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Inorganic Chemistry Commons

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Thermally Stable Encapsulated Intermetallic And Bimetallic Nanoparticles For Heterogeneous Catalysis, Raghu Maligal Ganesh 2017 Iowa State University

Thermally Stable Encapsulated Intermetallic And Bimetallic Nanoparticles For Heterogeneous Catalysis, Raghu Maligal Ganesh

Graduate Theses and Dissertations

Intermetallic compounds have shown promise as efficient heterogeneous catalysts, displaying improved performance over their monometallic parent metals for chemical transformations. Furthermore, colloidal intermetallic nanoparticles (iNPs) afford additional improvements via increased catalyst surface area and enhanced catalytic performance. However, these iNPs are not efficiently protected against sintering during thermal treatment procedures such as catalyst regeneration, resulting in a loss of their active surface area. Herein, we have successfully developed porous encapsulation strategies using inert silica that afford monodisperse iNPs that address this concern. These iNPs are highly stable thermally and the inert silica-based mesoporous encapsulation doesn't present mass transfer obstacles ...


Dna Binding Modes Of Novel Terpyridine Ruthenium(Ii) Complexes Containing A Chloroquine Analogue, Kyle B. Arriola 2017 University of Redlands

Dna Binding Modes Of Novel Terpyridine Ruthenium(Ii) Complexes Containing A Chloroquine Analogue, Kyle B. Arriola

Undergraduate Honors Theses

The discovery of cis-platin as a chemotherapeutic agent has pioneered the search for superior anticancer drugs within the domain of inorganic chemistry. Ruthenium complexes have had quite the spotlight in this search due to their chemical and biological properties; NAMI-A and KP1019, two ruthenium anticancer drugs, have made it to clinical trials. Ligands of the polypyridyl class are known to be good intercalators. Chloroquine, aside from its antimalarial qualities, has induced apoptosis in several tumor cell lines of glioma and when combined with ruthenium, has exhibited the induction of apoptosis upon multiple cell lines. The synthesis, spectroscopic characterization, and DNA ...


Behavioural And Biochemical Responses To Dietary Mercury Exposure In Two Commercially Important Marine Species, Cyntia Ayumi Yokota Harayashiki 2017 Southern Cross University

Behavioural And Biochemical Responses To Dietary Mercury Exposure In Two Commercially Important Marine Species, Cyntia Ayumi Yokota Harayashiki

Theses

Mercury is a toxic metal with a global distribution. Studies on waterborne exposure to inorganic mercury in aquatic organisms showed changes in biochemical markers and behaviour. Few studies have focused on the effects of inorganic mercury ingestion. This thesis investigated dietary exposure of mercuric chloride to post-larvae and juveniles of Penaeus monodon and juvenile Acanthopagrus australis and showed that biochemical marker response depends on the organism, age (post-larvae or juvenile), tissue analysed (e.g. muscle and neurologic tissue) and exposure period (up to 16 days). Additionally, swimming behaviour was a sensitive parameter for post-larvae prawn studies, but not for juvenile ...


Proceedings Of The 2nd Resrb 2017 Conference, June 19-21, 2017, Wrocław, Poland, Wojciech M. Budzianowski 2016 Wojciech Budzianowski Consulting Services

Proceedings Of The 2nd Resrb 2017 Conference, June 19-21, 2017, Wrocław, Poland, Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.


Separation Of Nitrito- And Nitropentamminecobalt (Iii) Chloride By High Performance Liquid Chromatography, Tisha Hutchinson 2016 Seton Hall University

Separation Of Nitrito- And Nitropentamminecobalt (Iii) Chloride By High Performance Liquid Chromatography, Tisha Hutchinson

Seton Hall University Dissertations and Theses (ETDs)

Reversed phase high performance liquid chromatography, chosen because of its ability to collect many data points over a long period of time with minimal involvement, was used to separate pentaamminenitritocobalt(III) chloride and pentaamminenitrocobalt(III) chloride. Pentaamminenitritocobalt(III) chloride was prepared, made into a concentrated solution, divided into aliquots and allowed to isomerize to pentaamminenitrocobalt(III) chloride over a period of twelve to eighteen hours. An injection was made approximately every forty-five minutes. The samples were analyzed at three wavelengths, 254 nm, 460 nm and 490 nm. The absorbance was collected and was used to determine the kinetics of the ...


Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree 2016 The University of Western Ontario

Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree

Electronic Thesis and Dissertation Repository

This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH3 with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.

To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl ...


Creating Functional Materials With Phosphorus, Tyler John Cuthbert 2016 The University of Western Ontario

Creating Functional Materials With Phosphorus, Tyler John Cuthbert

Electronic Thesis and Dissertation Repository

Understanding the relationship between small molecules or polymers and how they affect the properties of materials they compose is the basis of materials science. Using unique and versatile components can impart useful and interesting properties to materials. Here, we aimed to extend this understanding to phosphorus, and the known properties it possesses. This included the production of photopolymerizable coatings containing phosphonium molecules and polymers for antifouling and antibacterial applications. The synthesis and characterization of these phosphonium components was completed and materials were produced utilizing UV curing technology. Addition of these components produced coatings that could resist bacteria attachment and efficiently ...


First-Row Organometallics For Heavy-Metal Applications, And An Atomically-Precise Iron Oxide Nanocluster, Jonathan Kephart 2016 University of Wyoming

First-Row Organometallics For Heavy-Metal Applications, And An Atomically-Precise Iron Oxide Nanocluster, Jonathan Kephart

Honors Theses AY 16/17

Undergraduate research has been a cornerstone to my education at the University of Wyoming. In this text, I review my research experiences and independent projects in inorganic chemistry. Specifically I discuss my experience with iron organometallics for [2+2+2] cycloaddition, photoredox-activated C-N formation using nickel organometallics, and iron organometallics with bifunctional ligand frameworks for olefin metathesis. Another area of my research focuses on a class of nanomaterials known as magic number clusters. I discuss my work in the Hulley Group regarding the synthesis and characterization of an atomically-precise iron oxide cluster, Fe9O6(Np)6(TMEDA)3.


Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette 2016 The University of Western Ontario

Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette

Electronic Thesis and Dissertation Repository

The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties ...


Over Or Under: Hydride Attack At The Metal Versus The Coordinated Nitrosyl Ligand In Ferric Nitrosyl Porphyrins., E G. Abucayon, R L. Khade, D R. Powell, Michael J. Shaw, Y Yang, G B. Richter-Addo 2016 University of Oklahoma

Over Or Under: Hydride Attack At The Metal Versus The Coordinated Nitrosyl Ligand In Ferric Nitrosyl Porphyrins., E G. Abucayon, R L. Khade, D R. Powell, Michael J. Shaw, Y Yang, G B. Richter-Addo

SIUE Faculty Research, Scholarship, and Creative Activity

Hydride attack at a ferric heme–NO to give an Fe–HNO intermediate is a key step in the global N--‐cycle. We demonstrate differential reactivity when six--‐ and five--‐coordinate ferric heme--‐NO models react with hydride. Although Fe–HNO formation is thermodynamically favored from this reaction, Fe–H formation is kinetically favored for the 5C case.


Synthesis, Reactivity, And Nmr Trends Of Early Transition Metal Compounds, Tabitha Marie Cook 2016 University of Tennessee, Knoxville

Synthesis, Reactivity, And Nmr Trends Of Early Transition Metal Compounds, Tabitha Marie Cook

Doctoral Dissertations

This dissertation focuses of three different subjects. The first is the synthesis and characterization of heptacoordinate amidinate compounds. Heptacoordinate compounds are not common, but their structures have been studied. Group 4 amidinate compounds have been used as precursors in the CVD/ ALD processes. Ancillary ligands, such as amidinates, have been used to reduce air-sensitivity of complexes. Reactions of these complexes with water have been used to make metal oxide thin films.

In the first study, the complexes Zr[MeC(NiPr)2]3Cl [zirconium trisamidinate chloride], Hf[MeC(NiPr)2]3Cl [hafnium trisamidinate chloride], Zr ...


Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre 2016 University of Tennessee, Knoxville

Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre

Doctoral Dissertations

The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid ...


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 ...


Redox-Active Ligand Uranium Complexes For Approaches To Multi-Electron Chemistry, John J. Kiernicki 2016 Purdue University

Redox-Active Ligand Uranium Complexes For Approaches To Multi-Electron Chemistry, John J. Kiernicki

Open Access Dissertations

While transition metal complexes are known to participate in multi-electron redox chemistry to facilitate important organometallic transformations, actinides, due to their low redox potentials, have a propensity to perform single electron chemistry. Because of its highly reducing nature, the ability to control the electronics of low-valent uranium is highly sought after as this may lead to unprecedented reactivity. Our lab has specifically been interested in mediating multi-electron transformations at uranium by employing redox-active ligands. Redox-active ligands can be used to facilitate multi-electron processes such as oxidative addition and reductive elimination at single metal centers. Using primarily 2,6-((Mes)N ...


Synthesis And Characterization Of Novel Ligand For Use On Rhodium Paddlewheel Complexes, Gavin J. Rustin 2016 University of Tennessee, Knoxville

Synthesis And Characterization Of Novel Ligand For Use On Rhodium Paddlewheel Complexes, Gavin J. Rustin

Masters Theses

Dirhodium (II) paddlewheel complexes have proven to be useful catalysts in many transformations including C-H insertions, cyclopropanation, and silane insertion reactions. One deficiency of these catalysts is the inability to modulate the enantioselectivity with reactive diazo compounds. One avenue for potential improvement of paddlewheel complexes is coordinating ligands in the axial site to increase enantioselectivity. The axial site has been occupied by various ligands including Nheterocyclic carbenes, nitrogen compounds, and phosphorous compounds. This work examines compounds that can be used as ligands on dirhodium complexes that have a pendant chain containing a dibenzyl phosphite and dibenzyl phosphate, both of which ...


Metal-Organic Frameworks As Potential Platforms For Carbon Dioxide Capture And Chemical Transformation, Wenyang Gao 2016 University of South Florida

Metal-Organic Frameworks As Potential Platforms For Carbon Dioxide Capture And Chemical Transformation, Wenyang Gao

Graduate Theses and Dissertations

The anthropogenic carbon dioxide (CO2) emission into the atmosphere, mainly through the combustion of fossil fuels, has resulted in a balance disturbance of the carbon cycle. Overwhelming scientific evidence proves that the escalating level of atmospheric CO2 is deemed as the main culprit for global warming and climate change. It is thus imperative to develop viable CO2 capture and sequestration (CCS) technologies to reduce CO2 emissions, which is also essential to avoid the potential devastating effects in future. The drawbacks of energy-cost, corrosion and inefficiency for amine-based wet-scrubbing systems which are currently used in industry, have ...


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 ...


Visible-Light Generation Of High-Valent Metal-Oxo Intermediates And A Biomimetic Oxidation Catalyzed By Manganese Porphyrins With Iodobenzene Diacetate, Ka Wai Kwong 2016 Western Kentucky University

Visible-Light Generation Of High-Valent Metal-Oxo Intermediates And A Biomimetic Oxidation Catalyzed By Manganese Porphyrins With Iodobenzene Diacetate, Ka Wai Kwong

Masters Theses & Specialist Projects

High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes.

In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V ...


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 ...


Towards Direct Synthesis Of Alane: A Predicted Defect-Mediated Pathway Confirmed Experimentally, Lin-Lin Wang, A. Herwadkar, J. M. Reich, Duane D. Johnson, S. D. House, P. Peña-Martin, A. Rockett, I. M. Robertson, S. Gupta, Vitalij K. Pecharsky 2016 Ames Laboratory

Towards Direct Synthesis Of Alane: A Predicted Defect-Mediated Pathway Confirmed Experimentally, Lin-Lin Wang, A. Herwadkar, J. M. Reich, Duane D. Johnson, S. D. House, P. Peña-Martin, A. Rockett, I. M. Robertson, S. Gupta, Vitalij K. Pecharsky

Ames Laboratory Publications

Alane (AlH3) is a unique energetic material that has not found a broad practical use for over 70 years because it is difficult to synthesize directly from its elements. Using density functional theory, we examine the defect-mediated formation of alane monomers on Al(111) in a two-step process: (1) dissociative adsorption of H2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H2 exposure, alane monomers and clusters form ...


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