Physical Sciences and Mathematics Commons^™

Biological, Clinical, And Forensic Analysis Using Comprehensive Two-Dimensional Gas Chromatography, Nicholas Snow

Nicholas A Snow

No abstract provided.

Muon-Fluorine Entangled States In Molecular Magnets, T Lancaster, S J. Blundell, P J. Baker, M L. Brooks, W Hayes, F L. Pratt, Jamie L. Manson, M M. Conner, J A. Schlueter

Chemistry and Biochemistry Faculty Publications

The information accessible from a muon-spin relaxation experiment can be limited due to a lack of knowledge of the precise muon stopping site. We demonstrate here the possibility of localizing a spin polarized muon in a known stopping state in a molecular material containing fluorine. The muon-spin precession that results from the entangled nature of the muon spin and surrounding nuclear spins is sensitive to the nature of the stopping site. We use this property to identify three classes of sites that occur in molecular magnets and describe the extent to which the muon distorts its surroundings.

Exploiting Self-Assembly For Ligand-Scaffold Optimization: Substrate-Tailored Ligands For Efficient Catalytic Asymmetric Hydroboration, Shin A. Moteki, James M. Takacs

James Takacs Publications

A self-assembled ligand library (SAL XY) affords a wide range of R/S ratios in Rh-catalyzed asymmetric hydroboration (nbd = 2,5norbornadiene, R* is a chiral substituent). Ligand-scaffold optimization reveals “substrate-tailored” ligands that afford high regio- and enantioselectivity for a variety of ortho-substituted styrene derivatives.

Includes article (4 pp.) and supporting information (106 pp.).

Controlling The Inhibition Of The Sarcoplasmic Ca2+-Atpase By Tuning Phospholamban Structural Dynamics, Kim Ha, Nathaniel J. Traaseth, Raffaello Verardi, Jamillah Zamoon, Alessandro Cembran, Christine B. Karim, Gianluigi Veglia

Kim N. Ha, Ph.D.

No abstract provided.

Preparation Of Divalent And Trivalent Antigens For Immunogical Studies On Degranulation Of Mast Cells And Preparation Of Ceragenins For Antiviral Studies Against Vaccinia Virus., Dianliang Geng

Theses and Dissertations

CHAPTER 1

Aggregation of receptors for IgE (Fc RI) causes mast cells and basophils to release preformed contents of granules, including histamine and a variety of enzymes. This process, called degranulation plays a central role in allergic reactions. Methods to study this process are to create multivalent ligands which can interact with the receptors and, in turn, lead to aggregation of the receptors. We prepared a series of fluorophore-labeled divalent and trivalent antigens to study the degranulation of mast cells. Trivalent antigens proved to be much better stimulators for degranulation of mast cells than divalent antigens. These results indicate that …

Pyridinium Bisretinoids: Synthesis And Photoactivated Cytotoxicity, Junping Gao

Theses and Dissertations

This thesis discusses pyridinium bisretinoid compounds (PBRs), which were prepared for two purposes: 1) to use them as standards for detection of novel fluorophores in human RPE cells, which may be involved in age-related macular degeneration (AMD), and 2) to use them in the development of a targeted and triggered drug delivery system for cancer therapy. We prepared a selection of PBRs using a one-pot biomimetic method; synthesis, mechanisms for formation, and characterization of these compounds is described. We also explored the photoreactivity of three novel PBR compounds and found that these PBRs form oxidation products under blue-light irradiation. The …

Total Synthesis Of (+/-)-Goniomitine Via A Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization., Christian L Morales, Brian L Pagenkopf

Chemistry Publications

The total synthesis of (+/-)-goniomitine has been accomplished in 17 linear steps with 5.2% overall yield starting from commercially available delta-valerolactam. A synthetic highlight includes the first application of a formal [3 + 2] cycloaddition between a highly functionalized nitrile and a donor-acceptor cyclopropane to prepare an indole nucleus. The use of a microwave reactor is shown to greatly improve the reaction times for two steps.

Study Of The Reproducibility Of Proteomics Methods And Variability Of Fruit Fly Proteomes., Thomas Franklin Culwell

Theses and Dissertations

The reliability of biomarker discovery by means of proteomics has been called into question. It was speculated that "background noise" variation resulting from differences in preparation and handling of samples and proteome dynamics may mask subtle, yet important, differences due to the biological condition. Little is understood about complex proteomes and their variability. A critical aspect of proteomic biomarker research that is largely unexplored is the comparative reproducibility of certain methods such as two-dimensional gel electrophoresis and liquid chromatography/mass spectrometry. In particular, with liquid chromatography/mass spectrometry, it is not known whether variability in peptide quantitation is dependent on any of …

Nirt: Developing A Nanoscale Sensing Device For Measuring The Supply Of Iron To Phytoplankton In Marine Systems, Mark L. Wells, Karen Orcutt, D. Whitney King, Carl Tripp

University of Maine Office of Research Administration: Grant Reports

There is increasing evidence that Fe has a singularly unique role in marine ecosystems, both regulating total phytoplankton production in high nitrate, low chlorophyll regions of the world, and influencing the predominant composition of the phytoplankton assemblages found in others. It is remarkable then that there is no agreement about how to define biologically available Fe, in contrast to the macronutrients nitrogen, phosphorous or silicon. Current attempts to attain predictive insights to how ocean ecosystems will influence the magnitude of climate change are blocked in large part by this question, along with an extreme shortage of data on Fe distributions …

Pyridinium Bis-Retinoids A2-Dopamine And A2-Cadaverine: Implications In Age-Related Macular Degeneration And Cancer, Mckenzie Ruth Pew

Theses and Dissertations

Age-related macular degeneration (AMD) is the leading cause of blindness in the United States of America. The pyridinium bis-retinoid A2-ethanolamine (A2E) has been implicated to play a role in AMD. We have observed novel pyridinium bis-retinoids through melanolipofuscin and human RPE extractions that may also play a role in the pathology of AMD. We have begun the construction of an amino-retinoid library in order to identify these ocular compounds. The compounds from the amino-retinoid library are also used in a targeted and triggered drug delivery system for treating cancer. Folic acid is coupled with the amino-retinoids to specifically target cancer …

Structural Characterization Of Al10O6IBu16(Μ-H)2, A High Aluminum Content Cluster:  Further Studies Of Methylaluminoxane (Mao) And Related Aluminum Complexes, Feng-Jeng Wu, Larry S. Simeral, Anthony A. Mrse, Jan L. Eilertsen, Lacramioara Negureanu, Zhehong Gan, Frank R. Fronczek, Randall W. Hall, Leslie G. Butler

Randall W. Hall

Thermodynaimic Study Of Nucleic Acids Recognition By Aminoglycosides , Hongjuan Xi

All Dissertations

ABSTRACT


Since the origin of first aminoglycosides antibiotics, streptomycin, isolated by Selman Waksman about 60 years ago, a number of aminoglycosides antibiotics were discovered to treat different infections. Neomycin class aminoglycosides were found to originally target the A site 16S rRNA in the 30S subunit of the ribosome within the Gram-negative bacteria. In addition to its antibacterial effect, aminoglycosides were also found to binding to various other viral RNA structures such as TAR and RRE of HIV, Group I introns and hammerhead ribozyme, implying its potential to be used as antiviral reagent.

Furthermore, previous studies in our laboratory discovered a …

Lithium-Conducting Ionic Melt Electrolytes From Oligomeric Ethylene Glycols: Synthesis And Characterization, Boutros Hallac

All Dissertations

Commercial lithium ion cells consist of electrolytes that undergo salt concentration polarization which is acute upon high discharge currents. This type of polarization occurs as a result of the mobility of more than one ionic species in the presence of an electric field. One way to overcome it is by employing a material that would allow the mobility of one ionic species. This thesis will describe the synthesis and characterization of several fluorosulfonimide and fluorosulfonate based ionic liquids/melts as electrolytes having lithium as the only mobile ion. These materials were prepared by the nucleophilic addition reaction of a deprotonated polyether …

Studies Of The Stability And Potential Applications Of Pyrrolidinofullerenes And Other Fullerene Derivatives, Olena Lukoyanova

All Dissertations

Over the last decade, the variety of chemically modified fullerenes and their potential applications has increased significantly. Among fullerene derivatives, pyrrolidinofullerenes are one of the most widely synthesized types since they can be easily and efficiently obtained via simple reactions from both empty and endohedral fullerenes. Although fullerenes in general and pyrrolidinofullerenes in particular have been considered for numerous applications in electronic and optoelectronic devices, photovoltaics, medicinal chemistry, etc., their potential application in the evolving field of molecular electronics has not been extensively explored. The envisioned role of the fullerenes usually involves storage or transport of electrons. Therefore, studies of …

Development Of Fullerene Based Sturctures For Photovoltaic And Electronic Applications, Amit Palkar

All Dissertations

Solar energy can be envisioned as a long term alternative to rapidly depleting fossil fuels. The energy from the sun can be harnessed by constructing donor-acceptor (D-A) type devices where the incident photon induces the transfer of an electron from the donor to the acceptor. If recombination is prevented, this electron can then be channeled through an external circuit, thus leading to the generation of photocurrent. Porphyrins, which are the naturally occurring pigments in photosynthesis, have been widely established as donors while fullerenes, such as C₆₀ and C₇₀ , due to their unique electron accepting properties, have been …

Prevention Of Staphylococcus Epidermidis Biofilm Formation Using A Low-Temperature Processed Silver-Doped Phenyltriethoxysilane Sol–Gel Coating, Niall Stobie, Brendan Duffy, Declan Mccormack, John Colreavy, Martha Hidalgo, Patrick Mchale, Steven Hinder

Articles

Sol–gel coatings which elute bioactive silver ions are presented as a potential solution to the problem of biofilm formation on indwelling surfaces. There is evidence that high-temperature processing of such materials can lead to diffusion of silver away from the coating surface, reducing the amount of available silver. In this study, we report the biofilm inhibition of a Staphylococcus epidermidis biofilm using a low-temperature processed silver-doped phenyltriethoxysilane sol–gel coating. The incorporation of a silver salt into a sol–gel matrix resulted in an initial high release of silver in de-ionised water and physiological buffered saline (PBS), followed by a lower sustained …

Effects Of Water Vapor On The Kinetics Of The Methylperoxy Radical Self-Reaction And Reaction With Hydroperoxy, Alecia Mower

Theses and Dissertations

The gas phase reactions of CH3O2 + CH3O2, HO2 + HO2, and CH3O2 + HO2 in the presence of water vapor have been studied at temperatures between 263 and 303 K using laser flash photolysis coupled with UV time-resolved absorption detection at 220 nm and 260 nm. Water vapor concentration was quantified using tunable diode laser spectroscopy operating in the mid-IR. The HO2 self-reaction rate constant is significantly enhanced by water vapor, consistent with what others have reported, whereas CH3O2 self-reaction and the cross-reaction (CH3O2 + HO2) rate constants are nearly unaffected. The enhancement in the HO2 self-reaction rate coefficient …

Fabrication Of Pillar-Structured Thermal Neutron Detectors, Rebecca J. Nikolić, Adam M. Conway, Catherine E. Reinhardt, Robert T. Graff, Tzu Fang Wang, Nirmalendu Deo, Chin Li Cheung

Barry Chin Li Cheung Publications

Pillar detector is an innovative solid state device structure that leverages advanced semiconductor fabrication technology to produce a device for thermal neutron detection. State-of-the-art thermal neutron detectors have shortcomings in achieving simultaneously high efficiency, low operating voltage while maintaining adequate fieldability performance. By using a 3-dimensional silicon PIN diode pillar array filled with isotopic boron 10, (¹⁰B) a high efficiency device is theoretically possible. The fabricated pillar structures reported in this work are composed of 2 μm diameter silicon pillars with a 4 μm pitch and pillar heights of 6 and 12 μm. The pillar detector with a …

Total Synthesis Of An Analog Of Hydramycin And Derivatization Of Thiol-Terminated Carbohydrates And Development Of A Glycoconjugate Too Set For The Assembly And Presentation Of Carbohydrate Ligands On Surfaces, Medhanit Woldeghiorghis Bahta

Doctoral Dissertations

2-(1,2-Dihydroxy-1-(oxiran-2-yl)ethyl)-11-hydroxy-5-methyl-1Hnaphtho[ 2,3-h]chromene-4,7,12-trione (1), a pyranoanthraquinone isolated from Streptomyces violaceus P950-4, showed a potent antibacterial and cytotoxic activity. A model synthesis for analogs 2-(1,2-dihydroxy-1-(oxiran-2-yl)ethyl)-4H-chromen- 4-one (2) and2-(1-hydroxy-1-(oxiran-2-yl)ethyl)-1H-naphtho[2,3- h]chromene-4,7,12-trione (3) was developed by Dr. David White and Dr. Sarah Headrick. A new analog, 2-(1,2-dihydroxy-1-(oxiran-2-yl)ethyl)-1H-naphtho[2,3- h]chromene-4,7,12-trione (4), was designed to be structurally more similar to hydramycin with –CH2OH functionality on the pyranone ring and anthraquinone skeleton. Therefore, it is expected to have greater anticancer activity than either analogs 2 or 3. This dissertation will cover developments, challenges and solutions in …

Electroanalysis Of Metals In Biological And Environmental Samples At Bismuth Electrodes, Kristie Carter Armstrong

Doctoral Dissertations

An Advanced Oxidation Process (AOP) was designed for the decomposition of organic material in blood as a pretreatment for chromium analysis. Acidified porcine blood was treated with hydrogen peroxide and UV light for 60 min. The rate of decomposition was studied using UV/Vis spectroscopy. It was found that the order of the photolytic reaction with respect to hydrogen peroxide was 0.35. The pretreated blood was subsequently analyzed for chromium content by catalytic adsorptive stripping voltammetry at a bismuth film electrode. The concentration of chromium was determined to be 6.0 " 0.3 parts per billion (ppb). A bismuth bulk electrode was …

Tris(Dialkylamino)Aluminums: Syntheses, Characterization, Volatility Comparison, And Atomic Layer Deposition Of Alumina Thin Films, Casey R. Wade, Carter Silvernail, Chiranjib Banerjee, Axel Soulet, James Mcandrew, John A. Belot Jr.

Chemistry Department: Faculty Publications

The syntheses and characterization of both tris(diethylamino)aluminum and tris(diisopropylamino)aluminum are presented in this letter. Characterization includes vapor pressure measurements and comparison of the two non-pyrophoric precursors showing them to be viable alternatives to trimethylaluminum. Ultimately, tris(diisopropyl)aluminum was successful in the atomic layer deposition of alumina thin films.

Shake & Bake: Dual-Use Chemicals, Contexts, And The Illegality Of American White Phosphorus Attacks In Iraq, Joseph D. Tessier

The University of New Hampshire Law Review

[Excerpt] “On November 29, 2005, in a Department of Defense press conference with Secretary of Defense Donald Rumsfeld and Gen. Peter Pace, Chairman of the Joint Chiefs of Staff, General Pace stated that white phosphorus “is a legitimate tool of the military,” and can be used for illumination, smoke, and incendiary purposes. Incredibly, the Department of Defense released an addendum to the press conference clarifying that white phosphorus was not used as an incendiary weapon. According to General Pace, “it was well within the law of war to use white phosphorus . . . for marking and screening.” This was …

Nanomaterial Composites For The Detection Of Nerve Gas Analogs, Yogesh Datar

Masters Theses

The basis of the research work described here is the use of nanocomposite materials built by bottom-up approach for the selective detection of nerve gas analogs. Nanocomposites materials constructed by using nanoparticle-monomer-receptor (NMR) concept have been utilized to detect nerve gas analogs DCP and DMMP. Synthetic approach used in the construction of nanosensors involved use of robust platforms such as silica nanoparticles and fluorescent quantum dots. Highly conjugated receptor molecules were synthesized by using stilbeneoid compounds. A complete opto-nanosensor was developed by anchoring highly conjugated receptor molecules onto the silica nanoparticles as well as onto the quantum dots. The opto-nanosensors …

Exercise Makes You Feel Good, But Does Feeling Good Make You Exercise?: An Examination Of Obese Dieters, Robert Albert Carels, Carissa Coit, Bonnie Berger

Robert Albert Carels

Whereas exercise-induced mood enhancement has been well documented, the relationship between mood and exercise participation is less well understood. Mood states influence evaluative judgments that could plausibly influence a decision to exercise. Further, most exercise-mood research is limited to normal weight adults in response to a single exercise session. The current investigation examines the influence of (a) morning mood on exercise, (b) exercise intensity/duration on mood enhancement, and (c) daily change in mood on exercise days compared with nonexercise days in obese behavioral weight loss program (BWLP) participants. Participants (N=36) recorded morning, evening, and pre- and postexercise mood, as well …

Excited-State Equilibration Over 30 Angstrom In A Platinum(Ii) Quinolinolate-Bridge-Platinum(Ii) Porphyrin Complex, Victor A. Montes, Michael A. J. Rodgers, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

Long-range triplet excited-state equilibration occurs over a nanometric distance between platinum(II) 8-quinolinolate ((3)Ptq(2) = 1.87 eV) and platinum(II) tetraphenylporphyrin ((PtTPP)-Pt-3 = 1.89 eV). The equilibrium is mediated by a fluorene-thiophene-fluorene bridge ((FTF)-F-3 = 1.92 eV) and is characterized by a double-exponential decay (tau(1) = 39 +/- 4 ps; tau(2) = 351 +/- 15 ps) that suggests the participation of three separate excited states : (3)Ptq(2), (FTF)-F-3, and 3PtTPP, respectively. Numerical simulation of the dual equilibrium allowed for estimation of the individual rate constants for each of the reversible steps (k(ET) = 3.9 x 10(9)-4.1 x 10(10) s(-1)). As a result …

Formation Of Peptide Nanospheres And Nanofibrils By Metal Coordination, Mikhail V. Tsurkan, Michael Y. Ogawa

Chemistry Faculty Publications

Two amphipathic polypeptides were coordinated to the cis positions of a square planar Pt(II) complex in order to provide the metal center with two noncovalent oligomerization domains. This resulted in the formation of new metal-peptide nanoassemblies which are shown to exist as nanometer-sized spheres and fibrils. Construction of these assemblies was based on the 30-residue polypeptide AQ-Pal14 which was designed for its ability to self-assemble into the common protein oligomerization motif of a noncovalent coiled-coil, and modified to contain a metal-binding 4-pyridylalanine residue at its surface. When AQ-Pal14 was reacted with Pt(en)(NO3)(2), a new metal-peptide complex was formed in which …

The Development Of A Quality Risk Management Solution Designed To Facilitate Compliance With The Risk-Based Qualification, Validation And Change Control Gmp Requirement Of The Eu, Kevin O'Donnell

Doctoral

This research work was concerned with investigating the risk-based regulatory requirements that are currently in place in the European Union governing the manufacture of medicinal products. The main goal of this research was to develop a practical Quality Risk Management methodology that served as a solution for facilitating compliance with the EU GMP requirements in the area of risk-based Qualification, Validation and Change Control, and which was fully in line with the principles and guidance of ICH Q9, on Quality Risk Management. Following extensive testing and evaluation activities with a range of key stakeholders including the pharmaceutical manufacturing sector in …

Synthesis, Study Of Self-Assembly, And Trivalent Lanthanide Metal Ion Recognition Characteristics Of Amphiphilic Acylpyrazolones And Amphiphilic Acylisoxazolones, Venkat Reddy Guduru

Dissertations

This research project focused on the separation of trivalent lanthanide metal ions by HPLC using amphiphilic acylpyrazolones and amphiphilic acylisoxazolones. The central hypothesis of our research project is that the nanoscale self-assembly nature of amphiphilic ligands (chelating lingads) can influence their metal ion recognition and separation. To test the central hypothesis, we have synthesized a family of novel amphiphilic ligands and employed them as model systems for the separation of trivalent lanthanide metal ions. Several novel intermediates such as 4-acylated. N -acylated, O -acylated pyrazolones and isoxazolones, have been efficiently synthesized and fully characterized.*

The trivalent lanthanide metal ion recognition …

Synthesis And Characterization Of Ruthenium Bipyridyl Complexes For Detecting Nerve Gas Agents And Explosives, Arambe Gedara Aruna Weerasinghe

Masters Theses

Five novel 2,2 '-bis bi pyridine Ru(II) complexes have been synthesized and characterized using ¹H NMR, ¹³C NMR, ¹H-¹H-COSY, elemental analysis, fast atom bombardment or electrospray mass spectra and electronic absorption spectroscopy. Binding of Ru (11) complexes with nerve gas analogos such as diethyl chlorophosphate (DCP), dimethyl methyl phosphonate (DMMP) and hydrolyzed product (HCl) has been investigated by electronic absorption, fluorescence, and lifetime studies. Compound 1 showed a quenching in ³MLCT emission after an initial increase in intensity upon the addition of DCP with a bathochromic shift of 25 nm. Compound 2 exhibit a …

Design Of Multi-Electron Transfer Catalysts For The Reduction Of Trichloroethylene, Christopher Gerard Eman Ciptadjaya

Masters Theses

For decades, organohalide (RX) compounds have been heavily used in the chemical and pharmaceutical industries and in agriculture as pesticides. Improper disposal of organohalides has resulted in their presence in the environment as pollutants, and they have therefore presented serious environmental and toxicological concerns. These organohalides have been associated with various health and environmental problems. Therefore, effective methods for their remediation are required. We have developed a multi-electron transfer (MET) catalyst consisting of flavin mononucleotide anchored to nanocrystalline mesoporous titanium dioxide (TiO₂) thin films, and examined its reactivity toward the organohalide pollutant trichloroethylene (TCE). Various environmental factors were …