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JOURNAL OF CONTROLLED RELEASE · 2021 · IF 9.776

Unsaturated fatty acid-tuned assembly of photosensitizers for enhanced photodynamic therapy via lipid peroxidation

Yanxian Hou,Qiang Fu,Yafei Kuang,Dan Li,Yixin Sun,Zhe Qian,Zhonggui He,Jin Sun

Photodynamic therapy (PDT) destroys tumor cells mainly through singlet oxygen ( 1 O 2 ) generated by light-irradiated photosensitizers (PSs). However, the fleeting half-life of 1 O 2 greatly impairs PDT efficacy. Herein, we propose an unreported unsaturated fatty acid (UFA)-assisted PS co-assembly strategy to address this problem. Three UFAs, namely, oleic acid (OA), linoleic acid (LA) and linolenic acid (LNA), are capable of co-assembling with 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) into uniform nanoparticles. Under irradiation, TAPP produces 1 O 2 , which directly attacks tumor cells and simultaneously oxidizes UFAs to generate lipid hydroperoxides with sustained damage. Interestingly, the unsaturation degree of UFAs is not only related to their peroxidation rate but also has a remarkable impact on the intracellular TAPP release characteristic of the nanoparticles (NPs). The TAPP-LA NPs could release the cargo rapidly and produce the highest lipid peroxidation and reactive oxygen species levels upon irradiation. Such a unique finding sheds new light on UFA-based combination applications for enhanced photodynamic efficacy by boosting lipid peroxidation.

研究领域: 生物医学工程 · 肿瘤学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2020 · IF 5.162

Heparin modified photosensitizer-loaded liposomes for tumor treatment and alleviating metastasis in phototherapy

Dinglingge Cao,Huangjuan Li,Yuan Luo,Nianping Feng,Tianyuan Ci

Phototherapy holds promise in cancer treatment for its prominent antitumor efficacy and low systematic toxicity compared with traditional chemotherapy. However, the higher risk of tumor metastasis caused by the severe hypoxic state during phototherapy is a threat in practical use. Here, in order to tackle this challenge, we developed a delivery system via loading the photosensitizer indocyanine green (ICG) into the low molecular weight heparin (LMWH) modified liposomes (LMWH-ICG-Lip) to realize the synergistic effects between photosensitizer and drug vehicle, achieving better phototherapeutic efficacy and meanwhile alleviating the potential risk of tumor metastasis caused by phototherapy. In this system, besides elongating the photosensitizers' circulation time and enhancing their accumulating efficacy to tumor tissues, LMWH itself also exhibited anti-metastasis efficacy via inhibiting adhesion of platelets to tumor cells and decreasing migration and invasion capability of tumor cells. In vivo efficacy evaluation was conducted on orthotopic 4T1 breast cancer model, and the system of LMWH-ICG-Lip could alleviate metastasis potential of residual tumor cells after irradiation, and elicit optimistic antitumor and anti-metastasis efficacy for phototherapy.

CAS / MDL: 57-88-5
研究领域: 肿瘤学 · 药学 · 生物医学工程
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Small · 2016 ·Vol. 12 ·期 45 ·6223-6232 · IF 8.315

Glutathione Activatable Photosensitizer-Conjugated Pseudopolyrotaxane Nanocarriers for Photodynamic Theranostics

Hongxin Tong,Yangjun Chen,Zuhong Li,Huan Li,Tingting Chen,Qiao Jin,Jian Ji

Photodynamic theranostics has recently been extensively explored as a promising approach for precise localization and therapy. Herein, glutathione (GSH) activatable photosensitizer (PS)-conjugated pseudopolyrotaxane nanocarriers (α-CD-ss-Ce6 NPs) are reported for enhanced photodynamic theranostics by taking advantage of the noncovalent interactions between α-cyclodextrin (α-CD) and poly(ethylene glycol). The designed α-CD-ss-Ce6 NPs are nonactivated and stable during circulation but exhibited strong photodynamic theranostics through GSH activating after arriving at tumor site. More importantly, compared to free chlorin e6 (Ce6), such kind of pseudopolyrotaxane nanocarrier can dramatically enhance Ce6 accumulation in tumor and prolong its tumor retention time, demonstrating excellent therapeutic effects after light irradiation. Overall, the designed GSH activatable PS-conjugated pseudopolyrotaxane nanocarrier possessing high-performance photodynamic therapeutic efficacy together with reduced side effects offers a promising alternative for photodynamic theranostics.

研究领域: 生物医学工程 · 纳米医学 · 药物递送
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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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Bioengineering-Basel · 2022 ·Vol. 9 ·期 7 ·307 · IF 5.046

Rapid Degradation of Rhodamine B through Visible-Photocatalytic Advanced Oxidation Using Self-Degradable Natural Perylene Quinone Derivatives—Hypocrellins

Zhixian Huang,Fan Zhang,Yanbo Tang,Yongdi Wen,Zhenqiang Wu,Zhen Fang,Xiaofei Tian

Hypocrellins (HYPs) are natural perylene quinone derivatives from Ascomycota fungi. Based on the excellent photosensitization properties of HYPs, this work proposed a photocatalytic advanced oxidation process (PAOP) that uses HYPs to degrade rhodamine B (RhB) as a model organic pollutant. A synergistic activity of HYPs and H2O2(0.18 mM of HYPs, 0.33%w/vof H2O2) was suggested, resulting in a yield of 82.4% for RhB degradation after 60 min under visible light irradiation at 470–475 nm. The principle of pseudo-first-order kinetics was used to describe the decomposition reaction with a calculated constant (k) of 0.02899 min−1(R2= 0.983). Light-induced self-degradation of HYPs could be activated under alkaline (pH > 7) conditions, promising HYPs as an advanced property to alleviate the current dilemma of secondary pollution by synthetic photocatalysts in the remediation of emerging organic pollutants.Keywords:photocatalytic advanced oxidation;organic pollutants;photosensitizer;ring-opening reaction;self-degradation

CAS / MDL: 107-88-0
研究领域: 环境科学 · 生物化学
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2022 · IF 11.357

Anthraquinone-2-Sulfonate as a Microbial Photosensitizer and Capacitor Drives Solar-to-N2O Production with a Quantum Efficiency of Almost Unity

Man Chen,Quanhua Cai,Xiangyu Chen,Shaofu Huang,Qinyuan Feng,Tetsuro Majima,Raymond Jianxiong Zeng,Shungui Zhou

Semiartificial photosynthesis shows great potential in solar energy conversion and environmental application. However, the rate-limiting step of photoelectron transfer at the biomaterial interface results in an unsatisfactory quantum yield (QY, typically lower than 3%). Here, an anthraquinone molecule, which has dual roles of microbial photosensitizer and capacitor, was demonstrated to negotiate the interface photoelectron transfer via decoupling the photochemical reaction with a microbial dark reaction. In a model system, anthraquinone-2-sulfonate (AQS)-photosensitized Thiobacillus denitrificans, a maximum QY of solar-to-nitrous oxide (N2O) of 96.2% was achieved, which is the highest among the semiartificial photosynthesis systems. Moreover, the conversion of nitrate into N2O was almost 100%, indicating the excellent selectivity in nitrate reduction. The capacitive property of AQS resulted in 82–89% of photoelectrons released at dark and enhanced 5.6–9.4 times the conversion of solar-to-N2O. Kinetics investigation revealed a zero-order- and first-order- reaction kinetics of N2O production in the dark (reductive AQS-mediated electron transfer) and under light (direct photoelectron transfer), respectively. This work is the first study to demonstrate the role of AQS in photosensitizing a microorganism and provides a simple and highly selective approach to produce N2O from nitrate-polluted wastewater and a strategy for the efficient conversion of solar-to-chemical by a semiartificial photosynthesis system.

研究领域: 环境科学 · 微生物学 · 光合作用研究
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Journal of Materials Chemistry B · 2023 ·Vol. 11 ·期 25 ·5910-5921 · IF 7

A pectin-based photoactivated bactericide nanosystem for achieving an improved utilization rate, photostability and targeted delivery of hematoporphyrin

Yun Li,Zhi Cai,Yihua Yin,Ying Yi,Weiquan Cai,Shengxiang Tao,Mengting Du,Jingli Zhang,Ruyu Cao,Yijing Luo,Wenjin Xu

Photoactivated pesticides have many advantages, such as high activity, low toxicity, and no drug resistance. However, poor photostability and a low utilization rate limit their practical application. Herein, the photosensitizer hematoporphyrin (HP) was used as a photoactivated pesticide, covalently linked with pectin (PEC) via ester bonds, to prepare an amphiphilic polymer pro-bactericide, and subsequently self-assembled in aqueous solutions to obtain an esterase-triggered nanobactericide delivery system. The fluorescence quenching effect due to the aggregation of HP in nanoparticles (NPs) enabled the inhibition of photodegradation of HP in this system. Esterase stimulation could trigger HP release and increase its photodynamic activity. Antibacterial assays have shown that the NPs had potent antibacterial capacity, almost completely inactivating bacteria after 60 min of exposure to light. The NPs had good adherence to the leaves. Safety assessment indicated that the NPs have no obvious toxic effects on plants. Antibacterial studies on plants have shown that the NPs have excellent antibacterial effects on infected plants. These results provide a new strategy for obtaining a photoactivated bactericide nanosystem with a high utilization rate and good photostability and targeting ability.

CAS / MDL: 307554-62-7 9005-65-6
研究领域: 农药科学 · 植物保护 · 生物化学
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Chemical Engineering and Processing-Process Intensification · 2023 · IF 4.3

α-aminonitriles synthesis and kinetic investigation via photooxidative cyanation of amines in a visible LED-based photomicroreactor

Mohsin Pasha,Minjing Shang,Yuhan Wang,Saier Liu,Xiao Xue,Yuanhai Su

α-aminonitriles (AN) are valuable intermediates and building blocks with versatile applications in organic synthesis. Herein, we presented a visible LED-based photomicroreactor for the AN synthesis with three amine substrates, i.e., dibenzylamine (DBA), pyrrolidine (PYR) and piperidiene (PIP), using meso‑tetraphenylporphyrin (m-TPP) and trimethylsilyl cyanide (TMSCN) as photosensitizer and cyanide source, respectively. The results showed that the photooxidative cyanation is a chromoselective and wavelength-selective photochemical transformation with the optimum AN yield and selectivity of 98.2% and 99.5% at a residence time of 2.69 min. Computational studies indicated that a high energy gap between the molecular orbitals of PYP, PIR and their imine intermediates potentially led to their higher reactivity than DBA and formation of by-products with larger molecular weight. Kinetic investigation showed that the apparent rate constants of the DBA photooxidative cyantaion were improved by rising the LED input power, and the applied photosensitizer exhibited high photostability. The overall photonic efficiency of this photomicroreactor was found to be 54.3% within the wavelength range of 400–440 nm, which is higher than previously used photoreactors. Finally, linear correlations were developed between the input power of LED and apparent rate constants of DBA photooxidative cyanation, which would be beneficial for the design, optimization, and scale-up of this photochemical process.

CAS / MDL: 109-99-9
研究领域: 有机合成 · 光化学工程 · 动力学研究
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CHINESE JOURNAL OF POLYMER SCIENCE · 2014 ·Vol. 32 ·期 10 ·1413-1418 · IF 1.42

Protection of photoactivity of photosensitizers by amphiphilic polysaccharide micelles

Li Hua-jie,Yu Zhong,Wang Shuang-ping,Zhang Li-ming,Yang Li-qun

Photosensitizer (photosan)-encapsulated micelles were prepared by self-assembly of Photosan with two amphiphilic polysaccharide derivatives, including the cholesteryl conjugated sodium alginate derivative (CSAD) and the deoxycholic acid group conjugated chitosan derivative (DA-Chit). The results of UV-Vis and fluorescence spectroscopy indicated that the hydrogen bonding strength dominated the micelle formation. Methyl viologen was used as a model quencher of photosan. Using the steady-state fluorescence technology, the quenching constants were determined to be 2.05, 1.88 and 0.30 L/mmol for the free photosan, the photosan-CSAD micelle and the photosan-DA-Chit micelle, respectively. This suggested that photosan was protected from quenching of methyl viologen by the polysaccharide micelles. In addition, the protection effect of the photosan-DA-Chit micelle was significantly stronger than that of the photosan-CSAD micelle. The photosan-DA-Chit micelle is thus anticipated for protection of photoactivity of photosan during the blood circulation process in vivo .

研究领域: 药剂学 · 生物化学
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ADVANCED MATERIALS · 2024 · IF 27.4

Enhanced Photosensitizer Wettability via Anchoring Competition of Violet Phosphorus Quantum Dots for Breakthroughs in Photodynamic Film Sterilization

Zuwang Zhang,Chi Zhang,Na Wang,Yayun Hu,Lu Cui,Jianlong Wang,Lingyan Zhu,Jinying Zhang,Rong Wang

Wettability is important for photodynamic film sterilization since higher wettability enhances the capture of bacteria in contact with photosensitizers. Herein, a small number of violet phosphorus quantum dots (VPQDs) are anchored into hypericin bacterial cellulose films (VP/Hy-BC films) to improve wettability, reducing the water contact angle from 56.8° to 33.0°. This modification facilitated more effective interactions between the bacteria and photosensitizers, rapidly inactivating 7 log 10 CFU/mL of Staphylococcus aureus within 60 min. First-principles calculations and molecular dynamics simulations reveal that VPQDs, with their low spatial site resistance, reduced the intermolecular Hy self-aggregation force. This increased the solvent-accessible surface area of VP/Hy by ≈25.7%, thereby decreasing hydrophobic photosensitizer aggregation. Consequently, more active sites are exposed, remarkably improving the photoelectron transfer efficiency. VP/Hy-BC demonstrated exceptional efficacy in inhibiting bacterial proliferation; for instance, it extended beef shelf life by up to 10 days. The findings of this study will aid the development of health-conscious, eco-friendly, and efficient antimicrobial packaging films.

CAS / MDL: 108-77-0 872-50-4
研究领域: 材料科学 · 微生物学 · 环境科学
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JOURNAL OF MEDICINAL CHEMISTRY · 2024 · IF 6.8

Alkaline Phosphatase Activated Near-Infrared Frequency Upconversion Photosensitizers for Tumor Photodynamic Therapy

Chao Zhao,Wanlu Sun,Xiaoyan Huang,Yi Liu,Hai-Yan Wang

Photodynamic therapy (PDT) is a promising anticancer method due to its noninvasive features, high efficiency, and superior accuracy. The activated near-infrared upconversion photosensitizer has a high tissue penetration depth and could be explicitly released with minimal side effects. Therefore, we designed and synthesized a series of Br-substituted compounds (NFh-Br) based on the near-infrared upconversion hemicyanine dye. The heavy atomic effect improves the generation of 1O2 and upconversion luminous efficiency. Especially, NFh-Br11 exhibited an excellent 1O2 generation rate under 808 nm excitation and effectively killed tumor cells in vitro, and the alkaline phosphatase (ALP)-activatable photosensitizer (NFh-ALP) was obtained by modifying the NFh-Br11. NFh-ALP could be activated by ALP and release NFh-Br11, which induces apoptosis of tumor cells and has outstanding anticancer effects in vitro and in vivo. This work could provide a strategy for designing activatable upconversion photosensitizers.

研究领域: 生物医学工程 · 肿瘤学 · 药理学
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2025 · IF 5.2

Precision-targeted explosion of biomimetic nanoparticles for the effective treatment of uveal melanoma

Xiaoshuang Bi,Yaxin Deng,Chenxiao Chu,Mingli Wei,Jiansong Zhao,Jiaqi Zhao,Yuying Wang,Tian Yin,JingXin Gou,Haibing He,Xing Tang,Guofei Li,Yu Zhang

Uveal melanoma (UM) is the most prevalent primary intraocular malignancy in adults, originating from the melanocytes within the uvea. Currently, the treatment of ocular tumors predominantly relies on conventional approaches such as brachytherapy and enucleation. Despite the limited pharmaceutical treatment options for uveal melanoma (UM), the effectiveness of ocular drug delivery is hindered by the ocular barrier to local drug administration and the complex tumor microenvironment (TME). In response, biomimetic low-density lipoprotein nanoparticles (LD-DPVP NPs) with active targeting capabilities were designed. This nanodrug system combined photosensitizer (verteporfin, VP) with the tumor vascular normalization drug (dexamethasone, DEX) to achieve low-toxicity, high-efficacy treatment of intraocular tumors. After intravenous injection, the nanoparticles selectively targeted the tumor site and induced VP to produce reactive oxygen species (ROS) that killed tumor cells under near-infrared laser stimulation. The produced ROS could also trigger the cleavage of the DEX prodrug (DPD) and rapid release of DEX via breakage of the thioether bond (TK). Additionally, DEX could modulate the TME, improving the delivery of nanoparticles to the tumor and further enhancing the efficacy of LD-DPVP NPs. We believe the biomimetic nanoparticles designed in this study have a potential clinical application value in inhibiting UM growth and provided a promising strategy for addressing other ocular malignancies.

研究领域: 肿瘤学 · 药剂学 · 眼科
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