{"title":"Design and synthesis of a 2,5-Diarylthiophene chromophore for enhanced near-infrared two-photon uncaging efficiency of calcium ions","authors":"Tam Thi Thanh Tran, Manabu Abe","doi":"10.1007/s43630-024-00623-5","DOIUrl":"https://doi.org/10.1007/s43630-024-00623-5","url":null,"abstract":"<p>The design and synthesis of two-photon-responsive chromophores have recently garnered significant attention owing to their potential applications in materials and life sciences. In this study, a novel π-conjugated system, 2-dimethylaminophenyl-5-nitrophenylthiophene derivatives, featuring a thiophene unit as the π-linker between the donor (NMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>–) and acceptor (NO<sub>2</sub>C<sub>6</sub>H<sub>4</sub>–) units was designed, synthesized, and applied for the development of two-photon-responsive chromophores as a photoremovable protecting group in the near-infrared region. Notably, the positional effect of the nitro group (NO<sub>2</sub>), <i>meta</i> versus <i>para</i> position, was observed in the uncaging process of benzoic acid. Additionally, while the <i>para</i>-isomer exhibited a single fluorescence peak, a dual emission was detected for the <i>meta</i>-isomer in polar solvents. The caged calcium ion (Ca<sup>2+</sup>) incorporating the newly synthesized thiophene unit exhibited a sizable two-photon absorption cross-section value (σ<sub>2</sub> = 129 GM at 830 nm). Both one-photon and two-photon photoirradiation of caged calcium ions successfully released calcium ions, indicating the potential utility of 2,5-diarylthiophene derivatives in future biological studies.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142198718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alba Navarro-Bielsa, Tamara Gracia-Cazaña, Rosa del Campo, Raquel Barbero, Concepción López-Gómez, Pedro Gil-Pallares, Yolanda Gilaberte
{"title":"Analysis of the modification of skin and gut microbiota in psoriasis patients treated with phototherapy","authors":"Alba Navarro-Bielsa, Tamara Gracia-Cazaña, Rosa del Campo, Raquel Barbero, Concepción López-Gómez, Pedro Gil-Pallares, Yolanda Gilaberte","doi":"10.1007/s43630-024-00628-0","DOIUrl":"https://doi.org/10.1007/s43630-024-00628-0","url":null,"abstract":"","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142198719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"An insight into the role of ESIPT/TICT-based antioxidant flavone analogues in fluoro-probing diabetes-induced viscosity changes: a unified experimental and theoretical endeavour.","authors":"Trisha Samanta, Samanwita Mandal, Abhijit Karmakar, Anup Pramanik, Rakesh Kundu, Naznin Ara Begum","doi":"10.1007/s43630-024-00630-6","DOIUrl":"https://doi.org/10.1007/s43630-024-00630-6","url":null,"abstract":"<p><p>Potent antioxidants, like 3-hydroxy flavones, attracted considerable attention due to their excited state intramolecular proton transfer (ESIPT)-based fluorescence behaviour. This article is an interesting demonstration of a series of synthetic 3-hydroxy flavone analogues having high antioxidant activity as molecular rotor-like viscosity probes. Among these flavone analogues, 4'-N,N-dimethylamino-3-hydroxy flavone (3) is the most potent one, showing the twisted intramolecular charge transfer (TICT)-dependent fluoroprobing activity toward the blood viscosity changes associated with diabetes and free fatty acids (FFA)-induced nuclear viscosity changes of MIN6 cells. The TICT dynamics of (3), which instigates its viscosity probing activity, was comprehended with the help of DFT-based computational studies. Abnormal cellular viscosity changes are the pathological traits for various diseases, and non-toxic flavone-based viscosity probes can be useful for diagnosing such pathological conditions.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142152578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gulsah Evyapan, Halil Ozkol, Hatice Uce Ozkol, Özge Alvur, Sakine Akar
{"title":"The preventive effects of natural plant compound carvacrol against combined UVA and UVB-induced endoplasmic reticulum stress in skin damage of rats","authors":"Gulsah Evyapan, Halil Ozkol, Hatice Uce Ozkol, Özge Alvur, Sakine Akar","doi":"10.1007/s43630-024-00631-5","DOIUrl":"https://doi.org/10.1007/s43630-024-00631-5","url":null,"abstract":"<p>The skin is constantly exposed to a variety of environmental stressors, including ultraviolet (UV) radiation. Exposure of the skin to UV radiation causes a number of detrimental biological damages such as endoplasmic reticulum (ER) stress. The ER stress response is a cytoprotective mechanism that maintains homeostasis of the ER by increasing the capacity of the ER against the accumulation of unfolded proteins in the ER. Carvacrol (CRV) is a monoterpenoid phenol found in essential oils with antimicrobial and anti-inflammatory activities. We investigated for the first time in the literature the potential protective role of CRV against combined UVA and UVB-induced skin damage by targeting the ER stress pathway in a rat model. For this purpose, expressions of <i>Grp78, Perk, Atf6, Ire-1, Chop, Xbp1, Casp12, elF2α,</i> and <i>Traf2</i> genes related to ER stress were analyzed by RT-PCR and protein expression levels of GRP78, ATF6, CHOP, and XBP1 were determined by ELISA assay in tissue sections taken from the back of the rats. As a result of analysis, it was seen that the expression levels of aforementioned ER stress genes increased significantly in the UVA + UVB irradiated group compared to the control group, while their expression levels decreased markedly by supplementation of CRV in UVA + UVB + CRV group. With regard to expressions of foregoing proteins, their levels escalated notably with UVA + UVB application and decreased markedly by CRV supplementation. In conclusion, present study revealed that CRV ameliorates UVA + UVB-induced ER stress via reducing the expression of mRNA as well as proteins involved in the unfolded protein response (UPR) pathway and inducing apoptosis as evidenced from high <i>Caspase12</i> level.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142198720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The effect of fluence rate and wavelength on the formation of protoporphyrin IX photoproducts.","authors":"Sochi J Ogbonna, Katsuyoshi Masuda, Hisanao Hazama","doi":"10.1007/s43630-024-00611-9","DOIUrl":"https://doi.org/10.1007/s43630-024-00611-9","url":null,"abstract":"<p><p>Photodynamic diagnosis and therapy (PDD and PDT) are emerging techniques for diagnosing and treating tumors and malignant diseases. Photoproducts of protoporphyrin IX (PpIX) used in PDD and PDT may be used in the diagnosis and treatment, making a detailed analysis of the photoproduct formation under various treatment and diagnosis conditions important.Spectroscopic and mass spectrometric analysis of photoproduct formation from PpIX dissolved in dimethyl sulfoxide were performed under commonly used irradiation conditions for PDD and PDT, i.e., wavelengths of 405 and 635 nm and fluence rates of 10 and 100 mW/cm<sup>2</sup>. Irradiation resulted in the formation of hydroxyaldehyde photoproduct (photoprotoporphyrin; Ppp) and formyl photoproduct (product II; Pp II) existing in different quantities with the irradiation wavelength and fluence rate. Ppp was dominant under 635 nm irradiation of PpIX, with a fluorescence peak at 673 nm and a protonated monoisotopic peak at m/z 595.3. PpIX irradiation with 405 nm yielded more Pp II, with a fluorescence peak at 654 nm. A higher photoproduct formation was observed at a low fluence rate for irradiation with 635 nm, while irradiation with 405 nm indicated a higher photoproduct formation at a higher fluence rate.The photoproduct formation with the irradiation conditions can be exploited for dosimetry estimation and may be used as an additional photosensitizer to improve the diagnostics and treatment efficacies of PDD and PDT. Differences in environmental conditions of the present study from that of a biological environment may result in a variation in the photoproduct formation rate and may limit their clinical utilization in PDD and PDT. Thus, further investigation of photoproduct formation rates in more complex biological environments, including in vivo, is necessary. However, the results obtained in this study will serve as a basis for understanding reaction processes in such biological environments.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142152579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Masbooth Rasa Melechalil, Tetsuya Shimada, Tamao Ishida, Shinsuke Takagi
{"title":"Effect of remotely connected trialkyl ammonium groups on the dye molecules in the photochemical behavior on the clay nanosheet.","authors":"Masbooth Rasa Melechalil, Tetsuya Shimada, Tamao Ishida, Shinsuke Takagi","doi":"10.1007/s43630-024-00625-3","DOIUrl":"https://doi.org/10.1007/s43630-024-00625-3","url":null,"abstract":"<p><p>The enhanced emission properties of several cationic dye molecules on the clay surface established as a result of the strong electrostatic interaction and associated molecular flattening leading to either the suppression of non-radiative deactivation processes or the improvement of radiative deactivation processes has been verified, and it is known as surface-fixation induced emission (S-FIE). Here, the differences in the S-FIE properties as well as the self-fluorescence quenching behavior of the dimidium and propidium dyes were compared. Propidium differs from dimidium by the substitution of a propyl (diethyl methylammonium) group at the 5th position instead of the methyl group in dimidium. So, the differences induced by this substitution, which is not even in conjugation with the chromophore part of the dye molecule show a significant impact on the adsorption strength, S-FIE properties, and self-fluorescence quenching behavior. In propidium and dimidium, the suppression of k<sub>nr</sub> was the key factor for emission enhancement on the clay surface. Interestingly, the alkylammonium cation group in the Propidium helped for better adsorption strength as well as to reduce the self-fluorescence quenching behavior on the clay surface as compared to the dimidium. Since the trialkylammonium cation was not in conjugation with the core structure of the molecule and located at a specific distance, it did not interrupt the flattening of the molecule on the clay surface. These results could be beneficial in the construction of efficient photochemical reaction systems, where the molecule having low adsorption strengths can be modified by alkyl ammonium cations, which will not affect molecular planarization.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pedro A Pinheiro, Gabriel F M Pereira, Leandro O Cunha, Julia P S C Leal, Meiry E Alvarenga, Felipe T Martins, Heveline Silva, Jorge L S Milani, Thiago T Tasso
{"title":"Modulating the phototoxicity and selectivity of a porphyrazine towards epidermal tumor cells by coordination with metal ions.","authors":"Pedro A Pinheiro, Gabriel F M Pereira, Leandro O Cunha, Julia P S C Leal, Meiry E Alvarenga, Felipe T Martins, Heveline Silva, Jorge L S Milani, Thiago T Tasso","doi":"10.1007/s43630-024-00629-z","DOIUrl":"https://doi.org/10.1007/s43630-024-00629-z","url":null,"abstract":"<p><p>Porphyrazines (Pzs) are porphyrin derivatives that show potential application as photosensitizers for photodynamic therapy (PDT), but are still far less explored in the literature. In this work, we evaluate how the photophysics and phototoxicity of the octakis(trifluoromethylphenyl)porphyrazine (H<sub>2</sub>Pz) against tumor cells can be modulated by coordination with Mg(II), Zn(II), Cu(II) and Co(II) ions. Fluorescence and singlet oxygen quantum yields for the Pzs were measured in organic solvents and in soy phosphatidylcholine (PC) liposomes suspended in water. While H<sub>2</sub>Pz and the respective complexes with Cu(II) and Co(II) showed very low efficiency to fluoresce and to produce <sup>1</sup>O<sub>2</sub>, the Mg(II) and Zn(II) complexes showed significantly higher quantum yields in organic solvents. The fluorescence of these two Pzs in the liposomes was sensitive to the fluidity of the membrane, showing potential use as viscosity markers. The cytotoxicity of the compounds was tested in HaCaT (normal) and A431 (tumor) cells using soy PC liposomes as drug carriers. Despite the low <sup>1</sup>O<sub>2</sub> quantum yields in water, the Mg(II) and Zn(II) complexes showed IC<sub>50</sub> values against A431 cells in the nanomolar range when activated with low doses of red LED light. Their phototoxicity was ca. three times higher for the tumor cells compared to the normal ones, showing promising application as photosensitizers for PDT protocols. Considering that H<sub>2</sub>Pz and the respective Co(II) and Cu(II) complexes were practically non-phototoxic to the cells, we demonstrate the importance of the central metal ion in the modulation of the photodynamic activity of porphyrazines.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142144553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Grzegorz Szewczyk, Krystian Mokrzyński, Tadeusz Sarna
{"title":"Generation of singlet oxygen inside living cells: correlation between phosphorescence decay lifetime, localization and outcome of photodynamic action.","authors":"Grzegorz Szewczyk, Krystian Mokrzyński, Tadeusz Sarna","doi":"10.1007/s43630-024-00620-8","DOIUrl":"https://doi.org/10.1007/s43630-024-00620-8","url":null,"abstract":"<p><p>Photodynamic therapy (PDT) is a promising alternative treatment for localized lesions and infections, utilizing reactive oxygen species (ROS) generated by photosensitizers (PS) upon light activation. Singlet oxygen (<sup>1</sup>O<sub>2</sub>) is a key ROS responsible for photodynamic damage. However, the effectiveness of PS in biological systems may not correlate with the efficiency of singlet oxygen generation in homogeneous solutions. This study investigated singlet oxygen generation and its decay in various cellular microenvironments using liposome and ARPE-19 cell models. Rose Bengal (RB), methylene blue (MB), and protoporphyrin IX (PpIX) were employed as selected PS. Lifetimes of singlet oxygen generated by the selected photosensitizers in different cellular compartments varied, indicating different quenching rates with singlet oxygen. RB, located near cell membranes, exhibited the highest phototoxicity and lipid/protein peroxidation, followed by PpIX, while MB showed minimal cytotoxicity in similar conditions. Singlet oxygen decay lifetimes provide insights into PS localization and potential phototoxicity, highlighting the importance of the lipid microenvironment in PDT efficacy, providing useful screening method prior to in vivo applications.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"PDT and antitumor immunity: the beginnings of the story.","authors":"Gianfranco Canti, Valentina Rapozzi","doi":"10.1007/s43630-024-00627-1","DOIUrl":"https://doi.org/10.1007/s43630-024-00627-1","url":null,"abstract":"<p><p>This mini-review reports a brief description of the first experiments conducted by Canti's group on the role of photodynamic therapy in generating immunity against cancer. It highlights for the first time the effective role of PDT in the induction of anti-tumor T lymphocytes and shows that this effect is tumor-specific. It has also been reported how this adoptive immunity can improve the efficacy of chemotherapy. These studies have helped to open an important new field of scientific research on the role of PDT-generated immunity and to stimulate today's important new pre-clinical approaches.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"LED therapy modulates M1/M2 macrophage phenotypes and mitigates dystrophic features in treadmill-trained mdx mice.","authors":"Valéria Andrade Pereira, Heloina Nathalliê Mariano da Silva, Evelyn Mendes Fernandes, Elaine Minatel","doi":"10.1007/s43630-024-00626-2","DOIUrl":"https://doi.org/10.1007/s43630-024-00626-2","url":null,"abstract":"<p><p>The mdx mouse phenotype, aggravated by chronic exercise on a treadmill, makes this murine model more reliable for the study of Duchenne muscular dystrophy (DMD) and allows the efficacy of therapeutic interventions to be evaluated. This study aims to investigate the effects of photobiomodulation by light-emitting diode (LED) therapy on functional, biochemical and morphological parameters in treadmill-trained adult mdx animals. Mdx mice were trained for 30 min of treadmill running at a speed of 12 m/min, twice a week for 4 weeks. The LED therapy (850 nm) was applied twice a week to the quadriceps muscle throughout the treadmill running period. LED therapy improved behavioral activity (open field) and muscle function (grip strength and four limb hanging test). Functional benefits correlated with reduced muscle damage; a decrease in the inflammatory process; modulation of the regenerative muscular process and calcium signalling pathways; and a decrease in oxidative stress markers. The striking finding of this work is that LED therapy leads to a shift from the M1 to M2 macrophage phenotype in the treadmill-trained mdx mice, enhancing tissue repair and mitigating the dystrophic features. Our data also imply that the beneficial effects of LED therapy in the dystrophic muscle correlate with the interplay between calcium, oxidative stress and inflammation signalling pathways. Together, these results suggest that photobiomodulation could be a potential adjuvant therapy for dystrophinopathies.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142124275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}