Leonardo M F Oliveira, Danillo Valverde, Gustavo Juliani Costa, Antonio Carlos Borin
{"title":"Excited state relaxation mechanisms and tautomerism effects in 2,6-Diamino-8-Azapurine.","authors":"Leonardo M F Oliveira, Danillo Valverde, Gustavo Juliani Costa, Antonio Carlos Borin","doi":"10.1111/php.14045","DOIUrl":"10.1111/php.14045","url":null,"abstract":"<p><p>The photochemistry of 9H-2,6-diamino-8-azapurine (9H-8AZADAP), a promising fluorescent probe, was investigated using the Multi-State Complete-Active-Space Second-Order Perturbation Theory (MS-CASPT2) quantum chemical method, along with the Average Solvent Electrostatic Configuration and Free Energy Gradient (ASEC-FEG) and Polarizable Continuum Model (PCM) to take into account water solvation effects. For both isolated and solvated species, the main photochemical event is initiated by the absorption of light from ground-state to the bright <sup>1</sup>(ππ* L<sub>a</sub>) state, which undergoes barrierless evolution to its minimum energy region (<sup>1</sup>(ππ* L<sub>a</sub>)<sub>min</sub>) without crossing any other potential energy surface (PES). Subsequently, the excess of energy is released through fluorescence. From the <sup>1</sup>(ππ* L<sub>a</sub>)<sub>min</sub> region, two radiationless decay pathways back to the initial ground state, mediated by two distinct conical intersections between the ground and <sup>1</sup>(ππ* L<sub>a</sub>) states, are found to be unlikely due to the presence of high energy barriers in both environments. Our results also indicate that the solvation effects are more pronounced when using the ASEC-FEG method, which predicts larger structural and energy changes, especially concerning energetic barriers. Based on the free energy perturbation theory (FEP), a hypothetical thermodynamic cycle was devised, from which we infer that in an aqueous environment the N<sub>3</sub> site is the most favorable for protonation. We also conclude that the 8H-8AZADAP tautomer is responsible for the fluorescent band observed experimentally at 410 nm and elucidates the mechanism of phototautomerism.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":"1072-1085"},"PeriodicalIF":2.5,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143399582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Erick L Bastos, Carolina Lorente, Fabiano S Rodembusch, Andrés H Thomas
{"title":"Preface to the special issue on the XV ELAFOT/1st Lat-ASP conference.","authors":"Erick L Bastos, Carolina Lorente, Fabiano S Rodembusch, Andrés H Thomas","doi":"10.1111/php.70012","DOIUrl":"https://doi.org/10.1111/php.70012","url":null,"abstract":"","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":"101 4","pages":"787-789"},"PeriodicalIF":2.5,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144837337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paulo Newton Tonolli, Suely Kazue Nagahashi Marie, Sueli Mieko Oba-Shinjo, Leonardo Vinicius Monteiro de Assis, Maurício S Baptista
{"title":"Stage-specific phenotypic and transcriptional alterations in HaCaT keratinocytes exposed to acute and chronic blue light.","authors":"Paulo Newton Tonolli, Suely Kazue Nagahashi Marie, Sueli Mieko Oba-Shinjo, Leonardo Vinicius Monteiro de Assis, Maurício S Baptista","doi":"10.1111/php.14095","DOIUrl":"10.1111/php.14095","url":null,"abstract":"<p><p>Despite evidence that visible light (VL) has similar effects on human skin as those of UVA, VL is often viewed as harmless. High SPF sunscreen prevents erythema but can lead to overexposure to UVA and VL, with unknown consequences. To explore the impact of chronic blue light exposure, we irradiated (50 J/cm<sup>2</sup>, λ = 408 nm, three times a week) human immortalized keratinocytes under acute (3 irradiations), intermediate (14 irradiations), and chronic (42 irradiations) blue light exposure, monitoring phenotypic and gene expression changes. Chronically exposed keratinocytes exhibit increased nuclei area, chromatin alterations, higher proliferation, and apoptosis resistance, mirroring the consequences of chronic UVA exposure. While acute exposure upregulated keratinization and downregulated tissue repair and apoptosis genes, chronically exposed cells had upregulated genes involved in energy metabolism and oxidative phosphorylation, and downregulated genes were enriched for immune and inflammatory responses. Specific transcription factors were identified in both the acute and chronic stages, some of which have been associated with UVB exposure. IRF1, EGR1, ELF3, FOSL1, and CENPX, SRF, CEBPB, KLF4 were identified in the acute and chronic stages, respectively. We identified some changes in chronically irradiated keratinocytes similar to malignant transformation, emphasizing the need for further research on the long-term impacts of blue light exposure on human skin.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":"947-959"},"PeriodicalIF":2.5,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143796145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nicolas Garimano, Taís Aguayo Frías, Daniel H González Maglio
{"title":"Beyond ultraviolet radiation: Immune system modulation through skin exposure to visible light and infrared radiation.","authors":"Nicolas Garimano, Taís Aguayo Frías, Daniel H González Maglio","doi":"10.1111/php.14117","DOIUrl":"10.1111/php.14117","url":null,"abstract":"<p><p>Sunlight profoundly affects skin health when it is exposed. After acute exposure, a robust inflammatory response is initiated locally. Moreover, chronic exposures lead to carcinogenesis and photoaging. Local and systemic immunosuppression is also triggered after skin irradiation, affecting adaptive immune responses. These effects are mainly produced by the ultraviolet radiation contained in sunlight and were extensively described and reviewed. However, using UV filters during sunbathing and outdoor activities may allow visible light (VL) wavelengths and infrared radiation (IRR) to reach skin cells. Additionally, the employment of therapeutic VL and IR-emitting lasers and LED devices is increasing for various skin conditions. This literature review aims to present current knowledge on the effects of VL and IRR modulating the skin and systemic immune system. These modulations impact healthy skin and can modify immune responses to diverse stimuli in various cell types. According to the wavelength and the dose, VL and IRR increase the production of reactive oxygen species and promote faster wound healing. Moreover, they modulate inflammatory mediators, such as several cytokines and prostaglandins. However, skin exposure to VL can also affect adaptive immune responses. The study of VL and IRR effects on immunity would promote new uses for phototherapy and may establish the need for new strategies in photoprotection.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":"846-857"},"PeriodicalIF":2.5,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144079529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yasuo Mitani, Shusei Kanie, Sosmitha Girisa, Ajaikumar B Kunnumakkara, Sunil C Kaul, Yoshihiro Ohmiya
{"title":"Characterization of luciferase from an Indian firefly Abscondita sp. (Coleoptera: Lampiridae).","authors":"Yasuo Mitani, Shusei Kanie, Sosmitha Girisa, Ajaikumar B Kunnumakkara, Sunil C Kaul, Yoshihiro Ohmiya","doi":"10.1111/php.70001","DOIUrl":"https://doi.org/10.1111/php.70001","url":null,"abstract":"<p><p>Among the luminescent animals, fireflies have been extensively investigated throughout the world. Enzymatic characterization using recombinant proteins has been achieved after the first cloning of the Photinus pyralis luciferase gene. Firefly luciferase is pH sensitive, emitting a red-shifted color when the pH of the reaction buffer is lowered. This trait is only known for fireflies and not in other luminescent beetles, including click beetles (Elateridae) and railroad worms (Phengodidae). Until now, firefly luciferases from North America, Central and South America, Europe, and East Asia have been intensively studied. Recently, molecular phylogenetic analyses using mitochondrial DNA have revealed relationships between firefly species in South Asia and India. However, the enzymatic characterization of luciferases from such species has not been thoroughly investigated. Here, we collected a firefly in India and enzymatically characterized its luciferase. Molecular phylogenetic analysis using cytochrome oxidase I suggested that this firefly is closely related to the genus Abscondita. The luciferase gene obtained from the RNA sequencing (RNA-Seq) was expressed using Escherichia coli and was used to characterize the luciferase. Its optimum temperature and pH were 30°C and 7.0, respectively. The maximum emission wavelength was around 570 nm when a pH 6.0 or 8.0 reaction buffer was used, and no apparent red shift was observed.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144326612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Evaluation of the disulfide bond positions in recombinant Gaussia luciferase expressed in Escherichia coli cells by site-directed mutagenesis.","authors":"Satoshi Inouye, Yuiko Sahara-Miura, Jun-Ichi Sato","doi":"10.1111/php.70003","DOIUrl":"https://doi.org/10.1111/php.70003","url":null,"abstract":"<p><p>Gaussia luciferase (GLase) is a secreted enzyme composed of 168 amino acids, including 10 cysteine residues, and catalyzes the oxidation of coelenterazine to emit light. To evaluate the disulfide bond positions in GLase, we generated 10 cysteine-to-serine substituted GLase genes, in which each cysteine residue was replaced with a serine residue (C52S, C56S, C59S, C65S, C77S, C120S, C123S, C127S, C136S, and C148S), using site-directed mutagenesis. In both bacterial and mammalian expression systems, four disulfide bonds formed between eight cysteine residues (C52, C56, C65, C77, C123, C127, C136, and C148) were found to be essential for luminescence activity. In bacterial cells, the single mutants C59S and C120S, as well as the double mutant C59S/C120S, exhibited luminescence activities of 258%, 2.8%, and 42.8%, respectively, relative to wild-type GLase (100%). Notably, all three mutants could be efficiently refolded by dialysis after treatment with 2-mercaptoethanol. In mammalian cells, only the double mutant C59S/C120S was secreted and showed luminescence activity of 11% in the culture medium, relative to wild-type GLase (100%). By integrating previously reported NMR-based structural data of recombinant GLase purified from bacterial cells with our experimental findings, we conclude that GLase contains five disulfide bonds: C52-C127, C56-C123, C59-C120, C65-C77, and C136-C148, which are consistent with those reported in PDB ID: 7D2O.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144310289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kamrun Nahar, Serah Essang, Lloyd Lapoot, Alexander Greer
{"title":"Tandem singlet oxygenation: Regioselective reaction of two <sup>1</sup>O<sub>2</sub> molecules by a nonconjugated diprenyl phenol.","authors":"Kamrun Nahar, Serah Essang, Lloyd Lapoot, Alexander Greer","doi":"10.1111/php.70005","DOIUrl":"https://doi.org/10.1111/php.70005","url":null,"abstract":"<p><p>Tandem reactions of singlet oxygen (<sup>1</sup>O<sub>2</sub>) with nonconjugated natural products, such as plastoquinones, have attracted attention. However, mechanistic clarity is needed for the <sup>1</sup>O<sub>2</sub> uptake sequence and regioselectivity. Our strategy was to study a tandem <sup>1</sup>O<sub>2</sub> reaction in a diprenylated phenol (geranyl phenol) bearing an inner and an outer prenyl group in the chain. Singlet oxygen first added to the inner prenyl group by H-bonding to the phenol OH, forming a gem-disubstituted and a tri-substituted dienyl dihydrobenzofuran. H<sub>2</sub>O<sub>2</sub> was also released as a by-product. A second equivalent of <sup>1</sup>O<sub>2</sub> added by an \"ene\" reaction, but now to the outer rather than the inner site of the nonconjugated diene to reach four hydroperoxy-dihydrobenzofurans. There was no evidence for <sup>1</sup>O<sub>2</sub> \"ene\" reactions on the inner prenyl sites, but product decomposition included the formation of oxygen-centered radicals and even methane by a β-scission process. The results are an essential step in resolving mechanistic puzzles of reactive oxygen uptake in natural prenylated systems, which are important topics not only in physical-organic and synthetic chemistry but also in plant oxidation chemistry.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144310291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mary A Ndiaye, Debra R Garvey, Gagan Chhabra, Chandra K Singh, Minakshi Nihal, Nihal Ahmad
{"title":"PLK4 is a potential therapeutic target in nonmelanoma skin cancers: Evidence from molecular and in vivo studies.","authors":"Mary A Ndiaye, Debra R Garvey, Gagan Chhabra, Chandra K Singh, Minakshi Nihal, Nihal Ahmad","doi":"10.1111/php.70006","DOIUrl":"10.1111/php.70006","url":null,"abstract":"<p><p>Nonmelanoma skin cancers (NMSC), consisting primarily of cutaneous squamous cell carcinoma (cSCC) and basal cell carcinoma (BCC), are the most prevalent cancers in the United States and have been associated with exposure to solar ultraviolet (UV) radiation. While a majority of NMSC are surgically resectable, the inoperable or metastatic tumors need intense therapies, including targeted and immunotherapies. However, novel targeted therapies are needed to improve treatment efficacy, reduce side effects, and limit recurrence, metastasis, and drug resistance. Polo-like kinase 4 (PLK4), a member of a serine/threonine family of kinases, is being investigated as a target for anticancer drug development. However, its role in NMSC is not established. In this study, we found PLK4 to be significantly overexpressed in BCC and cSCC cells and tissues. Further, small molecule inhibition of PLK4 activity with centrinone, a specific and reversible inhibitor, and CFI-400945, an ATP-competitive inhibitor, decreased cell viability, proliferation, and clonogenic survival of human cSCC and BCC cells. Furthermore, PLK4 inhibition induced significant cell cycle arrest and apoptosis as well as modulation of key cell cycle genes as determined using a PCR Array. Additionally, CRISPR/Cas9-mediated knockdown of PLK4 in the A431 cSCC cell line showed (i) significant growth inhibitory effects in vitro, along with significant modulation in key cancer-related genes via PCR array and (ii) significantly reduced tumorigenesis in vivo in a mouse xenograft model. Overall, this study suggested that PLK4 is a potential therapeutic target and a biomarker for NMSC management. However, additional studies are needed to validate and expand these findings in additional model systems.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12317374/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144310290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"An anthracene-based symmetrical azine linkage turn-on fluorogenic probe for selective and specific detection of sarin simulant, diethylchlorophosphate.","authors":"Anupama Rani Das, Sabbir Ahamed, Jyoti Chourasia, Subekchha Pradhan, Najmin Tohora, Upika Darnal, Shraddha Rai, Shubham Lama, Sudhir Kumar Das","doi":"10.1111/php.70004","DOIUrl":"https://doi.org/10.1111/php.70004","url":null,"abstract":"<p><p>Notably, the G-series nerve agents possess extreme toxicity and can be synthesized through a facile protocol; their abuse becomes a significant threat to the environment and human life. Hence, it is emerging to develop an efficient chemosensor for the selective identification of these nerve agents. In this report, we have presented an azine-based symmetrical fluorogenic probe, BAH, for the selective detection of sarin gas, one of the fatal G-series nerve agent surrogates, diethylchlorophosphate (DCP). BAH is non-fluorescent, but the progressive accumulation of DCP displays a naked-eye bright greenish cyan fluorometric change under a 365 UV lamp. Recognizable greenish cyan color fluorescence diminished completely for the accumulation of triethylamine (TEA), confirming its reusability multiple times. A paper strips-based test kit experiment has also been demonstrated for the onsite detection of these nerve agents, especially in remote areas in solution and vapor phases, respectively. A superior application combining the attractiveness and efficiency of BAH in the gaseous phase was also demonstrated. The BAH-based fluorogenic sensor shows excellent selectivity towards DCP with a detection and quantification limit in the μM range. The simple, rapid detection makes our probe unique and has significant utility for the recognition of DCP in real threat scenarios.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144275622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maressa D F de Souza, Pietro Ciancaglini, Rosangela Itri, Martha S Ribeiro
{"title":"Developing giant plasma membrane vesicles from Leishmania cells to investigate the role of membrane proteins in photodynamic inactivation.","authors":"Maressa D F de Souza, Pietro Ciancaglini, Rosangela Itri, Martha S Ribeiro","doi":"10.1111/php.70000","DOIUrl":"https://doi.org/10.1111/php.70000","url":null,"abstract":"<p><p>Interest in antimicrobial photodynamic therapy for treating cutaneous leishmaniasis has been rising, showing promising outcomes and good patient tolerance. In this study, we aimed to develop a protocol for producing giant plasma membrane vesicles (GPMVs) from Leishmania amazonensis promastigote cell membranes, focusing on the role of membrane-embedded proteins during methylene blue (MB) photooxidation with red light. Membrane extraction was achieved via centrifugation with various sucrose gradients. We then generated GPMVs by electroformation, applying different frequencies and voltages over four cycles, and examined them using phase contrast optical microscopy. For MB photooxidation, GPMVs were dispersed in an aqueous solution with 50 μM MB and exposed to 665 nm light at 830 μW. A comparable approach was used for mimetic membranes (giant unilamellar vesicles, GUVs) made of Leishmania membrane lipids. MB photoactivation in GUVs caused a transient increase in membrane area and full permeability. Conversely, GPMVs showed an earlier onset of contrast loss but exhibited less overall contrast reduction and no expansion, indicating that membrane proteins in GPMVs modulate the response to oxidative stress. Real-time monitoring revealed morphological changes in L. amazonensis promastigote cells consistent with apoptosis following photodynamic inactivation.</p>","PeriodicalId":20133,"journal":{"name":"Photochemistry and Photobiology","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144258661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}