Singlet Oxygen 1O2 Research Articles

Cairo pentagon tessellated covalent organic frameworks with mcm topology for near-infrared phototherapy

Despite the prevalent of hexagonal, tetragonal, and triangular pore structures in two-dimensional covalent organic frameworks (2D COFs), the pentagonal pores remain conspicuously absent. We herein present the Cairo pentagonal tessellated COFs, achieved through precisely chosen geometry and metrics of the linkers, resulting in unprecedented mcm topology. In each pentagonal structure, porphyrin units create four uniform sides around 15.5 Å with 90° angles, while tetrabiphenyl unit establish a bottom edge about 11.6 Å with 120° angles, aligning precisely with the criteria of Cairo Pentagon. According to the narrow bandgap and strong near-infrared (NIR) absorbance, as-synthesized COFs exhibit the efficient singlet oxygen (1O2) generation and photothermal conversion, resulting in NIR photothermal combined photodynamic therapy to guide cancer cell apoptosis. Mechanistic studies reveal that the good 1O2 production capability upregulates intracellular lipid peroxidation, leading to glutathione depletion, low expression of glutathione peroxidase 4, and induction of ferroptosis. The implementation of pentagonal Cairo tessellations in this work provides a promising strategy for diversifying COFs with new topologies, along with multimodal NIR phototherapy.

Regulating the dominant reactive oxygen species from Fe(IV)-oxo to 1O2 by deprotonation of Fe(IV)-oxo in electro-Fe(II)/periodate system

The ferrous species (Fe(II))-periodate (PI) system employs efficient decontamination by generating ferryl species (Fe(IV)-oxo) under acidic pH conditions. However, the mechanisms by which the Fe(II)/PI system operates across a broad pH range remain elusive. In light of the rapid oxidation and consumption of Fe(II) at neutral pH, we developed an electro-Fe(II) system utilizing an iron plate anode to activate PI (E(Fe/C)/PI). Efficient sulfamethoxazole (SMX) degradation was achieved under the E(Fe/C)/PI system across a range of pH values. Quenching and chemical probe experiments revealed a transition from Fe(IV)-oxo to singlet oxygen (1O2) as the predominant reactive species from acidic to near-neutral pH, respectively. Density functional theory (DFT) calculations indicated that the differences in one-electron transfer capacity and hydrolysis pathways for various protonated Fe(IV)-oxo species underlie the variations in catalytic mechanisms. This study not only enhances the efficiency of the Fe(II)/PI system but also provides a comprehensive understanding of the activation mechanisms at different pH levels.

Tensing Flipper: Photosensitized Manipulation of Membrane Tension, Lipid Phase Separation, and Raft Protein Sorting in Biological Membranes.

The lateral organization of proteins and lipids in the plasma membrane is fundamental to regulating a wide range of cellular processes. Compartmentalized ordered membrane domains enriched with specific lipids, often termed lipid rafts, have been shown to modulate the physicochemical and mechanical properties of membranes and to drive protein sorting. Novel methods and tools enabling the visualization, characterization, and/or manipulation of membrane compartmentalization are crucial to link the properties of the membrane with cell functions. Flipper, a commercially available fluorescent membrane tension probe, has become a reference tool for quantitative membrane tension studies in living cells. Here, we report on a so far unidentified property of Flipper, namely, its ability to photosensitize singlet oxygen (1O2) under blue light when embedded into lipid membranes. This in turn results in the production of lipid hydroperoxides that increase membrane tension and trigger phase separation. In biological membranes, the photoinduced segregated domains retain the sorting ability of intact phase-separated membranes, directing raft and nonraft proteins into ordered and disordered regions, respectively, in contrast to radical-based photo-oxidation reactions that disrupt raft protein partitioning. The dual tension reporting and photosensitizing abilities of Flipper enable simultaneous visualization and manipulation of the mechanical properties and lateral organization of membranes, providing a powerful tool to optically control lipid raft formation and to explore the interplay between membrane biophysics and cell function.

Efficient photocatalytic water decontamination over a wide pH range by C and O co-doped carbon nitride with tunable band structure

The metal-free, non-toxic, and highly tunable structure of carbon nitride confers unique advantages in photocatalytic advanced oxidation processes. Regulating the generation of radical and non-radical species during photocatalysis to maintain high degradation efficiency across different water matrices is of great practical significance for the application of carbon nitride. In this study, a C and O co-doped modified carbon nitride (UCN) with a high specific surface area was developed for efficient photodegradation of p-chlorophenol (p-Cl) without exogenous oxidants. Characterizations demonstrated that UCN in higher specific surface area exposed more active sites. Additionally, with rising doping levels, UCN exhibited enhanced light absorption capability and a narrower bandgap, which favored the separation of photogenerated electron-hole pairs. The primary active species were identified as holes, accompanied by the generation of superoxide radicals (·O2–) and singlet oxygen (1O2) depending on the pH value. Under acidic conditions, 1O2 was predominantly generated, whereas ·O2– dominated under alkaline conditions. As a result, the removal efficiency of p-Cl was enhanced under both strongly acidic and alkaline conditions. The pseudo-first-order rate constants for p-Cl removal at pH 3, 7, and 11 were 0.0558, 0.0354, and 0.0443 min−1, respectively. Moreover, combining DFT calculations and LC-MS data, analysis on the intermediate products of p-Cl degradation revealed unique characteristics at different pH values, further proving the flexible tunability and providing insights into the practical application of modified carbon nitride.

Plant competition cues activate a singlet oxygen signaling pathway in Arabidopsis thaliana.

Oxidative stress responses of Arabidopsis to reflected low red to far-red signals (R:FR ≈ 0.3) generated by neighboring weeds or an artificial source of FR light were compared with a weed-free control (R:FR ≈1.6). In the low R:FR treatments, induction of the shade avoidance responses (SAR) coincided with increased leaf production of singlet oxygen (1O2). This 1O2 increase was not due to protochlorophyllide accumulation and did not cause cell death. Chemical treatments, however, with 5-aminolevulinic acid (the precursor of tetrapyrrole biosynthesis) and glutathione (a quinone A reductant) enhanced cell death and growth inhibition. RNA sequencing revealed that transcriptome responses to the reflected low R:FR light treatments minimally resembled previously known Arabidopsis 1O2 generating systems that rapidly generate 1O2 following a dark to light transfer. The upregulation of only a few early 1O2 responsive genes (6 out of 1931) in the reflected low R:FR treatments suggested specificity of the 1O2 signaling. Moreover, increased expression of two enzyme genes, the SULFOTRANSFERASE ST2A (ST2a) and the early 1O2-responsive IAA-LEUCINE RESISTANCE (ILR)-LIKE6 (ILL6), which negatively regulate jasmonate level, suggested that repression of bioactive JAs may promote the shade avoidance (versus defense) and 1O2 acclimation (versus cell death) responses to neighboring weeds.

Cyclic homodimer formation by singlet oxygen-mediated oxidation of carnosine.

Although carnosine (β-Ala-L-His) is one of physiological protectants against in vivo damages caused by reactive oxygen species (ROS), its reactivity against singlet oxygen (1O2), an ROS, is still unclear at the molecular level. Theoretically, the reaction consists of two steps: i) oxygenation of the His side chain to form an electrophilic endoperoxide and ii) nucleophilic addition to the endoperoxide. In this study, the end product of 1O2-mediated carnosine oxidation was evaluated using 2D-NMR and other analytical methods both in the presence and absence of external nucleophiles. Interestingly, as the end product without external nucleophile, a cyclic homodimer was confirmed under our particular conditions. The reaction was also replicated in pork specimens.

Nonradical peroxymonosulfate activation via high-level pyrrolic-nitrogen and electron-deficient carbon at 2D ultrathin carbonaceous nanosheets for efficient BPA removal

Activation of persulfate by N-doped carbon is an emerging advanced oxidation process (AOP) for removing organic pollutants from water via singlet oxygen (1O2)-dominated non-radical way, however, the efficient generation of 1O2 is a hot topic worth deep exploration. In this study, glucose was used as an additional carbon and oxygen of prefabricated supramolecular melamine-cyanuric acid precursor, the final co-thermal polymerization products completely changed from conventional graphitic carbon nitride to ultrathin carbonaceous materials when the mass of glucose up to 0.72 g. The simple one-pot strategy can easily generate active electron-deficient carbon sites due to nitrogen and oxygen doping by modulating the electronic structure of the carbon framework, which is critical for the activation of peroxymonosulfate (PMS) to produce 1O2. The glucose content can adjust the degree of disorder of the amorphous carbonaceous nanosheet, and significantly improve the exposure of active pyrrolic nitrogen sites (27.47 %) and doped oxygen through the defective structure, which is another essential factor for the generation of 1O2 in the activation of PMS. The MCAG-0.72/ PMS exhibited excellent performance in BPA degradation, 95 % BPA (20 mg L−1) can be removed in 60 min with 1.0 mM PMS with reaction constant k=0.0209 min−1. Furthermore, MCAG-0.72 also demonstrated excellent BPA degradation in different actual water metrics and performance well in the four consecutive cycles. This study provides a novel convenient strategy to synthesize cost-effective N/O co-doped carbonaceous material for efficient activating PMS to remove refractory organics in water and wastewater, it sheds light on practical large-scale industrial applications in PMS-based AOPs.

Activation of peroxymonosulfate by FeOOH modified biochar for the degradation of tetracycline hydrochloride

For preventing environmental pollution and realizing resource utilization of agricultural and forestry wastes, biochar was formed after high temperature pyrolysis of citrus peels under anoxic conditions, and employed as catalyst to activate peroxymonosulfate (PMS) for degrading tetracycline hydrochloride (TC) in wastewater. Furthermore, α-FeOOH modified biochar was fabricated through an alcohol-assisted hydrothemal method for proving the catalytic activity of biochar. The prepared catalysts were characterized by several characterization techniques. Results showed that the catalytic activity of α-FeOOH modified biochar was much better than that of biochar or α-FeOOH, which is attributed to the synergistic effects of biochar and α-FeOOH on the PMS activation. Meanwhile, the effects of PMS concentration, co-existing ions (Cl-, NO3−), and humic acids (HA) on the degradation of TC were investigated through static experiments. More importantly, radical trapping experiment tests suggested that hydroxyl radical (•OH), sulfate radical (SO4•-), and singlet oxygen (1O2) were generated during the process of catalyst activation of PMS, and 1O2 played the main role for TC degradation.

Anchoring highly dispersed FeCo/C nanoparticles within zeolite 13X to promote 1O2 generation in the degradation of tetracycline hydrochloride

This paper reports the preparation of a FeCo/C@13X catalyst derived from FeCo/ZIF using Na-13X molecular sieves as substrates through the ion-exchange method, followed by in situ FeCo/ZIF growth and a carbonization step. Compared with FeCo/ZIF@13X and Co/C@13X, FeCo/C@13X exhibited an improved peroxymonosulfate (PMS) activation effect owing to the well-dispersed FeCo sites embedded in the carbon@13X matrix, as confirmed by high-resolution transmission electron microscopy, Fourier transform infrared spectra and X-ray diffraction. The cobalt loading in the FeCo/C@13X catalysts was up to 15.32 wt% as determined by ICP-OES. FeCo/C@13X, prepared by the introduction of organic Fe and calcining FeCo/ZIF@13X, exhibited good reusability and stability, viz. 92 % degradation efficiency after five cycles compared to 84 % of Co/C@13X and 79 % of FeCo/ZIF@13X. The FeCo/C@13X/PMS system was highly stable over a wide pH range and showed excellent tolerance for background substances in aqueous environments because of non-radical-dominated degradation. Quenching experiments and electron paramagnetic resonance analysis demonstrated that singlet oxygen (1O2) primarily facilitated the tetracycline hydrochloride (TCH) removal during the FeCo/C@13X catalytic process. The electron transfer and free radicals (SO4∙−, ∙OH, and O2∙−) were engaged in the TCH degradation. Through electrochemical measurements and in situ Raman spectroscopy, electrons were rapidly transferred from FeCo/C@13X to PMS, consuming HSO5− to generate metastable active species (FeCo/C@13X-PMS* complexes), which can efficiently accelerate the cycling of Fe3+/Co3+ to Fe2+/Co2+ and enhance 1O2 production. This study provides a suitable method for designing heterogeneous Fenton-like catalysts with high and stable catalytic performances for the continuous production of 1O2.

Self-Initiated Nano-Micelles Mediated Covalent Modification of mRNA for Labeling and Treatment of Tumors.

As a promising gene therapy strategy, controllable small molecule-mRNA covalent modification in tumor cells could be initiated by singlet oxygen (1O2) to complete the modification process. However, in vivo generation of 1O2 is usually dependent on excitation of external light, and the limited light penetration of tissues greatly interferes the development of deep tumor photo therapy. Here, we constructed a tumor-targeting nano-micelle for the spontaneous intracellular generation of 1O2 without the need for external light, and inducing a high level of covalent modification of mRNA in tumor cells. Luminol and Ce6 were chemically bonded to produce 1O2 by chemiluminescence resonance energy transfer (CRET) triggered by high levels of hydrogen peroxide (H2O2) in the tumor microenvironment (TME). The sufficient 1O2 oxidized the loaded furan to highly reactive dicarbonyl moiety, which underwent cycloaddition reaction with adenine (A), cytosine (C) or guanine (G) on the mRNA for interfering with the tumor cell protein expression, thereby inhibiting tumor progression. In vitro and in vivo experiments demonstrated that this self-initiated gene therapy nano-micelle could induce covalent modification of mRNA by 1O2 without external light, and the process could be monitored in real time by fluorescence imaging, which provided an effective strategy for RNA-based tumor gene therapy.

A self-powered theranostic DNA nanodevice for amplification of both intracellular microRNA imaging and photodynamic therapy

While numerous methods exist for diagnosing tumors through the detection of miRNA within tumor cells, few can simultaneously achieve both tumor diagnosis and treatment. In this study, a novel graphene oxide (GO)-based DNA nanodevice (DND), initiated by miRNA, was developed for fluorescence signal amplification imaging and photodynamic therapy in tumor cells. After entering the cells, tumor-associated miRNA drives DND to Catalyzed hairpin self-assembly (CHA). The CHA reaction generated a multitude of DNA Y-type structures, resulting in a substantial amplification of Ce6 fluorescence release and the generation of numerous singlet oxygen (1O2) species induced by laser irradiation, consequently inducing cell apoptosis. In solution, DND exhibited high selectivity and sensitivity to miRNA-21, with a detection limit of 11.47 pM. Furthermore, DND discriminated between normal and tumor cells via fluorescence imaging and specifically generated O21 species in tumor cells upon laser irradiation, resulting in tumor cells apoptosis. The DND offer a new approach for the early diagnosis and timely treatment of malignant tumors.

Effect of dissolved oxygen on the peroxymonosulfate activation pathway in an electrochemical Co/P/CA cathode system

Although dissolved oxygen plays an important role in electro-Fenton-like processes, few investigations have revealed its underlying effects in such processes. Herein, the effect of dissolved oxygen on peroxide activation in an electro-Fenton-like system comprising electrochemical cells and peroxymonosulfate (PMS) was investigated. Cobalt phosphide-modified carbon aerogel (Co/P/CA) was used as the cathode material owing to the high conductivity and catalytic activity of Co/P/CA. Several free radicals and their effects on organic pollutant removal were observed using electron paramagnetic resonance spectrometry and quenching experiments, respectively. The observations revealed that in the presence of O2, hydroxyl radical (·OH), superoxide (O2−·), and singlet oxygen (1O2) served as the primary active species in the PMS activation process, while in the presence of N2, ·OH and sulfate radical (SO4−·) served as the dominant active species in this process. The factor responsible for the difference in the PMS activation pathways available under O2 and N2 conditions was investigated using rotating disk electrode tests and free energy calculations. The tests indicated that O2 facilitates PMS activation to form ·OH instead of SO4−·. The dissolved oxygen subsequently underwent a single-electron-reduction reaction and was converted into O2−·, which could serve as a source of 1O2. When N2 was introduced, Co species, particularly Co(II), played a key role in activating PMS. The free radicals ·OH and SO4−· were generated during the PMS activation process. This study clearly demonstrates the mediating catalysis role of dissolved oxygen in electro-Fenton-like system through experimental data and theoretical calculations, thereby positively contributing to future studies regarding the continuous activation of peroxides in composite systems and improvement of the efficiency of waterbody remediation.

Amorphous CoSx in heterogeneous electro-Fenton: A 1O2-mediated system for efficient and selective water decontamination

Heterogeneous electro-Fenton (hetero-EF) technology represents a promising and safe approach to water treatment. However, conventional hetero-EF catalysts still face the challenges of removing contaminants selectively and operating efficient in complex water quality. We proposed a novel system utilizing amorphous CoSx (A-CoSx) that overcame these limitations. This material generated only singlet oxygen (1O2), a highly specific oxidant, for contaminants degradation. Unlike traditional crystalline catalysts, A-CoSx efficiently utilized hydrogen peroxide (H2O2) to directly produce 1O2, exhibiting high catalytic activity across a wide pH range (3.0–11.0). The formation mechanism of 1O2 was confirmed through experimental investigations, density functional theory (DFT) calculations, and advanced characterization techniques. This system effectively degraded contaminants even in complex water with interferences and enabled selective targeting of pollutants with electron-donating groups. This innovative approach using amorphous materials offers a promising strategy for the regulation of ROS and enabling selective contaminant removal in water treatment.

Bimetallic Nanozymes‐Integrated Parachute‐Like Au2Pt@PMO@ICG Janus Nanomotor with Dual Propulsion for Enhanced Tumor Penetration and Synergistic PTT/PDT/CDT Cancer Therapy

AbstractNanocatalytic therapeutic agents with triple synergistic treatment modes of chemodynamic therapy (CDT), photothermal therapy (PTT) and photodynamic therapy (PDT) are emerging nanomaterials in malignancy treatment. Nevertheless, the passive diffusion and transport of nanomaterials result in poor permeability in tumor lesions, severely affecting the effectiveness of synergistic therapy. Herein, a dual‐source‐driven parachute‐like Au2Pt@PMO@ICG Janus nanomotor (APIJNS) is prepared by an interfacial energy‐mediated anisotropic growth strategy for PTT‐mediated CDT/PDT triple synergistic cancer therapy. Such nanomotor can realize self‐thermophoresis drive under the trigger of near‐infrared light, which can effectively enhance the active permeability and uptake of the APIJNS in the tumor tissue, thus achieving efficient PTT/PDT/CDT synergistic therapeutic effect. In addition, parachute‐like APIJNS exhibits high‐efficiency catalase (CAT)‐like activity and can catalyze the overexpressed H2O2 in the tumor microenvironment (TME) to generate oxygen (O2), not only alleviating the hypoxia in the tumor lesion, but also converting it into singlet oxygen (1O2) to activate the photosensitizer ICG, achieving PDT. This work provides new ideas for enhancing triple synergistic cancer therapy by improving tumor permeability with dual‐drive Janus nanomotors based on dual noble metal nanozymes.

Dissolved Black Carbon Facilitates the Photodegradation of Microplastics via Molecular Weight-Dependent Generation of Reactive Intermediates.

Photodegradation of microplastics (MPs) induced by sunlight plays a crucial role in determining their transport, fate, and impacts in aquatic environments. Dissolved black carbon (DBC), originating from pyrolyzed carbon, can potentially mediate the photodegradation of MPs owing to its potent photosensitization capacity. This study examined the impact of pyrolyzed wood derived DBC (5 mg C/L) on the photodegradation of polystyrene (PS) MPs in aquatic solutions under UV radiation. It revealed that the photodegradation of PS MPs primarily occurred at the benzene ring rather than the aliphatic segments due to the fast attack of hydroxyl radical (•OH) and singlet oxygen (1O2) on the benzene ring. The photosensitivity of DBC accelerated the degradation of PS MPs, primarily attributed to the increased production of •OH, 1O2, and triplet-excited state DBC (3DBC*). Notably, DBC-mediated photodegradation was related to its molecular weight (MW) and chemical properties. Low MW DBC (<3 kDa) containing more carbonyl groups generated more •OH and 1O2, accelerating the photodegradation of MPs. Nevertheless, higher aromatic phenols in high MW DBC (>30 kDa) scavenged •OH and generated more O2•-, inhibiting the photodegradation of MPs. Overall, this study offered valuable insights into UV-induced photodegradation of MPs and highlighted potential impacts of DBC on the transformation of MPs.

Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions.

Three homoleptic Al(III) complexes (Al1-Al3) with different degrees of methylation at the 2-pyridylpyrrolide ligand were systematically tested for their function as photosensitizers (PS) in two types of energy transfer reactions. First, in the generation of reactive singlet oxygen (1O2), and second, in the isomerization of (E)- to (Z)-stilbene. 1O2 was directly evidenced by its characteristic NIR emission at around 1276 nm and indirectly by the reaction with an organic substrate [e.g. 2,5-diphenylfuran (DPF)] using in situ UV/vis spectroscopy. In a previous study, the presence of additional methyl groups was found to be beneficial for the photocatalytic reduction of CO2 to CO, but here Al1 without any methyl groups exhibits superior performance. To rationalize this behavior, a combination of photophysical experiments (absorption, emission and excited state lifetimes) together with photostability measurements and scalar-relativistic time-dependent density functional theory calculations was applied. As a result, Al1 exhibited the highest emission quantum yield (64%), the longest emission lifetime (8.7 ns) and the best photostability under the reaction conditions required for the energy transfer reactions (e.g. in aerated chloroform). Moreover, Al1 provided the highest rate constant (0.043 min-1) for the photocatalytic oxygenation of DPF, outperforming even noble metal-based competitors such as [Ru(bpy)3]2+. Finally, its superior photostability enabled a long-term test (7 h), in which Al1 was successfully recycled seven times, underlining the high potential of this new class of earth-abundant PSs.

Water oxidation coupled singlet oxygen electrochemiluminescence at C4N3 nanosheets/TiO2 nanotubes/Ti electrodes and its sensing application

Singlet oxygen (1O2) electrochemiluminescence (ECL) induced by water oxidation might intrigue new kinds of ECL-based sensors to be developed, but remains nascent due to its difficulty to be achieved. Herein, we report a water oxidation coupled ECL emission from dimeric aggregates of 1O2 at C4N3 nanosheets (NSs)/TiO2 nanotubes (NTs)/Ti electrodes (C4N3/TiO2/Ti) in the presence of triethanolamine (TEOA) as the co-reactant. The half-metallic C4N3 NSs were introduced to TiO2 NTs/Ti electrodes via in-situ thermal polymorization of ionic liquid precursor, which endows the TiO2 NTs with more oxygen vacancies and faster charge transfer ability as well as provides more sites for oxygen enriching, leading to an ECL intensity being 5.5 folds that at the TiO2 NTs/Ti electrodes. Besides, the tubelike shape of TiO2 makes it easier for the generated 1O2 to react each other to form dimeric aggregates, resulting in a typical ECL emission peak at ∼ 642 nm. Using the 1O2 ECL to detect dopamine (DA) as a model target, a wide linear range from 20 pM to 400 nM is obtained with detection limit of 7.6 pM (S/N = 3). This work offers a deep insight into water oxidation coupled 1O2 ECL and also accelerates its biosensing applications.

Unveiling the versatile performance of transition metal sulfides in peroxymonosulfate activation

Advanced oxidation processes (AOPs) are promising treatment options for environmental remediation to reduce chemical oxygen demand (COD) and emerging contaminants. Transition metal sulfides (TMSs) are a class of common catalysts in AOPs, but actually, they also widely exist in the environment in the form of sulfide minerals and seriously contaminated water bodies as black-odorous substances. Therefore, it is crucial to find out their roles during water decontamination using AOPs. This study investigated different mechanisms and performance of four common TMSs (FeS, CuS, CoS and MnS) in peroxymonosulfate (PMS)-based AOPs for the removal of a representative micropollutant tetracycline (TC). The results showed that CoS/PMS was the most efficient with 100 % TC removal within 1 min, followed by FeS/PMS (100 %, 10 min) with the apparent rate constant (kobs) of 0.45 min−1. TC removal by CuS (kobs = 0.10 min−1) and MnS (kobs = 0.02 min−1) took 30 min with 96 % and 82 % removal, respectively. Interestingly, the dominant reactive species were different in these systems, i.e., high-valent iron (Fe(IV)) in FeS/PMS, mainly radicals (•OH, SO4•−, O2•−) and singlet oxygen (1O2) in CuS/PMS, and Co(IV) and 1O2 in CoS/PMS. In comparison, TC was removed in MnS/PMS mainly through cooperative adsorption, reduction and oxidation by MnS. Low valent sulfur species, such as S2− and S22−, may participate in the valence cycles of metals or TC reduction. The above four systems had a wide pH (3.6–11.1) adaptability and a strong anti-interference ability to co-existing Cl−, SO42− and NO3−, but could be hindered by CO32−, PO43− and humic acid. This study provides novel insights into the TMS-based catalysts in AOPs, which will pave the way for advancing AOP technology.

Transport of Zinc-Phthalocyanine to Cancer Cells Using Myoglobin-Albumin Fusion Protein for Photodynamic Therapy.

Photodynamic therapy (PDT) is a noninvasive approach to cancer treatment, wherein cell death is initiated by singlet oxygen (1O2) production via energy transfer from excited photosensitizers to ground-state O2. Effective clinical photosensitizers necessitate water solubility for in vivo administration. Hydrophobic dyes, such as phthalocyanines, cannot be used directly as photosensitizers. Herein, we synthesized a myoglobin-(human serum albumin) fusion protein reconstituted with zinc-phthalocyanine (ZnPc), termed ZnPcMb-HSA. The photophysical properties of ZnPcMb-HSA closely resemble those of ZnPc-substituted Mb. Notably, ZnPc dissociates from ZnPcMb-HSA and selectively accumulates within cancer cells, while the protein components remain extracellular. Treatment of four distinct cell lines with ZnPcMb-HSA, followed by red-light irradiation, effectively induced apoptosis. The half-maximal inhibitory concentrations (IC50) against these cancer cell lines ranged between 0.1-0.5 μM. Reconstituted Mb-HSA emerges as a promising carrier for transporting various water-insoluble porphyrinoid photosensitizer to target cancer cells in PDT applications.

Assessment of Photoactivated Chlorophyllin Production of Singlet Oxygen and Inactivation of Foodborne Pathogens

Singlet oxygen (1O2) is known to have antibacterial activity; however, production can involve complex processes with expensive chemical precursors and/or significant energy input. Recent studies have confirmed the generation of 1O2 through the activation of photosensitizer molecules (PSs) with visible light in the presence of oxygen. Given the increase in the incidence of foodborne diseases associated with cross-contamination in food-processing industries, which is becoming a major concern, food-safe additives, such as chlorophyllins, have been studied for their ability to act as PSs. The fluorescent probe Singlet Oxygen Sensor Green (SOSG®) was used to estimate 1O2 formation upon the irradiation of traditional PSs (rose bengal (RB), chlorin 6 (ce6)) and novel chlorophyllins, sodium magnesium (NaChl) and sodium copper (NaCuChl), with both simulated-solar and visible light. NaChl gave rise to a similar 1O2 production rate when compared to RB and ce6. Basic mixing was shown to introduce sufficient oxygen to the PS solutions, preventing the limitation of the 1O2 production rate. The NaChl-based inactivation of Gram-positive S. aureus and Gram-negative E. coli was demonstrated with a 5-log reduction with UV–Vis light. The NaChl-based inactivation of Gram-positive S. aureus was accomplished with a 2-log reduction after 105 min of visible-light irradiation and a 3-log reduction following 150 min of exposure from an initial viable bacterial concentration of 106 CFU mL−1. CHS-NaChl-based photosensitization under visible light enhanced Gram-negative E. coli inactivation and provided a strong bacteriostatic effect preventing E. coli proliferation. The difference in the ability of NaChl and CHS-NaChl complexes to inactivate Gram-positive and Gram-negative bacteria was confirmed to result from the cell wall structure, which impacted PS–bacteria attachment and therefore the production of localized singlet oxygen.