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Chemistry Faculty Publications

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Articles 31 - 60 of 71

Full-Text Articles in Inorganic Chemistry

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils May 2013

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils

Chemistry Faculty Publications

One way to improve fuel efficiency in today’s jet aircraft engines is to create an environment for higher operating temperatures and speeds. New and improved lubricants and bearing materials must be developed to remain stable in these elevated operating temperatures. Three lubricants, with varying amounts of tricresyl phosphate added as an anti-wear/extreme pressure additive were tested on two different stainless steels at varying temperatures ranging from 300 °C to 350 °C in vacuum. Significant decomposition of the lubricant base-stocks and the phosphate ester additive did occur in most of the trials resulting in the formation of carboxylic acids and phenols. …


Nanoparticle Film Assemblies As Platforms For Electrochemical Biosensing – Factors Affecting Amperometric Signal Enhancement Of Hydrogen Peroxide, Adrienne R. Schmidt, Natalie D. T. Nguyen, Michael C. Leopold Mar 2013

Nanoparticle Film Assemblies As Platforms For Electrochemical Biosensing – Factors Affecting Amperometric Signal Enhancement Of Hydrogen Peroxide, Adrienne R. Schmidt, Natalie D. T. Nguyen, Michael C. Leopold

Chemistry Faculty Publications

Factors affecting the enhanced amperometric signal observed at electrodes modified with polyelectrolyte–gold nanoparticle (Au-NP) composite films, which are potential interfaces for first-generation biosensors, were systematically investigated and optimized for hydrogen peroxide (H2O2) detection. Polyelectrolyte multilayer films embedded with citrate-stabilized gold nanoparticles exhibited high sensitivity toward the oxidation of H2O2. From this Au-NP film assembly, the importance of Au-NP ligand protection, film permeability, the density of Au-NPs within the film, and electronic coupling between Au-NPs (interparticle) and between the film and the electrode (interfacial) were evaluated. Using alternative Au-NPs, including those stabilized with thiols, polymers, and bulky ligands, suggests that the …


Monolayer-Protected Nanoparticle Doped Xerogels As Functional Components Of Amperometric Glucose Biosensors, Michael Hartley Freeman, Jackson R. Hall, Michael C. Leopold Mar 2013

Monolayer-Protected Nanoparticle Doped Xerogels As Functional Components Of Amperometric Glucose Biosensors, Michael Hartley Freeman, Jackson R. Hall, Michael C. Leopold

Chemistry Faculty Publications

First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during …


Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan Jan 2013

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.


Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils Jan 2013

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …


Reactions Of Methyl Perfluoroalkyl Ethers With Isopropyl Alcohol: Experimental And Theoretical Studies, Howard Knachel, Vladimir Benin, Chadwick Barklay, Janine C. Birkbeck, Billy D. Faubion, William E. Moddeman Aug 2012

Reactions Of Methyl Perfluoroalkyl Ethers With Isopropyl Alcohol: Experimental And Theoretical Studies, Howard Knachel, Vladimir Benin, Chadwick Barklay, Janine C. Birkbeck, Billy D. Faubion, William E. Moddeman

Chemistry Faculty Publications

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C4F9OCH3 (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and 1H and 19F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on …


Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan Jan 2012

Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan

Chemistry Faculty Publications

The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or …


The Tetrafluoroborate Salt Of 4-Methoxybenzyl N-2-(Dimethylamino)Ethyl-N-Nitrosocarbamate: Synthesis, Crystal Structure And Dft Calculations, Helene Hedian, Vladimir Benin Dec 2011

The Tetrafluoroborate Salt Of 4-Methoxybenzyl N-2-(Dimethylamino)Ethyl-N-Nitrosocarbamate: Synthesis, Crystal Structure And Dft Calculations, Helene Hedian, Vladimir Benin

Chemistry Faculty Publications

The tetrafluoroborate salt of 4-methoxybenzyl N-2-(dimethylamino)ethyl-N-nitrosocarbamate was prepared in two steps, via the corresponding carbamate. Its crystal structure is monoclinic, space group P21/c. The unit cell dimensions are: a = 19.499(8) Å, b = 5.877(3) Å, c = 15.757(7) Å, α = 90°, β = 110.019(7)°, γ = 90°, V = 1696.5(12) Å3, Z = 4. The structure exhibits an unexpected, pseudo-gauche conformation with respect to the C2–C3 bond, due to a stabilizing hydrogen bond between the carbonyl oxygen (O1) and the hydrogen atom at the trialkylammonium center (H3n), with a distance between them of …


Sweep, Step, Pulse, And Frequency-Based Techniques Applied To Protein Monolayer Electrochemistry At Nanoparticle Interfaces, Debbie S. Campbell-Rance, Tran T. Doan, Michael C. Leopold Nov 2011

Sweep, Step, Pulse, And Frequency-Based Techniques Applied To Protein Monolayer Electrochemistry At Nanoparticle Interfaces, Debbie S. Campbell-Rance, Tran T. Doan, Michael C. Leopold

Chemistry Faculty Publications

Protein monolayer electrochemistry (PME), a strategy using synthetic platforms to study the electron transfer (ET) properties of adsorbed proteins, has been successfully applied to proteins adsorbed at monolayer-protected gold cluster (MPCs) assembled films, an adsorption interface shown to be an effective alternative, compared to traditional self-assembled monolayer (SAM) films, for the immobilization and study of ET proteins. Within PME studies, cyclic voltammetry (CV) remains the most commonly applied electrochemical technique in spite of several limitations that occur when the sweep technique is used at either platform. In particular, CV for PME at MPC films results in analysis complications stemming from …


Optical And Electrochemical Properties Of Multi-Layer Polyelectrolyte Thin Films Incorporating Spherical, Gold Colloid Nanomaterials, Tran T. Doan, Robert W. Day, Michael C. Leopold Sep 2011

Optical And Electrochemical Properties Of Multi-Layer Polyelectrolyte Thin Films Incorporating Spherical, Gold Colloid Nanomaterials, Tran T. Doan, Robert W. Day, Michael C. Leopold

Chemistry Faculty Publications

Polyelectrolyte multilayer (PEM) films incorporating various types of spherical, gold nanomaterials (NMs) were investigated to assess the existence of electrochemical and/or optical signal enhancement effects directly attributable to embedded NMs and the relationship of these effects to film structure and composition. Specifically, electrostatically assembled films of cationic poly-L-lysine (PLL) and anionic poly(4-styrene sulfonate) (PSS) incorporating one of four types of spherical, gold colloid NMs were constructed on 3-(aminopropyl)trimethoxysilane (3-APTMS)-modified glass substrates for optical studies or 11-mercaptoundecanoic (MUA)-modified gold electrodes for electrochemical studies. The NMs inserted into the PEM films include citrate-stabilized gold nanoparticles, thioctic acid-stabilized gold nanoparticles (TAS-NPs), MUA-modified monolayer …


Application Of Raman Spectroscopy To Lubricants, Lubricated Surfaces And Lubrication Phenomena, David W. Johnson Jul 2011

Application Of Raman Spectroscopy To Lubricants, Lubricated Surfaces And Lubrication Phenomena, David W. Johnson

Chemistry Faculty Publications

Recent advances in lasers and detector technologies and the development of low-cost instruments and fiber-optic probes have brought about an explosion in the lubrication systems being studied by Raman spectroscopy. This article provides examples of the use of Raman spectroscopy in the study of lubrication phenomena, including the characterization of liquid lubricants, lubricant additives, and solid lubricants; the study of vapor-phase lubrication; and the use of coated nanoparticles as lubricants.


A Sodium Salt Of The Dimer Of Boronoterephthalic Acid Anhydride, Scott Simmons, Albert Fratini, Vladimir Benin Apr 2011

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

Chemistry Faculty Publications

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.


Theoretical Investigation Of A Reported Antibiotic From The 'Miracle Tree' Moringa Oleifera, Michael Horwath, Vladimir Benin Apr 2011

Theoretical Investigation Of A Reported Antibiotic From The 'Miracle Tree' Moringa Oleifera, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

Moringa oleifera, sometimes called the “Miracle Tree,” has received international attention for its potential to improve health in impoverished tropical areas. In addition to high vitamin content in the leaves and pods, the tree contains compounds with antioxidant and antibacterial properties. This study focused on the theoretical investigation of the suggested structure of one antibacterial compound, “pterygospermin,” whose existence was proposed after some studies of the roots of M. oleifera. The structure of pterygospermin was first proposed by a research group working in the 1950s, but later studies have not found evidence of this compound and have instead …


Synthesis, Assembly, And Characterization Of Monolayer-Protected Gold Nanoparticle Films For Protein Monolayer Electrochemistry,, Tran T. Doan, Michael H. Freeman, Adrienne R. Schmidt, Natalie T. Nguyen, Michael C. Leopold Jan 2011

Synthesis, Assembly, And Characterization Of Monolayer-Protected Gold Nanoparticle Films For Protein Monolayer Electrochemistry,, Tran T. Doan, Michael H. Freeman, Adrienne R. Schmidt, Natalie T. Nguyen, Michael C. Leopold

Chemistry Faculty Publications

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified …


Electrochemical Investigation Of Azurin Thermodynamic And Adsorption Properties At Monolayer-Protected Cluster Film Assemblies – Evidence For A More Homogeneous Adsorption Interface, Tran Doan, Morgan Lynn Vargo, John K. Gerig, Chris P. Gulka, Matthew L. Trawick, Jonathan D. Dattelbaum, Michael C. Leopold Dec 2010

Electrochemical Investigation Of Azurin Thermodynamic And Adsorption Properties At Monolayer-Protected Cluster Film Assemblies – Evidence For A More Homogeneous Adsorption Interface, Tran Doan, Morgan Lynn Vargo, John K. Gerig, Chris P. Gulka, Matthew L. Trawick, Jonathan D. Dattelbaum, Michael C. Leopold

Chemistry Faculty Publications

Thermodynamic and adsorption properties of protein monolayer electrochemistry (PME) are examined for Pseudomonas aeruginosa azurin (AZ) immobilized at an electrode modified with a networked film of monolayer-protected clusters (MPCs) to assess if nanoparticle films of this nature offer a more homogeneous adsorption interface compared to traditional self-assembled monolayer (SAM) modified electrodes. Specifically, electrochemistry is used to assess properties of surface coverage, formal potential, peak broadening, and electron transfer (ET) kinetics as a function of film thickness. The modification of a surface with dithiol-linked films of MPCs (Au225C675) provides a more uniform binding interface for AZ that results in voltammetry with …


Enhanced Electrochemistry Of Nanoparticle-Embedded Polyelectrolyte Films: Interfacial Electronic Coupling And Distance Dependence, Callie E. Dowdy, Michael C. Leopold Nov 2010

Enhanced Electrochemistry Of Nanoparticle-Embedded Polyelectrolyte Films: Interfacial Electronic Coupling And Distance Dependence, Callie E. Dowdy, Michael C. Leopold

Chemistry Faculty Publications

Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte–nanoparticle (PE–NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN)63−/4−) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-l-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE–NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between …


Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold Aug 2009

Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold

Chemistry Faculty Publications

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed …


Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold Mar 2009

Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell …


Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin Jan 2009

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.


Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis May 2008

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …


C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin Feb 2008

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …


Monolayer-Protected Nanoparticle Film Assemblies As Platforms For Controlling Interfacial And Adsorption Properties In Protein Monolayer Electrochemistry, Andrew F. Loftus, Katelyn P. Reighard, Susanna A. Kapourales, Michael C. Leopold Jan 2008

Monolayer-Protected Nanoparticle Film Assemblies As Platforms For Controlling Interfacial And Adsorption Properties In Protein Monolayer Electrochemistry, Andrew F. Loftus, Katelyn P. Reighard, Susanna A. Kapourales, Michael C. Leopold

Chemistry Faculty Publications

Assembled films of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), are investigated as adsorption platforms in protein monolayer electrochemistry (PME), a strategy for studying the electron transfer (ET) of redox proteins. Modified electrodes featuring MPC films assembled with various linking methods, including both electrostatic and covalent mechanisms, are employed to immobilize cytochrome c (cyt c) for electrochemical analysis. The background signal (non-Faradaic current) of these systems is directly related to the structure and composition of the MPC films, including nanoparticle core size, protecting ligand properties, as well as the linking mechanism utilized during assembly. Dithiol-linked films of Au225(C6)75 are …


Stable Aqueous Nanoparticle Film Assemblies With Covalent And Charged Polymer Linking Networks, Lesley E. Russell, Anne A. Galyean, Sherilyn M. Notte, Michael C. Leopold Jun 2007

Stable Aqueous Nanoparticle Film Assemblies With Covalent And Charged Polymer Linking Networks, Lesley E. Russell, Anne A. Galyean, Sherilyn M. Notte, Michael C. Leopold

Chemistry Faculty Publications

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(l-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The …


A Series Of Vertically Integrated Nanotechnology Experiments For The Undergraduate Curriculum, Kevin W. Kittredge, Lesley E. Russell, Michael C. Leopold Jun 2007

A Series Of Vertically Integrated Nanotechnology Experiments For The Undergraduate Curriculum, Kevin W. Kittredge, Lesley E. Russell, Michael C. Leopold

Chemistry Faculty Publications

We have designed three nanotechnology experiments that are vertically integrated for an undergraduate chemistry curriculum. They are an evolving set of experiments for sequential courses in an undergraduate chemistry program. These experiments are designed to match the student's level of understanding for each particular course. The participating student is involved in a "research" project that progresses in both theory and experimental technique. Students benefit from these vertically integrated experiments by being involved in multiple facets of a simulated research project. This mimics a traditional research project under an advisor's supervision without the undesired drawback of an unknown outcome.


Crown Ether-Metal ‘Sandwiches’ As Linking Mechanisms In Assembled Nanoparticle Films, Rebecca R. Pompano, Phillip G. Wortley, Leslie M. Moatz, D. J. Tognarelli, Kevin W. Kittredge, Michael C. Leopold Jul 2006

Crown Ether-Metal ‘Sandwiches’ As Linking Mechanisms In Assembled Nanoparticle Films, Rebecca R. Pompano, Phillip G. Wortley, Leslie M. Moatz, D. J. Tognarelli, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Crown ether ligands attached to monolayer-protected clusters (MPCs) were assembled as films and the linking mechanism between the crown ether–metal ion–crown ether bridges between nanoparticles was examined. Thicker films exhibited a red shift in the absorbance maximum for the surface plasmon band which was attributed to the increasing aggregation and cross linking within the film. Quantized double layer charging peaks suggest that film growth is selective toward a specific core size or exchange rate, either of which affect the number of potential linking ligands in the periphery of the MPCs. Multi-layer growth of films was only achieved with metal ions …


Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin May 2006

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …


Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin Jan 2006

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.


Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin Jan 2006

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.


(E)-9,10-Dihydro-9-Methyl-9-Nitro-10-(Trinitro­Meth­Yl)Anthracene, Mustafa Arslan, Ronald J. Baker, John Masnovi, Erol Asker Dec 2005

(E)-9,10-Dihydro-9-Methyl-9-Nitro-10-(Trinitro­Meth­Yl)Anthracene, Mustafa Arslan, Ronald J. Baker, John Masnovi, Erol Asker

Chemistry Faculty Publications

The title compound, C16H12N4O8, was prepared by the photochemical reaction of 9-methyl­anthracene and tetra­nitro­methane in dichloromethane. Intermolecula face-to-face π–π stacking inter­actions are present along the a axis.


Covalently Networked Monolayer Protected Nanoparticle Films, D. J. Tognarelli, Robert B. Miller, Rebecca R. Pompano, Andrew F. Loftus, Daniel J. Shiebley, Michael C. Leopold Oct 2005

Covalently Networked Monolayer Protected Nanoparticle Films, D. J. Tognarelli, Robert B. Miller, Rebecca R. Pompano, Andrew F. Loftus, Daniel J. Shiebley, Michael C. Leopold

Chemistry Faculty Publications

No abstract provided.