A conjugated bis-benzimidazole chromophore is predicted to show absorptions in the near-infrared (NIR) region of the electromagnetic spectrum. However, there are no reports to-date of any NIR absorbing and emitting dyes that are based on a bis-benzimidazole structural backbone. This thesis reports recent advancements in the discovery and study of this new class of dyes. Following literature procedures, the syntheses of bis(benzimidazolyl)methane compounds are successful. An unexpected product isolated during the attempted oxidation of a bis(benzimidazolyl)methane compound using p-chloranil showed intense absorption in the NIR (λmax = 712 nm, ε = 14600 L·mol-1·cm-1), solubilities in polar solvents like methanol and water, and electrochemical activities. X-ray crystallography, mass spectrometry, and NMR spectroscopy confirmed the connectivity and structure of the product to contain a combination of quinone and benzimidazole moieties, which later revealed to be the core chromophore by computational studies. This unprecedented combination of moieties gave a chromophore that is predicted to absorb in the far-red even without substitution. Attempts to synthesize boron-based bis-imidazole dyes with N-methylation shed light on the feasibility of the design of such moiety. Considering the additional functionality that could be accessed through the methylation of the labile benzimidazole nitrogen atoms, N-methylated bis(benzimidazolyl)methane precursors were successfully synthesized and fully characterized. Attempts of the boron coordination showed promising signs, as the 1H, 11B, and 19F NMR spectra showed solid evidence of the successful isolation of the boron chelate. Computational studies of methyl, phenyl, and triazole-substituted boron chelate derivatives projected absorptions in the NIR region. Intense transitions are found to be based on frontier molecular orbitals and differ significantly among the derivatives, predicting substantial tunability of this type of dyes. / Graduate / 2022-02-18

Supramolecular chemistry - chemistry of non-covalent bonds including different type of intermolecular interactions viz., ion-pairing, ion-dipole, dipole-dipole, hydrogen bonding, cation-p and Van der Waals forces. Applications based on supramolecular concepts for developing catalysts, molecular wires, rectifiers, photochemical sensors have been evolved during recent years. Mimicking natural photosynthesis to build energy harvesting devices has become important for generating energy and solar fuels that could be stored for future use. In this dissertation, supramolecular chemistry is being explored for creating light energy harvesting devices. Photosensitization of semiconductor metal oxide nanoparticles, such as titanium dioxide (TiO2) and tin oxide (SnO2,), via host-guest binding approach has been explored. In the first part, self-assembly of different porphyrin macrocyclic compounds on TiO2 layer using axial coordination approach is explored. Supramolecular dye sensitized solar cells built based on this approach exhibited Incident Photon Conversion Efficiency (IPCE) of 36% for a porphyrin-ferrocene dyad. In the second part, surface modification of SnO2 with water soluble porphyrins and phthalocyanine resulted in successful self-assembly of dimers on SnO2 surface. IPCE more than 50% from 400 - 700 nm is achieved for the supramolecular self-assembled heterodimer photocells is achieved. In summary, the axial ligation and ion-pairing method used as supramolecular tools to build photocells, exhibited highest quantum efficiency of light energy conversion with panchromatic spectral coverage. The reported findings could be applied to create interacting molecular systems for next generation of efficient solar energy harvesting devices.

Porphyrins offer a very synthetically flexible template which can be modified in numerous ways to synthesize molecules with very useful properties applicable in areas such as non-linear optical properties, photodynamic therapy, dye-sensitized solar cells, chemical sensors and organic electronic devices. β-Substituted π-extended porphyrins offer unique capabilities in tuning the properties of the molecule towards practical applications. Increased π-conjugation allows the HOMO-LUMO gap to decrease and hence to redshift the absorption into the near-IR region. β-Fused benzoporphyrins offer additional benefits in which the benzene ring itself can be further modified using electron donating substituents and electron donating substituents to electronically tune these porphyrins for various uses. The goal of the research pursued in this dissertation was to develop new methods for the development of β-Substituted π-extended porphyrins and to study their optical and electronic properties. To accomplish this goal, we developed new method to synthesize A2B2 type tetrabenzoporphyrins and we studied the electron transfer in such systems. We also studied the effectiveness of such systems in dye sensitized solar cells. A new method to synthesize functionalized naphthalene fused porphyrins was also developed and we were also able to use this method to synthesize a push-pull naphthalene fused porphyrin.

Small-molecule inhibitors of tau fibrillization are under investigation as tools for interrogating the tau aggregation pathway and as potential therapeutic agents for Alzheimer's disease. Established inhibitors include thiacarbocyanine dyes, which can inhibit recombinant tau fibrillization in the presence of anionic surfactant aggregation inducers. In an effort to increase inhibitory potency, a cyclic bis-thiacarbocyanine molecule containing two thiacarbocyanine moieties was synthesized and characterized with respect to tau fibrillization inhibitory activity by electron microscopy and ligand aggregation state by absorbance spectroscopy. Results showed that the inhibitory activity of the bis-thiacarbocyanine was qualitatively similar to a monomeric cyanine dye, but was more potent with 50% inhibition achieved at ∼80 nM concentration. At all concentrations tested in aqueous solution, the bis-thiacarbocyanine collapsed to form a closed clamshell structure. However, the presence of tau protein selectively stabilized the open conformation. These results suggest that the inhibitory activity of bis-thiacarbocyanine results from multivalency, and reveal a route to more potent tau aggregation inhibitors.

Gels are colloidal states of matter in which a solid matrix is dispersed in a liquid phase. Supramolecular gels are formed due to the self-assembly of small gelator molecules in a suitable solvent as a result of specific weak non-covalent interactions between the gelators. The last several decades have witnessed an upsurge in research activities in the area of supramolecular gels not only for academic interests but also for applications in material science. Gels have been investigated as potential avenues for drug delivery and oil recovery applications. Despite their huge potential, the properties of gels are discovered through trial-and-error approaches, which makes control of properties a challenging task. The control becomes extremely hard in a multicomponent gel system, which is a common model for applications in material science. The aim of this thesis is to design a pathway to gain a fundamental understanding on how multiple components in the gel contribute to new properties. This pathway is an attempt to move away from trial-and-error approaches for the development of gels and allows us to make correlations between structure, dynamics and function. The studies reported in this thesis were performed on a two-component gel system comprising a gelator and an additive. The gelator, sodium deoxycholate (NaDC), is a bile salt known for its ability to form a supramolecular gel within a certain pH range. NaDC gels are made up of aggregates distributed between the aqueous phase and the gel structure. NaDC gels are reversible and considered as promising candidates from a functional point of view. The additive, cucurbit[6]uril (CB[6]), is a macrocycle and is known to affect the mechanical properties of NaDC gels at the macroscopic level. In the first project, I studied the effect of CB[6] on the NaDC gel at the microscopic level using dynamic light scattering and fluorescence microscopy experiments. These techniques were used to determine the effect of CB[6] on the gel’s morphology, size of NaDC aggregates, thermo-reversible properties of NaDC gels and the kinetics of NaDC gel formation. My results showed that the effect of CB[6] on NaDC aggregates begins in solutions and is translated to sols and gels. Thermo-reversibility and kinetic studies showed that the effect of CB[6] on NaDC gels goes beyond changes to the gel’s structure and CB[6] was also shown to affect both the gel-sol transition temperatures and time of the gel formation. In the second project, I studied how the release of dyes of different hydrophobicities from NaDC gels was affected by the addition of CB[6]. The release of the dyes pyrene and rhodamine 6G was investigated using a static diffusion method, which was referred to as the top layer method. My results showed that CB[6] has a different effect on the release kinetics of a hydrophilic dye compared to the release of a hydrophobic dye. The observed difference in the release kinetics was attributed to differences in the localization of the dyes in NaDC gels and the role of CB[6] in affecting the distribution of dyes in different regions in the gel. In the third project, I studied the colocalization of a hydrophobic and a hydrophilic dye in NaDC-CB[6] gels with the goal to confirm my hypothesis from the release studies. Dynamics of diffusion of dyes within NaDC-CB[6] gels was investigated using the fluorescence recovery after photobleaching (FRAP) technique. Results from colocalization experiments showed that the addition of CB[6] changes the distribution of hydrophilic dye in the gel. Through colocalization experiments, I was able to showcase the active role of CB[6] in incorporating aggregates from the aqueous phase into the gel structure. Results from FRAP studies showed that, in the presence of CB[6], recovery after bleaching of a hydrophobic dye in the gel structure is slower compared to the dye in the NaDC gel structure. / Graduate

In order to become a viable alternative to silicon photovoltaics, dye-sensitized solar cells must overcome several issues primarily resulting from their use of a liquid electrolyte. Much research has gone into correcting these shortcomings by replacing the liquid electrolyte with solid-state hole-transport media. Using these solid-state materials brings new difficulties, such as completely filling the pores in the TiO₂nanostructure, and achieving good adhesion with the dye-coated TiO₂. A novel approach to addressing these difficulties is the inverse dye-sensitized solar cell design. In this method the devices are constructed in reverse order, with the solid-state hole-transport medium providing the nanostructure instead of the TiO₂. This allows new materials and methods to be used which may better address these issues. In this project, inverse dye-sensitized solar cells using polyaniline nanofibers as the hole transport medium were prepared and characterized. The devices were prepared on fluorine-doped tin oxide (FTO) coated glass electrodes. The first component was a dense spin-coated polyaniline blocking layer, to help prevent short circuiting of the devices. The second layer was a thin film of drop cast polyaniline nanofibers which acted as the hole transport medium and provided high surface area for the dye attachment. The dye used was 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP), which was covalently attached to the nanofibers using a Friedel-Crafts acylation. Titania gel was then deposited into the pores of the nanofiber film by controlled hydrolysis of a titanium complex (Tyzor LA). A back electrode of TiO₂nanoparticles sintered on FTO was pressed on top to complete the devices. A typical device generated an open circuit voltage of 0.17 V and a closed circuit current of 5.7 nA/cm² while the highest open circuit voltage recorded for any variation on a device was 0.31 V and the highest short circuit current was 52 nA/cm² under AM 1.5 simulated olar spectrum at 100 mW/cm². Initially prepared devices did not generate a measureable photocurrent due to two materials flaws. The first was traced to the poorly developed conduction band of the titania gel, as deposited from Tyzor LA hydrolysis, resulting in poor electron conduction. This prevented the titania gel from efficiently functioning as the electron transport medium. A remedy was found in adding a layer of sintered anatase TiO₂nanoparticles on the back electrode to serve as the electron transport medium. However, this remedy does not address the issue of the inability of titania gel to efficiently transport electrons photogenerated deep in the nanofiber film to the back electrode. The second flaw was found to originate from fast recombination kinetics between electrons in TiO₂and holes in polyaniline. However, a positive feature was that the titania gel intended to be used as the electron transport medium was found to sufficiently insulate the interface such that the recombination rate slowed enough to allow generation of a measureable photocurrent. Electronic insulation was further enhanced by co-attaching decanoic acid onto the polyaniline nanofibers to fill in pinholes between the dye molecules. While these solutions were not ideal, they were intended to be diagnostic in nature and supplied critical information about the weak links in the device design, thus pointing the way toward improving device performance. Significant enhancements can be expected by addressing these issues in further detail.

No description available.

Groundwater flow through fractured karst conduit systems can be complex and difficult to diagnose. This project explores the role of geologic structures that influence the location of recharge points, flow paths, velocities, and discharge locations within Morrell Cave and at the resurgence of Morrell Spring, both of which are located near the city of Bluff City, TN. Understanding of the groundwater sources and flow paths in the Bluff City area will allow future researchers to more readily identify sources of pollution and better resolve local agricultural well drawdown conflicts among residents. The objectives of this project are to: 1) identify the active allogenic recharge sources of Morrell Spring, the largest known spring in the Bluff City area; 2) delineate a springshed for Morrell Spring and; 3) diagnose the structural controls for groundwater flow paths to Morrell Spring. It was found that surface streams flowing across the Sevier Shale on the northern slope of Holston Mountain enter the subsurface karst system through swallets along the Sevier shale and the Jonesboro Limestone contact. Once underground the water flows to the NW following 2 dominant joint sets until it reaches the NE/SW oriented fault line along which Morrell Cave has formed. Upon entering the cave the groundwater flows to the NE to Morrell Spring and into the South Fork Holston River.

In the paper industry the appearance and optical performance of coated and uncoated paperboard is important, therefore colour dyes are widely used to enhance the paperboard. In order to enhance the appearance of paper products, the dyes are added directly into the pulp and/or in the coating. This addition can lead to dye buildup in the white water system. The white water system recirculates back to the pulp and contains both chemicals, dye and fibers. A general assumption is, when the concentration of dyes builds up in the system, it can lead to changes of the optical properties. Previously studies have been conducted to investigate the white water system at Iggesund Paperboard Workington Ltd. mill. Suspicion of a potential dye buildup in the white water system arose because of notable changes in the optical properties of the collected samples. An assumption was, when the concentration of dye increases in the white water system, it led to changes of the optical properties. The purpose of this project was therefore to investigate if/how potential dye buildup occurred in the white water system at Iggesund paperboard Workington Ltd. Mill. The system will be analyzed for dye buildup and to see if it influences the optical properties of the coated paperboard as a final product as well as how quickly it builds up in the system. This report contains a theoretical background for relevant knowledge about the white water system and optical properties of paperboard. The methodology for this project was to collect samples from the boardmachines’ white water system and analyze them through laboratory trials. Collected data is presented in the form of diagrams, trends have been investigated to validate assumptions. The dye dosage point was also analyzed through laboratory trials, to confirm or deny whether it is possible to achieve an optimal dosage point. The analysis showed that there were changes in the optical properties in the white water over time, as a result of dye buildup. Due to the complex system and different parameters that may affect the system, the sample collection needs to be extended further for a more precise conclusion. Such as how the dye responds to longer shuts and addition of polymers. Apart from what influenced the optical changes in the white water system and may have affected the paperboard, when the top coating from the production is applied, no changes or variations cannot be seen. Therefore giving the conclusion, that the changes of the optical properties do not influence the paperboard as a final product. / Kartong är bland de vanligaste materialen att använda vid paketering. Den optiska egenskapen hos kartong är viktig för att den ska se tilltalande ut, samt vara mottaglig för tryck. Användning av färg är vanligt förekommande inom pappersindustrin för att förbättra de optiska egenskaperna i obelagt papper och belagt papper. Färgen tillsätts vanligen direkt i pappersmassan och vid bestrykning av beläggningen. Dock kan det leda till övermättnad i bakvattnet när man tillsätter färgen direkt i massan, vilket i sin tur kan påverka och även förändra de optiska egenskaperna. Bakvattnet recirkuleras i processen tillbaka till massaflödet då vattnet fortfarande innehåller användbara kemikalier, färg och fibrer som kan ansluta sig till massaflödet igen. Skulle det ske förändringar av de optiska egenskaperna behöver doseringen av färgen förändras vid beläggningen, vilket i sin tur kan leda till överdosering av färgen. Tidigare studier gällande bakvattensystemet vid Iggesund Paperboard Workington Ltd. mill har gjorts. Förändringar i de optiska egenskaperna från samlade prover från bakvattnet resulterade i misstankar av en potentiell ökning av färg i systemet. Detta utmynnade i antagandet att den ökande koncentrationen av färg i bakvattensystemet, i slutändan orsakar optiska förändringar. Syftet med detta projekt var därför att undersöka denna potentiella färgökning i bakvattensystemet vid Iggesund paperboard Workington Ltd. Mill. Bakvattensystemet har analyserats för att se en ökad färgkoncentration och om dessa optiska förändringar påverkar slutprodukten, samt hur snabbt färgens koncentration ökar. Denna rapport innehåller en teoretisk bakgrund för bland annat bakvattensystemet samt de optiska egenskaperna hos kartong. Metodiken för projektet var att samla prover från kartongmaskinens bakvattensystem och att analysera dessa prover. Insamlad data presenteras i diagram och trender undersöktes, för att validera antaganden modellerades trender. Doseringen av färgen undersöktes genom försök, för att kunna bekräfta om det är möjligt att upptäcka en optimal doseringspunkt. Analyserna visar att det sker förändringar i dem optiska egenskaperna över tid, som ett resultat av en ökad koncentration av färg. Då systemet är komplext och olika parametrar kan ha påverkat, behöver denna undersökning förlängas för en säkrare slutsats. Till exempel hur långa stop och hur addition av polymerer påverkar processen. Bortsett från vad som påverkar de optiska förändringarna i bakvattnet och kan påverka slutprodukten, när kartongen bestryks med beläggning, kan inga förändringar/variationer ses. Därför ges slutsatsen, att förändringar i de optiska egenskaperna i bakvattnet inte påverkar kartongen som slutprodukt.

Two indole-based squaraine dyes bonded to two pyrenyl groups through vinyl- and ethynyl- linkers were synthesized with the aim of enhancing the intramolecular charge transfer interaction in addition to improving their optical properties. The absorption and emission properties of these derivatives were determined in order to gain an insight into the intensity of this type of interaction, their aggregation behavior and compare them with results obtained through quantum chemical calculations. Both compounds presented high photochemical stability in THF, and the linear spectroscopic characterization revealed high extinction coefficients, large fluorescence quantum yields and relatively low tendency of forming excimers in several solvents. The nonlinear spectroscopic study revealed two-photon absorption cross section maxima greater than 10,000 GM (1 GM = 1 × 10-50 cm4 s/photon), which are improved values in comparison with the indole-based squaraine core. The experimental results were compared with time-dependent DFT calculations. These observations propose a new trend in the formulation of highly absorbing organic molecules containing pyrenyl groups for the development of new materials with Organic Light-Emitting Diode (OLED) applications. Moreover, this work contributes to the study of intramolecular charge transfer interaction and its tailoring for the improvement of the linear and nonlinear optical properties.