Chemistry Commons^™

Detection Of Ultra-Trace Levels Of Copper In Seawater Using A Bare Gold Microwire Electrode And A Portable Digital Voltammeter, Luke M. Brosnan, Wade Lonsdale, Paul Pringle, Paul Lewtas, Samantha Ridgway, Sebastien Allard, Magdalena Wajrak

Research outputs 2022 to 2026

The accumulation of biomass on ship hulls (biofouling) can greatly decrease their fuel efficiency. Many antifouling coatings contain copper as a biocidal agent, which can be released during hull cleanings and is of particular concern when cleaning the hulls in situ (i.e., without dry docking). Previously established voltammetric methods for the detection of copper in seawater using a gold microwire electrode have been modified and adapted to a portable on-site voltammetric technique. Notable differences from previous voltammetric methods include the use of linear sweep voltammetry, analysis under atmospheric conditions, alternating the potential during the deposition period and the use of …

Removal Of Heavy Metals From Motorcycle Washing Wastewater Using A Zeolite-Embedded Sheet, Noverita Dian Takarina, Hanies Ambarsari, Sekar Arum Pramudyawardhani, Maria Fatima Niken Kris Rahmawati, Erni Johan, Naoto Matsue, Mohammad Afdhal Adidharma

Makara Journal of Science

The increased use of motorcycles for transportation has heightened environmental challenges related to their washing, particularly the discharge of untreated wastewater containing heavy metals, such as copper (Cu) and lead (Pb), into drainage systems. This study explored the effectiveness of zeolite-embedded sheets (ZESs) in the removal of these pollutants from motorcycle washing wastewater. ZESs were prepared through treatment of nonwoven sheets with Linder Type A (LTA Zeolite) powder and heat treatment, washing, and drying. Characterization was performed via scanning electron microscopy with energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. Over a 60 min adsorption period, the ZES achieved removal …

Copper Line Shapes, Gareth R. Eaton

TeachEPR Submissions

The spectrum of Cu²⁺ has 4 lines, since I = 3/2. Cu has two major isotopes, ⁶³Cu (69.2%) and ⁶⁵Cu (30.8%). The magnetic moment of ⁶⁵Cu is 7% larger than that for ⁶³Cu, so the hyperfine coupling is 7% larger. If the lines are narrow enough, one can observe superposition of spectra due to complexes of the two isotopes.

Facile Synthesis Of Gold, Copper, And Silicon Nanostructures By Laser Ablation In Liquid, Nicholas Simpson

Theses and Dissertations

Metal nanoparticle (NP) synthesis is a continually evolving area of research, owing to the widespread application of NPs in fields such as catalysis, drug delivery, and biosensing. Compared to bulk metal material, NPs contain a larger proportion of surface atoms and exhibit unique optical properties, thus making them ideal for applications where maximizing surface interactions is key. Moreover, their compositions can be altered in several different ways, as evidenced by metal alloy, core/shell, supported, and defective NPs. While conventional synthesis methods are capable of producing NPs in large quantities, they often require conditions of high temperature and pressure, strong reducing …

Rings Of Power: Controlling Sod Mimic Activity By The Addition Of Pyridine Rings Within The Pyridinophane Scaffold, Katherine J. Smith, Timothy M. Schwartz, David M. Freire, Cameron Bowers, Sarah K. Dunn, Jackson F. Bonnell, Magy A. Mekhail, Giridhar Akkaraju, Kayla N. Green

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Superoxide dismutase enzymes are a major defense against superoxide, which is a potent reactive oxygen species. Misregulation of reactive oxygen species and subsequent neuronal damage are etiological hallmarks of neurodegenerative disease. Macrocyclic small molecules have offered inroads toward functional SOD1 mimics. Herein, we report a series of five tetra-aza macrocyclic ^RPy₂N₂ ligands, varied by 4-position substitution of the pyridine ring with both electron-donating (R = OMe) and withdrawing groups (R = Cl, I, and CF₃) to offer the first comparison to well-studied ^RPyN₃ congeners and other mimics in the literature. New ligands …

Synthesis And Characterization Of Water Soluble Thiosemicarbazone-Alkylthiocarbamate Ligands And Their Cu(Ii) Complexes, John J. Garvey Iv, Sanjit Karki, Haixun Guo, Levi J. Beverly, Craig A. Grapperhaus, Robert M. Buchanan

The Cardinal Edge

Thiosemicarbazone-alkylthiocarbamate N₂S₂ hybrid ligands are emerging as an important class of potential bioactive molecules that possess important pharmacokinetic properties. Resulting metal complexes have electronic properties that are composites of their homolog forms, bis-thiosemicarbazones and bis-alkylthiocarbamates, allowing for tuning redox potentials over a nearly 450 mV range. These versatile ligand frameworks possess remarkable antiproliferation activity against a broad range of solid tumors and low toxicity towards normal cells¹ indicating great promise for future drug development. Herein, we describe recent synthetic efforts to improve water solubility of thiosemicarbazone-alkylthiocarbamate hybrid ligand Cu(II) complexes. The parent 4-methyl-3-thiosemicarbazide half arm was …

Making And Breaking Bonds: Studying Intrinsic Chemistry In The Gas-Phase, Luke Metzler

Electronic Theses and Dissertations

The nature of chemical interactions can be difficult to ascertain in the condensed phase; chemistry can be observed, but with the plethora of variables such as solvation, mixes of counter-ions, and complex equilibria, the true intrinsic chemical properties of a given chemical species may be obfuscated. By conducting research in the gas-phase, many of these variables can be reduced, if not eliminated entirely, which can allow for the careful observation of the true physical phenomena driving chemical reactivity.

The research presented herein focuses on the use of ion-trapping (specifically in a linear ion trap) as a method for unveiling the …

Green Synthesis Of Carbonized Chitosan-Fe3o4-Sio2 Nano-Composite For Adsorption Of Heavy Metals From Aqueous Solutions, Dalia A. Ali Eng, Rinad Galal Ali Eng.

Chemical Engineering

Water pollution with heavy metals owing to industrial and agricultural activities have become a critical dilemma to humans, plants as well as the marine environment. Therefore, it is of great importance that the carcinogenic heavy metals present in wastewater to be eliminated through designing treatment technologies that can remove multiple pollutants. A novel green magnetic nano-composite called (Carbonized Chitosan-Fe3O4-SiO2) was synthesized using Co-precipitation method to adsorb a mixture of heavy metal ions included; cobalt (Co2+), nickel (Ni2+) and copper (Cu2+) ions from aqueous solutions. The novelty of this study was the synthesis of a new

nano-composite which was green with …

Sulfate Enhances The Adsorption And Retention Of Cu(Ii) And Zn(Ii) To Dispersed And Aggregated Iron Oxyhydroxide Nanoparticles, Emma M. Kocik, Abigail Kim, Miranda L. Aiken, Lauren Smith, Christopher S. Kim

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The adsorption and retention of metal ions to nanoscale iron (hydr)oxides in aqueous systems is significantly influenced by prevailing environmental conditions. We examined the influence of sulfate, the second most common anion in seawater that is present in many other natural aquatic systems, on the adsorption and retention of Cu(II) and Zn(II) to synthetic iron oxyhydroxide nanoparticles (NPs) and their aggregates. Batch uptake experiments with monodisperse NPs and NPs aggregated by changes in pH, ionic strength, and temperature were conducted over sulfate concentrations ranging from 0 to 0.30 M. The introduction of 0.03 M sulfate significantly increased the initial adsorption …

Chemical Strategies For Tailoring Properties Of Nanomaterials Produced By Pulsed Laser Interaction In Liquid Environments, Katharine M. Tibbetts

Chemistry Publications

Interactions of intense ultrashort laser pulses with liquid media and at solid-liquid interfaces produce plasmas with high densities of reactive chemical species that promote the formation of nanomaterials. This work discusses the current understanding of laser-induced chemical reactions in aqueous medium involving hydrated electrons and hydroxyl radicals, and the effects of chemical additives on these reactions. Two chemical strategies are presented for controlling the composition of the laser-induced plasma and nanomaterial properties. First, adding chemical scavengers of hydroxyl radicals will be shown to inhibit metal oxidation, enabling the synthesis of ligand-free Ag and Au-Ag alloy nanoparticles by reduction of Au …

Real-Time Spectroscopic Ellipsometry For Flux Calibrations In Multi-Source Co-Evaporation Of Thin Films: Application To Rate Variations In Cuinse₂ Deposition, Dhurba R. Sapkota, Balaji Ramanujam, Puja Pradhan, Mohammed A. Razooqi Alaani, Ambalanath Shan, Michael J. Heben, Sylvain Marsillac, Nikolas J. Podraza, Robert W. Collins

Electrical & Computer Engineering Faculty Publications

Flux calibrations in multi-source thermal co-evaporation of thin films have been developed based on real-time spectroscopic ellipsometry (RTSE) measurements. This methodology has been applied to fabricate CuInSe₂ (CIS) thin film photovoltaic (PV) absorbers, as an illustrative example, and their properties as functions of deposition rate have been studied. In this example, multiple Cu layers are deposited step-wise onto the same Si wafer substrate at different Cu evaporation source temperatures (TCu). Multiple In₂Se₃ layers are deposited similarly at different In source temperatures (TIn). Using RTSE, the Cu and In₂Se₃ deposition rates are determined as …

Copper-Indazolate Nanojars: Synthesis And Characterization, Nicholas Alexander Rudell

Masters Theses

The field of synthetic supramolecular chemistry has exploded since the first syntheses of crown ethers by Charles Pedersen in the 1960s, leading to further development in the area of macrocycles and incorporation into a vast array of metal-organic structures. Supramolecular chemistry came to the forefront of science with the 1987 Nobel Prize in Chemistry, awarded jointly to Donald J. Cram, Jean-Marie Lehn, and Charles Pedersen “for their development and use of molecules with structure-specific interactions of high selectivity.”

Nanojars are supramolecular metal-organic complexes with a high affinity for hydrophilic anions and can efficiently transfer such anions from water into organic …

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

Enhancement Of Metal Nanostructure Deposition On Silicon Laser-Induced Periodic Surface Structures By Galvanic Replacement, Nicholas Simpson, Eric J. Broadhead, Addison Casto, Katharine M. Tibbetts

Chemistry Publications

We report a chemically motivated, single-step method to enhance metal deposition onto silicon laser-induced periodic surface structures (LIPSSs) using reactive laser ablation in liquid (RLAL). Galvanic replacement (GR) reactions were used in conjunction with RLAL (GR-RLAL) to promote the deposition of Au and Cu nanostructures onto a Si LIPSS. To increase the deposition of Au, sacrificial metals Cu, Fe, and Zn were used; Fe and Zn also enhanced the deposition of Cu. We show that the deposited metal content, surface morphology, and metal crystallite size can be tuned based on the difference in electrochemical potentials of the deposited and sacrificial …

Synthesis Of Copper Nano/Microparticles Via Thermal Decomposition And Their Conversion To Copper Oxide Film, Çağdaş Allahverdi̇

Turkish Journal of Chemistry

Copper nano/microparticles were synthesized in octadecene at 290 °C by thermal decomposition method. Copper acetate monohydrate, stearic acid, and 1-octadecanol were used as copper precursor, capping and mild reducing agents, respectively, at the synthesis. Borosilicate glass substrates submerged into the reaction solution during the synthesis were coated by copper nano/ microparticles. Thermal decomposition and coating techniques were combined in this study. Copper nano/microparticles were thoroughly characterised via X-ray powder diffraction, X-ray photoelectron, Raman, and attenuated total reflectance-Fourier transform infrared spectroscopies, and scanning and transmission electron microscopies. The average minimum Feret?s diameter of these synthesized copper particles was measured as ~87 …

Copper-Catalyzed Dehydrogenative Decarboxylation Reactions Of Carboxylic Acids To Alkenes, Michael P. Stanton

Graduate Theses, Dissertations, and Problem Reports (ETD)

Linear alpha olefins (LAOs) are important building blocks in the production of linear low-density polyethylene, a plastic used in products such as shrink wraps, plastic bags, tubing, plasticizers, among others. Commercial methods for generating LAOs utilize ethylene oligomerization, but this method is reliant on fossil fuels and leads to unselective product formation. Synthesis of LAOs from renewable resources, namely carboxylic acids, by decarbonylative dehydration strategies has been well studied, however, this method has inherent drawbacks rooted in the formation of internal olefin side-products through isomerization pathways. With the goal of avoiding internal isomerization, this thesis explores a dehydrogenative decarboxylation strategy …

Surface Modification Of Carbon-Based Electrodes For Electrochemical Conversion Processes: Oxygen Reduction Reaction And Bicarbonate Conversion, Udari Shyamika Kodithuwakku Arachchige

Theses and Dissertations--Chemistry

Oxygen reduction reaction (ORR) and conversion of bicarbonate into value-added chemicals are two significant electrochemical processes for energy storage and conversion. ORR is an important electrochemical reaction in fuel cells and metal-air batteries that provide power conversion and storage capacity, respectively, for portable electronics, and electric vehicles. However, the performance of catalysts (e.g., platinum-based) is critically limited by slow kinetics, inefficient four-electron pathway, and surface deactivation. This limited performance of platinum-based catalysts, the scarcity of platinum, and vulnerable supply chains for critical minerals require the development of alternative electrocatalysts now more than ever. Carbon-based materials possess several key properties that …

Interactions Of Bioactive Trace Metals In Shipboard Southern Ocean Incubation Experiments, Shannon M. Burns, Randelle M. Bundy, William Abbott, Zuzanna Abdala, Alexa R. Sterling, P. Dreux Chappell, Bethany D. Jenkins, Kristen N. Buck

OES Faculty Publications

In the Southern Ocean, it is well‐known that iron (Fe) limits phytoplankton growth. Yet, other trace metals can also affect phytoplankton physiology. This study investigated feedbacks between phytoplankton growth and dissolved Fe, manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and cadmium (Cd) concentrations in Southern Ocean shipboard incubations. Three experiments were conducted in September–October 2016 near the West Antarctic Peninsula: Incubations 1 and 3 offshore in the Antarctic Circumpolar Current, and Incubation 2 inshore in Bransfield Strait. Additions of Fe and/or vitamin B₁₂ to inshore and offshore waters were employed and allowed assessment of metal (M) …

A Continuously Renewed Copper Electrode For Constant-Potential Amperometry, Andrew T. Franklin

Chemistry & Biochemistry Theses - Archive

Pulsed amperometric detection (PAD) is a well-established technique used for the detection of electroactive compounds following Ion Chromatography (IC). Target analytes, such as carbohydrates and amino acids, typically have no suitable chromophores and are not detectable by suppressed conductivity following IC separation. While direct current (DC) amperometry is simpler, the formation of oxidation products quickly fouls the electrode surface; PAD removes these products extending electrode longevity for up to ~2 weeks of operation. To further extend electrode lifespans, a new strategy is introduced herein using DC amperometry on a sacrificial copper wire anode. The wire face continually dissolves under oxidative …

Enantioselective Synthesis Of Enantioisotopomers With Quantitative Chiral Analysis By Chiral Tag Rotational Spectroscopy, Mitchell D. Mills, Reilly E. Sonstrom, Zoua Pa Vang, Justin L. Neill, Haley N. Scolati, Channing T. West, Brooks H. Pate, Joseph R. Clark

Chemistry Faculty Research and Publications

Fundamental to the synthesis of enantioenriched chiral molecules is the ability to assign absolute configuration at each stereogenic center, and to determine the enantiomeric excess for each compound. While determination of enantiomeric excess and absolute configuration is often considered routine in many facets of asymmetric synthesis, the same determinations for enantioisotopomers remains a formidable challenge. Here, we report the first highly enantioselective metal-catalyzed synthesis of enantioisotopomers that are chiral by virtue of deuterium substitution along with the first general spectroscopic technique for assignment of the absolute configuration and quantitative determination of the enantiomeric excess of isotopically chiral molecules. Chiral tag …

Alkylthiocarbamate Metal Complexes With Antiproliferation Activity., Kritika Bajaj

Electronic Theses and Dissertations

Bis(thiosemicarbazones) (BTSCs) and their metal complexes have been extensively studied for various applications including catalysis for hydrogen evolution reactions, treatment of neurodegenerative diseases, hypoxia imaging, and a wide range of pharmacological purposes including antitumor, antiviral, antibacterial, and antifungal agents. The paramount property that makes BTSC metal complexes interesting for their use in these applications is the reduction potential of the coordinated metal, which can be selectively tuned by varying the substituents present on the ligand framework. Although the BTSCs have shown a great deal of success as potential cancer therapeutic agents, they lack selectivity towards cancer cells. For this matter, …

Characterization Of Bimetallic Silver-Copper Nanoinks With Hydroxyethyl-Cellulose Additives, Daniel Brunick

Undergraduate Honors Theses

Coinage metal nanoparticles remain an intriguing subject for research due to their industrial versatility. Primary applications of coinage metal nanoparticles include printed electronics, solar panels, and sensors. Inks formulated with the nanoparticles are conductive and thus useful for fabricating sensors. Silver-copper nanoalloy inks are viable for the fabrication of flexible sensing devices for the detection of volatile organic compounds. One of the challenges is the ability to synthesize composition-controllable alloy nanoparticles at room temperature through wet chemical methods and achieve controllable sintering at room temperature. This work addresses the challenges by investigating the room-temperature synthesis of silver-copper alloy nanoparticles and …

Copper(I) And Silver(I) Complexes Of Olefins, Alkynes, And Cyclopropenes And Their Applications, Anurag Noonikara Poyil

Chemistry & Biochemistry Dissertations - Archive

Poly(pyrazolyl)borates are very popular ligands in organometallic chemistry due to their attractive properties. It is easy to modify the steric and electronic properties of these ligands by changing the pyrazolyl substituents. Fluorinated tris(pyrazolyl)borates are used to stabilize many reactive metal ions. The metal complexes of them are used for multiple applications. These ligands are extensively used to isolate and stabilize many coinage metal complexes (Cu, Ag, and Au). We have synthesized comparably less explored fluorinated bis(pyrazolyl)borate ligands and utilized them to isolate several π-ligands (olefin, alkyne, and cyclopropene) complexes of copper(I) and silver(I). Chapter 2 of this research work focuses …

The Effects Copper Has On Casting Glass, K. Malika Haver

Honors Projects

The aim of this honors project was to discern the difference between how various types of copper reacted with glass. The two disciplines that were connected were chemistry and glassblowing. The basic components learned in chemistry were applied to glass with an end goal of a project installation that visualized the discoveries with copper. The glassblowing technique used was lost wax casting, and the two types of copper used were copper foil and fine copper metal powder. The copper was found to turn the glass into various blues with the intensity and darkness of the blues being dependent on the …

Preconcentration Of Trace Amount Cu(Ii) By Solid-Phase Extraction Method Usingactivated Carbon-Based Ion-Imprinted Sorbent, Kübra Turan, Ruki̇ye Saygili Canlidi̇nç, Orhan Murat Kalfa

Turkish Journal of Chemistry

In this study, preconcentration conditions of trace amounts of copper ions were investigated with solid-phase extraction (SPE) method by synthesizing activated carbon-based ion-imprinted sorbent (Cu(II)-IAC) with a novel and selective approach. Flame atomic absorption spectrometry (FAAS) was used for the determination of metal ions concentrations. For the characterization of the sorbents, scanning electron microscopy, energy dispersive X-ray (SEM/EDX) analysis, and Fourier transform infrared spectroscopy (FTIR) were used. Optimum conditions for the SPE procedure, various parameters such as pH value, eluent type and concentration, sample volume, sample flow rate, adsorption capacity, and selectivity were studied. The adsorption isotherm was analyzed by …

Co2 Absorption Into Primary And Secondary Amine Aqueous Solutions With And Without Copper Ions In A Bubble Column, Hamed Yousefzadeh, Cansu Güler, Can Erkey, Erdal Uzunlar

Turkish Journal of Chemistry

Chemical absorption of CO2 into aqueous amine solutions using a nonstirred bubble column was experimentally investigated. The performance of CO2 absorption of four different primary and secondary amines including monoethanolamine (MEA), piperazine (PZ), 2-piperidineethanol (2PE), and homopiperazine (HPZ) were compared. The effects of initial concentration of amine, the inlet mole fraction of CO2, and solution temperature on the rate of CO2 absorption and CO2 loading (mol CO2/mol amine) were studied in the range of 0.02-1 M, 0.10-0.15, and 25-40 °C, respectively. The effect of the presence of copper ions in the amine solution on CO2 loading was also studied. By …

Analysis Of Copper(Ii) Using The Ascorbate/Oxygen System – A Valuable Undergraduate Resource, Sean Tobin, John Cassidy, Kevin Kurian, Tony Betts

Articles

In deionised water, ascorbic acid (AH−), through oxidation by oxygen in the presence of copper(II), was found to degrade with zero-order kinetics. The magnitude of the reaction rate varied directly with the copper(II) concentration. At a higher pH (7.4), the same reaction was found to be pseudo-first order. Once again, the magnitude of the rate increased linearly with copper(II) concentration at a micromolar level. Dissolved oxygen levels, in excess AH− and trace copper(II), displayed similar kinetics under both conditions. Monitoring of either AH− levels or dissolved oxygen concentration was found to be a useful novel undergraduate practical laboratory for trace …

Synthetic Methods For Improved Scope And Efficiency Of Copper-Catalyzed Regioselective Alkene Boracarboxylation, Steven William Knowlden

Graduate Theses, Dissertations, and Problem Reports (ETD)

The synthesis of carboxylic acids is important to the chemistry community, owing to the broad applicability of these compounds as fine chemicals and pharmaceuticals. Method development over the last decade has focused on the preparation of carboxylic acids through transition metal catalysis utilizing CO₂ as a C1 synthon. Copper-catalyzed heteroelement(bora and sila)-carboxylation protocols provide functional group rich carboxylic acid products, yet remain underdeveloped and thus underutilized. Consequently, catalytic reductive difunctionalization methodologies in which CO₂ and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) are installed across the double bond of a vinyl arene were recently developed. These boracarboxylation protocols provided novel, …

Multinuclear Copper(I) And Silver(I) Pyrazolates: Synthesis, Luminescence, And Catalysis, Monika R. Patterson

Chemistry & Biochemistry Dissertations - Archive

Copper and silver pyrazolate complexes have numerous fascinating properties such as luminescence, catalytic ability, and complexation with small molecules. Using both more widely studied non-fluorinated pyrazolates and less common highly fluorinated pyrazolates as supporting ligands, we successfully synthesized and investigated several new coinage metal complexes. Synthetic details, structures, and properties i.e., luminescence and catalytic ability, have been studied. Chapter 2 of this research describes the synthesis of a new pyrazole with highly fluorinated aryl groups and corresponding trinuclear copper(I), silver(I), and gold(I) complexes. All three metal complexes exhibit bright blue luminescence under exposure to UV light. Additionally, the copper(I) complex …

Cu-Catalyzed Phenol O-Methylation With Methylboronic Acid, Mairead E. Bartlett, Yingchuan Zhu, Uma Bhagwat Gaffney, Joyce Lee, Miranda Wu, Betemariam Sharew, Angela K. Chavez, David J. Gorin

Chemistry: Faculty Publications

A Cu-catalyzed oxidative cross-coupling of phenols with methylboronic acid to form aryl methyl ethers has been developed, expanding the scope of Chan-Evans-Lam alkylation. Electron-deficient phenol derivatives with a broad array of functional groups are methylated in high yields. Increased reaction temperature and catalyst loading enables the methylation of substrates incorporating pyridine and dihydroquinolone motifs. Electron-rich phenol derivatives are poor substrates for the methylation; the characterization of C−H homodimerization products formed from these substrates illuminates a competing mechanistic pathway.