Chemistry Commons^™

2,3-Bis(Bromomethyl)-1,4-Diphenylbenzene, Jonathan B. Briggs, Mikael D. Jazdzyk, Glen P. Miller

Chemistry

In the title compound, C(20)H(16)Br(2), the terminal phenyl groups are twisted away from the central ring by approximately 55 and -125 degrees (average of four dihedral angles each), respectively. The crystal structure is stabilized by a combination of interMolecular and intraMolecular interactions including interMolecular pi-pi stacking interactions [C atoms of closest contact = 3.423 ( 5) angstrom].

Free-Standing And Reactive Thin Films Fabricated By Covalent Layer-By-Layer Assembly And Subsequent Lift-Off Of Azlactone-Containing Polymer Multilayers, Maren E. Buck, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the fabrication of free-standing and amine-reactive thin films that is based on the reactive layer-by-layer assembly and subsequent lift-off of azlactone-containing polymer multilayers. We demonstrate that covalently cross-linked multilayers fabricated using the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and a primary amine-containing polymer [poly(ethyleneimine) (PEI)] can be delaminated from planar glass and silicon surfaces by immersion in mildly acidic aqueous environments to yield flexible freestanding membranes. These free-standing membranes are robust and can withstand exposure to strong acid, strong base, or incubation in high ionic strength solutions that typically lead to the disruption and erosion of polymer …

Laboratory Studies To Field Evaluation : Remediation Of Polychlorinated Biphenyl Contaminated Painted Surfaces Through The Use Of Activated Metal Treatment Systems, Erin Kristen Saitta

Electronic Theses and Dissertations

Polychlorinated Biphenyls (PCBs) are a group of 209 congeners that are regulated under the Toxic Substance Control Act. They enter the environment as a result of industrial processes and can travel long distances. PCBs are environmentally persistent and bioaccumulate in animal populations. Painted surfaces are a common point source for PCBs and there are few options for remediating structures painted with PCB-contaminated paint. Removal of the paint can often spread contamination and disposing or burning of large structures is expensive. Experiments employing reductive dehalogenation through the use of a bimetal have shown that PCBs can be degraded in mild laboratory …

Modular Synthesis Of Weinreb Amides Of 2-Fluoro-2,4-Dienoic Acids, Mohammad Chowdhury

Dissertations and Theses

No abstract provided.

Samuel J. Danishetsky And The Synthesis Of Globo-H Antigen, Chelsey Jones

Natural Sciences Student Research Presentations

Samuel J. Danishefsky is a research scientist at the Sloan-Kettering Institute. He uses his knowledge in organic chemistry to make biological advances in cancer research. Danishefsky has been conducting research and experiments on synthesizing anti-cancer vaccines with the use of carbohydrate antigens. Danishefsky has also been conducting research and experiments on homogeneous erythropoietin which could provide insight into how glycoproteins function. Knowledge of glycoprotein would allow scientists to better understand erythropoietin which can treat anemia in chemotherapy patients. All is valuable information in advances in cancer research and cancer research is important because it is a major disease affecting the …

Molecular Dynamics Simulations Of Human Quadruplexes In K+ Solution And The Role Of The Carboxyl Terminus Of Bacteriorhodopsin In Protein Stability, Farah Rezae

Seton Hall University Dissertations and Theses (ETDs)

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Synthesis Of Novel Glycosylidene-Based Quinolines, Peter H. Dobbelaar

Seton Hall University Dissertations and Theses (ETDs)

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Measurements Of Platinum Electrode Potential In Blood And Blood Plasma And Serum, Mogely Khubutiya, Anatoly K. Evseev, Vladimir Kolesnikov, Mikhail M. Goldin, Alexei Davydov, Alexander Volkov, Andrey Stepanov

Faculty Publications and Presentations

The method of electrochemical pretreatment of platinum electrode with the goal of standardizing the initial state of electrode surface and its open-circuit potential (OCP) in the blood and other biological media is proposed. The platinum electrode potential is measured in 0.14 M Na2SO4 aqueous solution, in the blood and blood plasma and serum. By the examples of OCP measured in the blood serum of patients with acute poisoning, acute cerebral pathology and patients treated by the method of hyperbaric oxygenation, it was found that the values of blood serum OCP were different for studied pathological states and healthy people.

Spectroscopic Analysis Of Therapeutic Drugs., Laura Perdisatt, Christine O'Connor, Samar Moqadasi, Luke O'Neill

Conference Papers

The aim of this project was to investigate the photochemistry of three new Ruthenium (II) complexes as possible therapeutics and their associated ligands. The objectives were to use the following spectroscopic techniques: Absorption, Emission and Raman spectroscopy. Luminescent lifetime measurements were obtained by laser studies (Nd:YAG laser and Time coupled single photon counting (TCSPC) ).

Progress Towards The Synthesis Of Type B Polycyclic Polyprenylated Acylphloroglucinol 7-Epi-Clusianone, Pushpa Suresh Jayasekara Mudiyanselage

University of Kentucky Doctoral Dissertations

Plants of the family Guttiferae produce polycyclic polyprenylated acylphloroglucinols (PPAPs), which have interesting biological activities including anticancer and antibacterial properties. The main structural features of PPAPs comprise of bicyclo[3.3.1]nonane-2,4,9-triketone with one acyl group together with prenyl, geranyl, or other C₁₀H₁₇ groups. 7-epi-Clusianone, a type B PPAP with C-7 endo stereochemistry, is being approached by establishing the cis relationship with C(4) allyl group and C(2) methyl ester in the early stage of the synthesis. Then C(2) methyl ester is converted to alkyne aldehyde and syn reduction followed by intramolecular aldol reaction to give bicyclo[3.3.1]nonane structure with …

Adrenocorticotropin Hormone Expression In The Developing Chicken Limb, Jodi F. Evans Ph.D., Michelle Vigliotti

Faculty Works: Biology, Chemistry, and Environmental Studies

In previous studies using mammalian models we have found both clinical and laboratory evidence of a role for melanocortins in endochondral ossification. The melanocortin system has remarkable conservation among vertebrates and melanocortin receptors are expressed with significant sequence homology in teleosts to mammals. The overall goal of these studies is to provide a more accessible model of melanocortin involvement in endochondral growth. We hope to determine if melanocortins play a role during endochondral ossification of the developing chicken limb. Like in mammals melanocortins are widely distributed throughout the body of chicken and participate in a wide range of physiological functions …

Mechanistic And Computational Studies Of Oxidatively-Induced Aryl-Cf3 Bond Formation At Palladium, J. Brannon Gary

Faculty Publications

This article describes the rational design of 1st generation systems for oxidatively-induced Aryl– CF3 bond-forming reductive elimination from PdII. Treatment of (dtbpy)PdII(Aryl)(CF3) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridium triflate) afforded the isolable PdIV intermediate (dtbpy)PdIV(Aryl)(CF3)(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl–CF3 bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this PdIV species proceeds via pre-equilibrium dissociation of TfO− followed by Aryl–CF3 coupling. DFT calculations reveal that the transition state for Aryl–CF3 bond formation involves the CF3 acting as an electrophile with the …

Process For Preparation Of Conducting Polymers, Reuben D. Rieke

Chemistry Department: Faculty Publications

Methods of preparing conducting polymers and the conductive polymers prepared therefrom are provided. The method includes a) combining a monomer-metal complex together with a manganese (II) halide to provide a monomer-manga nese complex, and b) combining the monomer-manganese complex together with a metal catalyst to provide the conductive polymer. Electronic devices can be made using the polymers prepared as described herein.

Concave Cubic Gold Nanocrystals With High-Index Facets, Jian Zhang, Mark R. Langille, Michelle L. Personick, Ke Zhang, Shuyou Li, Chad A. Mirkin

Chemistry Department: Faculty Publications

A new class of gold nanostructures, concave nanocubes, enclosed by 24 high-index {720} facets, have been prepared in a monodisperse fashion by a modified seed-mediated synthetic method. The Cl− counterion in the surfactant plays an essential role in controlling the concave morphology of the final product. The concave nanocubes exhibit higher chemical activities compared with low-index {111}-faceted octahedra.

Includes Supporting Information.

Corrosion Of Steel Shipwrecks In The Marine Environment: Uss Arizona—Part 2, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Chemistry Department: Faculty Publications

This article is a continuation of Part 1 (October 2006 MP) on the USS Arizona hull. It discusses additional methods being investigated for use in determining corrosion rates with a minimal impact on the existing structure. Marine biofouling (concretion) has accumulated on the hull. Concretion samples have been studied using x-ray diffraction, environmental electron microscopy, and corrosion potential (E_corr) to characterize the relationship between concretion and the steel substrate. The data presented in this study confirm the viability of concretion analysis as a minimum-impact procedure to estimate the corrosion rate of mild steel in seawater.

Corrosion Of Steel Shipwreck In The Marine Environment: Uss Arizona—Part 1, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Chemistry Department: Faculty Publications

The USS Arizona has remained submerged in Pearl Harbor, Hawaii, since the Japanese attack on December 7, 1941. The ship presents a potential hazard from fuel oil still present in the ship’s hull. As an important factor in management decisions, the effect of corrosion after nearly 65 years is being studied to determine the integrity of the ship’s structure. Coupon samples from the hull revealed decreasing corrosion rates from ~1 to 3 mpy (0.03 to 0.08 mm/y) from just below the water surface to the mudline. This is about one-third of that expected in the absence of biofouling or concretion. …

Particle Matter Measurements For Inspection/Maintenance Programs, Daniel Joseph Pope

Electronic Theses and Dissertations

Particle emissions from Heavy Duty Diesel Vehicles (HDDVs) are currently measured by opacity or dynamometer gravimetric analysis. The Electronic Tailpipe Particle Sensor (ETaPS) is an inexpensive measurement device purported to give real time response to particle mass and was proposed as a possible addition to Inspection/Maintenance (I/M) programs. There were three goals to this study. The first was to verify ETaPS response to particle mass of HDDV exhaust. Integrated ETaPS signal was plotted against filter weight from dynamometer gravimetric analysis and a correlation was found. The second goal was to find a correlation between ETaPS readings and the Remote Sensing …

Novel Photochemical Methodologies For Diversity Oriented Synthesis And Screening Of Combinatorial Libraries, Roman Askatovich Valiulin

Electronic Theses and Dissertations

The main goal of this project was to develop an efficient methodology allowing rapid access to structurally diverse scaffolds decorated with various functional groups.

Initially, we discovered and subsequently developed an experimentally straightforward, high-yielding photoinduced conversion of readily accessible diverse starting materials into polycyclic aldehydes and their (hemi)acetals decorated by various pendants. The two step sequence, involving the Diels-Alder addition of heterocyclic chalcones and other benzoyl ethylenes to a variety of dienes, followed by the Paternò-Büchi reaction, was described as an alkene-carbonyl oxametathesis. This methodology offers a rapid increase in molecular complexity and diversity of the target scaffolds.

To develop …

Breaking The Cycle: Impact Of Sterically-Tailored Tetra(Pyrazolyl)Lutidines On The Self-Assembly Of Silver(I) Complexes, Tyler James Morin, Andrew Merkel, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A improved preparation of the pentadentate ligand α,α,α′,α′-tetra(pyrazolyl)lutidine, pz₄lut, and the syntheses of three new alkyl-substituted pyrazolyl derivatives pz^4′₄lut (pz4′ = 4-methylpyrazolyl), pz*₄lut (pz* = 3,5-dimethylpyrazolyl), and pz^DIP₄lut (pzDIP = 3,5-diisopropylpyrazolyl) are described. The silver(I) complexes of these ligands were studied to ascertain the impact of pyrazolyl substitution, if any, on their binding modes and on solubility issues. In the solid state, [Ag(pz₄lut)](BF₄) (1), [Ag(pz^4′4lut)](BF4) (2), and [Ag(pz*₄lut)](BF4) (3 …

A Shortened Synthesis Of Optically Pure Tricarbonyl[Methyl (2e,4e)-6-Oxo-2,4-Hexadienoate]Iron Leading To Improved Yield, Rajesh K. Pandey, Sergey Lindeman, William Donaldson

Chemistry Faculty Research and Publications

The (+)- and (–)-enantiomers of tricarbonyl[methyl (2E,4E)-6-oxo-2,4-hexadienoate]iron are prepared in 4 steps from commercially available hexadienal (26% and 25% yields, respectively).