The syntheses of novel poly(paraphenyleneethynylene)s, PPEs, and poly(aryleneeethynylene)s, PAEs, as well as hybrid poly(paraphenyleneethynylene)- poly(paraphenylenevinylene)s, PPE-PPVs, are presented. Fluorescent PPEs decorated with biologically relevant ligands are utilized in model biosensing schemes. PPE-PPV hybrids, as well as their highly emissive oligomeric, cruciform model compounds are studied in an effort to modify the bandgap of the parent PPE backbone. Improved hole and electron injection capabilities are demonstrated with these hybrid conjugated materials. Structural variation and morphological effects of PPEs, PPE-PPVs and model compounds are studied to elucidate the effects upon the photophysical properties of the emissive materials.

The main theme of this thesis is to develop a fluorescent probe for imaging the subcellular distribution of kinetically labile copper pools that might play a critical role in copper homeostasis. Various copper-selective sensors were designed by combining 1,3,5-triaryl-2-pyrazoline fluorophores with polythioethers as receptor moieties. A series of donor-substituted 1,3,5-triaryl-2-pyrazoline fluorophores were synthesized and characterized in terms of their photophysical and electrochemical properties. Interestingly, the aryl substituents attached to the 1- and 3-position of the pyrazoline ring influence the photophysical properties of the fluorophore in distinctly different ways. The excited-state equilibrium energy is primarily influenced by changes of the substituent in the 1-position, whereas the reduction potential of the fluorophore is determined by the 3-aryl group. Results from computational analyses agree well with the experimental data. A pyrazoline fluorophore library was synthesized, and their photophysical and electrochemical properties were studied. The compounds cover a broad range of excited state energies and reduction potentials, and allow for selective and differential tuning of these two parameters. A series of thiazacrownethers and tripodal aniline copper(I) receptors were synthesized and their copper binding stoichiometries, stability constants, and copper-self-exchange kinetics were investigated. The measured self-exchange activation parameters revealed for all studied ligands a negative activation entropy, suggesting a predominant associative exchange mechanism. With detailed knowledge of the fluorophore platform and copper receptors, sensor CTAP-1 was designed, synthesized and characterized. The probe shows a 4.6-fold emission enhancement and reaches a quantum yield of 14% upon saturation with Cu(I). The sensor exhibits excellent selectivity towards Cu(I) and is insensitive towards millimolar concentrations of Mg(II) or Ca(II). Mouse fibroblast cells (3T3) incubated with the sensor produced a copper-dependent perinuclear staining pattern, which colocalizes with the subcellular location of the mitochondria and the Golgi apparatus. The subcellular topography of copper was further determined by synchrotron-based x-ray fluorescence (SXRF) microscopy. Furthermore, microprobe x-ray absorption measurements at various subcellular locations showed a near-edge feature that is characteristic for low-coordinate monovalent copper. The data provide a coherent picture with evidence for a kinetically labile copper pool, which is predominantly localized in the mitochondria and the Golgi apparatus.

Thesis (Ph. D.)--Ohio State University, 2009. / Title from first page of PDF file. Includes bibliographical references (p. 268-291).

Thesis (Ph.D)--Polymer, Textile and Fiber Engineering, Georgia Institute of Technology, 2010. / Committee Chair: Tsukruk, Vladimir; Committee Member: Gall, Ken; Committee Member: Griffin, Anselm; Committee Member: Jang, Seung Soon; Committee Member: Thio, Yonathan. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Supramolecular chemists can be thought of as architects, who combine individual non-covalently bonded molecular building blocks, designed to be held together by intermolecular forces to create functional architectures. Perhaps the most important assets of a supramolecular chemist, however, are imagination and creativity, which have given rise to a wide range of beautiful and functional systems. For years, analytical chemistry has taken advantage of supramolecular assemblies in the development of new analytical methods. The role of synthetic supramolecular chemistry has proven to be a key component in this multidisciplinary research. As such, the demand for synthetic receptors is rapidly increasing within the analytical sciences. The field “supramolecular analytical chemistry” involves analytical applications of synthetic organic and inorganic chemical structures that display molecular recognition properties and self-assembly but also signal these events. Chapter 1 presents an introduction to the background literature relevant to the central themes of the research presented in this thesis. The nonthermal production of visible light by a chemical reaction leads to the term “cool light”, and the process is called chemiluminescence. Although chemiluminescent reactions are not rare, the production of “cool light” holds such fascination for both chemists and nonchemists that demonstrations of chemiluminescent reactions are always well received. A glow assay technology for the detection of a chemical warfare simulant is presented in Chapter 2, which is based on modulating the peroxyoxalate chemiluminescence pathway by way of utilizing an oximate super nucleophile that gives an off-on glow response. As an alternative to highly analyte-specific synthetic receptors, trends in chemical sensing have shifted to the design of new materials and devices that rely on a series of chemo- or biosensors. The research relevant to Chapter 3 focuses on investigating the use of a single receptor, for sensing two different analytes; thiols and metal ions, utilizing a squaraine as the receptor in a sensor array format. The data is interpreted with principal component analysis. Finally Chapter 4 discusses an attempt to design and synthesize a chemosensor based on the luminophore-spacer-receptor format by incorporating the two concepts photoinduced electron transfer and peroxyoxalate chemiluminescence. / text

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Not available / text

There is significant need to improve the sensitivity and selectivity for detecting chemical and biological agents. This need exists in a myriad of human endeavors, from the monitoring of production of consumer products to the detection of infectious agents and cancers. Although many well established methodologies for chemical and biological sensing exist, such as mass spectrometry, gas or liquid phase chromatography, enzymelinked immunosorbent (ELISA) assays, etc., it is the goal of the work described herein to outline aspects of two specific platforms which can add two very important features, low cost and portability. The platforms discussed in this dissertation are organic semiconductor field-effect transistors (OFETS), in various architectural forms and chemical modifications, and ion channels immobilized in tethered lipid bilayers integrated with solid state devices. They take advantage of several factors to make these added features possible, low cost manufacturing techniques for producing silicon and organic circuits, low physical size requirements for the sensing elements, the capability to run such circuits on low power, and the ability of these systems to directly transduce a sensing event into an electrical signal, thus making it easier to process, interpret and record a signal. In the most basic OFET functionality, many types of organic semiconductors can be used to produce transistors, each with a slightly different range of sensitivities. When used in concert, they can produce a reversible chemical "fingerprint". These OFETS can also be integrated with silicon transistors - in a hybrid device architecture - to enhance their sensitivity while maintaining their reversibility. The organic semiconductors themselves can be chemically altered with the use of small molecule receptors designed for specific chemicals or chemical functional groups to greatly enhance the interaction of these molecules with the transistor. This increases both sensitivity and selectivity for discrete devices. Specially designed nanoscale OFET configurations with individually addressable gates can enhance the sensitivity of OFETS as well. Finally, ion channels can be selected for immobilization in tethered lipid bilayer sensors which are already inherently sensitive to the analyte of choice or can be genetically modified to include receptors for many kinds of chemical or biological agents. / text

To truly realize and exploit the extremely powerful information given from surface-enhanced Raman scattering (SERS) spectroscopy, it is critical to develop an understanding of how to design highly sensitive and selective substrates, produce specific and label-free spectra of target analytes, and fabricate long-lasting and in-the-field ready platforms for trace detection applications. The study presented in this dissertation investigated the application of two- and three-dimensional substrates composed of highly-ordered metal nanostructures. These systems were designed to specifically detect target analytes that would enable the trace, label-free, and real-time detection of chemicals and biomolecules. Specifically, this work provides new insight into the required properties for maximizing electromagnetic and chemical Raman enhancement in three-dimensional porous alumina substrates by designing metal nanostructure shape, density, aggregated state, and most importantly aligning the substrate pore size with the excitation wavelength used for plasmonic enhancement leading to the ppb detection of vapor phase hazardous chemicals. A new micropatterned silver nanoparticle substrate fabricated via soft lithography with specific functionalization was developed, which allows the simultaneous analyte and background detection for trace concentrations of the target biomolecule, immunoglobulin G. Also, a novel functionalized SERS hot spot fabrication technique, which utilizes highly specific aptamers as both the mediator for electrostatic assembly of gold nanoframe dimers as well as the biorecognition element for the target, riboflavin, to properly locate the tethered biomolecule within the enhanced region for trace detection, was demonstrated. We suggest that the understanding of SERS phenomena that occur at the interface of nanostructures and target molecules combined with the active functionalization and organization of metal nanostructures and trace detection of analytes discussed in this study can provide important insight for addressing some of the challenges facing the field of SERS sensor design such as high sensitivity and selectivity, reliable and repeatable label-free identification of spectral peaks, and the well-controlled assembly of functional metal nanostructures. This research will have a direct impact on the future application of SERS sensors for the trace detection of target species in chemical, environmental, and biomedical fields through the development of specific design criteria and fabrication processes.

The synthesis and biological sensing applications of novel water soluble poly(para-phenyleneethynylene)s (PPEs) are presented. The ease of synthesis, synthetic variability, and dramatic chromicity of PPEs makes them well suited for biological and sensing applications. Molecular recognition and signal transduction can be achieved by using PPEs as sensory materials. By incorporating biological functional groups (e.g. sugars), PPEs can efficiently detect the presence of toxic heavy metals, proteins, and bacteria through either fluorescence quenching or enhancement. Rapid, precise, and convenient sensory arrays for the detection of biological analytes are possible through the formation of gold nanoparticle-PPE constructs.