Chemistry Commons^™

Additive-Dependent Regioselective Boracarboxylation Of Alkenes Using Low Valent Copper And Co2, Carly H. Gordon Ph.D.

Graduate Theses, Dissertations, and Problem Reports (ETD)

As a major greenhouse gas, carbon dioxide (CO₂) is an abundant and renewable C₁ feedstock, and developing methods for fixing CO₂ into high-value products is a major interest for the movement of greener chemistry. The boracarboxylation of alkenes provides access to difunctionalized products containing pharmaceutically relevant motifs, including carboxylic acids and boron-containing moieties. Significant work has been done to improve the versatility and efficiency of this methodology, with the recent expansion into a wide variety of terminal alkenes. The use of different phosphine and alkene additives have demonstrated positive effects on reaction rates and productivity, indicating …

Room Temperature Decarboxylative Amination Reactions Of Carboxylic Acids, Rabina Basnet

Graduate Theses, Dissertations, and Problem Reports (ETD)

Anilines are important structural motifs present in numerous natural products and pharmaceutically relevant compounds. Among the various synthetic strategies that have been developed, transition-metal-catalyzed cross-coupling reactions represent one of the most commonly employed methods for the formation of anilines. However, these approaches generally require pre-functionalized aryl coupling partners, and the utilization of more readily available, and structurally diverse coupling partners, such as carboxylic acids, would be desirable. Decarboxylative coupling reactions have garnered significant attention as an alternative approach to form new C-N bonds, and substantial progress has been made in this area. Nevertheless, these methods remain limited, with a predominant …

Α-Hydroxy C–H Functionalization Of Alcohols Via Boronic Acid, Hat, Photoredox Triad Catalytic System, Seth Christopher Cowan

Graduate Theses, Dissertations, and Problem Reports (ETD)

This dissertation explores the research that I have conducted in my time at West Virginia University. Most of my work has focused on the development of methods and studies to further understand the α-OH C–H functionalization of alcohols. This work involves a system of catalysts including photocatalysts, HAT catalysts, and boronic acid catalysts. Chapter 1 highlights a background for each of these areas. Photoredox catalysis has been an increasing area of chemistry over the past two decades as this technique can be used to design conditions to form new bonds in a selective manner through the utilization of light energy. …

Nickel-Catalyzed Regioselective Three-Component Coupling Of Phenyl Vinyl Sulfones With Alkynes, Stephen M. Long

Graduate Theses, Dissertations, and Problem Reports (ETD)

Benzene rings are some of the most prevalent motifs found in small molecule drugs with only a few dominant substitution patterns, 1-, 1,2-, 1,4-, and 1,2,4-. Nucleophilic aromatic substitution and electrophilic aromatic substitution are traditional methods for the synthesis of substituted benzenes and are robust and commonly used by chemical manufacturers, which explains in part the observed distribution of substitution patterns. Current methods to access substituted benzenes comprise of transition-metal-catalyzed C-H activation, transition-metal-catalyzed cross-coupling, and aryne chemistry. In general, the present methods require directing/leaving groups in specific positions to proceed, which inherently puts a limitation on substrate scope. Transition-metal-catalyzed [2+2+2] …

Illuminating Function And Enabling Inhibition At The Protein-Membrane Interface Of Glutathione Peroxidase 4., Courtney L. Labrecque

Theses and Dissertations

Membrane proteins act as gateways to cells and are responsible not only for signaling, lipid transport, and cellular homeostasis, but they are also integral in disease pathologies. One class of membrane proteins, peripheral membrane proteins (PMPs), reside in aqueous compartments of the cell until they are recruited to the membrane to perform their function. Glutathione peroxidase 4 (GPx4) is a PMP enzyme responsible for engaging the membrane and reducing lipid hydroperoxides, thereby preventing cellular death via ferroptosis. Due to its central function surrounding ferroptosis, GPx4 is an interesting drug target that has recently gained interest for inflammatory diseases as well …

Chemical Synthesis And Biological Application Of Sensitive Rna, Alexander T. Apostle

Dissertations, Master's Theses and Master's Reports

In the field of epigenetics - the dynamic collection of chemical modifications that overlay DNA/RNA - there is increasing interest in the potential for therapeutic and research-based utilization of the epitranscriptomics: those epigenetic modifications specific to RNA. Epitranscriptomics can give us a new approach to understanding and treating RNA viruses, like SARS-CoV-2. Given viruses are often found modified by human epitranscriptomic machinery, understanding how these modifications can modulate virulence is of high interest. We have shown that the N1-methyladensoine modification causes RNA synthesis termination in the SARS-CoV-2 replication complex, and thus may explain the differences in symptoms observed in individuals. …

Green Oxidation Of Aromatic Hydrazide Derivatives Using An Oxoammonium Salt, Nidheesh Phadnis, Jessica A. Molen, Shannon M. Stephens, Shayne M. Weierbach, Kyle M. Lambert, John A. Milligan

Chemistry & Biochemistry Faculty Publications

Aromatic diazenes are often prepared by oxidation of the corresponding hydrazides using stoichiometric quantities of nonrecyclable oxidants. We developed a convenient alternative protocol for the oxidation of aromatic hydrazides using Bobbitt's salt (1), a metal-free, recyclable, and commercially available oxoammonium reagent. A variety of aryl hydrazides were oxidized within 75 min at room temperature using the developed protocol. Computational insight suggests that this oxidation occurs by a polar hydride transfer mechanism.

Unraveling Sources Of Cyanate In The Marine Environment: Insights From Cyanate Distributions And Production During The Photochemical Degradation Of Dissolved Organic Matter, Rui Wang, Jihua Liu, Yongle Xu, Li Liu, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton …

Toxicity Of Crude Oil-Derived Polar Unresolved Complex Mixtures To Pacific Herring Embryos: Insights Beyond Polycyclic Aromatic Hydrocarbons, Maxwell L. Harsha, Yanila Salas-Ortiz, Alysha D. Cypher, Ed Osborn, Eduardo Turcios Valle, Jacob L. Gregg, Paul K. Hershberger, Yuri Kurerov, Sarah King, Aleksandar I. Goranov, Patrick G. Hatcher, Anastasia Konefal, T. Erin Cox, Justin B. Greer, James P. Meador, Matthew A. Tarr, Patrick L. Tomco, David C. Podgorski

Chemistry & Biochemistry Faculty Publications

Crude oil toxicity to early life stage fish is commonly attributed to polycyclic aromatic hydrocarbons (PAHs). However, it remains unclear how the polar unresolved complex mixture (UCM), which constitutes the bulk of the water-soluble fraction of crude oil, contributes to crude oil toxicity. Additionally, the role of photomodification-induced toxicity in relation to the polar UCM is not well understood. This study addresses these knowledge gaps by assessing the toxicity of two laboratory generated polar UCMs from Cook Inlet crude oil, representing the readily water-soluble fraction of crude oil and photoproduced hydrocarbon oxidation products (HOPs), to Pacific herring (Clupea pallasii …

Evaluating The Influence Of Trypanosomiasis On Murine Model Using Corchorus Olitorius Leaf Extract As A Trypanocidal Agent, Fatima M. Madaki, Adamu Y. Kabiru, Ogunrombi D. Clinton, Sakariyau A. Waheed, Yunusa O. Ibrahim

Chemistry & Biochemistry Faculty Publications

Trypanosomiasis, a parasitic disease caused by trypanosomes, which are flagellate protozoa transmitted through the bite of the tsetse fly, manifests with symptoms including substantial weight loss, anemia, fever, edema, adenitis, dermatitis, and nervous disorders. This research investigated the impact of trypanosomiasis on a murine model while utilizing Corchorus olitorius leaf extract as a potential trypanocidal agent. An acute toxicity analysis was conducted following Lorke's method, and the antitrypanosomal efficacy was assessed in rats at doses of 100, 200, and 400 mg/kg over three weeks, monitoring changes in parasitemia count, body weight, and hematological parameters. Additionally, lipid profile, electrolyte concentration, and …

Advancements In The Synthesis Of Polyoxygenated Oxepanes And Thiepanes For Applications To Natural Products, Aditya R. Pote, Shayne M. Weierbach, Mark W. Peczuh, Kyle M. Lambert

Chemistry & Biochemistry Faculty Publications

Oxepanes are central motifs and tenants of many biologically important molecules, and their synthetic construction often presents a challenge to chemists due to consequential entropic and enthalpic barriers that have limited the synthetic toolbox to access these seven-membered oxacycles. This review covers the breadth of synthetic methods to afford the oxepane/thiepane moiety, with a focus on polyoxygenated oxepanes and includes radical cyclizations, Lewis acid-mediated cyclizations, ring closing-metathesis, Nicholas-Ferrier rearrangement, homologations, and ring-expansion strategies. Implementation of these tactics towards sugar-based and non-sugar based (de novo) approaches is presented alongside their extensive application to the total synthesis of several complex polyoxygenated oxepane-containing …

The Role Of Sugars In Aggregation Of The Protein Kassinin, Lillie G. Waldron

Student Summer Scholars Manuscripts

The aggregation of proteins to form amyloids is implicated in several diseases such as Alzheimer’s Disease, Parkinson’s Disease, and many others. This aggregation has several stages, progressing from isolated protein molecules (monomers) to small aggregates (oligomers), which are toxic to cells, and finally to large, string-like mature aggregates. Despite this association with disease, functional amyloids, which have normal biological functions, also result from protein aggregation. Kassinin, an amphibian peptide involved in nerve signal transmission, is a model system for functional amyloid study. To compare the aggregation of functional and disease-causing amyloids, we previously synthesized a fluorine-labeled kassinin through solid-phase peptide …

Synthesis Of Long Oligodeoxynucleotides, Yipeng Yin

Dissertations, Master's Theses and Master's Reports

Synthetic long oligodeoxynucleotides (ODNs) have found wide applications in diverse fields such as chemical biology, synthetic biology, and genes and genomes synthesis. Those applications leading to a significant demand for their production. However, traditional methods for purifying synthetic ODNs present notable drawbacks, particularly their inability to purify long ODNs, rendering long ODN synthesis challenging. To address these issues, chemical synthesis techniques for long ODNs coupled with non-chromatographic purification methods have been developed. This technology makes the purification of long synthetic ODNs feasible and offers a viable pathway for producing genes and genomes with extensive repeats or stable secondary structures, which …

Biliverdin Reductase-A Integrates Insulin Signaling With Mitochondrial Metabolism Through Phosphorylation Of Gsk3Β, Chiara Lanzillotta, Antonella Tramutola, Simona Lanzillotta, Viviana Greco, Sara Pagnotta, Caterina Sanchini, Silvia Di Angelantonio, Elena Forte, Serena Rinaldo, Alessio Paone, Francesca Cutruzzolà, Flavia Agata Cimini, Ilaria Barchetta, Maria Gisella Cavallo, Andrea Urbani, D. Allan Butterfield, Fabio Di Domenico, Bindu D. Paul, Marzia Perluigi, Joao M.N. Duarte

Markey Cancer Center Faculty Publications

Brain insulin resistance links the failure of energy metabolism with cognitive decline in both type 2 Diabetes Mellitus (T2D) and Alzheimer’s disease (AD), although the molecular changes preceding overt brain insulin resistance remain unexplored. Abnormal biliverdin reductase-A (BVR-A) levels were observed in both T2D and AD and were associated with insulin resistance. Here, we demonstrate that reduced BVR-A levels alter insulin signaling and mitochondrial bioenergetics in the brain. Loss of BVR-A leads to IRS1 hyper-activation but dys- regulates Akt-GSK3β complex in response to insulin, hindering the accumulation of pGSK3βS9 into the mito- chondria. This event impairs oxidative phosphorylation and fosters …

Synthesis Of Novel 5-Aryl 2’-Deoxyuridine And 2’-Deoxycytidine Analogues, Kevin E. Persaud

Dissertations and Theses

Briefly, the following report details a synthetic route to prepare 5-phenyl-2’-deoxycytidine analogues. This multistep synthesis began with silyl protection of the 3’- and 5’-hydroxyl groups of 5-iodo-2’-deoxyuridine. Next, the installation of a phenyl ring at the C5 position of the nucleobase via a Suzuki-Miyaura cross-coupling reaction, yielding 5-phenyl-2’-deoxyuridine (5-PdU). After that, modification of the obtained 5-PdU at the C4 position was performed with benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (BOP, a peptide-coupling agent) and a base (cesium carbonate) to activate the amide group of the uridine nucleobase for subsequent displacement with a variety of amines. Modification of the C4 position resulted in protected 5-phenyl-2’-deoxycytidine …

Assessing Interatomic Potentials For Molecular Dynamics Simulation Of Soybean Oil Pyrolysis, Tanner Garrett Rust

Graduate Theses/Dissertations

The world today relies on hydrocarbon combustion for many reasons, including its high energy density that provides ease of transportation. However, hydrocarbons sourced from fossil fuels are not expected to last forever. Biodiesel, a renewable alternative, has many attractive benefits but comes with other downsides. Biodiesel can gel in cold environments and may leave residue in an engine. Pyrolysis of biodiesel has shown promise in addressing these common detriments. Inducing pyrolysis on biodiesel feedstock (commonly soybean oil in the USA) would be an attractive option presuming it continues to produce fossil fuel analogs similar to biodiesel pyrolysis. Herein, Langevin molecular …

Photoinduced Alpha-Hydroxy C–H Alkylation Of Mono-Alcohols Via Hydrogen Atom Transfer (Hat) Of An Activated Boron-Containing Complex, Courtney Deanna Glenn

Graduate Theses, Dissertations, and Problem Reports (ETD)

Hydroxy (-OH) groups are one of the most abundant functional groups found in natural products and pharmaceuticals with many of these compounds containing multiple alcohol classes. The ability to selectively functionalize a specific α-OH C–H bond in the presence of other competitive sites would provide straightforward access to new, potentially bioactive compounds. In recent literature, photoredox catalysis has been implemented to perform site and stereoselective α-OH C–H functionalization of cis-diol containing substrates. Incorporating an organoboron cocatalyst into these systems have proven to be crucial in decreasing the bond dissociation energy (BDE) and increasing hydricity of the α-OH C–H bond …

Investigation Of Deoxyfluorination Of Alkyl Alcohols Using Pentafluoropyridines Through A Covalent Intermediate, Christopher Allen Bias

Graduate Theses, Dissertations, and Problem Reports (ETD)

Organofluorines are an omnipresent class of organic molecules, especially in pharmaceuticals. Selective fluorination of drug molecules allows for the influence of properties including metabolic activity, solubility, and intrinsic potency. Deoxyfluorinations are typically performed via generation of nucleophilic fluoride from a deoxyfluorination agent. Traditionally, diethylaminosulfur trifluoride (DAST) is the reagent of choice for these reactions, and it remains a popular reagent today. However, it has a propensity to form elimination side products and explode. Several research groups have recently developed new classes of deoxyfluorination agents including imidazole-based reagents (PhenoFluor) and sulfonyl fluorides (PyFluor) that exhibit better functional group tolerance and much …

C–H Alkylation Of Diol Substrates Using Bifunctional Boronic Acid Catalysts, Matthew Ryan Ross

Graduate Theses, Dissertations, and Problem Reports (ETD)

Boronic acid catalysts in combination with a Lewis base have been used in previous work to perform site-selective C–H alkylation reactions targeting the α-hydroxy C–H bond of diols through a photoredox activated hydrogen atom transfer. This is done by accessing a tetracoordinate boronic acid – Lewis base complex which then mediates the hydrogen atom transfer. The research hypothesizes that combining the boronic acid and Lewis base into one molecule not only simplifies the reaction but also has the potential to unlock C–H alkylation sites previously inaccessible. This is plausible because the Lewis base portion of the synthesized bifunctional boronic acid …

Chemical Synthesis Of Sensitive Dna, Komal Chillar

Dissertations, Master's Theses and Master's Reports

Over the past decades, researchers have tried various chemical methods to synthesize modified oligodeoxynucleotides (ODNs, i.e. short segments of DNAs). Traditional ODN synthesis methods require strong basic, and nucleophilic conditions for the deprotection and cleavage of the ODN from the solid support. However, the sensitive ODNs containing labile functionalities are vulnerable to such harsh conditions. Sensitive ODNs have a wide range of applications in research and pharmaceuticals. To synthesize sensitive ODNs, researchers devised different strategies but no practical methods have been developed. To overcome these challenges, we developed alkyl Dim alkyl Dmoc technology. This innovative technology uses weakly basic and …

Establishing A Two-Color Fluorescence Probe Assay For The Simultaneous Screening Of Glut5 And Glut2 Fructose Transporters In Live Cells, Oluwanifesimi Mary Afolabi

Dissertations, Master's Theses and Master's Reports

The mammalian facilitative glucose transporter (GLUT) family comprises 14 members that mediate the transport of hexoses across cell membranes. GLUT5 is the only member specific to fructose, and together with GLUT2, which transports fructose in addition to glucose, they make up the primary fructose transporters in humans. This study introduces a novel two-color fluorescence assay designed to simultaneously monitor the activity of GLUT5 and GLUT2 in live cells. 2,5-anhydro-D-mannitol (2,5-AM) a GLUT5 targeting compound has facilitated the development of various fructose-mimicking probes with a wide range of properties, such as radioactive imaging, fluorescent, photoactive, and drug delivery capabilities. Effective and …

Synthetic Strategies Toward The Development Of Stable Gold-Based Anticancer Agents And Their Mechanistic Insight, Adedamola Arojojoye

Theses and Dissertations--Chemistry

Despite notable advancements in the design and synthesis of novel chemotherapeutic drugs, cancer continues to be a leading cause of death in the United States. Metallodrugs, especially Au complexes, have played a prominent role in the search for the next generation of chemotherapeutic agents. Herein, I report on the synthetic strategies towards the rational design of stable Au (Au)-based agents, study their reactivity in biological environment, and offer insights into the cytotoxic mechanism of action in cancer. Chemotherapeutic Au compounds exist mainly in +I or +III oxidation states. Repurposing of the Au(I) FDA approved auranofin for the treatment of diseases …

Studies Towards Mechanistic Understanding Of The Suzuki-Miyaura Catalyst-Transfer Polymerization, Mitchell Tyler Howell

Graduate Research Theses & Dissertations

Semiconducting organic conjugated polymers show major promise for the manufacturing of organic electronic and optoelectronic devices. Their utility comes from inherent conductivity, elasticity, processability and low weight paving the way towards novel materials and applications. The molecular weight, polydispersity, and precise incorporation of structural elements into the conjugated backbone are among the important parameters that affect a conjugated polymer’s mechanical and electrical properties. Therefore, precise control over such parameters provides a path for electronic materials with tunable properties tailored for a specific application. Recent success in this endeavor has been achieved with Suzuki-Miyaura Catalyst-Transfer Polymerization (SCTP) which is a transition …

Synthesis Of A Basket-Shaped Host Molecule Based On P-Tert-Butylcalix[4]Arene Featuring Pyridinyl Groups For Volatile Guest Molecule, Boluwatife S. Ajewole

Masters Theses

Supramolecular and Molecular chemistry offer an expanding array of applications for the development of smart devices, with calixarene-based molecular baskets playing a pivotal role in host-guest chemistry. A key concept in this field is the design of "smart" molecules with gate-like features, which can selectively transport chemical or biochemical species that are volatile, reactive, or sensitive to typical solution environments. These molecular hosts are engineered with predefined groups that respond to external stimuli, such as changes in concentration, temperature, or pH.

Molecular baskets are synthetic host molecules designed to capture guest molecules selectively through adjustable gates. In our study, we …

Addition Reactions Of Olefinic Heterocycles And 4-Hydroxycoumarins, Benjamin Goka

Graduate Research Theses & Dissertations

The work outlined in this dissertation describes acid-base catalyzed projects facilitating the construction of key synthetic analogs with vast therapeutic applications. Three major projects have been covered demonstrating various synthetic routes developed by our research group to furnish key derivatives of heterocyclic compounds, including coumarins, carbohydrate moieties, and beta-lactams. By their catalytic nature, acids, and bases are known to enhance the reactivities of compounds. This allows synthetic chemists to design or chart new and better reaction pathways leading to the delivery of desired reaction products. The first chapter features a summary of the main concepts underpinning the projects.

Chapter 2 …

Superelectrophile Promoted Syntheses Of Aromatic Spirocycles, Jeffrey Caz Ferreira

Graduate Research Theses & Dissertations

Aromatic spirocycles are crucial organic scaffolds that are at the forefront of innovation in various fields of organic electronics, as well as in drug design. The synthesis of these compounds is challenging, especially on an industrial scale and often have suboptimal yields in many traditional syntheses. New synthetic methodologies are being continually explored for the installation of sp3 hydridized spiro junctions. Our research group, as well as other groups, have done exploration of using superelectrophilic synthetic routes that are nicely applied to the formation of aromatic spirocycles. Most relevant to the results discussed in this dissertation are condensation chemistry using …

Synthesis Of Bis-Thioacid Derivatives Of Diarylethene And Their Photochromic Properties, Pramod Aryal, Jonathan Bietsch, Gowri Sankar Grandhi, Richard Chen, Surya B. Adhikari, Ephraiem S. Sarabamoun, Joshua J. Choi, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Diarylethenes (DAEs) are an important class of photoswitchable compounds that typically undergo reversible photochemical conversions between the open and closed cyclized forms upon treatment with UV light or visible light. In this study, we introduced thioacid functional groups to several photochromic dithienylethene (DTE) derivatives and established a method that can be used to prepare these photoswitchable thioacids. Four thioacid-functionalized diarylethene derivatives were synthesized through the activation of carboxylic acids with N-hydroxysuccinimide, followed by reactions with sodium hydrosulfide with yields over 90%. These derivatives exhibited reversible photoswitching and photochromic properties upon treatment with ultraviolet (UV) and visible lights. The thioacid groups …

Use Of Interlaboratory Studies For The Development Of Consensus-Based Criteria For The Elemental Analysis Of Electrical Tapes, Lacey M. Leatherland

Graduate Theses, Dissertations, and Problem Reports (ETD)

Tape evidence is often used in criminal cases involving violent crimes, kidnappings, improvised explosive devices (IEDs), and drug trafficking. This evidence can reveal potential links between suspects, items, or scenes. The forensic examination of electrical tape can provide investigative leads or offer support to alternative hypotheses evaluated in the courtroom. A conventional analytical scheme includes microscopic examination, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy Energy Dispersive Spectrometry (SEM-EDS), and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS). Elemental analysis of electrical tapes is commonly achieved using SEM-EDS; however, recent scientific literature suggests that this analysis can evolve from using SEM-EDS to …

Synthesis Of Chiral Amino Acids Via Direct Amination Of Diazo Ester With A Rhodium-Based Catalyst, Steven J. Boyles

Honors College Theses

Amino acids are critical molecules within living organisms as they are the building blocks of proteins. In organisms, proteins serve as regulators of necessary processes, structural components in tissue, hormones, and neurotransmitters. Amino acid therapy is an emerging treatment in the medical field used to treat symptoms of diseases such as Alzheimer’s disease, Parkinson’s disease, and multiple sclerosis. Amino acid therapies have also shown promising effects when it comes to treating mood disorders and weight management. In order to increase the number of amino acids available and increase the potential treatments for other ailments, there is a drive to increase …

Hybridization And Duplex Stability Of Peptide Nucleic Acid Containing An Azobenzene Switch, Carmen J. Velasquez

College of Graduate Studies: Theses & Dissertations

Light-driven molecular switches that can be turned on and off on demand have found many biological applications. For DNA, RNA, and synthetic derivatives, the switch can be used to interfere with a hybridization event with a complementary strand. To explore this potential, we have synthesized three light-sensitive PNA which have an azobenzene group (PNA-5azo5 and PNA-4azo4), and two azobenzene groups (PNA-2azo5azo2) as part of the PNA backbone. UV experiments were used to verify the conversion to the cis-isomer from the initial trans state for all of the single-stranded Azo-PNA ( PNA-5azo5, PNA-4azo4, and PNA-2azo5azo2) by irradiating at 365 nm …