Photosensitization Mechanism Research Articles

Potent oxidation of DNA by Ru(ii) tri(polypyridyl) complexes under visible light irradiation via a singlet oxygen-mediated mechanism

The irradiation of Ru(ii) tri(polypridyl) complexes with visible light can induce potent oxidation of DNA mediated by 1O2via a type II photosensitization mechanism.

Theoretical Studies of Photodynamic Therapy Properties of Azopyridine <i>δ</i>-OsCl<sub>2</sub>(Azpy)<sub>2</sub> Complex as a Photosensitizer by a TDDFT Method

Photochemical reactions have an important place in photodynamic treatments. A good use of this therapeutic method requires a good mastery of the mechanisms of the reactions involved. Therefore, we have explored in this work the photosensitization mechanism of an organometallic complex of azopyridine δ-OsCl2(Azpy)2 through a calculation with the method of Time Dependent Density Functional Theory TDDFT. First, we evaluated the effect of polar and non-polar solvents on the triplet and singlet excited states of this complex. Then secondly, we highlighted the photosensitization mechanism to understand how the complex acts over the diseased cells. These investigations have shown that the δ-OsCl2(Azpy)2 complex is likely to develop photodynamic activity according to two mechanisms: on one hand, it can generate damage to DNA bases or target tissues indirectly through the production of singlet oxygen in water and in DMSO. On the second hand, through the production of the anionic superoxide radical in water can act directly or indirectly on these substrates. In addition, polar solvents are assumed to better carry out the photochemical reactions of this azopyridine complex of osmium.

Double-Stranded DNA Matrix for Photosensitization Switching

Photosensitization, originated from the activation of triplet states, is the basis of many photodynamic applications, but often competes with a series of nonradiative processes. Herein, we communic...

Latest Evidence Regarding the Effects of Photosensitive Drugs on the Skin: Pathogenetic Mechanisms and Clinical Manifestations.

Photosensitivity induced by drugs is a widely experienced problem, concerning both molecule design and clinical practice. Indeed, photo-induced cutaneous eruptions represent one of the most common drug adverse events and are frequently an important issue to consider in the therapeutic management of patients. Phototoxicity and photoallergy are the two different pathogenic mechanisms involved in photosensitization. Related cutaneous manifestations are heterogeneous, depending on the culprit drug and subject susceptibility. Here we report an updated review of the literature with respect to pathogenic mechanisms of photosensitivity, clinical manifestations, patient management, and prediction and evaluation of drug-induced photosensitivity. We present and discuss principal groups of photosensitizing drugs (antimicrobials, nonsteroidal anti-inflammatory drugs, anti-hypertensives, anti-arrhythmics, cholesterol, and glycemia-lowering agents, psychotropic drugs, chemotherapeutics, etc.) and their main damage mechanisms according to recent evidence. The link between the drug and the cutaneous manifestation is not always clear; more investigations would be helpful to better predict drug photosensitizing potential, prevent and manage cutaneous adverse events and find the most appropriate alternative therapeutic strategy.

Unexpected photosensitivity of the well-characterized heme enzyme chlorite dismutase

Chlorite dismutase is a heme enzyme that catalyzes the conversion of the toxic compound ClO2− (chlorite) to innocuous Cl− and O2. The reaction is a very rare case of enzymatic O–O bond formation, which has sparked the interest to elucidate the reaction mechanism using pre-steady-state kinetics. During stopped-flow experiments, spectroscopic and structural changes of the enzyme were observed in the absence of a substrate in the time range from milliseconds to minutes. These effects are a consequence of illumination with UV–visible light during the stopped-flow experiment. The changes in the UV–visible spectrum in the initial 200 s of the reaction indicate a possible involvement of a ferric superoxide/ferrous oxo or ferric hydroxide intermediate during the photochemical inactivation. Observed EPR spectral changes after 30 min reaction time indicate the loss of the heme and release of iron during the process. During prolonged illumination, the oligomeric state of the enzyme changes from homo-pentameric to monomeric with subsequent protein precipitation. Understanding the effects of UV–visible light illumination induced changes of chlorite dismutase will help us to understand the nature and mechanism of photosensitivity of heme enzymes in general. Furthermore, previously reported stopped-flow data of chlorite dismutase and potentially other heme enzymes will need to be re-evaluated in the context of the photosensitivity.Graphic abstractIllumination of recombinantly expressed Azospira oryzae Chlorite dismutase (AoCld) with a high-intensity light source, common in stopped-flow equipment, results in disruption of the bond between FeIII and the axial histidine. This leads to the enzyme losing its heme cofactor and changing its oligomeric state as shown by spectroscopic changes and loss of activity.

Photosensitization effect of curcumin for controlling plant pathogen Botrytis cinerea in postharvest apple

Photosensitization is a novel, non-thermal and effective technology to inactivate microorganisms. The inhibitory effect and its mechanism of curcumin-based photosensitization on plant pathogen B. cinerea are investigated in this study. Significant changes have been observed upon photosensitization, which include a reduction of 96.2% in spore germination when spores were mixed with 0.5 mM curcumin and exposed for 5 min, a complete control on lesion enlargement of gray mold in apple fruit after 10 min. Morphological changes, losses of membrane integrity and variations of cell wall polysaccharide deposition in treated B. cinerea cells were observed. Furthermore, after photosensitization, a series of apoptotic characteristics, such as the accumulation of ROS and Ca2+, the decrease of mitochondrial membrane potential (MMP) and nuclear fragmentation were observed. Collectively, these data provided evidence that curcumin-based photosensitization is an effective method to control the plant pathogen B. cinerea.

Enhancing photocatalytic performance of Zn2SnO4 by doping Yb: Oxygen vacancies formation and dye self-sensitization degradation

Abstract Zn2SnO4 (ZTO) is a photocatalyst with broad application prospects. To further improve the photocatalytic performance, cubic ZTO was modified by doping with the rare earth element ytterbium (Yb). A series of detections were used to characterize the photoelectric properties of the photocatalyst, the results demonstrate that Yb preferentially replaces Zn in the ZTO lattice, then Sn is substituted when excess Yb is present. Oxygen vacancies are formed in the lattice of Yb doped ZTO, the oxygen vacancies not only broaden the visible light response range of ZTO, but also reduce the recombination rate of photogenerated electron-hole pairs. Photocatalytic experiments show that Yb-doped ZTO has good photocatalytic performance, and self-sensitized photocatalytic mechanism has been proposed. This work provides an example for the formation and application of oxygen vacancy, and also discusses the mechanism of photosensitization, which provides a new concept for the treatment of dye wastewater.

Probe‐Free Direct Identification of Type I and Type II Photosensitized Oxidation Using Field‐Induced Droplet Ionization Mass Spectrometry

AbstractWhile Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home‐built field‐induced droplet ionization mass spectrometry (FIDI‐MS) method that selectively samples molecules at the air–water interface, here we show the facile determination of both Type I and II mechanisms of a poster‐child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI‐MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms.

Probe-Free Direct Identification of Type I and Type II Photosensitized Oxidation Using Field-Induced Droplet Ionization Mass Spectrometry.

While Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home-built field-induced droplet ionization mass spectrometry (FIDI-MS) method that selectively samples molecules at the air-water interface, here we show the facile determination of both Type I and II mechanisms of a poster-child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI-MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms.

Photophysical properties and theoretical photosensitization mechanism of non-peripherally dodecyloxy substituted metallophthalocyanines for photodynamic therapy

Non-peripherally tetradodecyloxy substituted copper (CuPc 3) and nickel (NiPc 4) phthalocyanines and the compounds were synthesized. The absorption spectra of synthesized Pcs were showed monomeric behavior evidenced by a narrow between 680 and 750 nm (Q band) for CuPc(3) and NiPc(4) in different solvents. The fluorescence behavior of the Pcs was studied in chloroform. The CuPc (3) showed outstanding stability in THF as solvent during photodegradation studies. The possible photodynamic therapy reaction mechanisms were studied through the calculation of ionization potentials and electron affinity in both vacuum and solvents using SCRF model.

Algae-induced photodegradation of antibiotics: A review.

Antibiotics are a typical group of pharmaceutical and personal care products (PPCPs) with emerging pollutant effects. The presence of residual antibiotics in the environment is a prominent issue owing to their potential hazards, toxic effects, and persistence. Several treatments have been carried out in aquatic environments in order to eliminate antibiotic residues. Among these, photodegradation is regarded as an environmentally-friendly and efficient option. Indirect photodegradation is the main pathway for the degradation of residual antibiotics in natural water, as opposed to direct photodegradation. Algae, working as photosensitizers, play an important role in the indirect photolysis of residual antibiotics in natural water bodies. They promote this reaction by secreting extracellular organic matters (EOMs) and inducing the generation of active species. In order to provide a thorough understanding of the effects of algae on residual antibiotic degradation in the environment, this paper comprehensively reviews the latest research regarding algae-induced antibiotic photodegradation. The summary of the different pathways and photosensitive mechanisms involved in this process show that EOMs are indispensable to antibiotic photodegradation. The influencing factors of algae-induced photodegradation are also discussed here: these include algae species, antibiotic types, and environmental variables such as light source, ferric ion presence, temperature, and ultrasound treatment. Based on the review of existing literature, this paper also considers several pathways for the future study of algae-induced antibiotic photodegradation.

An insight into curcumin-based photosensitization as a promising and green food preservation technology.

Consumer awareness on the side effects of chemical preservatives has increased the demand for natural preservation technologies. An efficient and sustainable alternative to current conventional preservation techniques should guarantee food safety and retain its quality with minimal side effects. Photosensitization, utilizing light and a natural photosensitizer, has been postulated as a viable and green alternative to the current conventional preservation techniques. The potential of curcumin as a natural photosensitizer is reviewed in this paper as a practical guide to develop a safe and effective decontamination tool for industrial use. The fundamentals of the photosensitization mechanism are discussed, with the main emphasis on the natural photosensitizer, curcumin, and its application to inactivate microorganisms as well as to enhance the shelf life of foods. Photosensitization has shown promising results in inactivating a wide spectrum of microorganisms with no reported microbial resistance due to its particular lethal mode of targeting nucleic acids. Curcumin as a natural photosensitizer has recently been investigated and demonstrated efficacy in decontamination and delaying spoilage. Moreover, studies have shown the beneficial impact of an appropriate encapsulation technique to enhance the cellular uptake of photosensitizers, and therefore, the phototoxicity. Further studies relating to improved delivery of natural photosensitizers with inherent poor solubility should be conducted. Also, detailed studies on various food products are warranted to better understand the impact of encapsulation on curcumin photophysical properties, photo-driven release mechanism, and nutritional and organoleptic properties of treated foods.

Contribution of Topical Antioxidants to Maintain Healthy Skin—A Review

The skin is constantly exposed to various environmental stresses, in particular to the damage caused by pollution and ultraviolet radiation (UV), and as a consequence, the horny extract can be negatively impacted by the harmful influence of some of its surface components. The mechanisms involved in the degradation processes promoted by UV radiation are driven by the direct absorption of radiation via cellular chromophores, the formation of excited states and the consequent chemical reactions, or even by the photosensitization mechanisms, in which UV light is absorbed by the sensitizers that are excited and their reactions promote the formation of reactive oxygen species (ROS). The mechanisms of polluting agents are not yet fully understood, however, they indicate that one of the main mechanisms involved is oxidative stress by lipid peroxidation, with the ability to promote damage to the composition of sebum, the quality of the stratum corneum and also, promote aging skin. Recent studies demonstrate the potential of antioxidant agents, with an emphasis on products of natural origin, which try to promote the maintenance of the physiological balance of the skin.

Unimolecular Photodynamic O2-Economizer To Overcome Hypoxia Resistance in Phototherapeutics.

Tumor hypoxia has proven to be the major bottleneck of photodynamic therapy (PDT) to clinical transformation. Different from traditional O2 delivery approaches, here we describe an innovative binary photodynamic O2-economizer (PDOE) tactic to reverse hypoxia-driven resistance by designing a superoxide radical (O2•-) generator targeting mitochondria respiration, termed SORgenTAM. This PDOE system is able to block intracellular O2 consumption and down-regulate HIF-1α expression, which successfully rescues cancer cells from becoming hypoxic and relieves the intrinsic hypoxia burden of tumors in vivo, thereby sparing sufficient endogenous O2 for the PDT process. Photosensitization mechanism studies demonstrate that SORgenTAM has an ideal intersystem crossing rate and triplet excited state lifetime for generating O2•- through type-I photochemistry, and the generated O2•- can further trigger a biocascade to reduce the PDT's demand for O2 in an O2-recycble manner. Furthermore, SORgenTAM also serves to activate the AMPK metabolism signaling pathway to inhibit cell repair and promote cell death. Consequently, using this two-step O2-economical strategy, under relatively low light dose irradiation, excellent therapeutic responses toward hypoxic tumors are achieved. This study offers a conceptual while practical paradigm for overcoming the pitfalls of phototherapeutics.

The Key Role of Sulfate in the Photochemical Renoxification on Real PM2.5.

The active nitrogen species (HONO, NO, and NO2) have important impacts on the atmospheric oxidative capacity and the transformation of many atmospheric species. In this study, a fast photochemical renoxification rate of adsorbed HNO3/NO3- to active nitrogen species (HONO, NO, and NO2) was detected on real urban PM2.5, and sulfate was found to play a key role in this process. Different from the reported direct photolysis pathway, the photochemical reaction of HNO3/NO3- on PM2.5 is dominated by a photosensitizing mechanism. Acidic protons are proved to be essential for this pathway. The role of sulfate, because of the nonvolatility of its conjugated acid, is to conserve the necessary acidic protons when interacting with HNO3 and thus maintain its photoreactivity. This work implies that sulfate will have important implications in atmospheric nitrogen cycling by accelerating the release of nitrogen oxides from photochemical renoxification of HNO3/NO3- adsorbed on ambient particulates and thus can cause major environmental problems.

Oxidative foliar photo-necrosis produced by the bacteria Pseudomonas cedrina

Background: Although bioactive metabolites capable of causing oxidative photo-necrosis in plant tissues have been identified in fungi, little is known about this type of mechanism in bacteria. These metabolites act as photosensitizers that generate reactive oxygen species (ROS) capable of causing damage to cells. In addition, these metabolites can pass into an energetically excited state when they receive some luminous stimulus, a condition in which they interact with other molecules present in the environment, such as molecular oxygen (O 2 ), also known as triplet oxygen ( 3 O 2 ), generating ROS. Results: The suspension of the bacterial culture of Pseudomonas cedrina was shown to produce foliar necrosis in papaya leaves ( Carica papaya L.) only in the presence of sunlight, which is evidence of photosensitizing mechanisms that generate singlet oxygen ( 1 O 2 ). From the chemical study of extracts obtained from this bacteria, 3-(4-(2-carboxipropyl) phenyl) but-2-enoic acid (1) was isolated. This compound, in the presence of light and triplet oxygen ( 3 O 2 ), was able to oxidize ergosterol to its peroxide, since it acted as a photosensitizer producing 1 O 2 , with which it was corroborated that a photosensitization reaction occurs, mechanism by which this bacterium could prove to cause oxidative foliar photo-necrosis. Conclusions: P. cedrina was able to induce oxidative foliar photo-necrosis because of its potential ability to produce photosensitizing metabolites that generate singlet oxygen in the plants it colonizes. Based on the above, it can be proposed that some bacteria can cause oxidative foliar photo-necrosis as an important mechanism in the pathogenesis of host species. Normal 0 false false false EN-US X-NONE X-NONE /* Style Definitions */ table.MsoNormalTable {mso-style-name:Tabla normal; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-parent:; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin-top:0cm; mso-para-margin-right:0cm; mso-para-margin-bottom:8.0pt; mso-para-margin-left:0cm; line-height:107%; mso-pagination:widow-orphan; font-size:11.0pt; font-family:Calibri,sans-serif; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:Times New Roman; mso-bidi-theme-font:minor-bidi;}

Insights into the photosensitization activity of zirconium-titanium pyrophosphate under visible light irradiation

Mesoporous zirconium-titanium pyrophosphate (ZTPP) was prepared by a facile sol-gel method. The ZTPP materials showed highly specific surface areas. XPS and EPR results confirmed the presence of Ti3+ and oxygen vacancies. The ZTPP exhibited excellent photosensitization activity for the degradation of Rhodamine B (RhB) under visible light irradiation. The possible photosensitization mechanism was proposed by using different active species quenchers, measurement of EPR and determining the band structure. This work suggests the oxygen vacancy defect state can be introduced by the bimetallic synergistic effect to enhance the photosensitization efficiency of the catalyst with a wide bandgap.

Riboflavin Plays a Pivotal Role in the UVA-Induced Cytotoxicity of Fibroblasts as a Key Molecule in the Production of H2O2 by UVA Radiation in Collaboration with Amino Acids and Vitamins.

To investigate environmental factors that contribute to ultraviolet A (UVA)-induced oxidative stress, which accelerates the senescence and toxicity of skin cells, we irradiated human fibroblasts cultured in commonly used essential media with UVA and evaluated their viability and production of reactive oxygen species. The viability of fibroblasts exposed to a single dose of 3.6 J/cm2 UVA was not reduced when cultured in Hanks balanced salt solution, but it was significantly decreased when cultured in Dulbecco’s modified Eagle’s medium (DMEM), which contains various amino acids and vitamins. Furthermore, cell viability was not reduced when fibroblasts were cultured in DMEM and treated with a hydrogen peroxide (H2O2) scavenger such as glutathione or catalase added after UVA irradiation. In addition, we confirmed that the production of H2O2 was dramatically increased by UVA photosensitization when riboflavin (R) coexisted with amino acids such as tryptophan (T), and found that R with folic acid (F) produced high levels of H2O2 after UVA irradiation. Furthermore, we noticed that R and F or R and T have different photosensitization mechanisms since NaN3, which is a singlet oxygen quencher, suppressed only R and T photosensitization. Lastly, we examined the effects of antioxidants (L-ascorbic acid, trolox, L-cysteine, and L-histidine), which are singlet oxygen or superoxide or H2O2 scavengers, on R and F or on R and T photosensitization, and found that 1 mM ascorbic acid, Trolox, and L-histidine were strongly photosensitized with R, and produced significant levels of H2O2 during UVA exposure. However, 1 mM L-cysteine dramatically suppressed H2O2 production by UVA photosensitization. These data suggest that a low concentration of R-derived photosensitization is elicited by different mechanisms depending on the coexisting vitamins and amino acids, and regulates cellular oxidative stress by producing H2O2 during UVA exposure.

Thionated organic compounds as emerging heavy-atom-free photodynamic therapy agents.

This minireview focuses on recent progress in developing heavy-atom-free photosensitizers based on the thionation of nucleic acid derivatives and other biocompatible organic compounds for prospective applications in photodynamic therapy. Particular attention is given to the use of thionated nucleobase derivatives as “one-two punch” photodynamic agents. These versatile photosensitizers can act as “Trojan horses” upon metabolization into DNA and exposure to activating light. Their incorporation into cellular DNA increases their selectivity and photodynamic efficacy against highly proliferating skin cancer tumor cells, while simultaneously enabling the use of low irradiation doses both in the presence and in the absence of molecular oxygen. Also reviewed are their primary photochemical reactions, modes of action, and photosensitization mechanisms. New developments of emerging thionated organic photosensitizers absorbing visible and near-infrared radiation are highlighted. Future research directions, as well as, other prospective applications of heavy-atom-free, thionated photosensitizers are discussed.

Importance of Internal Tensile Stress in Forming Low-Loss Fiber Draw-Tower Gratings

Internal tensile stress inside fiber core can impact significantly on formation of Draw-tower gratings (DTGs). We carry out online dynamic preparation experiments of DTG to analyze the effect of internal stress on grating reflectivity, as well as offline multi-pulse accumulation experiments to further investigate the underlying mechanisms for grating formation. The optimum laser energy density used to grating writing and the variation of reflectivity with exposure extent were obtained, which is instrumental for their optimization and rapid prototyping. A stress modulation model was proposed as the dominant mechanism to describe the formation of the grating structure by a single laser pulse in the low-loss fiber, which is of great significance for the research of the grating photosensitivity mechanism.