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Synthetic Investigation On The Biomimetic Metal-Catalyzed Sulfoxidations And Photochemical Generation Of A Highly Reactive Ruthenium(V)-Oxo Porphyrin, WeiLong Luo 2016 Western Kentucky University

Synthetic Investigation On The Biomimetic Metal-Catalyzed Sulfoxidations And Photochemical Generation Of A Highly Reactive Ruthenium(V)-Oxo Porphyrin, Weilong Luo

Masters Theses & Specialist Projects

Catalytic oxidation plays a crucial role in current chemical and pharmaceutical industries which is also a leading technology for green chemical processes. In Nature, the ubiquitous cytochrome P450 enzymes can catalyze a wide variety of oxidation reactions with high efficiency and selectivity. Many transition metal catalysts are designed as the biomimetic model of cytochrome P450 enzymes. In this work, series of metalloporphyrins and metallocorroles have been successfully synthesized to investigate and develop catalytic selective oxidation of sulfides to sulfoxides.

Manganese(III) porphyrin complexes (2) and manganese(III) corrole complexes (6) with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen ...


Synthesis And Applications Of Lanthanide Sulfides And Oxides, Christopher Marin 2016 University of Nebraska-Lincoln

Synthesis And Applications Of Lanthanide Sulfides And Oxides, Christopher Marin

Student Research Projects, Dissertations, and Theses - Chemistry Department

This dissertation focuses on two of the key fields where lanthanides find ready application: as optically active materials with a focus on the lanthanide sulfides, and as catalytic materials with a focus on cerium oxide.

The lanthanide sulfides have attracted considerable interest for their potential as solar energy conversion materials, pigments, infrared window materials, and phosphor host media. However, applications of these materials remain limited due to their synthetic difficulty along with their not well understood properties compounded by both their difficulty in manufacturing as well as in simulating largely due to the need to take into account f-shell electrons ...


Iron Uptake And Accumulation Is A Target Of Nickel Toxicity During The Lag Phase In Escherichia Coli, Geoffrey Tuttle Ford 2016 University of South Carolina

Iron Uptake And Accumulation Is A Target Of Nickel Toxicity During The Lag Phase In Escherichia Coli, Geoffrey Tuttle Ford

Theses and Dissertations

Various transition metals are essential to all forms of life, and are only required in trace amounts. But this dependence comes as a double-edged sword. All organisms must maintain a careful intracellular quota that does not traverse outside an acceptable range. One transition metal in particular is nickel. The importance of this transition metal has been debated widely and its function varies greatly between organisms, including bacteria. However, the adverse effects caused by over exposure to this metal have been the center of much experimentation in recent years. Still, the mechanisms of nickel toxicity and the subsequent effects on cellular ...


Palladium Catalyzed Hydrodechlorination Of 4-Chloroanisole In Phosphonium Ionic Liquids, Joseph Hennig 2016 The College at Brockport: State University of New York

Palladium Catalyzed Hydrodechlorination Of 4-Chloroanisole In Phosphonium Ionic Liquids, Joseph Hennig

Senior Honors Theses

Until their production was banned in 1979, polychlorinated biphenyls (PCB’s), formed as complex mixtures, were used in electrical equipment. Although they are no longer manufactured, some PCBs are still in service—albeit, in closed or semi-closed systems such as dielectric fluids for transformers and capacitors, or are still present in the environment. The continued presence of PCBs is problematic, due to their toxicity. Their hydrophobic nature and resistance towards metabolism leads to bio-accumulation up the food chain. resulting in long term effects in chronically exposed persons, like firefighters, factory workers or persons whose food have accumulated appreciable levels of ...


Metal Assisted Chemical Etching, Inayat Bajwa 2016 Quattrone Nanofabrication Facility

Metal Assisted Chemical Etching, Inayat Bajwa

Protocols and Reports

No abstract provided.


Dendrimer Modified Silica Nanoparticles As Fluorescent Chemosensors For The Detection Of Copper And Cyanide Ions, Alicia Luhrs 2016 University of San Francisco

Dendrimer Modified Silica Nanoparticles As Fluorescent Chemosensors For The Detection Of Copper And Cyanide Ions, Alicia Luhrs

Master's Theses

A series of silica nanoparticle-based fluorescent chemosensors were synthesized for the sensitive and selective detection of Cu2+ ions in aqueous solution and subsequent CN- ion detection. Silica nanoparticles (SNP) were modified with branching polyamidoamine (PAMAM) dendrimers, which function as selective turn-off Cu2+ ion chelators and platforms for the attachment of rhodamine isothiocyanate (RITC) or fluorescein isothiocyanate (FITC) fluorescent dyes. In the presence of Cu2+ ions, the emission of the fluorescent dye is quenched by Forster resonance energy transfer (FRET) and is dependent upon dendrimer generation, pH, fluorescent dye, and surface charge. The quenching effectiveness was analyzed by ...


Syntheses And Investigations Of Photo And Radioluminescent Stilbene- And Anthracene- Based Lanthanide Metal-Organic Frameworks, Stephan Roy Mathis II 2016 Clark Atlanta University

Syntheses And Investigations Of Photo And Radioluminescent Stilbene- And Anthracene- Based Lanthanide Metal-Organic Frameworks, Stephan Roy Mathis Ii

Electronic Theses & Dissertations Collection for Atlanta University & Clark Atlanta University

This research explores the synthesis of anthracene and stilbene-based metal-organic framework (MOF) structures as potential scintillating (radioluminescent) materials for use in the detection of gamma radiation. The organic molecules 9,10-anthracenedicarboxylic acid (ADCH2) and trans-4,4’-stilbenedicarboxylic acid (SDCH2), were each used as a linker, in combination with a range of lanthanide metal ions, to synthesize novel three dimensional MOF structures under hydrothermal conditions. With ADCH2, the early period lanthanides yield isostructures with the metal ion in higher coordination (nine) than for those with late period metals (seven). The ADC-MOFs show linker-based photoluminescence properties with well ...


High-Valent Organometallic Palladium And Nickel Complexes And Their Roles In Carbon-Carbon And Carbon-Heteroatom Bond Formation Reactions, Jason Wesley Schultz 2016 Washington University in St. Louis

High-Valent Organometallic Palladium And Nickel Complexes And Their Roles In Carbon-Carbon And Carbon-Heteroatom Bond Formation Reactions, Jason Wesley Schultz

Arts & Sciences Electronic Theses and Dissertations

The development of palladium catalysis has been influential in a wide range of organic transformations, in particular C-C coupling, C-Heteroatom coupling and C-H functionalization reactions. These catalytic transformations normally proceed through the Pd0/II catalytic cycle. These reactions are remarkably useful, however, they suffer from two major problems: -hydride elimination and palladium black deposition. To circumvent these problems, recent reports have been focused on developing novel organic transformations proceeding through high-valent palladium and nickel catalytic cycles.

To this point, we recently reported the isolation and characterization of various mononuclear PdIII complexes using the tetradentate ligands, N,N-di-alkyl-2,11-diaza[3.3 ...


Synthesis And Topochemical Manipulation Of New Layered Perovskites, Lea Gustin 2016 University of New Orleans

Synthesis And Topochemical Manipulation Of New Layered Perovskites, Lea Gustin

University of New Orleans Theses and Dissertations

Metastable layered perovskites containing interlayer transition metals can readily be obtained by simple ion exchange reactions on receptive hosts, such as those of the Dion-Jacobson and Ruddlesden-Popper structure types. In this work, we focused on adding to the library of layered perovskites by not only creating new compounds, but by also showing their ability to be further manipulated, and by studying the stability of the series through thermal behavior studies.

The reactions with transition metal halides are particularly interesting since they often lead to novel architectures and magnetic behavior. On subsequent heat treatment, these exchange products typically decompose to thermodynamically ...


Mining Uranium From Seawater: A Coordination Chemistry Approach, Nada Mehio 2016 University of Tennessee - Knoxville

Mining Uranium From Seawater: A Coordination Chemistry Approach, Nada Mehio

Doctoral Dissertations

Poly(acrylamidoxime) fibers are the current state-of-the-art adsorbent for mining uranium from seawater. However, the amidoxime group is not perfectly selective towards the uranyl cation, in particular, competition with transition metal cations remains a major challenge. In order for subsequent generations of chelating polymer adsorbents to be improved, the coordination chemistry of amidoxime-uranyl and -transition metal cation complexes needs to be better understood. While the coordination mode of amidoxime-uranyl complexes has been established in the literature, a number of amidoxime-transition metal cation complex binding motifs can be observed on the Cambridge Structrural Database. Likewise, the formation constants, or log K ...


Cd Transport In Eutectic Licl-Kcl And Contamination Of Zr Metal And Thermal Dehydration Of Bulk Licl-Kcl, Nicholas Azoy Earle 2016 University of Tennessee - Knoxville

Cd Transport In Eutectic Licl-Kcl And Contamination Of Zr Metal And Thermal Dehydration Of Bulk Licl-Kcl, Nicholas Azoy Earle

Masters Theses

Researchers at Idaho National Labs have noted unexpectedly high Cd content in empty cladding hulls after processing in the Mark-IV ER. It has been theorized that Cd metal is transporting from the LCC pool through the eutectic LiCl-KCl salt bath to the anode baskets containing the empty hull where it is retained as a Zr-Cd intermetallic. This study sought to replicate the Cd contamination in a dry Ar glovebox using small-scale analogue of the Mark-IV ER salt-Cd metal system.

Anhydrous eutectic LiCl-KCl was an essential regent in this research and experiments were conducted to investigate the feasibility of dehydrating nominally ...


Developing Synthetic Methods To Prepare Discrete Metal-Organic Nanotubes, Derek L. Mull 2016 University of Tennessee - Knoxville

Developing Synthetic Methods To Prepare Discrete Metal-Organic Nanotubes, Derek L. Mull

Masters Theses

Metal-organic nanotubes (MONTs) are an emerging class of discrete materials that are the 1D variant of metal-organic frameworks (MOFs). MONTs have potential to become an alternative 1D material to carbon nanotubes, metal oxide nanotubes, and boron nitride nanotubes because they possess an organic ligand that can be functionalized and tuned for specific applications. Despite this potential, only a handful of structures have been reported and only two examples of discrete MONTs exist in the literature. It is thus imperative to develop general methods to prepare and characterize discrete MONTs to bring them to the forefront of the scientific literature.

Efforts ...


A Chemical Sensor For Cyanide, Rachel E. Lambert 2016 The University of Southern Mississippi

A Chemical Sensor For Cyanide, Rachel E. Lambert

Honors Theses

The cyanide ion and its gaseous form, hydrogen cyanide, are extremely toxic. Cyanide impairs cellular respiration by inhibiting cytochrome c oxidase, an enzyme in the electron transport chain, leading to cell death.

In a previous study, we synthesized an optical sensor that detects cyanide selectively. The aim of this project is to increase the sensitivity of this sensor. This can be achieved by utilizing the unique spectroscopic properties of lanthanide ions.

The lanthanide metal (europium or terbium) was added to a coumarin-glycine chemodosimeter in a DMSO solvent system. The sensor was titrated with several monodentate analytes including, nitrate, octylamine, 1-pentanethiol ...


Biodegradable Copolymers Made With Magnesium Complexes, Reile M. Slattery, Joseph M. Fritsch 2016 Pepperdine University

Biodegradable Copolymers Made With Magnesium Complexes, Reile M. Slattery, Joseph M. Fritsch

Seaver College Research And Scholarly Achievement Symposium

In this study, a bis-ligated magnesium complex was used to initiate the ring opening copolymerization of L-lactide (L-LA) and ϵ-caprolatone (ϵCL) and the isolated polymeric materials were characterized with NMR spectroscopy. First, the simultaneous feeding of both monomers resulted in the synthesis of homopolymer poly-lactic acid (PLA). Polymerization experiments with sequential addition of L-LA and ϵCL yielded surprising results. The ring opening polymerization of ϵCL yielded poly-caprolactone (PCL) which with the addition of L-LA yielded a di-block copolymer of PCL and PLA. The presence of the two homopolymer blocks in the copolymer was identified with 13C NMR where ...


Investigation Of The Interactions Between Pt(Ii) And Pd(Ii) Derivatives Of 5,10,15,20-Tetrakis (N-Methyl-4-Pyridyl) Porphyrin And G-Quadruplex Dna, Navin C. Sabharwal , '14, O. Mendoza, John Michael Nicoludis , '12, Thomas Ruan , '16, J.-L. Mergny, Liliya A. Yatsunyk 2016 Swarthmore College

Investigation Of The Interactions Between Pt(Ii) And Pd(Ii) Derivatives Of 5,10,15,20-Tetrakis (N-Methyl-4-Pyridyl) Porphyrin And G-Quadruplex Dna, Navin C. Sabharwal , '14, O. Mendoza, John Michael Nicoludis , '12, Thomas Ruan , '16, J.-L. Mergny, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

G-quadruplexes are non-canonical DNA structures formed by guanine-rich DNA sequences that are implicated in cancer and aging. Understanding how small molecule ligands interact with quadruplexes is essential both to the development of novel anticancer therapeutics and to the design of new quadruplex-selective probes needed for elucidation of quadruplex biological functions. In this work, UV–visible, fluorescence, and circular dichroism spectroscopies, fluorescence resonance energy transfer (FRET) melting assays, and resonance light scattering were used to investigate how the Pt(II) and Pd(II) derivatives of the well-studied 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP4) interact with quadruplexes formed by the human ...


Synthesis And Mechanistic Investigations Of Transition Metal Complexes And Ligands For Chemotherapeutic Applications, Jimmie Lee Bullock Jr. 2016 Old Dominion University

Synthesis And Mechanistic Investigations Of Transition Metal Complexes And Ligands For Chemotherapeutic Applications, Jimmie Lee Bullock Jr.

Chemistry & Biochemistry Theses & Dissertations

Transition metal complexes have played a critical role in antitumor therapy with many complexes incorporating platinum, ruthenium, and lanthanum having been investigated in preclinical and clinical trials. The best known transition metal therapeutic is cisplatin, which is utilized in nearly 50% of all cancer therapies, despite its significant toxic side effects. The toxic side effects of current FDA approved platinum-based chemotherapeutics are often overlooked due to the “special status” granted to these drugs due to their ability to fight, what is often considered an incurable disease with life expectancies often measured in months. Oncology drug development has therefore now focused ...


Oligomers And Polymers Of Copper(I) With Dicyanobenzene And Cyanopyridine Ligands, Mark K. Broderick 2016 College of William and Mary

Oligomers And Polymers Of Copper(I) With Dicyanobenzene And Cyanopyridine Ligands, Mark K. Broderick

Undergraduate Honors Theses

The copper(I) source material Cu(NCMe)4BF4 was reacted with two equivalents of triphenylphosphine and various cyanoaromatic bridging ligands in a variety of solvents to form six new metal-organic complexes. The bridging ligands used were 1,2-dicyanobenzene (oDCB), 1,3-dicyanobenzene (mDCB), 1,4-dicyanobenzene (pDCB), 2-cyanopyridine (oCPy), 3-cyanopyridine (mCPy), and 4-cyanopyridine (pCPy). The resulting complexes consisted of the dimers [Cu2(PPh3)4(oDCB)2](BF4)2 and [Cu2(PPh3)4(oCPy)2](BF4)2, the trimer [Cu3(PPh3)6(mCPy)3](BF4)3, and the polymers {[Cu(PPh3 ...


Development Of New Ligand Scaffolds For The Preparation Of Heterobimetallic Complexes, Alexander Richard Treleven 2016 Marquette University

Development Of New Ligand Scaffolds For The Preparation Of Heterobimetallic Complexes, Alexander Richard Treleven

Master's Theses (2009 -)

There is currently much interest in the development of methods to harness sustainable, CO2 neutral, non-fossil fuel based energy sources due to diminishing worldwide supply of fossil fuels and concerns over historically high levels of CO2 in the atmosphere, which may have a devastating impact on the world’s climate. One such avenue is through the conversion of atmospheric CO2 into useful, high-energy density, organic fuel sources. Photosynthesis is the biological process by which plants convert sunlight, water, and CO2 into the reduced organic materials that we extract from the earth and burn (completing the cycle back to CO2) to ...


A Sodium Salt Of The Dimer Of Boronoterephthalic Acid Anhydride, Scott Simmons, Albert Fratini, Vladimir Benin 2016 University of Dayton

A Sodium Salt Of The Dimer Of Boronoterephthalic Acid Anhydride, Scott Simmons, Albert Fratini, Vladimir Benin

Albert Fratini

The title compound, sodium bis­(6-carb­oxy-1-hy­droxy-3-oxo-1,3-dihydro-2,1-benzoxaborol-1-yl)oxidanium, Na+·C16H15B2O13-, was prepared in two steps from 2-bromo-p-xylene. Its crystal structure was determined at 140 K and has triclinic (P) symmetry. The compound presents a unique structural motif, including two units of the cyclic anhydride of boronoterephthalic acid, joined by a protonated, and thereby trivalent, oxonium center. Association in the crystal is realized by complementary hydrogen bonding of the carboxyl groups, as well as by coordination of the sodium cations to the oxygen centers on the five-membered rings.


Synthesis, Structural Characterization And Catalytic Activity Of Indenyl Tris-N-Pyrrolyl Phosphine Complexes Of Ruthenium, Matthew J. Stark, Michael J. Shaw, Nigam P. Rath, Eike B. Bauer 2016 University of Missouri-Saint Louis

Synthesis, Structural Characterization And Catalytic Activity Of Indenyl Tris-N-Pyrrolyl Phosphine Complexes Of Ruthenium, Matthew J. Stark, Michael J. Shaw, Nigam P. Rath, Eike B. Bauer

SIUE Faculty Research, Scholarship, and Creative Activity

The synthesis, characterization and catalytic activity of new ruthenium complexes of the tris-N-pyrrolyl phosphine ligand P(pyr)3 is described. The new ruthenium complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] (ind = indenyl ligand η5-C9H7−) were synthesized in 73% and 63% isolated yield, respectively, by thermal ligand exchange of [RuCl(ind)(PPh3)2] with P(pyr)3. The electronic and steric properties of the new complexes were studied through analysis of the X-Ray structures and through cyclic voltammetry. The new complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr ...


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