Physical Sciences and Mathematics Commons^™

Extraction/Transportation Of Co2+ Metal Ions With Bis(2-Ethylhexyl) Phosphate Dissolved In Kerosene Using A Multidropped Liquid Membrane Technique, Volkan Demi̇rel, Ramazan Donat

Turkish Journal of Chemistry

The transport properties of Co2+ ions from the aqueous donor phase to aqueous acceptor phase with the recently developed multidroplet liquid membrane (MDLM) extraction system were studied. This system serves as a continuous process for the transportation of ions and requires fewer reagents for starting and conducting the procedure. Moreover, the procedure results in fewer waste chemicals and mixtures in comparison to traditional extraction methods. During extraction, bis(2-ethylhexyl) phosphate (D2EHPA) was used as a carrier material and 5% potassium thiocyanate (KSCN) solution was used to obtain a colored complex for UV-Vis detection. By means of several experiments, the optimum D2EHPA …

Architecture Of Extraction: Imagining New Modes Of Inhabitation And Reclamation In The Mining Lifecyle, Erica Dewitt

Masters Theses

Mining is the primary method through which modern society obtains the minerals needed to fuel the global economy, provide for modern energy requirements, and support the built environment. Presently, mining accounts for nearly 1% of the global ice-free land surface, with a dramatic increase anticipated in the coming decades. Mining permanently changes and often destroys the pre-existing topography, hydrology, and ecology of the ground, and efforts to reclaim mining landscapes—with the aim of encouraging reforestation and soil replenishment—are often unsuccessful, rendering the land of abandoned mines both unusable and uninhabitable.

This thesis addresses the current state of mining in the …

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) …

Reversible Dioxygen Binding To Co(Ii) Complexes With Noninnocent Ligands, Praveen Kumar, Laxmi Devkota, Maximilian C. Casey, Anne A. Fischer, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

A series of mononuclear Co(II) complexes with noninnocent (redox-active) ligands are prepared that exhibit metal–ligand cooperativity during the reversible binding of O₂. The complexes have the general formula, [Co^II(L^S,N)(Tp^R2)] (R = Me, Ph), where L^S,N is a bidentate o-aminothiophenolate and Tp^R2 is a hydrotris(pyrazol-1-yl)borate scorpionate with R-substituents at the 3- and 5-positions. Exposure to O₂ at room temperature results in one-electron oxidation and deprotonation of L^S,N. The oxidized derivatives possess substantial “singlet diradical” character arising from antiferromagnetic coupling between an iminothiosemiquinonate (ITSQ^•–) …

Research Progresses Of Cobalt Interconnect And Superfilling By Electroplating In Chips, Li-Jun Wei, Zi-Han Zhou, Yun-Wen Wu, Ming Li, Su Wang

Journal of Electrochemistry

Copper interconnect using dual damascene technology has always been the main means for metallization in the back end of line process. However, with the size effect becoming more and more obvious due to feature size reduction, copper interconnect can no longer meet the demand for high circuit speed in Post-Moore era. Following copper interconnection, cobalt interconnection in chips attracts much attention as an interconnect technology by the next generation, which has been introduced in 7 nm node of integrated circuit manufacturing and below. The electron mean free path of cobalt (~10 nm) is much shorter than copper’s (39 nm), thus …

Location Of Cobalt Impurities In The Surface Oxide Of Stainless Steel 316l And Metal Release In Synthetic Biological Fluids, Xuying Wang, Jonas Hedberg, Heng-Yong Nie, Mark Biesinger, Inger Odnevall, Yolanda S. Hedberg

Chemistry Publications

Since 2021, cobalt (Co) is in Europe classified as carcinogen in quantities exceeding 0.1 wt-%. This affects nickel-rich stainless steels, which contain about 0.2 wt-% Co impurities. Previous findings show the bioaccessibility of Co in stainless steel to be primarily determined by the corrosion resistance. It has been unclear whether Co is distributed heterogeneously in the alloy and the outermost surface and whether a specific location would pose a risk for Co release under specific exposure conditions. This study aimed at locating Co in stainless steel 316L (0.2 wt-% Co) surfaces prior to and after exposure to different synthetic body …

Examination Of The Catalytic Role Of The Axial Cystine Ligand In The Co-Type Nitrile Hydratase From Pseudonocardia Thermophila Jcm 3095, Irene Anyango Ogutu, Martin St. Maurice, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

The strictly conserved αSer162 residue in the Co-type nitrile hydratase from Pseudonocardia thermophila JCM 3095 (PtNHase), which forms a hydrogen bond to the axial αCys108-S atom, was mutated into an Ala residue. The αSer162Ala yielded two different protein species: one was the apoform (αSer^A) that exhibited no observable activity, and the second (αSer^B) contained its full complement of cobalt ions and was active with a k_cat value of 63 ± 3 s⁻¹ towards acrylonitrile at pH 7.5. The X-ray crystal structure of was determined at 1.85 Å resolution and contained no detectable …

Skin Permeation Of Nickel, Cobalt And Chromium Salts In Ex Vivo Human Skin, Visualized Using Mass Spectrometry Imaging, Lina Hagvall, Masoumeh Dowlatshahi Pour, Jiabao Feng, Moshtak Karma, Yolanda Hedberg, Per Malmberg

Chemistry Publications

Skin permeation and distribution of three of the most common skin sensitizers was investigated using a previ-ously developed animal-free exposure method combined with imaging mass spectrometry. Nickel, cobalt, and chromium (III) salts were dissolved in a buffer and exposed to human skin ex vivo, to be analyzed using time of flight secondary ion mass spectrometry (ToF-SIMS). Our findings demonstrate that metal haptens mainly accumulated in the stratum corneum, however all three metal sensitizers could also be detected in the epidermis. Cobalt and chromium (III) species penetrated into the epidermis to a larger extent than nickel species. The degree of penetration …

Effects Of Cobalt Treatment On Growth Of Five Legume Species, Yu Lu, Qinghua Yuan

IGC Proceedings (1997-2023)

No abstract provided.

Purification And Activity Analysis Of A Highly Active Recombinant Catalase From Psychrophilic Bacterium Psychrobacter Cryohaloentis, Andrew Stewart

Honors Program Theses

To date, the genus Psychrobacter includes 37 recognized bacterial species isolated from different sources ranging from Siberian permafrost (P. cryohalolentis) to seal feces (P. lutiphocae). Due to its diverse ecological niches, several species belonging to the genus have different enzymatic activities with potential applications in bioremediation and the food industry. In this study, a bioprospecting approach was used to perform a in depth analysis of a Psychrobacter-like bacterial strain isolated from goose feces (designated as Psychrobacter unknown). The phylogenetic analysis of 16S rRNA gene and homologous sequence studies suggest that the strain may represent a novel species of the Psychrobacter …

Bacteria-Mediated Synthesis Of Cobalt(Ii,Iii) Oxide Nanostructures, Ryan Loughran

Honors Program Theses and Projects

This work describes the synthesis of Co₃O₄ using rod-shaped Gram-positive bacteria Lactobacillus rhamnosus as a template. The motivation behind this project was to find potentially cheaper and environmentally benign protocols in comparison to the current solution-based methods.

Synthesis, Characterization, And Kinetics Studies Of New Cobalt Complexes For The Production Of H2 In Acidic Media, Michael John Celestine

Chemistry & Biochemistry Theses & Dissertations

The kinetics and mechanism of the oxidation of [Co(dmgBF₂)₂(OH₂)₂] (where dmgBF₂ = difluoroboryldimethylglyoximato) by sodium hypochlorite (NaOCl), sodium bromate (NaBrO₃), and bromine (Br₂₎ was investigated by stopped-flow spectrophotometry at 450 nm over a wide temperature range. The pK_a1 value for [Co(dmgBF₂)₂(OH₂)₂] was calculated as 5.27 ± 0.14 at I = 0.60 (NaCl). From the variation in pH studies, the activation parameters were derived from the proposed mechanisms for NaOCl, ΔH_1*, ΔH_2*, ΔS_1*, and …

Spectrophotometric Characterization Of The Complexation Of Gossypol Acetic Acid With Cobalt Ion, Ugilay Abdurahmanova, Habibjon Kushiev, Maral Askarova, Dilafruz Allanazarova

Karakalpak Scientific Journal

The authors of the article suggest simple and express method of spectrophotometric determination of cobalt with the help of derivatives of gossypol. Optimal conditions of determining cobalt are found. Under optimal conditions there was created a graded graph, which is more linear in the range for cobalt concentration of 10.0 – 50.0 microgram/25 ml, contents and constants of cobalt complex with gossypol vinegar acid.

Effects Of Se And Co Combined Fertilizer On Production Of Alfalfa, Xiao Guo, Xiao-Lei Jie, Hua-Feng Hu

IGC Proceedings (1997-2023)

Selenium(Se) and cobalt (Co) are important essential trace elements for forage and animal production (Yang et al. 1998, Arvy 1993). The supplementation of Se in animal diet significantly increases Se-Glutathione peroxidase (GSH-Px ) activities in the liver, testes, spermatozoa and seminal plasma (Abdelrahman et al.1998), Selenium is also a key component of a number of functional seleno-proteins. GSH-Px is the best characterized of the family of selenoproteins. In Henan Province, the fine grass and green milk production zones are mainly distributed along the riverbank of the Yellow River where soils are sandy and sterile with lower Se and Co …

Reactions Of First-Row Transition Metal Complexes In Bis(Alkoxide) Ligand Environments With Diazoalkanes: Formation Of Carbenes Versus Reductive Coupling To Form Bridging Tetrazenes, Amanda Grass

Wayne State University Dissertations

This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) Å, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ½ complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. …

Allylic Amination And Carbon–Carbon Double Bond Transposition Catalyzed By Cobalt(Ii) Azodioxide Complexes, Kylin A. Emhoff, Ahmed M.H. Salem, Lakshmi Balaraman, Drew M. Kingery, W. Christropher Boyd

Chemistry Faculty Publications

The unusual cobalt(II) diphenylazodioxide complex salts [Co(az)₄](PF₆)₂ and [Co(bpy)(az)₂](PF₆)₂ have been shown to catalyze the allylic amination/C–C double bond transposition reaction of 2-methyl-2-pentene with PhNHOH, with a turnover number of about 4. The mechanism is proposed to involve a nitroso-ene-like transfer of a PhNO moiety from the azodioxide ligand to the alkene, followed by reduction of the organic product to yield a cobalt(III) intermediate, which is itself reduced back to cobalt(II) by PhNHOH, regenerating PhNO. Hetero-Diels-Alder trapping experiments suggest that an “off-metal” mechanism, in which PhNO is released from the …

Cobalt Partitioning And Solubility In Low-Temperature Carbonate-Hydrothermal Systems, Seth Kurtis Coursey

Graduate Research Theses & Dissertations

Cobalt mineralization has been documented in low temperature Mississippi Valley-type (MVT) deposits in southeast Missouri. Lead and zinc are the most economically important metals in these deposits and are contained within galena (PbS) and sphalerite (ZnS), respectively. Cobalt is also mined in some of the deposits with cobalt-bearing ores, e.g., siegenite ((Ni,Co)3S4) and fletcherite (Cu,(Ni,Co)2S4), occurring stratigraphically below main-stage galena and sphalerite. The hydrothermal fluids responsible for cobalt mineralization are thought to be chemically distinct from the predominant MVT ore-bearing fluids and represent a distinct mineralizing event. Cobalt is likely transported as CoCl2 in hydrothermal fluids and sourced from structures …

Cobalt-Catalyzed Aerobic Oxidative Cyclization Reactions Of Bisnucleophiles: New Methodologies And The Role Of Bisnucleophiles In O2 Activation, Jiaqi Liu

Graduate Theses, Dissertations, and Problem Reports

Over the past few decades, transition metals have found wide applications in the development of selective oxidative transformations mediated by molecular oxygen. Due to the benign nature of molecular oxygen as an oxidant and an increasing awareness of green chemistry practice, tremendous progress has been made towards the development of Cu-and Pd-catalyzed aerobic oxidation reactions. As a first-row transition metal alternative to copper, cobalt has been employed in aerobic catalytic transformations for its cost-efficiency and earth abundance; however, redox-active mediators such as benzoquinone (BQ), N-hydroxyphthalimide (NHPI) or salen-type ligands are usually required. To date, reactions mediated by Co/O₂ catalytic …

Activation Of Nitrite And Carbon Dioxide By Cobalt Centered Redox Active Ligand Featuring A Hemilabile Pendant Amine, Douglas F. Baumgardner

WWU Graduate School Collection

Carbon dioxide (CO₂) and bioavailable nitrogen in the form of nitrates (NO₃^-) and nitrites (NO₂^-) are serious environmental pollutants. However, without economic incentives there is little interest in remediation of these pollutants outside of laboratory scale experiments. CO₂ can be converted to carbon monoxide (CO), a valuable building block in Fischer-Tropsch sourced fuel, and NO₃^- and NO₂^- can be converted to ammonia, another important chemical building block. However, both require effective, low-cost catalysts to be financially viable options. This thesis seeks to demonstrate the conversion of CO …

Synthesis And Effect Of Substituent Position, Metal Type On The Electrochemical Properties Of (3-Morpholin-4-Ylpropoxy) Groups Substituted Cobalt, Manganese Phthalocyanines, Zekeri̇ya Biyiklioğlu, Hüseyi̇n Baş

Turkish Journal of Chemistry

In this work, 4-(3-morpholin-4-ylpropoxy)phthalonitrile 2, 3-(3-morpholin-4-ylpropoxy)phthalonitrile 3, Co(II)Pc and Mn(III)Pcs containing (3-morpholin-4-ylpropoxy) groups at peripheral and nonperipheral positions were synthesized. Phthalonitrile derivatives (2 and 3), Co(II)Pc and Mn(III)Pcs (2a, 2b, 3a, 3b) were characterized by using FT-IR, NMR (only for 2 and 3), mass and UV-Vis (except 2 and 3) spectral data techniques. Also, electrochemistry of (3-morpholin-4-ylpropoxy) group substituted Co(II)Pc and Mn(III)Pcs were inspected by using cyclic voltammetry. Electrochemical studies show that (3-morpholin-4-ylpropoxy) group substituted Co(II)Pc and Mn(III)Pcs electropolymerized on the Pt working electrode.

Effect Of High Se And Co Alfalfa Forage On Animal Production, Xiao-Lei Jie, Xiao Guo, Hua-Feng Hu

IGC Proceedings (1997-2023)

Total and available selenium (Se) and cobalt (Co) concentrations are low in Chinese soils, especially those found in mainly in temperate humid sub-humid conditions in the northeast to the southwest band across China (Tan et al. 2002). The levels of Se and Co are marginally deficit in the brown soil of the Yellow River region which causes lower production level and quality in forage and crop plants. Application of Se and Co fertilizers to arable lands is essential to produce high Se and Co forages. Henan is a Province where produce high-quality grass forages are used to support dairy …

Synthesis Of Magnetic Ion Doped Ii-Vi Benzenechalcogenolate Molecular Clusters, Fumitoshi Kato

Doctoral Dissertations

Diluted magnetic semiconductor quantum dots (DMS-QDs) is a class of material prepared by introducing a small percentage of magnetic impurities to impart new magneto-optical properties to the host nanocrystal (NC). Such materials are regarded as promising candidates for their potential application in spintronic devices. The overall functionality of the DMS‑QD is highly dependent on the dopant position within the host structure. A thorough understanding of the doping mechanism is, therefore, critical to gain better control over the dopant speciation in nanocrystal lattice and material properties. In this work, we utilized II‑VI molecular clusters that are analogous to bulk semiconductors as …

Cationic Cobalt (Ii) Hydroformylation, Drew Michael Hood

LSU Doctoral Dissertations

While investigating a bimetallic cobalt hydroformylation catalyst a new class of monometallic cationic cobalt (II) hydroformylation catalyst were discovered. These newly discovered catalyst proved to be very unique with high hydroformylation activity under mild conditions. The pre-catalyst were characterized using various methods including NMR, EPR, MS, and X-ray crystallography. Similarly the active catalyst was also investigated using NMR, EPR, FTIR, and X-ray crystallography. Various catalyst modifications were investigated for their effects on hydroformylation activity. Likewise various reaction parameters were probed to determine their effect on hydroformylation activity. Finally the best cationic cobalt (II) catalyst were directly compared to industry standards …

Fischer–Tropsch: Product Selectivity–The Fingerprint Of Synthetic Fuels, Wilson D. Shafer, Muthu Kumaran Gnanamani, Uschi M. Graham, Jia Yang, Cornelius M. Masuku, Gary Jacobs, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

The bulk of the products that were synthesized from Fischer–Tropsch synthesis (FTS) is a wide range (C₁–C₇₀₊) of hydrocarbons, primarily straight-chained paraffins. Additional hydrocarbon products, which can also be a majority, are linear olefins, specifically: 1-olefin, trans-2-olefin, and cis-2-olefin. Minor hydrocarbon products can include isomerized hydrocarbons, predominantly methyl-branched paraffin, cyclic hydrocarbons mainly derived from high-temperature FTS and internal olefins. Combined, these products provide 80–95% of the total products (excluding CO₂) generated from syngas. A vast number of different oxygenated species, such as aldehydes, ketones, acids, and alcohols, are also embedded in this product range. …

Shelf Inputs And Lateral Transport Of Mn, Co, And Ce In The Western North Pacific Ocean, Peter L. Morton, William M. Landing, Alan M. Shiller, Amy Moody, Thomas D. Kelly, Michael Bizimis, John R. Donat, Eric H. De Carlo, Joseph Shacat

Chemistry & Biochemistry Faculty Publications

The margin of the western North Pacific Ocean releases redox-active elements like Mn, Co, and Ce into the water column to undergo further transformation through oxide formation, scavenging, and reductive dissolution. Near the margin, the upper ocean waters enriched in these elements are characterized by high dissolved oxygen, low salinity, and low temperature, and are a source of the North Pacific Intermediate Water. High dissolved concentrations are observed across the Western Subarctic Gyre, with a rapid decrease in concentrations away from the margin and across the subarctic-subtropical front. The particulate concentrations of Mn, Co, and Ce are also high in …

Effect Of Fe Substitution On The Partial Oxidation Of Methane To Syngas Over La$_{0.7}$Sr$_{0.3}$Co$_{1-Y}$Fe$_{Y}$O$_{3-\Delta}$ Perovskites, Adilah Aliyatulmuna, Perry Burhan, Bambang Prijamboedi, Hamzah Fansuri, Irmina Kris Murwani

Turkish Journal of Chemistry

In this research, a series of La$_{0.7}$Sr$_{0.3}$Co$_{1-y}$Fe$_{y}$O$_{3-\delta }$ ($y =$ 0.0--0.4) was successfully synthesized by a solid-state reaction method and syngas production studies were performed using gas chromatography. Thermogravimetric analysis characterized the concentration of Fe$^{3+}$, which gave a low H$_{2}$/CO ratio over La$_{0.7}$Sr$_{0.3}$Co$_{1-y}$Fe$_{y}$O$_{3-\delta }$ without the presence of molecular oxygen. All samples possessed a purely rhombohedral structure. The incorporation of more Fe increased the lattice parameter and changed XRD peaks of the La$_{1-x}$Sr$_{x}$Co$_{0.8}$Fe$_{0.2}$O$_{3}$ from sharp and single to double. Among the catalyst powders tested for syngas production activity, La$_{0.7}$Sr$_{0.3}$Co$_{0.6}$Fe$_{0.4}$O$_{3-\delta }$ ($y =$ 0.4) had the low molar ratio of H$_{2}$/CO …

Synthesis And Applications Of Ceramic (Silicon Carbide And Silicon Nitride), Metallic (Cobalt(0)) And Polymeric (Polyurethane) Aerogels, Parwani M. Rewatkar

Doctoral Dissertations

"A new method has been demonstrated for the synthesis of monolithic ceramic and purely metallic aerogels from xerogel powder compacts, and the use of polyurethane aerogels based on cyclodextrins as efficient desiccants.

I. Highly porous ( > 80%) monolithic SiC and Si₃N₄, aerogels were prepared from compressed compacts of polyurea-crosslinked silica xerogel powders. The process is time efficient as solvent-exchange through powders is fast, and energy efficient as it bypasses drying with supercritical fluids. The final ceramic objects were chemically pure, sturdy, with compressive moduli at 37 ±7 MPa and 59 ± 7 MPa, and thermal conductivities …

‘Cassette’-Ises (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds For Hydrolytic Kinetic Resolution Across A Range Of Epoxides, Sangeeta Dey, Douglas R. Powell, Chunhua Hu, David B. Berkowitz

Chemistry Department: Faculty Publications

‘Cassette’-ISES (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds for Hydrolytic Kinetic Resolution Across a Range of Epoxides

A new ‘Cassette’-In Situ Enzymatic Screen (ISES) for combinatorial catalysis is introduced. This allows the experimentalist to obtain an information-rich readout, in real time, providing an estimate of the sense and magnitude of enantioselectivity across more than one substrate. In its first iteration, the screen identified Co^III-salen catalysts with β-pinene- and α-naphthylalanine-derived chiral scaffolds with broad, yet complementary, substrate specificities.

Electrodeposition Of Cobalt From Eutectic-Based Ionic Liquid, Rostom Ali M., Sankar Saha S, Ziaur Rahman Md

Journal of Electrochemistry

The electrodeposition of cobalt from a solution containing cobalt chloride in either a urea-choline chloride based or an ethylene glycol (EG)-choline chloride based ionic liquid has been carried out onto copper and steel cathodes by constant current and constant potential methods at different temperatures. The influences of various experimental conditions on electrodeposition and morphology of the deposited layers have been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD)technique. It has been shown that the smooth, shiny with good adherence and bright metallic coloured cobalt coatings were obtained from both urea and EG based ionic liquids at the applied …

Microwave Popped Co(Ii)-Graphene Oxide Hybrid: Bifunctional Catalyst For Hydrogen Evolution Reaction And Hydrogen Storage, Lin Wei, Karen Lozano, Yuanbing Mao

Chemistry Faculty Publications and Presentations

In an effort to develop a multifunctional catalyst for hydrogen generation and adsorption applications, a facile and cost-effective microwave popping method was used to synthesize popped graphene oxide (PGO) and Co-PGO hybrid. Both samples have been explored and compared as hydrogen storage materials and as electrocatalysts for hydrogen evolution reaction (HER) for the first time. The loading of Co(II) species on the surface of the PGO enhanced the hydrogen storage capability of PGO from 0.04wt% to 0.08wt% as measured at 293K and 800 mmHg. Co-PGO is also acting as a better electrocatalyst for HER compared to the PGO counterpart.