Photochem doi: 10.3390/photochem6020020

Authors: Amal M. Al-Amri Muhammad Zulfiqar

In this study, we combined lead-free inorganic perovskite, CsSnI3, with a transition metal chalcogenide, MoS2, to develop a hybrid architecture for photodetectors utilizing the SCAPS-1D simulation tool. The performance of the photodetector was investigated across various thicknesses, doping concentrations, light intensities, and temperatures. An in-depth analysis of built-in potential, recombination rate, generation rate, quantum efficiency, I-V characteristics, and other performance parameters showed that the ideal thickness, doping density, bulk defect density, and interface defect density for enhanced photodetector performance are 800 nm, 1 × 1019 cm−3, 1 × 1014 cm−3, and 1 × 1010 cm−3, respectively. The photodetector exhibits optimal performance within the wavelength range of 200–500 nm and under illumination levels of 500–700 mW/m2, maintaining a consistent responsivity of 0.59 A/W, a detectivity of 4.28 × 1013 Jones, a photocurrent of 34.50 mA/cm2, and a low dark current of 10−6 mA/cm2, with good thermal stability over a wide range of temperatures. The findings indicate that the CsSnI3/MoS2 heterojunction photodetector exhibits superior performance characterized by enhanced sensitivities throughout a broad operational range within the UV–blue visible spectrum and paves the way for the development of cost-effective, high-performance photodetectors in future optoelectronic applications.

Photochem doi: 10.3390/photochem6020019

Authors: Brian Corbin Agampodi Dimagi Dasunika De Zoysa Margaret Hilliker Yi Pang

4-Dimethylamino-2′-hydroxy chalcone (DHC) 1 is an important natural compound that is nearly non-fluorescent in solution but highly fluorescent in its crystalline state. At room temperature, the weak fluorescence from the DHC solution is exclusively from its keto tautomer, without notable contribution from its enol tautomer. By using low-temperature fluorescence, the study found that the enol emission could be detected upon cooling with liquid N2 in a protic solvent (e.g., EtOH). This led to observation of the fluorescence vibronic structure of enol tautomer, in addition to its enol emission λem ≈ 473 nm that is well separated from its keto tautomer emission (λem ≈ 600 nm). By freezing DHC in a solvent matrix, the study revealed the fluorescent characteristics of a single molecule in a rigid environment. Further comparison of DHC in a solvent matrix and crystalline state disclosed that the emission of crystalline DHC was primarily from the keto tautomer, along with some minor contribution from the enol tautomer, despite the tight packing environment in the crystalline state.

Photochem doi: 10.3390/photochem6020018

Authors: Justine Auene Veikko Uahengo Habauka M. Kwaambwa Tobias Plessing Andy Gradel

TiO2 is normally a preferred photocatalyst; however, its photocatalytic performance is constrained by its low surface area, wide band gap, and high electron–hole pair recombination rates. The objective of this study was to optimize the photocatalytic efficiency of TiO2 by impregnating it onto activated carbon derived from Senegalia mellifera biomass. The quantitative study involved synthesizing TiO2 using the precipitation technique and preparing AC through both chemical and physical activation methods. The prepared AC samples were impregnated with TiO2 NPs using the wet impregnation method. The physicochemical properties of the samples were examined using several characterization techniques, namely, FTIR, EDS, Raman, UV reflectance, STA, SEM, and BET. The photocatalytic efficiency of AC/TiO2 composites was evaluated through methyl orange degradation. The results showed significant improvement in photocatalytic performance when TiO2 was supported on AC. The modified photocatalyst exhibited enhanced surface area, thus increased active sites for photocatalysis, improving electron–hole separation and reducing recombination. The 50%CO2/AC-0.5TiO2 composite demonstrated superior photocatalytic activity under both UV and visible light irradiation. It showed 52.1% MO removal under visible light and 76.1% MO removal under UV light. The study concludes that biomass-derived AC/TiO2 composites present a promising, cost-effective and sustainable approach of enhancing photocatalytic activities.

Photochem doi: 10.3390/photochem6020017

Authors: Edith Dube

The increasing prevalence of antimicrobial resistance, together with recurring infectious disease outbreaks, has intensified the need for alternative strategies to control microbial infections beyond conventional antibiotic therapies. Antimicrobial photodynamic therapy has emerged as a promising non-antibiotic approach in which light-activated photosensitising compounds generate reactive oxygen species that induce oxidative damage to microbial cells. Plant-derived photosensitisers have attracted increasing attention due to their structural diversity, biocompatibility, natural abundance, and potential for sustainability. Natural compounds such as curcumin, hypericin, chlorophyll derivatives, flavonoids, anthraquinones, and riboflavin exhibit favourable photochemical properties that enable efficient production of reactive oxygen species upon irradiation with visible light. Through radical- and singlet-oxygen-mediated photochemical pathways, these molecules exhibit broad-spectrum antimicrobial activity against bacteria, fungi, viruses, and biofilm-associated microorganisms. This review examines the photophysical properties and mechanisms of reactive oxygen species generation associated with plant-derived photosensitisers, together with key factors influencing their antimicrobial performance. Recent advances in nanocarrier-based delivery systems, dual-wavelength activation strategies, and synergistic combination therapies are also discussed for their potential to improve photostability, enhance reactive oxygen species generation, and increase microbial inactivation efficiency. Finally, current progress, challenges, and future research directions for advancing plant-derived photosensitisers in antimicrobial photodynamic therapy are discussed.

Photochem doi: 10.3390/photochem6020016

Authors: Stefania-Renata Stepanov Vasile Chiș

Seminaphtofluorones (SNAFRs) are a family of benzannulated xanthene dyes that exhibit strong fluorescence in both neutral and anionic states and can reach emission wavelengths in the deep-red to near-infrared region. Their optical response is highly sensitive to regioisomerism and functionalization, making them attractive candidates for systematic structure–property investigations. Here, we computed the photophysical properties of six SNAFR regioisomers for both neutral and anionic species and correlate the calculated results with available experimental data. From the six dyes, we further chose two of them, SNAFR4 and SNAFR6, to further investigate how phenyl-ring functionalization modulates SNAFR properties by introducing methyl (–CH3) and carboxyl (–COOH) substituents at the ortho (o), meta (m), and para (p) positions. The calculations indicate that substitution induces measurable changes in geometries, as well as in excitation and emission energies, with particularly pronounced effects for the anionic derivatives. Overall, these results provide a computational framework for the rational tuning of SNAFRs’ optical properties and the design of derivatives with tailored optical characteristics for fluorescence imaging and applications in photodynamic therapy.

Photochem doi: 10.3390/photochem6020015

Authors: Mariia Naumenko Vitaly Volosi Anastasia Leonteva Anna Nushtaeva Alexey Ivanenko Sergey Kulemzin Konstantin Baranov Alexander Moskalensky

Singlet oxygen (1O2) is a key mediator in photodynamic therapy (PDT), and its generation and reactivity in biological systems have been extensively studied. It has been shown that laser radiation at near-infrared (NIR) regions can be used to directly generate 1O2. In this work, we investigated photosensitizer-free 1O2 generation using an original all-fiber pulsed laser operating at 1066 nm and 1241 nm and evaluated its impact on mitochondrial activity in U-87 MG glioblastoma cells. Singlet oxygen was evaluated using the 1,3-diphenylisobenzofuran (DPBF) chemical probe and confirmed with argon-purging controls, demonstrating clear oxygen- and wavelength-dependent effects. Laser irradiation of glioblastoma cells demonstrated distinct effects depending on the wavelength, although decrease in cellular metabolic activity was observed in both cases. Interestingly, some inhibitory effect was also observed when the culture medium was pre-irradiated at 1241 nm and subsequently added to intact cells. These results demonstrate that laser radiation at both studied wavelengths can elicit measurable biological effects, although the relative efficiency in chemical versus cellular systems varies. Collectively, these findings provide a foundation for further systematic studies of wavelength-specific NIR interactions with cellular and molecular components in biological environments.

Photochem doi: 10.3390/photochem6020014

Authors: Pazhani Durgadevi Koyeli Girigoswami Chandni Thakkar Agnishwar Girigoswami

All forms of neural communications, from cognition to emotion, are regulated by neurotransmitters, which are otherwise the chemical language of the brain. Precise detection of these neurotransmitters is essential for the perception of neurophysiology and diagnosis of neurodegenerative diseases as well. Among the existing techniques for the detection of these molecules, fluorescence sensing is evolving as a powerful approach in terms of high sensitivity, rapid response, and real-time visualization of the chemical events occurring in the neural system. In recent years, nanomaterials have transformed this field by integrating tunable optical properties, excellent photostability, and modifiable surface chemistry into biocompatible nanostructures. We summarize the recent advances of these architectures to show how the material type and dimensionality, as well as the surface functionality, play roles in sensing through the mechanisms of Förster resonance energy transfer (FRET), photoinduced electron transfer (PET), inner filter effect (IFE), and aggregation-induced emission (AIE). The discussion has also been extended to the correlation of fluorescence modulation with the selectivity and sensitivity in the mechanism-to-function relationship. The potential utility of such innovative technologies, including artificial intelligence, spectral deconvolution analysis via big data algorithms, and chip-integrated sensing, was explored as a means to enable real-time neurochemical detection. This converging area of nanotechnology and neuroscience leaves a mark not just in analytical accuracy, but also parallels human brain rhythms.

Photochem doi: 10.3390/photochem6010013

Authors: A. Alfaro-Barajas D. Monllor-Satoca Jingshan Luo T. Lana-Villarreal

The direct thermal conversion of thiourea on fluorine-doped tin oxide (FTO) substrates is widely used to fabricate sulfur-doped carbon nitride (S-CN) photoelectrodes; however, substrate-induced effects often contribute to photoelectrochemical response. Here, we show that the sulfurization of FTO during thermal treatment leads to the in-situ formation of a tin sulfide underlayer, mainly SnS2, which significantly contributes to the observed photoresponse. A systematic study as a function of temperature reveals that the formation of sulfur-doped carbon nitride and tin sulfide occurs within a similar temperature window, making temperature control alone insufficient to suppress substrate sulfurization. To overcome this limitation, a thin compact carbon nitride interlayer synthesized from melamine was introduced between the FTO substrate and the S-CN film. This interlayer effectively prevents tin sulfide formation and enables the growth of an adherent S-CN film. The resulting photoanodes exhibit stable photoelectrochemical performance toward water oxidation under alkaline conditions (1M KOH), with an onset potential of ~+0.4 V vs. RHE and stable photocurrents up to 40 μA·cm−2 under AM 1.5G illumination. Electrochemical impedance spectroscopy confirms that the compact carbon nitride interlayer also acts as an effective charge-blocking barrier. This work provides a reliable strategy to avoid substrate-induced artifacts and establishes clear design guidelines to prepare truly sulfur-doped carbon nitride photoelectrodes.

Photochem doi: 10.3390/photochem6010012

Authors: Chrysoula Athanasekou

Hollow fibers (HFs) have recently gained attention as an advantageous photocatalyst immobilizer for heterogeneous catalysis. Depending on their fabrication method, they can come up, or not, with a porous network within their structure. In this case, they are sometimes referred to as membranes, although they are not applied in liquid flow applications as filters. This work provides a concise overview of all the studies encountered in the literature on photocatalytic hollow fibers (HFs) and hollow fiber membranes (HFMs), clarifying the prevailing confusion about the topic. All publications are categorized with respect to their reported applications in batch liquid, flow, or gas experiments.

Photochem doi: 10.3390/photochem6010011

Authors: Lisa M. Landino Antonios Tsompanidis Hannah McMinn Andrew Mooney Brandon Yu

Our recent work has focused on red light-mediated photoreduction of p-benzoquinones and both o-, and p-naphthoquinones using methylene blue and the chlorophyll metabolite, pheophorbide A as photosensitizers. Photoreduction of biologically relevant quinones mimics photoreduction of plastoquinone by chlorophyll in photosynthesis. We examined photo-oxidation and photoreduction reactions of catechols because their oxidation to o-quinones by reactive oxygen species is implicated in protein damage in neurodegeneration. Photo-oxidation of catecholamines including dopamine, epinephrine and norepinephrine required red light, methylene blue or pheophorbide A, and molecular oxygen. Their cyclized oxidation products, aminochrome, adrenochrome and noradrenochrome, were detected by UV/visible spectroscopy. Hydrogen peroxide was generated during photo-oxidation by singlet oxygen-dependent oxidation of catecholamines. Inclusion of tertiary amine electron donors decreased cyclized products but did not affect hydrogen peroxide yield consistent with concurrent photo-oxidation followed by photoreduction of the o-quinone intermediate. Unreacted dopamine and norepinephrine were quantified using 3-hydroxyphenyl boronic acid following photochemical reactions. Dopamine and norepinephrine boronate esters absorb at 417 and 550 nm. Photo-oxidation of dihydroxycaffeic acid and dihydroxyphenyl acetic acid was also evaluated by detecting their boronate esters at 475 nm. We hypothesize that photoreduction of transient o-quinones by the combination of red light and dietary chlorophyll metabolites may be a path to limit protein damage and to recycle catechol antioxidants.

Photochem doi: 10.3390/photochem6010010

Authors: Dongqi Li Yingshu Cui Xiaosong Li

Gastrointestinal (GI) malignancies have caused tremendous disease burden around the world; however, conventional therapy strategies, such as radiotherapy, chemotherapy, and immunotherapy, have achieved limited efficacy in the diagnosis and treatment. In further exploration of GI tumors, the complexity and heterogeneity of the tumor microenvironment (TME) have been increasingly recognized. Appropriate strategies to modulate the TME are necessary to enhance the therapeutic effect. Photosensitizers (PSs) are chemical substances that are activated at specific wavelengths of light to initiate photodynamic effects. Nanotechnology provides a platform for the targeted delivery of PSs and small-molecule drugs, enabling precise targeting and remodeling of the TME. In this review, we summarize the principles and mechanisms of photochemical reactions and elaborate on the effect of photochemical nanoplatforms in modulating the TME of GI tumors. Finally, we discuss the potential value of photochemical nanoplatforms for diagnosing GI malignancies.

Photochem doi: 10.3390/photochem6010009

Authors: Anna Lena Schäfer Cristina Gellini Rolf Diller Katrina T. Forest Uwe Kuhlmann Peter Hildebrandt

Time-resolved (TR) resonance Raman (RR) spectroscopy with continuous-wave excitation is a fundamental technique that has contributed substantially to the understanding of the structure and dynamics of retinal proteins. However, the underlying principles were developed about fifty years ago for instrumentation that is hardly in use anymore. Thus, the adaptation of the technique to the current state-of-the-art equipment is needed to satisfy the increasing demand for the spectroscopic characterization of novel retinal proteins. In this work, we focus on pump–probe TR RR experiments with a confocal spectrometer using a rotating cell. We define the parameters ensuring fresh-sample condition and the photochemical innocence of the probe beam as a prerequisite for studying retinal proteins that undergo a cyclic photoinduced reaction sequence. For the measurements of intermediate states and reaction kinetics, pump–probe experiments are required in which the two laser beams hit the flowing sample with a defined but variable delay time. An appropriate set-up for such two-beam experiments with a confocal spectrometer is proposed and tested in TR experiments of bacteriorhodopsin. The comparison with the results obtained with classical slit spectrometers using a 90-degree scattering illustrates the advantages and disadvantages of the confocal arrangement. It is shown that modern confocal spectrometers substantially decrease the spectra acquisition time but require a more demanding optical set-up. Furthermore, the extent of photoconversion by the pump beam is lower than for the 90-degree-scattering arrangement, which reduces the accuracy of kinetic measurements.

Photochem doi: 10.3390/photochem6010008

Authors: Ana Gabriela Urbanin Batista de Lima Claudinéia Aparecida Sales de Oliveira Pinto Thalita Marcílio Cândido Fabiana Vieira Lima Solino Pessoa Maria Valéria Robles Velasco Daniel Pecoraro Demarque André Rolim Baby

The transition to more sustainable models of production and consumption has encouraged the scientific community to seek innovative solutions that promote environmental responsibility and reduce waste. The cosmetic industry, in particular, has increasingly invested in natural and eco-friendly ingredients as alternatives to synthetic and environmentally harmful components. In this context, plant-derived bioactive compounds with antioxidant and anti-inflammatory potential have gained attention for their ability to enhance photoprotection and reduce the concentration of conventional ultraviolet (UV) filters in sunscreens. Humulus lupulus L. (hop), a plant traditionally used in the brewing industry, generates large amounts of organic waste after the beer production process, especially through the dry-hopping technique. Despite often being discarded, this residual biomass retains important secondary metabolites with high biological value. Our investigation researched the sustainable valorization of hop brewing residues as a source of bioactive compounds for the development of more natural photoprotective products. We performed HLPC-MS/MS analysis and confirmed the presence of α-acids in both pure and reused hop material extracts, while a xanthohumol-like prenylated flavonoid was tentatively detected exclusively in the extract obtained from reused hop extract. In vitro tests demonstrated that sunscreens containing extract obtained from reused material significantly increased the sun protection factor (SPF) without negatively altering the critical wavelength when water was used as the solvent. None of the samples developed higher UVAPF values compared to the control. Our investigation, to the best of our knowledge, constitutes the first successful proof of concept demonstrating the use of both pure (non-reused) and reused hop material extracts as functional photoprotective adjuvants in sunscreen formulations evaluated by a robust, standardized in vitro methodology. This work highlights the dual benefit of reducing industrial waste and developing more sustainable, consumer-friendly cosmetic products.

Photochem doi: 10.3390/photochem6010007

Authors: Valery M. Dembitsky Alexander O. Terent’ev

Sosnovsky’s hogweed (Heracleum sosnowskyi Manden.) is an invasive plant species widely distributed across Eastern Europe and Russia that poses a serious threat to human health due to its pronounced phototoxic properties. Contact with the plant sap followed by exposure to solar ultraviolet (UV) radiation frequently results in phytophotodermatitis, which is characterized by erythema, blistering, ulceration, and persistent hyperpigmentation. The development of these photochemical injuries—most notably furanocoumarins—act as potent photosensitizers and induce cellular and DNA damage upon UV activation. This review provides an integrated overview of the geographical spread and invasiveness of H. sosnowskyi, the chemical composition of its biologically active metabolites, and the molecular mechanisms underlying hogweed-induced skin injury. Particular emphasis is placed on the photochemical transformations of furanocoumarins, including psoralens and their photooxidation products, such as 1,2-dioxetanes, which generate reactive oxygen species and DNA crosslinks. In addition, the review examines other compounds derived from hogweed biomass—including furan derivatives, aromatic compounds, fatty acids, sterols, and their oxidative products—that may contribute to phototoxic and cytotoxic effects. Clinical manifestations of hogweed-induced burns, their classification, symptomatology, and current therapeutic approaches are critically discussed, highlighting the absence of standardized treatment guidelines. Rather than serving as a purely clinical or botanical survey, this review frames Sosnovsky’s hogweed injury as a solar-light-activated photochemical hazard, tracing the sequence from environmental sunlight exposure through molecular photochemistry to biological tissue damage. By integrating chemical, biological, and dermatological perspectives, the review aims to clarify injury mechanisms and support the development of more effective preventive and mitigation strategies under real-world exposure conditions.

Photochem doi: 10.3390/photochem6010006

Authors: Alexander Trujillo Romain Veillard Amédée Triadon Guillaume Grelaud Gilles Argouarch Thierry Roisnel Anu Singh Isabelle Ledoux Anissa Amar Abdou Boucekkine Marek Samoc Katarzyna Matczyszyn Xinwei Yang Adam Barlow Marie P. Cifuentes Mahbod Morshedi Mark G. Humphrey Frédéric Paul

We report the use of σ-alkynyl d6 electron-rich transition metal complexes as electron-releasing end-groups in octupolar molecules designed for nonlinear optical (NLO) applications, specifically, N,N′,N″-triarylisocyanurates (5,7,8,10,12) and 1,3,5-triarylbenzenes (6,9,11) functionalized by Fe(II) and Ru(II) organometallic moieties, and their NLO properties, as assessed by hyper-Rayleigh scattering (HRS) and Z-scan. The redox properties are briefly investigated through isolation of the corresponding Fe(III) trications 5[PF6]3 and 6[PF6]3. The second-harmonic generation (SHG) or two-photon absorption (2PA) performance of the Fe(II) and Ru(II) parents is compared with the help of TD-DFT calculations performed on models. Comparison with tris-ferrocenyl isocyanurate 4 reveals that the σ-connection of the metallic centers to the π-manifold is superior to the η5-connection for enhancing NLO properties. The positive effect of organometallic end-groups on NLO properties relative to purely organic electron-releasing substituents is established. The mechanism by which NLO enhancement occurs is complex and possibly connected to the polarizable π-electrons in the ligands surrounding the metal alkynyl units, but in most cases, the observed NLO enhancement must arise from the transition metal centers interacting with the central π-manifold.

Photochem doi: 10.3390/photochem6010005

Authors: Pietro Capurro Cristina Martini Andrea Basso

Synthesizing natural substances has always been a significant challenge for organic chemists. The key to a successful total synthesis lies in utilizing reactions that generate molecular complexity with high stereocontrol. Photochemical reactions offer immense potential in this regard, though their complex mechanisms require careful mastery. This review explores recent examples from the literature where light-mediated reactions are crucial, often irreplaceable by thermal alternatives. The manuscript is organized by different photochemical processes, each introduced with relevant background. This review does not offer a complete analysis of all recent light-assisted syntheses; rather, it offers a glimpse into the growing trend of using photo-driven transformations to address significant synthetic challenges.

Photochem doi: 10.3390/photochem6010004

Authors: Manel Boukazzoula Djamila Maghnia Frank Neumann Oualid Baghriche

Titanium dioxide (TiO2) thin films were deposited by DC magnetron sputtering and subsequently treated in hot water at 50, 70, and 95 °C for 72 h to investigate the influence of low temperature on their structural optical and functional properties. XRD analysis revealed a progressive transformation from amorphous to anatase phase with increasing treatment temperature, accompanied by an increase in crystallite size from 5.2 to 15.1 nm. FT-IR spectroscopy confirmed enhanced surface hydroxylation and contact angle measurements showed a decrease from 77.4° to 19.7°, indicating a significant improvement in superior wettability. The transmittance spectroscopy revealed a slight narrowing of the optical band gap from 3.34 to 3.21 eV, consistent with improved visible-light absorption. Photocatalytic tests using the Resazurin indicator demonstrated that the film treated at 95 °C exhibited the highest activity, achieving a bleaching time of 245 s three times faster than treated at 50 °C and twice as fast as treated at 70 °C. Under low-intensity solar irradiation, the same sample achieved complete E. coli inactivation within 90 min. These improvements are attributed to increased crystallinity, surface hydroxyl density, and enhanced ROS generation. Overall, this study demonstrates that mild hot-water treatment is an effective, substrate-friendly route to enhance TiO2 film wettability and multifunctional performance, enabling the fabrication of self-cleaning and antibacterial coatings on fragile materials such as plastics and textiles.

Photochem doi: 10.3390/photochem6010003

Authors: Fabiana L. Santos José B. G. Filho Vinícius M. F. Santos Karolina Furukawa Maraisa Gonçalves Juliana A. Torres Amanda S. Giroto Lucas S. Ribeiro Lucas Bonelli Caue Ribeiro André E. Nogueira

The increasing atmospheric concentration of CO2 is a major contributor to global climate change, underscoring the urgent need for effective strategies to convert CO2 into value-added products. In this sense, a composite was successfully synthesized by combining clinoptilolite zeolite (CZ) with varying amounts of copper oxide (CuO-1% and 10%) for CO2 photoreduction. The composites were characterized using insightful techniques, including XRD, nitrogen physisorption, DRS, and SEM. The results confirmed the incorporation and dispersion of CuO within the CZ support. The XRD analysis revealed characteristic crystalline CuO peaks. Despite the low surface area (<15 m2·g−1) and macroporous nature of the samples, EDS imaging revealed an effective and homogeneous dispersion of CuO, indicating efficient surface distribution. UV–Vis diffuse reflectance spectroscopy revealed band gap energies of 3.30 eV (CZ), 3.38 eV (1%-CuO/CZ), and 1.75 eV (10%-CuO/CZ), highlighting the pronounced electronic changes resulting from CuO incorporation. Photocatalytic tests conducted under UVC irradiation (λ = 254 nm) revealed that 10%-CuO/CZ exhibited the highest CO and CH4 production, 35 µmol·g−1 and 3.6 µmol·g−1, respectively. The composite also delivered the highest CO productivity (5.91 µmol·g−1·h−1), approximately 3.5 times that of pristine CZ, in addition to achieving the highest CH4 productivity (0.60 µmol·g−1·h−1). Furthermore, turnover frequency (TOF) analysis normalized per Cu site revealed that CuO incorporation not only enhances total productivity but also improves the intrinsic catalytic efficiency of the active copper centers. Overall, the synthesized composites demonstrate promising potential for CO2 photoreduction, driven by synergistic structural, electronic, and morphological features.

Photochem doi: 10.3390/photochem6010002

Authors: Salvatore Genovese Federica Giorgianni Alessandro Amadeo Scolastica Serroni Sebastiano Campagna

The photochemistry of transition metal complexes has been crucial for the development of many fundamental topics, as well as to pave the way for several important applications. However, in most cases, photoactive transition metal complexes involved precious metals, with luminescent ruthenium polypyridine complexes playing the dominant role. Developing photoactive species based on earth-abundant metals is highly important for fundamental and applicative reasons. Iron is one of the most abundant metals on Earth’s crust, so luminescent iron complexes are highly desired. The recent search for iron complexes with long-lived and luminescent excited states is here presented, including Fe(II) species with metal-to-ligand charge transfer (MLCT) excited states and Fe(III) species with luminescent ligand-to-metal charge transfer (LMCT) states. The excited-state equilibration approach to prolong the luminescence lifetimes of Fe(III) compounds in multichromophoric species is also discussed. This latter approach can increase the possibility of luminescent iron complexes being involved in bimolecular processes as well as in photoinduced electron and energy transfer at interfaces, which is relevant for many applications.

Photochem doi: 10.3390/photochem6010001

Authors: Pinghui Yang Yuexian Cao Jianhua Wang Jiaju Zhou Minyong Du Dexu Zheng

Two-dimensional (2D) metal halide perovskites have attracted considerable interest for their markedly improved environmental stability and versatile compositional tunability compared to their three-dimensional (3D) counterparts. Nevertheless, the anisotropic charge transport caused by insulating organic spacers often leads to inefficient charge transport and limiting device performance. Precise control over crystallographic orientation, particularly achieving vertical alignment of the inorganic layers, is essential to facilitate out-of-plane charge transport and enhance device efficiency. This review systematically summarizes recent advances in understanding and controlling the crystallographic orientation of 2D perovskites, emphasizing manipulating strategies such as processing optimization, composition engineering, spacer design, solvent selection, and additive assistance to promote vertical alignment of inorganic layers and improve interlayer charge transport. We also discuss the influence of phase distribution, quantum well width, and crystal growth kinetics on device performance. Finally, we outline prevailing challenges and future opportunities for achieving the ideal microstructure and high-efficiency 2D perovskite solar cells.

Photochem doi: 10.3390/photochem5040040

Authors: Begench Gurbandurdyyev Berdimyrat Annamuradov Justice ben Yosef Yaran Allamyradov Brayden Gross Ali Oguz Er

Gold nanoparticles (AuNPs) synthesized via picosecond pulsed laser ablation were investigated as enhancers of methylene blue (MB)-mediated photodynamic therapy (PDT) against Escherichia coli. AuNPs produced at 532 and 1064 nm with frequencies of 20–50 kHz showed frequency- and size-dependent effects, with 50 kHz yielding the highest particle concentrations and smaller particles enhancing reactive oxygen species (ROS) generation. UV-Vis and fluorescence spectroscopy confirmed nanoparticle formation and plasmonic properties consistent with TEM measurements. Photobleaching assays demonstrated that AuNPs significantly increased MB singlet oxygen generation, while the efflux pump inhibitor INF-55 further amplified bacterial killing without altering net ROS yield. In vitro assays revealed that INF-55 combined with MB/AuNPs achieved ~59% higher bacterial deactivation compared to MB/AuNPs alone. Molecular docking confirmed stronger binding of INF-55 to the AcrB efflux pump (−9.1 kcal/mol) than MB, supporting its role as a competitive inhibitor that promotes intracellular MB retention. These findings establish a dual-action PDT strategy in which AuNPs enhance ROS production and INF-55 augments antibacterial efficacy via efflux pump inhibition. Together, this platform provides a proof of concept for future translation to biofilm- and tissue-based infection models, and potentially to localized clinical applications such as prosthetic joint, catheter-associated, or chronic wound infections where conventional sterilization or systemic antibiotics are insufficient.

Photochem doi: 10.3390/photochem5040039

Authors: Shipra Gupta

Natural Product Synthesis (NPS) is a cornerstone of organic chemistry, historically rooted in the dual goals of structure elucidation and synthetic strategy development for bioactive compounds. Initially focused on identifying the structures of medicinally relevant natural products, NPS has evolved into a dynamic field with applications in drug discovery, immunotherapy, and smart materials. This evolution has been propelled by advances in reaction design, mechanistic insight, and the integration of green chemistry principles. A particularly promising development in NPS is the use of photochemistry, which harnesses light—a renewable energy source—to drive chemical transformations. Photochemical reactions offer unique excited-state reactivity, enabling synthetic pathways that are often inaccessible through thermal methods. Their precision and sustainability make them ideal for modern synthetic challenges. This review explores a wide range of photochemical reactions, from classical to contemporary, emphasizing their role in total synthesis. By showcasing their potential, the review aims to encourage broader adoption of photochemical strategies in the synthesis of complex natural products, promoting innovation at the intersection of molecular complexity, sustainability, and synthetic efficiency.

Photochem doi: 10.3390/photochem5040038

Authors: Xiaoman Shi Huimin Li Ruiping Deng Su Zhang Hongjie Zhang

Long persistent phosphors are widely used in many fields, such as LED, bioimaging, urgent lighting, temperature sensors, etc. Although green and blue long persistent phosphors are well developed, efficient orange-yellow long persistent phosphors are still relatively rare. In this work, a novel orange-yellow long-persistent phosphors Ca2LuScGa2Ge2O12:xPr3+ (CLSGGO:xPr3+, x = 0.003, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05) are prepared and systematically investigated through its crystal structural information, photoluminescence, and persistent luminescence properties. Under ultraviolet light excitation, these phosphors exhibit orange-yellow emission stemming from the 3P0 and 1D2 multiple electron transitions in the 4f level of Pr3+ ion. In addition, the material exhibits bright persistent luminescence. The complex garnet matrix structure of Ca2LuScGa2Ge2O12 provides excellent conditions for the formation of traps. Through the testing of thermoluminescence curve and function fitting, the density and depth of traps are studied; also, the storage and release process of carriers in the material are calculated in detail. A reasonable persistent luminescence mechanism is proposed for CLSGGO:0.01Pr3+. This work enriches the research content of photoluminescence and long persistent luminescence of Pr3+-doped garnet-based phosphors and paves the way for the future research of long persistent luminescent materials doped with rare earth ions.

Photochem doi: 10.3390/photochem5040037

Authors: Jineun Lee Toshikazu Sakaguchi Giseop Kwak

In this study, the fluorescence (FL) behavior of a fluorenone derivative (FDMFA) in four chlorinated hydrocarbon solvents was investigated. While all four solvents have low polarities, their proticities are considerably different. Therefore, the FL properties of FDMFA could be considered to depend solely on the solvent’s proticity, with any polarity effects being insignificant. The hydrogen bond donor acidity was used as a measure of proticity, with higher values representing greater FL quenching due to vibronic coupling. The hydrogen bonding between FDMFA and the solvents could be thermodynamically controlled; thus, the FL emission was substantially enhanced during the heating process and quenched again during the cooling process. This change occurred reversibly and repeatedly. Because chlorinated hydrocarbon solvents are widely used for reaction and cleaning purposes in industrial applications, the findings of this study will be helpful in ensuring that such solvents are appropriately handled.

Photochem doi: 10.3390/photochem5040036

Authors: Ziyang Wang Miao Yang Yuxi Chen Xinyue Yang Bowen Xie Xiaoke Duan Haoyue Shen Chengyuan Wang

Organic luminogens (OLs) with piezochromic (PC) properties have attracted significant attention for their varied applications in chemical sensors, organic optoelectronic devices, biological imaging, etc. In this work, we designed and synthesized three donor–acceptor–donor- or donor–acceptor-structured OLs with different donor or acceptor moieties. Their photophysical properties in both dilute solution and aggregated states were studied through various spectroscopic analytical methods, and their PC properties were investigated under mechanical grinding (MG) conditions. The OLs containing cyanostilbene moiety exhibited a photoemission shift up to ~45 nm after simple grinding, while that was only ~10 nm for cyanostyrene-containing OL. Combined with the powder X-ray diffraction analysis, the incorporation of the cyanostilbene moiety is inferred to play an important role in inducing the apparent PC properties. Our study not only reports novel OLs with good PC properties, but also discusses the structure–property relationships in order to provide guidance for future rational design and the development of novel PC materials.

Photochem doi: 10.3390/photochem5040035

Authors: Shize Zheng Xiangshi Liu Bingqian Guo Yanou Qi Xifeng Lv Bin Wang Di Cai

Biocatalysis is fundamental to biological processes and sustainable chemical productions. Over time, the biocatalysis strategy has been widely researched. Initially, biomanufacturing and catalysis of high-value chemicals were carried out through direct immobilization and application of biocatalysts, including natural enzymes and living cells. With the evolution of green chemistry and environmental concern, hybrid photoelectro-biocatalysis (HPEB) platforms are seen as a new approach to enhance biocatalysis. This strategy greatly expands the domain of natural biocatalysis, especially for bio-based components. The selective valorization of renewable furan derivatives, such as 5-hydroxymethylfurfural (HMF) and furfural, is central to advancing biomass-based chemical production. Biocatalysis offers high chemo-, regio-, and stereo-selectivity under mild conditions compared with traditional chemical catalysis, yet it is often constrained by the costly and inefficient regeneration of redox cofactors like NAD(P)H. Photoelectrocatalysis provides a sustainable means to supply reducing equivalents using solar or electrical energy. In recent years, hybrid systems that integrate biocatalysis with photoelectrocatalysis have emerged as a promising strategy to overcome this limitation. This review focuses on recent advances in such systems, where photoelectrochemical platforms enable in situ cofactor regeneration to drive enzymatic transformations of furan-based substrates. We critically analyze representative coupling strategies, materials and device configurations, and reaction engineering approaches. Finally, we outline future directions for developing efficient, robust, and industrially viable hybrid catalytic platforms for green biomass valorization.

Photochem doi: 10.3390/photochem5040034

Authors: José A. Rodrigues Bruno Esteves Patrícia Costa José H. Correia

Experimental analysis of the viscoelastic properties of natural polymers over different testing durations and response time scales yields complementary insights into their static and dynamic mechanical behavior. Within this context, Brillouin spectroscopy has emerged as a contactless, non-invasive and label-free tool for the mechanical characterization of materials. In this review article, we provide a comprehensive overview of recent advances in Brillouin spectroscopy techniques applied to various natural polymers, including proteins, carbohydrates, and polysaccharides. We discuss the principles of Brillouin scattering and their application in investigating the mechanical properties of natural polymers. Additionally, we explore future perspectives and challenges. This review aims to provide researchers and practitioners with a comprehensive understanding of the capabilities and limitations of Brillouin spectroscopy for the mechanical characterization of natural polymers, promoting new advances in this interdisciplinary field.

Photochem doi: 10.3390/photochem5040033

Authors: Rim El Jeni Gian Luca Chiarello Elena Selli Annamaria Costa Alessia Di Giancamillo Daniela Bertotto Giuseppe Radaelli Tarek Temraz Nadia Chérif

This study examines the potential in vitro application of different concentrations of titanium dioxide (TiO2) nanoparticles (NPs) irradiated with UV light for the sanitation of recirculating aquaculture systems (RASs) and their antiviral activity. The diverse effects of Nodavirus on immune gene expression (i.e., pro-inflammatory and anti-inflammatory genes, cellular response genes, humoral response genes, and stress genes) were studied using RT-qPCR (Reverse Transcription Quantitative Polymerase Chain Reaction). In addition, the viability and cytopathic effect in E-11 fish cells were also investigated. The results obtained did not show a clear cytopathic effect under the reversed-phase microscope observation at different TiO2 concentrations. A significant decrease in viral coat protein gene expression was observed when using 2.5 and 1.25 g/L TiO2 suspensions under UV irradiation. TiO2 at 1.25 g/L induced an inflammatory response to Nodavirus by increasing the expression of all target genes. Thus, this work suggests that TiO2 NPs can strengthen the immune system of fish to fight virus infection and make aquaculture a greener and more sustainable activity.

Photochem doi: 10.3390/photochem5040032

Authors: Gustavo Teixeira Machado Caio Rui Chiabai Isaac dos Santos Orgino Leticia Neves Ferraz Flavia Dayrell França Fábio Luiz Partelli Paulo Eduardo Narcizo de Souza Ana Sofia Fernandes Ana Luísa Gomes Júlio André Rolim Baby George Ricardo Santana Andrade Fabiana Vieira Lima Solino Pessoa

Sustainable ultraviolet (UV) filters that couple photoprotection with antioxidant activity are needed. Carbon dots (CDots) derived from agro-industrial waste have emerged as promising candidates. CDots were prepared from Coffea canephora (coffee leaf) residues by a one-pot microwave route and characterized by UV–Vis, FTIR, and TEM. Antioxidant capacity was determined by CUPRAC and DPPH-EPR. The photoprotective efficacy was assessed in vitro by diffuse reflectance spectrophotometry before and after solar-simulator exposure. Nearly spherical CDots (3.3 ± 0.7 nm) displayed a 4.16 eV optical bandgap and broad absorption from 200 to 400 nm. At 10 μg mL−1, CDots exhibited 24.62 ± 0.19% antioxidant activity relative to Trolox by CUPRAC, while by DPPH-EPR, they showed 99.9 ± 12.5% of radical quenching at 240 µg mL−1. Addition of 4.5% w/w (dry basis) CDots to the sunscreen system increased the in vitro SPF from 26 ± 13 to 161 ± 8 (p < 0.05) while maintaining the critical wavelength at 380 ± 0.64 nm. After 30 min of irradiation, the SPF dropped only 10%, versus 44% for the CDots-free sample (control), indicating superior photostability. Coffee leaf CDots acted as an efficient broadband UV absorber and antioxidant that markedly enhanced and stabilized a conventional sunscreen formulation. The work positions waste-derived CDots as an eco-friendly, next-generation multifunctional ingredient, aligning with circular economy principles.

Photochem doi: 10.3390/photochem5040031

Authors: Madyan A. Yaseen Zhifang Guo Peter C. Junk Michael Oelgemöller

The [2+2]-photocycloaddition of 2-acetoxy-1,4-naphthoquinone with 1,1-diphenylethylene, styrene and cyclopentene was conducted in a conventional batch reactor. Prolonged irradiation selectively produced the corresponding anti and head-to-head cyclobutanes in acceptable to good yields. The batch process was subsequently transferred to continuous-flow operation in a simple capillary device. Likewise, the photocycloaddition with diphenylacetylene gave the corresponding cyclobutene and a benzoanthracenone derivative in acceptable yields. The crystal structures of all main photoproducts were successfully determined.

Photochem doi: 10.3390/photochem5040030

Authors: Elisenda Pulido-Melián Cristina Valeria Santana-Fleitas Javier Araña Óscar Manuel González-Díaz

In this work, the photocatalytic reduction of CO2 was innovatively tested with the simultaneous removal and mineralization of a textile contaminant, methylene blue (MB), which acts as a sacrificial agent. The process was carried out in a flow regime under atmospheric conditions, using a liquid-phase photoreactor under UVA illumination with a duration of 24 h per test. Two commercial TiO2-based photocatalysts, P25 and P90 from Evonik, were used and surface modified through the photodeposition of metallic nanoparticles of Pt, Au, and Pd, as they did not show gas-phase products from CO2 reduction on their own. The optimal pH was 5, the decreasing order of activity by metal was Pt > Au > Pd, and the optimal MB concentration was 20 ppm. The major products were CH4 and H2 in the gas phase. The presence of CH4 was only detected in the presence of a CO2 flow. In the liquid phase, carboxylic acids were also detected in small amounts, and in the test, 100 ppm of MB ethanol was additionally detected. A 100% degradation of MB and 72.5% mineralization was achieved under the conditions of highest CH4 production (20 ppm MB at pH 5 with 4 g·L−1 P25-0.70%Pt).

Photochem doi: 10.3390/photochem5040029

Authors: Sara Pimenta José H. Correia

Raman spectroscopy is a widely used technology in the biomedical field, including specific applications from cancer diagnosis to an active role in the pharmaceutical industry. Despite the extensive use of Raman spectroscopy in research studies, there are still some limitations to its applicability in daily clinical diagnosis. This review initially presents the main principles of Raman spectroscopy and then its most relevant applications in the biomedical field, exploring the main advantages, challenges, and limitations. Additionally, other Raman-based techniques are identified as alternatives to the conventional technique. Overall, this review aims to present the currently available applications of Raman spectroscopy in the biomedical field and future appropriate perspectives, as possible guidance for new Raman-based biomedical devices.

Photochem doi: 10.3390/photochem5040028

Authors: Julietta Moustaka Michael Moustakas

In the light reactions of photosynthesis, reactive oxygen species (ROS), such as superoxide anion radical (O2•−), hydrogen peroxide (H2O2), singlet oxygen (1O2*), and hydroxyl radical (OH•), are continuously generated at basal levels and are kept in homeostasis by the antioxidative enzymatic and non-enzymatic systems. Nevertheless, under abiotic or biotic stress conditions, this balance between the creation and elimination of ROS is disrupted, and the increased ROS production leads to oxidative stress, which is involved in the growth retardation of plants. However, ROS are also beneficial, since they trigger the plant’s defense mechanisms for handling oxidative stress and are fundamental signaling molecules for the regulation of a range of physiological functions under optimum growth conditions or environmental stress circumstances, activating a plethora of acclimation responses. Gaining insight into the relationship between ROS generation, ROS scavenging, and the protective role of ROS will contribute to improving agricultural sustainability in the face of global climate change.

Photochem doi: 10.3390/photochem5030027

Authors: Angela Liao Lucas Teuber Robert Pike Christopher Abelt

Four 8-acyl-1-pyrrolidinylnaphalenes are prepared where the acyl group is pivaloyl (6), benzoyl (7), benzyloxycarbonyl (8), and ethyloxycarbonyl (9). Crystal structures for 6–8 show that both the carbonyl and pyrrolidinyl groups are nearly perpendicular to the naphthalene ring. Esters 8 and 9 fluoresce more strongly than ketones 6 and 7. All show some solvatofluoro-chromic emission from a charge-transfer excited state. Calculations suggest that both the acyl and amino groups twist back toward planarity with the naphthalene in the relaxed first singlet excited state. With 8 and 9, co-planarity is within 20°, while with 6 and 7, the carbonyl approaches no closer than 30°. With 6 and 7, the charge-transfer emission is replaced with a shorter wavelength band with more polar solvents. Despite the twisted geometries and steric interference toward planarization, these systems do not show emission from a twisted intramolecular charge-transfer (TICT) state.

Photochem doi: 10.3390/photochem5030026

Authors: Lily M. Guidry Sofia E. Guidry Tanima Barua Barbara Marchetti Michael F. Vansco Tolga N. V. Karsili

Organic peroxy (ROO•) and hydroperoxy (•QOOH) radicals are key reactive intermediates that are formed via the oxidation of volatile organic compounds during combustion or in the Earth’s atmosphere. Their primary fate is continued unimolecular decay or bimolecular chemistry, the relative branching for which is heavily structure- and temperature-dependent. This article outlines a combined single- and multi-reference quantum chemical study to characterize the near-UV accessible electronically excited states of the prototypical ROO• and •QOOH intermediates, tert-butyl peroxy and hydroperoxy-tert-butyl radicals—the ground-state chemistries of which have been well studied both experimentally and computationally. Additionally, we simulate the electronic absorption profiles of these ROO• and •QOOH intermediates with a variety of multi- and single-reference methods. The results show an interesting conformer dependence on the electronically excited-state character and electronic absorption maxima of •QOOH. The results show promise for electronic absorption spectroscopy to be used as a selected probe for determining •QOOH conformers. Additionally, electronic absorption may contribute to the daytime removal of long-lived •QOOH intermediates formed in the troposphere. We expect that our studies will motivate experiments on the electronic absorption spectra of experimentally achievable ROO• and •QOOH.

Photochem doi: 10.3390/photochem5030025

Authors: Soichiro Kawamorita Koyo Okamoto Shufang Huang Takeshi Naota

In this study, we investigated environmentally responsive photoluminescence color changes in water using an amphiphilic flavin derivative (1a) functionalized with an alkylsulfonate group. At low concentrations and room temperature, 1a exhibited a green emission. Upon increasing the concentration, thermodynamically stable micelle-like aggregates were formed, leading to a yellow emission. In contrast, under rapid freezing conditions, fibrous aggregates were formed under kinetic control, which also exhibited a yellow emission. These distinct aggregation modes are attributed to the cooperative effects of molecular design: the π-stacking ability of the tricyclic isoalloxazine core, flexible long alkyl chains, and the hydrophilic sulfonate moiety. This work demonstrates photoluminescent color switching based on aggregation-state control of a biogenic and potentially sustainable flavin luminophore, offering a new perspective for designing responsive and sustainable photofunctional materials.

Photochem doi: 10.3390/photochem5030024

Authors: Aristides Marcano Olaizola

We determine the efficiency of generating singlet oxygen molecules through Raman excitation in distilled water. Focused nanosecond light pulses in the spectral blue region induce a Raman transition toward the singlet oxygen state, generating a Stokes signal in the red spectral region. The signal is proportional to the number of photons corresponding to the number of excited oxygen molecules. We calculate the efficiency by dividing the number of generated singlet oxygen molecules by the number of incoming pump photons, determining an efficiency of (8 ± 2) × 10−5 for water when pumping at 410 nm with a pulse energy of 13 mJ. We demonstrate that the Raman method results in no photobleaching, a phenomenon typically observed when photosensitizers are used. Thanks to this property, Raman excitation can continue for as long as the sample is irradiated, generating more singlet oxygen molecules over time than the photosensitization method.

Photochem doi: 10.3390/photochem5030023

Authors: Vanam Hariprasad Kavya S. Keremane Praveen Naik Dickson D. Babu Sunitha M. Shivashankar

Aggregation-induced emission (AIE) luminogens are materials that exhibit enhanced light emission in the aggregated state, primarily due to the restriction of intramolecular motions, which reduces energy loss through non-radiative pathways. Tetraphenylethylene (TPE) and its derivatives are prominent examples of AIE-active materials, owing to their ease of synthesis, tuneable photophysical properties, and strong aggregation tendencies. This review provides an overview of the fundamental AIE mechanisms in TPE-based systems, with a focus on the role of restricted intramolecular rotation (RIR) and π-twisting in governing their emission behaviour. It explores the influence of molecular structure, electronic configuration, and intermolecular interactions on fluorescence properties. Furthermore, recent advances in practical applications of TPE-based AIE luminogens are highlighted across a spectrum of biological imaging domains, including cellular imaging, tissue and in vivo imaging, and organelle-targeted imaging. Additionally, their integration into multifunctional and theranostic platforms, along with the development of stimuli-responsive and self-assembled systems, underscores their versatility and expanding potential in biomedical research and diagnostics. This review aims to offer valuable insights into the design principles and functional potential of TPE-based AIE luminogens, guiding the development of next-generation materials for advanced bioimaging technologies.

Photochem doi: 10.3390/photochem5030022

Authors: Erika Kopcsik Péter Kun Miklós Nagy

Accurate detection of water in organic solvents is essential for various industrial and analytical applications. In this study, we present a simple, rapid, and sensitive fluorescence-based method for water quantification using 1,5-diaminonaphthalene (1,5-DAN) as a solvatochromic probe. This method exploits the excited-state intramolecular charge transfer (ICT) behavior of 1,5-DAN, which undergoes a symmetry-breaking transition in the presence of protic solvents such as water, leading to a distinct redshift in its emission spectrum and a change from a structured double-band to a single ICT band. We demonstrate that, in solvents like acetonitrile and tetrahydrofuran, the emission maxima of 1,5-DAN correlate linearly with water content up to 100%, while ratiometric analysis of peak intensities allows for sensitive detection in low concentration ranges. This method achieved limits of detection as low as 0.08% (v/v) in MeCN, with high reproducibility and minimal sample preparation. Application to a real MeCN–water azeotrope confirms the method’s accuracy, matching classical refractometric measurements. Our findings highlight the potential of 1,5-DAN as a low-cost, efficient, and non-destructive fluorescent sensor for monitoring moisture in organic solvents, offering a practical alternative to conventional methods such as Karl Fischer titration for both bulk and trace water analysis.

Photochem doi: 10.3390/photochem5030021

Authors: Alexandre Mau Guillaume Noirbent Céline Dietlin Bernadette Graff Didier Gigmes Frédéric Dumur Jacques Lalevée

The journal retracts the article entitled “Panchromatic Copper Complexes for Visible Light Photopolymerization” [...]

Photochem doi: 10.3390/photochem5030020

Authors: Rekha K. Hebasur Varsha V. Koppal Deepak A. Yaraguppi Neelamma B. Gummagol Raviraj Kusanur Ninganagouda R. Patil

This study details how 3-(naphthalen-2-yl)-1-phenylprop-2-en-1-one (3NPEO) behaves in terms of photophysics when exposed to different solvents. The solvatochromic effect study reveals significant polarity shifts in the excited states of the 3NPEO compound, likely due to an intramolecular proton transfer mechanism. Measurements of dipole moments provide insight into their resonance structures in both ground and excited states. Electrochemical analysis revealed a reversible redox process, indicating a favorable charge transport potential. HOMO and LUMO energies of the compound were computed via oxidation and reduction potential standards. 3NPEO exhibits optimal one-photon and two-photon absorption characteristics, validating its suitability for visible wavelength laser applications in photonic devices. Furthermore, molecular docking and dynamics simulations demonstrated strong interactions between 3NPEO and the progesterone receptor enzyme, supported by structure–activity relationship (SAR) analyses. In vitro cytotoxicity assays on the MDAMB-231 breast cancer cell line showed moderate tumor cell inhibitory activity. Apoptosis studies confirmed the induction of both early and late apoptosis. These findings suggest that 3NPEO holds promise as a potential anticancer agent targeting the progesterone receptor in breast cancer cells. Overall, the findings highlight the substantial influence of solvent polarity on the photophysical properties and the design of more effective and stable therapeutic agents.

Photochem doi: 10.3390/photochem5030019

Authors: Meredith G. Warsen Soren Zimmer Katherine Phan Lisa M. Landino

Photosynthesis in plants and the electron transport chain in mitochondria are examples of life-sustaining electron transfer processes. The benzoquinones plastoquinone and ubiquinone are key components of these pathways that cycle through their oxidized and reduced forms. Previously, we reported direct photoreduction of biologically relevant quinones mediated by photosensitizers, red light and electron donors. Herein we examined direct photoreduction of the quinone imine 2,6-dichlorophenolindophenol (DCPIP) using red light, methylene blue as the photosensitizer and ethylenediaminetetraacetic acid (EDTA) as the electron donor. Photoreduction of DCPIP by methylene blue and EDTA was very pH-dependent, with three-fold enhanced rates at pH 6.9 vs. pH 7.4. Photochemical redox cycling of DCPIP produced hydrogen peroxide via singlet oxygen-dependent reoxidation of reduced DCPIP. Histidine enhanced photoreduction by scavenging singlet oxygen, whereas increased molecular oxygen exposure slowed DCPIP photoreduction. Attempts to photoreduce DCPIP with pheophorbide A, a chlorophyll metabolite, and triethanolamine as the electron donor in 20% dimethylformamide were unsuccessful. Photoreduced benzoquinones including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ0), methoxy-benzoquinone and methyl-benzoquinone were used to examine electron transfer to DCPIP. For photoreduced CoQ0 and methoxy-benzoquinone, electron transfer to DCPIP was rapid and complete, whereas for reduced methyl benzoquinone, it was incomplete due to differences in reduction potential. Nonetheless, electron transfer from photoreduced quinols to DCPIP is a rapid and sensitive method to investigate quinone photoreduction by chlorophyll metabolites.

Photochem doi: 10.3390/photochem5030018

Authors: Sawako Sentoku Mari Kurashina Keiko Kida

Cyanotypes, known as photographs and architectural plans made by photo-reproduction from the 19th and 20th centuries, are subjects for conservation. Wet cleaning for conservation treatment has been reported to be unsuitable for cyanotypes because Prussian blue on cyanotypes is thought to move physically with the application of water. The manner in which Prussian blue is fixed onto the paper substrate is important for determining the treatment method. This study is the first step toward clarifying this mechanism. The presence of Prussian blue in cyanotypes was first confirmed using X-ray diffraction analysis (XRD). Then, the location of Prussian blue in the fibre was confirmed using optical microscopy and micro-Raman spectroscopy analysis, by observing the blue colour and by detecting its cyanide bond. With field-emission scanning electron microscopy (FE-SEM), particles approximately 20–100 nm in size were observed on the surface of cyanotype paper fibres, and particles approximately 20–50 nm in size were observed from the cross-section of the paper fibres. The location where the particles were observed agreed with the location where the blue colour was observed and cyanide bond was detected. The fact that the sensitiser solution soaked into the paper fibres and formed Prussian blue within the paper fibres when exposed to light is thought to be important for the blue fixation of cyanotypes.

Photochem doi: 10.3390/photochem5030017

Authors: Elisa Leyva Silvia E. Loredo-Carrillo Irving R. Rodríguez-Gutiérrez Denisse de Loera Gabriela Navarro-Tovar Lluvia I. López

Quinolones and fluoroquinolones are heterocyclic compounds with important antibacterial properties, and they have been extensively used in medicinal chemistry to treat diverse bacterial infections. However, their clinical applications have been limited by several factors. On one side, there is an increasing number of resistant bacterial strains. On the other side, some of these heterocyclic compounds have shown several adverse effects such as photocarcinogenic cutaneous reactions, with the development of skin tumors. These adverse properties have motivated a large number of studies on the photophysical, photochemical and phototoxic properties of these compounds. In this review, several important chemical aspects about quinolones and fluoroquinolones are discussed. In the first sections, their basic structure is presented, along with some important physicochemical properties. In the next sections, their photochemical and photophysical processes are discussed. Upon photolysis in aqueous neutral conditions, these heterocyclic compounds generate several highly reactive intermediates that could initiate diverse reactions with molecules. In a biological environment, quinolones and fluoroquinolones are known to associate with biomolecules and generate complexes. Within these complexes, photophysical and photochemical processes generate intermediates, accelerating diverse reactions between biomolecules and these heterocyclic compounds. For several decades, diverse fluoroquinolones have been prepared for the treatment of a variety of bacterial infections. However, their prescription has been restricted due to the associated severe side effects. In the last decade, new derivatives have been developed and are already in use. Their introduction into actual practice extends the number of antibiotics and provides new options for difficult-to-treat infections. Thus, for new pharmaceutical compounds to be used in medicinal practice, it is important to investigate their biological activity, as well as other biological properties and adverse effects, such as phototoxicity.

Photochem doi: 10.3390/photochem5020016

Authors: Sean A. Roget Wade C. Henke Maxwell Taub Pyosang Kim Jonathan T. Yarranton Xiaosong Li Karen L. Mulfort Lin X. Chen

Understanding electron density migration along excited-state pathways in photochemical systems is critical for optimizing solar energy conversion processes. In this study, we investigate photoinduced electron transfer (PET) in a covalently linked donor–bridge–acceptor (D-B-A) system, where [Cu(I)-bis(1,10-phenanthroline)]+ acts as an electron donor, and anthraquinone, tethered to one of the phenanthroline ligands via a vibrationally active ethyne bridge, behaves as an electron acceptor. Visible transient absorption spectroscopy revealed the dynamic processes occurring in the excited state, including PET to the acceptor species. This was indicated by the spectral features of the anthraquinone radical anion that appeared on a timescale of 30 ps in polar solvents. Time-resolved infrared (TRIR) spectroscopy of the alkyne vibration (CC stretch) of the ethyne bridge provided insight into electronic structural changes in the metal-to-ligand charge transfer (MLCT) state and along the PET reaction coordinate. The observed spectral shift and enhanced transition dipole moment of the CC stretch demonstrated that there was already partial delocalization to the anthraquinone acceptor following MLCT excitation, verified by DFT calculations. An additional excited-state TRIR signal unrelated to the vibrational mode highlighted delocalization between the phenanthroline ligands in the MLCT state. This signal decayed and the CC stretch narrowed and shifted towards the ground-state frequency following PET, indicating a degree of localization onto the acceptor species. This study experimentally elucidates charge redistribution during PET in a Cu(I) diimine D-B-A system, yielding important information on the ligand design for optimizing PET reactions.

Photochem doi: 10.3390/photochem5020015

Authors: Qinlin Yuan Hanwei Wang Pingping Sun Chaoyuan Zeng Weijie Chi

Near-infrared (NIR) rhodamine dyes are pivotal for bioimaging due to the minimal tissue interference. Yet, their rational design is hindered by unreliable computational methods for excited-state property prediction. We benchmarked the time-dependent density functional theory (TDDFT) with the linear-response (LR) and state-specific (SS) solvation models across five functionals (CAM-B3LYP, M06-2X, ωB97X-D, B3LYP, MN15) and optimized the ground/excited states for 42 rhodamine derivatives. A robust linear calibration framework was established by connecting the computed and experimental wavelengths, which was rigorously validated through six-fold cross-validation. The key metrics included the mean absolute error (MAE) and R2 to assess the prediction robustness. CAM-B3LYP combined with LR solvation achieved the highest accuracy (absorption: MAE = 6 nm, R2 = 0.94; emission: MAE = 12 nm, R2 = 0.72). By integrating the TDDFT with a calibrated linear-response solvation model, we achieved sub-12 nm accuracy in predicting the NIR fluorescence peaks. This framework enabled the rational design of nine novel rhodamine derivatives with emissions beyond 700 nm, offering a paradigm shift in bioimaging probe development.

Photochem doi: 10.3390/photochem5020014

Authors: Bong Lee Agnieszka Jablonska Rajveer Sagoo Danh Pham Trang Thien Pham Sergei V. Dzyuba Zygmunt Gryczynski Ignacy Gryczynski

N-phenyl-1H-Indole-5-carboxamide (Ind-CA) exhibits previously unknown room-temperature phosphorescence (RTP) when immobilized in poly (vinyl alcohol) film (PVA film). High-fluorescence anisotropy of Ind-CA in PVA suggests that the fluorophores are strongly immobilized in a polymer matrix, while a relatively low (ca. 0.1) quantum yield indicates a strong non-radiative singlet excited state deactivation. With an increased triplet-state population, Ind-CA can be used for various phosphorescence studies. The room-temperature phosphorescence (RTP) capability of Ind-CA indicates that there is an intricate balance between RTP and the structure of the indole-containing luminophore, as an isomeric N-1H-indole-5-ylbenzamide (Ind-BA) does not show any appreciable levels of RTP. Moreover, the phosphorescence lifetime of Ind-CA is about two orders of magnitude longer than many other 5-substituted indoles. These results further highlight the prospects for the potential rational designs of small molecules with desired triplet-state configuration and RTP characteristics.

Photochem doi: 10.3390/photochem5020013

Authors: Daniel Álvarez-Gutiérrez Paola Domínguez Domínguez Raúl Pérez-Ruiz David Díaz Díaz M. Consuelo Jiménez

Visible-light photoredox catalysis using biacetyl (BA) as a low-cost photosensitizer enables the efficient formation of triarylethylenes (TAEs) via a Mizoroki–Heck-type coupling. The reaction proceeds efficiently in acetonitrile upon blue LED irradiation under anaerobic conditions. Alternatively, supramolecular viscoelastic gels have also been explored as reaction media, allowing the possibility of working under aerobic atmosphere. Mechanistic investigations by means of transient absorption spectroscopy and quenching experiments support a charge-separated intermediate pathway. Reaction quantum yield measurements further validate the efficiency of BA, demonstrating its potential as an alternative to transition-metal catalysts. Overall, this work presents a sustainable and scalable strategy for TAEs synthesis, integrating photoredox catalysis with soft material engineering. These findings pave the way for broader applications in green chemistry and functional materials.

Photochem doi: 10.3390/photochem5020012

Authors: Yousef M. Hijji Rajeesha Rajan Amjad M. Shraim Bassam Attili Sisay Uota Fasil Abebe

IR-780 is a heptamethine cyanine dye that exhibits strong absorbance in the near-infrared region. Herein, we report IR-780 dye as a dual sensor for chromogenic cyanide detection and azide’s fluorogenic sensing in acetonitrile. Cyanide and hydroxide cause instant, dramatic color changes in the dye solution from green to yellow and dramatic spectral changes in the UV-Vis spectrum. The interaction of cyanide and hydroxide with the dye caused a dramatic decrease in the intensity of the strong absorption band at 780 nm and a concomitant band appearance at 435 nm. Other monovalent ions, including fluoride, chloride, bromide, iodide, dihydrogen phosphate, thiocyanate, acetate, and dihydrogen arsenate, caused no significant color or spectral changes. UV-Vis studies showed that the IR-780 dye is sensitive and selective to both ions. The detection limits for cyanide and azide are 0.39 µM and 0.50 µM, respectively. Interestingly, the IR-780 dye exhibited strong fluorescence at 535nm upon interaction with azide, while its initial emission at 809 nm was quenched. Both UV-Vis and fluorescence spectroscopy accomplished the detection of cyanide and azide using IR-780. Furthermore, the sensor’s effectiveness in fluorescence imaging of intracellular CN⁻ ions is demonstrated in live HeLa cells.

Photochem doi: 10.3390/photochem5020011

Authors: Antonietta Mancuso Olga Sacco Vincenzo Vaiano

This review examines the production of terephthalic acid via the oxidation of p-xylene, comparing catalytic and photocatalytic approaches. The commercial AMOCO process employs a cobalt/manganese/bromide catalyst system but requires harsh conditions, including high temperatures and acidic environments, raising environmental and safety concerns. While effective, its complexity and severe reaction conditions highlight the need for further optimization. In contrast, photocatalytic oxidation under milder conditions offers a more sustainable alternative. However, research on truly heterogeneous photocatalysts remains limited. The development of hybrid catalysts that exclude expensive noble metals holds promise for selective terephthalic acid production with minimal by-products. Advances in photocatalyst design—particularly in non-metallic and hybrid systems—could address key challenges such as limited light absorption and charge recombination, enhancing overall efficiency. Despite these advancements, maintaining high selectivity for terephthalic acid while minimizing by-product formation remains a critical challenge. Additionally, scaling up the photocatalytic process for industrial applications requires overcoming issues related to catalyst stability, recyclability, and cost-effectiveness. Continued research on improving catalyst performance and long-term stability will be essential for establishing photocatalytic oxidation of p-xylene as a viable and environmentally friendly route for terephthalic acid production.

Photochem doi: 10.3390/photochem5020010

Authors: Simone König

Porphyrins play important roles in biological systems including oxygen transport and catalysis. Due to their tetrapyrrole core structure, they exhibit exceptional photophysical and electrochemical properties and find many applications in both technical and life science fields, including photodynamic therapy and neurosurgery. The irradiation of porphyrins may cause modifications to their molecular structure or their degradation. Such photobleaching processes potentially affect the success and sensitivity of photosensitizer applications. While there have been many studies using fluorescence spectroscopy to investigate this phenomenon, reports about analytically validated structures of photoproducts are scarce. It is, however, necessary to know the individual contributions of different molecules to the fluorescence signal in order to evaluate it correctly. This review provides a summary of the current state of knowledge in this respect, discussing especially the validated hydroxyaldehyde and formyl photo-oxidation products of protoporphyrin IX.

Photochem doi: 10.3390/photochem5010009

Authors: Daniel Arturo Acuña Leal Claudia Rosa Santiago Ramírez Norma A. Ramos Delgado Sadasivan Shaji Bindu Krishnan David Avellaneda Avellaneda Josue Amilcar Aguilar Martínez Shadai Lugo Loredo Arian Espinosa Roa Miguel Ángel Gracia Pinilla

In this work, we report the fabrication of CuI@g-C3N4/MoS2 thin films by the thermal evaporation of Cu films and their conversion into hybrid films by a simple wet chemical method. Compared to pure CuI, CuI@g-C3N4/MoS2 shows enhanced absorption near the UV region, which improves its DC photoconductivity. The conductivity of the films is enhanced by the addition of g-C3N4/MoS2, which is distributed on the surface of the CuI film. The band gap of the films red-shifts upon adding g-C3N4/MoS2. We evaluate this material’s potential application as a photodetector and in photocatalysis by evaluating its photoelectrochemical properties using impedance spectroscopy measurements, cyclic voltammetry, and DC photoresponse measurements. We find that upon the addition of g-C3N4/MoS2, the conductivity of the films is increased, as evidenced by the time-dependent photo amperometry measurements. Also, a higher DC photoresponse is observed upon increasing the concentration of MoS2. This work marks the first time a hybrid CuI@g-C3N4/MoS2 film and its photoelectrochemical characteristics have ever been reported.

Photochem doi: 10.3390/photochem5010008

Authors: Tarikul I. Milon Khairum H. Orthi Krishna Rauniyar Rhen M. Renfrow August A. Gallo Wu Xu

Chemically identical chlorophyll (Chl) molecules undergo conformational changes when they are embedded in a protein matrix. The conformational changes will modulate their absorption spectra to meet the need for programmed excitation energy transfer or electron transfer. To interpret spectroscopic data using the knowledge of pigment–protein interactions requires a single pigment embedded in one polypeptide matrix. Unfortunately, most of the known photosynthetic systems contain a set of multiple pigments in each protein subunit. This makes it complicated to interpret spectroscopic data using structural data due to the potential overlapping spectra of two or more pigments. Chl–protein interactions have not been systematically studied to answer three fundamental questions: (i) What are the structural characteristics and commonly shared substructures of different types of Chl molecules (e.g., Chl a, b, c, d, and f)? (ii) How many structural groups can Chl molecules be divided into and how are different structural groups influenced by their surrounding environments? (iii) What are the structural characteristics of pigment surrounding environments? Having no clear answers to the unresolved questions is probably due to a lack of computational methods for quantifying conformational changes in individual Chls and individual surrounding amino acids. The first version of the Triangular Spatial Relationship (TSR)-based method was developed for comparing protein 3D structures. The input data for the TSR-based method are experimentally determined 3D structures from the Protein Data Bank (PDB). In this study, we take advantage of the 3D structures of Chl-binding proteins deposited in the PDB and the TSR-based method to systematically investigate the 3D structures of various types of Chls and their protein environments. The key contributions of this study can be summarized as follows: (i) Specific structural characteristics of Chl d and f were identified and are defined using the TSR keys. (ii) Two and three clusters were found for various types of Chls and Chls a, respectively. The signature structures for distinguishing their corresponding two and three clusters were identified. (iii) Histidine residues were used as an example for revealing structural characteristics of Chl-binding sites. This study provides evidence for the three unresolved questions and builds a structural foundation through quantifying Chl conformations as well as structures of their embedded protein environments for future mechanistic understanding of relationships between Chl–protein interactions and their corresponding spectroscopic data.

Photochem doi: 10.3390/photochem5010007

Authors: Aristides Marcano Olaizola

We report on the phosphorescence of singlet oxygen photogenerated through a stimulated Raman process. Nanosecond radiation in the green spectral region focused on hexane and carbon tetrachloride induces a Raman transition of the dissolved solvent oxygen molecules towards the singlet oxygen state, producing a Stokes signal in the near-infrared. The excited oxygen relaxes to the ground, emitting an infrared photon at 1272 nm. While the Stokes signal’s wavelength changes with the light’s wavelength, the wavelength of the phosphorescent photon remains unaltered. The result confirms previous reports on the stimulated Raman excitation of singlet oxygen.

Photochem doi: 10.3390/photochem5010006

Authors: Bishweshwar Pant Allison A. Kim Enkhtsatsaral Munkhtur Mira Park

Visible-light-responsive silver-phosphate-sensitized fly-ash particles loaded on polyurethane nanofiber (Ag3PO4–FA/PU NFs) membrane photocatalysts were prepared by electrospinning followed by an ion-exchange method and characterized with state-of-art techniques. With the assistance of Ag3PO4–FA/PU NFs, 98 % of methylene blue (MB) was degraded within 60 min. The combination of FA and Ag3PO4 particles provided simultaneous adsorption and degradation of MB in an aqueous solution, resulting in the fast removal of the dye. Also, the Ag3PO4–FA/PU NFs exhibited excellent antibacterial performance toward Escherichia coli and Staphylococcus aureus bacteria. Thus, the prepared photocatalyst may provide a potential outcome for environmental remediation, especially wastewater treatment applications.

Photochem doi: 10.3390/photochem5010005

Authors: Daniel A. B. Oliveira Víctor S. A. Bonfim Felipe Fantuzzi Sergio Pilling

Astrophysical ices play a crucial role in the chemistry of cold interstellar environments. However, their diverse compositions, temperatures, and grain morphologies pose significant challenges for molecular identification and quantification through infrared observations. We investigate the ability of implicit solvation approaches to capture temperature-dependent infrared spectral features of CO2 molecules embedded in astrophysical ice analogues, comparing their performance to that of explicit ice models and experimental data. Using DFT calculations and vibrational frequency scaling, we model CO2 trapped in both amorphous (cold) and crystalline (warm) H2O ice clusters. The implicit model qualitatively identifies certain trends but fails to reliably capture the magnitude of frequency shifts and band strengths. Explicit models correctly reproduce the gas-to-solid redshifts for both the asymmetric stretch and bending modes; however, neither approach successfully replicates the experimentally observed temperature-dependent trend in the bending mode. While continuum-like methods may be useful as first-order approximations, explicit modelling of the molecular environment is essential for accurately simulating the infrared spectral behaviour of CO2 in astrophysical ices and for interpreting observational data on ice composition and evolution.

Photochem doi: 10.3390/photochem5010004

Authors: Piotr Filipiak Katarzyna Grzyb Monika Borkowska Tomasz Pedzinski

This communication aims to comprehensively elucidate the intricate mechanism governing the interaction between the excited triplet state of 4-Carboxybenzophenone (CB*) and the anionic form of 2-Naphthalene Sulfonate (NpSO3−), employing the 337 nm Nanosecond Laser Flash Photolysis technique for this investigation. When the CB is selectively excited by a 337 nm laser, two primary processes become possible: (i) energy transfer from 3CB* to NpSO3− and (ii) electron transfer from NpSO3− to 3CB*. The dynamics of these interactions are explored through experimental observations of transient absorption spectra and the analysis of respective kinetic traces. The primary process dominating in the 3(CB...NpSO3−)* system is identified as triplet energy transfer from excited 3CB* to 3(NpSO3−), as demonstrated by characteristic spectral features observed at 410–420 nm. Comparisons are made with a similar system studied by Yamaji and co-workers, 3(BP•−...NpO•)*, revealing differences in the priority of primary process occurrences. These findings contribute to a deeper understanding of the intricate interactions between excited molecules and ground-state donors, aiding in the comprehension of mechanisms governing these reactions.

Photochem doi: 10.3390/photochem5010003

Authors: Matylda Wacławska Wojciech Dzwolak

Atomically precise noble metal nanoclusters protected by ligands are broadly discussed in the literature as a promising new class of materials with many interesting properties. Of those, the most prominent is the characteristic luminescence in the visible and near-infrared light. Within the plethora of conjugates of metal nanoclusters to various protective ligands, protein-enveloped systems present several unique features arising from an interplay of the nanocluster photophysics and the protein chemistry along its macromolecular dynamics. The specific properties of protein–metal nanocluster conjugates underlie various applications of these systems, especially in bioimaging. This review, in contrast to many already published, focuses on protein-protected gold nanoclusters (AuNCs) from the standpoint of the proteinaceous shell which plays a crucial role in the biocompatibility, solubility, and excellent in-solution stability of such nanohybrid complexes. Factors such as the protein’s size, structural rigidity, amino acid composition, electric charge, and the electron donor properties of composite amino acids are discussed.

Photochem doi: 10.3390/photochem5010002

Authors: Debosreeta Bose Agnishwar Girigoswami

Biomarker detection is imperative in the realms of modern medicine, biology, and environmental science, owing to the numerous avenues for its application. The recent scientific upsurge in the development of molecules, materials, and mechanisms for such scientific development has garnered considerable attention among scientists. In this connection, excited-state intramolecular proton transfer (ESIPT) properties of photoluminescent compounds provide considerable insights into the designing, development, and detection of biomarkers. ESIPT molecules significantly show a Stokes-shifted emission due to their sensitive nature and unique photophysical properties. Leveraging this photophysical property and tunable nature, several fluorescent probes of this genre can be designed and synthesized for a plethora of application spheres. Schiff bases encompass one such category of functional molecules displaying ESIPT properties, which can be mitigated by adding several other functionalities and desired optical characteristics. The current review article spans the basics of ESIPT properties of certain photoluminescent molecules and also envisages biosensing applications of recently developed imine–functionalized Schiff base molecules with such properties as the prima-foci, along with other applications.

Photochem doi: 10.3390/photochem5010001

Authors: Paul P. Debes Melanie Pagel Simeon Muntean Janis Hessling Bernd M. Smarsly Monika Schönhoff Teresa Gatti

The textile industry is a major contributor to environmental pollution, primarily through the discharge of wastewater loaded with dyes and contaminants that disrupt natural ecosystems. This study aims to develop a hybrid material by functionalizing carbon nanodots (CNDs) with the donor-π-acceptor organic dye L1 via amide coupling. By chemically modifying the surface of CNDs, we can enhance their multifunctionality and tailor their molecular composition. This innovative approach seeks to replace expensive dyes with cost-effective CNDs synthesized from citric acid and ethylenediamine using a domestic microwave oven, potentially improving the stability of the resulting hybrid. Additionally, TiO2 anatase particles were synthesized as a metal oxide platform and sensitized with both pristine materials and the CND-L1 hybrid. A range of physicochemical methods was employed to analyze the elemental, structural, and optical properties of these materials. In photocatalytic degradation tests of methyl orange, the sensitized catalysts demonstrated significantly improved efficiency compared to TiO2 alone. While CNDs exhibited good stability and enhanced L1’s stability, scavenger experiments revealed that holes and hydroxyl radicals play crucial roles in the degradation mechanism. This research underscores the promise of CND hybrids in advancing pollutant degradation technologies while reducing reliance on costly photocatalysts.

Photochem doi: 10.3390/photochem4040033

Authors: Tatsuya Yamazaki Yoshinori Murakami

A time-resolved chemiluminescence study of luminol formed by 355 nm laser-irradiated BiVO4 photocatalysts is reported. It was found that the addition of alcohol to 355 nm laser-irradiated BiVO4 photocatalysts enhanced the luminol chemiluminescent, but the addition of Ag ions to 355 nm laser-irradiated BiVO4 photocatalysts reduced the luminol chemiluminescent. The plausible mechanism for the present experimental results is discussed based on the generation and lifetime of active oxygen species formed by 355 nm laser-irradiated BiVO4 photocatalysts.

Photochem doi: 10.3390/photochem4040032

Authors: Marcelo I. Guzman

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 [...]

Photochem doi: 10.3390/photochem4040031

Authors: Alexis Mercier Alizée Monet Madyan A. Yaseen M. Iris Hermanns Michael Oelgemöller

A variety of 1-(1,4-dihydroxynaphtalen-2-yl) ketones was synthesized using the photo-Friedel–Crafts acylation of 1,4-naphthoquinone with aldehydes. Subsequent oxidation using silver oxide readily furnished the corresponding 2-acylated 1,4 naphthoquinones. Notably, these naphthoquinone derivatives underwent spontaneous partial reduction upon storage. The synthesized compounds were subjected to antimicrobial screening. High inhibition effects on Staphylococcus aureus were found for the majority of compounds, which makes them interesting for potential future medicinal applications.

Photochem doi: 10.3390/photochem4040030

Authors: Syed Atif Iqrar Aisha Bibi Raghavan Chinnambedu Murugesan Daniel Hill Alex Rozhin

Micro- and nanoplastics (MNPs) pose a significant threat to marine and human life due to their immense toxicity. To protect these ecosystems, the development of reliable technologies for MNP detection, characterisation, and removal is vital. While FTIR and Raman spectroscopy are established methods for MNP analysis, fluorescence (FL) spectroscopy has recently emerged as a promising alternative. However, most prior research relies on FL emission probing with a single excitation wavelength for MNP detection. In this study, we introduce a two-dimensional (2D) fluorescence excitation–emission (FLE) mapping method for the detection of commonly found microplastics, namely polystyrene (PS), polyethylene terephthalate (PET), and polypropylene (PP). The FLE mapping technique enables the collective recording of emission spectra across a range of excitation wavelengths, revealing the dominant excitation–emission features of different microplastics. This research advances the field by offering a non-destructive and label-free identification of MNP contamination through the use of FL spectral fingerprints.

Photochem doi: 10.3390/photochem4040029

Authors: Bozhidar I. Stefanov Hristo G. Kolev

This study investigated the influence of the ultraviolet (UV) dose (DUV) on the photodeposition of MnOx and Pd cocatalysts on 300-nm-thick anatase TiO2 thin films, which were prepared via sol–gel dip-coating on a glass substrate. MnOx and Pd were photodeposited using increasing UV doses ranging from 5 to 20 J cm−2, from 5 mM aqueous electrolytes based on Mn2+/IO3− or Pd2+, respectively. The effect of the DUV on the MnOx photodeposition resulted in an increase in Mn2+ surface content, from 2.7 to 5.2 at.%, as determined using X-ray photoelectron spectroscopy (XPS). For Pd, increasing the UV dose led to a reduction in the oxidation state, transitioning from Pd2+ to Pd0, while the overall Pd surface content range remained relatively steady at 2.2–2.4 at.%. Both MnOx/TiO2 and Pd/TiO2 exhibited proportional enhancements in photocatalytic activity towards the degradation of methylene blue. Notably, Pd/TiO2 demonstrated a significant improvement in photocatalytic performance, surpassing that of pristine TiO2. In contrast, TiO2 samples functionalized through wet impregnation and thermal treatment in the same electrolytes showed overall lower photocatalytic activity compared to those functionalized via photodeposition.

Photochem doi: 10.3390/photochem4040028

Authors: Hiroto Tachikawa

The excited state proton transfer (ESPT) reaction plays a crucial role in DNA defense and ON-OFF proton-switching molecular devices. o-Hydroxybenzaldehyde (OHBA) is the simplest model-molecule for the ESPT reactions where a proton is transferred from OH to C=O carbonyl groups by photo-excitation. In the present study, the reaction mechanism of ESPT in OHBA was investigated by means of the direct ab initio molecular dynamics (AIMD) method. The triplet (T1) state of OHBA, OHBA(T1), was considered as the excited state of OHBA. The dynamic calculations showed that fast PT occurred from OH to C=O carbonyl groups at the T1 state. The time of PT was calculated to be 34–57 fs in OHBA(T1). The spin density was mainly distributed on the benzene ring (Bz) at time zero. The density was gradually transferred from Bz to C=O as a function of time on the T1 surface. When the spin density on C=O was larger than that on Bz (at time = 35–43 fs), the proton of OH was rapidly transferred to C=O. The localization of spin density on C=O dominated strongly the PT rate. Next, the effects of residual water (H2O) on the PT rate were investigated using OHBA-H2O 1:1-complexes to elucidate the effects of H2O on the PT rate in the ON-OFF proton-switching molecular devices. The PT rates were strongly dependent on the position of H2O around OHBA. The reaction mechanism is discussed based on theoretical results.

Photochem doi: 10.3390/photochem4040027

Authors: Yaran Allamyradov Justice ben Yosef Berdimyrat Annamuradov Mahmood Ateyeh Carli Street Hadley Whipple Ali Oguz Er

Photodynamic therapy (PDT) is a medical treatment that utilizes photosensitizing agents, along with light, to produce reactive oxygen species that can kill nearby cells. When the photosensitizer is exposed to a specific wavelength of light, it becomes activated and generates reactive oxygen that can destroy cancer cells, bacteria, and other pathogenic micro-organisms. PDT is commonly used in dermatology for treating actinic keratosis, basal cell carcinoma, and other skin conditions. It is also being explored for applications in oncology, such as treating esophageal and lung cancers, as well as in ophthalmology for age-related macular degeneration. In this study, we provide a comprehensive review of PDT, covering its fundamental principles and mechanisms, as well as the critical components for its function. We examine key aspects of PDT, including its current clinical applications and potential future developments. Additionally, we discuss the advantages and disadvantages of PDT, addressing the various challenges associated with its implementation and optimization. This review aims to offer a thorough understanding of PDT, highlighting its transformative potential in medical treatments while acknowledging the areas requiring further research and development.

Photochem doi: 10.3390/photochem4040026

Authors: Jiro Karlo Syed S. Razi Mahamkali Sri Phaneeswar Arunsree Vijay Surya Pratap Singh

Surface-enhanced Raman scattering (SERS) is a powerful tool for biosensing with high sensitivity, selectivity, and capability of multiplex monitoring for both in vivo and in vitro studies. This has been applied for the identification and detection of different biological metabolites such as lipids, nucleic acids, and proteins. The present review article explores the vast applications of metallic nanoparticles for SERS-based biosensing. We have summarized and discussed the fundamental principles, theories, developments, challenges, and perspectives in the field of SERS-based biosensing using different metal nanoparticle substrates namely gold, silver, copper, and bimetallic nanoparticles.

Photochem doi: 10.3390/photochem4040025

Authors: Caitlyn Clark Filip Pawłowski David J. R. Brook Christopher Grieco

While the photophysics of closed-shell organic molecules is well established, much less is known about open-shell systems containing interacting radical pairs. In this work, we investigate the ultrafast excited state dynamics of a singlet verdazyl diradical system in solution using transient absorption (TA) spectroscopy for the first time. Following 510 nm excitation of the excitonic S0 → S1 transition, we detected TA signals in the 530–950 nm region from the S1 population that decayed exponentially within a few picoseconds to form a vibrationally hot S0* population via internal conversion. The dependence of the S1 decay rate on solvent and radical–radical distance revealed that the excited state possesses charge-transfer character and likely accesses the S0 state via torsional motion. The ultrafast internal conversion decay mechanism at play in our open-shell verdazyl diradicals is in stark contrast with other closed-shell, carbonyl-containing organic chromophores, which exhibit ultrafast intersystem crossing to produce long-lived triplet states as the major S1 decay pathway.

Photochem doi: 10.3390/photochem4030024

Authors: Tatiana Montagni Mauricio Ávila Sofía Fernández Sylvia Bonilla María Fernanda Cerdá

Three filamentous freshwater cyanobacterial strains were grown at high light intensity to produce lipidic dyes composed of xanthophylls, carotenes, and chlorophyll a. The properties of the pigments were evaluated as suitable natural compounds to be applied in dye-sensitized solar cells (DSSC). The assembled DSSC were characterized using the density current vs. potential profiles and electrochemical impedance spectroscopy. With an efficiency of 0.127%, our results are higher than those previously reported using similarly structured compounds from natural sources such as algae and cyanobacteria, among others. The best efficiencies were probably related to myxoxanthophyll-like derivates and aphanizophyll are carotenoids with many hydroxyl groups being able to interact with the semiconductor surface. The stability of the bonding between the dyes and the titanium oxide of the photoelectrode is crucial to ensuring the acceptable performance of the DSSC, which was successfully achieved in our experiments with carotenoids with many hydroxyl groups. Our results point to cyanobacterial pigments as a promising source of natural dyes for use in solar cells.

Photochem doi: 10.3390/photochem4030023

Authors: Kohei Kawabata Minami Tsukimori Kyoka Hirai Shiori Akimoto Naoto Uramaru Masanori Inagaki Hiroyuki Nishi

Manidipine (MP) is widely used for reducing high blood pressure. Calslot® (CALS) tablets, which are the original MP medicines, and their generic medicines have been used for patients in clinical situations. The authors hypothesized that the photodegradability of MP drug substance in CALS tablets might be enhanced when the tablets were photo-exposed after the change of the dosage form by the presence of riboflavin (RF), which is utilized as a coloring agent and a well-known photosensitizer. The present study clarified that RF enhanced the photodegradation of MP when the powders and the suspensions of CALS tablets were ultraviolet light (UV) irradiated. The addition of RF to the suspension of MP standard substances also promoted MP photodegradation along with the increase of the generation rate of its main photoproduct, benzophenone. Finally, the authors performed the photostabilization of MP suspensions based on the addition of quercetin (QU), which is one of polyphenols and has both the antioxidative potency and the UV filtering potency. It is summarized that QU has a protective potency for MP’s own photodegradation, and it partially suppresses the photocatalytic effect of RF. Further studies focused on the photochemical behaviors of utilized additives for medicines are needed for their safe use.

Photochem doi: 10.3390/photochem4030022

Authors: Cinzia Michenzi Francesca Scaramuzzo Chiara Salvitti Federico Pepi Anna Troiani Isabella Chiarotto

Photoinduced chemical reactions and the development of new materials represent a current and significant topic. We present a sustainable and eco-friendly approach to the Knoevenagel condensation reaction involving carbonyl and active methylene compounds. Our method utilizes photo-activated carbon dots (CDs) derived from 5-hydroxymethylfurfural (5HMF) within an aqueous medium and does not require acidic, basic, or thermal conditions. This protocol operates effectively with aromatic, aliphatic, and heteroaromatic aldehydes and ketones. The 5HMF-derived-CDs can be reused four times without significant loss of activity. Moreover, this methodology is suitable for scaling up reactions, thereby highlighting its potential for industrial applications.

Photochem doi: 10.3390/photochem4030021

Authors: Katherine Phan Emily E. Lessard Joseph A. Reed Meredith G. Warsen Soren Zimmer Lisa M. Landino

Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, we continue our studies of the direct photoreduction of para-quinones and ortho-quinones that were generated by the photo-oxidation of catechols. Chlorophyll metabolites, including pheophorbide A, chlorin e6, and pyropheophorbide A, as well as methylene blue were employed as photosensitizers. We detected hydrogen peroxide using horseradish peroxidase following the photo-oxidation of the catechol dopamine, even in the presence of EDTA, a tertiary amine electron donor. Under ambient oxygen, hydrogen peroxide was also detected after the photoreduction of several para-quinones, including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ0), methoxy-benzoquinone, and methyl-benzoquinone. The combinations of methylene blue and EDTA or pheophorbide A and triethanolamine as the electron donor in 20% dimethylformamide were optimized for photoreduction of the para-quinones. Chlorin e6 and pyropheophorbide A were less effective for the photoreduction of CoQ0 but were equivalent to pheophorbide A for generating hydrogen peroxide in photo-oxidation reactions with photosensitizers, oxygen, and triethanolamine. We employed dinitrophenylhydrazine to generate intensely colored adducts of methoxy-benzoquinone, methyl-benzoquinone, and 1,4-benzoquinone.

Photochem doi: 10.3390/photochem4030020

Authors: Ahed H. Zyoud

This study investigates the relationships among redox couple activity, electrolyte concentration, and efficiency in CdSe thin-film photoelectrochemical solar cells. A CdSe photo-electrode was prepared using the electro-depositing technique to produce well-staged layering of CdSe, followed by chemical bath deposition to produce a layer with an acceptable thickness to absorb enough photons to create a suitable amount of photocurrent. The CdSe photo-electrochemical cell was tested under various concentrations of a NaOH/Na2S/S electrolyte solution. The results showed that the activity of the redox couple greatly affected the efficiencies of the solar cells. Correlation plots between ionic strength and PEC efficiency with the Debye–Hückel equation yielded an R² value of 0.96, while those between ionic strength and photocurrent density had an R² value of 0.92. The correlation between concentration and PEC efficiency was much weaker. This paper highlights how optimal ionic activity increases the performance of photoelectrochemical solar cells, which consequently improves the conversion efficiency of solar energy.

Photochem doi: 10.3390/photochem4030019

Authors: Naoki Ueoka Achmad Syarif Hidayat Hisayoshi Oshima Yoshimasa Hijikata Yutaka Matsuo

Perovskite solar cells with an indium tin oxide (ITO)/SnO2/CH3NH3PbI3/Spiro-OMeTAD/2,2,2-trifluoroethanol (TFE) doped single-walled carbon nanotube (SWCNT) structure were developed by dropping TFE onto SWCNTs, which replaced the metal back electrode, and a conversion efficiency of 14.1% was achieved. Traditionally, acidic doping of the back electrode, SWCNT, has been challenging due to the potential damage it may cause to the perovskite layer. However, TFE has facilitated easy doping of SWCNT as the back electrode. The sheet resistance of the SWCNTs decreased and their ionization potential shifted to deeper levels, resulting in improved hole transport properties with a lower barrier to carrier transport. Furthermore, the Seebeck coefficient (S) increased from 34.5 μV/K to 73.1 μV/K when TFE was dropped instead of EtOH, indicating an enhancement in the behavior of p-type charge carriers. It was observed that hydrophilic substances adhered less to the SWCNT surface, and the formation of PbI2 was suppressed. These effects resulted in higher conversion efficiency and improved solar cell performance. Furthermore, the decrease in conversion efficiency after 260 days was suppressed, showing improved durability. The study suggests that combining SWCNTs and TFEs improves solar cell performance and stability.

Photochem doi: 10.3390/photochem4030018

Authors: María Ángeles Cortés Carlos Díaz Raquel de la Campa Alejandro Presa-Soto María Luisa Valenzuela

Starting from poly(4-vinylpyridine) ((P4VP)n), poly(2-vinylpyridine) ((P2VP)n), and [N=P(O2CH2CF3)]m-b-P2VP20 block copolymers, a series of metal-containing homopolymers, (P4VP)n⊕MXm, (P2VP)n⊕MXm, and [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm = PtCl2, ZnCl2, and Eu(NO3)3, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu2O3, and EuPO4) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu2O3 nanostructures were obtained from europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), EuPO4 nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm with MXm = Eu(NO3)3. Importantly, and although both Eu2O3 and EuPO4 nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO3)3]6000, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm= Eu(NO3)3, were used (highest emission intensity corresponded to [N=P(O2CH2CF3)]100-b-[P2VP(Eu(NO3)3)x]20). The intensity ratio of the emission transitions: 5D0 → 7F2/5D0 → 7F1, suggested a different symmetry around the Eu3+ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu2O3, and EuPO4 nanostructures.

Photochem doi: 10.3390/photochem4030017

Authors: Raqueline Caldas do Nascimento Arthur Cahino Larissa Granjeiro Lucena Inalmar D. Barbosa Segundo Jonathan Cawettiere Espíndola Elisângela M. R. Rocha

The use of heterogeneous photocatalysis has garnered significant attention, mainly due to its remarkable efficacy in degrading recalcitrant compounds. The main objective of this research was to investigate this process applied to pharmaceutical treatment. For that, an analysis of a Final Bibliographic Portfolio (FBP), using the systematic review of the PRISMA and the ProKnow-C method, and a meta-analysis study in a historical series from 2010 to 2020, were performed for scientific works published in indexed journals from the Scopus and Web of Science databases and fully available in English. The works were filtered after a careful reading of the titles, followed by the exclusion of repeated documents and those that were not aligned with the research from 3498 articles, 40 of which were chosen to compose the FBP that addressed the classes of antibiotics, antihypertensives, analgesics, and anti-inflammatory drugs after scientific recognition and exclusion due to not fitting into one of the four FBP structured stages: (1) identification, (2) triage, (3) eligibility, and (4) inclusion. The following gaps were highlighted: (i) a limited number of studies working with interactions of the interfering variables; (ii) a large number of experiments not considering the natural constituents of wastewater; (iii) the use of drug concentrations high above the values found in aquatic matrices; (iv) little applicability of the process at the real scale. In this meta-analysis study, operational parameter optimization was fundamental to guarantee degradation efficiencies above 80% with a variety of pharmaceutical pollutants, the main representatives studied of which were tetracycline, nimesulide, diclofenac, ibuprofen, and atenolol. However, there is still a need to determine the best conditions for this technique when using real effluents, which have the utmost importance for the process on a large scale.

Photochem doi: 10.3390/photochem4020016

Authors: Julia Exeler Thomas Jüstel

The global demand for sustainable energy sources has led to extensive research regarding (green) hydrogen production technologies, with water splitting emerging as a promising avenue. In the near future the calculated hydrogen demand is expected to be 2.3 Gt per year. For green hydrogen production, 1.5 ppm of Earth’s freshwater, or 30 ppb of saltwater, is required each year, which is less than that currently consumed by fossil fuel-based energy. Functional ceramics, known for their stability and tunable properties, have garnered attention in the field of water splitting. This review provides an in-depth analysis of recent advancements in functional ceramics for water splitting, addressing key mechanisms, challenges, and prospects. Theoretical aspects, including electronic structure and crystallography, are explored to understand the catalytic behavior of these materials. Hematite photoanodes, vital for solar-driven water splitting, are discussed alongside strategies to enhance their performance, such as heterojunction structures and cocatalyst integration. Compositionally complex perovskite oxides and high-entropy alloys/ceramics are investigated for their potential for use in solar thermochemical water splitting, highlighting innovative approaches and challenges. Further exploration encompasses inorganic materials like metal oxides, molybdates, and rare earth compounds, revealing their catalytic activity and potential for water-splitting applications. Despite progress, challenges persist, indicating the need for continued research in the fields of material design and synthesis to advance sustainable hydrogen production.

Photochem doi: 10.3390/photochem4020015

Authors: Mounir Maafi

The dependence of photochemistry on excitation wavelength is not a recently observed phenomenon; nonetheless, it has, surprisingly enough, been largely ignored in the field. The reasons for this situation are not fully understood but might be related to a provisional extension of Kasha’s rule to photochemistry, or perhaps to a difficulty to justify the kind of short time-scales implied in such photochemistry, that challenges the usually held view giving predominance to fast internal conversion and vibrational relaxation. Regardless of the reasons, it is still a matter of fact that a complete and satisfactory interpretation for experimentally proven wavelength-dependent photochemistry is not yet available and the community endeavor to build a holistic understanding and a comprehensive view of the phenomenon. The present review is a non-exhaustive overview of the published data in the field, reporting on some of the most prominent features, issues, and interpretations.

Photochem doi: 10.3390/photochem4020014

Authors: Alondra A. Lugo-Ruiz Sonia J. Bailón-Ruiz

The use of semiconductor materials, specifically TiO2, for photocatalysis of organic pollutants has gained global interest as an effective method for contaminant removal from wastewater. Titanium dioxide (TiO2) is a widely studied photocatalyst and is considered one of the best for wastewater treatments due to its high stability, affordability, and nontoxicity. The discharge of wastewater from the textile industries, which constitutes around 20% of total textile effluent, has become a significant environmental concern, posing a threat to both the aquatic ecosystem and human health. We aimed to investigate the photodegradation of organic dyes like Amaranth (AM), Methyl Orange (MO), and Quinoline Yellow (QY), individually and in combination, in an aqueous suspension with varying concentrations of TiO2. Results indicate a significant degradation of all three dyes in the multicomponent, with approximately 40% degradation in the presence of the 0.050 g/L TiO2 after 360 min. These findings suggest that TiO2 has a significant potential as a nanocatalyst in complex matrices.

Photochem doi: 10.3390/photochem4020013

Authors: Dirk Poelman

Photochemistry is a broad subject [...]

Photochem doi: 10.3390/photochem4020012

Authors: Isabella Natali Sora Francesca Fontana Renato Pelosato Benedetta Bertolotti

This review summarizes the progress over the last fifteen years in visible light reactive photocatalysts for environmental arsenic remediation. The design and performance of several materials including (1) doped and surface functionalized TiO2, (2) binary composites combining TiO2 with another semiconductor that absorbs visible light radiation or a metal (Pt), (3) ternary composites incorporating TiO2, a conductive polymer that can retard electron-hole recombination and an excellent adsorbent material for the removal of As(V), (4) tungsten, zinc, and bismuth oxides, (5) g-C3N4 based catalysts, and (6) M@AgCl core–shell structures. These results show that long reaction time remains a major challenge in achieving high As(III) oxidation.

Photochem doi: 10.3390/photochem4020011

Authors: Konstantin Moritz Knötig Domenic Gust Kawon Oum Thomas Lenzer

Thin films of carbazole (Cz) derivatives are frequently used in organic electronics, such as organic light-emitting diodes (OLEDs). Because of the proximity of the Cz units, the excited-state relaxation in such films is complicated, as intermolecular pathways, such as singlet–singlet annihilation (SSA), kinetically compete with the emission. Here, we provide an investigation of two benchmark systems employing neat carbazole and 3,6-di-tert-butylcarbazole (t-Bu-Cz) films and also their thin film blends with poly(methyl methacrylate) (PMMA). These are investigated by a combination of atomic force microscopy (AFM), femtosecond and nanosecond transient absorption spectroscopy (fs-TA and ns-TA) and time-resolved fluorescence. Excitonic J-aggregate-type features are observed in the steady-state absorption and emission spectra of the neat films. The S1 state shows a broad excited-state absorption (ESA) spanning the entire UV–Vis–NIR range. At high S1 exciton number densities of about 4 × 1018 cm−3, bimolecular diffusive S1–S1 annihilation is found to be the dominant SSA process in the neat films with a rate constant in the range of 1–2 × 10−8 cm3 s−1. SSA produces highly vibrationally excited molecules in the electronic ground state (S0*), which cool down slowly by heat transfer to the quartz substrate. The results provide relevant photophysical insight for a better microscopic understanding of carbazole relaxation in thin-film environments.

Photochem doi: 10.3390/photochem4020010

Authors: Konstantin Moritz Knötig Domenic Gust Thomas Lenzer Kawon Oum

Carbazole-based molecular units are ubiquitous in organic optoelectronic materials; however, the excited-state relaxation of these compounds is still underexplored. Here, we provide a detailed investigation of carbazole (Cz) and 3,6-di-tert-butylcarbazole (t-Bu-Cz) in organic solvents using femtosecond and nanosecond UV–Vis–NIR transient absorption spectroscopy, as well as time-resolved fluorescence experiments upon photoexcitation in the deep-UV range. The initially prepared Sx singlet state has a (sub-)picosecond lifetime and decays to the S1 state by internal conversion (IC). The S1 state exhibits absorption peaks at 350, 600 and 1100 nm and has a lifetime of 13–15 ns, which is weakly dependent on the solvent. Energy transfer from vibrationally hot S1 molecules (S1*) to the surrounding solvent molecules takes place with a time constant of 8–20 ps. The T1 triplet state is populated by intersystem crossing (ISC) from S1 with a typical quantum yield of 51–56% and shows a lifetime which is typically in the few microseconds regime. The S1 and T1 states of both carbazole compounds in solution are strongly quenched by O2. Two-photon excitation leads to the formation of a small amount of the respective radical cation. The influence of the tert-butyl substituents on the photophysics is relatively weak and mainly reflects itself in a small increase in the Stokes shift. The results provide important photophysical information for the interpretation of carbazole relaxation in more complex environments.

Photochem doi: 10.3390/photochem4020009

Authors: Ashim Pramanik Martina Maria Calvino Luisa Sciortino Pooria Pasbakhsh Giuseppe Cavallaro Giuseppe Lazzara Fabrizio Messina Alice Sciortino

This study explores the use of Halloysite NanoTubes (HNTs) as photocatalysts capable of decomposing organic dyes under exposure to visible or ultraviolet light. Through a systematic series of photocatalytic experiments, we unveil that the photodegradation of Rhodamine B, used as a model cationic dye, is significantly accelerated in the presence of HNTs. We observe that the extent of RhB photocatalytic degradation in 100 min in the presence of the HNTs is ~four times higher compared to that of bare RhB. Moreover, under optimized conditions, the as-extracted photodegradation rate of RhB (~0.0022 min−1) is comparable to that of the previously reported work on the photodegradation of RhB in the presence of tubular nanostructures. A parallel effect is observed for anionic Coumarin photodegradation, albeit less efficiently. Our analysis attributes this discrepancy to the distinct charge states of the two dyes, influencing their attachment sites on HNTs. Cationic Rhodamine B molecules preferentially attach to the outer surface of HNTs, while anionic Coumarin molecules tend to attach to the inner surface. By leveraging the unique properties of HNTs, a family of naturally occurring nanotube structures, this research offers valuable insights for optimizing photocatalytic systems in the pursuit of effective and eco-friendly solutions for environmental remediation.

Photochem doi: 10.3390/photochem4010008

Authors: David Bain Julia Chang Yihuan Lai Thomas Khazanov Phillip J. Milner Andrew J. Musser

Cumulenes are linear molecules consisting of consecutive double bonds linking chains of sp-hybridized carbon atoms. They have primarily been of interest for potential use as molecular wires or in other nanoscale electronic devices, but more recently, other applications such as catalysis or even light harvesting through singlet fission have been speculated. Despite the recent theoretical and experimental interest, the photoexcitation of cumulenes typically results in quenching on the picosecond timescale, and the exact quenching mechanism for even the simplest of [3]-cumulenes lacks a clear explanation. In this report, we perform transient absorption spectroscopy on a set of model [3]-cumulene derivatives in a wide range of environmental conditions to demonstrate that the planarization of phenyl groups ultimately quenches the excited state. By restricting this intramolecular motion, we increase the excited state lifetime by a few nanoseconds, strongly enhancing photoluminescence and demonstrating an approach to stabilize them for photochemical applications.

Photochem doi: 10.3390/photochem4010007

Authors: Jacobo Soilán Leonardo López-Cóndor Beatriz Peñín José Aguilera María Victoria de Gálvez Diego Sampedro Raúl Losantos

Avobenzone is one of the most widely used sunscreens in skin care formulations, but suffers from some drawbacks, including photo instability. To mitigate this critical issue, the use of octocrylene as a stabilizer is a common approach in these products. However, octocrylene has been recently demonstrated to show potential phototoxicity. The aim of this work is to analyze the performance of a series of mycosporine-like amino acid (MAA)-inspired compounds to act as avobenzone stabilizers as an alternative to octocrylene. Different avobenzone/MAA analogue combinations included in galenic formulations were followed under increasing doses of solar-simulated UV radiation. Some of the synthetic MAA analogues analyzed were able to increase by up to two times the UV dose required for 50% of avobenzone photobleaching. We propose some of these MAA analogues as new candidates to act as avobenzone-stabilizing compounds in addition to their UV absorbance and antioxidant properties, together with a facile synthesis.

Photochem doi: 10.3390/photochem4010006

Authors: Valli Kamala Laxmi Ramya Chittoory Marketa Filipsika Radim Bartoš Marcela Králová Petr Dzik

Advanced oxidation processes are emerging technologies for the decomposition of organic pollutants in various types of water by harnessing solar energy. The purpose of this study is to examine the physicochemical characteristics of tungsten(VI) oxide (WO3) photoanodes, with the aim of enhancing oxidation processes in the treatment of water. The fabrication of WO3 coatings on conductive fluorine-doped tin oxide (FTO) substrates was achieved through a wet coating process that utilized three different liquid formulations: a dispersion of finely milled WO3 particles, a fully soluble WO3 precursor (acetylated peroxo tungstic acid), and a combination of both (applying a brick-and-mortar strategy). Upon subjecting the WO3 coatings to firing at a temperature of 450 °C, it was observed that their properties exhibited marked variations. The fabricated photoanodes are examined using a range of analytical techniques, including profilometry, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), and voltammetry. The experimental data suggest that the layers generated through the combination of particulate ink and soluble precursor (referred to as the brick-and-mortar building approach) display advantageous physicochemical properties, rendering them suitable for use as photoanodes in photoelectrochemical cells.

Photochem doi: 10.3390/photochem4010005

Authors: Denis S. Tikhonov Diksha Garg Melanie Schnell

Ultrafast pump–probe spectroscopic studies allow for deep insights into the mechanisms and timescales of photophysical and photochemical processes. Extracting valuable information from these studies, such as reactive intermediates’ lifetimes and coherent oscillation frequencies, is an example of the inverse problems of chemical kinetics. This article describes a consistent approach for solving this inverse problem that avoids the common obstacles of simple least-squares fitting that can lead to unreliable results. The presented approach is based on the regularized Markov Chain Monte-Carlo sampling for the strongly nonlinear parameters, allowing for a straightforward solution of the ill-posed nonlinear inverse problem. The software to implement the described fitting routine is introduced and the numerical examples of its application are given. We will also touch on critical experimental parameters, such as the temporal overlap of pulses and cross-correlation time and their connection to the minimal reachable time resolution.

Photochem doi: 10.3390/photochem4010004

Authors: Muhammad Imran Dongyi Liu Kaiyue Ye Xue Zhang Jianzhang Zhao

We prepared a rhodamine (RB)–perylene (Pery) compact electron donor/acceptor dyad (RB–Pery) to study the spin-orbit charge-transfer intersystem crossing (SOCT–ISC). The UV–vis absorption spectrum indicates a negligible electronic interaction between the donor and acceptor at ground state. However, the fluorescence of both the RB and Pery units are quenched in the dyad, which is attributed to the photoinduced electron transfer, supported by the electrochemical studies. Nanosecond transient absorption (ns-TA) spectra show delocalized triplet states, i.e., there is an excited-state equilibrium between Pery and the RB triplet states. The triplet state lifetime was determined as 109.8 μs. With intermolecular triplet–triplet energy transfer, monitored using ns-TA spectra, the triplet-state energy balance between RB and Pery in RB–Pery was confirmed. The proposed cascade photophysical processes of the dyad are 1RB*-Pery→RB–Pery+•→[3RB*-Pery↔RB-3Pery*]. Moreover, long-lived rhodamine radical cation (in milliseconds) was detected in both deaerated/aerated non-polar or low-polarity solvents (i.e., p-xylene, toluene). The potential energy curve of the dyad against the variation in the dihedral angle between the two units indicates large torsional freedom (53°~128°) in RB–Pery, which leads to inefficient SOCT–ISC; consequently, low singlet-oxygen quantum yields (ΦΔ = 2~8%) were observed.

Photochem doi: 10.3390/photochem4010003

Authors: Likius Shipwiisho Daniel Salatiel Kapofi Martha Kandawa-Schulz Habauka Majority Kwaambwa

Even with significant developments in nanoscience, relatively little is known about the interactions of nanocrystal semiconducting materials with bio-macromolecules. To investigate the interfacial phenomena of cadmium selenide quantum dot (CdSe QD) nanocrystals with proteins extracted from Moringa oleifera seeds, different concentrations of cadmium selenide quantum dots–Moringa oleifera seed protein (CdSe–MSP) complexes were prepared. Respective CdSe QDs with hexagonal phase and crystalline size in the range of 4–7 nm were synthesized and labelled with the purified mesoporous MSP having a surface area of 8.4 m2/g. The interaction mechanism between CdSe QDs and MSP was studied using UV–Vis absorption, fluorescence emission and Fourier Transform Infrared spectroscopies. The UV–Vis absorption spectra showed absorption bands of CdSe–MSP complexes at 546.5 nm. The fluorescence intensity of CdSe QDs was found to decrease with increasing concentration of MSP. The thermodynamic potentials ∆Hθ (−321.3 × 103 Jmol−1); ∆Sθ (156.0 JK−1mol−1) and ∆Gθ (−46.6 × 103 Jmol−1) were also calculated. The stability of the complex found is strongly influenced by electrostatics interaction and surface-bound complexation equilibrium attraction. This information can help to elucidate the surface characteristics of MSP and its potential interactions with other molecules or nanoparticles.

Photochem doi: 10.3390/photochem4010002

Authors: Guoying Yao Zhenyu Yang Tao Zeng

Singlet fission is a desired process in photovoltaics since it enhances photoelectric conversion efficiency. Intramolecular singlet fission is of special interest as the fission efficiency can be improved through tuning configurations between chromophore units that are covalently connected. However, intramolecular singlet fission chromophores feature a large tetraradical character, and may tend to dissatisfy the ET2>2ET1 criterion for all singlet fission chromophores, intramolecular or not. We performed spin-flip time-dependent density functional theory calculations for a collection of representative intramolecular singlet fission chromophores to show that this is indeed the case.

Photochem doi: 10.3390/photochem4010001

Authors: Christopher Abelt Kirsten Sweigart

Fluorescence from dialkylamino donor–acyl acceptor substituted 1,8-naphthalene derivatives can occur either from a planar (PICT) or a twisted (TICT) intramolecular charge transfer excited state. The photophysical properties of 8-acetyl-1-(dimethyl-amino)naphthalene (3) and 8-pivaloyl-1-(dimethyl-amino)naphthalene (4) are compared with 1-methyl-2,3-dihydronaphtho[1,8-bc]azepin-4(1H)-one (5). In 3 and 4, both the carbonyl and amino groups are forced to twist out of the plane of the naphthalene ring. In 5, these groups are nearly coplanar with the naphthalene. Neither 3 nor 4 fluoresce as strongly as 5, but all three show similar degrees of solvato-chromism and all are strongly quenched by alcohol solvents. Nitrile 6, 8-cyano-1-(dimethyl-amino)naphthalene, does not show the same degree of solvato-chromism as 3–5, nor is it as affected by alcohols. Calculations corroborate the experimental results, indicating that 3–5 emit from a PICT excited state.

Photochem doi: 10.3390/photochem3040030

Authors: Frédéric Dumur

The design of biosourced and/or bioinspired photoinitiators is an active research field as it offers a unique opportunity to develop photoinitiating systems exhibiting better biocompatibility as well as reduced toxicity. In this field, flavonoids can be found in numerous fruits and vegetables so these structures can be of interest for developing, in the future, polymerization processes, offering a reduced environmental impact but also better biocompatibility of the polymers. In this review, the different flavonoids reported to date as photoinitiators of polymerization are presented. Over the years, different modifications of the flavonoid scaffold have been examined including the grafting of well-known chromophores, the preparation of Type II photoinitiators or the introduction of photocleavable groups enabling the generation of Type I photoinitiators. Different families of flavonoids have also been investigated, enabling to design of high-performance photoinitiating systems.

Photochem doi: 10.3390/photochem3040029

Authors: Gordon A. Ochsner Jaren S. Meikle Jacob C. Dean

Provitamin D3 is the biological precursor to naturally formed vitamin D3 in humans, and its conversion is initiated via photoexcitation by near ultraviolet light. Following an initial photolysis, the primary intermediate, known as previtamin D3, is prone to light-induced isomerization or recyclization, which creates byproducts that limit the desired final thermal conversion to vitamin D3. The branching of the photochemical reaction is highly wavelength-dependent, whereby excitation toward the blue edge of the provitamin D3 absorption spectrum tends to terminate the reaction with the most undesired tachysterol byproduct and the lowest previtamin D3 concentration. In this work, the influence of introducing the natural amino acid phenyalanine as an excitation energy donor to the photochemical reaction is investigated. We find that the incorporation of phenylalanine into provitamin D3 solution results in greater intermediate concentrations and prolonged lifetimes of the desired previtamin D3 while simultaneously reducing the final concentration of tachysterol when exposing the solution to wavelengths at the blue edge of the provitamin D3 spectrum. The results, coupled with quantum chemical analysis, suggest that phenylalanine indeed helps to funnel energy from shorter wavelengths more effectively into the provitamin D3 precursor, while simultaneously screening those wavelengths from direct excitation, which otherwise leads to enhanced concentrations of tachysterol byproduct at the expense of previtamin D3.

Photochem doi: 10.3390/photochem3040028

Authors: Julie Hot Kevin Castelló Lux Erick Ringot

Self-cleaning products are commercially available to protect surfaces against soiling and avoid the high consumption of energy and chemical detergents necessary for cleaning. They are based on semiconductor oxides, mostly titanium dioxide (TiO2), which induce photocatalytic oxidation activity and superhydrophilicity. Therefore, we present an experimental procedure at a lab scale to assess the self-cleaning ability of various photocatalytic coatings (five TiO2-based commercial products and one lab-grade zinc oxide (ZnO) product) applied to mortar surfaces. The samples were artificially stained with three types of soiling: Congo red dye, diesel soot, and motor oil. They were exposed to the environmental cycle of UV illumination and water flow for two weeks and the changes in stain colors were first assessed with visual inspection. Then, spectrophotometry measurements were conducted before and after the self-cleaning experiment to calculate the color differences for each stain in the CIELab color space data. In addition, the coatings were characterized via X-ray diffraction analyses and water contact angle measurements. Results highlighted color changes for each stain and higher wettability (induced by OH radicals) of the coated surfaces, which favored surface washing and thus stain removal. Light also had a positive effect on the attenuation of the stains, particularly for the Congo red dye.

Photochem doi: 10.3390/photochem3040027

Authors: Artemis Pappa Feidias Bairamis Ioannis Konstantinou

In this study, the aqueous photolytic degradation of the neonicotinoid pesticide clothianidin was studied in suspensions and aqueous extracts of hydrochar produced from olive kernels. A slight and nonsignificant decrease in the photodegradation rate of clothianidin in aqueous extracts of hydrochar (HCw) with an initial concentration of hydrochar ranged from 50 to 400 mg L−1 (rate constants ranged between k = 0.0034 and 0.0039 min−1) was observed in comparison to the respective rate in the bi-distilled water (k = 0.0040 min−1). On the contrary, in the presence of hydrochar suspensions (HCp), a significant decrease was observed for 50 mg L−1 hydrochar particle concentration (k = 0.020 min−1), while for higher concentrations (100 to 400 mg L−1), rate constants increased but with nonsignificant differences compared with the kinetics followed in the absence of them. Generally, the photodegradation rate of clothianidin, in the presence of HCw and HCp, is reduced compared to the photodegradation rate in bi-distilled aqueous solutions, except in the case of the aqueous suspension with an HCp concentration of 200 mg L−1. The transformation products (TPs) of clothianidin formed in the photolytic degradation processes were identified using ultrahigh-performance liquid chromatography coupled with accurate high-resolution mass spectrometry technique (UHPLC-LTQ-ORBITRAP). The formation profiles of TPs varied according to the matrix showing different degrees of participation of direct and indirect (photosensitized) phototransformation pathways. Photolytic degradation of clothianidin takes place mainly through denitration, hydroxylation and dechlorination pathways. Finally, the toxicity of the identified TPs was studied using the Vibrio fischeri bioassay. Toxicity was slightly reduced after 300 min of irradiation while maximum value was observed after 180–240 min of irradiation showing the formation of more toxic TPs along the photochemical degradation.

Photochem doi: 10.3390/photochem3040026

Authors: Mikayla Browning Alexandra Jefferson Jazz Geter Kesete Ghebreyessus

A visible-light-responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand was designed and synthesized, and it was found to form metallogels with reversible photo-responsive properties in mixed methanol/water (MeOH/H2O) solvents. The gelation behavior of the 4-MeS-AAP-NF ligand in the presence of different divalent metal ions in mixed methanol/water (MeOH/H2O) solvents at pH~11.60 was studied. It was found that the 4-MeS-AAP-NF ligand alone could not self-assemble to form any gels. However, in the presence of divalent metal ions, it readily formed the assembled metallogels in an alkaline aqueous/methanol solution with various morphologies. The results suggest that the gelation process was triggered by divalent metal ions. The presence of the AAP moiety in the gel matrix rendered the metallogel assemblies photo-responsive, and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow, reversible visible-light-induced gel-to-sol phase transition under blue (λ = 405 nm) and then sol-to-gel transition by green light (λ = 530 nm) irradiation, resulting in the re-formation of the original gel state. The morphology and viscoelastic properties of the yellow–orange opaque metallogels were characterized by scanning electron microscopy (SEM) and rheological measurement, respectively.

Photochem doi: 10.3390/photochem3040025

Authors: Werner Fudickar Melanie Metz Tobias Krüger-Braunert Alexandra Kelling Eric Sperlich Pablo Wessig Torsten Linker

β-γ-unsaturated spirolactones are easily available by Birch reduction. We describe their photochemistry in the presence of or without carbonyl compounds. The spirolactones show a distinct absorption band at 230 nm, which is not present in other cyclohexadienes. We explain this behavior by an interaction of the double bonds with the carbonyl group through space, further proven by TDDFT calculations. This allows their direct excitation with UV-C light. Interestingly, we obtain only products of an oxa-di-π-methane rearrangement, hitherto unknown for lactones. This speaks for a reaction pathway starting from singlet states, confirmed by calculated relative energies of biradical intermediates. Although polymerization is the main side reaction, we were able to isolate tricyclic lactones in moderate yields in a pure form. In the presence of benzaldehyde or benzophenone, excitation with UV-B light was possible, leading to H-atom abstraction in the allylic position and formation of alcohols. With an electron-rich double bond, the Paternó–Büchi products were isolated as well. The different diastereomers were separated by column chromatography or HPLC. Their relative configurations were determined using NOESY measurements or X-ray structure analysis. Overall, β-γ-unsaturated spirolactones show a remarkably different photochemistry compared to other cyclohexadienes, affording new products in only a few steps.

Photochem doi: 10.3390/photochem3040024

Authors: Abraham Jorge Carmona-Carmona Enrique Sánchez Mora Jesús Ivan Peña Flores César Márquez-Beltrán María Dolores Castañeda-Antonio Marlén Alexis González-Reyna María Concepción Barrera Khashayar Misaghian Jesús Eduardo Lugo Miller Toledo-Solano

In this study, opal–magnetite photocatalysts based on SiO2 artificial opal crystals infiltrated with different concentrations of Fe3O4 nanoparticles (NPs) were synthesized using a combination of lateral infiltration and co-assembly methods. By adjusting the concentration of Fe3O4 NPs in the SiO2 opal crystal, the energy band gap (Eg) was tuned to enable efficient degradation of methylene blue (MB) under visible light (410 nm and 575 nm). The photocatalytic process involved two stages: MB adsorption on the surface due to charge differences in the composite film and subsequent degradation through oxidative radicals on the catalyst’s surface. The developed material exhibited potential for applications in water remediation.