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学者姓名：郑碧远
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Abstract ：
Photodynamic immunotherapy (PIT) has emerged as a promising approach for efficient eradication of primary tumors and inhibition of tumor metastasis. However, most of photosensitizers (PSs) for PIT exhibit notable oxygen dependence. Herein, a concept emphasizing on transition from molecular PSs into semiconductor-like photocatalysts is proposed, which converts the PSs from type II photoreaction to efficient type I photoreaction. Detailed mechanism studies reveal that the nanostructured phthalocyanine aggregate (NanoNMe) generates radical ion pairs through a photoinduced symmetry breaking charge separation process, achieving charge separation through a self-substrate approach and leading to exceptional photocatalytic charge transfer activity. Additionally, a reformed phthalocyanine aggregate (NanoNMO) is fabricated to improve the stability in physiological environments. NanoNMO showcases significant photocytotoxicities under both normoxic and hypoxic conditions and exhibits remarkable tumor targeting ability. Notably, the NanoNMO-based photodynamic therapy and PD-1 checkpoint inhibitor-based immunotherapy synergistically triggers the infiltration of cytotoxic T lymphocytes into the tumor sites of female mice, leading to the effective inhibition of breast tumor growth.
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| GB/T 7714 | Liu, Hao , Li, Ziqing , Zhang, Xiaojun et al. Phthalocyanine aggregates as semiconductor-like photocatalysts for hypoxic-tumor photodynamic immunotherapy [J]. | NATURE COMMUNICATIONS , 2025 , 16 (1) . |
| MLA | Liu, Hao et al. "Phthalocyanine aggregates as semiconductor-like photocatalysts for hypoxic-tumor photodynamic immunotherapy" . | NATURE COMMUNICATIONS 16 . 1 (2025) . |
| APA | Liu, Hao , Li, Ziqing , Zhang, Xiaojun , Xu, Yihui , Tang, Guoyan , Wang, Zhaoxin et al. Phthalocyanine aggregates as semiconductor-like photocatalysts for hypoxic-tumor photodynamic immunotherapy . | NATURE COMMUNICATIONS , 2025 , 16 (1) . |
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The weakness of visible and near-infrared light penetration depth limits the application of photodynamic therapy (PDT) in deep-seated tumors. Based on the high penetrability of X-rays, X-ray-induced PDT (X-PDT) is a promising new method for treating deep-seated tumors. However, it requires the development of suitable X-ray-induced sensitizers that could employ X-ray energy to produce reactive oxygen species (ROS) efficiently. In this study, a novel X-ray-induced sensitizer (NanoSRF) was developed through a microemulsion method, in which copper iodine cluster compound Cu2I2(tpp)2(2,5-dm-pz) (CIP) and rose bengal (RB) worked as scintillator and photosensitizer, respectively. CIP was synthesized by a simple mechanical grinding method, and subsequently folic acid (FA)-modified albumin was introduced to enable its alliance with RB. NanoSRF exhibited excellent dispersion stability and generated a large amount of ROS under X-ray irradiation. The results of in vitro studies demonstrated its high selectivity for FA receptor-positive cancer cells. Following systemic administration, NanoSRF accumulated in H22 tumors of xenograft-bearing mice, and X-ray irradiation (5.46 Gy) induced a significant inhibition rate of 96.7% in tumor growth. This study pioneers the use of copper iodide cluster as a scintillator in X-PDT, presenting new possibilities for designing scintillators with exceptional X-ray absorption and efficient X-PDT capabilities. (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic). (sic)(sic)X(sic)(sic)(sic)(sic)(sic)(sic)(sic), X(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)X(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)X(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)Cu2I2(tpp)2(2,5-dm-pz) (CIP), (sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(RB)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)CIP(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)X(sic)(sic)(sic)(sic)(sic)(NanoSRF), (sic)(sic)(sic) (sic)(sic)CIP(sic)(sic)(sic)(sic), RB(sic)(sic)(sic)(sic). NanoSRF(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic) (sic)(sic)X(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)ROS. (sic)(sic)(sic)(sic)(sic)(sic), NanoSRF(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)(sic)(sic), NanoSRF(sic)(sic)(sic)(sic)(sic)(sic)H22 (sic)(sic)(sic)(sic)(sic), (sic)X(sic)(sic)(sic)(sic)(5.46 Gy)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) 96.7%. (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)X-PDT, (sic)(sic)(sic)(sic)(sic) (sic)(sic)X(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)X-PDT(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).
Keyword ：
copper iodine cluster copper iodine cluster nanoparticle nanoparticle target target tumor tumor X-ray-induced photodynamic therapy X-ray-induced photodynamic therapy
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| GB/T 7714 | Xie, Wei , Chen, Junyun , Zhang, Yuxin et al. Copper iodine cluster nanoparticles for tumor-targeted X-ray-induced photodynamic therapy [J]. | SCIENCE CHINA-MATERIALS , 2024 , 67 (10) : 3358-3367 . |
| MLA | Xie, Wei et al. "Copper iodine cluster nanoparticles for tumor-targeted X-ray-induced photodynamic therapy" . | SCIENCE CHINA-MATERIALS 67 . 10 (2024) : 3358-3367 . |
| APA | Xie, Wei , Chen, Junyun , Zhang, Yuxin , Zheng, Biyuan , Li, Xingshu , Huang, Jian-Dong . Copper iodine cluster nanoparticles for tumor-targeted X-ray-induced photodynamic therapy . | SCIENCE CHINA-MATERIALS , 2024 , 67 (10) , 3358-3367 . |
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The development of a simple drug formulation capable of achieving both activatable type I photoreaction and tumor-responsive release of immunomodulator is crucial for advancing photodynamic immunotherapy (PDIT). Herein, we present a nanostructured photosensitizer (NP5) that is activated by the acidic tumor microenvironment to produce type I reactive oxygen species (ROS) under light irradiation and release the immunomodulator demethylcantharidin (DMC) for PDIT. The NP5 is formed by self-assembly of a versatile phthalocyanine molecule which is composed of DMC and phthalocyanine linked via a pH-responsive amide bond. NP5 produces minimal ROS under light irradiation at the condition of pH 7.4. However, NP5 can release DMC at the condition of pH 6.5 and concurrently trigger type I photoreactions. The results of in vivo experiments indicate that NP5-mediated PDIT induce the increase of cytotoxic T lymphocytes and decrease of regulatory T lymphocytes, which can effectively inhibit the bilateral tumor growth. This work is anticipated to serve as a reference for the development of innovative agents for precise PDIT of hypoxic tumors.
Keyword ：
Activatable photosensitizer Activatable photosensitizer Demethylcantharidin Demethylcantharidin Photodynamic immunotherapy Photodynamic immunotherapy Phthalocyanine Phthalocyanine Type I Type I
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| GB/T 7714 | Zhang, Ling , Que, Rong-Bin , Ke, Ting-Ting et al. A tumor-pH-responsive phthalocyanine as activatable type I photosensitizer for improved photodynamic immunotherapy [J]. | JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY , 2024 , 261 . |
| MLA | Zhang, Ling et al. "A tumor-pH-responsive phthalocyanine as activatable type I photosensitizer for improved photodynamic immunotherapy" . | JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY 261 (2024) . |
| APA | Zhang, Ling , Que, Rong-Bin , Ke, Ting-Ting , Wang, Chao , Xie, Wei , Sun, Hong-Jie et al. A tumor-pH-responsive phthalocyanine as activatable type I photosensitizer for improved photodynamic immunotherapy . | JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY , 2024 , 261 . |
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Phthalocyanines (Pcs) are considered promising in cancer phototherapy. However, their maximum absorption wavelengths are only around 700 nm, which cannot allow deep tissue penetration and leads to poor therapeutic efficacy. To expand their clinical application, significantly shifting their absorption to longer wavelengths is urgently required. Dye J-aggregates exhibit a redshifted absorption relative to its monomer. However, Pc Jaggregates with enormous-redshifted and intense absorption is rarely reported, and little is known about the relationships between Pc structure and J-aggregation. Herein, such Pc J-aggregates are ingeniously conceived. With a yeast beta-D-glucan-ursodeoxycholic acid conjugate as a potential tumor-associated macrophages (TAMs)targeting carrier and 1-(4-carboxyethylphenoxy) zinc (II) phthalocyanine (Pc1) as a model, Pc1 J-aggregate nanoparticle (NanoPc1) is obtained via ultrasonication-aided emulsification-solvent evaporation technique. NanoPc1 displays strong absorption at 830 nm, with a 156 nm redshift. Further investigation on another twentyfour Pcs demonstrates that unsubstituted zinc (II) or magnesium (II) Pc and hydrophobic mono-substituted zinc (II) or magnesium (II) Pcs with mono-substituted phenoxy or phenylthio or naphthoxy as a substituent can readily form desired Pc J-aggregates with significant redshifts (140-165 nm). The other Pcs fail to form expected J-aggregates probably due to absence of central metals, steric hindrance on central metals (atoms), forming axial coordination on central metals, disorder tendency during self-assembly or hydrophilicity. The theoretical calculation indicates that Pc1 in its J-aggregates exhibits a spiral-like arrangement, and the reduction in the energy gap between HOMO and LUMO and variation of intermolecular it-it interaction caused by J-aggregate formation are responsible for the huge redshift. Additionally, using NanoPc1 as an exemplar, such Pc J-aggregate nanoparticles are substantiated to afford TAMs-targeted and efficient tri-modal imaging and photothermal therapy in a H22 mouse model.
Keyword ：
J -aggregate J -aggregate Large redshift Large redshift Multimodal phototheranostics Multimodal phototheranostics Phthalocyanine Phthalocyanine Yeast glucan Yeast glucan
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| GB/T 7714 | Tang, Fengxiang , Yu, Haodong , Huang, Yanzong et al. Phthalocyanine J-aggregate nanoparticles with enormous-redshifted and intense absorption: Potential structure-J-aggregation relationships and application in tumor-associated macrophages-targeted phototheranostics [J]. | CHEMICAL ENGINEERING JOURNAL , 2024 , 496 . |
| MLA | Tang, Fengxiang et al. "Phthalocyanine J-aggregate nanoparticles with enormous-redshifted and intense absorption: Potential structure-J-aggregation relationships and application in tumor-associated macrophages-targeted phototheranostics" . | CHEMICAL ENGINEERING JOURNAL 496 (2024) . |
| APA | Tang, Fengxiang , Yu, Haodong , Huang, Yanzong , Zhao, Xue , Chen, Zixuan , Ma, Honglin et al. Phthalocyanine J-aggregate nanoparticles with enormous-redshifted and intense absorption: Potential structure-J-aggregation relationships and application in tumor-associated macrophages-targeted phototheranostics . | CHEMICAL ENGINEERING JOURNAL , 2024 , 496 . |
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With a view to developing highly efficient photosensitizers for photodynamic therapy, herein, we prepared a series of tetra-substituted zinc(II) phthalocyanine analogues (ZPOP, ZPSP, ZPNP, and ZPNPM) modified with O-, S-, and N-bridging substituents, respectively. Compared to O- and S-bridging analogues, the N-bridging phthalocyanines showed eminent red-shifted Q band absorption (750-780 nm) and excellent reactive oxygen species (ROS) generation ability (Phi Delta = 0.90-0.97), due to the HOMO destabilization, as well as the smaller Delta EST. To improve the hydrophility and biocompatibility, we further prepared two N-bridging zinc(II) phthalocyanines (ZPN1 and ZPN2) modified with morpholine and N,N-dimethylamine moieties, respectively, along with their quaternized counterparts (QZPN1 and QZPN2). These compounds exhibited NIR-absorbing Q bands at 774-777 nm and efficient ROS generation ability in aqueous solutions, especially formulated with 1 % Cremophor EL (Cel). In vitro studies indicated that ZPN2 exhibited the highest photodynamic activity against HepG2 cells (IC50 = 0.44 +/- 0.02 mu M), because of superior cellular uptake and moderate ROS generation ability. Moreover, ZPN2 could selectively accumulate and retain in tumor tissue of H22 tumor-bearing mice. The work presents a new strategy for the development of NIR-absorbing photosensitizers.
Keyword ：
N -bridging phthalocyanine N -bridging phthalocyanine Near-infrared Near-infrared Photodynamic therapy Photodynamic therapy Reactive oxygen species Reactive oxygen species
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| GB/T 7714 | Ke, Mei-Rong , Wang, Chao , He, Qinxue et al. N-bridging tetra-substituted zinc(II) phthalocyanines with Q-band absorption up to 780 nm and eminent photosensitizing activities for photodynamic therapy [J]. | DYES AND PIGMENTS , 2024 , 227 . |
| MLA | Ke, Mei-Rong et al. "N-bridging tetra-substituted zinc(II) phthalocyanines with Q-band absorption up to 780 nm and eminent photosensitizing activities for photodynamic therapy" . | DYES AND PIGMENTS 227 (2024) . |
| APA | Ke, Mei-Rong , Wang, Chao , He, Qinxue , Que, Rongbin , Wei, Ying , Zheng, Bi-Yuan et al. N-bridging tetra-substituted zinc(II) phthalocyanines with Q-band absorption up to 780 nm and eminent photosensitizing activities for photodynamic therapy . | DYES AND PIGMENTS , 2024 , 227 . |
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Although specific responsive theranostics biomaterials were essencial for precision medicine, the univariate responsive strategy was restricted by high false-positive rates. Herein, we designed a novel phthalocyanine-iron-based complex FeS2@PcD, as a theranostics nanoreactor, which was program-regulated by bivariate factors of H+ and H2O2 in tumor microenvironment (TME). We found that FeS2@PcD had the excellent capability of tumor fluorescence imaging (FLI), with a 52.21-fold increase in fluorescence signal by the programmable response, while the signal of the univariate factor was almost unchanged. We also revealed that FeS2@PcD reacted with H+ to release PcD and produced Fe2+, then Fe2+ was further oxidized by H2O2 to produce Fe3+, finally recovering the fluorescence of PcD whose fluorescence activity was significantly suppressed due to the photoinduced electron transfer (PET) effect. Notably, except for fluorescence signal, magnetic resonance (MR) signal and sonosensitive activity of FeS2@PcD also changed from "OFF" state to "ON" state under the programmable regulation of H+ and H2O2. The program-regulated strategy based on FeS2@PcD realized specific fluorescence and MR dual-modality imaging-guided sono/chemodynamic therapies, representing a promising precision medicine approach.
Keyword ：
Dual -modality imaging Dual -modality imaging Programmable -regulation Programmable -regulation Sonosensitization Sonosensitization Specific Fe 3+-response Specific Fe 3+-response Tumor microenvironment Tumor microenvironment
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| GB/T 7714 | Li, Dong , Pan, Jie , Xu, Shuyu et al. Programmable phthalocyanine-iron-based nanoreactor for fluorescence/ magnetic resonance dual-modality imaging-guided sono/ chemodynamic therapies [J]. | CHEMICAL ENGINEERING JOURNAL , 2023 , 452 . |
| MLA | Li, Dong et al. "Programmable phthalocyanine-iron-based nanoreactor for fluorescence/ magnetic resonance dual-modality imaging-guided sono/ chemodynamic therapies" . | CHEMICAL ENGINEERING JOURNAL 452 (2023) . |
| APA | Li, Dong , Pan, Jie , Xu, Shuyu , Cheng, Bingwei , Wu, Shuaiying , Dai, Qixuan et al. Programmable phthalocyanine-iron-based nanoreactor for fluorescence/ magnetic resonance dual-modality imaging-guided sono/ chemodynamic therapies . | CHEMICAL ENGINEERING JOURNAL , 2023 , 452 . |
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Phthalocyanines are potentially promising photosensitizers (PSs) for photodynamic therapy (PDT), but the inherent defects such as aggregation-caused quenching effects and non-specific toxicity severely hinder their further application in PDT. Herein, we synthesized two zinc(II) phthalocyanines (PcSA and PcOA) monosubstituted with a sulphonate group in the alpha position with "O bridge" and "S bridge" as bonds and prepared a liposomal nanophotosensitizer (PcSA@Lip) by thin-film hydration method to regulate the aggregation of PcSA in the aqueous solution and enhance its tumor targeting ability. PcSA@Lip exhibited highly efficient production of superoxide radical (O-2(center dot-)) and singlet oxygen (O-1(2)) in water under light irradiation, which were 2.6-fold and 15.4-fold higher than those of free PcSA, respectively. Furthermore, PcSA@Lip was able to accumulate selectively in tumors after intravenous injection with the fluorescence intensity ratio of tumors to livers was 4.1:1. The significant tumor inhibition effects resulted in a 98% tumor inhibition rate after PcSA@Lip was injected intravenously at an ultra-low PcSA@Lip dose (0.8 nmol g(-1) PcSA) and light dose (30 J cm(-2)). Therefore, the liposomal PcSA@Lip is a prospective nanophotosensitizer possessing hybrid type I and type II photoreactions with efficient photodynamic anticancer effects.
Keyword ：
anticancer anticancer fluorescence imaging fluorescence imaging liposome liposome photodynamic therapy photodynamic therapy phthalocyanine phthalocyanine
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| GB/T 7714 | Chen, Zixuan , Zhao, Yuan-Yuan , Li, Li et al. A Sulfur-Bridging Sulfonate-Modified Zinc(II) Phthalocyanine Nanoliposome Possessing Hybrid Type I and Type II Photoreactions with Efficient Photodynamic Anticancer Effects [J]. | MOLECULES , 2023 , 28 (5) . |
| MLA | Chen, Zixuan et al. "A Sulfur-Bridging Sulfonate-Modified Zinc(II) Phthalocyanine Nanoliposome Possessing Hybrid Type I and Type II Photoreactions with Efficient Photodynamic Anticancer Effects" . | MOLECULES 28 . 5 (2023) . |
| APA | Chen, Zixuan , Zhao, Yuan-Yuan , Li, Li , Li, Ziqing , Fu, Shuwen , Xu, Yihui et al. A Sulfur-Bridging Sulfonate-Modified Zinc(II) Phthalocyanine Nanoliposome Possessing Hybrid Type I and Type II Photoreactions with Efficient Photodynamic Anticancer Effects . | MOLECULES , 2023 , 28 (5) . |
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本发明公开了一种酞菁‑青蒿琥酯携氧脂质体复合物及其在肿瘤声动力治疗中的应用。所述脂质体复合物中同时含有携氧载体全氟三丁胺和酞菁锌‑青蒿琥酯偶联物，其在常氧和缺氧条件下，均可经超声波激发而产生较高量的单线态氧与明显的声敏活性，因而可以改善肿瘤缺氧微环境，具有较高的声动力抗癌活性，在缺氧肿瘤的治疗领域具有显著的应用前景。
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| GB/T 7714 | 李雪岩 , 黄剑东 , 柯美荣 et al. 酞菁-青蒿琥酯携氧脂质体复合物及在声动力中的应用 : CN202210710761.0[P]. | 2022-06-22 00:00:00 . |
| MLA | 李雪岩 et al. "酞菁-青蒿琥酯携氧脂质体复合物及在声动力中的应用" : CN202210710761.0. | 2022-06-22 00:00:00 . |
| APA | 李雪岩 , 黄剑东 , 柯美荣 , 李兴淑 , 郑碧远 . 酞菁-青蒿琥酯携氧脂质体复合物及在声动力中的应用 : CN202210710761.0. | 2022-06-22 00:00:00 . |
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本发明涉及植骨技术领域，提供了十六胺基或十六铵基修饰的酞菁锌及其制备方法和应用。 在锌酞菁结构中，3-(二甲基氨基)苯氧基取代基或3-(三甲基铵)苯氧基取代基存在于酞菁环周围的α位和β位。 得到的锌酞菁配合物具有高光敏活性和高水溶性的特点，以单体的形式存在于水中，有利于在水中发挥光动力活性； 而且，锌酞菁配合物的吸收光谱红移至720nm，位于更有利于穿透人体组织的近红外区。 因此，所述锌酞菁配合物具有高肿瘤靶向性和光动力抑瘤效应，并迅速清除体外，可用于制备光敏剂、光动力药物或光敏药物。 而且，本发明中所得锌酞菁配合物具有较高的光动力抗真菌活性。
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| GB/T 7714 | Huang Jiandong , Zheng Bingde , Ke Meirong et al. 十六烷基铵基修饰的酞菁及其制备方法和作为光动力药物的应用 : AU2021362841[P]. | 2021-02-03 00:00:00 . |
| MLA | Huang Jiandong et al. "十六烷基铵基修饰的酞菁及其制备方法和作为光动力药物的应用" : AU2021362841. | 2021-02-03 00:00:00 . |
| APA | Huang Jiandong , Zheng Bingde , Ke Meirong , Zheng Biyuan . 十六烷基铵基修饰的酞菁及其制备方法和作为光动力药物的应用 : AU2021362841. | 2021-02-03 00:00:00 . |
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本发明公开了一种具有双摄取通路的轴向磺酸基修饰酞菁硅及其制备方法和应用。本发明设计的酞菁硅可以通过磺酸阴离子和白蛋白介导的双摄取途径被HepG2细胞吸收，产生极高的光细胞毒性，IC50值为2.0 nM。另外，本发明所述的磺酸基修饰酞菁与白蛋白复合物不仅提高了酞菁的光活性(如荧光发射和活性氧的产生)，而且能在血液中的FBS的存在下完全解聚，产生最大的光敏活性。磺酸基修饰酞菁与白蛋白复合物的肿瘤靶向性也显著增强，能够实现有效的体内荧光成像和光动力治疗。这是首个阴离子酞菁通过有机阴离子转运多肽(OATP)途径摄取的例子，也是光敏剂通过分子和超分子介导的双重细胞摄取途径的首个例子。
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| GB/T 7714 | 黄剑东 , 刘浩 , 李兴淑 et al. 具有双摄取通路的轴向磺酸基修饰酞菁硅及其制备方法及和应用 : CN202210395012.3[P]. | 2022-04-15 00:00:00 . |
| MLA | 黄剑东 et al. "具有双摄取通路的轴向磺酸基修饰酞菁硅及其制备方法及和应用" : CN202210395012.3. | 2022-04-15 00:00:00 . |
| APA | 黄剑东 , 刘浩 , 李兴淑 , 柯美荣 , 郑碧远 . 具有双摄取通路的轴向磺酸基修饰酞菁硅及其制备方法及和应用 : CN202210395012.3. | 2022-04-15 00:00:00 . |
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