This thesis presents the first reported grafted PPE - polycaprolactone-g-PPE; the first PPE based sensing model: biotinylated grafted PPE/streptavidin coated sphere; the first photocrosslinkable PPE ¨C allyloxy PPE; and the new mechanism which demonstrates morphology control on a single molecular level

Dendritic encapsulation of poly(phenyleneethynylene)s or PPEs has been shown to enhance photoluminescent quantum efficiency and facilitate energy transfer by funneling photonic energy absorbed on the dendron periphery efficiently to the conjugated polymeric core. The research presented herein focuses on incorporating degradable dendron onto PPEs, examining whether or not similar benefits were conferred upon the proposed system and controlling polymer luminescence through the elimination of the insulating macromolecules. PPEs appended with disassembling dendrons of various generation sizes were synthesized and their optical properties studied. Polymer luminescence was then quenched via chemical degradation of the disassembling dendrons. Furthermore, the macromolecules resulting from disassembly exhibited tunable luminescence properties upon manipulation of pH. Consequently, it was determined that polymer luminescence could be controlled upon forming phenolic moieties along the PPE backbone. Tunable emission was later realized in the thin film as well through the integration of crosslinkable dendrons onto the polymer core.Recently, helical synthetic linear polymers have demonstrated the ability to facilitate stereoselective processes such as catalysis, recognition and separation. Consequently, it has become increasingly desirable to develop new platforms capable of imparting asymmetry. The work presented herein describes the synthesis of a series of polymers based upon chiral hydrobenzoin and the subsequent conformational analysis performed on these materials. It was envisioned that these polymeric materials might inherently possess conformational asymmetry and as result could be able to impart configurationally chirality by introducing a diastereomeric bias for the formation of one enantiomer over the other during the course of the reaction.

<p dir="ltr">Prevention of the spread of diseases caused by airborne biological pathogens is of great concern. This was highlighted by the Covid-19 Pandemic, which was caused by the SARS-CoV-2 virus. One method for preventing the transmission of airborne pathogens is UV-C irradiation, which has been proven to effectively inactivate a wide range of airborne pathogens, including influenza viruses and coronaviruses. Disinfection of air using UV-C is usually employed through upper-room Ultraviolet Germicidal Irradiation (UVGI), UV-C based air cleaners in HVAC ducts, or stationary cabinets. In the research presented herein, near-field applications of UV-C disinfection are explored through implementation in personal protective equipment.</p><p dir="ltr">A series of personal protective devices were developed for real-time inactivation of airborne pathogens in military or civilian applications. The devices use UV-C radiation from low-pressure mercury lamps (254 nm) and UV-C LEDs (nominally 277 or 282 nm) to inactivate airborne pathogens that are inhaled or exhaled by users, thereby reducing the risk of disease transmission. The devices employ Porex PMR20, a material highly reflective of UV-C radiation, to promote photon recycling and improve the fluence rate fields inside the reactors. To quantify the efficacy of these UV-C devices, testing procedures were developed and applied. A two-part procedure was employed: (1) measurement of the fluence rate using the Micro Fluorescent Silica Device (MFSD) together with a positioning device and (2) biological experiments using T1 bacteriophage as an aerosolized challenge agent to quantify virus inactivation.</p><p dir="ltr">The fluence rate measurements were completed by fixing the location of the MFSD probe and moving the reactors to precise locations using the positioning device. The MFSD measurements were converted to fluence rate using measurements from an NIST-calibrated radiometer and collimated UV-C sources. When comparing the measurements with and without the PMR20, the local fluence rate for the LED reactors was found to be amplified by up to 10 times the value without the PMR20. A central peak was also found for both LED reactors, which was not present in measurements without the PMR20. Of the two LED reactors, the Nichia Reactor was found to have higher peaks in fluence rate, probably due to the higher output from the LEDs when compared to the JLED LEDs. The LP Hg Pod was found to have less significant amplification from the PMR20, with the maximum amplification being only 3 times the value without PMR20. The fluence rate near the walls lined with PMR20 was found to have the highest amplification for the Pod reactor, due to the lamp being located at the center of the reactor (unlike the LED reactors, where UV-C sources were positioned along the reactor walls).</p><p dir="ltr">The biological experiments were conducted using aerosolized T1 bacteriophage as a challenge agent. T1 was selected for these experiments because it has been shown to be more resistant to inactivation at the wavelengths of interest than most airborne pathogens; as such, T1 is a conservative surrogate for airborne pathogens in these applications. Experiments were conducted first at one flow rate and subsequently at a range of flow rates to quantify the effectiveness of the reactors and the impact the PMR20 on the inactivation response. When tested at the lowest flow rate of 2.5 L/min, all three reactors were found to provide inactivation at least as effective as the nominal removal provided by an N95 mask (95% or 1.3 log₁₀ units). The LP Hg Pod reactor was found to provide at least this level of inactivation (1.3 log₁₀ units) at flow rates up to 52.5 L/min when PMR20 lined the reactor. When tested without the PMR20, the loss in inactivation was substantial at 52.5 L/min but not at the lower flow rates.</p><p dir="ltr">The testing protocol developed and applied in this project could be applied to a range of other reactors intended for disinfection of air. A need exists to standardize testing and validation methods for UV-C based reactors and devices that are used to disinfect air. As such, the methods described herein may allow translation to other UV-C based devices.</p>

This research serves as a meticulous examination into cross-conjugated materials and how alterations of the frontier molecular orbitals can be utilized for applications in "chemical tongue" organic sensing devices. With conjugated materials being used in the development of new sensory devices for detection of metals, bacteria, and chemical warfare agents, the field of organic sensing is growing faster than ever. The purpose of this dissertation is to provide a precedence for the synthesis of new cross-conjugated compounds and outline potential applications of these materials as chemical sensors and molecular probes.