Inorganic Chemistry Commons^™

Oxidation Of Benzylic Alcohols And Lignin Model Compounds With Layered Double Hydroxide Catalysts, Justin K. Mobley, John A. Jennings, Tonya Morgan, Axel Kiefer, Mark Crocker

Chemistry Faculty Publications

Alcohol oxidation to carbonyl compounds is one of the most commonly used reactions in synthetic chemistry. Herein, we report the use of base metal layered double hydroxide (LDH) catalysts for the oxidation of benzylic alcohols in polar solvents. These catalysts are ideal reagents for alcohol oxidations due to their ease of synthesis, tunability, and ease of separation from the reaction medium. LDHs synthesized in this study were fully characterized by means of X-ray diffraction, NH₃-temperature programmed desorption (TPD), pulsed CO₂ chemisorption, N₂ physisorption, electron microscopy, and elemental analysis. LDHs were found to effectively oxidize benzylic alcohols …

Covalency Is Frustrating: La2sn2o7 And The Nature Of Bonding In Pyrochlores Under High Pressure–Temperature Conditions, Christian Childs, Keith V. Lawler, Andrew L. Hector, Sylvain Petitgirard, Ori Noked, Jesse S. Smith, Dominik Daisenberger, Lucile Bezacier, Marek Jura, Chris J. Pickard, Ashkan Salamat

Chemistry and Biochemistry Faculty Research

Natural specimens of the pyrochlore (A2B2O7) compounds have been found to retain foreign actinide impurities within their parent framework, undergoing metamictization to a fully amorphous state. The response to radionuclide decay identifies pyrochlore systems with having high radiation tolerance and tailored use in radioactive waste applications and radionuclide sequestration. High pressure is a powerful pathway to high density states and amorphization with parallels to radiation-induced processes. Here, La2Sn2O7 is evaluated under extreme conditions via the combination of laser heating in a diamond anvil cell with X-ray diffraction and Raman spectroscopy. The measurements are supported by ab initio random structure searching …

Development Of Chemistry Activities For Local Outreach In Stem, Emily Knight

Chemistry & Biochemistry Student Projects

Introduction: This research project was started because of an increase in outreach opportunities for the Department of Chemistry and Biochemistry. For similar opportunities, we now have bins of content that are simple to use, encouraging more students to participate in volunteer research.

Purpose: to find, modify, and/or create grade-level appropriate labs and demonstration activities for 5th-8th graders, with a specific focus on activities hat involve easily available components. These activities are intended to be used for outreach to local schools by chemistry student volunteers and released online to act as a resource for teachers.

Educational Resources: Polymers, Emily Knight

Chemistry & Biochemistry Student Projects

The document is meant to act as a resource for elementary through middle school teachers, featuring a science activity connected to Indiana state standards with grade-appropriate science connections aimed toward 5th, 6th, 7th, and 8th grade.

This document contains 3 polymer-based activities demonstrating different properties of polymers - the physical characteristics, possible absorbency, and elasticity. These activities can be abbreviated and used in rotating stations, planned over multiple days, or you can pick on that fits best with the classroom environment.

Educational Resources: Ionic Matching, Emily Knight

Chemistry & Biochemistry Student Projects

The document is meant to act as a resource for elementary through middle school teachers, featuring a science activity connected to Indiana state standards with grade-appropriate science connections aimed toward 5th, 6th, 7th, and 8th grade.

The entire point of this piece is simply to introduce balancing charges in ionic compounds. This is a simpler method to get students thinking about the idea, which also makes it suitable for pre-high school students. It gives a visual representation of how charges balance and cow cations pair with anions. At this level, it is very similar to least common denominator calculations.

Educational Resources: Homemade Fluorometer, Emily Knight

Chemistry & Biochemistry Student Projects

The document is meant to act as a resource for elementary through middle school teachers, featuring a science activity connected to Indiana state standards with grade-appropriate science connections aimed toward 5th, 6th, 7th, and 8th grade.

Educational Resources: Exchange Rates And Unit Conversion, Emily Knight

Chemistry & Biochemistry Student Projects

The document is meant to act as a resource for elementary through middle school teachers, featuring a science activity connected to Indiana state standards with grade-appropriate science connections aimed toward 5th, 6th, 7th, and 8th grade.

Students might have experience in 3rd-6th grade with converting basic ideas such as volume and measurements. This is intended to expand that idea and introduce the mole. It's also a general interactive conversion/exchange activity. All items in here are just based on what we had available and convenient, so feel free to swap out items such as rubber stoppers with something more easily available …

Educational Resources: Curie Point Engine, Emily Knight

Chemistry & Biochemistry Student Projects

The document is meant to act as a resource for elementary through middle school teachers, featuring a science activity connected to Indiana state standards with grade-appropriate science connections aimed toward 5th, 6th, 7th, and 8th grade.

The Curie point of a metal is the temperature at which it loses its magnetic characteristics. Heat can cause magnets to stop being magnetic, which is why heating up magnets is not advised. The engine works because the Curie point of nickel is 354 degrees Celsius, a temperature that can be reached with a simple candle flame. Included are instructions about how to build …

Educational Resources: Magnets, Emily Knight

Chemistry & Biochemistry Student Projects

No abstract provided.

Photochemical Investigation Of High-Valent Metal-Oxo Intermediates Containing Corrole And Light-Harvesting Porphyrin Ligands, Jonathan Malone

Masters Theses & Specialist Projects

In enzymatic and synthetic catalytic oxidations, high-valent iron-oxo intermediates play a vital role as the active oxidant. In this regard, many synthetic metal catalysts are designed as biomimetic models to resemble the active site of Cytochrome P450 enzymes (P450) which are the predominant oxidation catalysts in nature. Vitamin B12 cofactors, with a corrole-like structure corrin, are also utilized in some of the more difficult reactions in nature such as rearrangement and reductase reactions.

In this work, application of the promising photochemical method to corrolecontaining ligands systems showed much success in the generation of manganese(V)-oxo corrole intermediates using two electron-deficient corrole …

An Entirely New Molecular Glue For Mof Using Unusual Structural Transformation Of A Coordination Polymer, Sukwoo Jung, Hangyeol Kim, Junseok Ahn

The International Student Science Fair 2018

In this research, an entirely new molecular glue is reported. This ‘coordination polymer glue’ is synthesized from zinc metal and BDC-NPE(2,5-bis{4-[1-(4-nitrophenyl)ethylamino]butoxy}terephthalic acid). Molecular glue transforms from 1D coordination polymer to a 3D cross-linked framework, resulting in a phase change of solution to solid. The carboxylate group of this glue makes the preformed MOF bind to its framework. Therefore, when the solution of molecular glue is mixed with preformed MOF powder and heated, homogeneous and thin MOF film – MOF/ZnNPE film – is fabricated. The film is irrelevant to the kind of its substrate, and its thermal stability was enhanced in …

Steric Effects Of Alkyl Ammonium Salts On The Combustion Of Exchanged Smectite Clays, Celeste A. Keith

Electronic Theses and Dissertations

Bomb calorimetry was explored as a new method for determining the cation exchange capacity (CEC) of clays. Smectite clays were modified with several alkyl ammonium salts varying in number of carbons and the spatial orientation of the carbons about the central nitrogen atom. The clays used, standards purchased from the Source Clay Repository, have CECs of 44, 80, 88, and 120 meq/100 g. Theoretically, the combustion energy of the organo-clays should be approximately the same for each salt. Any differences in energy would be due to the different structures of the salts and how they are oriented in the interlamellar …

An Entirely New Molecular Glue For Mof Using Unusual Structural Transformation Of A Coordination Polymer, Sukwoo Jung, Hangyeol Kim, Junseok Ahn

The International Student Science Fair 2018

In this research, an entirely new molecular glue is reported. This ‘coordination polymer glue’ is synthesized from zinc metal and BDC-NPE(2,5-bis{4-[1-(4-nitrophenyl)ethylamino]butoxy}terephthalic acid). Molecular glue transforms from 1D coordination polymer to a 3D cross-linked framework, resulting in a phase change of solution to solid. The carboxylate group of this glue makes the preformed MOF bind to its framework. Therefore, when the solution of molecular glue is mixed with preformed MOF powder and heated, homogeneous and thin MOF film – MOF/ZnNPE film – is fabricated. The film is irrelevant to the kind of its substrate, and its thermal stability was enhanced in …

New Platinum(Ii) And Rhenium(I) Complexes Of "Linear" Chelate Ligands Terminated With Pyridyl Or Imidazolyl N-Donor Groups, Himali Kokila Ranasinghe Pilana Vithanage

LSU Doctoral Dissertations

The overall goal of this dissertation research is to design, synthesize, and study new Pt(II) and Re(I) complexes relevant to biomedical applications. One of the projects involves the assessment of the interactions of bulky tridentate carrier ligands with a bound guanine nucleobase derivative (G) in platinum complexes, with a goal of developing chemistry potentially relevant to active anti-cancer Pt drugs. In another project, the fac-[Re^I(CO)₃]⁺ core is used to prepare novel Re(I) complexes with the purpose of developing new linking chemistry relevant to ^99mTc and ¹⁸⁷Re radiopharmaceuticals. This research explores …

A Multi-Size Study Of Gold Nanoparticle Degradation And Reformation In Ceramic Glazes, Nathan Nl. Dinh, Luke T. Dipasquale, Michael C. Leopold, Ryan H. Coppage

Chemistry Faculty Publications

Most traditional ceramic glazes employ high amounts of transition metal colorants that are toxic to the environment and can cause health issues in humans through surface leaching. Gold nanoparticles (Au-NPs) have been found to be environmentally friendly and non-toxic alternative metal colorant in ceramic glazes. The plasmon band observed with Au-NPs can result in vibrant solutions by manipulating NP size, shape, and concentration; however, the effects of traditional firing in both reductive and oxidative kilns on Au-NPs are poorly understood. Aside from ancient art processes whose mechanisms have not been fully explored, the use of Au-NPs as suspended ceramic glaze …

Synthesis And Characterization Of (Pyno−)2gacl: A Redox-Active Gallium Complex, Jacob M. Kirsh , '17, Audra J. Woodside , '19, B. C. Manor, P. J. Carroll, Paul R. Rablen, Christopher R. Graves

Chemistry & Biochemistry Faculty Works

We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO−)2GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1H and 13C NMR spectroscopies, X-ray diffraction, and theory. UV–Vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties of the complex, respectively. Our discussion focuses primarily on a comparison of the gallium complex to the corresponding aluminum derivative and shows that although the complexes are very similar, small differences in the electronic structure of the complexes can be correlated to the identity of the metal.

Quadruplexes In ‘Dicty’: Crystal Structure Of A Four-Quartet G-Quadruplex Formed By G-Rich Motif Found In The Dictyostelium Discoideum Genome, A. Guédin, Linda Yingqi Lin , '20, S. Armane, L. Lacroix, J.-L. Mergny, S. Thore, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

Guanine-rich DNA has the potential to fold into non-canonical G-quadruplex (G4) structures. Analysis of the genome of the social amoeba Dictyostelium discoideum indicates a low number of sequences with G4-forming potential (249–1055). Therefore, D. discoideum is a perfect model organism to investigate the relationship between the presence of G4s and their biological functions. As a first step in this investigation, we crystallized the dGGGGGAGGGGTACAGGGGTACAGGGG sequence from the putative promoter region of two divergent genes in D. discoideum. According to the crystal structure, this sequence folds into a four-quartet intramolecular antiparallel G4 with two lateral and one diagonal loops. The G-quadruplex …

Multi-Reference Systems In Chemistry; Unconventional Bonding In Organic Chemistry; Covalent Bonding In Transition Metal Clusters, Alan Wilfred Humason

Chemistry Theses and Dissertations

The geometries, chemical properties, and reactivities of molecules are determined by their electronic structure. The field of ab initio computational chemistry works to calculate the kinetic and potential energies between the nuclei and electrons of a molecule. These calculations usually begin with the determination the electronic ground state.

Molecules that cannot be adequately described with a single, ground state configuration are called \textit{multi-reference systems}, which require the calculation of a linear combination of all pertinent electronic configurations, with a corresponding increase in computational cost. This is not `black box' methodology, because solving these systems requires a good understanding of the …

Tumor-Targeting Fluorinated Phthalocyanines For Theranostic Applications, Erik Nathaniel Carrión

Seton Hall University Dissertations and Theses (ETDs)

Hydrocarbon-based therapeutics and imaging agents are prone to chemical oxidation and degradation resulting in loss of activity and limited functional utility. Thus, more material is required to achieve long-lasting therapeutic effects. Phthalocyanines (Pcs) and their metal complexes (PcMs) can be utilized as prodrugs requiring only renewable energy resources namely, air and light, for cancer therapy and diagnostic (theranostic) applications related to photodynamic therapy (PDT). Replacement of labile C-H bonds in the Pc scaffold with a combination of fluoro and perfluoroisopropyl groups has resulted in a stable yet reactive oxidation catalyst of biological significance and importance. For example, F₆₄PcZn, …

Detection Of Salen-Type Tracers For Subterranean Fluid Flow Monitoring Using Surface-Enhanced Raman Spectroscopy, Jenny C. Sanchez

Chemistry and Chemical Biology ETDs

A series of hydrocarbon and aqueous soluble salen-type ligands have been synthesized and characterized by electronic and vibrational spectroscopy. Aqueous soluble salen-type ligands were complexed to a metal and investigated as potential underground fluid flow tracers using Surface-Enhanced Raman Spectroscopy (SERS) as the analytical technique. Vibrational spectra obtained from SERS was shown to have enhanced the spectral signal for these complexes in low concentrations though did not show significant differences between the free ligands and their metal complexes. This research has shown that, with some structural modifications, salen-type ligands can be effective candidates as subterranean fluid flow tracers when SERS …