Digital Commons Network^™

A Novel Deliberative Multicriteria Evaluation Approach To Ecosystem Service Valuation, Georgia Mayrommati, Mark E. Borsuk, Richard B. Howarth

New Hampshire EPSCoR

Although efforts to address ecosystem services in decision making have advanced considerably in recent years, there remain challenges related to valuation. In particular, conventional economic approaches have been criticized for their inability to capture the collective nature of ecosystem services, for their emphasis on monetary metrics, and the difficulty of assessing the value of ecosystem services to future generations. We present a deliberative multicriteria evaluation (DMCE) method that combines the advantages of multicriteria decision analysis with a deliberation process that allows citizens and scientists to exchange knowledge and evaluate ecosystem services in a social context. Compared with previous applications we …

Tuning Shear Thinning Factors Of 3d Bio-Printable Hydrogels Using Short Fiber, Slesha Tuladhar, Scott Clark, Ahasan Habib

New Hampshire EPSCoR

Among various available 3D bioprinting techniques, extrusion-based three-dimensional (3D) bioprinting allows the deposition of cell-laden bioink, ensuring predefined scaffold architecture that may offer living tissue regeneration. With a combination of unique characteristics such as biocompatibility, less cell toxicity, and high water content, natural hydrogels are a great candidate for bioink formulation for the extrusion-based 3D bioprinting process. However, due to its low mechanical integrity, hydrogel faces a common challenge in maintaining structural integrity. To tackle this challenge, the rheological properties, specifically the shear thinning behavior (reduction of viscosity with increasing the applied load/shear rate on hydrogels) of a set of …

Fabrication Of Multifunctional Electronic Textiles Using Oxidative Restructuring Of Copper Into A Cu-Based Metal–Organic Framework, Aileen M. Eagleton, Michael Ko, Robert M. Stolz, Nataliia Vereshchuk, Zheng Meng, Lukasz Mendecki, Adelaide M. Levenson, Connie Huang, Katherine C. Macveagh, Akbar Mahdavi-Shakib, John J. Mahle, Gregory W. Peterson, Brian G. Frederick, Katherine A. Mirica

New Hampshire EPSCoR

This paper describes a novel synthetic approach for the conversion of zero-valent copper metal into a conductive two-dimensional layered metal–organic framework (MOF) based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to form Cu3(HHTP)2. This process enables patterning of Cu3(HHTP)2 onto a variety of flexible and porous woven (cotton, silk, nylon, nylon/cotton blend, and polyester) and non-woven (weighing paper and filter paper) substrates with microscale spatial resolution. The method produces conductive textiles with sheet resistances of 0.1–10.1 MΩ/cm2, depending on the substrate, and uniform conformal coatings of MOFs on textile swatches with strong interfacial contact capable of withstanding chemical and physical stresses, such as detergent …

Sensor Technologies For Quality Control In Engineered Tissue Manufacturing, Mary Clare Mccorry, Kenneth F. Reardon, Marcie Black, Chrysanthi Williams, Greta Babakhanova, Jeffrey M. Halpern, Sumona Sarkar, Nathan S. Swami, Katherine A. Mirica, Sarah Boermeester, Abbie Underhill

New Hampshire EPSCoR

The use of engineered cells, tissues, and organs has the opportunity to change the way injuries and diseases are treated. Commercialization of these groundbreaking technologies has been limited in part by the complex and costly nature of their manufacture. Process-related variability and even small changes in the manufacturing process of a living product will impact its quality. Without real-time integrated detection, the magnitude and mechanism of that impact are largely unknown. Real-time and non-destructive sensor technologies are key for in-process insight and ensuring a consistent product throughout commercial scale-up and/or scale-out. The application of a measurement technology into a manufacturing …

Protocol For Deposition Of Conductive Oxides Onto 3d-Printed Materials For Electronic Device Applications, Julia E. Huddy, William J. Scheideler

New Hampshire EPSCoR

Additively manufactured (AM) three-dimensional (3D) mesostructures can be designed to enhance mechanical, thermal, or optical properties, driving future device applications at the micron to millimeter scale. We present a protocol for transforming AM mesostructures into 3D electronics by growing nanoscale conducting films on 3D-printed polymers. In this generalizable approach, we describe steps to utilize precision thermal atomic layer deposition (ALD) of conducting, semiconducting, and dielectric metal oxides. This can be applied to ultrasmooth, customizable photopolymer lattices printed by high-resolution microstereolithography. For complete details on the use and execution of this protocol, please refer to Huddy et al. (2022).

Epitaxial Self-Assembly Of Interfaces Of 2d Metal–Organic Frameworks For Electroanalytical Detection Of Neurotransmitters, Robert M. Stolz, Anna F. Kolin, Brunno C. Rocha, Anna Brinks, Aileen M. Eagleton, Lukasz Mendecki, Harish Vashisth, Katherine A. Mirica

New Hampshire EPSCoR

This paper identifies the electrochemical properties of individual facets of anisotropic layered conductive metal–organic frameworks (MOFs) based on M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HHTP)2) (M = Co, Ni). The electroanalytical advantages of each facet are then applied toward the electrochemical detection of neurochemicals. By employing epitaxially controlled deposition of M3(HHTP)2 MOFs on electrodes, the contribution of the basal plane ({001} facets) and edge sites ({100} facets) of these MOFs can be individually determined using electrochemical characterization techniques. Despite having a lower observed heterogeneous electron transfer rate constant, the {001} facets of the M3(HHTP)2 systems prove more selective and sensitive for the detection of dopamine …

Designing An Interchangeable Multi-Material Nozzle System For The 3d Bioprinting Process, Cartwright Nelson, Slesha Tuladhar, Md Habib

New Hampshire EPSCoR

Three-dimensional bioprinting is a rapidly growing field attempting to recreate functional tissues for medical and pharmaceutical purposes. Development of functional tissue requires deposition of multiple biomaterials encapsulating multiple cell types i.e. bio-ink necessitating switching ability between bio-inks. Existing systems use more than one print head to achieve this complex interchangeable deposition, which decreases efficiency, structural integrity, and accuracy. In this research, we developed a nozzle system capable of switching between multiple bio-inks with continuous deposition ensuring the minimum transition distance so that precise deposition transitioning can be achieved. Finally, the effect of rheological properties of different bio-material compositions on the …

Self-Assembly In Mixtures Of Charged Lobed Particles, Arpita Srivastava, Brunno C. Rocha, Harish Vashisth

New Hampshire EPSCoR

We report coarse-grained Langevin dynamics simulations of homogeneous mixtures of lobed colloidal particles with opposite charges. We show that dumbbell, trigonal planar, tetrahedral, square planar, trigonal bipyramidal, and octahedral shaped particles form distinct self-assemblies including chains, sheets, crystalline, and spherical structures. The dumbbell and square planar particles predominantly form chains and sheets while other particles form network-like self-assembled morphologies. At higher temperatures and lower charges, non-planar particles form three-dimensional aggregates. We further report on packing arrangements of particles which lead to differences in porosities within self-assembled morphologies. Our results show that the trigonal planar particles form larger porous structures. The …

Uav And Structure-From-Motion Photogrammetry Enhance River Restoration Monitoring: A Dam Removal Study, Alexandra D. Evans, Kevin H. Gardner, Scott Greenwood, Brett Still

New Hampshire EPSCoR

Dam removal is a river restoration technique that has complex landscape-level ecological impacts. Unmanned aerial vehicles (UAVs) are emerging as tools that enable relatively affordable, repeatable, and objective ecological assessment approaches that provide a holistic perspective of restoration impacts and can inform future restoration efforts. In this work, we use a consumer-grade UAV, structure-from-motion (SfM) photogrammetry, and machine learning (ML) to evaluate geomorphic and vegetation changes pre-/post-dam removal, and discuss how the technology enhanced our monitoring of the restoration project. We compared UAV evaluation methods to conventional boots-on-ground methods throughout the Bellamy River Reservoir (Dover, NH, USA) pre-/post-dam removal. We …

Transforming 3d-Printed Mesostructures Into Multimodal Sensors With Nanoscale Conductive Metal Oxides, Julia E. Huddy, Md Saifur Rahman, Andrew B. Hamlin, Youxiong Ye, William J. Scheideler

New Hampshire EPSCoR

Additively manufactured (AM) three-dimensional (3D) mesostructures exhibit geometrically optimal mechanical, thermal, and optical properties that could drive future microrobotics, energy harvesting, and biosensing technologies at the micrometer to millimeter scale. We present a strategy for transforming AM mesostructures into 3D electronics by growing nanoscale conducting films on 3D-printed polymers. This highly generalizable method utilizes precision atomic layer deposition (ALD) of conducting metal oxides on ultrasmooth photopolymer lattices printed by high-resolution microstereolithography. We demonstrate control of 3D electronic transport by tuning conformal growth of ultrathin amorphous and crystalline conducting metal oxides. To understand the scaling of 3D electrical properties, we apply …

Bimetallic Two-Dimensional Metal–Organic Frameworks For The Chemiresistive Detection Of Carbon Monoxide, Aylin Aykanat, Zheng Meng, Robert M. Stolz, Colin T. Morrell, Katherine A. Mirica

New Hampshire EPSCoR

This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal–organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm levels of carbon monoxide (CO). Devices achieve a sub-part-per-million (ppm) limit of detection (LOD) of 0.53 ppm toward CO at a low driving voltage of 0.1 V. MPc-based Cu-linked MOFs can continuously detect CO at 50 ppm, the permissible exposure limit required by the Occupational Safety and Health Administration (OSHA), for multiple exposures, and realize CO detection in air and in humid environment. Diffuse reflectance infrared Fourier …

3d Bio-Printability Of Hybrid Pre-Crosslinked Hydrogels, Cartwright Nelson, Slesha Tuladhar, Loren Launen, Ahasan Habib

New Hampshire EPSCoR

Maintaining shape fidelity of 3D bio-printed scaffolds with soft biomaterials is an ongoing challenge. Here, a rheological investigation focusing on identifying useful physical and mechanical properties directly related to the geometric fidelity of 3D bio-printed scaffolds is presented. To ensure during- and post-printing shape fidelity of the scaffolds, various percentages of Carboxymethyl Cellulose (CMC) (viscosity enhancer) and different calcium salts (CaCl2 and CaSO4, physical cross-linkers) were mixed into alginate before extrusion to realize shape fidelity. The overall solid content of Alginate-Carboxymethyl Cellulose (CMC) was limited to 6%. A set of rheological tests, e.g., flow curves, amplitude tests, and three interval …

Probing Secondary Coordination Sphere Interactions Within Porphyrin-Cored Polymer Nanoparticles, Brian F. Patenaude, Erik B. Berda, Samuel Pazincni

New Hampshire EPSCoR

A suite of zinc porphyrin-cored random coil polymers and polymeric nanoparticles with varying degrees of potential hydrogen bonding character and steric bulk were synthesized and characterized to study secondary coordination sphere interactions. The reaction of cyanide with N,N-dimethylformamide in the presence of porphyrin-cored polymeric nanoparticles was monitored via UV-Vis spectroscopy. It is shown that the zinc porphyrin-cored polymers and nanoparticles catalyzed the reaction of cyanide with N,N-dimethylformamide with the highest reaction rates occurring with polymeric nanoparticles with a greater number of potential hydrogen bond donors and greater steric bulk.

Conductive Stimuli-Responsive Coordination Network Linked With Bismuth For Chemiresistive Gas Sensing, Aylin Aykanat, Christopher G. Jones, Evan Cline, Robert M. Stolz, Zheng Meng, Hosea M. Nelson, Katherine A. Mirica

New Hampshire EPSCoR

This paper describes the design, synthesis, characterization, and performance of a novel semiconductive crystalline coordination network, synthesized using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligands interconnected with bismuth ions, toward chemiresistive gas sensing. Bi(HHTP) exhibits two distinct structures upon hydration and dehydration of the pores within the network, Bi(HHTP)-α and Bi(HHTP)-β, respectively, both with unprecedented network topology (2,3-c and 3,4,4,5-c nodal net stoichiometry, respectively) and unique corrugated coordination geometries of HHTP molecules held together by bismuth ions, as revealed by a crystal structure resolved via microelectron diffraction (MicroED) (1.00 Å resolution). Good electrical conductivity (5.3 × 10–3 S·cm–1) promotes the utility of this material …

Covalent Organic Frameworks As Multifunctional Materials For Chemical Detection, Zheng Meng, Katherine A. Mirica

New Hampshire EPSCoR

Sensitive and selective detection of chemical and biological analytes is critical in various scientific and technological fields. As an emerging class of multifunctional materials, covalent organic frameworks (COFs) with their unique properties of chemical modularity, large surface area, high stability, low density, and tunable pore sizes and functionalities, which together define their programmable properties, show promise in advancing chemical detection. This review demonstrates the recent progress in chemical detection where COFs constitute an integral component of the achieved function. This review highlights how the unique properties of COFs can be harnessed to develop different types of chemical detection systems based …

Unraveling The Electrical And Magnetic Properties Of Layered Conductive Metal-Organic Framework With Atomic Precision, Zheng Meng, Christopher G. Jones, Sidra Farid, Islam Ullah Khan, Hosea M. Nelson, Katherine A. Mirica

New Hampshire EPSCoR

This paper describes structural elucidation of a layered conductive metal-organic framework (MOF) material Cu3(C6O6)2 by microcrystal electron diffraction with sub-angstrom precision. This insight enables the first identification of an unusual π-stacking interaction in a layered MOF material characterized by an extremely short (2.73 Å) close packing of the ligand arising from pancake bonding and ordered water clusters within pores. Band structure analysis suggests semiconductive properties of the MOF, which are likely related to the localized nature of pancake bonds and the formation of a singlet dimer of the ligand. The spin of CuII within the Kagomé arrangement dominates the paramagnetism …

Role Of Salt-Bridging Interactions In Recognition Of Viral Rna By Arginine-Rich Peptides, Lev Levintov, Harish Vashisth

New Hampshire EPSCoR

Interactions between RNA molecules and proteins are critical to many cellular processes and are implicated in various diseases. The RNA-peptide complexes are good model systems to probe the recognition mechanism of RNA by proteins. In this work, we report studies on the binding-unbinding process of a helical peptide from a viral RNA element using nonequilibrium molecular dynamics simulations. We explored the existence of various dissociation pathways with distinct free-energy profiles that reveal metastable states and distinct barriers to peptide dissociation. We also report the free-energy differences for each of the four pathways to be 96.47 ± 12.63, 96.1 ± 10.95, …

Recent Advances In Non-Enzymatic Electrochemical Detection Of Hydrophobic Metabolites In Biofluids, Zahra Panahi, Luciana Custer, Jeffrey M. Halpern

New Hampshire EPSCoR

This review focuses on recent advances in non-enzymatic electrochemical biosensors for detection of hydrophobic metabolites. Electrochemical approaches have been widely applied in many established and emerging technologies and a large range of electrochemical biosensors have been used for detection of various hydrophobic metabolites. Despite the progress made in this field, some problems still exist, specifically, electrochemical detection of hydrophobic biomarkers can be challenging in complex biological fluids. In this review, we have highlighted some of the most representative surface modification technologies that have been employed in electrochemical biosensors to counter the problems of poor sensitivity and selectivity towards hydrophobic metabolites. …

Water Dynamics In A Peptide-Appended Pillar[5]Arene Artificial Channel In Lipid And Biomimetic Membranes, Daniel Ryan Barden, Harish Vashisth

New Hampshire EPSCoR

Peptide-appended Pillar[5]arene (PAP) is an artificial water channel that can be incorporated into lipid and polymeric membranes to achieve high permeability and enhanced selectivity for angstrom-scale separations [Shen et al. Nat. Commun. 9:2294 (2018)]. In comparison to commonly studied rigid carbon nanotubes, PAP channels are conformationally flexible, yet these channels allow a high water permeability [Y. Liu and H. Vashisth Phys. Chem. Chem. Phys. 21:22711 (2019)]. Using molecular dynamics (MD) simulations, we study water dynamics in PAP channels embedded in biological (lipid) and biomimetic (block-copolymer) membranes to probe the effect of the membrane environment on water transport characteristics of PAP …

Conformational Dynamics And Energetics Of Viral Rna Recognition By Lab-Evolved Proteins, Amit Kumar, Harish Vashisth

New Hampshire EPSCoR

The conserved and structured elements in viral RNA genomes interact with proteins to regulate various events in the viral life cycle and have become key targets for developing novel therapeutic approaches. We probe physical interactions between lab-evolved proteins and a viral RNA element from the HIV-1 genome. Specifically, we study the role of an arginine-rich loop in recognition of designed proteins by the viral RNA element. We report free energy calculations to quantitatively estimate the protein/RNA binding energetics, focusing on the mutations of arginine residues involved in recognition of the major groove of RNA by proteins.

Self-Assembly Of Porous Structures From A Binary Mixture Of Lobed Patchy Particles, Sanjib Paul, Harish Vashisth

New Hampshire EPSCoR

We report simulation studies on the self-assembly of a binary mixture of snowman and dumbbell shaped lobed particles. Depending on the lobe size and temperature, different types of self-assembled structures (random aggregates, spherical aggregates, liquid droplets, amorphous wire-like structures, amorphous ring structures, crystalline structures) are observed. At lower temperatures, heterogeneous structures are formed for lobed particles of both shapes. At higher temperatures, homogeneous self-assembled structures are formed mainly by the dumbbell shaped particles, while the snowman shaped particles remain in a dissociated state. We also investigated the porosities of self-assembled structures. The pore diameters in self-assemblies increased with an increase …

Design Of Functionalized Lobed Particles For Porous Self-Assemblies, Biswajit Gorai, Brunno C. Rocha, Harish Vashisth

New Hampshire EPSCoR

Colloidal particles fabricated with anisotropic interactions have emerged as building blocks for designing materials with various nanotechnological applications. We used coarse-grained Langevin dynamics simulations to probe the morphologies of self-assembled structures formed by lobed particles decorated with functional groups. We tuned the interactions between the functional groups to investigate their effect on the porosity of self-assembled structures formed by lobed particles with different shapes (snowman, dumbbell, trigonal planar, tetrahedral, square planar, trigonal bipyramidal, and octahedral) at different temperatures. The dumbbell, trigonal planar, and square planar shaped particles, with planar geometries, form self-assembled structures including elongated chains, honeycomb sheets, and square …

I’Ll Be Dammed! Public Preferences Regarding Dam Removal In New Hampshire, Natallia Leuchanka Diessner, Catherine M. Ashcraft, Kevin H. Gardner, Lawrence C. Hamilton

New Hampshire EPSCoR

Decisions about dams, like other environmental conflicts, involve complex trade-offs between different water uses with varying human and ecological impacts. Given the many upcoming dam decisions in New England, an improved understanding of public preferences is needed to steward resources. This research asks (1) What does the public want to see happen with dams? and (2) How do public preferences regarding dam removal vary with demography and politics? We address these questions using data from three random sample statewide telephone polls conducted in New Hampshire over 2018 that asked people for their preferences concerning dam removal versus maintaining dams for …

Role Of Conformational Heterogeneity In Ligand Recognition By Viral Rna Molecules, Lev Levintov, Harish Vashisth

New Hampshire EPSCoR

Ribonucleic acid (RNA) molecules are known to undergo conformational changes in response to various environmental stimuli including temperature, pH, and ligands. In particular, viral RNA molecules are a key example of conformationally adapting molecules that have evolved to switch between many functional conformations. The transactivation response element (TAR) RNA from the type-1 human immunodeficiency virus (HIV-1) is a viral RNA molecule that is being increasingly explored as a potential therapeutic target due to its role in the viral replication process. In this work, we have studied the dynamics in TAR RNA in apo and liganded states by performing explicit-solvent molecular …

I’Ll Be Dammed! Public Preferences Regarding Dam Removal In New Hampshire, Natallia Leuchanka Diessner, Catherine Ashcraft, Kevin H. Gardner, Lawrence C. Hamilton

New Hampshire EPSCoR

Decisions about dams, like other environmental conflicts, involve complex trade-offs between different water uses with varying human and ecological impacts, have significant impacts on public resources, and involve many stakeholders with diverse and often conflicting interests. Given the many upcoming dam decisions in New England and across the United States, an improved understanding of public preferences about dam decisions is needed to steward resources in the public interest. This research asks (1) What does the public want to see happen with dams? and (2) How do public preferences regarding dam removal vary with demography and politics? We address these questions …

Enhanced Porosity In Self-Assembled Morphologies Mediated By Charged Lobes On Patchy Particles, Brunno C. Rocha, Sanjib Paul, Harish Vashisth

New Hampshire EPSCoR

Colloidal patchy particles are particles with anisotropic “patches” decorating their surfaces. Several properties of these patches including their size, number, location, and interactions provide control over self-assembly of patchy particles into structures with desired properties. We report on simulation studies of particles where patches take the form of lobes. Based on the number and locations of lobes, these particles have different shapes (trigonal planar, square planar, tetrahedral, trigonal bipyramidal, and octahedral). We investigated the effect of incorporating charges on the lobes in achieving porous self-assembled morphologies across a range of temperatures. We observed that an increase in the charge on …

Can Science-Informed, Consensus-Based Stakeholder Negotiations Achieve Optimal Dam Decision Outcomes?, Cuihong Song, Natallia Leuchanka Diessner, Catherine M. Ashcraft, Weiwei Mo

New Hampshire EPSCoR

Integrating science and decision-making in dam management is needed to address complex tradeoffs among environmental, economic, and social outcomes across varied geographic scales and diverse stakeholder interests. In this study, we introduce an approach that integrates system dynamics modeling (SDM) and role-play simulation (RPS) to facilitate use of the best available knowledge in dam decision-making. Using a hypothetical dam decision context in the New England region of the United States, this research investigates: (1) How do science-informed, negotiated outcomes compare to Pareto-optimal outcomes produced by a scientific model that balance selected system performance tradeoffs?; and (2) How do science-informed, negotiated …

Reaction Coordinate And Thermodynamics Of Base Flipping In Rna, Lev Levintov, Sanjib Paul, Harish Vashisth

New Hampshire EPSCoR

Base flipping is a key biophysical event involved in recognition of various ligands by ribonucleic acid (RNA) molecules. However, the mechanism of base flipping in RNA remains poorly understood, in part due to the lack of atomistic details on complex rearrangements in neighboring bases. In this work, we applied transition path sampling (TPS) methods to study base flipping in a double-stranded RNA (dsRNA) molecule that is known to interact with RNA-editing enzymes through this mechanism. We obtained an ensemble of 1000 transition trajectories to describe the base-flipping process. We used the likelihood maximization method to determine the refined reaction coordinate …

On Numerical Modeling Of Equal Channel Angular Extrusion Of Ultra High Molecular Weight Polyethylene, Kostiantyn Vasylevskyi, Kateryna I. Miroshnichenko, Stanislav Buklovskyi, Igor I. Tsukrov, Hannah Grover, Douglas Van Citters

New Hampshire EPSCoR

Ultra high molecular weight polyethylene (UHMWPE) is widely used in biomedical applications, e.g. as a bearing surface in total joint arthroplasty. Recently, equal channel angular extrusion (ECAE) was proposed as a processing method to achieve higher molecular entanglement and superior mechanical properties of this material. Numerical modeling can be utilized to evaluate the influence of such important manufacturing parameters as the extrusion rate, temperature, geometry of the die, back pressure and friction effects in the ECAE of polyethylenes.

In this paper we focus on the development of efficient FE models of ECAE for UHMWPE. We study the applicability of the …

Coordinated River Infrastructure Decisions Improve Net Social-Ecological Benefits, Samuel G. Roy, Adam Daigneault, Joseph Zydlewski, Allison Truhlar, Sean Smith, Shaleen Jain, David Hart

New Hampshire EPSCoR

We explore the social, ecological, economic, and technical dimensions of sustainable river infrastructure development and the potential benefits of coordinating decisions such as dam removal and stream crossing improvement. Dam removal is common practice for restoring river habitat connectivity and ecosystem health. However, stream crossings such as culverts are often 15 times more abundant than dams and may pose similar ecological impacts. Using multi-objective optimization for a model system of 6100 dams and culverts in Maine, USA, we demonstrate substantial benefit-cost improvements provided by coordinating habitat connectivity decisions. Benefit-cost efficiency improves by two orders of magnitude when coordinating more decisions …