Singlet Oxygen 1O2 Research Articles

Boosting oxygen storage capacity of Fe-Cu bimetallic catalysts through sulfide modification for efficient and selective molecular oxygen activation

Molecular oxygen (O2), a reactive oxygen species precursor, has great potential for water purification, but its spin-forbidden resistance hinders its direct involvement in the redox reactions of organic compounds under mild ambient conditions. In this study, a facile strategy was employed to synthesize sulfide-modified Fe-Cu bimetallic catalysts (FeCu-S) to enhance the activation efficiency of O2. The results showed that the FeCu-S material exhibited a tenfold increase in O2 activation compared to that of the control group, primarily attributed to the increased specific surface area of the catalysts with an optimized Fe/Cu site distribution and promoted generation of Cu-containing crystalline phases (e. g., CuFeS2 and CuO) to significantly enhanced the oxygen storage capacity. Moreover, such Cu-containing crystalline phases strengthened surface electron transfer, thus remarkably promoting the selective generation of singlet oxygen (1O2) for sulfamethoxazole (SMX) degradation. The FeCu-S/O2 system maintained high activity after the fifth recycle with stable reaction pH and negligible leaching of Cu and Fe ions, also exhibited great performance in the advanced treatment of the real biological effluent and ultrafiltration effluent from landfill leachate, confirming its great potential for practical water purification applications.

Frenkel defects facilitate oriented 1O2 formation in birnessite for enhanced catalytic oxidation of formaldehyde

Defect strategy is one of the most effective approaches for enhancing the efficiency of Mn-based catalysts in removing formaldehyde (HCHO) under ambient conditions. Herein, the interlayer Mn-O octahedra in birnessite synergistically form with Mn vacancies through proton exchange in acidic solutions, creating surface Frenkel defects. As evidenced by highly combined physicochemical characterization and density functional theory calculations, surface Frenkel defects are highly active sites on the surface of birnessite. The surface Frenkel defects can induce surface electronic reconstruction, generating strong electrophilicity, which promotes the evolution of superoxide radicals (O2•−) into singlet oxygen (1O2). In-situ quenching DRIFTS indicates that 1O2 is the most important ROS in the oxidation process of HCHO. Additionally, the surface Frenkel defects enhance the adsorption of HCHO, promoting the dehydrogenation of HCHO to form CO, which is then rapidly oxidized to CO2 and H2O under the action of 1O2. This provide a more effective kinetic and thermodynamic catalytic pathway. The defect-rich birnessite (R-Bir) achieved complete HCHO removal in the dynamic test at 10 ppm within 10 hours, significantly outperforming defect-free birnessite (F-Bir) and most previously reported catalysts. This study precisely reveals the catalytic mechanism of HCHO over R-Bir and provides valuable insights for the design of high-performance environmental catalysts.

Electronic structure regulation of Cu-based Ruddlesden-Popper perovskites by cobalt doping for enhanced degradation of oilfield fracturing wastewater in electrocatalytic peroxymonosulfate system

Purification of oilfield fracturing wastewater is the most challenging type of oilfield wastewater treatment. In this work, a heterogeneous electrocatalytic peroxymonosulfate (PMS) system was established to treat oilfield wastewater using Co-doping induced Cu-based Ruddlesden-Popper (RP) perovskites as catalysts. Characterization results illustrated that the obtained catalysts were generated the heterojunction of LaCoO3/La2CuO4 and the Co would transfer electrons to Cu, resulting in a higher chemical oxygen demand (COD) degradation efficiency (> 80 %) of oilfield fracturing wastewater under the neutral environment. Singlet oxygen (1O2) played the main function for COD removal with analysis results of reactive oxygen species (ROS). Experimental results and theoretical calculations indicated that the reduction effect of carbon felt (GF) cathode and the redox cycle of Cu(I)/Cu(II) and Co(II)/Co(III) accelerated the activation of PMS. Moreover, the lattice oxygen participated in the generation of ROS. Significantly, the LaCoO3/La2CuO4 heterojunction displayed a higher total density of states (TDOS) value near the Fermi level, implying their favorable electron transfer for PMS activation. This study opens new avenue for resolving the challenge of oilfield fracturing wastewater pollution.

Multifunctional hyaluronic acid ligand-assisted construction of CD44- and mitochondria-targeted self-assembled upconversion nanoparticles for enhanced photodynamic therapy.

Upconversion nanoparticles (UCNPs) have been used as a potential nanocarrier for photosensitizers (PSs), which have demonstrated a great deal of promise in achieving an effective photodynamic therapy (PDT) for deep-seated tumors. However, overcoming biological barriers to achieve mitochondria-targeted PDT remains a major challenge. Herein, CD44- and mitochondria-targeted photodynamic nanosystems were fabricated through the self-assembly of hyaluronic acid-conjugated-methoxy poly(ethylene glycol)-diethylenetriamine-grafted-(chlorin e6-dihydrolipoic acid-(3-carboxypropyl)triphenylphosphine bromide) polymeric ligands (HA-c-mPEG-Deta-g-(Ce6-DHLA-TPP)) and NaErF4:Tm@NaYF4 core-shell UCNPs (termed CMPNs). The CMPNs presented ideal physiological stability, a good drug loading capacity and an improved capacity for the generation of singlet oxygen (1O2) based on the FRET mechanism. Significantly, confocal images revealed that CMPNs not only facilitated cellular uptake through CD44-receptor-targeted endocytosis, subsequently enabling rapid evasion from endo-lysosomal sequestration, but also specifically targeted mitochondria, ultimately inducing a profound disruption of mitochondrial membrane potential, which triggered apoptosis upon laser irradiation, thereby significantly enhancing the therapeutic effect. Furthermore, in vitro antitumor experiments further confirmed the substantial enhancement in cancer cell killing efficiency achieved by treating with CMPNs upon near-infrared (NIR) laser irradiation. This innovative approach holds promise for the development of NIR-laser-activated photodynamic nanoagents specifically designed for mitochondria-targeted PDT, thus addressing the limitations of the current PDT treatments.

A hexanuclear Iridium(III) cluster for histidine-induced singlet oxygen and superoxide radicals generation

Photosensitizers (PSs) play key roles in photodynamic therapy (PDT). PDT is typically reliant on the local concentration of oxygen. A big challenge for PSs is to develop oxygen-independent photosensitizers, which can work well in hypoxic tumor microenvironment. In this piece of work, a hexanuclear Ir(III) cluster (Ir6) is highly selective towards histidine and histidine-rich (His-rich) proteins to form mononuclear Ir(III) complexes of [Ir(bpy)2(His)]. After the selective response to histidine or his-rich proteins, [Ir(bpy)2(His)] generates both singlet oxygen(1O2) and superoxide (O2−). This work opens an avenue for the potential application of Ir6 for type Ι and ΙΙ synergic photodynamic therapy.

Tetraphenylethene-Based Molecular Cage with Coenzyme FAD: Conformationally Isomeric Complexation toward Photocatalysis-Assisted Photodynamic Therapy.

Flavin adenine dinucleotide (FAD), serving as a light-absorbing coenzyme factor, can undergo conformationally isomeric complexation within different enzymes to form various enzyme-coenzyme complexes, which exhibit photocatalytic functions that play a crucial role in physiological processes. Constructing an artificial photofunctional system using FAD or its derivatives can not only develop biocompatible photocatalytic systems with excellent activities but also further enhance our understanding of the role of FAD in biological systems. Here, we demonstrate a supramolecular approach for constructing an artificial enzyme-coenzyme-type host-guest complex with photoinduced catalytic function in water. First, we have designed and synthesized a water-soluble tetraphenylethene (TPE)-based octacationic molecular cage (1) with a large and flexible cavity, which can adaptively encapsulate with two FAD molecules with "U-shaped" conformation (uFAD) to form a 1:2 host-guest complex (1⊃uFAD2) in water. Second, based on the conformationally isomeric complexation of FAD within 1, the 1⊃uFAD2 complex facilitates electron and energy transfers to molecular oxygen upon the white-light illumination, efficiently producing reactive oxygen species (ROS) such as superoxide radical (O2•-) and singlet oxygen (1O2). To our knowledge, the 1⊃uFAD2 complex acts as a photocatalyst to achieve the highest turnover frequency (TOF) of 35.6 min-1 for the photocatalytic oxidation reaction of NADH via a photoinduced superoxide radical catalysis mechanism in an aqueous medium. At last, combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH, 1⊃uFAD2 as a supramolecular photosensitizer displays an excellent oxygen-independent photocatalysis-assisted photodynamic therapy in hypoxic tumors.

Iron–Cobalt Bimetallic Metal–Organic Framework-Derived Carbon Materials Activate PMS to Degrade Tetracycline Hydrochloride in Water

Organic pollutants entering water bodies lead to severe water pollution, posing a threat to human health. The activation of persulfate advanced oxidation processes using carbon materials derived from MOFs as substrates can efficiently treat wastewater contaminated with organic pollutants. This research uses NH2-MIL-101(Fe) as a substrate, doped with Fe2+ and Co2+, to prepare Fe/Co-CNs through a one-step carbonization method. The surface morphology, pore structure, and chemical composition of Fe/Co-CNs were investigated using characterization techniques such as XRD, SEM, TEM, XPS, FT-IR, BET, and Raman. A comparative study was conducted on the performance of catalysts with different Fe/Co ratios in activating PMS for the degradation of organic pollutants, as well as the effects of various influencing factors (the dosage of Fe/Co-CNs, the amount of peroxymonosulfate (PMS), the initial pH of the solution, the TC concentration, and inorganic anions) on the catalyst’s activation of persulfate for TC degradation. Through radical quenching experiments and post-degradation XPS analysis, the active radicals in the FeCo-CNs/PMS system were investigated to explain the possible mechanism of TC degradation in the Fe/Co-CNs/PMS system. The results indicate that Fe/Co-CNs-2 (with a Co2+ doping amount of 20%) achieves a degradation rate of 93.34% for TC (tetracycline hydrochloride) within 30 min when activating PMS, outperforming other Co2+ doping amounts. In addition, singlet oxygen (1O2) is the main reactive species in the reaction system.

A combination of covalent and noncovalent restricted‐intramolecular‐rotation strategy for supramolecular AIE‐type photosensitizer toward photodynamic therapy

AbstractPhotodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation‐caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted‐intramolecular‐rotation strategies to develop supramolecular PSs with aggregation‐induced emission (AIE) characteristics. Firstly, a water‐soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single‐molecule‐level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single‐layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2−•) and singlet oxygen (1O2) upon white‐light irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2−• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type‐I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE‐type PS to exhibit strong photo‐induced cytotoxicity upon white‐light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.

Advancing wastewater treatment: The efficacy of carbon-based electrochemical platforms in removal of pharmaceuticals

The study addresses the efficiency of innovative biochar- and g-C3N4-coated electrochemical platforms in removing selected pharmaceuticals and their metabolites from wastewater, with a focus on cost-effective and scalable materials. Analysis of effluent from the wastewater treatment plant revealed significant concentrations of 25 pharmaceuticals, highlighting the plant’s limited treatment efficacy. Notably higher levels of Telmisartan, Tramadol, and Diclofenac were found. The novelty of this work lies in the use of biochar- and g-C3N4-coated Raschig rings and glass beads as efficient electrochemical anodes offering high degradation capabilities. Adsorption-only tests (without voltage load) confirmed that no significant pharmaceutical removal occurs without electrochemical activation, highlighting the importance of electrochemical degradation. For the first time, we observed the formation of hydroxyl radicals (•OH) and singlet oxygen (1O2) during the electrochemical degradation process using g-C3N4-coated anodes, significantly enhancing degradation efficiency. The biochar-coated Raschig rings achieved over 80 % removal efficiency for all tested pharmaceuticals, with a power consumption of 85.2 kWh/m3. In comparison, biochar-coated beads exhibited a removal efficiency ranging from 9 % to 99 %, consuming 75 kWh/m3, while g-C3N4-coated rings showed the lowest performance at an energy consumption of 45 kWh/m3. These findings demonstrate the potential of both, biochar- and g-C3N4-based electrochemical platforms as a viable, scalable solution for advanced wastewater treatment, particularly for pharmaceutical degradation.

Triad photosensitizers based on iodo-aza-Bodipy and naphthalenediimides (NDI) with broadband absorption: Study of resonance energy transfer and electron transfer

Two organic photosensitizers based on resonance energy transfer (A-1 and A-2) are prepared. Naphthalenediimides was used as intramolecular energy donor and iodo-aza-Bodipy was used as intramolecular energy acceptor/spin converter. A-1 (ε = 42,800 at 618 nm and ε = 59,600 at 674 nm) and A-2 (ε = 33,300 at 514 nm and ε = 68,300 at 674 nm) give the two strong absorption band and both of them show broadband absorption in visible region. The photophysical properties of the compounds were studied with steady state and time-resolved spectroscopy in detail. With steady state and time-resolved spectroscopy, we found that photoexcitation into the energy donor was followed by singlet energy transfer, then via the intersystem crossing (ISC) of the energy acceptor. By nanosecond time-resolved transient absorption spectroscopy and DFT calculation, triplet excited state is localized on the iodo-aza-Bodipy moiety. Quantum yield of singlet oxygen of A-1 and A-2 is 39.7 % and 40.9 %, respectively. Based on fluorescence lifetime quenching, the efficiency of intramolecular energy transfer is estimated to be 15.9 % and 27.7 % for A-1 and A-2. And PET is responsible for the relatively low efficiency, which is identified by the calculation of kcs/kFRET and the Gibbs free energy change (△G0cs). A-1 and A-2 were used for singlet oxygen (1O2) mediated photooxidation of 1,5-dihydroxylnaphthalene and the photosensitizing ability are more efficient than the triplet photosensitizers with the mono-chromophore photosensitizer.

Fe/Mo bimetallic synergy system for ultra-highly efficient degradation of Rhodamine B

The traditional Fenton process, which depends on the use of Fe2+/H2O2, is constrained by the consumption of ferrous ions and the requirement for large amounts of H2O2. However, the assembly of bimetallic synergy systems with adjustable valence metal cations and enhanced dispersion of active sites has been evidenced to address these limitations. In this work, the Fe/Mo bimetallic synergy system in FexMo-CN materials is explored, utilized for the degradation of dyes with the assistance of H2O2. The cooperative effect of Fe/Mo bimetallic and the highly dispersed FeMoO4 as active sites make materials to achieve ultra-highly efficient degradation of dyes, approximately 100 % Rhodamine B (RhB) degradation within 6 min. And the corresponding degradation rate constant is 1.3471 min−1. Additionally, FexMo-CN materials exhibit excellent stability and versatility in solutions containing various cations, anions, or other dyes. Quenching experiments and EPR tests demonstrate that singlet oxygen (1O2) serves as the main reactive oxygen species (ROS) to degrade RhB. And the mechanism of generated 1O2 is revealed. The degradation path and mechanism of RhB are analyzed and the toxicology of intermediate products are calculated in detail. This work presents a novel approach for enhancing efficiency in Fenton-like reactions within the field of environmental remediation.

Synthesis of Novel Fe-CNs-P/S Carbon Materials for Sustainable Water Treatment: Activation of Persulfate for Efficient Tetracycline Degradation

This study presents a novel Fe-CNs-P/S carbon composite material, synthesized by doping elements P and S into NH2-MIL-101 (Fe) using the carbonization method. The material’s application in sustainable water treatment was evaluated, focusing on its effectiveness in activating persulfate for pollutant degradation. The research thoroughly investigates the synthesis process, structural characteristics, and performance in degrading pollutants. The results indicate that Fe-CNs-P/S-5 with 50% P and S co-doping is higher than that of other samples, where the degradation rate of TC in 30 min is as high as 98.11% under the optimum conditions, that is temperature at 25 °C, 0.05 g/L of catalyst concentration, and 0.2 g/L of PMS concentration. The composite material demonstrates robust versatility and stability, maintaining high degradation efficiency across multiple organic pollutants, with no significant reduction in catalytic performance after four cycles. Furthermore, the free radical quenching experiments display that the singlet oxygen 1O2 is the main active species. It is demonstrated that the doping of P and S play a role in the enhancement of PMS activation over the Fe-CNs-P/S catalyst. This material demonstrates remarkable efficacy in treating a range of organic contaminants and exhibits excellent reusability, presenting a promising approach for enhancing sustainability in water treatment applications.

The influence of photosynthetic pigment chlorophyllin in light-driven LPMO system on the hydrolytic action of cellulases

It has been demonstrated that LPMO reactions can be driven by light, using the photosynthetic pigment chlorophyllin to achieve efficient oxidative degradation of cellulose. However, the effect of chlorophyllin on cellulases remains unclear. This study discovered that chlorophyllin does not affect the hydrolytic activity of cellulases under dark conditions. However, under light exposure, chlorophyllin-derived reactive oxygen species (ROS) exhibit a strong inhibitory effect on cellulases. These ROS primarily inhibit the hydrolytic action of endoglucanase II (Cel5A) and cellobiohydrolase II (Cel6A), while the action of cellobiohydrolase I and β-glucosidase remains unaffected. Scavenger studies revealed that singlet oxygen (1O₂) is the key inhibitory ROS responsible for the inhibition of Cel5A and Cel6A. The removal of 1O₂ by sodium azide effectively mitigates this inhibition, increasing the conversion yield of cellulose to glucose by 25.9 % when using the light-driven LPMO system in conjunction with cellulases. This study provides new insights into the role of chlorophyllin-derived 1O₂ in hindering hydrolytic action of cellulases and demonstrates the successful mitigation of this inhibition by sodium azide, thereby enhancing the cooperative degradation of cellulose to glucose by the light-driven LPMO system and cellulases.

S-Fe/Co@GC reduction-oxidation sequential reaction system for the high-efficiency mineralization of tetrabromobisphenol a in water

The lipophilic, bioaccumulative, persistent nature of Tetrabromobisphenol A (TBBPA) contributes to its widespread detection in various environmental media, posing significant negative implications for the living environment and human health. In this study, a reduction system and a reduction-oxidation sequential reaction system were developed using a magnetic core-shell bimetallic amendment (S-Fe/Co@GC) to investigate the degradation and mineralization properties of TBBPA. Additionally, the degradation mechanism and degradation pathway of TBBPA in various systems were analyzed. In the sole S-Fe/Co@GC reduction system, sulfurized nano-zero-valent iron (S-Fe) and Co0 exhibited remarkable reductive capabilities towards TBBPA. The reaction of S-Fe/Co@GC gradually facilitated the debromination of TBBPA, ultimately leading to its conversion into bisphenol A. The reaction process demonstrated the synergistic effect among S-Fe, Co0, and graphite carbon, leading to a remarkable enhancement in the reduction performance of the material. Consequently, TBBPA removal efficiency reached 97.5% within a time frame of 10 h. In the reduction-oxidation sequential reaction system, the debromination of TBBPA during the reduction stage enhanced the subsequent oxidation stage's total organic carbon (TOC) removal rate. During the oxidation stage (0.03 mmol of PMS added at 30 min), TBBPA underwent attack by sulfate radical (SO4·-), hydroxyl radical (·OH), superoxide radical (O2·-), and singlet oxygen (1O2), leading to cleavage and opening of its structure. This process resulted in the conversion of TBBPA into short-chain fatty acids, ultimately mineralizing it into CO2 and H2O. Thus, this degradation pathway mitigated potential environmental risk associated with intermediates. The final TOC removal rate significantly increased to 72.7% when the dose of composite material was set at 1.0 g/L, surpassing that achieved by the conventional advanced oxidation system. Hence, the S-Fe/Co@GC reduction-oxidation sequential reaction system provides a new strategy for treating high-concentration TBBPA-contaminated water.

Oxidative Processes and Xenobiotic Metabolism in Plants: Mechanisms of Defense and Potential Therapeutic Implications.

Plants are continuously exposed to environmental challenges, including pollutants, pesticides, and heavy metals, collectively termed xenobiotics. These substances induce oxidative stress by generating reactive oxygen species (ROS), which can damage cellular components such as lipids, proteins, and nucleic acids. To counteract this, plants have evolved complex metabolic pathways to detoxify and process these harmful compounds. Oxidative stress in plants primarily arises from the overproduction of hydrogen peroxide (H2O2), superoxide anions (O2•-), singlet oxygen (1O2), and hydroxyl radicals (•OH), by-products of metabolic activities such as photosynthesis and respiration. The presence of xenobiotics leads to a notable increase in ROS, which can result in cellular damage and metabolic disruption. To combat this, plants have developed a strong antioxidant defense mechanism that includes enzymatic antioxidants that work together to eliminate ROS, thereby reducing their harmful effects. In addition to enzymatic defenses, plants also synthesize various non-enzymatic antioxidants, including flavonoids, phenolic acids, and vitamins. These compounds effectively neutralize ROS and help regenerate other antioxidants, offering extensive protection against oxidative stress. The metabolism of xenobiotic substances in plants occurs in three stages: the first involves modification, which refers to the chemical alteration of xenobiotics to make them less harmful. The second involves conjugation, where the modified xenobiotics are combined with other substances to increase their solubility, facilitating their elimination from the plant. The third stage involves compartmentalization, which is the storage or isolation of conjugated xenobiotics in specific parts of the plant, helping to prevent damage to vital cellular functions. Secondary metabolites found in plants, such as alkaloids, terpenoids, and flavonoids, play a vital role in detoxification and the defense against oxidative stress. Gaining a deeper understanding of the oxidative mechanisms and the pathways of xenobiotic metabolism in plants is essential, as this knowledge can lead to the formulation of plant-derived strategies aimed at alleviating the effects of environmental pollution and enhancing human health by improving detoxification and antioxidant capabilities, as discussed in this review.

Single-atom cobalt enables efficient catalytic ozonation for advanced wastewater treatment: Mechanisms and application

Heterogeneous catalytic ozonation (HCO) triggered by single-atom catalysts (SACs) is an emerging and promising advanced wastewater treatment technology. The catalytic ozonation mechanisms involving single-atom sites and the application of SAC-based HCO require further exploration. Herein, a single-atom Co catalyst with Co-N4 active sites was synthesized for HCO. Oxalic acid (OA) and p-hydroxybenzoic acid (pHBA) with different structural and chemical properties were utilized as the model contaminants. Compared with ozonation and Co nanoparticle-based HCO, single-atom Co-based HCO exhibited superior removal for the two model pollutants, with the removal rate constants of 0.098 and 0.076 min−1 for OA and pHBA, respectively. In the single-atom Co-based HCO, ozone was decomposed and converted to nonradical ROS of surface-adsorbed atomic oxygen (*Oad) and singlet oxygen (1O2). OA was mainly removed on the catalyst surface, relying on the adsorption by the catalyst and the oxidation of *Oad, while electron-rich pHBA was oxidized by O3 and 1O2 in solution. Furthermore, using 3–5 mm Al2O3 pellets as the carrier, single-atom Co-doped carbon-Al2O3 pellets were fabricated and applied for the advanced treatment of landfill leachate, and the COD decreased from 110 mg/L to 38 mg/L after treatment. This work provided new insights into the oxidation mechanisms and applications of SAC-based HCO.

A Bacterial Capturing, Neural Network-Like Carbon Nanotubes/Prussian Blue/Puerarin Nanocomposite for Microwave Treatment of Staphylococcus Aureus-Infected Osteomyelitis.

Staphylococcus aureus (S. aureus)-infected osteomyelitis is a deep tissue infection that cannot be effectively treated with antibiotics. Microwave (MW) thermal therapy (MTT) and MW dynamic therapy (MDT) based on MW-responsive materials are promising for the therapy of bacteria-infected osteomyelitis occurring in deep tissues that cannot be effectively treated with antibiotics. In this work, the MW-responsive system of carbon nanotubes (CNTs)/Prussian blue (PB)/puerarin (Pue) with stable network-like structures is constructed. The PB is grown in situ on the CNTs, and its introduction not only reduces the aggregation of the network-like structures of the CNTs, but the large specific surface area and mesoporous structure can also provide many active sites for the adsorption of oxygen and polar molecules. Pue is a natural anti-inflammatory material that reduces inflammation at the infection site. The composite of the CNTs and PB avoids the skin effect and thus can improve dielectric and reflection losses. The MW thermal response of CNTs/PB/Pue is mainly due to the occurrence of reflection loss, dielectric loss, multiple reflections and scattering, interface polarization, and dipole polarization. In addition, under MW irradiation, the CNTs/PB/Pue can produce reactive oxygen species (ROS), such as singlet oxygen (1O2), hydroxyl radical (·OH).

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

AbstractAs 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.

Theoretically obtained insight into the origin of singlet oxygen chemiluminescence probe, SOCL

Singlet oxygen (1O2) is well known in cancer photodynamic therapy, however, its real-time monitoring still faces certain challenges. In the past decades, a great deal of phenoxy-dioxetane-based chemiluminescence probes had become widespread to detect 1O2. However, much detail in this process is still unclear, for instance, the oxygen addition reaction happened in ground state or singlet biradical state. In this work, take SOCL as an example, the chemiluminescent mechanisms were studied by DFT and TDDFT method. The results found that both the neutral and anionic SOCL undergoes an oxygen addition reaction at ground state, not singlet biradical state. In the gas phase, DMSO and water, the deprotonation process makes the intrinsic barrier of anionic SOCL smaller than that of neutral SOCL. Moreover, the solvents can greatly reduce the reaction barrier and change the potential determining steps oxygen addition reaction. In contrast, the solvents have almost no effect on the decomposition mechanism.

Intelligent nanocatalyst mediated lysosomal ablation pathway to coordinate the amplification of tumor treatment

The production of reactive oxygen species (ROS) is susceptible to external excitation or insufficient supply of related participants (e.g., hydrogen peroxide (H2O2) and sensitizer), liming ROS-driven tumor treatment. Additionally, the lysosomal retention effect severely hinders the utilization of ROS-based nanosystems and severely restricted the therapeutic effect of tumors. Therefore, first reported herein an intelligent nanocatalyst, TCPP-Cu@MnOx ((MnII)1(MnIII)2.1(MnIV)2.6O9.35), and proposed a programmed ROS amplification strategy to treat tumors. Initially, the acidity-unlocked nanocatalyst was voluntarily triggered to generate abundant singlet oxygen (1O2) to mediate acid lysosomal ablation to assist nanocatalyst escape and partially induce lysosomal death, a stage known as lysosome-driven therapy. More unexpectedly, the high-yielding production of 1O2 in acid condition (pH 5.0) was showed compared to neutral media (pH 7.4), with a difference of about 204 times between the two. Subsequently, the escaping nanocatalyst further activated H2O2-mediated 1O2 and hydroxyl radical (•OH) generation and glutathione (GSH) consumption for further accentuation tumor therapy efficiency, which is based on the Fenton-like reaction and Russell reaction mechanisms. Therefore, in this system, a program-activatable TCPP-Cu@MnOx nanocatalyst, was proposed to efficiently destruct organelle-lysosome via1O2 inducing, and stimulated H2O2 conversion into highly toxic 1O2 and •OH in cytoplasm, constituting an attractive method to overcome limitations of current ROS treatment.