Feature Papers in Photochemistry
1
Department of Chemistry, College of Arts and Sciences, University of Kentucky, Lexington, KY 40506, USA
2
Lewis Honors College, University of Kentucky, Lexington, KY 40506, USA
Photochem 2024, 4(4), 511-517; https://doi.org/10.3390/photochem4040032
Submission received: 3 December 2024
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Accepted: 9 December 2024
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Published: 10 December 2024
(This article belongs to the Special Issue Feature Papers in Photochemistry II)
1. Introduction
As the Special Issues “Feature Papers in Photochemistry” and “Feature Papers in Photochemistry II” conclude, it is crucial to acknowledge the remarkable progress and persistent gaps that continue to shape the journey of photochemistry research. The field of photochemistry has seen unprecedented advancements, driven by novel techniques and interdisciplinary approaches. The study of light-induced molecular transformations [1,2], the application of photochemical processes in organic synthesis [1,3,4], the development of high-efficiency photocatalysts [5], and the discovery of novel environmental photochemical mechanisms [2,6] have all marked significant progress in recent years. Moreover, photochemical reactions in astrochemical mimics have been investigated to understand the chemical evolution of interstellar environments [7].
Groundbreaking synthetic applications of light-induced photodecarboxylation reactions have been made through the use of ligand-to-iron charge transfer for hydrodifluoromethylation and hydromethylation of alkenes [1]. The mechanistic contributions of ligand-to-metal charge-transfer (LMCT) complexes in the photocatalysis of adsorbates at the air-solid interface of TiO2 and the role of water vapor have been recently revealed [6]. Similarly, molecular electron donor–acceptor systems have been examined to shed light on charge transfer processes capable of advancing electronic and photonic applications, including solar energy and organic electronics [4]. Novel reaction pathways of diazoalkanes excited with visible light have expanded the synthetic toolkit for constructing complex molecules [8].
Innovative medical applications such as targeted drug delivery using light have been proposed to enable the controlled release of therapeutic agents with unmatched spatial and temporal resolution [9]. In the realm of skincare, the depth penetration of light into skin has been investigated across various wavelengths, providing critical data for medical and cosmetic applications [10]. Moreover, combined photodynamic and photothermal therapy using a bacteria-responsive porphyrin might facilitate more effective treatments for bacterial infections [11].
Environmental sciences have also seen significant advancements in photochemistry. The catalyst-free photochemical activation of peroxymonosulfate in xanthene-rich systems demonstrated the efficacy of proton transfer processes in Fenton-like synergistic decontamination for environmental cleanup [12]. The photochemistry of 2-oxocarboxylic acids in aqueous atmospheric aerosols resulting in the formation of secondary organic aerosols has significant implications for atmospheric chemistry and climate models [2]. The photodegradation of organic micropollutants in aquatic environments has garnered interest for its potential in managing water quality and reducing the environmental impact of emerging pollutants [13]. The design of sustainable covalent organic frameworks (COFs) as heterogeneous photocatalysts and their reaction mechanisms for organic synthesis have been reviewed [14]. Innovative solutions for sustainable energy storage technologies have been proposed, such as the application of photoelectrochemistry in oxygen evolution for rechargeable Li-O2 batteries [15]. The use of periodic illumination advanced the understanding of photoelectrocatalytic systems for CO2 reduction, offering a sustainable strategy for reducing greenhouse gasses and generating fuel feedstock [16].
Innovative photochemical techniques for controlled polymerizations might enable precise polymer architectures and advanced materials with tailored properties [17]. The field of asymmetric synthesis has seen progress through enantioselective photochemical reactions, which were enabled by triplet energy transfer [18]. The advanced understanding of the E → Z isomerization of alkenes using small-molecule photocatalysts might facilitate precise control in organic synthesis and materials science [19].
The challenges of scaling up photochemical reactions from lab scale to industrial production has been initially tackled from a technical and practical viewpoint [20]. Technological innovations in photochemistry for organic synthesis have been reviewed, such as flow chemistry, high-throughput experimentation, scale-up, and photoelectrochemistry implementation, driving significant progress in the field [21].
Despite the multiple advancements in the field of photochemistry, many knowledge gaps existed. Among these gaps were the creation of novel metal complexes for efficient and photostable organic dye degradation and for visible light photopolymerization reactions. Moreover, metal-doped photocatalysts for CO2 reduction with enhanced methane and hydrogen production were desired. Synthetic molecules with polycyclic aromatic hydrocarbon moieties, if created, could provide materials with a high quantum yield for bioimaging and anti-counterfeiting applications. Progress in the research of molecular solar fuels, fundamental absorption and fluorescence, the light-induced transitions of metal nitroprussides materials, and the photoluminescence of lanthanide complexes for advanced displays was also needed. The gaps included problems in spectroscopy and the study of photophysical properties, applications to bioimaging, the E → Z photoisomerization of dyes, relaxation processes, and inverse problems in pump–probe spectroscopy. Photobiology and photoprotection gaps included targeted analysis of the spectral properties of biological tissues for disease diagnosis, photostability mechanisms, DNA nucleobase photoprotection, and the photostabilization and degradation of pharmaceuticals and sunscreens.
The Special Issues, “Feature Papers in Photochemistry” and “Feature Papers in Photochemistry II”, have played a pivotal role in addressing these gaps. By bringing together a diverse collection of research papers, they highlighted groundbreaking work in photochemistry, showcased novel methodologies, and provided insights into emerging trends. They created a platform for exchanging ideas and fostering collaborations, thereby accelerating the pace of discovery in the field. Twenty high-quality contributions in these Special Issues highlight advances in the field of photochemistry by providing both research articles and reviews, which offer a comprehensive overview of innovative results and methodologies in the field of photochemistry.
Each of the twenty contributions advances the understanding of how photochemical processes can be harnessed for practical applications, such as pollution control, renewable energy, and the synthesis of complex molecules with functional properties. The Special Issues have been specially curated to ensure that they represent the cutting edge of today’s photochemical research. The inclusion of diverse perspectives and interdisciplinary approaches underscores the importance of photochemistry in addressing global challenges. Researchers, educators, and students can explore these photochemistry advancements in the provided open-access platform of these Special Issues. By bringing together high-quality research and review articles, these Special Issues serve as valuable resources for anyone interested in the latest developments in photochemistry. Highlights of the twenty important contributions are presented in the section below, categorized into three themes.
2. An Overview of the Published Articles
2.1. Contributions on Applications in Environmental Science and Materials Science
Vallavoju et al. (Contribution 1) presented the synthesis and characterization of novel tetradentate Schiff’s base Cu (II) complexes, which may find potential application as photocatalysts for environmental remediation, e.g., for organic dye degradation. The produced complexes with superior photocatalytic performance were of high photostability, low band-gap energy, and efficient visible-light activity. A different study by Mau et al. (Contribution 2) using copper complexes suggested their possible use as photoinitiators for visible light photopolymerization. The work of Edelmannová et al. (Contribution 3) explored the use of iron-modified graphitic carbon nitride (g-C3N4) photocatalysts for CO2 reduction. The systematic study in Contribution 3 determined that the photocatalyst with the lowest iron content showed superior gas evolution of methane and hydrogen as compared to higher iron content samples. Optimizing iron content in g-C3N4 was demonstrated by Edelmannová et al. as an important task for efficient CO2 photoreduction with advanced materials for sustainable energy solutions.
Malpicci et al. (Contribution 4) studied the synthesis and photophysical properties of cyclic triimidazole derivatives substituted with pyrene. The study revealed that these chromophoric compounds exhibit impressive quantum yields and room-temperature phosphorescence (RTP) properties, with phosphorescence lifetimes increasing with the number of pyrene moieties. Promising applications of these materials for bioimaging, anti-counterfeiting, and display technologies could be recognized based on the work of Malpicci et al. The research of Stefanello et al. (Contribution 5) examined the photophysical properties of a series of 5-(alkyl/aryl/heteroaryl)-2-methyl-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidines, reporting their UV-visible absorption and fluorescence properties in solution and solid state and assessing their thermal stability using thermogravimetric analysis.
An attractive study conducted by Joo et al. (Contribution 6) demonstrated that a europium complex electrodeposited on bare and terpyridine-functionalized porous silicon surfaces exhibited enhanced photoluminescence properties. The characterization of the surfaces created in Contribution 6 by amperometry electrodeposition was performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). These characterizations supported the materials’ composition and properties, which are valuable for developing advanced materials for display technologies and photoelectrochemical applications. Gimenez-Gomez et al. (Contribution 7) provided a comprehensive review of molecular solar fuels, focusing on their design challenges and recent advances. The review highlighted the optical and photochemical properties of compounds such as norbornadiene, azobenzene, and dihydroazulene, which are promising candidates for practical applications in solar energy storage. Crespo et al. (Contribution 8) provided a valuable perspective delving into the photochemistry of metal nitroprussides and emphasized the pivotal role of the nitrosyl group’s electronic structure. The work in Contribution 8 explained light-induced electronic transitions of metal nitroprussides and their impact on the stability and functional properties of these compounds, which may find applications in tuning the magnetic, electrical, and optical properties of advanced materials.
2.2. Contributions on Spectroscopy and Photophysical Properties
Sider et al. (Contribution 9) investigated the infrared spectrum and UV-induced photochemistry of matrix-isolated phenyl 1-hydroxy-2-naphthoate using matrix isolation infrared spectroscopy and density functional theory (DFT) computations. The insights offered about the fundamental photochemical processes and spectral properties of 1-hydroxy-2-naphthoate contribute to the understanding of photochemical reactions in isolated environments. The work in Contribution 9 identified the most stable conformer and studied its UV photodecarbonylation yielding 2-phenoxynaphthalen-1-ol and carbon monoxide, a reaction that showed dependence on the excitation wavelength. Barnes et al. (Contribution 10) examined the electronic absorption, emission, and two-photon absorption properties of extended 2,4,6-triphenyl-1,3,5-triazines. DFT calculations were used by Barnes et al. to examine their linear optical properties and two-photon absorption cross-sections, which may be valuable for fluorescence bioimaging applications. Vasilev et al. (Contribution 11) studied the reversible E → Z photoisomerization of a photoswitchable merocyanine dye present in a polar acidic medium, which was induced with visible light at λ = 450 nm. A combination of UV-visible spectroscopy measurements and DFT calculations demonstrated in Contribution 11 the potential of this dye for harvesting visible light and for developing light-responsive materials.
Moritz Knötig et al. (Contribution 12) shed light on the excited state dynamics of carbazole and 3,6-di-tert-butylcarbazole in organic solvents, an intricate photophysical problem. The use of advanced ultrafast spectroscopy techniques in Contribution 12 revealed the mechanisms behind the compounds’ relaxation processes, providing valuable insights for more stable organic optoelectronic materials. An additional study by Moritz Knötig et al. (Contribution 13) provided a detailed photophysical understanding of the intermolecular pathways and energy transfer mechanisms of carbazole derivatives in thin films used in organic electronics, such as organic light-emitting diodes (OLEDs). The work of Tikhonov et al. (Contribution 14) addressed the inverse problems in pump–probe spectroscopy, an ultrafast kinetic technique that provides deep insights into photophysical and photochemical processes. The research in Contribution 14 presented a consistent approach for solving these inverse problems, avoiding the pitfalls of simply using least-squares fitting. By employing regularized Markov Chain Monte Carlo sampling, Tikhonov et al. offered a robust solution to the nonlinear inverse problem. Python-based software for implementing the fitting routine was made available by Contribution 14, together with a discussion of critical experimental parameters, such as pulse overlap and minimal time resolution.
2.3. Contributions on Photobiology and Photoprotection
In the photobiology context, Gonçalves et al. (Contribution 15) investigated the spectral optical properties of brain cortex from rabbit tissues using transmittance and reflectance spectroscopy. The study identified melanin and lipofuscin pigments and evaluated their impact on the absorption properties of the cortex. Insights into the aging of brain tissues were provided in Contribution 15 to enable the potential development of optical methods to diagnose and monitor brain diseases. The article by Frederick et al. (Contribution 16) offered new computational insights into the photophysics of a heterodimer model system made of eumelanin, which contains the catechol and benzoquinone functionalities. The study investigated the mechanisms behind the photostability of eumelanin, a skin pigment that protects against UV damage, using multi-reference computational methods. The results of Contribution 16 revealed a photoinduced intermolecular hydrogen transfer that is key to the photoprotective properties of eumelanin. The work of Frederick et al. improved the understanding of eumelanin’s photophysics and its role in protecting chromosomal deoxyribonucleic acid (DNA) from UV-induced damage. Moreover, Segarra-Martí et al. (Contribution 17) investigated the photoionization processes of DNA nucleobase derivatives using advanced computational methods. The study by Segarra-Martí et al. revealed ultrafast decay and photostability mechanisms, providing insights into the photoprotection of DNA and potential implications for understanding UV-induced DNA damage and related health concerns.
Kawabata et al. (Contribution 18) developed a photostabilization strategy to ensure the quality and quantity of photodegradable pharmaceuticals. In their study, polyphenols with antioxidant and photostabilizing properties were evaluated during the UV photodegradation of naproxen (NPX) in the solid state. The molecules of quercetin, curcumin, and resveratrol efficiently suppressed NPX photodegradation by behaving as antioxidants with strong UV filtering activity. The findings in Contribution 18 might be applied to photostabilize crushed or decapsulated medicines in the future. In a related context, Kodikara et al. (Contribution 19) investigated the impact of benzophenone-type UV filters on the photodegradation of sulfamethoxazole in water. The research revealed that benzophenone and its derivative oxybenzone significantly enhance the degradation rate of sulfamethoxazole by sensitizing reactive intermediates. Indeed, the work in Contribution 19 showed that coexisting benzophenone and its derivative oxybenzone possess promising potential to be used as effective photosensitizers, which may facilitate the photodegradation processes of organic micropollutants in aquatic environments. Soilán et al. (Contribution 20) studied the photostability of avobenzone, a popular sunscreen agent in the skin care industry, which under UV light loses effectiveness as it is degraded. Soilán et al. revealed that mycosporine-like amino acid (MAA) analogs were demonstrated as potential alternative stabilizers to octocrylene, resulting in enhanced avobenzone photostability and a promising next generation of sunscreens.
3. Conclusions
Overall, the “Feature Papers in Photochemistry” and “Feature Papers in Photochemistry II” Special Issues are a testament to the dynamic and impactful nature of photochemical research, offering insights and innovations that have the potential to shape the future of science and technology in the field of photochemistry. Multiple advancements in the field of photochemistry have been provided in the Special Issues. However, several areas for future exploration remain, including the intricacies of light–matter interactions at the quantum level, the stability and efficiency of photocatalytic systems under practical conditions, and the environmental impact of photochemical processes. Continued research and innovation in photochemistry is further needed to address these matters. Looking ahead, it is imperative that future research in photochemistry focuses on several key areas.
First, there is a need for more in-depth studies on the mechanistic aspects of photochemical reactions. Understanding the fundamental processes that govern these reactions will enable the development of more efficient and selective photochemical systems. Second, the integration of photochemistry with other disciplines, such as materials science, biology, food science, and environmental science, holds great promise. Interdisciplinary approaches can lead to the discovery of new photochemical applications and the optimization of existing ones. Third, the development of sustainable photochemical processes remains a critical goal. Researchers should aim to design photocatalysts and photoreactors that are not only highly efficient but also environmentally benign and economically viable. Finally, advancing computational and theoretical methods to predict and design photochemical reactions will be crucial. These methods can provide valuable insights into the behavior of photochemical systems and guide experimental efforts.
In conclusion, the Special Issues have laid a strong foundation by addressing current gaps and highlighting innovative research in photochemistry. Moving forward, a concerted focus on fundamental understanding, interdisciplinary integration, sustainability, and advanced computational methods will be essential to unlocking the full potential of photochemistry. This concerted strategy should drive the field toward a future filled with new discoveries and transformative technologies.
Gratitude is extended to all authors and reviewers for their contributions, which have significantly enriched these Special Issues.
Acknowledgments
M.I.G. acknowledges support under NSF award 2403875.
Conflicts of Interest
The author declares no conflicts of interest.
List of Contributions
- Vallavoju, R.; Kore, R.; Parikirala, R.; Subburu, M.; Gade, R.; Kumar, V.; Raghavender, M.; Chetti, P.; Pola, S. Synthesis and Characterization of New Tetradentate N2O2-Based Schiff’s Base Cu (II) Complexes for Dye Photodegradation. Photochem 2023, 3, 274–287.
- Mau, A.; Noirbent, G.; Dietlin, C.; Graff, B.; Gigmes, D.; Dumur, F.; Lalevée, J. Panchromatic Copper Complexes for Visible Light Photopolymerization. Photochem 2021, 1, 167–189.
- Edelmannová, M.; Reli, M.; Kočí, K.; Papailias, I.; Todorova, N.; Giannakopoulou, T.; Dallas, P.; Devlin, E.; Ioannidis, N.; Trapalis, C. Photocatalytic Reduction of CO2 over Iron-Modified g-C3N4 Photocatalysts. Photochem 2021, 1, 462–476.
- Malpicci, D.; Giannini, C.; Lucenti, E.; Forni, A.; Marinotto, D.; Cariati, E. Mono-, Di-, Tri-Pyrene Substituted Cyclic Triimidazole: A Family of Highly Emissive and RTP Chromophores. Photochem 2021, 1, 477–487.
- Stefanello, F.S.; Vieira, J.C.B.; Araújo, J.N.; Souza, V.B.; Frizzo, C.P.; Martins, M.A.P.; Zanatta, N.; Iglesias, B.A.; Bonacorso, H.G. Solution and Solid-State Optical Properties of Trifluoromethylated 5-(Alkyl/aryl/heteroaryl)-2-methyl-pyrazolo[1,5-a]pyrimidine System. Photochem 2022, 2, 345–357.
- Joo, M.H.; Park, S.J.; Jang, H.J.; Hong, S.-M.; Rhee, C.K.; Sohn, Y. Enhanced Photoluminescence of Electrodeposited Europium Complex on Bare and Terpyridine-Functionalized Porous Si Surfaces. Photochem 2021, 1, 38–52.
- Gimenez-Gomez, A.; Magson, L.; Peñin, B.; Sanosa, N.; Soilán, J.; Losantos, R.; Sampedro, D. A Photochemical Overview of Molecular Solar Thermal Energy Storage. Photochem 2022, 2, 694–716.
- Crespo, P.M.; Odio, O.F.; Reguera, E. Photochemistry of Metal Nitroprussides: State-of-the-Art and Perspectives. Photochem 2022, 2, 390–404.
- Sidir, İ.; Góbi, S.; Gülseven Sıdır, Y.; Fausto, R. Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Phenyl 1-Hydroxy-2-Naphthoate. Photochem 2021, 1, 10–25.
- Barnes, A.G.; Richy, N.; Amar, A.; Blanchard-Desce, M.; Boucekkine, A.; Mongin, O.; Paul, F. Electronic Absorption, Emission, and Two-Photon Absorption Properties of Some Extended 2,4,6-Triphenyl-1,3,5-Triazines. Photochem 2022, 2, 326–344.
- Vasilev, A.A.; Baluschev, S.; Ilieva, S.; Cheshmedzhieva, D. E–Z Photoisomerization in Proton-Modulated Photoswitchable Merocyanine Based on Benzothiazolium and o-Hydroxynaphthalene Platform. Photochem 2023, 3, 301–312.
- Knötig, K.M.; Gust, D.; Lenzer, T.; Oum, K. Excited-State Dynamics of Carbazole and tert-Butyl-Carbazole in Organic Solvents. Photochem 2024, 4, 163–178.
- Knötig, K.M.; Gust, D.; Oum, K.; Lenzer, T. Excited-State Dynamics of Carbazole and tert-Butyl-Carbazole in Thin Films. Photochem 2024, 4, 179–197.
- Tikhonov, D.S.; Garg, D.; Schnell, M. Inverse Problems in Pump–Probe Spectroscopy. Photochem 2024, 4, 57–110.
- Gonçalves, T.M.; Martins, I.S.; Silva, H.F.; Tuchin, V.V.; Oliveira, L.M. Spectral Optical Properties of Rabbit Brain Cortex between 200 and 1000 nm. Photochem 2021, 1, 190–208.
- Frederick, V.C.; Ashy, T.A.; Marchetti, B.; Ashfold, M.N.R.; Karsili, T.N.V. Photoprotective Properties of Eumelanin: Computational Insights into the Photophysics of a Catechol:Quinone Heterodimer Model System. Photochem 2021, 1, 26–37.
- Segarra-Martí, J.; Nouri, S.M.; Bearpark, M.J. Modelling Photoionisations in Tautomeric DNA Nucleobase Derivatives 7H-Adenine and 7H-Guanine: Ultrafast Decay and Photostability. Photochem 2021, 1, 287–301.
- Kawabata, K.; Miyoshi, A.; Nishi, H. Photoprotective Effects of Selected Polyphenols and Antioxidants on Naproxen Photodegradability in the Solid-State. Photochem 2022, 2, 880–890.
- Kodikara, D.; Guo, Z.; Yoshimura, C. Effect of Benzophenone Type UV Filters on Photodegradation of Co-existing Sulfamethoxazole in Water. Photochem 2023, 3, 288–300.
- Soilán, J.; López-Cóndor, L.; Peñín, B.; Aguilera, J.; de Gálvez, M.V.; Sampedro, D.; Losantos, R. Evaluation of MAA Analogues as Potential Candidates to Increase Photostability in Sunscreen Formulations. Photochem 2024, 4, 128–137.
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Guzman, M.I. Feature Papers in Photochemistry. Photochem 2024, 4, 511-517. https://doi.org/10.3390/photochem4040032
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Guzman MI. Feature Papers in Photochemistry. Photochem. 2024; 4(4):511-517. https://doi.org/10.3390/photochem4040032
Chicago/Turabian StyleGuzman, Marcelo I. 2024. "Feature Papers in Photochemistry" Photochem 4, no. 4: 511-517. https://doi.org/10.3390/photochem4040032
APA StyleGuzman, M. I. (2024). Feature Papers in Photochemistry. Photochem, 4(4), 511-517. https://doi.org/10.3390/photochem4040032
