Trident Scholar Abstracts 2023

William T. Ashe
Midshipman First Class
United States Navy

Enhancement of Metal Organic Frameworks for Degradation of Nerve Agents

Metal-organic frameworks (MOFs) show great potential as Lewis acid catalysts for the destruction of organophosphate nerve agents such as sarin gas. Previously, they required a separate volatile aqueous base to achieve results that demonstrated ideal degradation reaction kinetics. Recent success has been achieved in incorporating azole bases into MOFs that enhance the catalytic degradation of organophosphate nerve agent mimic. This project details the effects of encapsulating azole derivatives, namely imidazole and triazoles, into zirconium-based MOF structures to yield MOF composites. Four mesoporous MOFs with average pore diameter of 2 - >10 nm were synthesized and studied. Nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA) and physisorption experiments confirmed each MOF’s structure and physical properties. The reaction kinetics of each MOF were evaluated via hydrolysis of dimethyl p-nitrophenyl phosphate (DMNP), a nerve agent mimic of sarin, using 31-P NMR; these data reveal that MOF composites containing imidazole and 3-amino-1,2,4-triazole increased reaction rates >250% compared to controls. These reaction rates approached the fastest degradation rates reported in the literature, without the use of a volatile aqueous base. Each baseline MOF was then immobilized within a mesoporous natural fiber welded cellulose fabric. The kinetics of successful DMNP degradation by these MOF-fabrics was monitored utilizing a UV-Vis spectroscopy method developed in-house. The discovery of new MOF composites that do not require constant replenishment of base to carry out catalyzed hydrolysis of organophosphate
nerve agents provides a realistic and time-effective approach to combating chemical warfare in both arid and humid environments. Integrating these nanomaterials into mesoporous natural fiber welded cellulose fabric is a novel and effective way to implement MOF structures for many Department of Defense and civilian applications, including gas mask filters and clothing that protect personnel during chemical warfare attacks.

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El Salvador’s monetary regime change in September of 2021 made bitcoin a legal tender alongside the U.S. Dollar. I evaluate the effects of this partial cryptoization on El Salvador’s sovereign credit default swap (CDS) spreads using difference-in-differences (DiD) estimation. My methodology indicates that the regime change caused an increase in El Salvador’s CDS spreads and in the variance of those spreads. These increases are indicative of a 16% increase in country risk. I calibrate a Dynamic Stochastic General Equilibrium (DSGE) model using the results of my DiD analysis to simulate how this increase in the variance of CDS spreads may impact macroeconomic behavior. My results suggest that El Salvador’s GDP will experience three times greater fluctuation as a result of bitcoin adoption. This paper also examines the causal impact of the monetary regime change on remittance inflows to El Salvador. Using the synthetic control method (SCM) and DiD estimation, I do not consistently find a causal effect on remittances.

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The debate over commercial versus public-funded ventures left the United States with two concurrent human spaceflight programs–one focused on commercial development to continue regular operations, and the other on exploration through government ventures. Focusing on the Columbia accident as a catalyst, this project charts the history and impact of the Columbia Accident Investigation Board, the Constellation program, the Commercial Orbital Transportation Services (COTS) program, and finally, the Commercial Crew program. This investigation finds that the emergence of commercial human spaceflight pivoted on a desire to replace the Space Shuttle, the economic realities of the mid-to-late 2000’s, and the placement of key personnel inside the Obama administration coinciding with the technological success of companies like SpaceX, leading to an opportunity for commercial ventures to prove their worth in the human spaceflight sector.

This project focuses first on the challenges faced by the Space Shuttle program that led ultimately to an experimental vehicle that never realized its objectives for hundreds of missions and rapid reusability. The loss of fourteen lives and two orbiters led to the Columbia Accident Investigation Board, which published its report nearly a year after the accident. The board found that mismanagement of scheduling, the mixing of precious crew and cargo, and the general mischaracterization of the shuttle as an operational, not experimental, vehicle led to the demise of Columbia and Challenger. Their report forced an examination of human spaceflight by NASA, Congress, and the President. President Bush responded in 2005 with the Vision for Space Exploration, setting a return to the Moon as the goal for NASA and commissioning NASA to develop a new program known as Constellation. This new program faced immediate challenges–primarily a lack of Congressional support for increased budgets and a variety of continuing resolutions that strung out work and froze funding on the program. By the time President Obama came into office, Constellation was years behind schedule.

Concurrently with Constellation, Mike Griffin, then the NASA Administrator, made an investment in commercial cargo transportation through the Commercial Orbital Transportation Services (COTS) program. A development program designed to help companies create cargo capsules, the program was NASA’s first investment in private space vehicles. Griffin believed in slowly building up commercial industry, including an option to provide crew to the International Space Station (ISS) within the COTS contracts, but principally planned on the Constellation program to provide access to the ISS.

President Obama and his space policy advisor, Lori Garver, came into office with an objective of fostering commercial space. A committee chaired by Norm Augustine recommended an influx of cash to NASA, and recommended potentially turning ISS crew responsibilities over to commercial providers. The Obama administration embraced this recommendation, capitalizing on an opportunity to turn over routine operations to commercial ventures. Lori Garver led a small group inside NASA that created the Commercial Crew Program and rejected government programs such as Constellation. Debates between Congress, the old guard of NASA, and the Obama administration ultimately resulted in two concurrent programs; Commercial Crew for the ISS, and the Space Launch System for exploration.

FACULTY ADVISORS
Professor Brian VanDeMark
History Department

Professor Howard McCurdy
American University

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Ryan M. Conway
Midshipman First Class
United States Navy

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Currently, there is no convenient way to measure local, microscopic thermal properties of soft and biological materials with single-digit, micron scale resolution or isolate the materials thermal conductivity from that of the thermal contact resistance between the sample and the measurement device. Due to this lack of ability to thermally characterize soft tissue, models for the melting and freezing of soft tissue cannot optimize performance and prevent damage during cryopreservation.

In this project, we lay the foundation for an all-fiber Frequency Domain Thermoreflectance (FDTR) characterization system that operates using the same basic working principles as the recently developed free-space FDTR system, which will allow for system portability. These enhanced qualities will allow for the testing of soft and biological materials in advanced microscopy (e.g., electron microscopes) and in environmental chambers to characterize the thermal properties of biological materials through freezing and thawing cycles during typical cryopreservation processes. Our all-fiber FDTR system will therefore provide the scientific community with a method to characterize the local thermal properties of biological materials with simultaneous monitoring of material morphology.

In this project, we progress the feasibility through several avenues. 1. Simulation of the fiber probe in COMSOL coupled with a sensitivity analysis of the system. These sensitivity studies included the probe in a liquid and with the probe contacting a particle. This led to findings for how several parameters such as conductivity of the transducer, thermal boundary conductance with the transducer, and particle size, could affect sensitivity to the surroundings thermal properties. 2. The Free Space FDTR system was set up and used to characterize transducer alloys. Several experimental techniques, including profilometry, four point probe measurement, and reflectivity measurements were used in tandem with our FDTR system to characterize the 2 potential transducer alloys relative properties, specifically thermoreflectance. 3. We have constructed the all fiber system ready for validation and have obtained an entirely internal thermoreflectance signal from 4 permutations of novel coated transducers.

Through modeling, characterization of transducer alloys, and early success on all fiber FDTR, the background necessary to develop a system capable of thermally characterizing soft and biological materials is well prepared. The sensitivity results, alloy characterization, and proof of concept provide the information necessary to complete and validate the system and use it to measure previously uncharacterized materials.

FACULTY ADVISORS
Associate Professor Brian Donovan
Physics Department

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Derek T. Gess
Midshipman First Class
United States Navy

Nanomaterials-Based Liquid Crystal Devices for Improving Their Stability and Electro-Optic Responses

Liquid crystals (LC) are molecules with unique properties that allow them to be extensively employed in display technology, commonly known as liquid crystal displays (LCDs). However, LC develop free-ion impurities that stem from the LC chemical synthesis process, the LC cell's electrodes, and the organic polyimide alignment layers that are used to align the LC in a uniform direction. These ionic impurities cause issues in electro-optic properties in current LCDs, such as slower response times, short-term flickering, and long-term image sticking effects. Ridding the LC cell of these ionic impurities can increase the electro-optic functionality of LCDs, allowing computer displays to function better. Two studies were conducted over the course of the project. The first study presents research showing that a small concentration of 50nm gold nano-urchin (AuNUs) particles doped in the LC significantly reduces the concentration of free ions due to the spike-like formations that exist on the AuNU surface. These spikes trap the free ions within the LC solution, reducing their overall mobility. The experiments showed a significant reduction in free-ion concentration for some of the AuNU samples, as well as an improvement in LC on-off switching time, rotational viscosity, and dielectric anisotropy. This study also analyzes the effect of varying the concentration of AuNU particles on LCs and shows how an increase in AuNU concentration does not necessarily correlate to superior performance.

The second study was an extension of the first, where five more samples - utilizing 60 nm, 70 nm, 80 nm, 90 nm, and 100 nm AuNU - were synthesized at the optimal concentration acquired through the 50nm AuNU experiments. Experiments run on each of these samples showed the effects that AuNU diameter has on the electro-optic functions of LC cells. This study also showed that an increase in LC diameter does not correlate with a decrease in free ion concentration. By performing various experiments on multiple concentrations, it was shown that an optimal concentration and diameter exist in which all tested properties were significantly improved.

FACULTY ADVISOR
Professor Rajratan Basu
Physics Department

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Cellulose, the world’s most abundant biopolymer, forms the foundation of numerous durable, renewable materials such as cotton. Through Natural Fiber Welding (NFW) with ionic liquids, cotton can be engineered into a functional biocomposite without destroying the desirable material properties it has evolved over millennia. Our lab has recently discovered how to use NFW to transform a low surface area native cotton textile into a high surface area mesoporous scaffold. After re-exposure to a polar solvent and subsequent solvent removal, this scaffold collapses into a low surface area structure with closed pores. In the current study, we explore how to use this mechanism to trap two different kinds of functional nanoparticles into cotton textiles: (i) 5 nm diameter titanium dioxide nanoparticles (TiO₂NPs) for UV protection and (ii) a nanoscale metal organic framework (MOF, UiO-67) catalyst to degrade chemical nerve agents. Diffuse transmittance UV/Vis spectroscopy was used to measure the UV-protective properties of the TiO₂NP composite textiles, while UV/Vis spectroscopy was used to evaluate the effectiveness of the MOF composite textiles. In each case, the data reveals the advantage of preparing functional biocomposites from mesoporous cellulose scaffolds, where effective nanoparticle loadings and desired physicochemical properties are achieved, even after prolonged rinsing in water.

FACULTY ADVISORS
CDR David Durkin, USN
Chemistry Department 

Professor Paul Trulove
Chemistry Department 

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Robert L. Hare
Midshipman First Class
United States Navy

Quantum Engineering in the Undergraduate Laboratory: Tests and Violations of Local Realism

The application of quantum mechanics to computing, communication, and sensing may constitute a revolution in technology. Furthermore, the field of quantum foundations has experienced high-profile success, especially in recent years, prompting the need to provide exposure to applied quantum engineering at the undergraduate level in order to ensure the development of a "quantum workforce." Entanglement is a critical aspect of quantum technology and is fundamental to quantum foundations, but entangled systems behave in strange ways. Classical systems behave in accordance with the concepts put forth by local realism, which characterizes systems as only being affected by their surroundings and that this influence cannot travel faster than the speed of light, as well as that properties of such a system are real and exist independent of a measurement made on those properties. Quantum systems, on the other hand, do not abide by the concepts of local realism and often behave in strange ways that are counter-intuitive to our classical view of the world. This project analyzes the behavior of entangled systems and the concepts of local realism through experimental verification. The initial phase of this project builds and characterizes the first entangled photon source available to undergraduates at the United States Naval Academy. Utilizing the techniques of spontaneous parametric down-conversion, we have built a high luminosity source of entangled photons integrated to optical fiber and characterized with modular single photon avalanche photodiodes. The final phase of this project conducts tests of local realism set forth by John Glauser and Alain Aspect. The primary focus of this phase is a test of the CHSH inequality as an experimentally accessible test of Bell's theorem. We use this test of local realism to further characterize the system and enable future exploration in applications of quantum information science, such as quantum computing and quantum cryptography.

FACULTY ADVISORS
Associate Professor Seth Rittenhouse
Physics Department

Associate Professor Joel Helton
Physics Department

CDR Michael Manicchia, USN
Physics Department

Dr. Peter Brereton
NASA Goddard Space Flight Center

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Jack C. Metcalf
Midshipman First Class
United States Navy

Increasing Application Security Through Interpretation

In this project, we examine the role of interpreted, higher level languages in the field of vulnerability reduction. The C programming language, despite its widespread use, has many vulnerable features that create an attack surface for an otherwise secure program. Because interpreted languages have more runtime checks than compiled binaries, they are not typically vulnerable to the same kinds of attacks. Furthermore, insecurities discovered in an interpreted language can be eliminated through patching the interpreter itself, rather than needing to update every program written in the language.

Much of what makes the C language insecure is its ‘undefined behavior.’ Rather than crash when the programmer does something they shouldn’t, C programs continue executing, and many different things can happen depending on the environment, the input to the program, and the timing of the program. This is a known in many C standards as ”undefined behavior,” and is a common vector for attackers. Because the actual behavior that occurs when a program enters an undefined state varies with the execution environment, attackers are able to manipulate the environment to control the program. Python, however, does not allow this gray area. When a Python program performs an action that is not clearly defined, the program displays an error message and exits. This behavior decreases the attack surface for Python programs, making them more secure.

Additionally, as a compiled language, C cannot perform runtime checks. A compiler is limited in that it can only perform checks when creating a program executable, but an interpreter has oversight on a process while it is running. While compilers for the C language can only statically view a program, the Python interpreter can examine the program dynamically as it executes, giving a view of the environment during execution.

To explore this method of increasing program security, we created a C to Python transpiler. A transpiler is a type of compiler, though instead of compiling a program to machine code it converts source code written in one language into source code written in another. The tool we created for this project is attempting to prove that by translating between C and Python, with no security-centered design choices, programs are less vulnerable to common exploits.

Our transpiler is built using the LLVM project’s libclang library and the Python AST library. It uses the Python3 libclang bindings to expose and manipulate the C Abstract Syntax Tree (AST), and then uses the Python AST library to create an equivalent Python tree that is reassembled into source code. While our aim is to achieve functional equivalence and clarity in the produced Python code, key differences in how Python handles memory allocation, variable typing, and structures force us to make design decisions to accommodate.

The resulting Python programs excel in reducing the security impact of the trademark memory errors that have plagued C programs for decades. Array-out-of-bounds accesses, buffer overflows, and integer overflows are all effectively eliminated in the output Python code, creating a safer, albeit slower, program with equivalent functionality to the original. To test the effectiveness of our vulnerability reduction, we tested vulnerable C programs from the NIST Juliet test suite against their Python equivalent, examining whether or not the vulnerabilities were still present.

FACULTY ADVISOR
Professor Daniel Roche
Computer Science Department 

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Rachel E. Sanborn
Midshipman First Class
United States Navy

Evaluation of Novel Atypical β-Lactams Against Mycobacterial Ldt Enzymes Toward Combating Antibiotic Resistance

Antimicrobial resistance continues to grow as a global issue. This work aims to combat this growing concern by investigating L,D-transpeptidase (Ldt) enzymes as potential new drug targets using atypically modified β-lactam compounds. Ldts perform an essential function in the formation of the peptidoglycan layer of mycobacterial cell walls. These unique Ldt enzymes provide an avenue of drug design by exploiting their essentiality in mycobacterial cell wall biosynthesis and nature specific to mycobacterial infections.

There are six evolutionarily distinct classes of mycobacterial Ldts and different mycobacteria species may have all or varying numbers of Ldt classes present. Class 2 Ldts are the most well studied due to their predominance in literature. Class 2 Ldts from various mycobacterial species—including that which causes tuberculosis—were inactivated by both a commercial and synthetic carbapenem, imipenem and compound 10a respectively. Compound 10a is an atypically modified carbapenem, a subclass of β-lactam, with demonstrated promise as a potential treatment since it more effectively killed both Mycobacterium tuberculosis (Mtb) and Mycobacterium abscessus (Mab) than a commercial carbapenem in vitro.

The two carbapenems of interest were evaluated based on their acylation kinetic profiles generated via stopped-flow tryptophan fluorescence and DynaFit non-linear regression software. Mass spectrometry data supported the nonlinear fits and rate constants produced by DynaFit software and aided in monitoring the conformational changes that occurred during inactivation, thus elucidating the mechanism by which inactivation occurs. Investigating the acylation kinetics of these compounds will further guide drug design studies toward identifying new Ldt inhibitors. Ldt-specific inhibitors would minimize undesirable gastrointestinal side-effects that are often attributed to long term antibiotic use by avoiding interaction with enzymes that are active in other biochemical processes.

FACULTY ADVISOR
Associate Professor Leighanne Basta
Chemistry Department 

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Jen Sun
Midshipman First Class
United States Navy

Tracing Learning through Historical Records using Digital Methods: The U.S. Navy Fleet Problems

The study of history preserves the lessons of the past for the benefit of the present. Times of conflict often force organizations like the Navy to learn these lessons, but usually at the cost of human life. However, from 1923 to 1940, the Navy ran a series of exercises, collectively called the Navy Fleet Problems, that provided opportunities to test new technology, revise outdated doctrine, prepare for future conflict, and advance a common understanding of naval operations. The fact that the Navy learned lessons in areas such as carrier aviation and submarine tactics with little danger to ships, resources, or personnel made the exercises noteworthy. The Fleet Problems represented a unique period when Admirals, those at the highest level of naval command, critiqued their commanders in an open forum to improve the fleet. Likewise, the commanders, motivated by the same reasons, also felt free to point out institutional deficiencies. The forum also provided junior officers the opportunity to present their lessons to all the officers in attendance. These forums produced the after-action reports on which this project focuses.

This project brought together concepts in database design, statistics, and historical research. Consequently, research and technology have become increasingly inextricable for modern history students. Whereas previous writers on the Fleet Problems scrolled through microfilms, current researchers can use the digitized versions of the reports that the National Archives published available online. Thus, digital means largely mitigate the problems ofm finding, accessing, and retrieving sources. This project deliberately designed a database informed by historical analysis to explore how participants reported their lessons learned across time, ships, and exercises. By paying attention to digital methods of making historical sources that store the learning of past generations more accessible, historians can better answer questions of institutional knowledge, naval doctrine, and the utility of fleet exercises.

FACULTY ADVISORS
Professor Marcus Jones
History Department 

Associate Professor Brice Nguelifack
Mathematics Department