Physical Sciences and Mathematics Commons^™

Synthesis And Reactivity Of Xanthene-Based Heterobimetallic Systems For Co Oxidation, Umesh Kaluarachchige Don

Wayne State University Dissertations

Nature provides a useful guideline for the design of an efficient earth-abundant catalyst for CO oxidation that relies on bimodal heterobimetallic cooperativity. Molybdenum-copper carbon monoxide dehydrogenase (Mo-Cu CODH) is an enzyme of the xanthine oxidoreductase family that catalyzes reversible oxidation of CO; it is inhibited by cyanide CN- and inserts isocyanide CNR between Cu and O/S. The active site contains molybdenum(VI) in a square pyramidal configuration with apical oxo and basal dithiolene, oxo, and sulfide ligands. The two-coordinate Cu(I) is coordinated by cysteinate and Mo-sulfide to form Mo-S-Cu bridge.While several groups have reported structural models of the active site of …

Cryptand-Based Low-Valent F-Block Complexes Toward Stabilization And Separation Of Actinides And Lanthanides, Deshika Nuwangi Kulasekara

Wayne State University Dissertations

ABSTRACTCRYPTAND-BASED LOW-VALENT F-BLOCK COMPLEXES TOWARD STABILIZATION AND SEPARATION OF ACTINIDES AND LANTHANIDES DESHIKA NUWANGI KULASEKARA August 2023 Advisor: Dr. Matthew J. Allen Major: Chemistry (Inorganic) Degree: Doctor of Philosophy This thesis consists of six chapters that include studies of the understanding of ligand environment on the stabilization and separation of low-valent lanthanides and actinides. The studies explain the trends in structural, spectroscopic, and electrochemical properties of lanthanide and actinides with respect to changes in donor atoms, denticity, basicity, and counter ions. This dissertation also discusses a ligand-modified solid–liquid extraction method to separate lanthanide from each other. A brief overview of …

Testing Different Approaches For The Stabilization Of Mdi: Design Of Low-Valent Molybdenum Complexes In Redox-Active Environments And Capture-Release Reactions Using N-Heterocyclic Carbenes, Asanka Indrajith Dissanayake

Wayne State University Dissertations

Methylene diphenyl diisocyanate (4,4’-MDI) is an aromatic diisocyanate, which is widely used as a monomer in the polyurethane industry. One of the main challenges with using 4,4’-MDI is its dimerization into uretdione. The polyurethane industry seeks solutions that could suppress dimerization of 4,4’-MDI and extend its shelf-life. The focus of this dissertation is on the design of chemical solutions to this problem including: (1) reversible coordination of MDI (heteroallene) to low-valent mono- or dimolybdenum complexes in redox-active ligand environment, and (2) reversible coordination of MDI with two equivalents of an appropriate N-heterocyclic carbene.

MDI (isocyanate) is a heteroallene, and heteroallenes …

Hyperpolarized Nitrogen-15 Mri Contrast Agents For Hypoxia Sensing Via Reversible Exchange With Parahydrogen, Mohammad Shah Hafez Kabir

Wayne State University Dissertations

The detection of hypoxia in hypoxic-related diseases can provide crucial information for treatment planning and assessment of therapy response. Although Positron Emission Tomography (PET) was employed as a research tool for imaging of hypoxia detection, it has several limitations. Our motivation is to develop a hyperpolarized (HP) molecular probe for hypoxia sensing. My dissertation presents the utility of Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) to hyperpolarize a wide range of N-heterocyclic compounds, which can be employed as MRI contrast agents for hypoxia sensing and other molecular imaging applications.SABRE-SHEATH is a rapid, simple, cost-effective …

Studies On Non-Transition Metal Substitution To Ab2 Metal Hydride Alloys For Battery Application, Shiuan Chang

Wayne State University Dissertations

Nowadays, multiphase transition metal-based AB2 metal hydride alloys and the rare-earth metal-based AB5 alloys (currently used in consumer NiMH batteries) are used as negative electrodes in NiMH batteries. It is of great interest to explore the possibility of significantly improving NiMH battery performance to compete with Li-ion batteries. In this area, the effect of dopant elements from Group-IA, -IIA, -IIIA non-transition metal family has not been thoroughly studied. In this study, lithium, magnesium, and boron (a metalloid considered metal in this study) were chosen as modifiers in the C14-phase predominant AB2 alloy by different dopant concentrations and synthesis methods, doping …

Improving Lidar Fidelity For Hd Mapping Using Pattern Transplanting And Temporal Infill, Micah Bojrab

Wayne State University Dissertations

High Definition (HD) Mapping for Autonomous Driving creates an easily accessible wealth of information to confirm and enrich feedback from on-vehicle sensors. HD Maps built offline generally use dedicated ground collection vehicles equipped with high-cost, survey-grade LiDAR to accurately map a vehicle's areas of operation. We focus our work on controlled-access, divided highways characterized by wide roadways that require complex permutations to cover all directions of travel and access ramps. We study two common issues when collecting this road class that cause low-fidelity (LF) point clouds for HD Maps. First, aerial collection covers all directions and all ramps in a …

Predictable Dnn Inference For Autonomous Driving, Liangkai Liu

Wayne State University Dissertations

Deep neural networks (DNNs) are widely used in autonomous driving due to their high accuracy for perception, decision, and control. Predictability of the perception module is essential for the AV's safety. Predictability generally consists of two aspects: temporal and functional. Temporal aspects mean the task should be finished before the deadline. Functional aspects mean the task should make correct decisions. However, non-negligible time and performance variations are observed in DNN inference. Current DNN inference studies either ignore the variation issue or rely on the scheduler or the algorithm itself to handle it. None of the current work explains the roots …

Study Of Bounds For Effective Moduli Of Polycrystals And Composites Using Variational Principle For Probabilistic Measures, Md. Tofiqul Islam

Wayne State University Dissertations

Tensors that are invariant with respect to subgroups of 3D group of rotations were constructed first by Lokhin and Sedov (J. Appl. Math. Mech. (PMM), 1963, 27, 597-629). In this paper we do one more step and derive formulas for the elastic modulus tensors for all symmetry groups from the Lokhin-Sedov results. The tensor basis obtained in this way has an advantage of being built upon the same tensors that are used in construction of nonlinear tensor functions. One consequence of the formulas derived is that the number of types of anisotropic elastic behaviors is ten. There is a long- …

Mathematics For Biomedical Physics, Jogindra M. Wadehra

Open Textbooks

Mathematics for Biomedical Physics is an open access peer-reviewed textbook geared to introduce several mathematical topics at the rudimentary level so that students can appreciate the applications of mathematics to the interdisciplinary field of biomedical physics. Most of the topics are presented in their simplest but rigorous form so that students can easily understand the advanced form of these topics when the need arises. Several end-of-chapter problems and chapter examples relate the applications of mathematics to biomedical physics. After mastering the topics of this book, students would be ready to embark on quantitative thinking in various topics of biology and …

Control Implemented On Quantum Computers: Effects Of Noise, Nondeterminism, And Entanglement, Kip Nieman, Keshav Kasturi Rangan, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

Quantum computing has advanced in recent years to the point that there are now some quantum computers and quantum simulators available to the public for use. In addition, quantum computing is beginning to receive attention within the process systems engineering community for directions such as machine learning and optimization. A logical next step for its evaluation within process systems engineering is for control, specifically for computing control actions to be applied to process systems. In this work, we provide some initial studies regarding the implementation of control on quantum computers, including the implementation of a single-input/single-output proportional control law on …

Actuator Cyberattack Handling Using Lyapunov-Based Economic Model Predictive Control, Keshav Kasturi Rangan, Henrique Oyama, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

Cybersecurity has gained increasing interest as a consequence of the potential impacts of cyberattacks on profits and safety. While attacks can affect various components of a plant, prior work from our group has focused on the impact of cyberattacks on control components such as process sensors and actuators and the development of detection strategies for cybersecurity derived from control theory. In this work, we provide greater focus on actuator attacks; specifically, we extend a detection and control strategy previously applied for sensor attacks and based on an optimization-based control technique called Lyapunov-based economic model predictive control (LEMPC) to detect attacks …

Test Methods For Image-Based Information In Next-Generation Manufacturing, Henrique Oyama, Dominic Messina, Renee O'Neill, Samantha Cherney, Minhazur Rahman, Keshav Kasturi Rangan, Govanni Gjonaj, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

Typical control designs in the process systems engineering literature have assumed that the primary sensing methodologies are traditional instruments such as thermocouples. Dig- italization is changing the landscape for manufacturing, and data-based sensing modalities (e.g., image-based sensing) are becoming of greater interest for plant control. These considerations require novel test/evaluation solutions. For example, process systems engineering researchers may wish to test image-based sensors in simulation. In this work, we provide preliminary thoughts on how image-based technologies might be evaluated via simulation for process systems.

Quantum Computing And Resilient Design Perspectives For Cybersecurity Of Feedback Systems, Keshav Kasturi Rangan, Jihan Abou Halloun, Henrique Oyama, Samantha Cherney, Ilham Azali Assoumani, Nazir Jairazbhoy, Helen Durand, Simon Ka Ng

Chemical Engineering and Materials Science Faculty Research Publications

Cybersecurity of control systems is an important issue in next-generation manufac- turing that can impact both operational objectives (safety and performance) as well as process designs (via hazard analysis). Cyberattacks differ from faults in that they can be coordinated efforts to exploit system vulnerabilities to create otherwise unlikely hazard scenarios. Because coordination and targeted process manipulation can be characteristics of attacks, some of the tactics previously analyzed in our group from a control system cybersecurity perspective have incorporated randomness to attempt to thwart attacks. The underlying assumption for the generation of this randomness has been that it can be achieved …

Challenges And Opportunities For Next-Generation Manufacturing In Space, Kip Nieman, A. F. Leonard, Katie Tyrell, Dominic Messina, Rebecca Lopez, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

With commercial space travel now a reality, the idea that people might spend time on other planets in the future seems to have greater potential. To make this possible, however, there needs to be flexible means for manufacturing in space to enable tooling or resources to be created when needed to handle unexpected situations. Next-generation manufacturing paradigms offer significant potential for the kind of flexibility that might be needed; however, they can result in increases in computation time compared to traditional control methods that could make many of the computing resources already available on earth attractive for use. Furthermore, resilience …

The Short-Term Effects Of Fine Airborne Particulate Matter And Climate On Covid-19 Disease Dynamics, El Hussain Shamsa, Kezhong Zhang

Medical Student Research Symposium

Background: Despite more than 60% of the United States population being fully vaccinated, COVID-19 cases continue to spike in a temporal pattern. These patterns in COVID-19 incidence and mortality may be linked to short-term changes in environmental factors.

Methods: Nationwide, county-wise measurements for COVID-19 cases and deaths, fine-airborne particulate matter (PM_2.5), and maximum temperature were obtained from March 20, 2020 to March 20, 2021. Multivariate Linear Regression was used to analyze the association between environmental factors and COVID-19 incidence and mortality rates in each season. Negative Binomial Regression was used to analyze daily fluctuations of COVID-19 cases …

The Local Cohomology Spectral Sequence For Topological Modular Forms, Robert Bruner, John Greenlees, John Rognes

Mathematics Faculty Research Publications

We discuss proofs of local cohomology theorems for topological modular forms, based on Mahowald–Rezk duality and on Gorenstein duality, and then make the associated local cohomology spectral sequences explicit, including their differential patterns and hidden extensions.

On-Line Process Physics Tests Via Lyapunov-Based Economic Model Predictive Control And Simulation-Based Testing Of Image-Based Process Control, Henrique Oyama, A. F. Leonard, Minhazur Rahman, Govanni Gjonaj, Michael Williamson, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

Next-generation manufacturing involves increasing use of automation and data to enhance process efficiency. An important question for the chemical process industries, as new process systems (e.g., intensified processes) and new data modalities (e.g., images) are integrated with traditional plant automation concepts, will be how to best evaluate alternative strategies for data-driven modeling and synthesizing process data. Two methods which could be used to aid in this are those which aid in testing data-based techniques on-line, and those which enable various data-based techniques to be assessed in simulation. In this work, we discuss two techniques in this domain which can be …

The Adams Spectral Sequence For The Image-Of-J Spectrum, Robert R. Bruner, John Rognes

Mathematics Faculty Research Publications

We show that if we factor the long exact sequence in cohomology of a cofiber sequence of spectra into short exact sequences, then the d_2-differential in the Adams spectral sequence of any one term is related in a precise way to Yoneda composition with the 2-extension given by the complementary terms in the long exact sequence. We use this to give a complete analysis of the Adams spectral sequence for the connective image-of-J spectrum, finishing a calculation that was begun by D. Davis [Bol. Soc. Mat. Mexicana (2) 20 (1975), pp. 6–11].

The Gelfand Problem For The Infinity Laplacian, Fernando Charro, Byungjae Son, Peiyong Wang

Mathematics Faculty Research Publications

We study the asymptotic behavior as p → ∞ of the Gelfand problem

−Δ_pu = λe^u in Ω ⊂ Rⁿ, u = 0 on ∂Ω.

Under an appropriate rescaling on u and λ, we prove uniform convergence of solutions of the Gelfand problem to solutions of

min{|∇_u|−Λe^u, −Δ_∞u} = 0 in Ω, u = 0 on ∂Ω.

We discuss existence, non-existence, and multiplicity of solutions of the limit problem in terms of Λ.

Asymptotic Mean-Value Formulas For Solutions Of General Second-Order Elliptic Equations, Pablo Blanc, Fernando Charro, Juan J. Manfredi, Julio D. Rossi

Mathematics Faculty Research Publications

We obtain asymptotic mean-value formulas for solutions of second-order elliptic equations. Our approach is very flexible and allows us to consider several families of operators obtained as an infimum, a supremum, or a combination of both infimum and supremum, of linear operators. The families of equations that we consider include well-known operators such as Pucci, Issacs, and k-Hessian operators.

Lyapunov-Based Economic Model Predictive Control For Detecting And Handling Actuator And Simultaneous Sensor/Actuator Cyberattacks On Process Control Systems, Henrique Oyama, Dominic Messina, Keshav Kasturi Rangan, Helen Durand

Chemical Engineering and Materials Science Faculty Research Publications

The controllers for a cyber-physical system may be impacted by sensor measurement cyberattacks, actuator signal cyberattacks, or both types of attacks. Prior work in our group has developed a theory for handling cyberattacks on process sensors. However, sensor and actuator cyberattacks have a different character from one another. Specifically, sensor measurement attacks prevent proper inputs from being applied to the process by manipulating the measurements that the controller receives, so that the control law plays a role in the impact of a given sensor measurement cyberattack on a process. In contrast, actuator signal attacks prevent proper inputs from being applied …

The Cohomology Of The Mod 2 Steenrod Algebra, Robert R. Bruner, John Rognes

Open Data at Wayne State

The dataset contains a minimal resolution of the mod 2 Steenrod algebra in the range 0 < = s < = 128, 0 < = t < = 200, together with chain maps for each cocycle in that range and for the squaring operation Sq^0 in the cohomology of the Steenrod algebra. The included document CohomA2.pdf explains the contents and usage of the dataset in detail (also available as supplemental material in this record).

Dataset is also available at the NIRD Research Data Archive, https://doi.org/10.11582/2021.00077; Data Description also available at arXiv.org, https://doi.org/10.48550/arXiv.2109.13117.

Parametric And Reliability Estimation Of The Kumaraswamy Generalized Distribution Based On Record Values, Mohd. Arshad, Qazi J. Azhad

Journal of Modern Applied Statistical Methods

A general family of distributions, namely Kumaraswamy generalized family of (Kw-G) distribution, is considered for estimation of the unknown parameters and reliability function based on record data from Kw-G distribution. The maximum likelihood estimators (MLEs) are derived for unknown parameters and reliability function, along with its confidence intervals. A Bayesian study is carried out under symmetric and asymmetric loss functions in order to find the Bayes estimators for unknown parameters and reliability function. Future record values are predicted using Bayesian approach and non Bayesian approach, based on numerical examples and a monte carlo simulation.

Does The Type Of Records Affect The Estimates Of The Parameters?, Ayush Tripathi, Umesh Singh, Sanjay Kumar Singh

Journal of Modern Applied Statistical Methods

The maximum likelihood estimation of the unknown parameters of inverse Rayleigh and exponential distributions are discussed based on lower and upper records. The aim is to study the effect of the type of records on the behavior of the corresponding estimators. Mean squared errors are calculated through simulation to study the behavior of the estimators. The results shall be of interest to those situations where the data can be obtained in the form of either of the two types of records and the experimenter must decide between these two for estimation of the unknown parameters of the distribution.

Design Of Sksp-R Plan For Popular Statistical Distributions, Jaffer Hussain, S. Balamurali, Muhammad Aslam

Journal of Modern Applied Statistical Methods

The design of a Skip-lot sampling plan of type SkSP-R is presented for time truncated life test for the Weibull, Exponentiated Weibull, and Birnbaum-Saunders lifetime distributions. The plan parameters of the SkSP-R plan under these three distributions are determined through a nonlinear optimization problem. Tables are also constructed for each distribution. The advantages of the proposed plan over the existing sampling schemes are discussed. Application of the proposed plan is explained with the help of an example. The Birnbaum-Saunders distribution is economically superior to other two distributions in terms of minimum average sample number.

Parameter Estimation Based On Double Ranked Set Samples With Applications To Weibull Distribution, Mohamed Abd Elhamed Sabry, Hiba Zeyada Muhammed, Mostafa Shaaban, Abd El Hady Nabih

Journal of Modern Applied Statistical Methods

In this paper, the likelihood function for parameter estimation based on double ranked set sampling (DRSS) schemes is introduced. The proposed likelihood function is used for the estimation of the Weibull distribution parameters. The maximum likelihood estimators (MLEs) are investigated and compared to the corresponding ones based on simple random sampling (SRS) and ranked set sampling (RSS) schemes. A Monte Carlo simulation is conducted and the absolute relative biases, mean square errors, and efficiencies are compared for the different schemes. It is found that, the MLEs based on DRSS is more efficient than MLE using SRS and RSS for estimating …

A New Goodness Of Fit Measure Based On Income Inequality Curves, Shahryar Mirzaei, S. M. A. Jahanshahi

Journal of Modern Applied Statistical Methods

This paper uses inequality-measurement techniques to assess goodness of fit in income distribution models. It exposes the shortcomings of the use of conventional goodness of fit criteria in face of the big income data and proposes a new set of metrics, based on income inequality curves. In this note, we mentioned that the distance between theoretical and empirical inequality curves can be considered as a goodness of fit criterion. We demonstrate certain advantages of this measure over the other general goodness of fit criteria. Unlike other goodness of fit measures, this criterion is bounded. It is 0 in minimum difference …

Chemical Proteomic Identification And Functional Studies Of Cardiac Protein Glutathionylation, Maheeshi Yapa Abeywardana

Wayne State University Dissertations

Elevated intracellular levels of reactive oxygen species (ROS) are associated with induction of oxidative stress. Increased levels of ROS participate in development of cardiovascular diseases by modifying proteins reversibly or irreversibly. Especially, the cysteine residues can undergo oxidative post-translational modifications such as glutathionylation. Glutathionylation is an important regulatory reversible thiol oxidation. Identification and quantification of glutathionylated proteins is important for the understanding of the molecular mechanisms behind initiation and progression of many diseases. Our lab previously developed a click chemistry-based method to detect and identify glutathionylation in cells by synthesizing clickable-glutathione.We established a mass spectrometry-based strategy coupled with clickable glutathione …

Development Of New Photochemical Tools For Applications In Cancer Research And Enzymatic Signaling, Nicholas Paul Toupin

Wayne State University Dissertations

Photochemical tools empower researchers to act with precision and control over the cellular environment through production of reactive oxygen species (ROS), targeted drug delivery, and modulation of enzymatic activity. These molecular tools use light as a readily available, biorthogonal reagent for initiating advantageous light-activated reactions. Using light in this way allows researchers to affect the cellular environment in specific ways with high spatio-temporal control. This dissertation focuses on expanding the applications of, mostly Ru(II)-based, photoactivated chemicals. Complexes of this type are able to act as photosensitizers in photodynamic therapy (PDT), as photocages (PCT), or as dual-action compounds capable of both …

The Development Of Fundamental Insights Into The Electronic Behaviors Of Next-Generation Materials, Sydney Lavan

Wayne State University Dissertations

We develop the fundamental mechanistic understanding of the microscopic behavior of three next generation materials: antiferroelectrics, hybrid perovskites and metal organic frameworks. These materials have the potential to be used in energy and light related applications which could provide a solution for the energy efficiency challenges we face in todays society. Ideally we need to begin to bridge the gap of developing candidate materials that possess high power density and high energy density. The first step in bridging this gap is understanding how the material influ- ences its structure and thus the properties and performance. We leverage vibrational spectroscopy and …