Physical Chemistry Commons^™

Measuring And Enhancing The Ionic Conductivity Of Chloroaluminate Electrolytes For Al-Ion Batteries, Anthony J Lucio, Iwan Sumarlan, Elena Bulmer, Igor Efimov, Stephen Viles, A Robert Hillman, Christopher J Zaleski, Karl S Ryder

Faculty, Staff and Student Publications

At the core of the aluminum (Al) ion battery is the liquid electrolyte, which governs the underlying chemistry. Optimizing the rheological properties of the electrolyte is critical to advance the state of the art. In the present work, the chloroaluminate electrolyte is made by reacting AlCl3 with a recently reported acetamidinium chloride (Acet-Cl) salt in an effort to make a more performant liquid electrolyte. Using AlCl3:Acet-Cl as a model electrolyte, we build on our previous work, which established a new method for extracting the ionic conductivity from fitting voltammetric data, and in this contribution, we validate the method across a …

High Resolution Intracavity Laser Absorption Spectroscopy Of Transition Metal-Containing Diatomic Molecules, Kristin Bales

Dissertations

Three transition metal-containing diatomic molecules have been studied using intracavity laser spectroscopy. Many of the transitions were recorded using a Fourier-transform spectrometer for detection, allowing collection at Doppler-limited resolution for the gas phase molecules. Several vibrational bands in two electronic transition systems of tantalum fluoride (TaF) have been analyzed, and new molecular constants provided. Transitions involving six electronic states of tungsten sulfide (WS) have been analyzed, with new and updated constants provided, including a deperturbation analysis of three vibrational bands in two of the states. Finally, a fresh perspective on two electronic states of tungsten oxide (WO) included a deperturbation …

Photophysical Properties Of Synthetic Oligomeric Phenylene Ethynylene, Hugh F. Fritz Jr.

Chemistry and Chemical Biology ETDs

Oligomeric Phenylene Ethynylenes (OPEs) are a class of synthetically prepared compounds with the basic structure of phenylene rings connected by triple-bonded carbon atoms, also known as an ethyne link. This structure can be modified by incorporating functional groups onto one or more of the phenylene rings. The addition of functional groups, such as sulfoxide or imidazole, may alter the photophysical properties in detectable ways. The photophysical techniques used in this report include fluorescence, spectroscopy in the ultraviolet and visible light range (UVVIS), and photon-based excitation using a photo chamber.

One attractive function of OPEs is their antimicrobial property. Previously published …

First-Principles Simulations Of Attosecond Transient X-Ray Absorption, Min Chen

LSU Doctoral Dissertations

The first part of this dissertation presents calculations of the extinction spec- tra of gold-silver/silver-gold core-shell nanospheres. The goal of this projectsis to get a deeper understanding of surface plasmonic resonance in metal nanospheres with core-shell geometry. Here, we used the finite-difference time-domain (FDTD) method and total-field/scattered-field (TFSF) framework to compute the extinction spectra of nanoparticles to determine the geometry of gold-silver/silver-gold core-shell nanoparticles. This supported experimental work on monitoring the growth dynamics of colloidal gold- silver/silver-gold core-shell nanoparticles using in situ second harmonic generation (SHG) and extinction spectroscopy.

The second and main project involved simulating attosecond transient spectra for …

Clear As Glass: Novel Antibiotic Glasses Vitrified From Solution, Claire Lamberti

Chemistry Theses and Dissertations

The World Health Organization (W.H.O.) has maintained a list of essential medicines since 1977 (1). This list contains the medications considered to be the most effective and of the utmost importance to the needs of worldwide healthcare systems. If new forms of these drugs can be created, they can be studied for potential stability and transportation purposes, as well as drug delivery mechanisms. There are strategies to try and improve the physicochemical properties including forming polymorphs, salts, cocrystals, and amorphous formulations. There are issues with these techniques, and a large one is that in most cases the crystal structures of …

The Decomposition Of Normal Vibrational Modes In Different Chemistry Problems, Mateus Macedo Quintano

Chemistry Theses and Dissertations

The least action principle yields the Euler-Lagrange equations, which explain molecular vibrations in minimizing action. Subsequently, the Lagrangian gives rise to the equations of motion using the Euler-Lagrange equations. We can then solve the characteristic value problem to obtain normal vibrational modes. Ultimately, the vibrational spectrum of a molecule can be extracted from the characteristic values. Normal coordinates are linear combinations of internal or Cartesian coordinates. However, the delocalization of normal vibrational modes across the molecule restricts the direct use of normal mode frequencies and force constants for measuring bond strength. From the force constant matrix and the normal mode …

Adsorption Performance Of Mg0.33ni0.33co0.33fe2o4 Nanoparticles Doped With Gadolinium And Lanthanum For Lead (Ii) Removal, Mariam Rabaa, Amani Aridi, Ghassan Younes, Ramadan Awad

BAU Journal - Science and Technology

The issue of water pollution has become a major concern in recent times, and the need for effective strategies for treating contaminated water sources has become more urgent. One promising approach that has been gaining attention in the field of wastewater treatment is the use of nano-ferrites. In this regard, novel Mg_0.33Ni_0.33Co_0.33La_xFe_2-xO₄ and Mg_0.33Ni_0.33Co_0.33Gd_xFe_2-xO₄ nanoparticles (NPs), where x = 0.00, 0.01 and 0.08, were synthesized to test their adsorption performance for the removal of Pb (II). The structural …

Modeling Exciton Migration In Two-Dimensional Space, Christian D. Etnyre

DePaul Discoveries

Computational analysis through density matrix quantum mechanics was performed to model exciton migration in two-dimensional space for a zinc-substituted tetraazaphthalocyanine. The model produced resembles a two-dimensional sheet of molecules. Energy transport mechanisms, controlled by point dipole couplings, were evaluated while altering the size of the crystal lattice. It was determined that energy transport was much more significant with a decreasing size of the crystal lattice. Likewise, the result of increasing the size of the crystal lattice had the effect of dampening the rate of energy transport. It was of interest to determine, with varying crystal lattice dimensions, the time that …

Recent Advances In Electrochemical Impedance Spectroscopy-Based Pathogenic Bacteria Sensing, Tao Chen, Yuan-Hong Xu, Jing-Hong Li

Journal of Electrochemistry

Pathogenic bacteria have been throwing great threat on human health for thousands of years. Their real-time monitoring is in urgent need as it could effectively halt the spread of pathogenic bacteria and thus reducing the risk to human health. Up till now, diverse technologies such as electrochemistry, optics, piezoelectricity and calorimetry have been developed for bacteria sensing. Therein, electrochemical impedance spectroscopy (EIS)-based sensors show great potential in point-of-care bacterial analysis because of their low-cost, short read-out time, good reproducibility, and portable equipment construction. In this review, we will primarily summarize the typical applications of electrochemical impedance technology in bacteria sensing …

Metal-Organic Frameworks For Electrochemical And Electrochemiluminescent Immunoassay, Xiao-Li Qin, Zi-Ying Zhan, Sara Jahanghiri, Kenneth Chu, Cong-Yang Zhang, Zhi-Feng Ding

Journal of Electrochemistry

Development of ultrasensitive, highly accurate and selective immunosensors is significant for the early diagnosis, screening, and monitoring of diseases. Electrochemical and electrochemiluminescent (ECL) immunoassays have both attracted great attention and become a current research hotspot due to their advantages such as good stability, high sensitivity and selectivity, wide linear range, and good controllability. Metal-organic frameworks (MOFs), as a new class of porous crystalline materials, have been widely applied in electrochemical and ECL immunosensors owing to their large specific surface area, good chemical stability, as well as adjustable pore size and nanoscale framework structures. Various MOF nanomaterials with different properties for …

Preface To The Special Issue On Interfactial Regulation And Electrochemical Sensors, Jing-Hong Li, Yang Tian, Yuan-Hong Xu, Li-Min Zhang

Journal of Electrochemistry

No abstract provided.

Colorful "Stars" In The Dark, Chao Jing, Yi-Tao Long

Journal of Electrochemistry

Plasmonic nanoparticles such as Au and Ag with localized surface plasmon resonance (LSPR) property exhibit unique scattering and absorption features. The plasmonic scattering and absorption bands are mainly located at visible light region which can be easily applied in visual detections. By modulating the size, shape, and composition of gold and silver colloid solutions, plenty of colorimetric methods have been constructed for the detection of metal ions, biomolecules, and environmental contaminants, etc. For many years, the LSPR-based measurements are implemented in reagent tubes. Since 2000, the plasmon resonance scattering (PRS) light of metal nanoparticles captured by dark-field microscopy enables the …

An Aptamer-Based Microelectrode With Tunable Linear Range For Monitoring Of K+ In The Living Mouse Brain, Yuan-Dong Liu, Jia-Run Li, Li-Min Zhang, Yang Tian

Journal of Electrochemistry

Potassium ion (K⁺) is widely involved in several physiopathological processes, and its abnormal changes are closely related to the occurrence of brain diseases of cerebral ischemia. In vivo acquirement of K⁺ variation is significant to understand the roles of K⁺ playing in brain functions. A microelectrode based on single-stranded DNA aptamers was developed for highly selective detection of K⁺ in brain, in which the aptamer probes were designed to contain an aptamer part for specific recognition of K⁺, an alkynyl group used for stable confinement of aptamer probe on the gold surface, and …

Boronate Affinity-Assisted Electrochemically Controlled Atrp For Ultrasensitive Electrochemical Aptasensing Of Carcinoembryonic Antigen, Qiong Hu, Shi-Qi Li, Yi-Yi Liang, Wen-Xing Feng, Yi-Lin Luo, Xiao-Jing Cao, Li Niu

Journal of Electrochemistry

As an acidic glycoprotein, carcinoembryonic antigen (CEA) is of great value as a broad-spectrum tumor marker in the differential diagnosis and surveillance of malignant tumors. In this work, we report an electrochemical aptasensor for the ultrasensitive and highly selective detection of CEA, taking advantage of the dual amplification by the boronate affinity-assisted electrochemically controlled atom transfer radical polymerization (BA-eATRP). Specifically, the BA-eATRP-based electrochemical aptasensing of CEA involves the capture of target antigens by nucleic acid aptamers, the covalent crosslinking of ATRP initiators to CEA antigens via the selective interactions between the phenylboronic acid (PBA) group and the cis-diol group of …

Scanning Photoelectrochemical Microscopic Study In Photoinduced Electron Transfer Of Supramolecular Sensitizers-Tio2 Thin Films Systems, Sheng-Ya Zhang, Min Yao, Ze Wang, Tian-Jiao Liu, Rong-Fang Zhan, Hui-Qin Ye, Yan-Jun Feng, Xiao-Quan Lu

Journal of Electrochemistry

Crafting charge transfer channels at titanium dioxide (TiO₂) based photoanodes remain a pressing bottleneck in solar-to-chemical conversion technology. Despite the tremendous attempts, TiO₂ as the promising photoanode material still suffers from sluggish charge transport kinetics. Herein, we propose an assembly strategy that involves the axial coordination grafting metalloporphyrin-based photosensitizer molecules (MP) onto the surface-modified TiO₂ nanorods (NRs) photoanode, forming the composite MP/TiO₂ NRs photoelectrode. As expected, the resulted unique MP_B/TiO₂ NRs photoelectrode displays significantly improved photocurrent density as compared to TiO₂ NRs alone and MP_A/TiO₂ NRs photoelectrode. Scanning …

N–((2–Acetylphenyl)Carbamothioyl)Benzamide: Synthesis, Crystal Structure Analysis, And Theoretical Studies, Akin Oztaslar, Hakan Arslan

Karbala International Journal of Modern Science

N–((2–Acetylphenyl)carbamothioyl)benzamide has been synthesized and characterized. The molecular conformation of the investigated compound is stabilized by C16–H16B⋅⋅⋅O2ⁱ (i: 1+x, y, z) intermolecular and C14–H14⋅⋅⋅S1, N2–H2⋅⋅⋅O2, and N2–H2⋅⋅⋅O1 intramolecular H–bonds. All DFT calculations have been implemented at the B3LYP level with the 6–311G(d,p) basis set. The optimized molecular structure parameters have been compared with the experimental one in the solid phase. The energy gap, global chemical reactivity descriptor parameters, MEP, Fukui functions, DoS, NLO, and NBO analysis were also computed and investigated. The intermolecular interactions and their energies are evaluated using Hirshfeld surface and energy framework analyses. To determine …

Methods Of Magneto-Optical Spectroscopy And Analysis For Porphyrins And Polymer Thin-Films, Emigdio E. Turner

Chemistry and Chemical Biology ETDs

This dissertation describes the construction of two high precision magneto-polarimeters for performing Faraday rotation and Magnetic Circular Dichroism (MCD) measurements of polymer thin-films. There is a focus in materials science on the development of thin-film magneto-optically active materials. These materials could allow for the construction of a thin-film optical diode, an important device for next-generation photonic technology. Upon completion of the Faraday rotation spectrometer, two publications were generated from Faraday rotation measurements of novel polymer thin-film materials.

With growing interest by materials scientists in magneto-optically active transition-metal containing materials, an MCD spectrometer was constructed to study these materials. This spectrometer …

Metals And Metal Complexes In Diseases With A Focus On Covid-19: Facts And Opinions, Agnieszka Ścibior, Manuel Aureliano, Alvin A. Holder, Juan Llopis

Chemistry & Biochemistry Faculty Publications

In the present Special Issue on “Metals and Metal Complexes in Diseases with a Focus on COVID-19: Facts and Opinions”, an attempt has been made to include reports updating our knowledge of elements considered to be potential candidates for therapeutic applications and certain metal-containing species, which are extensively being examined towards their potential biomedical use due to their specific physicochemical properties. The Special Issue compiles data on the role of metals in COVID-19 and focuses on other illnesses and biological processes that affect metal metabolism. It consists of eight manuscripts, including five review articles and three original research papers (Figure …

Synthesis And Study Of High-Spin Stable Organic Radicals For Electrical Conductors And Mannosamine Nitroxide For Mri Contrast Agents, Shuyang Zhang

Department of Chemistry: Dissertations, Theses, and Student Research

In the first project, we describe the synthesis of an ambient stable high spin organic diradical 4 based on the Blatter moiety. The high-spin (S = 1) organic diradical 4, which consists of two Blatter radical moieties in a conjugated structure, exhibits a nearly exclusive population (88%) on triplet ground state at room temperature as a consequence of a large single-triplet energy gap (ΔEST = 0.5 kcal/mol). The target diradical molecule is synthesized over five steps with structural confirmation by single-crystal X-ray diffraction. The thermogravimetric analysis (TGA) shows the onset of decomposition at ~264 oC, indicating the diradical molecule has …

Sers For The Detection Of Trace Materials, Omari Kirkland

Dissertations, Theses, and Capstone Projects

In this dissertation are presented three projects that contribute to the body of research on SERS in the forensic, heritage, and semiconductor fields. The first project, Charge-Transfer mapping on GaN/Ag, a silver-decorated nanopillar semiconductor substrate fabricated from the GaN is used with the Raman probe Rhodamine 6 G (R6G) to map the effect of the nanofeatures on the CT resonance. The second project, in collaboration with Marco Leona from the Metropolitan Museum of Art, explores the use of AgNIFs to identify colorants used on textile fiber samples from four 19th century works of Japanese art. The final project analyzes the …

A Typological And Chemical Analysis Of Roman Oil Lamps From Poggio Del Molino, Brandon Tejo

Dissertations, Theses, and Capstone Projects

Terracotta lamps, known to the Romans as lucernae, are small, handheld, often decorated objects which provided ancient people light. To modern researchers, they serve as tools for dating stratigraphy and iconographic studies. Beyond their immediately apparent aesthetic and symbolic value, the chemical compositions of the clay of these lamps reflect their origin. This study complements archaeological typologies with chemometric analyses to describe 16 Late Republican and Imperial Roman lamps recovered from the villa at Poggio del Molino (PdM), Tuscany. These finds were recovered from the 2021 and 2022 PdM excavations. The combined approach of typology with X-ray Diffraction (XRD) …

The Effect Of The Carbon Nanotubes’ Surface Area On The Morphology And Performance Of Cellulose Acetate Nanocomposite Membranes In Nanofiltration Applications, Nouran Elbadawi

Theses and Dissertations

Population increase and climate change have significantly affected the availability of fresh water for consumption. Studies by UNESCO showed that more than 28% of the world population didn’t have access to clean safe drinking water in 2020. This situation is expected to get more serious over the coming 30 years with the limited availability of natural fresh water sources. The need to find solutions from alternative non-freshwater resources for drinking or irrigation is becoming a necessity. Within the context of desalination technologies, thousands of investigations are conducted to find the cheapest most efficient way of water treatment aiming at expanding …

The Kappa Opioid Receptor Agonist 16-Bromo Salvinorin A Has Anti-Cocaine Effects Without Significant Effects On Locomotion, Food Reward, Learning And Memory, Or Anxiety And Depressive-Like Behaviors, Ross Van De Wetering, Amy Ewald, Susan Welsh, Lindsay Kornberger, Samuel E. Williamson, Bryan D. Mcelroy, Eduardo R. Butelman, Thomas E. Prisinzano, Bronwyn M. Kivell

Markey Cancer Center Faculty Publications

Kappa opioid receptor (KOR) agonists have preclinical antipsychostimulant effects; however, adverse side effects have limited their therapeutic development. In this preclinical study, conducted in Sprague Dawley rats, B6-SJL mice, and non-human primates (NHPs), we evaluated the G-protein-biased analogue of salvinorin A (SalA), 16-bromo salvinorin A (16-BrSalA), for its anticocaine effects, side effects, and activation of cellular signaling pathways. 16-BrSalA dose-dependently decreased the cocaine-primed reinstatement of drug-seeking behavior in a KOR-dependent manner. It also decreased cocaine-induced hyperactivity, but had no effect on responding for cocaine on a progressive ratio schedule. Compared to SalA, 16-BrSalA had an improved side effect profile, with …

V-Shaped Temperature Dependences And Pressure Dependence Of Elementary Reactions Of Hydroxyl Radicals With Several Organophosphorus Compounds, Xiaokai Zhang

Dissertations

Organophosphorus compounds have brought increasing attention since they are widely used as flame-retardants, which can take effect in combustion via reactions with reactive radicals. These reactions are influenced by variables such as temperature and pressure, resulting in a temperature and pressure dependent rate constant. Studying this reaction kinetics has great importance in both combustion reaction and atmospheric environment.

This study is focused on kinetics of several elementary reactions of combustion importance. The kinetics of hydroxyl radicals were studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 295 - 837 K temperature range and the 1 - …

Vibrational, Rotational And Electronic Spectroscopy For Possible Interstellar Detection Of Alnh2 And Halnh, Tarek Trabelsi, Vincent J. Esposito, Joseph S. Francisco

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We obtained accurate vibrational frequencies, rotational constants, and vertical transition energy for AlNH₂(X¹A₁) and HAlNH(X¹A′) isomers using ab initio calculations at various levels of theory. These two isomers are potential candidates for astronomical observation. AlNH₂ and HAlNH are thermodynamically stable, with Al-NH₂ and HAl-NH bond dissociation energies predicted to be 4.39 and 3.60 eV, respectively. The two isomers are characterized by sizable dipole moments of 1.211 and 3.64 D, respectively. The anharmonic frequencies and spectroscopic constants reported for the two isomers should facilitate their experimental differentiation. In addition, we evaluated …

Electronically Modulated Feni Composite By Ceo2 Porous Nanosheets For Water Splitting At Large Current Density, Ming-Yu Ding, Wen-Jie Jiang, Tian-Qi Yu, Xiao-Yan Zhuo, Xiao-Jing Qin, Shi-Bin Yin

Journal of Electrochemistry

Exploiting highly active and non-noble metal bifunctional catalysts at large current density is significant for the advancement of water electrolysis. In this work, CeO₂ electronically structure modulated FeNi bimetallic composite porous nanosheets in-situ grown on nickel foam (NiFe₂O₄-Fe₂₄N₁₀-CeO₂/NF) is synthesized. Electrochemical experiments show that the NiFe₂O₄-Fe₂₄N₁₀-CeO₂/NF exhibited the outstanding activities toward both oxygen and hydrogen evolution reactions (OER and HER) (η₁₀₀₀ = 352 mV and η₁₀₀₀ = 429 mV, respectively). When assembled into a two-electrode system for …

P-Doped Ru-Pt Alloy Catalyst Toward High Performance Alkaline Hydrogen Evolution Reaction, Rong-Qin Huang, Wei-Ping Liao, Meng-Xuan Yan, Shi Liu, Yuan-Ming Li, Xiong-Wu Kang

Journal of Electrochemistry

Electrocatalytic water splitting represents grand promise for hydrogen fuel in modern energy equipment, and the design and fabrication of higher performance catalysts are at the central. Herein, we report the sequential phosphorus (P)-doping into ruthenium (Ru) nanoparticles (Ru-P/C) by thermal annealing of Ru nanoparticles in phosphine (PH₃) atmosphere and deposition of extremely low concentration of platinum (Pt) to obtain P-doped Ru-Pt alloy catalyst supported on carbon nanotubes (CNTs), which is denoted as (Ru-P)#Pt/C. The data by X-ray diffraction spectroscopy and transmission electron microscopy show that the Ru nanoparticles existed in the form of hexagonal close-packed (hcp) phase with …

Deep Euteceic Solvents-Assisted Synthesis Of Novel Network Nanostructures For Accelerating Formic Acid Electrooxidation, Jun-Ming Zhang, Xiao-Jie Zhang, Yao Chen, Ying-Jian Fan, You-Jun Fan, Jian-Feng Jia

Journal of Electrochemistry

Deep eutectic solvents (DESs) have been reported as a type of solvent for the controllable synthesis of metal nanostructures. Interestingly, flower-like palladium (Pd) nanoparticles composed of staggered nanosheets and nanospheres are spontaneously transformed into three-dimensional (3D) network nanostructures in choline chloride-urea DESs using ascorbic acid as a reducing agent. Systematic studies have been carried out to explore the formation mechanism, in which DESs itself acts as a solvent and soft template for the formation of 3D flower-like network nanostructures (FNNs). The amounts of hexadecyl trimethyl ammonium bromide and sodium hydroxide also play a crucial role in the anisotropic growth and …

Fe Nanoparticles Encapsulated In N-Doped Porous Carbon For Efficient Oxygen Reduction In Alkaline Media, Chun-Yan Li, Rui Zhang, Xiao-Jie Ba, Xiao-Le Jiang, Yao-Yue Yang

Journal of Electrochemistry

Rational design and synthesis of non-precious-metal catalyst plays an important role in improving the activity and stability for oxygen reduction reaction (ORR) but remains a major challenge. In this work, we used a facile approach to synthesize iron nanoparticles encapsulated in nitrogen-doped porous carbon materials (Fe@N-C) from functionalized metal-organic frameworks (MOFs, MET-6). Embedding Fe nanoparticles into the carbon skeleton increases the graphitization degree and the proportion of graphitic N as well as promotes the formation of mesopores in the catalyst. The Fe@N-C-30 catalyst showed the excellent ORR activity in alkaline solutions (E₀ = 0.97 V vs. RHE, E_{1/2 …}

Photophysical And Photochemical Processes In Small Molecules And Materials For Solar Energy Conversion, Ethan Lambert

Honors Theses

The work covered in this thesis all falls under the theme of photophysical processes after light and matter interact. Those of primary interest are Raman scattering induced vibrations and excited state dynamics probed by transient absorption spectroscopy. Small molecules are studied with Raman spectroscopy and computational chemistry. These studies unearth the shifts in vibrational frequency as a function of charge transfer or receipt and how a quantitative assay of natural orbital populations and delocalization can offer both the nature and magnitude of this charge transfer. Further, a method is presented that builds upon previous work within the academic family tree; …