Chemistry Commons^™

Machine Learning‑Assisted Low‑Dimensional Electrocatalysts Design For Hydrogen Evolution Reaction, Jin Li, Naiteng Wu, Jian Zhang, Hong‑Hui Wu, Kunming Pan, Yingxue Wang, Guilong Liu, Xianming Liu, Zhenpeng Yao, Qiaobao Zhang

Department of Chemistry: Faculty Publications

Efficient electrocatalysts are crucial for hydrogen generation from electrolyzing water. Nevertheless, the conventional "trial and error" method for producing advanced electrocatalysts is not only cost-ineffective but also time-consuming and labor-intensive. Fortunately, the advancement of machine learning brings new opportunities for electrocatalysts discovery and design. By analyzing experimental and theoretical data, machine learning can effectively predict their hydrogen evolution reaction (HER) performance. This review summarizes recent developments in machine learning for low-dimensional electrocatalysts, including zero-dimension nanoparticles and nanoclusters, one-dimensional nanotubes and nanowires, two-dimensional nanosheets, as well as other electrocatalysts. In particular, the effects of descriptors and algorithms on screening low-dimensional electrocatalysts …

Neuronal Nadph Oxidase Is Required For Neurite Regenerationof Aplysia Bag Cell Neurons, S.M. Sabbir Alam, Yuichiro Watanabe, Brooke L. Steeno, Soumyajit Dutta, Halie A. Szilagyi, Alexander Wei, Daniel M. Suter

Department of Chemistry Faculty Publications

NADPH oxidase (Nox), a major source of reactive oxygen species (ROS), is involved in neurodegeneration after injury and disease. Nox is expressed in both neuronal and non-neuronal cells and contributes to an elevated ROS level after injury. Contrary to the well-known damaging effect of Nox-derived ROS in neurodegeneration, recently a physiological role of Nox in nervous system development including neurogenesis, neuronal polarity, and axonal growth has been revealed. Here, we tested a role for neuronal Nox in neurite regeneration following mechanical transection in cultured Aplysia bag cell neurons. Using a novel hydrogen peroxide (H2O2)-sensing dye, 5′-(p-borophenyl)-2′-pyridylthiazole pinacol ester (BPPT), we …

Recent Advances In Crispr/Cas9-Assisted Gene Therapy, Apeksha Srivastava, Shikha Chauhan, Vishal Ahuja

Karbala International Journal of Modern Science

CRISPR/Cas9 (Clustered regularly interspaced short palindromic repeats) is an exponentially growing tool with wide-spread applications in therapeutics like gene modifications that focus on altering the hereditary material to repair or eliminate any defective gene-causing diseases like cancer, AIDS (Acquired immunodeficiency syndrome), etc. It also includes the identification of the target sequence with the help of sgRNA followed by the substitution of a malfunction-ing gene with a normal version. It offers high efficiency, specificity, and post-gene-editing efficacy, but have also some off-target impressions, and immunogenic effects. The contribution of CRISPR/Cas9 has already been proved primarily in in-vitro studies using animal germ …

Optical, Structural, And Electrochemical Properties Of P3ht:Y6 Photoactive Layer For Organic Photovoltaics, Hassan Tarikhum B., Furqan Almyahi, Basil Ali

Karbala International Journal of Modern Science

Recently, organic photovoltaics (OPV) have emerged as a promising technology for environmentally friendly energy production. Achieving high performance in OPV requires the discovery of novel compounds. This article aims to study the optical, structural, electrochemical, and electrical properties of a P3HT:Y6 blend. The UV-visible spectra of the blend provided insight into how composition affects the optoelectronic properties of OPV devices. The optimised P3HT:Y6 ratio (0.6:1) resulted in the largest redshift and the highest absorption intensity. Raman and X-ray diffraction tests showed low aggregation and low crystallinity of the polymer P3HT as Y6 content increased. In the OPV devices, the best …

Estimation Of Water Quality Of Dikhu River Of Nagaland Through A Combination Of Water Quality Index And Principal Component Analysis Techniques., Lanuyanger Longchar, Wati Temjen, Khikeya Semy, Wati Lemla

Karbala International Journal of Modern Science

Monitoring the physico-chemical attributes of water is essential for determining water quality. The present study explores the effect of various anthropogenic factors on the quality of Dikhu River, Nagaland. Water samples from three sampling stations were compared against three standards: Indian Council of Medical Research, Bureau of Indian Standards, and World Health Organization. Although all parameters were within the permissible limits, the Water Quality Index categorized all sites during the rainy season as "poor quality", highlighting anthropogenic impacts. A principal component analysis created a Minimum Data Set (MDS) explaining 100%, 93.27%, and 96.26% of the total variance for the three …

Phytochemical Constituent And Antioxidant Activity Evaluation Of Red Seaweed Eucheuma Sp., Ade Arsianti

Indonesian Journal of Medical Chemistry and Bioinformatics

Oxidative stress is a condition in which there is an imbalance between production of free radicals and protective response via antioxidant system. There are endogenous and exogenous antioxidants, however as age increases, there is a reduction in endogenous antioxidant, thus the search for potential exogenous antioxidants which could be derived from natural resources are needed. Indonesia is a megabiodiversity country which has more than 30,000 species of plants and animals. Red seaweed Eucheuma sp. is one of marine macroalgae species which shows potent biological activities. This study aims to determine the phytochemical constituent and to evaluate the antioxidant activity of …

Scope And Mechanism Of The Ruthenium-Catalyzed Deaminative Coupling Reaction Of Enones With Amines Via Regioselective CΑ–CΒ Bond Cleavage, Marat R. Talipov, Dulanjali S. Thennakoon, Chae S. Yi

Chemistry Faculty Research and Publications

A highly regioselective C–C bond cleavage method of enones has been devised from the ruthenium-catalyzed deaminative coupling reaction with simple amines. The analogous catalytic coupling reaction of enones with anilines has led to a regioselective C_α–C_β bond cleavage of enones in forming N-alkylanilines and 2,4-disubstituted quinolines. The reaction profile study showed the formation of a β-aminoimine intermediate prior to the C–C cleavage product formation. A Hammett plot from the reaction of (E)-2-octen-4-one with a series of para-substituted benzylamines established a strong promotional effect by an electron-donating group (ρ = −0.77 ± 0.1). The …

Ab Initio Quantum Scattering Calculations And A New Potential Energy Surface For The Hcl(X¹Σ+)-O2( X 3 Σ G − ) System: Collision-Induced Line Shape Parameters For O2-Perturbed R(0) 0-0 Line In H35cl, Artur Olejnik, Hubert Jóźwiak, Maciej Gancewski, Ernesto Quintas-Sánchez, Richard Dawes, Piotr Wcisło

Chemistry Faculty Research & Creative Works

The Remote Sensing of Abundance and Properties of HCl—the Main Atmospheric Reservoir of Cl Atoms that Directly Participate in Ozone Depletion—is Important for Monitoring the Partitioning of Chlorine between "Ozone-Depleting" and "Reservoir" Species. Such Remote Studies Require Knowledge of the Shapes of Molecular Resonances of HCl, Which Are Perturbed by Collisions with the Molecules of the Surrounding Air. in This Work, We Report the First Fully Quantum Calculations of Collisional Perturbations of the Shape of a Pure Rotational Line in H35Cl Perturbed by an Air-Relevant Molecule [As the First Model System We Choose the R(0) Line in HCl Perturbed by …

Investigating Rare Genetic Variants Of Unknown Significance In Ldha, Animesh Dali, Brennan Jensen, Olivia Lockette, Duyen Nguyen

Annual Student Research Poster Session

The exponential expansion and advancement of genetic sequencing has revealed the molecular basis of many genetic diseases. However, many genetic mutations are still classified as variants of unknown significance (VUS). Our lab focused on eleven missense variants in Lactate Dehydrogenase A (LDHA), an enzyme vital in anaerobic respiration. The intent with our research is to produce data on the kinetic functionality of wild type LDHA and compare this to its mutants of unknown significance. This data, supplemented with the structural information of the mutants can help reduce the ambiguity in the diagnosis of genetic disorders involving the LDHA enzyme. Currently, …

Investigating Sucrose And D-Trehalose In Aot Reverse Micelles, Delaney Collier, Bridget L. Gourley

Annual Student Research Poster Session

Reverse micelles are nanosized structures that encapsulate small water pools and allow us to investigate the fundamental interactions of small organic molecules in nanoconfinement. The behavior of small organic molecules, sometimes referred to as osmolytes, differs in bulk solution and confinement. Because reverse micelles are a good model for biological nanoconfinement, investigating osmolytes in reverse micelle systems can help us to better understand the role they play in biological systems. Optical spectroscopy such as UV-Vis, Fluorescence, and Red Edge Excitation (REES) was used to probe the environment of the reverse micelles. Three small organic molecules were studied: a monosaccharide, d-glucose, …

Gaxin2-Xo3 Surface Pyramids Interaction With Formaldehyde: Thermodynamic And Sensing Analysis, Mudar Ahmed Abdulsattar

Karbala International Journal of Modern Science

GaxIn2-xO3 surface pyramids' electronic structures are investigated using density functional theory, including dispersion corrections. Application of GaxIn2-xO3 surface pyramids as a gas sensor for formaldehyde is also performed and compared with experimental findings. These findings show that the energy gap of these pyramids follows closely with the bulk values. The energy gap increases between the two limits, In2O3 and Ga2O3. Applying GaxIn2-xO3 surface pyramids as a gas sensor uses transition state theory formalism. Thermodynamic quantities such as activation Gibbs energy, enthalpy, and entropy are needed for temperature-dependent calculations. A comparison of sensor response which is proportional to reaction rate as …

Substituent Effects And Mechanistic Insights On The Catalytic Activities Of (Tetraarylcyclopentadienone)Iron Carbonyl Compounds In Transfer Hydrogenations And Dehydrogenations, Bryn K. Werley, Xintong Hou, Evan P. Bertonazzi, Anthony Chianese, Timothy W. Funk

Chemistry Faculty Publications

(Cyclopentadienone)iron carbonyl compounds are catalytically active in carbonyl/imine reductions, alcohol oxidations, and borrowing hydrogen reactions, but the effect of cyclopentadienone electronics on their activity is not well established. A series of (tetraarylcyclopentadienone)iron tricarbonyl compounds with varied electron densities on the cyclopentadienone were prepared, and their activities in transfer hydrogenations and dehydrogenations were explored. Additionally, mechanistic studies, including kinetic isotope effect experiments and modifications to substrate electronics, were undertaken to gain insights into catalyst resting states and turnover-limiting steps of these reactions. As the cyclopentadienone electron density increased, both the transfer hydrogenation and dehydrogenation rates increased. A catalytically relevant, trimethylamine-ligated iron …

Modification Of Thermally Activated Delayed Fluorescence Emitters Comprising Acridan– Pyrimidine Moieties For Efficient Sky-Blue To Greenish-Blue Oleds, Yi-Zhen Li, Hsuan-Chi Liang, Chia-Hsun Chen, Ching-Huang Chiu, Bo-Yen Lin, Jake A. Tan, Jiun-Haw Lee, Tien-Lung Chiu, Man-Kit Leung

Chemistry Faculty Publications

Thermally activated delayed fluorescence (TADF) is a promising approach to harvest triplet excitons and achieve high-performance organic light-emitting diodes (OLEDs) for displays. In this study, we synthesized two new TADF emitters, 4Ac25CzPy and 4Ac35CzPy, featuring acridan–pyrimidine–carbazole moieties. Remarkably, a slight modification in the carbazole group position enables precise control of luminous color, resulting in emissions at 483 nm and 494 nm for 4Ac25CzPy and 4Ac35CzPy, respectively, in the electroluminescent device. Both compounds exhibit small energy difference between their singlet and triplet states (DEST) of 0.14 eV and 0.15 eV, confirming their TADF characteristics. Notably, OLEDs utilizing 4Ac35CzPy achieve outstanding performance …

Multiexciton Quintet State Populations In A Rigid Pyrene-Bridged Parallel Tetracene Dimer, Liang-Chun Lin, Tanner Smith, Qianxiang Ai, Brandon K. Rugg, Chad Risko, John E. Anthony, Niels H. Damrauer, Justin C. Johnson

UK CARES Faculty Publications

The multiexciton quintet state, 5 TT, generated as a singlet fission intermediate in pairs of molecular chromophores, is a promising candidate as a qubit or qudit in future quantum information science schemes. In this work, we synthesize a pyrene-bridged parallel tetracene dimer, TPT, with an optimized interchromophore coupling strength to prevent the dissociation of 5 TT to two decorrelated triplet (T1) states, which would contaminate the spin-state mixture. Long-lived and strongly spin-polarized pure 5 TT state population is observed via transient absorption spectroscopy and transient/pulsed electron paramagnetic resonance spectroscopy, and its lifetime is estimated to be >35 ms, with the …

Raman Spectral Cytopathology For Cancer Diagnostic Applications, Fiona Lyng, Damian Traynor, Isha Behl, Declan O'Dea, Hugh Byrne

Books/Book Chapters

Histopathology is currently regarded as the “gold standard” patient sampling technique for cancer diagnostics. It involves extraction of a tissue sample, or biopsy, which is then sectioned and stained for evaluation by a pathologist [1]. Cytopathology, on the other hand, is the field of disease diagnosis at the cellular level [2], necessitating only the microscopic evaluation of samples of cells which can be harvested by less invasive methods such as exfoliative brushing, needle probes or from biofluids. Based on the identification of abnormalities in cellular appearance, cytopathology is currently widely used to aid in the screening of cancer, as well …

Depolymerizing Self-Immolative Polymeric Lanthanide Chelates For Vascular Imaging., Eric Grolman, Quinton E A Sirianni, Joy Dunmore-Buyze, Charmainne Cruje, Maria Drangova, Elizabeth R Gillies

Chemistry Publications

Medical imaging is widely used clinically and in research to understand disease progression and monitor responses to therapies. Vascular imaging enables the study of vascular disease and therapy, but exogenous contrast agents are generally needed to distinguish the vasculature from surrounding soft tissues. Lanthanide-based agents are commonly employed in MRI, but are also of growing interest for micro-CT, as the position of their k-edges allows them to provide enhanced contrast and also to be employed in dual-energy micro-CT, a technique that can distinguish contrast-enhanced blood vessels from tissues such as bone. Small molecule Gd3+ chelates are available, but are excreted …

The Impact Of Lead Corrosion Relating To The Contamination Of Drinking Water In Canada And In Indigenous Communities., Jessie A. Mcdonald

Corrosion Research

No abstract provided.

Development Of Cu-Catalyzed Oxidative Alkylboron Homocoupling, Dan Khazaei, Andrew Baggett, Katie Russell

Student Presentations

No abstract provided.

The Coastal Monitor: Vol. 10 No. 2, John Tanacredi Ph.D.

The Coastal Monitor

Stephen J. Gould’s prophetic piece, “The Golden Rule: A Proper Scale for Our Environmental Crisis”, noted that, “Patience enjoys a long pedigree of favor”, which he elaborated, “usually involves a deep understanding of the fundamental principle… rarely grasped in daily life – the effects of scale.” Scientists observe changes incessantly, in dimensions and time, from microscopic conditions of cellular biology to the inconceivable distances of galaxies and their influences on Earth.

Scandium Triflate-Catalyzed Aromatic Aldehydic C-H Activation, Nicholas Griffin

Honors Projects

Herein described is a scandium triflate-catalyzed C-H activation of commercially available aromatic aldehydes achieved in low yields. The reaction occured in a one-pot synthesis over a two-hour duration and required minimal purification. Inclusion of a fluorine-tagged phenol allowed for reaction monitoring via ¹⁹FNMR.

George C. Caldwell (1834-1907): American Agricultural Chemist, Pat Munday

Interdisciplinary Arts and Sciences Articles

George Caldwell served as president of the American Chemical Society (ACS) in 1892. Prior to this time, the ACS had been a rather parochial New York City based organization. In 1890, the constituency of the ACS expressed its desire to become a truly national body. Toward this end, it forged closer ties with the Chemical Section of the American Association for the Advancement of Science (AAAS), and merged with the Chemical Section in 1891. As Caldwell had been active with the AAAS group for several years previous to this merger, his election to the presidency of the ACS can be …

Investigation, Synthesis And Rational Design Of Novel Transuranic Containing Extended Structures, Adrian Thomas Hines

Theses and Dissertations

The use of nuclear technology has proven useful for energy generation and for weapons manufacturing, but disposal and storage of nuclear waste is an ongoing problem. The accumulation of nuclear waste over the past decades has yielded a vast amount of waste that must be dealt with, and with space at interim storage facilities diminishing, it has become increasingly important to find solutions to nuclear waste storage. The vitrification process has been widely accepted as a viable route for immobilization of high-level waste; however, the process is inadequate for complex waste streams and has many drawbacks such as limited waste …

Exploring The Assembly Of Soluble Triphenylamine Bis-Urea Macrocycles; Synthesis Of Nsc243928 Derivatives For Triple-Negative Breast Cancer Treatment, Rahul Prakash

Theses and Dissertations

This dissertation is divided into two topics: I. Supramolecular polymerization of triphenylamine (TPA) bis-urea macrocycle behavior in solution, and II. Synthesis of fluorophore appended and biotinylated derivatives of NSC243928 for the treatment of triple-negative breast cancer. Supramolecular polymers are of interest due to their self-healing and stimuli responsiveness. Chapter 1 gives a brief overview of the importance of self-assembly to construct ordered structures from smaller building blocks, highlighting the mechanisms of self-assembly to form supramolecular polymers. The bis-urea macrocycle assembly unit is introduced and its assembly into tubular structures and crystals is highlighted, which are used as a control for …

Interfacial Ligand Transformation On Plasmonic Nanostructures: Mechanistic Insights Unraveled By Plasmon-Enhanced Spectroscopy, Kexun Chen

Theses and Dissertations

We employ surface-enhanced Raman scattering (SERS) as an in situ spectroscopic tool, in conjunction with density functional theory (DFT) calculations, to develop a detailed mechanistic understanding of plasmon-driven photocatalytic reactions and heterogeneous transfer hydrogenolysis reactions of molecular adsorbates on metallic nanostructure surfaces. The excitation and decay of plasmon resonances in metallic nanostructures give rise to intriguing photophysical and photochemical effects, including the generation of hot charge carriers, local field enhancements, and photothermal transduction. These effects can be intentionally harnessed to drive or enhance interfacial molecular transformations along unconventional reaction pathways. The first part of the thesis focuses on the plasmon-driven …

Improved Temperature Dependence Of Rate Coefficients For Rotational State-To-State Transitions In H2O + H2O Collisions, Bikramaditya Mandal, Dmitri Babikov

Chemistry Faculty Research and Publications

Aims. We present an improved database of temperature-dependent rate coefficients for rotational state-to-state transitions in H₂O + H₂O collisions. The database includes 231 transitions between the lower para-states of H₂O and 210 transitions between its lower ortho-states (up to j = 7) and can be employed in cometary and planetary applications up to the temperature of 1000 K.

Methods. We developed and applied a new general method that allows the generation of rate coefficients for excitation and quenching processes that automatically satisfy the principle of microscopic reversibility and also helps to cover …

A Work Towards A Single-Bridge Hydrazine Sensor, Brenden Jay Schmeltz

Theses and Dissertations

Hydrazine can currently be detected by irreversible methods, Carbazolopyridinophane (2,18-Dithia[3][1,8]carbazolo[3][2,6]pyridinophane) CP was synthesized by Brown et al. to detect hydrazine in real-time while also being reversible. The threshold for detection was 100 ppb, regulatory use requires 10 ppb as this is when permanent damage to humans can be caused. A more sensitive sensor will allow for safer workplaces for many people. A single, 3-atom bridge sensor will further examine the photophysical capabilities of carbazole-pyridine as an emitter/quencher pair. 1-Carbazole-1-methylpyridyl-2methyl sulfide SBCP will allow freedom of rotation as well as the bending of the bridge. These benefits will introduce conformers which …

College Of Natural Sciences Newsletter, September - October 2023, College Of Natural Sciences

College of Natural Sciences Newsletters and Reports

Page 1 Dean's Message
Page 2 New Faculty an Staff for the Fall 2023 Semester
Page 3 Awards
Page 4 Student Ambassadors in CNS
Page 5 Meet our Jacks
Page 6-8 Events
Page 9-11 Media Coverage of CNS
Page 12-13 Spring 2023 Dean's List
Page 14 Open PRAIRIE Data

Women As A Force Multiplier For Bringing Nuclear Forensic Capabilities To The International Stage, Heather M. Dion, Caterina Fox, Kim Knight, Anne Phillip

International Journal of Nuclear Security

In 2009, the US Department of Energy National Nuclear Security Administration’s (NNSA’s) Defense Nuclear Nonproliferation Program initiated a new nuclear forensics outreach effort under its Confidence Building Measures Program. Little did they know that the timing could not have been better. This article focuses on the early years (2009–2015) of the NNSA’s international nuclear forensics outreach, specifically the efforts and experiences of the women who helped establish this program, building it from a fledgling, bilateral effort into an enduring technical capacity provider engaging with dozens of countries and multilateral organizations. At the onset of the program, nuclear forensics was an …

Design And Synthesis Of N-Succinyl-L,L-2.6-Diaminopimelic Acid Desuccinylase Inhibitors As Potential Novel Antibiotics, Thomas Dipuma

Master's Theses

N-Succinyl-L,L-2,6-Diaminopimelic Acid Desuccinylase (DapE) is a bacterial enzyme located in the lysine biosynthetic pathway of all Gram-negative and most Gram-positive species of bacteria including the notorious ESKAPE pathogens, or pathogenic strains of bacteria that have developed significant levels of resistance to currently available antibiotics. As a means to combat this challenge of growing antimicrobial resistance, we have identified the bacterial enzyme DapE as a conserved, novel enzymate target within these resistant bacterial strains,as DapE is responsible for the production of m-DAP and lysine which are ultimately employed in bacterial cell wall synthesis. The overall aim of this research is to …

Structural Insights Into The Cl-Par-4 Protein: Ionic Requirements, Conformational Transitions, And Interaction With Cisplatin, Krishna Kumar Raut

Chemistry & Biochemistry Theses & Dissertations

Cancer continues to be the leading global cause of death, with challenges in early diagnosis, drug resistance, non-specific drug targeting, and cancer recurrence and metastasis posing formidable obstacles in cancer therapy. In this context, Prostate Apoptosis Response-4 (Par-4), a pro-apoptotic tumor suppressor protein, emerged as a promising therapeutic target due to its ability to selectively induce apoptosis in cancer cells, thereby minimizing the drug-associated adverse effects. However, a comprehensive understanding of the structural features of Par-4, specifically the caspase-cleaved fragment (cl-Par-4), is crucial for therapeutic advancements.

This dissertation investigated the effects of various ions, both monovalent and divalent, on the …