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Charge separation and ROS generation on tubular sodium titanates exposed to simulated solar light
摘要： The research focuses on a few key points concerning the light-driven processes taking place on TiO2 anatase and sodium titanates with tubular morphology, such as the relationship between the morphology and activity for H2 and CO2 production, density of surface hydroxyl groups, ROS (?OH and ?O2-) production and photocatalytic activity, and charge separation at the interface of semiconducting domains and enhancement of activity. One key point discussed is whether the materials with peculiar morphologies (i.e. tubular) are superior to the conventional ones. The experimental evidences show that the main advantage of the tubular morphology of sodium titanate is given by its significantly higher surface area compared to parental anatase. FTIR and XPS progressive analyses evidence that the density of surface hydroxyl groups decreases with the development of the tubular morphology. The radical trapping experiments show that the variation of surface hydroxyl density is, generally, followed by activities for ?OH and ?O2- generation, as well as by the photocatalytic production of H2 and CO2 from water/methanol mixture. Consequently, the ROS, formed by action of photogenerated electrons and holes on adsorbed O2 and hydroxyl groups, respectively, play an important role in determining the photocatalytic activity of titania-based materials. The other major aspect revealed by this research is that the charge separation at the interfaces formed between anatase and sodium titanate crystalline phases has remarkable effect on the activity formation rates of H2 and CO2.
关键词： titanate nanotubes,reactive oxygen species,charge separation,simulated solar light,photocatalysis
更新于2025-09-09 09:28:46
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Effects of TONS504?photodynamic therapy on mouse mammary tumor cells
摘要： In the present study, TONS504 (C51H58N8O5I2; molecular weight, 1,116.9), a novel cationic hydrophilic photosensitizer, was synthesized from protoporphyrin IX dimethyl ester through a five-step process according to a patented method for use in photodynamic therapy (PDT). The subcellular localization of TONS504 and the cytotoxic effects of TONS504-mediated PDT in the mouse mammary tumor EMT6 cell line were investigated. TONS504 was localized primarily in the lysosomes and partially in the mitochondria. The cytotoxic effects of TONS504-mediated PDT in the mouse mammary tumor EMT6 cell line were investigated using a WST8 assay and an Oxidative Stress kit. The cell viability values following treatment with 10 μg/ml TONS504 at light energies of 0, 1, 5 and 10 J/cm2 were 92.5, 101.8, 27.7 and 1.8%, respectively. The percentages of reactive oxygen species (ROS)(+) cells following the same treatment were 8.6, 8.5, 29.2 and 70.1%, respectively, whereas the percentages of apoptotic cells were 7.1, 5.6, 24.8 and 48.7%, respectively. The percentages of ROS(+) and apoptotic cells in the group subjected to TONS504-mediated PDT increased in a manner dependent on the TONS504 concentration and light energy. Further studies are required to evaluate the in vivo pharmacokinetics, tissue distribution and photodynamic effects of TONS504.
关键词： photodynamic therapy,apoptosis,mammary tumor,reactive oxygen species,TONS504
更新于2025-09-09 09:28:46
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Photochemical and Pharmacokinetic Characterization of Orally Administered Chemicals to Evaluate Phototoxic Risk
摘要： This study aimed to verify the applicability of a proposed photosafety screening system based on a reactive oxygen species (ROS) assay and a cassette-dosing pharmacokinetic (PK) study to chemicals with wide structural diversity. The orally taken chemicals, erythromycin, gati?oxacin, 8-methoxypsoralen (MOP), pirfenidone (PFD), tri?uoperazine (TFP), and voriconazole (VRZ), were selected as test compounds. The ROS assay was conducted to evaluate their photoreactivity, and all test compounds excluding erythromycin generated signi?cant ROS under simulated sunlight exposure. According to the ROS data, TFP had potent photoreactivity, and the photoreactivity of 4 other compounds was judged to be moderate. Regarding the oral cassette-dosing PK test in rats, the skin deposition of MOP, PFD, and VRZ was relatively high, and gati?oxacin and TFP exhibited moderate skin deposition properties. Based on the ROS and PK data of test compounds, PFD and TFP were judged to be potent phototoxic compounds, and MOP and VRZ were deduced to have phototoxic risk. The predicted phototoxic risk of test compounds by proposed screening was mostly in agreement with observed in vivo phototoxicity in the rat skin. The proposed screening system could provide reliable photosafety information on orally administered compounds with wide structural diversity.
关键词： cassette-dosing pharmacokinetic study,phototoxicity,structural diversity,reactive oxygen species,photosafety assessment
更新于2025-09-09 09:28:46
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Tuning Photoinduced Electron Transfer Efficiency of Fluorogenic BODIPY- <i>α</i> -Tocopherol Analogues
摘要： Fluorogenic analogues of α-tocopherol developed by our group have been instrumental in monitoring reactive oxygen species (ROS) within lipid membranes. Prepared as two-segment trap-reporter (chromanol-BODIPY) probes, photoinduced electron transfer (PeT) was utilized to provide these probes with an off/on switch mechanism warranting the necessary sensitivity. Herein we rationalize within the context of Marcus theory of electron transfer how substituents on the BODIPY core and linker length joining the trap and reporter segments, tune PeT efficiency. DFT and electrochemical studies were used to estimate the thermodynamic driving force of PeT in our constructs. By tuning the redox potential over a 400 mV range, we observed over an order of magnitude increase in PeT efficiency. Increasing the linker length between the chromanol and BODIPY by 2.8 angstroms in turn decreased PeT efficiency 2.7-fold. Our results illustrate how substituent and linker choice enable “darkening” the off state of fluorogenic probes based on BODIPY fluorophores, by favoring PeT over radiative emission from the singlet excited state manifold. Ultimately, our work brings light to the sensitivity ceiling one may achieve in developing fluorogenic antioxidants analogues of α-tocopherol. The work provides general guidelines applicable to those developing fluorogenic probes based on PeT.
关键词： electrochemical studies,α-tocopherol,lipid membranes,reactive oxygen species,redox potential,photoinduced electron transfer,Marcus theory,DFT,Fluorogenic analogues,BODIPY
更新于2025-09-09 09:28:46
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A Highly Efficient Au-MoS2 Nanocatalyst for Tunable Piezocatalytic and Photocatalytic Water Disinfection
摘要： Clean water is essential in our daily life. However, nearly one billion people are forced to drink water contaminated with bacteria, leading to diarrhea, dehydration, and even death. Previously, various photocatalysts have been applied to replace high-cost and highly toxic methods for sewage treatment. Nevertheless, the requirement of external light sources limits their application. Herein, we develop a new type of nanocatalyst based on single- and few-layered molybdenum disulfide (MoS2) nanosheets (NSs) that can catalyze the generation of reactive oxygen species (ROS) to inactivate bacteria either through a piezoelectric effect (mechanical vibration) or photocatalytic effect (light irradiation). After 60 minutes of mechanical vibration or visible-light irradiation, the MoS2 NSs can reduce Escherichia coli (E. Coli) by 99.999%. In addition, the ROS generation efficiency and bacterial disinfection performance of the catalyst can be enhanced by depositing Au nanoparticles (NPs) on MoS2 NSs. The period of mechanical vibration or visible-light irradiation that achieves the same 99.999% reduction in E. coli is shortened to 45 minutes. Moreover, a hybridization of the piezoelectric and photocatalytic effects results in a performance superior to that obtained with the individual effects. A 99.999% reduction in E. coli is also accomplished within 15 minutes through a combination of mechanical vibration and near-infrared (NIR)-light irradiation. This MoS2 nanocatalyst is a promising candidate for nextgeneration water purification systems because of its ability to be triggered by diverse environmental stimuli.
关键词： photocatalytic effect,nanosheets,Molybdenum disulfide,piezocatalytic effect,reactive oxygen species,bacterial disinfection
更新于2025-09-09 09:28:46
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A novel pro-apoptotic role of zinc octacarboxyphthalocyanine in melanoma me45 cancer cell's photodynamic therapy (PDT)
摘要： Zn-based phthalocyanine acts as drug or photosensitizer in photodynamic therapy (PDT) for the treatment of cancer cells. The activated zinc octacarboxyphthalocyanine (ZnPcOC) reacts with oxygen, to generate reactive oxygen species for the damage of melanoma cancer cells, Me45. This in vitro study aimed at investigating the cytotoxic effects of different concentrations of ZnPcOC activated with a diode laser (λ=685 nm) on Me45, and normal human fibroblast cells, NHDF. To perform this study 104 cells/ml were seeded in 96-well plates and allowed to attach overnight, after which cells were treated with different concentrations of ZnPcOC (10, 20 and 30 μM). After 4 h, cells were irradiated with a constant light dose of 2.5; 4.5 and 7.5 J/cm2. Post-irradiated cells were incubated for 24 h before cell viability was measured using the MTT viability assay. Data indicated that high concentrations of ZnPcOC (30 μM) in its inactive state are not cytotoxic to the melanoma cancer cells and normal fibroblasts. Moreover, the results showed that photoactivated ZnPcOC (30 μM) was able to reduce the cell viability of melanoma and fibroblast to about 50%, respectively. At this photosensitizing concentration the efficacy the treatment light dose of 2.5; 4.5 and 7.5 J/cm2 was evaluated against Me45 cells. ZnPcOC at a concentration of 30 μM activated with a light dose of 2.5; 4.5 and 7.5 J/cm2 was the most efficient for the killing of melanoma cancer cells. Melanoma cancer cells after PDT with a photosensitizing concentration of 30 μM ZnPcOC and a treatment light dose of 2.5; 4.5 and 7.5 J/cm2 showed certain pro-apoptotic characteristics, such as direct inducer (early apoptosis) and long-term inducer, also (late apoptosis). This concludes that low concentrations of ZnPcOC, activated with the appropriate light dose, can be used to induce cell death in melanoma cells via ROS-induces apoptosis pathway, what was confirmed with cytometric ROS measurements. Our in vitro study showed that ZnPcOC mediated photodynamic therapy is an effective treatment option for melanoma Me45 cancer cells. 30 μM of ZnPcOC with the treatment light dose of 2.5 J/cm2 from a LED diode laser source, with a wavelength of 685 nm, was adequate to destroy melanoma cancer cells via ROS-induced apoptosis pathway, with low killing effects on healthy NHDF normal fibroblasts.
关键词： photosensitizers,zinc octacarboxyphthalocyanine (ZnPcOC),UV-Vis spectra,pro-apoptotic activity,photodynamic therapy (PDT),reactive oxygen species (ROS),melanoma Me45 cancer cells
更新于2025-09-09 09:28:46
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Detecting intracellular thiol redox state in leukaemia and heterogeneous immune cell populations: An optimised protocol for digital flow cytometers
摘要： Flow cytometric methods for detecting and quantifying reduced intracellular thiol content using fluorescein-5-maleimide (F5M) in viable eukaryotic cells date back to 1983 (Durand and Olive [1]). There has been little development in these methodologies since that time, a period that has witnessed huge technological advances, particularly with the emergence of digital multi-parameter flow cytometric systems. Concurrent advancement in our understanding of redox regulation within eukaryotic cellular systems has also followed, whereby it is now accepted that cysteine thiols partake in redox reactions, which regulate protein activity and function (Groitl and Jakob (2014), Won et al. (2012)). Moreover, we are at the dawn of a new era in redox biology whereby the importance of 'reductive stress' in eukaryotic cellular systems is gathering momentum (Wadley et al. (2018) [4]). It is therefore critical that methods be continually advanced to better understand these concepts in more detail at the cellular level. Flow cytometry is a powerful technique that may be used for this purpose. Henceforth we have rejuvenated these methods to address modern scientific questions. In this paper, essential detail is provided on: The adaption of a protocol initially described by Durand and Olive [1] for use with modern digital flow cytometer configurations. Here we provide optimal conditions for labelling intracellular thiols with F5M for detection using digital flow cytometers. Our modifications avoid the use of methanol fixation thus preserving cell viability in single cell suspension cultures. Demonstration that flow cytometry can detect the gain and loss of reduced intracellular thiols in cells exposed to physiological doses of hydrogen peroxide mediated by glucose oxidase (Hole et al. (2013) [5]). Validation of F5M protein labelling by coupling method to confocal microscopy and downstream proteomics, thus permitting a powerful experimental platform for potential use with next generation flow cytometry e.g. CyTOF (Lin and Maecker (2018) [6]).
关键词： Fluorescein-5 maleimide,Reactive oxygen species,Oxidative stress,Reductive stress,Flow cytometry
更新于2025-09-09 09:28:46
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Identification and characterization of a core set of <scp>ROS</scp> wave‐associated transcripts involved in the systemic acquired acclimation response of Arabidopsis to excess light
摘要： Systemic acquired acclimation (SAA) plays a key role in optimizing growth and preventing damages associated with fluctuating or abrupt changes in the plant environment. To be effective, SAA has to occur at a rapid rate and depend on rapid signaling pathways that transmit signals from affected tissues to all parts of the plant. Although recent studies identified several different rapid systemic signaling pathways that could mediate SAA, very little is known about the extent of their involvement in mediating transcriptomic responses. Here we reveal that the systemic transcriptomic response of plants to excess light stress is extensive in its context and involves an early (2 minute) and transient stage of transcript expression that includes thousands of genes. This early response is dependent on the respiratory burst oxidase homolog D protein, and the function of the reactive oxygen species (ROS) wave. We further identify a core set of transcripts associated with the ROS wave and suggest that some of these transcripts are involved in linking ROS with calcium signaling. Priming of a systemic leaf to become acclimated to a particular stress during SAA involves thousands of transcripts that display a rapid and transient expression pattern driven by the ROS wave.
关键词： Arabidopsis thaliana,H2O2 signaling,systemic signaling,Reactive oxygen species (ROS) wave,Transcriptomics,light stress,MYB30,systemic acquired acclimation (SAA),WRKY
更新于2025-09-09 09:28:46
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Light-Induced Assembly of Metal Nanoparticles on ZnO Enhances the Generation of Charge Carriers, Reactive Oxygen Species and Antibacterial Activity
摘要： Increasing the photocatalytic activity of semiconductors by forming heterojunctions with metal improves their energy transfer efficiency and environmental remediation capabilities. However, our knowledge regarding the structure-activity relationship of semiconductor/metal hybrid nanostructures is lacking due to poor control over their physicochemical properties. Here, we report a facile way to make ZnO/metal heteronanoparticles by mixing/irradiation process of ZnO and metal nanoparticles. The resultant products provide an expedient model to explore the effects of various metal NPs on light-induced electron/hole separation, reactive oxygen species (ROS) production and antibacterial activities of ZnO NPs. Electron spin resonance spectroscopy was used to compare the effect of mixing Pt, Au, or Ag NPs at different size and concentration with ZnO NPs on light-induced electron-hole separation and ROS production. The enhancing effect of metal NPs depends on particle size, composition, and mass ratio of the metal NPs to the ZnO NPs. Smaller-sized Pt NPs are more efficient in promoting charge carrier generation and ROS production. At 5 nm, Ag NPs promoted charge carrier generation more efficiently than Pt and Au NPs, but Pt NPs promoted ROS generation more efficiently than Au and Ag NPs. These results provide valuable strategy to design the synthesis of semiconductor/metal hybrid nanostructures and easy tailoring of ROS and charge carrier production.
关键词： reactive oxygen species,photocatalytic activity,metal nanoparticles,antibacterial activity,ZnO
更新于2025-09-04 15:30:14
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Towards understanding the enhancement of antibacterial activity in manganese doped ZnO nanoparticles
摘要： In this work we focus on enhancing the antibacterial activity of ZnO nanoparticles by Mn doping, synthesized using a wet-chemical method. The as-obtained precursor powders were deeply investigated by thermal analyses correlated with the evolved gas analysis (TG-DTA-FT-IR) and by in situ high-temperature XRD to elucidate the thermally induced processes and to understand the manganese doped ZnO nanoparticles formation. The hexagonal wurtzite-type structure and the morphological characteristics of the thermally treated samples have been investigated by X-ray diffraction, and HRTEM. An average particle size ranging between 10 to 29 nm and a polyhedral and spherical morphology with a tendency to form aggregates were evidenced by TEM images. Optical absorption measurements reveal that the band gap of ZnO decreased from 3.19 to 2.99 eV, which confirmed the existence of Zn-O-Mn interaction. The incorporation of the Mn ions into the ZnO lattice has been studied by EPR spectroscopy and also, the generation of reactive oxygen species (ROS) has been evidenced by using the EPR coupled with the spin trapping probe technique. Here, we report that in addition to altering the crystallite size, morphology and optical absorption characteristics of ZnO, the introduction of Mn dopant also improves the antibacterial efficiency against pathogenic microorganisms, namely Escherichia coli and Bacillus cereus.
关键词： Mn doping,antibacterial activity,ZnO nanoparticles,reactive oxygen species,wet-chemical synthesis
更新于2025-09-04 15:30:14