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JOURNAL OF FLUORESCENCE · 2024 · IF 2.6

Fabrication of Carbon Dots with Singlet Oxygen Generation and Their Potential Photodynamic Therapy Applications

Zuo Pengli,Peng Jun,Yao Yuyang,Tan Wei,Cheng Lan,Zhang Jinyu,Lu Xiuhua

Due to the unique chemical and biomedical properties of carbon dots (CDs), they have increasingly obtained the attention in many research fields, for example, bioimaging, fluorescence sensing, and drug delivery, etc. Recently, it was found that, under light excitation, CDs can also be exploited as a novel photosensitizer to prepare reactive oxygen species (ROS), which expand their applications in the field of photodynamic therapy for cancer treatment. Nevertheless, the high cost and complex fabrication approach of CDs significantly limit their applications. To address this issue, bottom-up routes usually utilize sustainable and inexpensive carbon precursor as starting materials, employed N,N-dimethylformamide (DMF) or ethanol as an environmental-friendly solvent. Bottom-up approach was energy efficient, and the purification process was relatively simple by dialysis. Therefore, carbon dots (CDs) were facilely fabricated in a one-pot solvothermal process using 1-aminoanthraquinone as a precursor, and their application as photosensitizers for in vitro antitumor cells, especially photodynamic therapy (PDT) was established. Then the photophysical and nanoscale dimensions properties of the fabricated CDs were characterized via TEM, UV–visible, fluorescence, and FT-IR spectroscopy. The synthesized N-doped CDs can easily dissolve in water, possess very low biotoxicity, yellow-light emission (maximum peak at 587 nm). More importantly, PDT studies demonstrated that the obtained CDs possess a high singlet oxygen yield of 35%, and exhibit significant phototoxicity to cancer cells upon 635 nm laser irradiation. These studies highlight that N-doped CDs can be facilely synthesized from only one precursor, and are a potentially novel theranostic agent for in vivo PDT.

CAS / MDL: 82-45-1
研究领域: 材料科学 · 生物医学工程 · 肿瘤学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF CONTROLLED RELEASE · 2024 · IF 10.5

Mitigating the skin phototoxicity of sonodynamic therapy via singlet oxygen-consuming metal-organic frameworks

Xuan Meng,Ning Zhao,Delong Zhao,Huanyu Zhao,Mengjiao Wang,Tianyang Zhao,Shuli Man,Yujie Dai,Yanjun Zhao

Sonodynamic anti-cancer therapy relies on the highly active singlet oxygen to induce potent cell death. However, the non-specific biodistribution of sonosensitizers post systemic administration results in a significant accumulation in the skin, and hence the daylight-induced phototoxicity. Here, we report a smart metal-organic framework-based nanocarrier with titanium dioxide (TiO 2 ) as the sonosensitizer for reduced phototoxicity in the skin. The organic ligand bears the imidazole moiety that can facilely consume singlet oxygen in the skin without compromising the anti-cancer efficacy. The reaction between imidazole moiety and singlet oxygen was confirmed by the density functional theory (DFT). Upon light irradiation, the nanocarrier can significantly reduce the phototoxicity post light irradiation in a range of normal cells in vitro and in a mouse model in vivo . Meanwhile, the ligand contains a disulfide moiety that can deplete glutathione and orchestrate the singlet oxygen-induced toxicity in the CT-26 colon cancer cells. As a result, the nanocarrier showed superior in vivo antitumor efficacy in a CT-26 tumor-bearing mice model, leading to significant suppression of tumor growth and improved animal survival rates. The current work provides a tailored nanoscale particle engineering approach to simultaneously minimize phototoxicity in the skin and sensitize sonodynamic anti-cancer therapy.

研究领域: 癌症治疗 · 纳米技术 · 材料科学 · 生物医学工程
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JOURNAL OF INORGANIC BIOCHEMISTRY · 2025 · IF 3.2

Exploring the singlet oxygen generation of iridium(III) complex containing phenothiazine for photodynamic therapy

Qinglin Chen,Hong Zeng,Jie Wu,Yuanyan Li,Yibao Li,Yongquan Wu

As a photochemical-based treatment approach, photodynamic therapy (PDT) relies on a photosensitiser (PS) that produces reactive oxygen species (ROS) after irradiation, which lead to irreparable cell damage and hence cell death. Cyclometalated iridium(III) complexes are often used in the development of PSs attributed to their rich photophysical properties with high quantum yields, large Stokes shifts, long-lived phosphorescence and good photostability. In addition, phenothiazine has excellent electron-donating ability and good rigid structure, its derivatives have been shown to possess activity against bacteria, malignant cells, and protozoa. In this work, we designed and synthesized two iridium(III) complexes DF-Ir-CHO and DF-Ir-PTZ. The DF-Ir-PTZ contains a novel ligand functionalized with phenothiazine. DF-Ir-PTZ has a better singlet oxygen ( 1 O 2 ) production quantum yield of 0.357 upon light irradiation and negligible dark cytotoxicity, suggesting that its biological safety is favorable. In addition, DF-Ir-PTZ was able to generate 1 O 2 and ROS in cancer cells under light conditions, leading to cell apoptosis of MCF-7.

研究领域: 无机化学 · 光医学 · 癌症治疗 · 光化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF HAZARDOUS MATERIALS · 2020 · IF 9.038

Photochemical reactivity of nitrogen-doped biochars under simulated sunlight irradiation: Generation of singlet oxygen

Jingjing Yang,Wen Zhu,Qian Yao,Guining Lu,Chen Yang,Zhi Dang

This study explored the photochemical activity of nitrogen-doped biochars (NCMs) by investigating their role in the degradation of sulfamethazine under simulated sunlight irradiation. NCMs with different doping amounts were prepared from corn straw and urea. Results showed that nitrogen doping can notably enhance the photodegradation of SMT rather than raw char. NCMs are of photochemical activity under visible light, which was confirmed by monochromatic light experiments. Quenching experiments, ESR, pH effect, and the influence of O 2 were carried out to explore the involved oxidation mechanism in this system. Results showed that 1 O 2 was the main reactive oxygen species . 1 O 2 was produced from O 2 by both energy transfer and electron transfer . DFT calculations showed that pyridinic N doping can decrease the energy of intersystem crossing and thus benefit the generation of 1 O 2 by triplet-triplet energy transfer. Results underscore the explicit importance of nitrogen element in photochemical reactivity of chars under simulated light irradiation even when the nitrogen content is low. It is a meaningful reminder for us to pay more attention to the assessment of the fate and transport of contaminants in the soil where it is rich in NCMs as well as the potential use of NCMs for pollutants remediation, since visible light is very abundant near the earth’s surface.

研究领域: 环境科学 · 化学
✓ 已验证 DOI PubMed 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Ru doped graphitic carbon nitride mediated peroxymonosulfate activation for diclofenac degradation via singlet oxygen

Ying Yan,Qinxue Yang,Qigao Shang,Jing Ai,Xiaofang Yang,Dongsheng Wang,Guiying Liao

Metals doped carbon nitride (CN) is considered as a class of promising efficient catalysts for peroxymonosulfate (PMS) activation in water purification. Herein, ruthenium doped carbon nitride (CNRu) was synthesized via a facile one-pot method, and CNRu was in form of Ru–N 2 that could efficiently activate PMS for DCF degradation and detoxification via nonradical pathway. DCF was completely removed within 10 min under the optimized condition in a wide working pH range of 3.00–9.00, while other traditional transition metals (e.g. Fe, Co, Ni, Cu) doped CN showed negligible removal of DCF due to adsorption rather than activation of PMS, which was demonstrated by DFT calculations. CNRu showed high stability and reusability after seven cycles and very few Ru leaching was detected in DCF degradation process. Ru was highly dispersed in form of Ru–N bond via coordinating to pyridine nitrogen, and the electron defect transfer between Ru and coordinated N, rather than redox cycle of Ru, mediated superoxide radicals (O 2 •− ) evolution, which was further hydrolyzed into singlet oxygen ( 1 O 2 ) and responsible for DCF removal. Thus, the CNRu/PMS system showed high tolerance to inorganic anions. Much lower toxic intermediates/products than DCF were obtained via the strong electrophilic attack reaction between 1 O 2 and DCF in CNRu/PMS system. This study displayed a new practical application prospect of ruthenium-based materials for high-efficient removal and detoxification of DCF from wastewater.

研究领域: 环境科学 · 催化材料 · 水处理技术
✓ 已验证 DOI 高影响因子
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RSC Advances · 2015 ·Vol. 5 ·期 100 ·81897-81904 · IF 3.84

Absorption-dependent generation of singlet oxygen from gold bipyramids excited under low power density

Junliang Lv,Xin Zhang,Nana Li,Baoju Wang,Sailing He

Metal nanoparticles (MNPs) can be used as a kind of new photodynamic therapy (PDT) agent because singlet oxygen (1O2) can be generated through directly sensitizing MNPs. Gold nanorods, gold nanoshells and gold nanoechinus were confirmed to be efficient PDT agents in vivo. However, the major excitation spectra of 1O2 from all of them are not in the optical biological window (650–900 nm). Herein, gold bipyramids (GBPs) with tunable absorption wavelength were prepared and used to explore 1O2 generation capability. 1O2 can be generated when GBPs were excited by continuous-wave light within a wide range of wavelengths (660–975 nm). The highest 1O2 generation capabilities were obtained when they were excited at the wavelength of the absorption peak, which was quite different from those of other gold nanomaterials. It was also found that 1O2 can be generated efficiently by a laser of very low power density (200 mW cm−2). The capability of GBPs for PDT has been demonstrated through the destruction of cancer cells. The synergistic effect of PDT and photothermal therapy for the destruction of cancer cells was also demonstrated.

✓ 已验证 DOI 高影响因子
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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 5 ·1-8 · IF 5.705

A fluorescent nanoprobe for real-time monitoring of intracellular singlet oxygen during photodynamic therapy

Ping Jian-tao,Peng Hong-shang,Qin Jinglei,You Fang-tian,Wang Yi-quan,Chen Gen-xiang,Song Min

Sensing of intracellular singlet oxygen ( 1 O 2 ) is required in order to optimize photodynamic therapy (PDT). An optical nanoprobe is reported here for the optical determination of intracellular 1 O 2 . The probe consists of a porous particle core doped with the commercial 1 O 2 probe 1,3-diphenylisobenzofuran (DPBF) and a layer of poly-L-lysine. The nanoparticle probes have a particle size of ~80 nm in diameter, exhibit good biocompatibility, improved photostability and high sensitivity for 1 O 2 in both absorbance (peak at 420 nm) and fluorescence (with excitation/emission peaks at 405/458 nm). Nanoprobes doped with 20% of DPBF are best suited even though they suffer from concentration quenching of fluorescence. In comparison with the commercial fluorescent 1 O 2 probe SOSG, 20%-doped DPBF-NPs (aged) shows higher sensitivity for 1 O 2 generated at an early stage. The best nanoprobes were used to real-time monitor the PDT-triggered generation of 1 O 2 inside live cells, and the generation rate is found to depend on the supply of intracellular oxygen. A fluorescent nanoprobe featured with refined selectivity and improved sensitivity towards 1 O 2 was prepared from the absorption-based probe DBPF and used to real-time monitoring of the generation of intracellular 1 O 2 produced during PDT.

研究领域: 生物医学工程 · 化学 · 光学 · 诊疗学
✓ 已验证 DOI PubMed 高影响因子
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2021 · IF 19.503

Oxygen-vacancy-mediated energy transfer for singlet oxygen generation by diketone-anchored MIL-125

Wentao Zhang,Wenguang Huang,Jiyuan Jin,Yonghai Gan,Shujuan Zhang

The importance of singlet oxygen ( 1 O 2 ) in synthesis of fine chemicals, inactivation of viruses and bacteria, degradation of pollutants, and photodynamic therapy has promoted the research on photocatalytic generation of 1 O 2 . Metal-organic frameworks (MOFs), owing to the tunable structure, are good candidate photocatalysts for 1 O 2 generation. However, due to the poor visible-light absorption capacity and the invalid recombination of charge carriers, the 1 O 2 generation yields of most MOFs are still limited. Here, we demonstrate that β -diketone anchoring could improve the photocatalytic generation of 1 O 2 by MIL-125 through enhanced energy transfer. The enhanced energy transfer was attributed to both the narrowed bandgap and the diketone-derived oxygen vacancies, which function as the trapping sites for charge carriers. The results here shed light on the generation of 1 O 2 by visible-light-responsive MOFs and provide a new strategy for the design of MOFs-based photocatalysts.

CAS / MDL: 98-00-0 75-65-0
研究领域: 光催化 · 材料科学 · 化学工程 · 环境科学
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BIOLOGIA PLANTARUM · 2011 ·Vol. 55 ·期 4 ·669-674 · IF 1.582

Singlet oxygen as a signaling transducer for modulating artemisinin biosynthetic genes in Artemisia annua

Zeng Q. -P.,Zeng X. -M.,Yang R. -Y.,Yang X. -Q.

Although crosstalk between cytosolic and plastidic terpenoid pathways has been validated in many plant species, we report here for the first time a striking elevation of the nucleus-encoded artemisinin biosynthesis relevant DBR2 mRNA following the incubation of plants with fosmidomycin (FM). FM decreased singlet oxygen ( 1 O 2 ) scavengers such as β-carotene and α-tocopherol and subsequently invoked 1 O 2 burst. The treatment of plants with fluridone (FD) neither decreased α-tocopherol content nor triggered 1 O 2 emission. In conclusion, FM can up-regulate 1 O 2 -sensitive nuclear genes responsible for artemisinin biogenesis by mitigating the accumulation of plastidic scavenging terpenoids, thereby eliciting 1 O 2 generation and initiating 1 O 2 retrograde signaling.

CAS / MDL: 59756-60-4
研究领域: 植物生物化学 · 分子遗传学 · 植物化学
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RSC Advances · 2012 ·Vol. 2 ·期 32 ·12378-12383 · IF 0

Singlet oxygen photogeneration and 2,4,6-TCP photodegradation at Pt/TiO2 under visible light illumination

Xuefeng Hu,Huanhuan Ji,Lei Wu

Pure and Pt nanoparticle-modified rutile TiO2 were synthesized via hydrolysis of TiCl4 in the absence or presence of Pt nanoparticles. HRTEM, XRD, and SEM were used to characterize the structure of the prepared catalysts. The resulting modified TiO2 catalysts show extended visible light absorbance. Photodegradation of 2,4,6-trichlorophenol (2,4,6-TCP) over these photocatalysts was investigated under visible light illumination. The Pt nanoparticles facilitate the separation of photogenerated electron–hole pairs at low Pt content, then enhances the photodegradation rate of 2,4,6-TCP. 0.18Pt–TiO2 achieved the best photocatalytic activity among the tested catalysts. It was found that singlet oxygen rather than ˙OH acts as the main oxidative species for the degradation of 2,4,6-TCP according to the experimental results. The degradation intermediates of 2,4,6-TCP were identified and the degradation pathway was proposed. Pt nanoparticles on TiO2 significantly enhance O2 adsorption and the formation of ˙O2−. The rutile surface is a favorable condition for stabilizing ˙O2−. These properties of the Pt nanoparticle-modified rutile TiO2 facilitate the formation of 1O2via the reaction of superoxide anions with holes.

CAS / MDL: 88-06-2
研究领域: 环境科学 · 材料科学 · 光催化技术
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Optical Materials Express · 2017 ·Vol. 7 ·期 3 ·913-923 · IF 2.591

Synthesis and singlet oxygen activities of near infrared photosensitizers by conjugation with upconversion nanoparticles

Qian Yang,Chuang Zhao,Jun Zhao,Yong Ye

Interaction between upconversion nanoparticles (UCNPs) and natural photosensitizers (Ps) has not been investigated so far. In order to make new near infrared photosensitizers, the conjugates (Ps-UCNPs) were synthesized by NaYF4 as a substrate and hydrothermal reaction of lanthanide ions Yb3+ with Er3+ or Tm3+, and then interaction with pheophorbide A (Pha) and resveratrol (Res) respectively. Based on the intensity of the fluorescence emission by Ps-UCNPs, the optimal reaction conditions are 16 mM Yb3+/0.4 mM Er3+ at 120°C for 20 h for Pha-UCNPs, and 80 mM Yb3+/0.1 mM Tm3+ at 180°C for 20 h for Res-UCNPs. The nanoparticles have a hexagonal phase or cubic phase with an average diameter size of 220 nm, and selectively emit the stronger red (670 nm) or violet (380 nm) fluorescence. Pha-UCNPs show the strong effects, and the maximum yield of singlet oxygen was seven times more than UCNPs and pheophorbide A alone under 980 nm illumination. It is attributed to the efficient resonance energy transfer from UCNPs to pheophorbide A. Pha-UCNPs is an effective NIR photosensitizer with potential for deep tissue disease photodynamic therapy.

研究领域: 生物医学工程 · 纳米医学
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CHEMISTRY OF MATERIALS · 2018 · IF 9.89

Synthesis of Metal–Organic Framework Nanosheets with High Relaxation Rate and Singlet Oxygen Yield

Yuewu Zhao,Ye Kuang,Min Liu,Jine Wang,Renjun Pei

A novel gadolinium–porphyrin metal–organic framework (MOF) nanosheet was synthesized by coordination chelation between gadolinium(III) ions and 4,4,4,4-(porphine-5,10,15,20-tetrayl) tetrakis (benzoic acid) (TCPP). The mechanism and molecular structure of the prepared Gd-TCPP products were analyzed through the comparison of 4,4,4,4-(porphine-5,10,15,20-tetrayl) tetrakis (benzenesulfonic acid) (TPPS) and TCPP. The Gd-TCPP MOF nanosheets exhibit a high relaxation rate of 40.8 mM–1 s–1, which is better than the rates for most reported contrast agents. In addition, the photosensitive activity of the Gd-TCPP nanosheets was enhanced compared to TCPP owing to the special periodic porous structure of the MOF, indicating that the Gd-TCPP nanosheets could produce the singlet oxygen (1O2) more effectively under irradiation by visible light. Performance enhancement was observed for both metal ions and organic ligands in the Gd-TCPP MOF nanosheets. This study presents a new concept in the development bifunctional MOF nanomaterials with enhanced performance in magnetic resonance imaging and photodynamic therapy.

CAS / MDL: 14609-54-2
研究领域: 材料科学 · 医学影像 · 光敏剂研究
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