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Design And Synthesis Of Novel Octacarboxy Porphyrinic Metal-Organic Frameworks, Jacob A. Johnson 2016 University of Nebraska - Lincoln

Design And Synthesis Of Novel Octacarboxy Porphyrinic Metal-Organic Frameworks, Jacob A. Johnson

Student Research Projects, Dissertations, and Theses - Chemistry Department

Metal-Organic Frameworks (MOFs) are a class of nanoporous crystalline materials constructed via the interconnection between metal-ions/inorganic clusters and organic ligands. Since the surface area, pore size and distribution, and chemical functionalities of MOFs are highly tunable via the judicious combinations of inorganic clusters and organic ligands, MOFs have attracted intensive interests for a variety of applications including gas adsorption and separation, catalysis, chemical sensing, and drug delivery among others. Porphyrin based ligands are of particular interest for building functional MOFs due to their unique photo-, electro-, and catalytic properties. In addition, the four-fold symmetry of porphyrin ligands offers an ...


Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson 2016 Portland State University

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Michael Johnson

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO3 and ClF with subsequent multiple fluorine treatments at 120°c. On the basis of its infrared spectrum, the purple CrOF3 was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°c, where it decomposes with the loss of oxygen to CrF3.


Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson 2016 Portland State University

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Michael Johnson

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO3 and ClF with subsequent multiple fluorine treatments at 120°c. On the basis of its infrared spectrum, the purple CrOF3 was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°c, where it decomposes with the loss of oxygen to CrF3.


Solvothermal Preparation And Characterization Of Superstructures Of Nanoscopic Cds And Cdse, Tetyana Levchenko 2016 The University of Western Ontario

Solvothermal Preparation And Characterization Of Superstructures Of Nanoscopic Cds And Cdse, Tetyana Levchenko

Electronic Thesis and Dissertation Repository

Micrometer-sized superparticles, self-assembled from metallic or semiconducting nanoclusters, can be used as convenient building blocks for preparing functional materials, utilizing the electronic and photophysical properties resulting from the quantum confinement as well as from the coupling between individual nanoscopic constituents.

This research aimed at developing a novel approach utilizing the conversion of a cadmium phenylchalcogenolate precursor (Me4N)2[Cd(EPh)4] (where E = S or Se) under solvothermal conditions for the preparation of nanoscopic CdE, including both crystalline superlattices of large discrete nanoclusters and superstructures with more complex morphology. In particular, 3D cubic superlattices of molecular CdS nanoclusters ...


The Investigation Of The Electrical Control Of Hemimicelles And Admicelles On Gold For Analyte Preconcentration, Dheyaa Hussein Al-Karawi 2016 Western Kentucky University

The Investigation Of The Electrical Control Of Hemimicelles And Admicelles On Gold For Analyte Preconcentration, Dheyaa Hussein Al-Karawi

Masters Theses & Specialist Projects

Hemimicelles and admicelles are well-investigated wonders in modern science; they are surfactant monolayers and surface adsorbed micelles, respectively. Capacitance measurements for monitoring the formation of dodecyl sulfate (DS) surfactant monolayer on positively charged gold substrates (planar gold) and the adsorbance of 2-naphthol onto DS surfactant monolayer were performed. The investigation of the electrical control of DS at various concentrations (4, 6, 16, and 32 mM) below and above the critical micelle concentration (CMC= 8 mM) on gold surfaces for analyte preconcentration, prior to chromatographic analysis, is presented. Charged ionic surfactants, such as DS, drawn to a surface of opposite charge ...


Koh Etching Of (100) Si Wafer, No 2, Inayat Bajwa 2016 Quattrone Nanofabrication Facility

Koh Etching Of (100) Si Wafer, No 2, Inayat Bajwa

Protocols and Reports

This report describes KOH etching of (100) Si wafer through a hard mask of silicon oxide, and reveals that the scattered etch rate is ascribed to the etch rates of the different crystal planes exposed during the etching.


Corn Stalk Nitrate Interpretation, John E. Sawyer 2016 Iowa State University

Corn Stalk Nitrate Interpretation, John E. Sawyer

John E. Sawyer

You’ve gotten results from corn stalk nitrate samples collected this fall. (Corn stalk nitrate analysis form.) Now, what do the results mean? The stalk nitrate test is based on the concentration of nitrate-N in the lower corn stalk (8 inch segment from 6 to 14 inches above the ground) when the plant reaches maturity (See Cornstalk testing to evaluate nitrogen management, PM 1584). In general, a larger amount of plant-available N in the soil during the time period before plant maturity results in a greater concentration of nitrate in the lower stalk. However, the stalk nitrate-N concentration can be ...


Electrochemistry And Spectroscopy Of A Molybdenum Porphyrin Compound, Jay S. Bhanot, Kyle A. Grice 2016 DePaul University

Electrochemistry And Spectroscopy Of A Molybdenum Porphyrin Compound, Jay S. Bhanot, Kyle A. Grice

DePaul Discoveries

Carbon dioxide has been a problematic greenhouse gas since the beginning of the industrial age. In an effort to remediate its effects on the climate, multiple techniques have been utilized in the chemical and electrochemical reduction of CO2. Homogeneous electrocatalysis for carbon dioxide reduction has been a topic of increasing interest. However, a full examination of the catalytic performance of early transition metals supported by macroligands has yet to be done. The research reported involves synthesis of a chelate of molybdenum within a tetraphenylporphyrin, and then synthesis, purification, and characterization of its ability to reduce carbon dioxide. The complex ...


Synthesis And Studies Of Cyclopentadienyl Molybdenum Complexes, Cesar Saucedo, Kyle A. Grice 2016 DePaul University Department Of Chemistry

Synthesis And Studies Of Cyclopentadienyl Molybdenum Complexes, Cesar Saucedo, Kyle A. Grice

DePaul Discoveries

The synthesis and electrochemical responses of [CpMo(CO)3]2, CpMo(CO)3I, CpMo(CO)3(OTf), and [CpMo(bpy)(CO)2] (Cp = cyclopentadienyl, bpy = 2,2’-bipyridine, OTf = trifluoromethansulfonate) in organic solvent are reported. Transition metal compounds such as Re(bpy)(CO)3Cl have been shown to be effective carbon dioxide reduction catalysts. The molybdenum metal complexes studied herein were examined under argon and carbon dioxide gas for the potential reduction of carbon dioxide. Proton Nuclear Magnetic Resonance (NMR) spectroscopy, infrared (IR) spectroscopy and an electrochemical method know as cyclic voltammetry were used to gather data on ...


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 ...


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 ...


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 ...


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 ...


Pyrazole Pendant Tetraazamacrocyclic Ligands For Possible Medicinal Applications, Anjuli Bhandari 2016 Buffalo State College

Pyrazole Pendant Tetraazamacrocyclic Ligands For Possible Medicinal Applications, Anjuli Bhandari

Forensic Science Theses

Gadolinium is the element typically used for MRI contrast agents, which are sometimes injected prior to performing an MRI. The element accumulates in inflamed areas, which indicates where there may be an infection or a tumor. However, gadolinium is more toxic to the body than preferred and the potential long-term effects have been studied in individuals who experience health issues.

Complexes containing metal ions that are naturally occurring have been proposed to replace gadolinium use. Complexing a metal ion (i.e. copper(II) or iron(II)) to a macrocyclic ligand that has a high water exchange rate would potentially be ...


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 ...


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