Routes to N-amino heterocycles were reviewed and findings applied to generate flash vacuum pyrolysis (FVP) precursors of two types - ketene generators and azol-1-yl radical generators. N-Amino heterocycles can be used as nitrogen radical generators, the N-N bond being homolytically cleaved at furnace temperatures of approximately 850 °C. A number of 2-substituted benzimidazoles were synthesised and subsequently Naminated. The 2-arylbenzimidazole precursors 1-amino-2-(2-methylphenyl)-1Hbenzimidazole and 1-amino-2-(2-ethylphenyl)-1H-benzimidazole were synthesised and subjected to FVP. The hydrogen transfer processes of the resulting azol-1-yl radicals were investigated. Pyrolysis of 1-amino-2-(2-methylphenyl)-1Hbenzimidazole resulted in three products; 2-(2-methylphenyl)-1H-benzimdazole, 11H-benzo[4,5]imidazo[1,2-a]isoindole and 1-(2-methylphenyl)-1Hbenzo[ d]imidazol-2-amine. Pyrolysis of 1-amino-2-(2-ethylphenyl)-1Hbenzimidazole resulted in five products, four of which have been successfully isolated and identified as 2-(2-ethylphenyl)-1H-benzimidazole, 5,6- dihydrobenzo[4,5]imidazo[2,1-a]isoquinoline, 1-(2-ethylphenyl)-1Hbenzo[ d]imidazol-2-amine and 11-methyl-11H-benzo[4,5]imidazo[2,1-a]isoindole. The mechanism of formation of most products is initiated by hydrogen atom transfer to the azol-1-yl radical position. N-Aminopyrazole was reacted with 5-methoxymethylene-2,2-dimethyl-1,3-dioxane- 4,6-dione to form the corresponding 5-(N-aminopyrazolyl)methylene derivative, which, when subjected to FVP, eliminates acetone and carbon dioxide to form a methyleneketene. This subsequently undergoes a [1,3]-hydrogen shift giving an imidoylketene which can collapse onto the neighbouring nitrogen atom forming pyrazolo[1,2-a][1,2,3]triazin-5-ium-4-olate (a novel heterocyclic mesomeric betaine system) or cyclise onto the adjacent carbon atom to yield a pyrazolopyridazinone. On variation of the furnace temperature it was apparent the former forms at relatively moderate temperatures (~500 °C) whereas the latter begins to predominate as the furnace temperature increases (~700 °C). The relationship between these kinetic and thermodynamic products was modelled using DFT calculations. By using substituted pyrazole precursors, substituents could be incorporated into all three available positions around the pyrazole ring. Using substituted acrylic esters as alternative imidoylketene generators, substituents could also be incorporated into both available positions in the pyridazinone ring. All corresponding betaine and pyrazolopyridazinone products were isolated and characterised.

The addition of benzyltrimethylsilane to maleic anhydride mediated by TiO2 photocatalysis was initially investigated. The affect of changing the catalyst, the radical trap loading and the substitution of the benzyltrimethylsilane molecule was assessed. Cyclisation precursors based on benzyltrimethylsilane were prepared, but were found not to cyclise via TiO2 photocatalysis. A number of other systems were assessed for their ability to cyclise under TiO2 photocatalysis; tertiary amines, aminomethyltrimethylsilanes, phenoxymethyltrimethylsilanes and phenoxyacetic acids. Phenoxymethyltrimethylsilane and phenoxyacetic acid were found to add effectively to maleic anhydride under TiO2 photocatalysis conditions, however they were unreactive with regards to cyclisation. EPR spectroscopy has been employed to characterise further the reaction of benzylsilanes with maleic anhydride under TiO2 photocatalytic conditions. A number of EPR active species were observed; trapped holes and electrons, which reside within the TiO2 catalyst. In addition, methyl and benzyl radicals were observed and were found to originate from the oxidation of the benzylsilanes by trapped holes in the TiO2 catalyst. However, no radical species were observed from the maleic anhydride. These observations had the following consequences for the currently proposed reaction mechanism for the addition of benzyltrimethylsilane with maleic anhydride under TiO2 photocatalysis.  The observation of the benzyl radical definitely proved that the reactive intermediate was indeed the proposed benzyl radical  The absence of any maleic anhydride EPR active species cast doubt on the role of maleic anhydride as an electron trap. Moreover when maleic anhydride is removed from the reaction system, interstitial Ti3+ species is absent from the EPR spectra, indicating that maleic anhydride is in fact acting as a hole trap.

The characters of Forlorn Days have been beaten down, be it personally or professionally. These stories are meant to present these characters as they struggle in their own indecisions and adversities. Some are more successful than others, while some come to the realization that it is nearly impossible to escape their flaws. The worlds they occupy are filled with a sense of disillusionment, whether it be soul crushing jobs, fractured relationships, or a lack of communicating with those around them. The characters that populate these stories are looking for a connection of any kind to break out of the fates that await them. In this yearning to break out of their disillusionment, they find that it’s more difficult than they thought. Life continues to go around regardless of the decisions they have made.

This thesis describes the development of new thermal and oxidative radical cyclization methodologies and their application to the total syntheses of alkaloids, particularly to bridged diketopiperazine (DKP) alkaloids. A practical solvent free approach to diverse DKPs and quinazolines is described. The methodology proceeds by thermal silica gel mediated deprotection of the Boc protecting group and intramolecular condensation of the resulting free dipeptides and tripeptides. It was applied to the total syntheses of alkaloids glyantrypine and ardeemin. A major part of the thesis concerns with the discovery and applications of novel diketopiperazine derived alkoxyamines. Their propensity to undergo facile thermal C-O bond homolysis to generate captodative DKP radicals and persistent TEMPO radical allowed using them as radical surrogates. The methodology takes advantage of the persistent radical effect (PRE). The methodology based on PRE was applied in an asymmetric approach to the alkaloid asperparaline C. An asymmetric synthesis of a very advanced precursor to asperparaline C, 8- oxoasperparaline C, was accomplished in 11 steps and 15% overall yield. The key steps of the synthesis include a direct oxidative cyclization of DKPs, regioselective furan dearomatization with singlet oxygen and a reductive...

Muitas espécies de animais vivenciam situações nas quais há uma profunda depressão metabólica, como na anóxia, na hipóxia e na hibernação. Durante a reoxigenação ou o despertar, ocorre aumento da produção de espécies reativas de oxigênio (ROS), que tendem a causar danos oxidativos. Diferentes enzimas antioxidantes protegem o organismo contra as ROS, porém não se sabe qual a real importância de cada uma delas durante a reoxigenação. A hibernação é uma das formas de hipometabolismo menos estudadas, fazendo com que haja questionamentos sobre como os hibernantes se protegem das ROS durante o despertar. A análise dos dados existentes é complexa devido à existência de variáveis não controladas, como o efeito do jejum associado à hibernação. Nesta tese, foram desenvolvidos dois projetos. Em um, investigou-se a importância da catalase num ciclo de anóxia e reoxigenação em caramujos pulmonados. No segundo, investigou-se o efeito da hibernação e da privação alimentar no intestino de lagartos teiús. Com base nos resultados, foi possível concluir que a catalase exerce um papel complementar contra os danos oxidativos causados pelas ROS e em conjunto com os demais componentes do sistema antioxidante. Porém, sua função não parece ser essencial, sendo em grande parte compensada pela atividade de glutationa peroxidase. Também foi possível concluir que a hibernação, estudada sem a interferência de drásticas quedas da temperatura, causa nítidas alterações no metabolismo de radicais livres no intestino de lagartos, com queda de atividades enzimáticas e de concentração de glutationa. A ausência de grandes danos oxidativos durante o despertar dos animais mostra que eles têm um sistema antioxidante eficiente. A privação alimentar resultou em respostas semelhantes as da hibernação, mas parece ter causado um certo grau de estresse oxidativo. Os resultados apresentados nesta tese respondem dois questionamentos no estudo do metabolismo de radicais livres em situações que envolvem flutuações na disponibilidade e no consumo de oxigênio. / Many species of animals experience situations in which occurs a profound metabolic depression, like anoxia, hypoxia and hibernation. During reoxygenation or arousal, there is an increase of the production of reactive oxygen species (ROS), which tend to cause oxidative damage. Different antioxidant enzymes protect the organims against the ROS, however the real importance of each one of them during reoxygenation is not known. Hibernation is one of the types of hypometabolism less studied, and questions about how the hibernators protect themselves from ROS during the arousal have not yet been answered. The analysis of the existent data is complex due to the existence of uncontrolled variables. In this thesis were carried out two studies in which were investigated: the importance of catalase in a cycle of anoxia and reoxygenation in pulmonate snails, and the effect of hibernation and of food deprivation in the intestine of tegu lizards. Considering the results, it was possible to conclude that catalase plays an complementary role against the damages caused by ROS and in association with the other components of the antioxidant system. However, its function seems to be non-essential, being greatly compensated by the glutathione peroxidase activity. It was also possible to conclude that hibernation, studied without the interference of drastic falls in temperature, causes clear alterations in free radicals metabolism in the lizards intestine, with a reduction in enzymes activities and in glutathione concentration. The absence of big oxidative damage during the arousal of the animals shows that they have an efficient antioxidant system. Food deprivation resulted in similar responses of those from hibernation, but seemed to cause some degree of oxidative stress. The results presented in this thesis answer two questions in the study of the free radical metabolism in situations that involve fluctuations in oxygen availability and consumption.

Este trabalho teve por objetivos: levantar conceitos alternativos sobre radicais livres na mídia impressa e em livros de Bioquímica; examinar os conceitos alternativos prevalentes em pós-graduandos e em professores de Química e Biologia do Ensino Médio; e, planejar e aplicar intervenção para reduzir a influência destes conceitos. Para o levantamento na mídia impressa, foi selecionada a revista Veja, período de 01/01/2000 a 31/07/2014, e foram criadas as seguintes categorias para classificar o material encontrado: Conceito Alternativo (CA), Informação Indutiva (II), Conceito Indutivo (CI) e Generalização Indevida (GI), formando o grupo dos Conceitos Não Científicos (CNC); Conceito Correto (CC); Conceito Errado (CE); e, não preenche os critérios de inclusão (NPCI). Foram encontrados 294 trechos dos quais: 55,4% CA; 21,1% II; 9,2% CI; 5,4% GI; 4,1% CC; 2,7% CE; 2,0% NPCI; e, 91,2% CNC. Para o levantamento em livros de Bioquímica foram selecionados: Campbell - Bioquímica; Lehninger - Princípios de Bioquímica; Marzzoco e Torres Bioquímica Básica; Stryer - Bioquímica; e, Voet e Voet - Bioquímica. A maior parte dos conceitos encontrados nos livros foram conceitos corretos, contudo 77,5% dos conceitos encontrados destacavam aspectos negativos sobre radicais livres. Para o levantamento de conceitos alternativos em pós-graduandos e professores foi desenvolvido o Questionário de Radicais Livres (QRL), versões piloto e final, aplicadas, respectivamente, a 14 pós-graduandos matriculados na disciplina de pós-graduação Planejamento e Aplicação de Sequências Didáticas Envolvendo o Conteúdo Radicais Livres e 31 professores matriculados no curso de extensão Radicais Livres e suas Interfaces com a Vida, planejado com o auxílio dos pós-graduandos da disciplina. O QRL é um questionário de múltipla-escolha em etapas, composto por uma etapa de avaliação do conteúdo e outra sobre a percepção do participante sobre seu nível de certeza. Os pós-graduandos revelaram baixo domínio sobre o tema e baixo nível de certeza. Os professores, testados pré- e pós-intervenção, também apresentaram alta frequência de erros, bastante semelhante no pré- e no pós-teste, e baixo nível de certeza no pré-teste e aumento do nível de certeza no pós-teste. Acredita-se que estes resultados, tanto entre os pós-graduandos e como entre os professores, sejam reflexo da falta de contato acadêmico com o tema. Aos professores, também foram aplicados dois questionários complementares denominados Perfil Profissional e Conhecimentos Sobre Radicais Livres. Entre outras informações, os dados coletados a partir destes questionários, indicaram que os professores lecionam juntos para aproximadamente 12000 estudantes e que o curso de extensão contribuiu para aumentar seus conhecimentos sobre radicais livres. Estes dados oferecem suporte para a escolha do público-alvo e justificam a execução de cursos de extensão, tanto pelo o potencial de alcançar indiretamente um grande número de pessoas, como pela possibilidade de difusão do tema. Tanto o curso de extensão como a disciplina de pós-graduação foram muito bem avaliados pelos professores e pós-graduandos. Os altos percentuais de conceitos não científicos, principalmente conceitos alternativos, encontrados na mídia impressa, bem como os conceitos alternativos apresentados por pós-graduandos e professores, devem preocupar especialistas e cientistas, pois este tema é objeto de muitos anúncios publicitários que frequentemente incentivam o consumo de suplementos de antioxidantes. Em livros de Bioquímica, o aumento de conteúdo destacando o papel fisiológico dos radicais livres deve contribuir para desfazer o conceito disseminado de que radicais livres seriam prejudiciais à saúde. / This work aimed to survey the misconceptions regarding free radicals published in printed media and in biochemistry textbooks; to examine the misconceptions regarding free radicals prevalent among graduate students and chemistry and biology high school teachers; and to design and implement instructional intervention to reduce the influence of these misconceptions. For surveying printed media, publications from Veja magazine, dating from 01/01/2000 to 07/31/2014, were selected. The published material was categorized as follows: Misconception (MC), Inductive Information (II), Inductive Concept (IC), and Inadequate Generalization (IG) - collectively called Non-Scientific Concepts (NSC) - and Right Concept (RC), Wrong Concept (WC), and not fit for the inclusion criteria (NFIC). A total of 294 text excerpts were obtained, comprising 55.4% MC, 21.1% II, 9.2% IC, 5.4% IG, 4.1% RC, 2.7% WC, 2.0% NFIC, and 91.2% NSC. In order to examine the content in biochemistry textbooks, the following were selected: Campbell - Biochemistry; Lehninger - Principles of Biochemistry; Marzzoco & Torres - Basic Biochemistry; Stryer - Biochemistry; and Voet & Voet - Biochemistry. Most of the excerpts selected from the biochemistry textbooks were right concepts. However, 77.5% of the concepts highlighted negative aspects of free radicals. To investigate misconceptions among graduate students and high school teachers, a Free Radicals Questionnaire (FRQ) was developed. Pilot and final versions were given to 14 students enrolled in the graduate course Planning and Application of Didactical Sequences Encompassing Free Radicals Content and to 31 high school teachers enrolled in the extension course Free Radicals and its Interfaces with Life, respectively. The extension course was planned with the assistance of graduate students enrolled in the graduate course. FRQ is a multiple choice tier test with tiers for content evaluation and the participants perception of their level of certainty. Graduate students exhibited low levels of subject expertise and certainty. Teachers were tested pre- and post-intervention, and exhibited a high frequency of mistakes, comparable to graduate students, with similar pre- and post-test outcomes. However, their certainty level increased post-test. It is believed that these results may have occurred due to an academic lack of contact with the subject of free radicals. Additionally, two complementary questionnaires were given to the teachers: Professional Profile and Free Radicals Knowledge. Data collected from these questionnaires indicated that teachers collectively taught approximately 12,000 students and that the extension course contributed to increasing the teachers knowledge on free radicals. These results support the choice of the target audience and justify the implementation of the extension courses, because these courses have the potential to indirectly reach a large audience and can be used for thematic dissemination of knowledge in the subject area. The extension and graduate courses were highly rated by the teachers and graduate students, respectively. The high percentage of non-scientific concepts, especially misconceptions, found in printed media, as well as the misconceptions regarding free radicals prevalent among graduate students and teachers must concern specialists and scientists, as this topic is the subject of many advertisements encouraging consumption of antioxidant supplements. In biochemistry textbooks, increasing the content highlighting the physiological role of free radicals would contribute considerably in dispelling the widespread notion that free radicals are harmful to health.

by Hui Yee Han, Ellen. / Thesis (M.Sc.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 68-71). / acknowledgements --- p.i / abstract --- p.ii / table of contents --- p.iii-vi / list of figures --- p.vii / LIST OF TABLES --- p.viii / chapter / Chapter chapter i : --- introduction --- p.1 / Chapter chapter ii : --- background knowledge --- p.2 -33 / Chapter 2.1 --- Definition of Free Radical --- p.2 / Chapter 2.2 --- Oxygen Derived Radicals and Their Generation In Vivo --- p.2 -9 / Chapter 2.2.1 --- Production of Singlet Oxygen --- p.4 / Chapter 2.2.2 --- Production of Superoxide Radical (O2-) and Hydrogen Peroxide (H2O2) --- p.4 -8 / Chapter I. --- Endogenous Production --- p.4-7 / Chapter II. --- Exogenous Production --- p.7-8 / Chapter 2.2.3 --- Generation of Hydroxy Radical (OH) through H2O2 and O2- --- p.8 -9 / Chapter 2.3 --- Free Radical Damage and Lipid Peroxidation --- p.9 -13 / Chapter 2.4 --- Lipid Peroxidation and Atherosclerosis --- p.13 -14 / Chapter 2.5 --- Antioxidant --- p.15-21 / Chapter 2.5.1 --- Primary Preventive Antioxidants --- p.15-17 / Chapter 2.5.2 --- Secondary Radical Scavenging Antioxidants --- p.18-21 / Chapter I. --- Lipid Soluble Radical-Scavenging Antioxidants --- p.18-19 / Chapter II. --- Water Soluble Radical-Scavenging Antioxidants --- p.20 -21 / Chapter 2.6 --- Measurement of Oxygen-Derived Radical in Vivo --- p.21 -26 / Chapter 2.7 --- Principle of the TRAP assay --- p.27-33 / Chapter 2.7.1 --- Oxygen Consumption Method --- p.29 -30 / Chapter 2.7.2 --- Chemiluminescence Method --- p.31-33 / Chapter chapter III： --- materials and methods --- p.34 -43 / Chapter 3.1 --- Instrumentation and Materials --- p.34 / Chapter 3.2 --- Method --- p.34-43 / Chapter 3.2.1 --- Establishment of Chemiluminescence Method for Determination of TRAP --- p.34 -36 / Chapter I. --- Preparation of Luminometer --- p.35 / Chapter II. --- Preparation of Sample before Analysis --- p.3 5 / Chapter III. --- Manual Operation of the Chemiluminescence Method --- p.35-36 / Chapter IV. --- Calculation of TRAP --- p.36 / Chapter 3.2.2 --- Evaluation of the Chemiluminescence Method --- p.37 -42 / Chapter I. --- Linearity --- p.37 / Chapter II. --- Recovery --- p.37-38 / Chapter III. --- Precision --- p.39 / Chapter IV. --- Interference Experiment --- p.39 -41 / Chapter V. --- Effect of Storage on TRAP --- p.42 / Chapter 3.2.3 --- "Determination of Analytical, Intraindividual and Interindividual Biological Variation of TRAP in A Group of Healthy Chinese" --- p.42-43 / Chapter CHAPTER IV: --- ANALYTICAL RESULTS --- p.44-56 / Chapter 4.1 --- Method Evaluation --- p.44-51 / Chapter 4.1.1 --- Linearity --- p.44 / Chapter 4.1.2 --- Recovery --- p.45 / Chapter 4.1.3 --- Within-Day and Between-Day Precision --- p.46-47 / Chapter 4.1.4 --- Interference --- p.47-48 / Chapter 4.1.5 --- Effect of Storage on TRAP --- p.48-51 / Chapter 4.2 --- "Analytical, Intraindividual and Interindividual Variation of TRAP in A Group of Healthy Chinese Population" --- p.52 -56 / Chapter 4.2.1 --- Difference in TRAP value obtained from the 22 subjects over time --- p.52 -54 / Chapter 4.2.2 --- The Effect of Genders on Trap --- p.55 / Chapter 4.2.3 --- "Determination of Analytical, Intraindividual and Interindividual Variation of TRAP in A Group of Healthy Chinese" --- p.55-56 / Chapter CHAPTER V: --- DISCUSSION --- p.57-67 / Chapter 5.1 --- Validation of the Method Performance --- p.57 / Chapter 5.2 --- Effect of Storage on TRAP --- p.57 / Chapter 5.3 --- Interference of Hemolysis and Lipemia on TRAP assay --- p.58-60 / Chapter 5.3.1 --- Effect of Hemolysis on TRAP --- p.58-59 / Chapter 5.3.2 --- Effect of Lipemia on TRAP --- p.59-60 / Chapter 5.4 --- Possible Sources of Variation in TRAP Over Time --- p.60 -63 / Chapter 5.5 --- Usefulness of the Variation Data of TRAP obtained from a Group of Healthy Chinese --- p.64 -67 / reference --- p.68 -71

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by John Wesley Frost. / Ph.D.

During the course of the systematic study, it was also discovered that doubly-protonated diarginated peptides containing multiple glutamic acid residues (E) (n>4) could suppress the backbone fragmentation of [M+2H]+· . Together with the results obtained from conformational searches, it was hypothesized that the interactions between carboxylic oxygens of E side chains and backbone amide hydrogens could stabilize the radical intermediate and thereby inhibiting the usual N-Calpha cleavages and H · loss from [M+2H]+·. / In order to ascertain the impacts of the structural features of polypeptide and oligosaccharide ions on the dissociation of these biomolecules under typical collision induced dissociation (CID) and electron capture dissociation (ECD) conditions, the dissociation patterns of even-electron precursor ions generated by protonation ([M+nH]n+)/metalation ([Metal+M]n+), odd-electron hydrogen-deficient precursor ions (M+·) generated by SORI-CID of [Cu(Tpy)M]2+ and odd-electron hydrogen-surplus precursor ions ([M+2H]+·) generated by ECD of [M+2H] 2+ were examined. It was found that backbone cleavages, with the generation of b/y and c/z ions, were dominant in the dissociation of [M+H]+ and [M+2H]+· respectively. Whilst in the dissociation of M+·, side chain loss reactions were the major fragments generated. For post translational modification (PTM)-containing peptides, the labile PTM groups were found to cleave preferentially in the dissociation of M+· and [M+H]+, but were found to be retained in the intact peptides and peptide fragments in the dissociation of [M+2H]+·. It is hypothesized that the different dissociation pathways is attributed to the different nature of radicals. Further to these, it was found that in the dissociation of oligosaccharides, similar cleavage patterns (glycosidic and cross-ring cleavages) were obtained regardless of the nature of the precursor ions (i.e. whether odd- or even-electron) and the ion activation conditions. / Chan, Wai Yi. / Adviser: T.W. Dominic Chan. / Source: Dissertation Abstracts International, Volume: 73-02, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 145-152). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Stable radicals have enjoyed widespread use in a variety of fields including synthetic chemistry, materials chemistry, energy storage, and biochemistry. This thesis outlines our investigations of cyclopropenium-based stable radicals and their application as redox mediators, redox-active ligands, catalysts, and materials for energy storage. The first chapter gives a brief overview of the use of radicals in synthetic chemistry. The principles that govern the stability of radicals is discussed and notable examples are highlighted. The second section of the first chapter reviews the aromatic platforms that have been developed by the Lambert group and how they might be converted into stable radical species. The second chapter details our study of 2,3-diaminocyclpropenones as stable radicals. These electron rich cyclopropenium derivatives undergo facile oxidation to yield a radical cation species. The origin of the stability of this oxygen-centered radical was elucidated by density functional theory calculations and analysis of the crystal structure. Diaminocyclopropenones were also found to be effective neutral L-type ligands in Ce(IV) complexes. EPR and UV-VIS experiments revealed that these complexes exhibited reversible homolytic dissociation of their diaminocyclopropenone ligands. The third chapter describes the use of trisaminocyclopropeniums as catholytes for nonaqueous redox flow batteries. A newly designed trisaminocyclopropenium structure could be accessed in large quantities and showed long lasting stability in its oxidized state. A new composite polyionic material was developed for use as a membrane suitable for organic solvent and high voltages. Cycling in combination with a perylenediimide anolyte yielded a 1.7 V battery that exhibited excellent coulombic efficiency and capacity retention. Using a spiro-bis(phthalimido) anolyte afforded a battery with an open circuit voltage of 2.8 V. The fourth chapter details how our battery studies with trisaminocyclopropenium radical dications led us to discover their photoinduced reactivity. We developed an electrophotocatalytic platform using trisaminocyclopropeniums as a species capable of being activated by both photochemical and electrochemical energy. The excited state oxidation potential of the doubly activated species was found to be +3.33 V, which was capable of effecting oxidative coupling reactions using both arenes and ethers as substrates. Density functional theory calculations and spectroscopic experiments revealed that the photoreactivity was due to a SOMO-inversion event. The trisaminocyclopropenium radical dication could be prepared on scale via direct electrolysis and subsequently used in high throughput screening.