Photosensitizer Encryption with Aggregation Enhanced Singlet Oxygen Production

Bloyet, Clarisse; Sciortino, Flavien; Matsushita, Yoshitaka; Karr, Paul A.; Liyanage, Anuradha; Jevasuwan, Wipakorn; Fukata, Naoki; Maji, Subrata; Hynek, Jan; D’Souza, Francis; Shrestha, Lok Kumar; Ariga, Katsuhiko; Yamazaki, Tomohiko; Shirahata, Naoto; Hill, Jonathan P.; Payne, Daniel T.

doi:10.1021/jacs.2c02596

Cited by 27 publications

(19 citation statements)

References 111 publications

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“…As shown in Figure S23, for Fe 1 /ND SAC, after adding 1 O 2 quencher, 2,2,6,6-tetramethyl-4-piperidinyloxyl (TEMP), into reaction system, no degradation activity of TC was observed. Meanwhile, in the corresponding EPR results (Figure d and Figure S24), three obvious peaks ascribed to TEMP- 1 O 2 species were identified. − Nevertheless, after introducing 5,5-dimethyl-1-pyrroline N -oxide (DMPO) to capture • OH, • SO 4 – and • O 2 – , only a weak DMPO- • OH signal emerged and there was scarcely any characteristic peak for • SO 4 – or • O 2 – . These results suggested that the 1 O 2 active species was solely generated in Fe 1 /ND-PMS system.…”

Section: Resultsmentioning

confidence: 99%

Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation

Yang

Sun

et al. 2022

ACS Catal.

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The design of catalysts and catalytic processes for high efficiency and selectivity of important singlet oxygen ( 1 O 2 ) active species generation in oxidation reactions is still challenging, especially utilizing abundant and environmental O 2 without photoelectric field or extra thermal condition. Herein, a curved Fe 1 −N 4 single-atom site is developed by incorporating isolated Fe single atom into nanodiamond with high-curvature surface. It leads to an unprecedented relay catalysis route, in which the activation of O 2 is coupled with peroxymonosulfate (PMS) activation, to efficiently generate 1 O 2 species. In detail, PMS is first activated on the curved Fe 1 −N 4 site with electron donation to Fe single atom, accompanied by 1/2 equiv of 1 O 2 production. More importantly, due to the compressive strain of the curved Fe 1 −N 4 site with a higher energy level of Fe 3d z 2 orbital, the curved Fe 1 −N 4 site with electron charge acquisition can directly transfer electron to O 2 molecule and consequently trigger the generation of additional 1 equiv of 1 O 2 . Taking advantage of this tandem process, remarkable efficiency and near 100% selectivity of 1 O 2 generation are achieved, which leads to an ultrahigh metal catalytic efficiency of 0.77 min −1 for tetracycline oxidative degradation and an outstanding catalytic performance for benzene alcohol selective oxidation. This work, on the one hand, opens up an efficient way to generate 1 O 2 by O 2 activation in peroxide-based catalytic oxidations, and on the other hand, develops a bifunctional Fe 1 −N 4 single-atom site with rapid electron gain and loss ability, which sheds light on further improving catalytic performance in single-atom catalysts via relay catalysis mechanism.

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Section: Resultsmentioning

confidence: 99%

Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation

Yang

Sun

et al. 2022

ACS Catal.

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“…A photosensitizer (PS) is needed for PDT. Under the excitation of a laser, the PS converts the oxygen into reactive oxygen species (ROS), many of which are singlet oxygen ( 1 O 2 ) species. − Porphyrin-based PSs account for a large proportion of PSs. − They are mainly divided into hematoporphyrins, metalloporphyrins, , porphycenes, , pheophorbides, , purpurins, chlorins, , protoporphyrin, , and phthalocyanines. , These porphyrin PSs have shown prodigious potentials in PDT, and some of the porphyrin derivatives (e.g., Photofrin, Visudyne, and Foscan) have been approved by the Food and Drug Administration (FDA) and applied in the clinic. Although porphyrin PSs possess good biosafety and a suitable biological wavelength window (650–900 nm) for deep tissue penetration, their poor water solubility significantly lowers 1 O 2 generation in physiological solution and thereby limits their biomedical applications. , Hence, various strategies were proposed to enhance the water solubility of the porphyrin PSs.…”

Section: Introductionmentioning

confidence: 99%

Apoptosis-Amplified Assembly of Porphyrin Nanofiber Enhances Photodynamic Therapy of Oral Tumor

et al. 2023

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Oral squamous cell carcinoma (OSCC) is the most common oral cancer, having high recurrence and metastasis features. In addition to surgery, photodynamic therapy (PDT) is considered as another effective approach for OSCC treatment. The water solubility of currently available PDT photosensitizers (PSs) is poor, lowering their singlet oxygen (1O2) yield and consequent PDT efficiency. Strategies of PS assembly have been reported to increase 1O2 yield, but it is still possible to further enhance PDT efficiency. In this work, we utilized apoptosis to amplify the assembly of porphyrin nanofibers for enhanced PDT of OSCC. A water-soluble porphyrin derivative, Ac-Asp-Glu-Val-Asp-Asp-TPP (Ac-DEVDD-TPP), was designed for this purpose. Upon caspase-3 (Casp3, an activated enzyme during apoptosis) cleavage and laser irradiation, Ac-DEVDD-TPP was converted to D-TPP, which spontaneously self-assembled into porphyrin nanofibers, accompanied by 1.4-fold and 2.1-fold 1O2 generations in vitro and in cells, respectively. The as-formed porphyrin nanofiber induced efficient cell apoptosis and pyroptosis. In vivo experiments demonstrated that, compared with the scrambled control compound Ac-DEDVD-TPP, Ac-DEVDD-TPP led to 6.2-fold and 1.3-fold expressions of Casp3 in subcutaneous and orthotopic oral tumor models, respectively, and significantly suppressed the tumors. We envision that our strategy of apoptosis-amplified porphyrin assembly might be applied for OSCC treatment in the clinic in the near future.

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“…Generally, an ideal PS is expected to possess the necessary virtues, including a straightforward synthetic approach, high chemical purity, excellent biocompatibility and water solubility [ 13 ]. In recent years, a series of PSs have been fabricated, greatly facilitating the development of PDT techniques [ 14 , 15 , 16 , 17 , 18 ]. Moreover, dual or multi-modal treatment strategies with stimuli-responsive drug delivery have demonstrated satisfactory anticancer performance, such as PDT combined with chemotherapy [ 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

A pH-Responsive Drug Delivery System Based on Conjugated Polymer for Effective Synergistic Chemo-/Photodynamic Therapy

et al. 2023

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Stimuli-responsive drug release and photodynamic therapy (PDT) have aroused extensive attention for their enormous potential in antitumor treatment. pH-responsive drug delivery systems (PFE-DOX-1 and PFE-DOX-2) based on water-soluble conjugated polymers were constructed in this work for high-performance synergistic chemo-/PDT therapy, in which the anticancer drug doxorubicin (DOX) is covalently attached to the side chains of the conjugated polymers via acid-labile imine and acylhydrazone bonds. Concurrently, the intense fluorescence of poly(fluorene-co-ethynylene) (PFE) is effectively quenched due to the energy/electron transfer (ET) between the PFE-conjugated backbone and DOX. Effective pH-responsive drug release from PFE-DOX-2 is achieved by the cleavage of acylhydrazone linkages in the acidic tumor intracellular microenvironment. Additionally, the drug release process can be monitored by the recovered fluorescence of conjugated polymers. Furthermore, the conjugated polymers can produce reactive oxygen species (ROS) under light irradiation after drug release in an acidic environment, which prevents possible phototoxicity to normal tissues. It is noted that PFE-DOX-2 demonstrates remarkable antitumor cell performance, which is attributed to its efficient cell uptake and powerful synergistic chemo-/PDT therapeutic effectiveness. This report thus provides a promising strategy for in vivo anticancer treatment with the construction of a stimuli-responsive multifunctional drug delivery system.

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Photosensitizer Encryption with Aggregation Enhanced Singlet Oxygen Production

Cited by 27 publications

References 111 publications

Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation

Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation

Apoptosis-Amplified Assembly of Porphyrin Nanofiber Enhances Photodynamic Therapy of Oral Tumor

A pH-Responsive Drug Delivery System Based on Conjugated Polymer for Effective Synergistic Chemo-/Photodynamic Therapy

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Photosensitizer Encryption with Aggregation Enhanced Singlet Oxygen Production

Cited by 27 publications

References 111 publications

Unprecedented Relay Catalysis of Curved Fe1–N4 Single-Atom Site for Remarkably Efficient 1O2 Generation

Unprecedented Relay Catalysis of Curved Fe1–N4 Single-Atom Site for Remarkably Efficient 1O2 Generation

Apoptosis-Amplified Assembly of Porphyrin Nanofiber Enhances Photodynamic Therapy of Oral Tumor

A pH-Responsive Drug Delivery System Based on Conjugated Polymer for Effective Synergistic Chemo-/Photodynamic Therapy

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Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation

Unprecedented Relay Catalysis of Curved Fe₁–N₄ Single-Atom Site for Remarkably Efficient ¹O₂ Generation