Photochemistry and Photobiology最新文献

Toluidine blue O (TBO) is a type I-type II photosensitizer that has shown good efficacy and selectivity in antimicrobial and anticancer photodynamic therapy applications. However, its complex photochemistry with multiple photoproducts hinders its application as a photosensitizer. We have previously described the mechanism for photooxidative demethylation of TBO which in acetonitrile yields two main products: demethylated-TBO (d-TBO) and double-demethylated-TBO (dd-TBO). In the current work, we describe the photophysical properties of these two photoproducts. In acetonitrile and phosphate buffer, demethylation induces an hypsochromic shift in the absorption and fluorescence emission maxima. Fluorescence quantum yields increase slightly for the demethylated photoproducts, in agreement with the lengthening of the fluorescence lifetimes. Triplet excited states lifetimes in the presence of oxygen decreased slightly upon demethylation. However, the singlet oxygen quantum yield increased significantly reaching unity for the dd-TBO photoproduct. These results are interpreted in terms of the competing pathways of TBO photochemistry. For TBO, demethylation is the main pathway for deactivation of the excited state, while for d-TBO, demethylation and singlet oxygen generation are significant. For dd-TBO, singlet oxygen generation is the main deactivation pathway. Overall, TBO demethylated photoproducts demonstrate good potential as candidates for photodynamic therapy applications.

Recently (Photochem Photobiol. 2023;100:1277-1289. doi:10.1111/php.13898), we described the anti-Kasha effect in tribenzo-6H-1,4-diazepinoporphyrazins with C_2v symmetry, where the ultrafast spin changes successfully compete with the internal conversion. In this study, we show the presence of this effect in 2 (3),9 (10),16(17),23(24)-tetra-tert-butyl-29H,31H-phthalocyanine (1) and 1,4-di-[2-(2-methoxyethoxy)ethoxy]-29H,31H-phthalocyanine (2), which also possess reduced molecular symmetry and do not bear 6H-1,4-diazepine fragments. The anti-Kasha effect in 1 and 2 supplemented by Mg(II) tribenzo-6H-1,4-diazepinoporphyrazinates 3 and 4 exhibits a close-to-linear dependence on energy gap value between the zero vibrational levels of two lowest singlet excited states S₁ ⁰ and S₂ ⁰ (these states are degenerate in D_4h symmetry) and enhances with increase. The theoretical kinetic model of excited state dynamics, which takes into account the observed effects and follows Fermi's golden rule, predicts the presence of an additional excited state with enhanced spin-orbit coupling compared to S₁ ⁰, S₂ ⁰ and the corresponding triplet states, which is not predicted by TDDFT calculations in the Born-Oppenheimer approximation. The combination of the above indicates that the key role in the observed anti-Kasha effect and the mechanism of dissipation of the excited state in porphyrazines and their analogs is played by vibronic excited states, which requires theoretical research methods beyond the Born-Oppenheimer approximation.

Globally, 537 million people suffer from diabetes mellitus (DM), a condition often associated with sensory disturbances, wound development, and chronic pain, which significantly affects the quality of life and imposes a substantial economic burden. This study evaluated the effects of photobiomodulation (PBM) therapy on nociceptive and sensory changes in diabetic patients to understand pain manifestations and explore PBM's molecular mechanisms on wound healing. Twenty patients with type 2 DM underwent clinical assessments, completed pain and quality of life questionnaires, and had their pain sensitivity evaluated using the quantitative sensory test (QST). A 5 mm skin biopsy was taken for fibroblast culture. PBM therapy, using 660 nm red light, was administered twice weekly for 7 weeks on lower limb wounds. Results indicated that DM patients faced significant sensory impairments, impacting their quality of life. PBM therapy improved pain scores, alleviated neuropathic pain, and enhanced sensory function, leading to better quality of life and reduced anxiety and depression. It also accelerated wound healing, enhancing mobility and autonomy. In vitro studies showed PBM therapy increased cell proliferation through the ERK signaling pathway and modulation of matrix metalloproteinases (MMP-1/8 and 2) and tissue inhibitors of metalloproteinases (TIMP).

Virus-laden aerosols play a substantial role in the spread of numerous infectious diseases, particularly in enclosed indoor settings. Ultraviolet-C (UVC) disinfection is known to be a highly efficient method for disinfecting pathogenic airborne viruses. Recent recommendations suggest using far-UVC radiation (222 nm) emitted by KrCl* (krypton-chloride) excimer lamps to disinfect high-risk public spaces due to lower exposure risks than low-pressure (LP) mercury lamps (254 nm). This study experimentally explored the comparative effectiveness of far-UVC (222 nm) and germicidal UVC (254 nm) in inactivating virus-laden aerosols of different protective vector media in an air disinfection chamber. The UVC inactivation performances of individual filtered KrCl* excimer lamp and LP mercury lamp were determined for inactivating the bacteriophages, MS2 (icosahedral and non-enveloped ssRNA virus) and Phi6 (spherical and enveloped dsRNA virus) aerosolized from artificial human saliva or sodium chloride and magnesium sulfate (SM) buffer as a vector media. Disinfection efficacy of filtered KrCl* excimer lamp (222 nm) and LP mercury lamp (254 nm) were evaluated for highly concentrated viral aerosols, which replicate those exhaled from infected individuals and remain suspended in air or deposited on surfaces as fomites. Our results show that using individual filtered KrCl* excimer lamp (222 nm) and LP mercury lamp (254 nm) could greatly accelerate the inactivation of the viral bioaerosols formed from artificial human saliva and SM buffer. In the case of 222 nm exposure, Phi6 exhibited significantly more susceptibility in artificial human saliva than in SM buffer whereas MS2 showed comparable vulnerability in both artificial human saliva and SM buffer. However, in the case of 254 nm exposure, both Phi6 and MS2 demonstrated significantly greater susceptibility in artificial human saliva than in SM buffer. This study offers valuable insights and improves our understanding of the influence of different vector media on UVC disinfection of exhaled virus-laden aerosols in indoor environments. These findings can guide the deployment of UVC devices which could greatly contribute to mitigating the transmission of exhaled bioaerosols in public settings.

Ultraviolet-C (UVC) irradiation is being used as an effective approach for the disinfection of pathogenic viruses present in air, surfaces, and water. Recently, far-UVC radiation (222 nm) emitted by KrCl* (krypton-chloride) excimer lamps have been recommended for disinfecting high-risk public spaces to reduce the presence and transmission of infectious viruses owing to limited human health exposure risks as compared to germicidal UVC (254 nm). In this study, the UVC inactivation performances of individual filtered KrCl* excimer lamp (222 nm) and germicidal UVC lamp (254 nm) were determined against four viruses, bacteriophages MS2, Phi6, M13, and T4, having different genome compositions (ssRNA, dsRNA, ssDNA and dsDNA, respectively) and shapes (i.e., spherical (Phi6), linear (M13), and icosahedral (MS2 and T4)). Here, the disinfection efficacies of filtered KrCl* excimer lamp (222 nm) and germicidal UVC lamp (254 nm) were evaluated for highly concentrated virus droplets that mimic the virus-laden droplets released from the infected person and deposited on surfaces as fomites. Filtered KrCl* excimer (222 nm) showed significantly better inactivation against all viruses having different genome compositions and structures compared to germicidal UVC (254 nm). The obtained sensitivity against the filtered KrCl* excimer (222 nm) was found to be in the order, T4 > M13 > Phi6 > MS2 whereas for the germicidal UVC (254 nm) it was T4 > M13 > MS2 > Phi6. These results provide a strong basis to promote the use of filtered KrCl* excimer lamps (222 nm) in disinfecting contagious viruses and to limit the associated disease spread in public places and other high-risk areas.

P-glycoprotein (P-gp, ABCB1) is a well-researched ATP-binding cassette (ABC) drug efflux transporter linked to the development of cancer multidrug resistance (MDR). Despite extensive studies, approved therapies to safely inhibit P-gp in clinical settings are lacking, necessitating innovative strategies beyond conventional inhibitors or antibodies to reverse MDR. Photodynamic therapy is a globally approved cancer treatment that uses targeted, harmless red light to activate non-toxic photosensitizers, confining its cytotoxic photochemical effects to disease sites while sparing healthy tissues. This study demonstrates that photodynamic priming (PDP), a sub-cytotoxic photodynamic therapy process, can inhibit P-gp function by modulating cellular respiration and ATP levels in light accessible regions. Using chemoresistant (VBL-MDA-MB-231) and chemosensitive (MDA-MB-231) triple-negative breast cancer cell lines, we showed that PDP decreases mitochondrial membrane potential by 54.4% ± 30.4 and reduces mitochondrial ATP production rates by 94.9% ± 3.46. Flow cytometry studies showed PDP can effectively improve the retention of P-gp substrates (calcein) by up to 228.4% ± 156.3 in chemoresistant VBL-MDA-MB-231 cells, but not in chemosensitive MDA-MB-231 cells. Further analysis revealed that PDP did not alter the cell surface expression level of P-gp in VBL-MDA-MB-231 cells. These findings indicate that PDP can reduce cellular ATP below the levels that is required for the function of P-gp and improve intracellular substrate retention. We propose that PDP in combination with chemotherapy drugs, might improve the efficacy of chemotherapy and overcome cancer MDR.

The red algae Gracilariopsis lemaneiformis is extensively cultivated at high densities, leading to significant increases in regional seawater pH due to its photosynthetic removal of inorganic carbon. We conducted a study on G. lemaneiformis cultured under various pH conditions (normal pH, pH 9.3, and pH 9.6) and light levels (dark and 100 μmol photons m^-2 s^-1) to investigate how high pH seawater environments affect the metabolic processes of G. lemaneiformis. The high pH did not directly damage the photosynthetic light reactions or the Calvin cycle. Instead, the observed reduction in photosynthetic rates was primarily due to CO₂ limitation. However, under illuminated conditions, a high pH environment leads to a decrease in electron transport efficiency (ETo/RC) and reaction center density (RC/CSo), while simultaneously increasing the levels of hydrogen peroxide (H₂O₂), malondialdehyde (MDA), and the activity of antioxidant enzymes. Under illuminated conditions, the limitation of inhibit the photosynthetic electron transport process, leading to energy imbalance and excessive production of reactive oxygen species, which in turn resulted in lipid peroxidation of the cell membrane. This might be one of the inducing factors responsible for the bleaching in sea-farmed G. lemaneiformis plants.

Photochemical generation of singlet oxygen (¹O₂) often relies on homogenous systems; however, a dissolved photosensitizer (PS) may be unsuitable for some applications because it is difficult to recover, expensive to replenish, and hazardous to the environment. Isolation of the PS onto a solid support can overcome these limitations, but implementation faces other challenges, including agglomeration of the solid PS, physical quenching of ¹O₂ by the support, photooxidation of the PS, and hypoxic environments. Here, we explore a superhydrophobic polydimethylsiloxane (SH-PDMS) support coated with the photosensitizer 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin (TFPP). This approach seeks to address the challenges of a heterogeneous system by using a support that exhibits low ¹O₂ physical quenching rates, a fluorinated PS that is chemically resistant to photooxidation, and a superhydrophobic surface that entraps a layer of air, thus preventing hypoxia. Absorbance and fluorescence spectroscopy reveal the monomeric arrangement of TFPP on SH-PDMS surfaces, a surprising but favorable characteristic for a solid-phase PS on ¹O₂ yields. We also investigated the effect of incident wavelength on ¹O₂ yields for TFPP in aqueous solution and immobilized on SH-PDMS and found overall yields to be dependent on the absorption coefficient, while the yield per absorbed photon exhibited wavelength independence, in accordance with Kasha-Vavilov's rule.

This research investigated the duration of the influence of red light-emitting diodes (LED, 630 nm; output power: 2452.5 mW; laser beam: 163.5 cm²; irradiance: 15 mW/cm²; radiant exposure: 4 J/cm²) on different periods after irradiation (6, 12, 24, 48, and 72 h) on adipose-derived mesenchymal stem cells' (AdMSCs) metabolism and paracrine factors. AdMSCs were irradiated three times every 48 h. Twenty-four hours after the last irradiation, there was a higher MTT absorbance, followed by a decrease after 48 h. The cells' secretome showed increased levels of IL-6 and VEGF after 12 and 24 h, but this was reversed after 48 h. Additionally, LED irradiation resulted in higher levels of nitrite and did not affect oxidative stress markers. LED irradiation had significant effects on AdMSCs after 24 h compared to other groups and its control group.

The skin microbiome undergoes constant exposure to solar radiation (SR), with its effects on health well-documented. However, understanding SR's influence on host-associated skin commensals remains nascent. This review surveys existing knowledge on SR's impact on the skin microbiome and proposes innovative sun protection methods that safeguard both skin integrity and microbiome balance. A team of skin photodamage specialists conducted a comprehensive review of 122 articles sourced from PubMed and Research Gateway. Key terms included skin microbiome, photoprotection, photodamage, skin cancer, ultraviolet radiation, solar radiation, skin commensals, skin protection, and pre/probiotics. Experts offered insights into novel sun protection products designed not only to shield the skin but also to mitigate SR's effects on the skin microbiome. Existing literature on SR's influence on the skin microbiome is limited. SR exposure can alter microbiome composition, potentially leading to dysbiosis, compromised skin barrier function, and immune system activation. Current sun protection methods generally overlook microbiome considerations. Tailored sun protection products that prioritize both skin and microbiome health may offer enhanced defense against SR-induced skin conditions. By safeguarding both skin and microbiota, these specialized products could mitigate dysbiosis risks associated with SR exposure, bolstering skin defense mechanisms and reducing the likelihood of SR-mediated skin issues.