Chemistry Commons^™

Higher Energy Gap Control Of Fluorescence In Conjugated Polymers, Chien-Hung Chiang

LSU Doctoral Dissertations

Chemo- and biosensors based on fluorescent conjugated polymer benefit from greater detection sensitivity due to amplification of the electronic perturbations produced by analyte binding. This amplification stems from the exciton-transporting properties of conjugated polymers. A conventional design paradigm relies on the analyte binding events which generate sites of lower energy relative to the polymer energy: either fluorescence quenching sites (turn-off sensors) or bathochromically shifted fluorophores (turn-on sensors). In both type sensors, the excitons migrate to the lower-energy site created by analyte binding.

This dissertation primarily focused the investigation of an alternative paradigm when analyte binding creates higher energy gap sites …

Determination Of Atrazine Concentration In Freshwaters Using Fluorescence Spectroscopy, Boniface Osei Amankona

Online Theses and Dissertations

Atrazine is the most widely used herbicides in USA, but its negative impact on aquatic ecosystem cannot be over-looked. Atrazine was traditionally determined through liquid/gas chromatography or IR spectroscopy. However, these methods are either time-consuming or costly, so fluorescence spectroscopy is investigated as a more cost and time efficient alternative. Literature value of the optimal wavelength of atrazine was found to be 350 nm emission. Experimental value for emission scanned of atrazine resulted in an optimal wavelength of 363 nm. Known and unknown concentrations of atrazine will be analyzed using fluorescence spectrophotometer to develop a calibration curve.

The calibration concentration …

Development Of A High Performance Liquid Chromatography Method For The Analysis Of Next-Generation Cyanide Antidote, 3-Mercaptopyruvate, In Plasma, Elaf Alzhrani

Electronic Theses and Dissertations

Although the current FDA approved cyanide antidotes (i.e., sodium nitrite, sodium thiosulfate, and hydoxocoboalamine) are effective for treating cyanide poisoning, each individual antidote has major limitations, including large effective dosage, delayed onset of action, or dependence on enzymes generally confined to specific organs. To overcome these current limitations, next-generation cyanide antidotes are being investigated, including 3-mercaptopyruvate (3-MP). Analytical methods capable of detecting 3-MP from plasma are essential for the development of 3-MP as a nextgeneration cyanide antidote. Although 3-MP has been analyzed by LC-MS-MS, this instrument is not widely available. Therefore, a high performance liquid chromatography (HPLC) method with fluorescence …

Experimental Evaluation Of Uranyl Transport Into Mesoporous Silica Gel Using Fluorescence, Brandon M. Dodd

Theses and Dissertations

This research investigated parameters that can affect the use of nanoporous silica gel as a media for accumulating a detectable amount of uranium. The unique fluorescence of the Uranyl (UO₂²⁺) ion was used to evaluate the transport kinetics and accumulation within silica gel in a static fluid and under pressure driven flow. The addition of fluid flow decreased the time constant from on the order of an hour to approximately 2s with a very low fluid velocity of 0.36cm/s. The 0.36cm/s fluid velocity was found to be the critical velocity above which there was no gain in …

Organelle-Specific Single-Molecule Imaging Of Α4Β2 Nicotinic Receptors Reveals The Effect Of Nicotine On Receptor Assembly And Cell-Surface Trafficking, Ashley M. Fox-Lee, Faruk H. Moonschi, Christopher I. Richards

Chemistry Faculty Publications

Nicotinic acetylcholine receptors (nAChRs) assemble in the endoplasmic reticulum (ER) and traffic to the cell surface as pentamers composed of α and β subunits. Many nAChR subtypes can assemble with varying subunit ratios, giving rise to multiple stoichiometries exhibiting different subcellular localization and functional properties. In addition to the endogenous neurotransmitter acetylcholine, nicotine also binds and activates nAChRs and influences their trafficking and expression on the cell surface. Currently, no available technique can specifically elucidate the stoichiometry of nAChRs in the ER versus those in the plasma membrane. Here, we report a method involving single-molecule fluorescence measurements to determine the …

Real-Time Sensing Of Single-Ligand Delivery With Nanoaperture-Integrated Microfluidic Devices, W. Elliott Martin, Ning Ge, Bernadeta R. Srijanto, Emily Furnish, C. Patrick Collier, Christine A. Trinkle, Christopher I. Richards

Chemistry Faculty Publications

The measurement of biological events on the surface of live cells at the single-molecule level is complicated by several factors including high protein densities that are incompatible with single-molecule imaging, cellular autofluorescence, and protein mobility on the cell surface. Here, we fabricated a device composed of an array of nanoscale apertures coupled with a microfluidic delivery system to quantify single-ligand interactions with proteins on the cell surface. We cultured live cells directly on the device and isolated individual epidermal growth factor receptors (EGFRs) in the apertures while delivering fluorescently labeled epidermal growth factor. We observed single ligands binding to EGFRs, …

From The Making To The Tuning To The Use Of Chlorins For Biomedical Applications, Junior Gonzales

Dissertations, Theses, and Capstone Projects

Chlorins are porphyrins missing a double bond. These pigments are optimal platforms for the development of novel dyes that display drug-like attributes such as photodynamic therapy (PDT) agents. More recently, it was demonstrated that chlorins can serve both as a PDT agent and as a modality for fluorescence or PET imaging. Thus, multifunctional chlorins eliminate the differences that may occur in specificity, uptake, and distribution between separate compounds or constructs for imaging and therapy. The overall goal of this dissertation is to take advantage of the reputed intrinsic attributes of chlorins as a viable tool in biomedical applications. In this …

Formation, Characterization, And Optimization Of Antibody-Gold Nanoparticle Conjugates, Seth L. Filbrun

Theses and Dissertations

Protein modified gold nanoparticle based immunoassays are the basis of many novel detection techniques. There are many groups working on novel immunoassays but there is still much to understand about how many proteins are attached onto each nanoparticle and much to improve on immobilization methods. This thesis work is devoted to improving techniques for the quantification of protein immobilized on the gold nanoparticle and development of a novel approach to immobilize protein independent of pH.

The ability to evaluate antibody immobilization onto gold nanoparticles is critical for assessing coupling chemistry and optimizing the sensitivity of nanoparticle-enabled biosensors. Herein, we developed …

Investigation Of Solvent Effect On Photophysical Properties Of Some Sulfonamides Derivatives, Ebru Bozkurt, Hali̇se İnci̇ Gül, Mehtap Tuğrak

Turkish Journal of Chemistry

The photophysical properties of new sulfonamides synthesized recently were investigated in different solvents. Shifts in the absorption and fluorescence spectra of both compounds (S10 and S11) occurred depending on the solvents used. Ground and excited state dipole moments of the molecules were calculated using the spectral shifts of the compounds in different solvents and polarity function of solvents, respectively. They were 1.32 and 1.46 D for S10 and 1.71 and 4.89 D for S11. These results suggested that the excited state dipole moments are greater than those in ground state for both molecules. This means that the dyes were more …

Investigation Of Photochemical And Photophysical Properties Of Novel Silicon(Iv) Phthalocyanines And Their $\Mu $-Oxo Dimers, Ömer Güngör, Mahmut Durmuş, Vefa Ahsen

Turkish Journal of Chemistry

The synthesis and characterization of novel tetraalkylthio (SC$_{6}$H$_{13}$ or SC$_{12}$H$_{25})$ substituted $\mu $-oxo silicon(IV) phthalocyanines (3a and 3b) and their $\mu$-oxo derivatives (4a and 4b) were described in this study. These silicon(IV) phthalocyanines were characterized using different spectroscopic techniques such as UV-Vis, $^{1}$H NMR, FT-IR, and mass and elemental analysis, as well. Furthermore, the photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of the newly synthesized silicon(IV) phthalocyanines (3a, 3b, 4a, and 4b) were investigated in dimethylformamide solution. The absorption and fluorescence excitation wavelengths of the studied silicon(IV) phthalocyanines were blue-shifted when they converted to their …

Fluorescence Polarization Measurements To Probe Alignment Of A Bithiophene Dye In One-Dimensional Channels Of Self-Assembled Phenylethynylene Bis-Urea Macrocycle Crystals, Preecha Kittikhunnatham

Theses and Dissertations

This thesis describes the use of polarized fluorescence microscopy to directly probe guest molecule orientation in bis-urea macrocycle crystals. These macrocycles assemble to afford one-dimensional (1D) microchannels ∼9 Å in diameter that have previously been shown to exhibit normal Fickian diffusion and induce selective reactivity among the confined guest molecules. In the present work, we take advantage of the quasi-1D morphology of fiber-like microcrystals with the extended dimension corresponding to the channel axis to measure excitation and emission polarization values for a bithiophene guest. Guest fluorescence is shown to be polarized along the fiber axis with emission polarization values up …

Synthesis And Fluorescent Properties Of A New Flavonoid Compound, Ashley L. Ingle

Williams Honors College, Honors Research Projects

Flavonoids are highly luminescent compounds that are used in diagnosing and treating certain diseases.They are composed of two aromatic rings (ring A and ring B) and a six-membered heterocyclic pyran ring (ring C) that contains a carbonyl and hydroxyl group, which are responsible for unique photophysical characteristics associated with flavonoids. The target flavonoids (compound 1, or 1, and compound 2 or 2) were synthesized, purified and characterized by NMR spectroscopy. The photophysical properties of the flavonoid were investigated in varying solvents by using UV-vis and fluorescence spectroscopy. Such properties include Excited State Intramolecular Proton Transfer (ESIPT), Intramolecular Charge …

Quantifying The Interactions Of Nickel With Marine Dissolved Organic Matter Using Fluorescence, Elissa Dow

Theses and Dissertations (Comprehensive)

Nickel (Ni) is a versatile metal with an abundance of applications, namely its role in stainless steel, electronics, and batteries, making it a popular choice in industry. Unfortunately, with increasing demand and production comes higher amounts of Ni pollution. Nickel enters ocean waters - either directly or indirectly - and can have profound effects on marine life. Nickel has been established as a toxicant to a variety of aquatic biota, with the divalent cation (Ni²⁺) thought to be the most bioavailable fraction and thus the most toxic. Having a reliable means of quantifying free Ni ion is pertinent …

Cucurbit[7]Uril-Tetramethylrhodamine Conjugate For Direct Sensing And Cellular Imaging, Andrew T. Bockus, Lauren C. Smith, Amy G. Grice, Omar A. Ali, Carolyn C. Young, William Mobley, Ashley Leek, James Lewis Roberts, Brittany Vinciguerra, Lyle D. Isaacs, Adam R. Urbach

Chemistry Faculty Research

This paper describes the design and synthesis of a conjugate (Q7R) comprising the synthetic host cucurbit[7]uril (Q7) linked to the fluorescent dye tetramethylrhodamine (TMR), and the characterization of its optical and guest-binding properties as well as its cellular uptake. Q7R was synthesized in two steps from monofunctionalized azidobutyl-Q7 and NHS-activated TMR. The fluorescence of Q7R is quenched upon guest binding, and this observable was used to determine equilibrium dissociation constant (K_d) values. Unexpectedly, the K_d values for guests binding to Q7R and to unmodified Q7 were essentially identical. Therefore, Q7R can directly report binding to Q7 without …

Development Of Oligo(P-Phenylene Ehynylene)(Ope) Applications Against Chemical And Biological Threats, Suhyun Yoon

Chemistry and Chemical Biology ETDs

Four new applications of oligo-phenylene ethynylene (OPE) and poly-PE (PPE) compounds for detection and destruction of biological and chemical threats have been investigated. Mixed surfaces composed of PPEs and a thermoswitchable polymer were created, and were shown to be able to capture, kill, and reversibly release pathogenic bacteria. In order to develop fluorescent sensors for CW agents, the spectral changes of OPEs with surfactants and malathion (a simulant for nerve agents) were measured. Formation of OPE-dimers in the presence of surfactants can cause fluorescence enhancement (turn-on) or quenching (turn-off). Among six positive and negative OPEs, only OPEs with ethyl ester …

Rhenium(I) Complexes Of Tetraazatetrapyridopentacene (Tatpp): Synthesis, Characterization, Reactivity, Anticancer Potential And Luminescent Probe To Determine Cellular Localization, Pooja Ahuja

Chemistry & Biochemistry Dissertations - Archive

The ruthenium polypyridyl complexes [(phen)2Ru(tatpp)Ru(phen)2]4+ ([P]4+) and [(phen)2Ru(tatpp)]2+ ([MP]2+) are promising anti-tumor agents that arrest H358 NSCLC tumor growth in mouse tumor models and show cytotoxicity in the low micromolar range towards a number of platinum sensitive NSCLC lines (H358, H226, HOP62, H2087). Dose escalation toxicity studies in mice reveal that [MP]2+ and [P]4+ are tolerated without any short term side effects at levels up to 40 mg drug/kg mouse and >160 mg drug/kg mouse respectively with no obvious side effects, when administered as IP injection. Mechanistic studies reveal that much of the anti-tumor activity is primarily due to the …

A Chemical Sensor For Cyanide, Rachel E. Lambert

Honors Theses

The cyanide ion and its gaseous form, hydrogen cyanide, are extremely toxic. Cyanide impairs cellular respiration by inhibiting cytochrome c oxidase, an enzyme in the electron transport chain, leading to cell death.

In a previous study, we synthesized an optical sensor that detects cyanide selectively. The aim of this project is to increase the sensitivity of this sensor. This can be achieved by utilizing the unique spectroscopic properties of lanthanide ions.

The lanthanide metal (europium or terbium) was added to a coumarin-glycine chemodosimeter in a DMSO solvent system. The sensor was titrated with several monodentate analytes including, nitrate, octylamine, 1-pentanethiol, …

Investigation Of The Interactions Between Pt(Ii) And Pd(Ii) Derivatives Of 5,10,15,20-Tetrakis (N-Methyl-4-Pyridyl) Porphyrin And G-Quadruplex Dna, Navin C. Sabharwal , '14, O. Mendoza, John Michael Nicoludis , '12, Thomas Ruan , '16, J.-L. Mergny, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

G-quadruplexes are non-canonical DNA structures formed by guanine-rich DNA sequences that are implicated in cancer and aging. Understanding how small molecule ligands interact with quadruplexes is essential both to the development of novel anticancer therapeutics and to the design of new quadruplex-selective probes needed for elucidation of quadruplex biological functions. In this work, UV–visible, fluorescence, and circular dichroism spectroscopies, fluorescence resonance energy transfer (FRET) melting assays, and resonance light scattering were used to investigate how the Pt(II) and Pd(II) derivatives of the well-studied 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP4) interact with quadruplexes formed by the human telomeric DNA, Tel22, and by the G-rich sequences …

Fluorescence Of Supported Phospholipid Bilayers Recorded In A Conventional Horizontal-Beam Spectrofluorometer, Elizaveta A. Kovrigina, Evgeni L. Kovrigin

Chemistry Faculty Research and Publications

Supported phospholipid bilayers are a convenient model of cellular membranes in studies of membrane biophysics and protein-lipid interactions. Traditionally, supported lipid bilayers are formed on a flat surface of a glass slide to be observed through fluorescence microscopes. This paper describes a method to enable fluorescence detection from the supported lipid bilayers using standard horizontal-beam spectrofluorometers instead of the microscopes. In the proposed approach, the supported lipid bilayers are formed on the inner optical surfaces of the standard fluorescence microcell. To enable observation of the bilayer absorbed on the cell wall, the microcell is placed in a standard fluorometer cell …

Synthesis And Photochromism Of New Asymmetrical Diarylethenes With A Variable Heteroaryl Ring And A Quinoline Unit, Hongyan Xu, Renjie Wang, Congbin Fan, Gang Liu, Shouzhi Pu

Turkish Journal of Chemistry

Three new asymmetrical photochromic diarylethenes containing a variable heteroaryl ring and a quinoline unit were synthesized and their structures were determined by single-crystal X-ray diffraction analysis. Their properties, including photochromism, acidichromism, and fluorescence, were investigated systematically. For these diarylethenes, the one with an indole moiety had the largest absorption maximum, cyclization quantum yield, photoconversion ratio, emission peak, and fluorescent modulation efficiency. In addition, these diarylethenes exhibited an evident dual switching behavior induced by the stimulation of acid/base and UV/Vis. Addition of trifluoroacetic acid to solution of the diarylethenes produced protonated derivatives with notable changes in their absorption spectra. These results …

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

Kinetic Decay Of A Polymer/Ink Complex As An O2 Indicator, Becca Hoene

All Master's Theses

Indicator inks are an important part of the continued consumption of packaged goods. This thesis is focused on understanding the kinetics and reaction mechanism for a unique indicator ink that is based upon the oxidation of indigotetrasulfonate (ITS) encapsulated in the polyelectrolyte poly(diallyldimethylammonium chloride) (polyDADMAC). Sodium bisulfite (NaHSO₃) was used as the initial oxygen scavenger and to drive the reduction of the ITS. Studies were predominantly done in solution phase through the dilution of the ink systems. Fluorescence spectroscopy was the primary method used to determine the kinetic decay rates and interaction between the ITS dye molecules and …

Physical Property Control In Core/Shell Inorganic Nanostructures For Fluorescence And Magnetic Targeting Applications, Stephen K. Roberts

Theses and Dissertations

Nanomaterials show immense promise for the future in numerous areas of application. Properties that are unique from the bulk material and are tunable allow for innovation in material design. This thesis will focus on controlling the physical properties of core/shell nanostructures to enhance the utility of the materials.

The first focus is on the impact of different solvent mixtures during the shell growth phase of SILAR based core/shell quantum dot synthesis is studied. Gaining insight into the mechanism for SILAR growth of core/shell nanoparticles allows improved synthetic yields and precursor binding, providing enhanced control to synthesis of core/shell nanoparticles. The …

Fabrication, Characterization, And Application Of Carbon Nanoparticles For The Detection Of Heavy Metal Ions In Aqueous Media, Aaron Michael Simpson

Graduate Theses/Dissertations

This research set out to develop a method for producing Carbon nanoparticles (CNPs) from glycerol and use them to detect Cu2+, Hg2+, and Pb2+ ions in aqueous solution. Three synthesis methods were developed using the following mixtures: (1) glycerol and silica, (2) glycerol, silica, and H3PO4, and (3) glycerol with H3PO4. The structure of the particles was characterized using a variety of spectroscopic techniques. Size distributions were obtained from scanning electron microscopy images. The particles were spherical with average diameters of 66, 58, and 89 nm respectively and believed to consist of a carbon core with carboxylic acid and alcohol …

Influence Of Shelling Temperature And Time On The Optical And Structural Properties Of Cuins2/Zns Quantum Dots, Colette Robinson

Graduate Theses and Dissertations

CIS/ZnS core/shell QDs are an important class of nanomaterials for optoelectronic, photovoltaic and photoluminescence applications. They consist of lower toxicity materials than the prototypical II-VI Cd-based QDs and show long fluorescence lifetimes, which generates prospective in biological imaging applications. It is vital to develop reproducible synthetic methods for this new class of nanomaterials in order to maintain small sizes with high QYs. CIS core QDs have been shelled with ZnS at various temperatures from 90-210°C for reaction times ranging from 20-140 minutes to examine the role of thermodynamics and kinetics on the shell growth. Using HR-TEM and ICP-MS, it was …

The Nicotine Metabolite, Cotinine, Alters The Assembly And Trafficking Of A Subset Of Nicotinic Acetylcholine Receptors, Ashley M. Fox, Faruk H. Moonschi, Christopher I. Richards

Chemistry Faculty Publications

Exposure to nicotine alters the trafficking and assembly of nicotinic receptors (nAChRs), leading to their up-regulation on the plasma membrane. Although the mechanism is not fully understood, nicotine-induced up-regulation is believed to contribute to nicotine addiction. The effect of cotinine, the primary metabolite of nicotine, on nAChR trafficking and assembly has not been extensively investigated. We utilize a pH-sensitive variant of GFP, super ecliptic pHluorin, to differentiate between intracellular nAChRs and those expressed on the plasma membrane to quantify changes resulting from cotinine and nicotine exposure. Similar to nicotine, exposure to cotinine increases the number of α4β2 receptors on the …

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

Structural And Functional Analysis Of The Reaction Center Complexes From The Photosynthetic Green Sulfur Bacteria, Guannan He

Arts & Sciences Graduate Student Theses and Dissertations

The reaction center (RC) complex of the green sulfur bacterium Chlorobaculum tepidum is composed of the Fenna-Matthews-Olson (FMO) antenna protein and the reaction center core (RCC) complex. The RCC complex has four subunits: PscA, PscB, PscC, and PscD. The structure of the intact and functional FMO-RCC complex was studied by chemically cross-linking the purified sample followed by biochemical and spectroscopic analysis. The interaction sites of the cross-linked complex were also studied using LC-MS/MS. A structural model is proposed based on those results. In addition, the RCC complexes were purified, both the PscA-PscC complex from the Chlorobaculum tepidum and the PscA-PscB …

Studies Of Optical And Electronic Properties Of Nanoparticles For Solar Energy Conversion, Caitlin Kruse, Libai Huang

The Summer Undergraduate Research Fellowship (SURF) Symposium

The higher energy needs for today's technological society requires sustainable and renewable energy source, such as solar energy. This study focuses on using semiconducting quantum dots and fluorescent dyes as light absorbers for solar energy conversion devices such as solar cells. Quantum dots are small nanocrystals (usually 2-10 nm in diameter) with tunable absorbing properties. The smaller the dot, the shorter the wavelength being absorbed. Quantum dots are extremely efficient light absorbers and emitters. Fluorescent dyes have a high quantum yield. In order to examine the energy conversion, cadmium selenide (CdSe) quantum dots and Rhodamine 6G (R6G) dye were spin …

A Structurally-Tunable 3-Hydroxyflavone Motif For Visible Light-Induced Carbon Monoxide-Releasing Molecules (Corms), Stacey N. Anderson, Jason M. Richards, Hector J. Esquer, Abby D. Benninghoff, Atta M. Arif, Lisa M. Berreau

Chemistry and Biochemistry Faculty Publications

Molecules that can be used to deliver a controlled amount of carbon monoxide (CO) have the potential to facilitate investigations into the roles of this gaseous molecule in biology and advance therapeutic treatments. This has led to the development of light-induced CO-releasing molecules (photoCORMs). A goal in this field of research is the development of molecules that exhibit a combination of controlled CO release, favorable biological properties (e.g., low toxicity and trackability in cells), and structural tunability to affect CO release. Herein, we report a new biologically-inspired organic photoCORM motif that exhibits several features that are desirable in a next-generation …