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Heterogeneous Conductorlike Solvation Model, Hui Li, Dejun Si

Department of Chemistry: Faculty Publications

A heterogeneous conductorlike solvation model (conductorlike screening model/conductorlike polarizable continuum model) that uses different local effective dielectrics for different portions of the solute cavity surface is implemented for quantum chemical Hartree–Fock and Kohn–Sham methods. A variational treatment is used to form the heterogeneous solvation operator, so a simple analytic expression of the energy gradients, which are vital for geometry optimization and molecular dynamics simulation, is derived and implemented. Using the new Fixed Points with Variable Areas surface tessellation scheme, continuous and smooth potential energy surfaces as well as analytic gradients are obtained for this heterogeneous model.

Direct Binding Of Cytosolic Ndp Kinases To Membrane Lipids Is Regulated By Nucleotides, Kimberly A. P. Mitchell, Gabor Szabo, Angela De S . Otero

Faculty Publications and Presentations

In spite of their complete lack of any structural features that characterize membrane proteins, cytosolic nucleoside-diphosphate kinases (NDPKs) have been found repeatedly to associate with membranes. In some instances the recruitment of cytosolic NDPKs to membranes was attributed to interactions with peripheral or integral membrane proteins, but in many cases the mechanism underlying the association of NDPKs with membranes remained unknown. We show here that cytosolic NDPKs bind directly to membrane lipids in a dynamic process that is controlled by its substrates, nucleoside tri- and diphosphates, and can be fully reconstituted with chemically defined, protein-free phospholipids and recombinant NDPK, or …

Methods For The Isolation Of Sensory And Primary Cilia—An Overview, Kimberly A. P. Mitchell, Gabor Szabo, Angela De S. Otero

Faculty Publications and Presentations

Detailed proteomic analyses of mammalian olfactory and rod photoreceptor sensory cilia are now available, providing an inventory of resident ciliary proteins and laying the foundation for future studies of developmental and spatio-temporal changes in the composition of sensory cilia. Cilia purification methods that were elaborated and perfected over several decades were essential for these advances. In contrast, the proteome of primary cilia is yet to be established, because purification procedures for this organelle have been developed only recently. In this chapter we review current techniques for the purification of olfactory and photoreceptor cilia, and evaluate methods designed for the selective …

Applying Scanning Probe Microscopy For The Investigation Of Molecular Self-Assembly Mechanisms And Properties Of Designed Nanomaterials, Algernon Tremayne Kelley

LSU Doctoral Dissertations

Scanning probe microscopy (SPM) for conducting surface characterizations of nanomaterials and molecular self-assembly processes is emerging as an important contribution in nanotechnology, especially towards the design of molecular electronic devices. Another area of importance is the characterization of the properties of nanomaterials for fundamental understanding of structure-function inter-relationships. Understanding the properties and behavior of molecules and finding approaches to control surface self-organization through nanolithography provides essential information for the development of workable applications for nanotechnology. This dissertation describes the methodologies of AFM for characterizing molecules and nanostructures produced with scanning probe lithography (SPL). Automated software for nanografting and nanoshaving produce …

Scanning Probe Microscopy Investigations Of (1) Arrays Of Cysteine-Coated Cds Nanoparticles And (2) Structures Formed During The Early Stages Of The Corrosion Of Copper Surfaces, Brian Robert Lewandowski

LSU Doctoral Dissertations

Scanning probe microscopy (SPM) characterizations are becoming more prevalent for surface investigations due to their capabilities for obtaining structural information and physical measurements. New capabilities of SPM for studying and controlling nanoscale processes are emerging as valuable assets in research. A fundamental understanding of the interactions of surface reactions provides essential information for developing workable applications for nanotechnology. Two applications of SPM are discussed in this dissertation. The first investigation uses atomic force microscopy (AFM) for the characterization of nanostructures produced with a newly developed lithographic technique called “two-particle” lithography. This new technique is based on particle lithography for the …

Atom-Based Computer Simulation Studies Of Gas-To-Liquid Nucleation In Atmospherically Relevant Systems: Clarifying Discrepancies And Elucidating Mechanisms, Ricky Bendanillo Nellas

LSU Doctoral Dissertations

For over a century, nucleation for all systems was thought simplistically to be a process that advances through the formation of critical clusters with a well-defined composition. Our results show intriguing nucleation mechanisms that challenge the aforementioned notion. We employed the simple TraPPE-UA (transferable potential for phase equilibria – united atom) force field and the AVUS-HR approach (a combination of aggregation-volume-bias Monte Carlo, umbrella sampling, and histogram reweighting), to investigate the homogeneous vapor-to-liquid nucleation of various nucleating systems. We found out that these systems could nucleate through a variety of unique non-ideal mechanisms. Alongside existing experimental investigations, this dissertation presents …

Synthesis And Characterization Of Transition Metal And Metal Oxide Nanoparticles Using Dendritic Complexes, Elisabeta Mitran

LSU Doctoral Dissertations

The research in this dissertation focuses on the synthesis and characterization of metal/metal oxide nanoparticles in solution and on surfaces with a high degree of control over size and size dispersity; such well-defined nanoparticles were made using metal ion-dendrimer complexes and silica-supported organometallic dendrimers. The metal oxide-based materials can be used as laboratory surrogates for combustion-generated nanoparticles to assess their role in mediating pollutant formation. Nickel nanoparticles with low size dispersity were prepared by a dendrimer-ligand-based method employing five generations amine-terminated poly(propylene imine) dendrimer, DAB-Amn. After coordination, borohydride reduction of Ni(II) ion-dendrimer complexes yielded Ni(0) nanoparticles, as determined by X-ray …

Phytochemical Analyses Of Bioactive Compounds In The Roots Of Cassia Alata Linn And The Anti-Angiogenic Evaluation Of Rhein As A Therapeutic Agent Against Breast Cancer Cells, Vivian Esther Fernand

LSU Doctoral Dissertations

The research presented in this dissertation includes the novel phytochemical analysis of root extracts of Cassia alata L. and the anti-angiogenic evaluation of rhein in the treatment of breast cancer. To conduct these studies a combination of analytical techniques were employed, namely, chromatographic, spectroscopic, and bioanalytical. The first part of this research is focused on the phytochemical analysis of C. alata root extracts. A high performance liquid chromatography method was developed and validated for the determination of six phenolic compounds in the root extracts. The investigated compounds were identified by their ultraviolet spectra. Additionally, the presence of these phenolics was …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Amyloid Aggregation-Mitigating Peptides As Potential Alzheimer's Drugs, Cyrus Kipkurui Bett

LSU Doctoral Dissertations

Neuronal cytotoxicity observed in Alzheimer¡¦s disease (AD) is linked to the aggregation of £]-amyloid peptide (A£]) into toxic forms. Increasing evidence points to oligomeric species as the neurotoxic species compared to fibrils; disruption or inhibition of A£]ƒnself-assembly into oligomeric or fibrillar forms remains a viable therapeutic strategy to reduce A£] neurotoxicity. Amyloid aggregation mitigating peptides (AAMPs) were designed based on the A£]ƒn¡§hydrophobic core¡¨ A£]17-20, with C£\,£\-disubstituted amino acidsƒnƒv£\£\AAs) added into this core as disrupting agents. The number, distribution, and side chain functionality of £\£\AAs incorporated into the mitigator sequence was found influences the resultant aggregate morphology as indicated by ex-situ …

F₂-Isoprostanes Study After Exposure To Selected Nanoparticles By Liquid Chromatography/Tandem Mass Spectrometry And Investigation Of Nanoparticles On The Cytotoxicity Effect Of Arsenic In Vitro, Xiaoqian Liu

Doctoral Dissertations

"Nanopartices as a new class of materials found their applications in industry, aerospace, clinical diagnosis and cancer therapy. Recently, the health effects of nanoparticles have caused people great concerns. This dissertation studies the mechanisms of nanoparticle cytotoxicity in human lung epithelial cells (A549). F₂-isoprostanes are novel reliable biomarkers for lipid peroxidation. In the first part of this work, total free F₂-isoprostanes were quantified by high performance liquid chromatography/mass spectrometry followed by the exposure of SiO₂ (15 nm), CeO₂ (20 nm), Fe₂O₃ (30 nm), and ZnO (70 nm) nanoparticles for 24 hours. For the first time, the results showed that F₂-isoprostanes …

Investigation Of The Interactions Between Selected Nanoparticles And Human Lung Carcinoma Cells At The Single Cell And Single Particle Level, Isaac Stayton

Doctoral Dissertations

"The recent advances in nanomaterials development and applications have sparked concerns regarding the safety of these materials in living organisms. This body of work investigates specific interactions between chosen nanoparticles and living human lung carcinoma (A549) cells"--Abstract, page iv.

Gold Nanoparticles: Synthesis, Property Study And Applcications For Biomolecular Detection And Photothermal Therapy, Xiong Liu

Electronic Theses and Dissertations

This dissertation presents a systematic study on gold nanoparticles: from their chemical synthesis, modification of surface functionalities, optical properties studies with emphasis on the absorption and scattering properties, to applications of gold nanoparticles in biomolecular detection, imaging and photothermal therapy. In chapter 2, we studied the kinetics of gold nanoparticle growth under Brust-Shiffrin reaction conditions. In chapter 3, we further examined the reaction mechanism and growth kinetics of gold nanoparticles using oleylamine as both a reducing reagent and particle growth passivation ligand. From these two projects, important understanding was revealed on gold nanoparticle formation and growth mechanism. Chapter 4 describes …

Imaging And Spectroscopy Of Conducting Polymer-Fullerene Composite Materials, Daeri Tenery

Electronic Theses and Dissertations

Since the development and optical study of conjugated (conducting) polymers it has become apparent that chain conformation and aggregation at the molecular scale result in complex heterogeneous nanostructured bulk materials for which a detailed insight into morphological, spectroscopic as well as optoelectronic properties and mechanisms is overwhelmingly difficult to obtain. Nanoparticles composed of the conjugated polymer poly (MEH-PPV) and nanocomposite nanoparticles consisting of MEH-PPV doped with 1-(3-methoxycarbonylpropyl)-1-phenyl-C61 (PCBM) were prepared as model systems to study these materials at the length scale of one to a few domains. The MEH-PPV and PCBM doped nanoparticles were analyzed by single imaging/particle spectroscopy (SPS) …

Asymmetric Transfer Hydrogenation Of Allylic Alcohols With Homogeneous Chiral Ruthenium Catalysts: A Proposed Mechanism, Marie G. Beauchamps

Seton Hall University Dissertations and Theses (ETDs)

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Statins Induce Apoptosis In Ovarian Cancer Cells Through Activation Of Jnk And Enhancement Of Bim Expression, Hongli Liu, Shu Ling Liang, Sheetal Kumar, Crystal M. Weyman, Wendy Liu, Aimin Zhou

Chemistry Faculty Publications

Purpose:Ovarian cancer is the leading cause of death among all gynecological malignancies in Western countries. Although therapy for ovarian cancer has been greatly improved in the past 20 years, the overall survival for patients with advanced ovarian cancer has not changed significantly. The poor survival rates in patients with advanced ovarian cancer are due both to late diagnosis and to lack of effective drugs for the majority of patients who have a relapse and develop resistance to current chemotherapy agents used for ovarian cancer. Thus, developing and discovering effective novel drugs with different molecular structures from conventional chemotherapy agents have …

Design Of Novel Anticancer Drugs Utilizing Busulfan For Optimizing Pharmacological Properties And Pattern Recognition Techniques For Elucidation Of Clinical Efficacy, Ronald Bartzatt

Chemistry Faculty Publications

Chronic myelogenous leukemia (CML) is a disorder in which an excessive number of blood stem cells develop into the white blood cell group called granulocytes. The anticancer drug Busulfan is a cell cycle non-specific alkylating agent which is utilized to maintain white blood cell counts below 15000 cells/microliter. The side effects induced by busulfan are significant and affirms the intimation for new drug constructs. Fifteen analogous compounds were generated from the molecular structure of busulfan . These compounds retain the double methanesulfonate functional groups descriptive of this class of alkylating anticancer drugs. However, the carbon chain substituent separating the methanesulfonate …

Atp-Dependent Unwinding Of U4/U6 Snrnas By The Brr2 Helicase Requires The C Terminus Of Prp8, Corina Maeder, A. K. Kutach, C. Guthrie

Chemistry Faculty Research

The spliceosome is a highly dynamic machine requiring multiple RNA-dependent ATPases of the DExD/H-box family. A fundamental unanswered question is how their activities are regulated. Brr2 function is necessary for unwinding the U4/U6 duplex, a step essential for catalytic activation of the spliceosome. Here we show that Brr2-dependent dissociation of U4/U6 snRNAs in vitro is activated by a fragment from the C terminus of the U5 snRNP protein Prp8. In contrast to its helicase-stimulating activity, this fragment inhibits Brr2 U4/U6-dependent ATPase activity. Notably, U4/U6 unwinding activity is not stimulated by fragments carrying alleles of prp8 that in humans confers an …

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.

A Preliminary Study Of A Non-Invasive Glucose Sensor Based On A Mercury Sensor, Erin Wood

Electronic Theses and Dissertations

Diabetes mellitus is a potentially lethal disease that affects 7.6 percent of American people. In the US, it is recognized as the 6th leading cause of death. Failure to control blood glucose levels (BGL) in patients with either type of diabetes can lead to other serious complications as well, such as loss of limb, blindness and other health problems. Controlling and monitoring the BGL in post-op and intensive care patients in the hospital is also vital to their health. Currently the most reliable method of monitoring BGL is through an invasive procedure which monitors the amount of glucose in blood …

Room Temperature Synthesis And Systematic Characterization Of Ultra-Small Ceria Nanoparticles, Chetak Patel

Electronic Theses and Dissertations

Cerium oxide (ceria, CeOâ‚‚) is a rare earth oxide that has attracted wide-spread research interest because of its unique properties such as high mechanical strength, oxygen ion conductivity, oxygen storage capacity and autocatalytic property. In recent years, researchers have discovered that ceria nanoparticles (NPs) are capable of protecting cells from free radical induced damage. Interestingly, it was found that nanometer size (~ 5 nm) ceria can scavenge free radicals quite efficiently, thus acting as an anti-oxidant. This phenomenon has been explained based on the autocatalytic property of ceria NPs. Several methods have been developed for the synthesis of ceria NPs …

A Chemical Ionization Mass Spectrometer For Continuous Underway Shipboard Analysis Of Dimethylsulfide In Near-Surface Seawater, Eric S. Saltzman, Warren J. De Bruyn, M. J. Lawler, Christa Marandino, C. A. Mccormick

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ('mini-CIMS') has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified …

6-Ketomethyl Phenanthridine As A New Carrier In The Construction Of A Highly Selective Fe(Iii) Ion-Selective Membrane Electrode, R. Maleki, Reza Hosseinzadeh, Hossein Mehrabi, Ali Hassanzadeh, Khalil Farhadi

Turkish Journal of Chemistry

A new Fe^{3+} ion-selective membrane electrode based on 6-ketomethyl phenanthridine (6-KMPT) and 1-(4-dimethyl aminophenyl)-2-(5H-phenanthridine-6-ylidene)-ethanone, which were incorporated in a plasticized polyvinyl chloride (PVC) membrane, is described. The optimized membrane demonstrated a linear dynamic range of 5.2 \times 10^{-6}-1.0 \times 10^{-2} M, with a near Nernstian slope of 19.5 \pm 1.5 mV per decade and a detection limit of 1.2 \times 10^{-6} M. The electrode showed high selectivity for Fe^{3+} ions in comparison to other metal ions. The effect of membrane composition on the potential response of the electrode was studied. The best performance was observed for the membrane comprised of …

A Facile Method For The Preparation Of Poly(4-Vinylpyridine) Nanoparticles And Their Characterization, Nurettin Sahiner

Turkish Journal of Chemistry

Submicron size particles were synthesized from 4-vinylpyridine (4-VP) using an oil-in-water emulsion system. Divinyl benzene (DVB) and ethylene glycol dimethacrylate (EGDMA) were utilized as crosslinkers for the synthesis of p(4-VP) hydrogel nanoparticles in sodium dodecyl sulfate (SDS) surfactant systems. Characterization of the particles was made by transmission electron microscopy (TEM) and dynamic light scattering (DLS) methods. To render a positive charge, p(4-VP) particles were reacted with 1-bromo butane (1-BB).

Synthesis And Leishmanicidal Evaluation Of Novel 4-Substituted-2,2-Dimethyl-7-(Prop-2-Ynyloxy)Chromenes, Babak H. Alizadeh, Alireza Foroumadi, Susan K. Ardestani, Fatemeh Poorrajab, Abass Shafiee

Turkish Journal of Chemistry

Substituted 4-chromenes were synthesized via the Grignard coupling reaction of various substituted phenyl- and benzylmagnesium chlorides with 2,2-dimethyl-7-(prop-2-ynyloxy)chroman-4-one (1) in relatively good yield (60%-85%). The benzylic-substituted derivatives were a mixture of 2 exo and endo regioisomers, and the exo compounds were a mixture of E and Z isomers. Structural analysis of the exo and endo isomers, as well as E and Z of exo isomers were based on H-NMR, ^{13}C-NMR, and NOESY experiments. The synthetic compounds were examined for in vitro activity against Leishmania major and compound 9 (a, b) was the most active, with inhibitory activity of 36%.

Nitric Oxide Releasing Derivatives Of [(2-Chloroethyl)Ureido] Benzoic Acid Esters As Potential Antineoplastic Agents, Hülya Akgün, Barkin Berk, Di̇lek Demi̇r Erol, Güldem Mercanoğlu, Ömer Faruk Bayrak, Berrak Çağlayan, Asli Dedeağaç, Işil Aksan Kurnaz

Turkish Journal of Chemistry

New series of [(2-chloroethyl)ureido] benzoic acids (compounds 3-8) and nitric oxide releasing derivatives of [(2-chloroethyl)ureido] benzoic acid esters (compounds 9-14) were synthesized as potential anti-cancer agents. These compounds were screened for their anti-proliferative activities on A549 (human lung carcinoma) cells and for their cytotoxic effects on L929 (mouse fibroblast) cells. The compounds 3-8 exhibited mild cytotoxic effects on L929 cells (cell viability from 100% to 85% -- 90% only) whereas they had very little anti-proliferative activities towards A549 lung carcinoma cells. On the other hand, compounds 10, 11, and 13 had some growth inhibition activity in A549 (human lung carcinoma) …

Synthesis And Antimicrobial And Antitumor Activity Of Some New [1,2,4] Triazole-5-One Derivatives, Yasemi̇n Ünver, Esra Düğdü, Kemal Sancak, Mustafa Er, Sengül Alpay Karaoğlu

Turkish Journal of Chemistry

4-[Arylidene-amino]-3-thiophen-2-ylmethyl-4,5-dihydro[1,2,4]triazole-5-one compounds (3a-g) with Schiff base character were obtained from the reaction of 4-amino-3-thiophen-2-ylmethyl-4,5-dihydro-1H-[1,2,4]triazole-5-one (2) with various aldehydes. 1-(2-Oxo-2-phenyl-ethyl)-4-[arylidene-amino]-3-thiophen-2-ylmethyl-4,5- dihydro-1H-[1,2,4]triazole-5-ones (4a-g) were synthesized from the reaction of corresponding compounds 3a-g with bromoacetophenone. 1-(2-Hydroxy-2-phenyl-ethyl)- 3-thiophen-2-ylmethyl-4-[aryl-amino]4,5-dihydro-1H-[1,2,4]triazole-5-ones (5a-g) and 1-(2-hydroxy-2-phenyl-ethyl)-3-thiophen-2-ylmethyl-4-[arylidene-amino] 4,5-dihydro-1H-[1,2,4]triazole-5-ones (6b,d,e) were obtained from the selective reduction of 1-(2-oxo-2-phenyl-ethyl)-4-[arylidene-amino]-3-thiophen-2ylmethyl- 4,5-dihydro-1H-[1,2,4] triazole-5-ones (4) with NaBH_4. They were characterized by IR, H-NMR,^{13}C-NMR, and elemental analyses. Compounds 2, 3a, 3c, 3g, 4f, 5b, and 5g showed good antifungal activity against yeast-like fungi. Compounds selected by the National Cancer Institute (NCI, USA) were investigated for antitumor activity.

Quantitative Structure--Retention Study Of Some 2,4-Dioksotetrahydro- 1,3--Thiazole Derivatives Using The Partial Least Squares Method, Tatjana Djakovic-Sekulic, Costel Sarbu, Nada Perisic-Janjic, Zagorka Lozanov-Crvenkovic

Turkish Journal of Chemistry

Thin-layer chromatography on rice starch support and aqueous ammonia--organic modifier (methanol, dioxane, and acetone) mobile phases was used to study the effect on retention of the chromatographic system and the physicochemical properties of twelve 2,4-dioxotetrahydro-1,3-thiazoles. A multivariate approach to the retention behaviour of the investigated compounds with 3 quite different organic solvents was used to explain the interactions between the 1,3-thiazoles and the mobile phases. Partial least-squares (PLS) regression was used to quantify differences between the observed data and recognize the molecular properties with the greatest effect on retention for each modifier. Good correlation was obtained between experimental and calculated …

Chiral Calixarenes, Abdulkadi̇r Sirit, Mustafa Yilmaz

Turkish Journal of Chemistry

No abstract provided.

Ferric Hydrogen Sulfate As An Efficient Heterogeneous Catalyst For Environmentally Friendly Greener Synthesis Of 1,8-Dioxo-Octahydroxanthenes, Hamid Reza Shaterian, Asghar Hosseinian, Majid Ghashang

Turkish Journal of Chemistry

Ferric hydrogen sulfate was used as an environmentally friendly heterogeneous acidic catalyst for the greener, 1-pot, 3-component synthesis of 1,8-dioxo-octahydroxanthene via condensation reactions between aromatic aldehydes and dimedone under solvent-free thermal and microwave irradiation as well as in aqueous media conditions in short periods of times with excellent yields. The catalyst was easily separated in simple work-up and was recycled several times without loss of reactivity under the described reaction conditions.