Chemistry Commons^™

Mixed Quantum/Classical Theory For Inelastic Scattering Of Asymmetric-Top-Rotor + Atom In The Body-Fixed Reference Frame And Application To The H2O + He System, Alexander Semenov, Marie-Lise Dubernet, Dmitri Babikov

Chemistry Faculty Research and Publications

The mixed quantum/classical theory (MQCT) for inelastic molecule-atom scattering developed recently [A. Semenov and D. Babikov, J. Chem. Phys.139, 174108 (2013)] is extended to treat a general case of an asymmetric-top-rotor molecule in the body-fixed reference frame. This complements a similar theory formulated in the space-fixed reference-frame [M. Ivanov, M.-L. Dubernet, and D. Babikov, J. Chem. Phys.140, 134301 (2014)]. Here, the goal was to develop an approximate computationally affordable treatment of the rotationally inelastic scattering and apply it to H₂O + He. We found that MQCT is somewhat less accurate at lower scattering energies. For example, below E …

Probing The Human Estrogen Receptor-Α Binding Requirements For Phenolic Mono- And Di-Hydroxyl Compounds: A Combined Synthesis, Binding And Docking Study, Christopher Mccullough, Terrence S. Neumann, Jayapal Reddy Gone, Zhengjie He, Christian Herrild, Julie Lukesh, Rajesh K. Pandey, William A. Donaldson, Daniel S. Sem

Chemistry Faculty Research and Publications

Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and …

Stability Of High Band Gap P3ht: Pcbm Organic Solar Cells Using Tiox Interfacial Layer, Kurniawan Foe, Gon Namkoong, Matthew Samson, Enas M. Younes, Ilho Nam, Tarek M. Abdel-Fattah

Electrical & Computer Engineering Faculty Publications

We fabricated a poly [3-hexylthiophene] (P3HT) and [6,6] -phenyl-C61-butyric acid methyl ester (PC₆₁BM with the TiO_x layer. We found that a solution based TiO_x coated at a spin speed of 3000 rpm improved the photon absorption of the active layer. An optimized TiO_x layer was also used as the interfacial layer to investigate the stability of P3HT: PC₆₁BM OPC. After 70 days of storage, we observed that the short-circuit current density (J_SC) dropped by 16.2%, fill factor (FF) dropped by 10.6%, and power conversion efficiency (PCE) dropped approximately by 25%, while …

Development Of Visible Light-Promoted Photocatalytic O-Glycosylation, C-H Activation Of Alkanes And Deoxygenation Of N-(Mesyloxy) Amides, Xiaoping Wang

LSU Master's Theses

This thesis is divided into four chapters reporting various aspects of the background of studies and the preliminary results I obtained in three projects. Chapter 1 gives a brief introduction to the concepts of photoredox catalysis, O-glycosylation, C-H functionalization and amidyl radicals. Chapter 2 describes the development of a visible light-promoted O-glycosylation catalyzed by Ru(bpy)3(PF6)2 or diphenyldiselenide under mild conditions. The glycosylation of primary and secondary alcohols with selenoglycosides was demonstrated with good yields, and disaccharides were constructed by coupling of the selenoglycosides in acetonitrile or dichloromethane with a glucosyl acceptor in moderate yields. The reactions catalyzed by Ru(bpy)3(PF6)2 were …

Particle Formation In Ambient Mass Spectrometry, Thabiso Musapelo

LSU Doctoral Dissertations

A particle sizing system was developed that couples a light scattering particle sizer with a differential mobility analyzer for particle detection and elucidation with the capability for measuring particle sizes in the range of 10 nm to 20 μm. The particle sizing system was used to investigate particle formation that is associated with several methods of atmospheric pressure ion formation used in mass spectrometry: atmospheric pressure matrix-assisted laser desorption ionization (MALDI) and inlet ionization. The methods for particle formation were 1) ultraviolet (UV) laser ablation, 2) infrared (IR) laser ablation, and 3) shock-generated particle formation. Particles formed by UV laser …

Bio-Imprinted Hydro-Gels (Bigs) For Protein And Virus Detection, Wei Bai

LSU Doctoral Dissertations

Detection of bio-markers at low concentration is becoming a more and more important topic in scientific research due to its importance in applications crucially related to people’s life like medical diagnosis, environment protection and national security. In the past decades, as the improvement of the modern analytical technologies progressed, plenty of methodologies have been developed to realize the fast and accurate detection of bio-markers in liquid media. However, some drawbacks still remain like the expensive cost, high requirement of operational environment, and need for skilled operators. Here, a new kind of aptamer-based bio-imprinted hydrogel sensor (BIG) with specific macroscopic volume …

Synthetic Routes To Therapeutic Agents Via Masked Functionalities: From Orthogonal Peptide Crosslink To Photothermal Cancer Prodrug, Chyree Shantel Batton

LSU Doctoral Dissertations

The theonellamides are a family of compounds distinguished by their crosslinking ô-histidinoalanine (ô-HAL) residue. Part one of this dissertation details the synthesis of an orthogonally protected ô-HAL building block that will be incorporated into a total synthesis of theonellamide C. Selective deprotection of each amine and acid of this orthogonally protected building block is also demonstrated. Various reaction partners for the assembly of ô-histidinoalanine were explored. One approach involved the coupling of N-Fmoc-â-iodoalanine benzyl ester and (Nðim)-blocked histidine nucleophiles including a fused bicyclic urea and a Boc-His(Nð-Pac)-OMe. While the imidazolium salts were identified by mass spectrometry, elimination of the iodide …

Polymer Micro- And Nanofluidic Systems For In Vitro Diagnostics: Analyzing Single Cells And Molecules, Swathi Reddy Pullagurla

LSU Doctoral Dissertations

Polymer micro- and nanofluidic systems, with their critical dimensions, offer a potential to outperform conventional analysis techniques and diagnostic methods by enhancing speed, accuracy, sensitivity and specificity. In this work, applications of microfluidics have been demonstrated to address the existing challenges in stroke diagnosis, by mRNA expression profiling from whole blood within <20 min. A brief overview of various biomarkers for stroke diagnosis is given in chapter 1 followed by design and testing of individual microfluidic modules (chapter 2 and 3) required for the development of POC diagnostic strategy for stroke. We have designed and evaluated the performance of polymer microfluidic devices for the isolation of leukocyte subsets, known for their differential gene expression in the event of stroke. Target cells (T-cells and neutrophils) were selected from with greater purities, from 50 µl whole human blood by using affinity based capture in COC devices within a 6.6 min processing time. In addition, we have also demonstrated the ability to isolate and purify total RNA by using UV activated polycarbonate solid phase extraction platform. Polymer-based nanofluidic devices were used to study the effects of surface charge on the electrodynamic transport dynamics of target molecules. In this work, we report the fabrication of mixed-scale micro- and nanofluidic networks in poly(methylmethacrylate), PMMA, using thermal nanoimprint lithography using a resin stamp and surface modification of polymer nanoslits and nanochannels for the assessment of the associated electrokinetic parameters – surface charge density, zeta potential and electroosmotic flow. This study provided information on possible routes that can be adopted to engineer proper wall chemistry of polymer nanochannels for the enhancement or reduction of solute/wall interactions in a variety of relevant single-molecule studies.

Design, Synthesis, And Evaluation Of Small Molecule-Based, Profluorogenic Activatable Substrate Probes For Detection And Visualization Of Human Cancer Enzyme Nad(P)H:Quinone Oxidoreductase-1, Suraj Uditha Hettiarachchi

LSU Doctoral Dissertations

Cancer comprises many specific diseases, and it is currently responsible for millions of deaths worldwide. This broad disease profile is a great challenge for personalized oncology. Critical for the success of cancer therapy is the exploration of improved methodologies for the early detection of localized and disseminated tumor cells in patients, where bio-molecular imaging has become an indispensable tool. Being one of many different imaging techniques, optical fluorescence imaging has been translated over the years from the bench to clinical research, and it is now on the verge of being able to address some of the pressing challenges in molecular …

Fabrication Of Nanoporous Gold And Biological Applications, Badharinadh Uppalapati

Theses and Dissertations

FABRICATION OF NANOPOROUS GOLD AND BIOLOGICAL APPLICATIONS By Badharinadh Uppalapati A Dissertation submitted in partial fulfillment of the requirements for the degree of Master of Science at Virginia Commonwealth University. Virginia Commonwealth University, 2014 Major Director: Maryanne M. Collinson, Professor, Department of Chemistry Fabrication of nanoporous gold electrodes by dealloying Au:Ag alloys has attracted much attention in sensing applications. In the first part of this work, the electrochemical response of the redox active molecule, potassium ferricyanide, in a solution of bovine serum albumin in buffer, serum or blood was studied using nanoporous gold and comparisons made to planar gold. Nanoporous …

Affinity Enrichment And Mass Spectrometric Quantitation Of Protein Carbonyls, Suresh Narayanasamy

Theses and Dissertations

The importance of the role of oxidative stress in aging and numerous age-related diseases has become undeniable due to enormous weight of supporting evidence from the field of free radical biology. One of the most prominent oxidative modifications of proteins is the introduction of carbonyl groups. As with oxidative stress, protein carbonylation has been correlated with various disease states and natural aging. While protein carbonyls are relatively stable, reproducible detection and modification site localization are still challenging. This thesis details attempts to improve the analytical methodology used for the identification and quantitation of carbonylated proteins. We have studied the impact …

Light Mediated Drug Delivery Using Photocaged Molecules And Photoswitchable Peptides, Deboleena Mitra

Theses and Dissertations

There are many different types of targeted therapy for cancer treatment. The method of light mediated targeted therapy that we have developed uses photocaged molecules and photoswitchable peptides.

In photocaging, a biologically active molecule is made inactive by the attachment of a photocleavable blocking group. On exposure to UV radiation the photocleavable entity is removed and the biologically active molecule is released. Using this concept we have designed a prodrug that consists of a cell impermeable hydrophilic molecule attached to a photocaged doxorubicin. Upon irradiation with UV light the photosensitive group is removed and cytotoxic doxorubicin is released at the …

A Computational Study Of Small Gold Clusters With H2s, Thiols, H2o, And Alcohols, Silvija C. Smith

Theses and Dissertations (Comprehensive)

Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Au_n. Initially a RSH-Au_n complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAu_nH complex. We examine the rate of this reaction for small neutral gold clusters, with n=1-2 and short-chain thiols with R = H, CH₃, and CH₃CH₂, using transition state theory. The comparison of DFT (with the functionals, BP86 and M06-2X), and MP2 was performed. A pseudopotential was employed to account for the large relativisitic effects …

Surface Complexation Of Monosubstituted Organoarsenicals On Hematite: Atr-Ftir Investigations, Md Abdus Sabur

Theses and Dissertations (Comprehensive)

Little is known about the surface chemistry of organoarsenic compounds with iron-containing materials commonly found in geosorbents and arsenic removal technologies. In this thesis, these organoarsenicals include aliphatic and aromatic arsenicals that historically have been used as herbicides, pesticides and in the poultry feed industry, respectively. Attenuated total internal reflectance Fourier transform infrared spectroscopy has been used to study the surface interactions of organoarsenicals at the molecular level under various environmentally-relevant conditions. Kinetic and thermodynamic parameters extracted from these molecular level experiments provide trends that are not observed in any published bulk experiments. Apparent initial rates of adsorption and desorption …

Synthesis And Characterization Of Coloumnar Mesophases Of Novel Substituted Dibenzanthracenes And Their Donor-Acceptor Mixtures, Katie M. Psutka

Theses and Dissertations (Comprehensive)

In this thesis, the synthesis and liquid crystalline properties of a series of novel dibenz[a,c]anthracenes are reported. Specifically, two dibenzanthracenecarboxylate derivatives were prepared and were found not to exhibit a mesophase. In contrast, a series of novel N-substituted dibenzanthracenedicarboximides was also synthesized and found to exhibit broad columnar temperature ranges. Several dibenzanthracenedicarboximides substituted with different alkyl chains on the nitrogen atom were prepared and their mesomorphic temperature ranges were characterized. In general, it was found that having a longer, more flexible alkyl chain on the nitrogen atom resulted in a broadening of the columnar temperature range via a lowering …

Relative Equilibria Of Isosceles Triatomic Molecules In Classical Approximation, Damaris Miriam Mckinley

Theses and Dissertations (Comprehensive)

In this thesis we study relative equilibria of di-atomic and isosceles tri-atomic molecules in classical approximations with repulsive-attractive interaction. For di-atomic systems we retrieve well-known results. The main contribution consists of the study of the existence and stability of relative equilibria in a three-atom system formed by two identical atoms of mass $m$ and a third of mass $m_3$, constrained in an isosceles configuration at all times.

Given the shape of the binary potential only, we discuss the existence of equilibria and relative equilibria. We represent the results in the form of energy-momentum diagrams. We find that fixing the masses …

Bisbenzylisoquinoline And Hasubanane Alkaloids From Stephania Abyssinica (Dillon & A. Rich) (Menispermeceae), Ruth A. Omole, Jeremiah Gathirwa, Hosea Akala, Hamisi M. Malebo, Alex K. Machocho, Ahmed Hassanali, Isaiah O. Ndiege

All Peer-Reviewed Publications

Two bisbenzylisoquinoline and one hasubanane alkaloids: (-)-pseudocurine (1), (-)-pseudoisocurine (2) and (-)-10-oxoaknadinine (3), were isolated from leaf extract of Stephania abyssinica, a plant used in traditional medicine in South Nyanza region of Kenya. They were characterized using 1D (1H, 13C and DEPT) and 2D (COSY, NOESY, HMQC and HMBC) NMR techniques. (-)-Pseudocurine (1) and (-)-pseudoisocurine (2) exhibited strong to moderate anti-plasmodial activity while (-)-10-oxoaknadinine (3) showed moderate to mild activity. © 2014 Elsevier Ltd. All rights reserved.

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …

Advances In Understanding The Molecular Composition Of Dissolved Organic Matter And Its Reactivity In The Environment, Rajaa Mesfioui

Chemistry & Biochemistry Theses & Dissertations

Dissolved organic matter (DOM) is the ultimate product of Earth's systems dynamics. DOM chemical signature is strongly shaped by the interaction among Earth's spheres, such as the atmosphere, the geosphere, the biosphere, and the hydrosphere, but also life and human activity. DOM source, composition, photochemical alteration and availability affect freshwater ecosystems, their carbon and nitrogen fluxes and, thus, the global carbon and nitrogen cycles. The aim of this thesis was to gain an understanding of the molecular composition of DOM and its photochemical and biological reactivity in an environment impacted by anthropogenic disturbance. The York and James River systems within …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into The Linkage Between Sources And Chemical Composition, Xiaoyan Cao

Chemistry & Biochemistry Theses & Dissertations

This dissertation investigated the chemical structure of DOM by advanced solid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques, as well as isotopic measurements and UV-visible spectroscopy, to shed light on the linkages between DOM sources and DOM composition. Unique and extensive sets of DOM samples studied here were isolated from various aquatic systems, covering end-member environments in which DOM is considered either microbially derived or terrestrially derived, and areas in which DOM has characteristics intermediate between the two end members. Important insights into specific site-related questions were also gained such as …

Synthesis And Characterization Of Sugar Based Low Molecular Weight Gelators And The Preparation Of Chiral Sulfinamides, Hari Prasad Reddy Mangunuru

Chemistry & Biochemistry Theses & Dissertations

Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications.

Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D …