Reaction Of Singlet Oxygen Research Articles

Antiviral activity of porphyrins and porphyrin-like compounds against tick-borne encephalitis virus: Blockage of the viral entry/fusion machinery by photosensitization-mediated destruction of the viral envelope

Tick-borne encephalitis virus (TBEV), the causative agent of tick-borne encephalitis (TBE), is a medically important flavivirus endemic to the European–Asian continent. Although more than 12,000 clinical cases are reported annually worldwide, there is no anti-TBEV therapy available to treat patients with TBE. Porphyrins are macrocyclic molecules consisting of a planar tetrapyrrolic ring that can coordinate a metal cation. In this study, we investigated the cytotoxicity and anti-TBEV activity of a large series of alkyl- or (het)aryl-substituted porphyrins, metalloporphyrins, and chlorins and characterized their molecular interactions with the viral envelope in detail. Our structure–activity relationship study showed that the tetrapyrrole ring is an essential structural element for anti-TBEV activity, but that the presence of different structurally distinct side chains with different lengths, charges, and rigidity or metal cation coordination can significantly alter the antiviral potency of porphyrin scaffolds. Porphyrins were demonstrated to interact with the TBEV lipid membrane and envelope protein E, disrupt the TBEV envelope and inhibit the TBEV entry/fusion machinery. The crucial mechanism of the anti-TBEV activity of porphyrins is based on photosensitization and the formation of highly reactive singlet oxygen. In addition to blocking viral entry and fusion, porphyrins were also observed to interact with RNA oligonucleotides derived from TBEV genomic RNA, indicating that these compounds could target multiple viral/cellular structures. Furthermore, immunization of mice with porphyrin-inactivated TBEV resulted in the formation of TBEV-neutralizing antibodies and protected the mice from TBEV infection. Porphyrins can thus be used to inactivate TBEV while retaining the immunogenic properties of the virus and could be useful for producing new inactivated TBEV vaccines.

Direct observation of triplet energy transfer between chlorophylls and carotenoids in the core antenna of photosystem I from Thermosynechococcus elongatus

Quenching of chlorophyll triplet states by carotenoids is an essential photoprotective process, which prevents formation of reactive singlet oxygen in photosynthetic light-harvesting complexes. The process is usually very efficient in oxygenic organisms under physiological conditions, thus preventing any observable accumulation of chlorophyll triplets. However, it subsequently prevents also the determination of the triplet transfer rate. Here we report results of nanosecond transient absorption spectroscopy on photosystem I core complexes, where a major part of chlorophyll a triplet states (~60 %) accumulates on a nanosecond time scale at ambient temperature. As a consequence, the triplet energy transfer could be resolved and the transfer time was determined to be about 24 ns. A smaller fraction of chlorophyll a triplet states (~40 %) is quenched with a faster rate, which could not be determined. Our analysis indicates that these chlorophylls are in direct contact with carotenoids. The overall chlorophyll triplet yield in the core antenna was estimated to be ~0.3 %, which is a value two orders of magnitude smaller than in most other photosynthetic light-harvesting complexes. This explains why slower quenching of chlorophyll triplet states is sufficient for photoprotection of photosystem I. Nevertheless, the core antenna of photosystem I represents one of only few photosynthetic complexes of oxygenic organisms in which the quenching rate of the majority of chlorophyll triplets can be directly monitored under physiological temperature.

In-situ utilization of EPS improves the directional oxidation ability of Fe(III)/H2O2 and enhances sludge dewaterability

Inefficient sludge dewatering can result in high costs for sludge treatment and disposal, as well as increased pollution of the environment. In this study, we constructed a double oxidation–reduction (Redox) cycle system of Fe(II)/Fe(III) and Fe(II)-extracellular polymeric substance (EPS)/Fe(III)-EPS by utilizing EPS in situ and collaborating with Fe (III) and H2O2 so as to regulate the performance of Fenton oxidation for efficiently enhancing the dewaterability. Results displayed the specific resistance to filtration (SRF) reduced from 34.1 ± 2.4 × 1012 m/kg to 16.2 ± 1.5 × 1012 m/kg with only 0.15 mmol Fe(III)/g VSS and 1.46 mmol H2O2/g VSS. Notably, the formation of relative stable Fe(III)-EPS complex was found under the interval addition of Fe(III) and H2O2. Four types of reactive species (hydroxyl radical (•OH), singlet oxygen (1O2), superoxide radical (O2•-) and Fe(IV)) which could effective destroy EPS structure during conditioning process, were generated after the addition of H2O2. It effectively promoted the transition from intracellular oxidation to extracellular oxidation under Fenton oxidation conditions, which reduced negative effects of cell lysis under excessive oxidation during sludge conditioning. The structure of EPS damaged significantly during the oxidation process, leading to the effective conversion of bound water to free water. Meanwhile, the existence of dissociative Fe(III) promoted the aggregation of sludge flocs, generating large channels or pores for sludge water to discharge, and then improving the dewaterability. Overall, [Fe(III)-EPS]/H2O2 treatment as an efficient sludge conditioning method can provide guidance for sludge dewaterability enhancement in urban sludge treatment and disposal.

β-Pyrrole Functionalized Push or Pull Porphyrins: Excited Charge Transfer Promoted Singlet Oxygen Generation.

Singlet oxygen (1O2) producing photosensitizers are highly sought for developing new photodynamic therapy agents and facilitating 1O2-involved chemical reactions. Often singlet oxygen is produced by the reaction of triplet-excited photosensitizers with dioxygen via an energy transfer mechanism. In the present study, we demonstrate a charge transfer mechanism to produce singlet oxygen involving push or pull functionalized porphyrins. For this, 20 β-pyrrole functionalized porphyrins carrying either an electron-rich push or electron-deficient pull group have been newly synthesized. Photoexcitation of these push-pull porphyrins has been shown to produce high-energy MPδ+-Aδ- or MPδ--Dδ+ charge transfer states. Subsequent charge recombination results in populating the triplet excited states of extended lifetimes in the case of the push group containing porphyrins that eventually react with dioxygen to produce the reactive singlet oxygen of relatively higher quantum yields. The effect of the push and pull groups on the porphyrin periphery in governing initial charge transfer, the population of triplet excited states and their lifetimes, and resulting in improved singlet oxygen quantum yields are systematically probed. The improved performance of 1O2 generation by porphyrins carrying push groups is borne out from this study.

Assessing the Efficacy of A Mo2C/Peroxydisulfate System for Tertiary Wastewater Treatment: A Study of Losartan Degradation, E. coli Inactivation, and Synergistic Effects

This work examines the use of pristine Mo2C as an intriguing sodium persulfate (SPS) activator for the degradation of the drug losartan (LOS). Using 500 mg/L Mo2C and 250 mg/L SPS, 500 μg/L LOS was degraded in less than 45 min. LOS decomposition was enhanced in acidic pH, while the apparent kinetic constant decreased with higher LOS concentrations. According to experiments conducted in the presence of scavengers of reactive species, sulfate radicals, hydroxyl radicals, and singlet oxygen participated in LOS oxidation, with the latter being the predominant reactive species. The presence of competitors such as bicarbonate and organic matter reduced the observed efficiency in actual matrices, while, interestingly, the addition of chloride accelerated the degradation rate. The catalyst showed remarkable stability, with complete LOS removal being retained after five sequential experiments. The system was examined for simultaneous LOS decomposition and elimination of Escherichia coli. The presence of E. coli retarded LOS destruction, resulting in only 30% removal after 3 h, while the system was capable of reducing E. coli concentration by 1.23 log. However, in the presence of simulated solar irradiation, E. coli was reduced by almost 4 log and LOS was completely degraded in 45 min, revealing a significant synergistic effect of the solar/Mo2C/SPS system.

Photocatalytic selective C-C bond cleavage of biomass-based monosaccharides and xylan to co-produce lactic acid and CO over an Fe-doped GaN catalyst

The utilization of photocatalysis for the simultaneous production of valuable fine chemicals and fuels from biomass-derived feedstocks holds significant promise; however, its practical implementation remains constrained. In this study, we present the development of an Fe-doped gallium nitride (GaN) catalyst treated by calcination (Fe@GaN-X) for the selectively conversion of biomass-based monosaccharides and xylan into lactic acid and carbon monoxide (CO). Fe@GaN-400 exhibited broader visible light absorption, lower resistance, and reduced photoluminescence intensity in comparison to pristine GaN, thereby affording exceptional photocatalytic activity (lactic acid yield: 71.38%; CO evolution rate: 385.74 μmol g−1 h−1). When monosaccharides and xylan were used as substrates, the Fe@GaN-400 system demonstrated outstanding photocatalytic activity, particularly in the case of xylan system (CO evolution rate = 923.21 μmol g−1 h−1). Additionally, the experimental results revealed the generation of distinctive reactive species, encompassing holes (h+), superoxide anion (·O2-), hydroxyl radical (·OH) and singlet oxygen (1O2) within this catalytic system. Remarkably, the ·O2- and h+ exhibit heightened selectivity towards CO and lactic acid, respectively. This work establishes a novel pathway for the co-production of fine chemicals and fuels through the photocatalytic conversion of biomass.

Photochemical and Photophysical Properties of Carotenoids and Reactive Oxygen Species: Contradictions Relating to Skin and Vision

Molecular mechanisms based on photo-physical processes involving dietary carotenoids, their radicals, and the role of oxygen are discussed and used to suggest explanations of the poorly understood and often contradictory results related to mainly skin and vision. Differing and conflicting efficiencies of singlet oxygen reactions with carotenoids of biological importance are discussed in environments from ‘simple’ organic solvents to single He La cells. A range of free radical reactions with carotenoids, and the corresponding radicals of the carotenoids themselves, are compared and used to explain the switch from beneficial to deleterious processes involving dietary carotenoids and to unravel their differing functions; of particular interest is a possible role for vitamin C.

Enhanced catalytic ozonation performance by CuOx nanoclusters/TiO2 nanotube and an insight into the catalytic mechanism

Highly reactive nanoclusters of metal oxides are extremely difficult to be synthesized due to their thermodynamic instability. For the first time, CuOx nanoclusters supported on anatase TiO2 nanotubes (NT) with many defects as anchoring sites were successfully prepared. Although the copper loading reached as high as 2.5 %, the size of CuOx nanoclusters in the sample of 2.5 %CuOx/NT were mainly around 1.0 nm. The aggregation of copper species during the calcination process was undoubtedly hampered by the anchoring effects of the abundant defects in NT support. Due to the highly exposed undercoordinated atoms of CuOx nanoclusters, the mixed valences of copper, and the strong interface interaction between CuOx nanoclusters and NT support, 2.5 %CuOx/NT-catalyzed ozonation showed the highest pseudo-first-order reaction rate constant of 8.5 × 10−2 min−1, 2.2 and 4.0 times that of NT-catalyzed ozonation and ozonation alone, respectively. Finally, the catalytic mechanism was revealed by both experiments and density functional theory calculations (DFT). The results demonstrated that the undercoordinated Cu in CuOx/NT could highly promote the adsorption of ozone with a high adsorption energy of −125.16 eV and the adsorbed ozone was activated immediately, tending to dissociate into a O2 molecule and a surface O atom. Thus, abundant reactive oxygen species, e.g., hydroxyl radical (·OH), superoxide radical (·O2–) and singlet oxygen (1O2), could be generated via chain reactions. Especially, ·OH mainly contributed to the removal of ibuprofen pollutants. This work sheds a light on the design and preparation of highly reactive nanoclusters of metal oxide catalysts for catalytic ozonation of refractory organic pollutants.

New Insights on Singlet Oxygen Release from Li-Air Battery Cathode: Periodic DFT Versus CASPT2 Embedded Cluster Calculations.

Li-air batteries are a promising energy storage technology for large-scale applications, but the release of highly reactive singlet oxygen (1O2) during battery operation represents a main concern that sensibly limits their effective deployment. An in-depth understanding of the reaction mechanisms underlying the 1O2 formation is crucial to prevent its detrimental reactions with the electrolyte species. However, describing the elusive chemistry of highly correlated species such as singlet oxygen represents a challenging task for state-of-the-art theoretical tools based on density functional theory. Thus, in this study, we apply an embedded cluster approach, based on CASPT2 and effective point charges, to address the evolution of 1O2 at the Li2O2 surface during oxidation, i.e., the battery charging process. Based on recent hypothesis, we depict a feasible O22-/O2-/O2 mechanisms occurring from the (112̅0)-Li2O2 surface termination. Our highly accurate calculations allow for the identification of a stable superoxide as local minimum along the potential energy surface (PES) for 1O2 release, which is not detected by periodic DFT. We find that 1O2 release proceeds via a superoxide intermediate in a two-step one-electron process or another still accessible pathway featuring a one-step two-electron mechanism. In both cases, it represents a feasible product of Li2O2 oxidation upon battery charging. Thus, tuning the relative stability of the intermediate superoxide species can enable key strategies aiming at controlling the detrimental development of 1O2 for new and highly performing Li-air batteries.

Collaborative CuMn diatomic nanozyme to boost nanocatalytic/mild photothermal/chemo-therapy through overcoming therapeutic resistance

The combined mild-temperature photothermal/chemo-therapy has emerged as a promising approach to complement traditional tumor treatment and enhance therapeutic effects while reduce side effects. However, therapeutic resistance caused by up-regulation of heat shock proteins (HSPs) and P-glycoprotein (P-gp) drastically compromises the synergetic therapeutic effect. Herein, we develop a multifunctional CuMn dual-atom nanozyme loaded with the chemotherapeutic agent doxorubicin (DOX@CuMn-DAzymes) for P-gp and HSPs simultaneous silencing induced synergistic trimodal therapy. The resulting CuMn double-atom pairs with significant synergistic effects can efficiently catalyze cascade reactions of catalase (CAT)-like and oxidase (OXD)-like with endogenous H2O2 as the initial reactant to produce highly reactive singlet oxygen (1O2) under the trigger of acidic tumor microenvironment, destroying the P-gp and HSPs in tumor cells. Benefitting from their black polyporous nanocarbon support, DOX@CuMn-DAzymes not only show superior 1064 nm laser triggered photothermal performance, but also possess high DOX encapsulation efficiency and dual pH- and NIR-responsive DOX release properties. Moreover, in vitro and in vivo study results demonstrate that DOX@CuMn-DAzymes effectively overcome therapeutic resistance by boosting intracellular 1O2 level to simultaneously silence P-gp and HSPs, thereby achieving an impressive synergetic therapeutic efficacy.

Nitrogen doped magnetic porous carbon derived from starch of oatmeal for efficient activation peroxymonosulfate to degradation sulfadiazine

Nitrogen doped magnetic porous carbon catalyst based on starch of oatmeal was obtained by mixing and pyrolysis process, and its catalytic activity of peroxymonosulfate activation for sulfadiazine degradation was evaluated. When ratio of oatmeal/urea/iron was 1: 2: 0.1, CN@Fe-10 had the best catalytic activity to degrade sulfadiazine. Around 97.8 % removal of 20 mg L−1 sulfadiazine was achieved under incorporating of 0.05 g L−1 catalyst and 0.20 g L−1 peroxymonosulfate. Good adaptability, stability and universality of CN@Fe-10 were verified under different conditions. Electron paramagnetic resonance and radical quenching test suggested that surface-bound reactive oxides species and singlet oxygen were the main reactive oxides species in this reaction. Electrochemical analysis indicated that CN@Fe-10 had a good electrical conductivity and electron transferred did occur among CN@Fe-10 surface, peroxymonosulfate and sulfadiazine. X-ray photoelectron spectroscopy suggested that Fe0, Fe3C, pyridine nitrogen and graphite nitrogen were the potential active sites for peroxymonosulfate activation. Therefore, the work provided a practical approach for recycling biomass.

Multiple paths of plant host toxicity are associated with the fungal toxin cercosporin.

The Cercospora species of fungi are responsible for leaf spot disease affecting many key economic crops. Most of these fungi secrete a toxic photodynamic molecule, cercosporin, that reacts with light and oxygen to produce reactive singlet oxygen (1 O2 ) contributing to fungal virulence. We show similar cellular localization and aetiology of cercosporin in the non-host Arabidopsis and the host Nicotiana benthamiana. Cercosporin accumulates in cell membranes in an oxidized state and in plastids in a mixture of redox states in a manner that is dependent on ongoing photosynthetic processes. We observed that cercosporin rapidly compromised photosynthesis as measured by Fv /Fm , NPQ, and photosystem I (PSI) parameters. Stomatal guard cells in particular demonstrated rapid light-dependent membrane permeabilization that led to changes in leaf conductance. We showed that cercosporin-mediated 1 O2 generation oxidized RNA to form 8-oxoguanosine (8-oxoG), leading to translational attenuation and induction of 1 O2 signature gene transcripts. We also identified a subset of cercosporin-induced transcripts that were independent of the photodynamic effect. Our results point to the multimodal action of cercosporin that includes the inhibition of photosynthesis, the direct oxidation of nucleic acid residues and the elicitation of complex transcriptome responses.

Photolysis mechanism of eleven insecticides under simulated sunlight irradiation: Kinetics, pathway and QSAR

Insecticides are widely used in crop protection against insects and frequently detected in aquatic environment. Photolysis kinetics are directly related with exposure assessment and risk assessment. However, the photolysis mechanism of neonicotinoid insecticides with different structures has not been studied and compared systematically in the literature. In this paper, the photolysis rate constants in water were determined for eleven insecticides under irradiation of simulated sunlight. At the same time, the photolysis mechanism and effect of dissolved organic matter (DOM) on their photolysis were studied. The results showed that photolysis rates of eleven insecticides vary in a large range. The photolysis rates of nitro-substituted neonicotinoids and butenolide insecticide are much faster than that of cyanoimino-substituted neonicotinoids and sulfoximine insecticide. The ROS scavenging activity assays reveal that direct photolysis dominates the degradation of seven insecticides and, on the other hand, self-sensitized photolysis dominates four insecticides. The shading-effect from DOM can reduce the direct photolysis rates, on the other hand, ROSs generated by triplet-state DOM (3DOM*) can also accelerate photolysis of insecticides. According to the photolytic products identified from HPLC-MS, these eleven insecticides have different photolysis pathways. Six insecticides are degraded from the removal of nitro group from their parent compounds and four insecticides are degraded through ·OH reaction or singlet oxygen (1O2) reaction. QSAR (quantitative structure-activity relationship) analysis showed that photolysis rate was directly related to the energy gap between the highest occupied molecular orbital to the lowest unfilled molecular orbital (Egap = ELUMO−EHOMO) and dipole moment (δ). These two descriptors reflect the chemical stability and reactivity of insecticides. The pathways developed from identified products and the molecular descriptors of QSAR models can well verify the photolysis mechanisms of eleven insecticides.

(±)-3-Deoxyradicinin Induces Stomata Opening and Chloroplast Oxidative Stress in Tomato (Solanum lycopersicum L.).

Radicinin is a phytotoxic dihydropyranopyran-4,5-dione isolated from the culture filtrates of Cochliobolus australiensis, a phytopathogenic fungus of the invasive weed buffelgrass (Cenchrus ciliaris). Radicinin proved to have interesting potential as a natural herbicide. Being interested in elucidating the mechanism of action and considering radicinin is produced in small quantities by C. australiensis, we opted to use (±)-3-deoxyradicinin, a synthetic analogue of radicinin that is available in larger quantities and shows radicinin-like phytotoxic activities. To obtain information about subcellular targets and mechanism(s) of action of the toxin, the study was carried out by using tomato (Solanum lycopersicum L.), which, apart from its economic relevance, has become a model plant species for physiological and molecular studies. Results of biochemical assays showed that (±)-3-deoxyradicinin administration to leaves induced chlorosis, ion leakage, hydrogen peroxide production, and membrane lipid peroxidation. Remarkably, the compound determined the uncontrolled opening of stomata, which, in turn, resulted in plant wilting. Confocal microscopy analysis of protoplasts treated with (±)-3-deoxyradicinin ascertained that the toxin targeted chloroplasts, eliciting an overproduction of reactive singlet oxygen species. This oxidative stress status was related by qRT-PCR experiments to the activation of transcription of genes of a chloroplast-specific pathway of programmed cell death.

Cytotoxicity Evaluation of Photosensitizer-Conjugated Hexagonal Upconverting Nanoparticles.

In this report, we synthesized hexagonal NaYF4:Yb,Er upconverting nanoparticles (UCNPs) of 171 nm in size with a narrow particle size distribution. To address their colloidal stabi-lity in aqueous media and to incorporate a photosensitizer that can produce reactive singlet oxygen (1O2) to kill tumor cells, UCNPs were conjugated with 6-bromohexanoic acid-functionalized Rose Bengal (RB) and coated with PEG-alendronate (PEG-Ale). The particles were thoroughly characterized by transmission electron microscopy, dynamic light scattering, ATR FTIR, X-ray photoelectron spectroscopy, thermogravimetric analysis, and spectrofluorometry, and 1O2 formation was detected using a 9,10-diphenylanthracene spectrophotometric probe. Cytotoxicity determination on rat mesenchymal stem cells by using the MTT assay showed that neutralization of the large positive surface charge of neat UCNPs with PEG-Ale and the bound RB sensitizer significantly reduced the concentration-dependent cytotoxicity. The presented strategy shows great potential for the use of these particles as a novel agent for the photodynamic therapy of tumors.

Metal-Organic Framework in Pharmaceutical Drug Delivery.

Metal-organic frameworks (MOFs) are porous, crystalline materials made up of organic ligands and metal ions/metal clusters linked by coordinative bonds. This large family is becoming increasingly popular for drug delivery due to their tuneable porosity, chemical composition, size and shape, and ease of surface functionalization. There has been a growing interest over the last decades in the design of engineered MOFs with controlled sizes for a variety of biomedical applications. Starting with the MOFs classification adapted for drug delivery systems (DDSs) based on the types of constituting metals and ligands. MOFs are appealing drug delivery vehicles because of their substantial drug absorption capacity and slow-release processes, which protect and convey sensitive drug molecules to target areas. Other guest materials have been incorporated into MOFs to create MOF-composite materials, which have added additional functionalities such as externally triggered drug release, improved pharmacokinetics, and diagnostic aids. Magnetic nanoparticles in MOFs for MRI image contrast and polymer coatings that increase blood circulation time are examples of synthetically adaptable MOF-composites. By including photosensitizers, which exert lethal effects on cancer cells by converting tumour oxygen into reactive singlet oxygen (1O2), metalorganic frameworks have been employed for photodynamic treatment (PDT) of malignancies among a multitude of nanosized therapies. Importantly, a variety of representative MOF applications are described from the perspectives of pharmaceutics, disease therapy, and advanced drug delivery systems. However, because of their weak conductivity, selectivity, and lack of modification sites, MOF materials' uses in electrochemical biosensing are restricted. MOF-based composites provide excellent electrical conductivity and robust catalytic activity by adding functionalized nanoparticles into MOF structures, which process benefits over single component MOFs.

A Cyclodextrin Polymer as Supramolecular Matrix for Scalable Green Photooxygenation of Hydrophobic Substrates in Homogeneous Phase.

In the quest for new therapies targeting hypoxia, aromatic endoperoxides have intriguing potential as oxygen releasing agents (ORAs) able to free O2 in tissues upon suitable trigger. Four aromatic substrates were synthesized and the formation of their corresponding endoperoxides was optimized in organic solvent upon selective irradiation of Methylene Blue, a low-cost photocatalyst, producing the reactive singlet oxygen species. Complexation of the hydrophobic substrates within a hydrophilic cyclodextrin (CyD) polymer allowed their photooxygenation in homogeneous aqueous environment using the same optimized protocol upon dissolution in water of the three readily accessible reagents. Notably, reaction rates were comparable in buffered D2 O and organic solvent and, for the first time, the photooxygenation of highly hydrophobic substrates was achieved for millimolar solutions in non-deuterated water. Quantitative conversion of the substrates, straightforward isolation of the endoperoxides and recovery of the polymeric matrix were achieved. Cycloreversion of one ORA to the original aromatic substrate was observed upon thermolysis. These results hold great potential for the launch of CyD polymers both as reaction vessels for green, homogeneous photocatalysis and as carrier for the delivery of ORAs in tissues.

An Easily Accessible NIR-Absorbing Tetraimide Dye and its Biotherapeutics Based Photothermal and Photodynamic Therapy.

Organic π-systems with strong absorption in the near-infrared (NIR) region are promising candidates for photothermal therapy (PTT) and photodynamic therapy (PDT). However, the synthesis of NIR π-systems involves several steps and many of them display poor photothermal conversion efficiency (PTCE). Here we present the synthesis of a tetraimide-based donor-acceptor NIR π-system, 2EHex-B having absorbance in the range of 350-900 nm. Importantly, 2EHex-B is synthesized in two steps with a 70 % high yield. Moreover, 2EHex-B shows excellent PTCE up to 50 % and good biocompatibility when encapsulated in liposomes. The liposome coated 2EHex-B, (L-2EHex-B) showed good thermal stability and efficiently kills cancer cells via PTT. Additionally, L-2EHex-B shows good reactive singlet oxygen generation ability when irradiated with a 750 nm laser. 3D cell culture model - multicellular spheroids test was performed to evaluate the efficiency of PTT. The spheroids treated with L-2EHex-B after NIR light irradiation showed increased cell death from the core of the tumor toward the periphery. The easy access to 2EHex-B makes it a potential candidate for minimally invasive cancer treatment.

Green Chemistry for Crosslinking Biopolymers: Recent Advances in Riboflavin-Mediated Photochemistry.

Riboflavin (RF), which is also known as vitamin B2, is a water-soluble vitamin. RF is a nontoxic and biocompatible natural substance. It absorbs light (at wavelengths of 380 and 450 nm) in the presence of oxygen to form reactive singlet oxygen (1O2). The generated singlet oxygen acts as a photoinitiator to induce the oxidation of biomolecules, such as amino acids, proteins, and nucleotides, or to initiate chemical reactions, such as the thiol-ene reaction and crosslinking of tyramine and furfuryl groups. In this review, we focus on the chemical mechanism and utilization of the photochemistry of RF, such as protein crosslinking and hydrogel formation. Currently, the crosslinking method using RF as a photoinitiator is actively employed in ophthalmic clinics. However, a significant broadening is expected in its range of applications, such as in tissue engineering and drug delivery.

Practical Aspects in the Study of Biological Photosensitization Including Reaction Mechanisms and Product Analyses: A Do's and Don'ts Guide†.

The interaction of light with natural matter leads to a plethora of photosensitized reactions. These reactions cause the degradation of biomolecules, such as DNA, lipids, proteins, being therefore detrimental to the living organisms, or they can also be beneficial by allowing the treatment of several diseases by photomedicine. Based on the molecular mechanistic understanding of the photosensitization reactions, we propose to classify them in four processes: oxygen-dependent (type I and type II processes) and oxygen-independent [triplet-triplet energy transfer (TTET) and photoadduct formation]. In here, these processes are discussed by considering a wide variety of approaches including time-resolved and steady-state techniques, together with solvent, quencher, and scavenger effects. The main aim of this survey is to provide a description of general techniques and approaches that can be used to investigate photosensitization reactions of biomolecules together with basic recommendations on good practices. Illustration of the suitability of these approaches is provided by the measurement of key biomarkers of singlet oxygen and one-electron oxidation reactions in both isolated and cellular DNA. Our work is an educational review that is mostly addressed to students and beginners.