. National Fact Sheet No. 35.

Journal of Geophysical Research: Atmospheres, 122(1), 121–139. doi: 10.1002/2016jd025362

Journal of Geophysical Research: Biogeosciences, 121(12), 3072–3088. doi:10.1002/2016jg003450

Journal of Clinical Microbiology, 55(2), 645–648. doi:10.1128/jcm.02162-16

SAGE Open, 6(4), 215824401667629. doi:10.1177/2158244016676296

Global Change Biology, 23(4), 1610-1625. doi:10.1111/gcb.13517

Ocean & Coastal Management, 130, 196–204. doi:10.1016/j.ocecoaman.2016.06.005

Sociology, 50(5), 913-933. doi: 10.1177/0038038516648547

Great Bay Matters, Spring/Summer 2015

Journal of Geophysical Research: Biogeosciences, 121(8), 2019-2029. doi: 10.1002/2015JG003204

Carsey Research Policy Brief, Carsey School of Public Policy, University of New Hampshire. Regional Issue Brief No. 45

New Hampshire EPSCoR. 2.

Global Biogeochemical Cycles, 30(8), 1183-1191. doi: 10.1002/2016GB005468

Ecosystem Services, 20, 104-112. doi: 10.1016/j.ecoser.2016.06.007

Journal of Planning Education and Research, 0739456X1665560. doi:10.1177/0739456x16655601

Ecology and Society, 21(2). doi: 10.5751/es-08437-210248

Carsey Research Policy Brief, Carsey School of Public Policy, University of New Hampshire. National Issue Brief No. 99

Journal of Physical Oceanography, 46(5), 1421–1436. doi: 10.1175/jpo-d-13-0271.1

Conservation Biology, 30(6), 1173-1181. doi: 10.1111/cobi.12745

Elementa: Science of the Anthropocene, 4, 000090. doi: 10.12952/journal.elementa.000090

Regional Environmental Change, 16(9), 1819-1832. doi: 10.1007/s10113-015-0914-y

Ecological Applications, 26(1), 146-161. doi: 10.1890/14-2207

Journal of Applied Communication Research, 44(1), 78–95. doi:10.1080/00909882.2015.1116707

Technical report provided to the Campus Compact and Campuses for Environmental Stewardship program

Journal of Geophysical Research: Biogeosciences, 121(1), 205–217. doi: 10.1002/2015jg003146

Arctic Report Card: Update for 2015, p. 60.

Geophysical Research Letters, 42, 9319–9327. doi: 10.1002/2015GL065912

Hydrological Processes, 29(25), 5193–5202. doi: 10.1002/hyp.10706

Climate Change and Society, 269–299. doi: 10.1093/acprof:oso/9780199356102.003.0009

Environmental Research Letters, 10(9), 095003. doi: 10.1088/1748-9326/10/9/095003

SIGSPATIAL Special, 7(2), 3–13. doi: 10.1145/2826686.2826689

SAGE Open, 5(3), 215824401560275. doi: 10.1177/2158244015602752

Nature Climate Change, 5(8), 704–704. doi: 10.1038/nclimate2720

Freshwater Science, 34(2), 456–471. doi: 10.1086/680985

Canadian Journal of Fisheries and Aquatic Sciences, 72(8), 1272–1285. doi: 10.1139/cjfas-2014-0400

Nature, 520(7549), 661–665. doi: 10.1038/nature14401

Final Report

Journal of Clinical Microbiology, 53(6), 1864–1872. doi:10.1128/jcm.00034-15

Ecosphere, 6(3). doi: 10.1890/es14-00542.1

Geomorphology, 232, 33–46. doi: 10.1016/j.geomorph.2014.12.036

Estuaries and Coasts, 38(6), 2117–2131. doi:10.1007/s12237-015-9958-y

The Guardian, Op-Ed

PLoS ONE, 10(2), e0117975. doi: 10.1371/journal.pone.0117975

Arctic, 68(5), 59. doi: 10.14430/arctic4448

Environmental Studies and Sciences, 5(1), 54–57. doi: 10.1007/s13412-015-0222-3

Ecology and Society, 20(1). doi: 10.5751/es-06644-200102

Ecology and Society, 20(2). doi: 10.5751/es-07283-200204

Biogeosciences, 11(23), 6667–6682. doi: 10.5194/bg-11-6667-2014

Environmental Politics, 24(2), 212–227. doi: 10.1080/09644016.2014.976485

Geoscientific Model Development, 7(5), 2077–2090. doi: 10.5194/gmd-7-2077-2014

Community Development, 45(5), 474–489. doi: 10.1080/15575330.2014.951374

M.S. Dissertation, Department of Natural Resources & the Environment, College of Life Science and Agriculture, University of New Hampshire, Durham, NH, 93 pages

Geoscientific Model Development, 8(2), 151–170. doi: 10.5194/gmd-8-151-2015

Environmental Science and Technology, 48(14), 7756–7765. doi: 10.1021/es500252j

Environmental Management, 54(4), 875–887. doi: 10.1007/s00267-014-0304-0

Global Change Biology, 20(10), 3191–3208. doi: 10.1111/gcb.12615

Carsey Institute Policy Brief, Carsey Institute, University of New Hampshire. Regional Issue Brief No. 40

M.S. Dissertation, Department of Natural Resources & the Environment, College of Life Science and Agriculture, University of New Hampshire, Durham, NH, 94 pages

Climatic Change, 124(1-2), 53–63. doi: 10.1007/s10584-014-1109-0

Climate of the Past, 10(2), 523–536. doi: 10.5194/cp-10-523-2014

Frontiers in Ecology and the Environment, 12(1), 5–14. doi: 10.1890/130017

Geomorphology, 205, 1–4. doi: 10.1016/j.geomorph.2013.04.004

Weather, Climate, and Society, 6(1), 119–134. doi: 10.1175/wcas-d-13-00029.1

H. Huang, J. Hahn, C. Claramunt, T. Reichenbacher, (Eds). Proceedings of the 1st International Workshop on Context-Awareness in Geographic Information Services (in conjunction with GIScience 2014). pp 3-16.

Final Report, University of New Hampshire Cooperative Extension

Climate Solutions New England Report, Sustainability Institute at the University of New Hampshire.

M.S. Dissertation, Department of Natural Resources & the Environment, College of Life Science and Agriculture, University of New Hampshire, Durham, NH, 50 pages

Abstract #C13A-0-649 presented at the 2013 Fall Meeting, AGU, San Francisco, CA, 9-13 Dec.

Abstract #C21D-0674 presented at the 2013 Fall Meeting, AGU, San Francisco, CA, 9-13 Dec

Abstract presented at Proceedings of the North East ARC Users Group Conference, Nashua, NH, Sunday, September, 29 2013

Sustainability, 5(10), 4195-4221. doi: 10.3390/su5104195

International Journal of Climatolology, 34(5), 1723–1728. doi: 10.1002/joc.3796

The Cryosphere, 8, 319-328. doi: 10.5194/tc-8-319-2014

Global Biogeochemical Cycles, 27(2), 578–591. doi: 10.1002/gbc.20049

Environmental Research Letters, 8(2), 025017. doi: 10.1088/1748-9326/8/2/025017

Environmental Research Letters, 8(2), 025010. doi: 10.1088/1748-9326/8/2/025010

Forestry, 86(3), 377–389. doi: 10.1093/forestry/cpt008

Proceedings of the National Academy of Sciences, 110(15), 5999–6003. doi: 10.1073/pnas.1302445110

Photogrammetric Engineering and Remote Sensing, 79(3), 245–257. doi: 10.14358/pers.79.3.245

Elements, 8(6), 435-438. doi: 10.2113/gselements.8.6.435

Urban Forestry & Urban Greening, 12(1), 61–68. doi: 10.1016/j.ufug.2012.10.003

Ecosystems, 16(2), 310–322. doi: 10.1007/s10021-012-9616-1

Weather, Climate, and Society, 4(4), 236–249

Forestry, 86(1), 129–143. doi: 10.1093/forestry/cps039

Inland Waters, 2(4), 229–236. doi: 10.5268/iw-2.4.502

Forestry, 86(1), 119–128. doi: 10.1093/forestry/cps059

Forest Ecology and Management, 282, 53–62. doi: 10.1016/j.foreco.2012.06.014

NH Energy and Climate Collaborative Report.

Oecologia, 169(4), 915–925. doi: 10.1007/s00442-012-2263-6

M.S. Dissertation, Department of Natural Resources & the Environment, College of Life Science and Agriculture, University of New Hampshire, Durham, NH, 66 pages

Biogeochemistry, 108(1-3), 183–198. doi: 10.1007/s10533-011-9589-8