abstract: Photosynthesis, one of the most important processes in nature, has provided an energy basis for nearly all life on Earth, as well as the fossil fuels we use today to power modern society. This research aims to mimic the photosynthetic process of converting incident solar energy into chemical potential energy in the form of a fuel via systems capable of carrying out photo-induced electron transfer to drive the production of hydrogen from water. Herein is detailed progress in using photo-induced stepwise electron transfer to drive the oxidation of water and reduction of protons to hydrogen. In the design, use of more blue absorbing porphyrin dyes to generate high-potential intermediates for oxidizing water and more red absorbing phthalocyanine dyes for forming the low potential charge needed for the production of hydrogen have been utilized. For investigating water oxidation at the photoanode, high potential porphyrins such as, bis-pyridyl porphyrins and pentafluorophenyl porphyrins have been synthesized and experiments have aimed at the co-immobilization of this dye with an IrO2-nH2O catalyst on TiO2. To drive the cathodic reaction of the water splitting photoelectrochemical cell, utilization of silicon octabutoxy-phthalocyanines have been explored, as they offer good absorption in the red to near infrared, coupled with low potential photo-excited states. Axially and peripherally substituted phthalocyanines bearing carboxylic anchoring groups for the immobilization on semiconductors such as TiO2 has been investigated. Ultimately, this work should culminate in a photoelectrochemical cell capable of splitting water to oxygen and hydrogen with the only energy input from light. A series of perylene dyes bearing multiple semi-conducting metal oxide anchoring groups have been synthesized and studied. Results have shown interfacial electron transfer between these perylenes and TiO2 nanoparticles encapsulated within reverse micelles and naked nanoparticles. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time. Photoinduced electron transfer from the singlet excited state of the perylenes to the TiO2 conduction band is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2. / Dissertation/Thesis / Ph.D. Chemistry 2013

Ultraviolet A is a major spectral component of solar electromagnetic energy reaching the surface of the earth. Excessive exposure to solar UVA is a known contributor to skin photoaging and photocarcinogenesis, associated with increased incidence rates and a significant health burden imposed by skin cancer worldwide. However, the molecular mechanisms underlying UVA-induced skin photodamage remain largely undefined. UVA radiation has been shown to cause cutaneous oxidative stress and photosensitization reactions involving the light-driven photochemistry of specific skin chromophores upstream of reactive oxygen species formation, recognized as key players in skin photooxidative damage. Consequently, there has been significant interest in the identification of endogenous compounds that facilitate these reactions serving as endogenous photosensitizers. In my graduate research, we assessed the potential of selected endogenous chromophores, pyridoxal and 6-formylindolo[3,2-b]carbazole (FICZ), to elicit UVA-induced photo- and genotoxicity in relevant models of human skin, and further identified the underlying molecular mechanisms involved. We demonstrated for the first time that the B6-vitamer pyridoxal, previously shown to contain the phototoxic 3-hydroxypyridine moiety, is a micromolar sensitizer of UVA-induced genotoxicity in human primary keratinocytes and human epidermal reconstructs, which may be relevant to human skin exposed to high concentrations of B6-vitamers. Additionally, we have demonstrated that FICZ, a tryptophan photoproduct and endogenous high-affinity aryl hydrocarbon receptor (AhR) agonist, as the most potent endogenous UVA- and visible light-activated photosensitizer identified as of today. FICZ potentiates photooxidative stress, an effect that occurs independent of AhR ligand activity. Given the extraordinary photodynamic potency of FICZ, which surpasses that of any known endogenous photosensitizer, including protoporphyrin IX, and its rapid metabolic turnover, we tested the feasibility of using FICZ for the photodynamic elimination of malignant skin cancer cells in vitro and in vivo. Indeed, light photoactivation of FICZ-induced phototoxidative damage and cytotoxicity in a panel of cultured human malignant skin cells, and furthermore suppressed post-UVB tumorigenic progression in high-risk SKH-1 mice. Based on these pilot studies, follow up experiments will further optimize FICZ-based photodynamic interventions targeting human skin malignancies in relevant model systems. In pursuit of minimizing the need for invasive therapeutic methods, exploitation of stress response pathways has become a topic of interest for interventions aimed at the eradication of skin cancer at early or late progressional stages. Therefore, we tested feasibility of harnessing the cellular metal stress response for the elimination of skin cancer cells using the zinc-ionophore and FDA-approved microbicidal agent zinc pyrithione (ZnPT). Indeed, in a panel of cultured malignant skin cancer cells it was observed that ZnPT treatment caused rapid intracellular zinc overload and redox dysregulation, followed by a loss of genomic integrity and induction of caspase-independent cell death. In a murine photocarcinogenesis model, chronic topical ZnPT-administration post-UV caused epidermal zinc-overload and stress response gene expression with pronounced blockade of tumorigenic progression. These data suggest the feasibility of repurposing a topical OTC-drug for zinc-directed photochemoprevention of solar UV-induced nonmelanoma skin cancer. In summary, these studies contribute to our mechanistic understanding of photosensitizer- and zinc-induced stress responses in human skin, and furthermore provide the molecular basis for innovative therapeutic strategies aimed at the elimination of skin cancer cells.

The synthesis and comprehensive characterization of diamine and diimine derivatives of thioindigo are reported. X-ray crystal structures demonstrate a planar structure for the diimine derivatives and a twisted conformation for the diamines. The diamine compounds absorb in the UV (λmax 324 nm - 328 nm), and exhibit moderate fluorescence (ΦF = 0.25, 0.045). A transient triplet state is observed in laser flash photolysis (LFP) experiments, with lifetimes an order of magnitude longer than those of the triplet state of thioindigo. The diimine compounds absorb at longer wavelengths than the diamines (λmax 495 nm - 510 nm), but are still slightly blue-shifted from thioindigo. The diimines have molar extinction coefficients 17 – 70% higher than thioindigo. The diimine compounds are not emissive, and LFP studies show transient species with microsecond lifetimes. The transient absorption spectra and quenching experiments of the diimines are consistent with trans-cis isomerisation about the central double bond. Mono- and diruthenium hexafluoroacetylacetonate (hfac) complexes of thioindigo-N,Nʹ-diphenyldiimine have been prepared. The monoruthenium complex was isolated as a racemic mixture and the diruthenium complexes were isolated as the meso (ΔΛ) and rac (ΔΔ and ΛΛ) diastereomers. Extensive structural characterization of the compounds revealed intrinsic diastereomeric differences in the X-ray crystal structures, cyclic voltammograms, and NMR spectra. Variable temperature NMR experiments demonstrated that the rac diastereomer undergoes conformational exchange with a rate constant of 8700 sec-1 at 298 K, a behavior that is not observed in the meso diastereomer. Ground state optical properties of the complexes were examined, showing that all the complexes possess metal-to-ligand charge transfer (MLCT) absorption bands in the near-infrared (λmax 689 nm – 783 nm). The compounds do not display photoluminescence in room temperature solution-phase experiments or in experiments at 77 K. Ultrafast transient absorption spectroscopy measurements revealed excited states with picosecond lifetimes. Unexpectedly, the transient absorption measurements revealed differences in the transient spectra and disparate time constants for the excited state decay of the diastereomers, which are linked to the conformational changes observed in the NMR experiments. Investigations into the synthesis of azaDIMEs and azaDicarbazolyls are described. Examination of the Buchwald-Hartwig amination produced reaction conditions that enabled preparation of amino-diindoles. Oxidation of the amino-diindoles to azaDIMEs was complicated by concomitant oligomerization of the substrates. Substitution of the reactive positions of the amino-diindole afforded increased stability towards oxidative oligomerization. Scalable synthetic routes to azaDicarbazolyl precursors were identified and optimized, and preparation of amino and azaDicarbazolyl compounds was explored. / Graduate / 2021-04-18

Phytochromes (Phys) are biliproteins that regulate light responses in plants, fungi, and microorganisms through photoconversion between a dark state and a photoproduct. Thermal reversion of the photoproduct is an intrinsic property of all Phys, typically occurring on a timescale of seconds to days. Despite methodological advances, the structural and spectroscopic determination of short-lived photoproducts has proven challenging. We herein present an innovative approach for photoproduct stabilisation by incorporating the protein into trehalose glasses (TGs). The resulting Phy–trehalose matrices were investigated by UV/Vis absorption and solid-state NMR spectroscopies. Our results demonstrate that the TGs strongly inhibit thermal reversion of the incorporated Phy proteins for periods as long as several weeks at room temperature (RT), during which the proteins fully sustain their native structures and spectral and biochemical properties. This sample preparation approach is beneficial for revealing bona fide structure/ function relationships of short-lived photoproducts that are otherwise not accessible, thus paving the way towards a deeper molecular understanding of the diversified spectral properties of Phys. Our results also provide new insights into the molecular mechanism of trehalose bioprotection.

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This thesis is divided into four parts with organic chromophores for dye sensitized solar cells as the common feature and an introduction with general concepts of the dye sensitized solar cells. The first part of the thesis describes the development of an efficient organic chromophore for dye sensitized solar cells. The chromophore consists of a triphenylamine moiety as an electron donor, a conjugated linker with a thiophene moiety and cyanoacrylic acid as an electron acceptor and anchoring group. During this work a strategy to obtain an efficient sensitizer was developed. Alternating the donor, linker or acceptor moieties independently, would give us the tool to tune the HOMO and LUMO energy levels of the chromophores. The following parts of this thesis regard this development strategy. The second part describes the contributions to the HOMO and LUMO energy levels when alternating the linker moiety. By varying the linker the HOMO and LUMO energy levels was indeed shifted. Unexpected effects of the solar cell performances when increasing the linker length were revealed, however. The third part describes the investigation of an alternative acceptor group, rhodanine-3-acetic acid, in combination with different linker lengths. The HOMO and LUMO energy level tuning was once again successfully shifted. The poor electronic coupling of the acceptor group to the semiconductor surface proved to be a problem for the overall efficiency of the solar cell, however. The fourth part describes the contributions from different donor groups to the HOMO and LUMO energy levels and has so far been the most successful in terms of reaching high efficiencies in the solar cell. A top overall efficiency of 7.1 % was achieved. / QC 20101108

Le principal objectif de ce travail de thèse était d’imaginer, de synthétiser et de caractériser de nouveaux chromophores «push-pull» pour finalement évaluer leurs propriétés photovoltaïques en cellules solaires à colorant. Deux approches distinctes ont été développées : i) la première consiste en l’élaboration de chromophores tout-organiques de type « push-pull » basés sur un motif électro-donneur carbazole à potentiel d’oxydation élevé. Ces nouveaux colorants ont été conçus dans le but d’être utilisés avec des électrolytes à potentiel standard supérieur à celui du couple rédox I-/I3- ; ii) la seconde approche est basée sur un nouveau concept de chromophores organométalliques de type ruthénium-acétylure. Ces chromophores ont été développés dans le but de combiner à la fois les propriétés avantageuses d’une structure de type « push-pull » et les transferts de charges (MLCT) impliquant le motif [Ru(dppe)2], également connu pour constituer un excellent relai électronique. / The aim of this PhD research work was to design, synthesize and characterize new push-pull chromophores and finally to determine their photovoltaic properties in dye-sensitized solar cells. Two different approaches were developed: i) the first one consists in the preparation of metal-free organic push-pull chromophores based on a carbazole electron-donor part presenting high oxidation potential. These new chromophores were designed in view of being used with electrolytes showing standard potential superior to that of I-/I3-; redox couple ii) the second approach is based on a new concept of ruthenium-diacetylide organometallic complex dyes. These chromophores were developed in order to combine the advantageous properties of a push-pull structure and the charge transfer processes (MLCT) due to the [Ru(dppe)2] metal fragment, also known as an excellent electron relay.