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Formation of plasmon quenching dips greatly enhances ^1O2 generation in a chlorin e6-gold nanorod coupled system

Nano Research 2018年第3期11卷 1456-1469页

作者： Hui Zhang Haiyun Li Huizhen Fan Jiao Yan Dejing Meng Shuai Hou Yinglu Ji Xiaochun Wu CAS Key Laboratory of Standardization and Measurement for Nanotechnology CAS Center for Excellence in Nanoscience NationalCenter for Nanoscience and Technology Beijing 100190 China University of the Chinese Academy of Sciences Beijing 100190 China

Photodynamic therapy （PDT）, as a noninvasive therapeutic method, has been actively explored recently for cancer treatment. However, owing to the weak absorption in the optically transparent windows of biological tissues, most com- mercial photosensitizers （PSs） exhibit low singlet oxygen （^1O2） quantum yields when excited by light within this window. Finding the best way to boost ^1O2 production for clinical applications using light sources within this window is, thus, a great challenge. Herein, we tackle this problem using plasmon resonance energy transfer （PReT） from plasmonic nanoparticles （NPs） to PSs and demonstrate that the formation of plasmon quenching dips is an effective way to enhance ^1O2 generation. The combination of the photosensitizer chlorin e6 （Ce6） and gold nanorods （AuNR） was employed as a model system. We observed a clear quenching dip in the longitudinal surface plasmon resonance （LSPR） band of the AuNRs when the LSPR band overlaps with the Q band of Ce6 and the spacing between Ce6 and the rods is within the acting distance of PReT. Upon irradiation with 660 nm continuous-wave laser light, we obtained a seven-fold enhancement in the ^1O2 signal intensity compared with that of a non-PReT sample, as determined using the ^1O2 electron spin resonance probe 2,2,6,6-tetramethyl-4-piperidine （TeMP）. Furthermore, we demonstrated that the PReT effect is more efficient in enhancing ^1O2 yield than the often-employed local field enhancement effect. The effectiveness of PReT is further extended to the in vitro level. Considering the flexibility in manipulating the localized SPR properties of plasmonic nanoparticles/nanostructures, our findings suggest that PReT-based strategies may be a general way to overcome the deficiency of most commercial organic PSs in biological optically transparent windows and promote their applications in clinical tumor treatments.

关键词： plasmon resonance energy transfer gold nanorods chlorin e6 singlet oxygen photodynamic therapy

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An effective method to generate controllable levels of ROS for the enhancement of HUVeC proliferation using a chlorin e6-immobilized PeT film as a photo-functional biomaterial

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Regenerative Biomaterials 2021年第2期8卷 94-103页

作者： Seung Hee Hong Min-Ah Koo Mi Hee Lee Gyeung Mi Seon Ye Jin Park HaKyeong Jeong Dohyun Kim Jong-Chul Park Cellbiocontrol Laboratory Department of Medical Engineering Department of Medical engineering Graduate School of Medical ScienceBrain Korea 21 Project Department of Medical Device engineering and Management Yonsei UniversityCollege of MedicineSeoul 03722Republic of Korea

Reactive oxygen species(ROS)are byproducts of cellular metabolism;they play a significant role as secondary messengers in cell *** cells,high concentrations of ROS induce apoptosis,senescence,and contact inhibition,while low concentrations of ROS result in angiogenesis,proliferation,and cytoskeleton ***,controlling ROS generation is an important factor in cell *** designed a chlorin e6(Ce6)-immobilized polyethylene terephthalate(PeT)film(Ce6-PeT)to produce extracellular ROS under red-light *** application of Ce6-PeT films can regulate the generation of ROS by altering the intensity of light-emitting diode *** confirmed that the Ce6-PeT film could effectively promote cell growth under irradiation at 500 μW/cm^(2) for 30 min in human umbilical vein endothelial *** also found that the Ce6-PeT film is more efficient in generating ROS than a Ce6-incorporated polyurethane film under the same ***6-PeT fabrication shows promise for improving the localized delivery of extracellular ROS and regulating ROS formation through the optimization of irradiation intensity.

关键词： reactive oxygen species chlorin e6 dopamine covalent bond HUVeC proliferation

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chlorin e6声动力对小鼠S180肉瘤生长的作用

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中国超声医学杂志 2012年第11期28卷 961-963页

作者：刘端张为民王晓怀陈蓓郑静娴广州军区广州总医院肿瘤科

目的声动力治疗（sonodynamic therapy,SDT）是通过超声波激活肿瘤细胞内聚集的声敏剂治疗肿瘤的一种新方法。本实验用chlorin e6为声敏剂,观测其在S180肉瘤荷瘤小鼠肿瘤组织的富集情况及联合超声对S180肉瘤的杀伤作用。方法 S180肉瘤... 详细信息

目的声动力治疗（sonodynamic therapy,SDT）是通过超声波激活肿瘤细胞内聚集的声敏剂治疗肿瘤的一种新方法。本实验用chlorin e6为声敏剂,观测其在S180肉瘤荷瘤小鼠肿瘤组织的富集情况及联合超声对S180肉瘤的杀伤作用。方法 S180肉瘤荷瘤小鼠腹腔注射chlorin e6后,共聚焦显微镜观测其在肿瘤的富集情况,18 h后超声处理（1.0 MHz,180 s）,每2天测量肿瘤大小,第15天剥离肿瘤进行质量比较。结果腹腔给药后18 h,chlorin e6在肿瘤组织和肌肉组织含量达峰值,且二者含量差异最明显,此时为最佳的超声辐射时间。单独使用超声照射（0.4～1.6 W/cm;）或单独注射chlorin e6（10～40mg/kg）对小鼠S180肉瘤无明显杀伤作用。chlorine6联合超声可明显抑制肿瘤生长,抑瘤作用随超声强度（0.4～1.6 W/cm;）和chlorin e6质量分数（10～40 mg/kg）的增加而增强。结论 chlorin e6在S180肉瘤荷瘤小鼠具肿瘤靶向聚集性,联合超声介导的SDT对小鼠S180肉瘤有明显杀伤作用。

关键词：声动力疗法 chlorin e6 S180肉瘤超声

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Preparation and characterization of pH-sensitive calcium carbonate-chlorin e6 nanoparticles for photodynamic therapy

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Journal of Chinese Pharmaceutical Sciences 2021年第11期30卷 904-911页

作者： Jingru Wang Shuang Zhang Zhuoyue Li Meiqi Xu Guangxue Wang Xuan Zhang Beijing Key Laboratory of Molecular Pharmaceutics and New Drug Delivery Systems School of Pharmaceutical SciencesPeking University Health Science CenterBeijing 100191China Department of Pharmaceutics School of Pharmaceutical SciencesPeking University Health Science CenterBeijing 100191China

In the present study,we combined CaCO_(3)NPs and Ce6 to construct CaCO_(3)-Ce6 nanoparticles (NPs).CaCO_(3)-Ce6 NPs were characterized in terms of particle size,zeta potential,UV-Vis absorption spectrum,fluorescence spectrum,FTIR spectrum,and pH-responsive *** reactive oxygen species (ROS) generation in vitro was measured in 4T1 *** results showed that CaCO_(3)-Ce6 NPs were uniform-sized NPs with excellent fluorescence properties and pH-responsive *** ability of ROS generation by CaCO_(3)-Ce6 NPs was stronger compared with Ce6 in 4T1 cells because Ca;could enhance the ROS generation,which could contribute to a stronger anti-tumor effect.

关键词： Calcium carbonate nanoparticles chlorin e6 Photodynamic therapy Reactive oxygen species pH-responsive

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chlorin e6声动力对小鼠S180肉瘤生长的作用

Chlorin e6声动力对小鼠S180肉瘤生长的作用

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作者：刘端南方医科大学

学位级别：硕士

恶性肿瘤是威胁人类生命健康的头号杀手之一,手术、放疗、化疗和靶向治疗是目前恶性肿瘤治疗的主要方法,大部分患者诊断时已是局部晚期或有远处转移,失去手术机会。化疗和放疗在杀伤肿瘤细胞的同时,对正常细胞也不加选择性的造成了严重... 详细信息

恶性肿瘤是威胁人类生命健康的头号杀手之一,手术、放疗、化疗和靶向治疗是目前恶性肿瘤治疗的主要方法,大部分患者诊断时已是局部晚期或有远处转移,失去手术机会。化疗和放疗在杀伤肿瘤细胞的同时,对正常细胞也不加选择性的造成了严重的损伤,毒副反应较大,许多患者因体质差或无法耐受毒副作用而放弃治疗。靶向治疗虽不良反应小,但其疗效与基因突变相关。因此,寻找其他高效、低毒的恶性肿瘤治疗新方法,是医学界面临的重要问题。声动力疗法（Sonodynamic therapy, SDT）是在光动力疗法（Photodynamic therapy, PDT）基础上发展起来的一种治疗恶性肿瘤的新理念、新方法。肿瘤患者口服或静脉注射声敏剂,而后用一定频率和强度的超声照射肿瘤部位,通过超声激活聚集在肿瘤部位的声敏剂,使其产生一系列声化学反应（如产生单态氧、自由基）,导致肿瘤细胞的不可逆性损伤。与光动力疗法（激光激活光敏剂,产生单态氧或自由基,从而起到杀伤肿瘤的作用）相比,超声对人体组织有很强的无创穿透能力,无需借助其他介入手段即可对深部肿瘤进行治疗,故有着广阔的发展前景。目前SDT存在的主要问题是所用的声敏剂多为血卟啉及其衍生物为代表的第一代光敏剂,肿瘤靶向性不强,排泄缓慢,易发生光毒副反应,影响了SDT疗效及其临床实际应用。因此,寻找靶向性高、毒副作用小的新型声敏剂以及探索最佳的声动力治疗模式是必要的。 chlorin e6是一种结构类似于血卟啉的叶绿素降解产物,早先被应用于光动力治疗中,显示确切的抗肿瘤作用及肿瘤靶向性强、正常组织清除快、毒副反应低的优点。但是chlorin e6作为声敏剂应用于声动力治疗恶性肿瘤的研究目前还比较少,我们前期的细胞学研究工作显示chlorin e6具有在肺癌、乳腺癌等肿瘤细胞特异聚集性和声动力治疗靶向杀伤肿瘤细胞作用,是一个有临床应用前景的声敏剂,但目前缺乏整体动物的肿瘤靶向特异聚集性和声动力作用的实验证据。因此,本研究的第一个目的是采用激光共聚焦显微镜观测chlorin e6在S180肉瘤荷瘤小鼠肿瘤组织的富集情况。第二个目的是研究chlorin e6联合超声对S180肉瘤的杀伤作用,探索理想的声动力治疗模式。第一部分chlorin e6在S180荷瘤小鼠肿瘤组织和肌肉组织的分布目的研究chlorin e6在肿瘤组织的富集情况,探索给药后最佳的超声辐射时间。方法 S180肉瘤荷瘤小鼠腹腔注射chlorin e6（10mg/kg）,分别于给药后3、6、12、18、24、48、72h断颈处死小鼠,剥离肿瘤组织和周围肌肉组织,制备冷冻切片,并在激光共聚焦显微镜下测定和观察肿瘤和肌肉组织的荧光强度及荧光显像（显示为红色荧光）。采用SPSS13.0统计软件进行两个重复测量因素的方差分析,以P＜0.05为差异有统计学意义。结果腹腔注射后24h内,chlorin e6（10mg/kg）在肿瘤及周围肌肉组织中的含量随时间递增,肿瘤组织含量明显高于周围肌肉组织,18h时达最高峰,且此时肿瘤组织和肌肉组织中的差异最明显,荧光强度相差6.14倍。后随着时间延长荧光逐渐减弱,24h后接近正常,72h后基本检测不到荧光。由此可见chlorine6（10mg/kg）在腹腔注射后可靶向性富集于肿瘤组织,18h含量达到最高,且此时与正常组织的含量差异最明显。此时若对肿瘤进行辐照处理,既能达到最有效的杀伤肿瘤细胞作用,又对正常组织损伤较小。给药24h后,chlorin e6在肿瘤及正常组织中含量均很少,72h后基本清除完毕,提示chlorin e6具有代谢迅速、清除快的特点,可以有效减少对正常组织的毒副作用。第二部分chlorin e6声动力对小鼠S180肉瘤生长的作用目的研究chlorin e6联合超声对S180肉瘤的杀伤作用,探索理想的声动力治疗模式。方法 1、单独超声照射对S180肉瘤生长的作用 S180肉瘤荷瘤小鼠随机分为4组,每组5只小鼠：（1）对照组;（2）单独超声（声强0.4W/cm2）组;（3）单独超声（声强0.8W/cm2）组;（4）单独超声（声强1.6W/cm2）组。超声频率固定为1.0MHz,超声辐照时间固定为180s。 2、单独chlorin e6腹腔注射对S180肉瘤生长的作用 S180肉瘤荷瘤小鼠随机分为4组,每组5只小鼠：（1）对照组;（2）单独chlorin e6（剂量10mg/kg）组;（3）单独chlorin e6（剂量20mg/kg）组;（4）单独chlorin e6（剂量40mg/kg）组。 3、chlorin e6介导的声动力治疗对肿瘤的杀伤作用 S180肉瘤荷瘤小鼠随机分为

关键词：声动力疗法 chlorin e6 S180肉瘤超声波共聚焦显微镜(LSCM) S180肉瘤

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MnO_(2)-coated nanodiamond-driven photodynamic therapy for enhanced antitumor effect by addressing hypoxia and glutathione depletion

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Particuology 2024年第9期92卷 305-315页

作者： Jicheng Cui Dongmei Zhang Hui Qiao Zeyu Yan Wenxia Zhang Yingqi Li Key Laboratory of Chemical Biology and Molecular engineering of Ministry of education Institute of Molecular ScienceShanxi UniversityTaiyuan030006China Taiyuan Central Hospital Taiyuan030009China School of Chemistry and Chemical engineering Shanxi UniversityTaiyuan030006China

The generation of reactive oxygen species(ROS)at the tumor site to induce destruction is emerging as a novel strategy for cancer treatment,which involves photodynamic therapy(PDT).Nevertheless,tumors typically create a hypoxic environment and are equipped with an endogenous antioxidant defense system that could potentially impede the efficiency of the therapeutic *** overcome these drawbacks,herein,a tumor microenvironment-responsive the ND-PAA-CD-Ce6@MnO_(2)(NPCC@M)delivery system was fabricated by disulfide bond coupling chlorin e6(Ce6)to nanodiamond(ND)and further wrapped by MnO_(2)nanosheets to facilitate *** use of disulfide bond not only stabilizes Ce6 in the blood circulation to prevent premature leakage,but also destroys the antioxidant barrier of overexpressed glutathione(GSH)in tumor ***,the outer MnO_(2)was rapidly degraded by the endogenous hydrogen peroxide(H_(2)O_(2))in the acidic pH and GSH within the tumor cells,which leads to an abundance of O_(2)and while increases the level of 1O_(2)under laser *** results eventually broke the redox homeostasis and attenuate hypoxia,thereby inducing apoptosis and necrosis of tumor *** in vitro and in vivo biological effect has revealed a good biosafety profile and a high tumor suppression *** a novel ND-based system with tumor microenvironment-modulating capability to elevate oxygen content and promote GSH consumption in tumor cells opens new opportunities for enhanced ROS treatment paradigms.

关键词： Nanodiamond Photodynamic chlorin e6 MnO_(2) Tumor suppression

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Brain endothelial cell-derived extracellular vesicles with a mitochondria-targeting photosensitizer effectively treat glioblastoma by hijacking the blood-brain barrier

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Acta Pharmaceutica Sinica B 2023年第9期13卷 3834-3848页

作者： Thuy Giang Nguyen Cao Ji Hee Kang Su Jin Kang Quan Truong Hoang Han Chang Kang Won Jong Rhee Yu Shrike Zhang Young Tag Ko Min Suk Shim Division of Bioengineering Incheon National UniversityIncheon 22012Republic of Korea College of Pharmacy Gachon UniversityIncheon 21936Republic of Korea Department of Pharmacy Integrated Research Institute of Pharmaceutical Sciencesand BK21 PLUS Team for Creative Leader Program for Pharmacomics-based Future PharmacyCollege of Pharmacythe Catholic University of KoreaGyeonggi-do 14662Republic of Korea Research Center for Bio Materials&Process Development Incheon National UniversityIncheon 22012Republic of Korea Division of engineering in Medicine Department of MedicineBrigham and Women’s HospitalHarvard Medical SchoolCambridgeMA 02139USA

Glioblastoma(GBM)is the most aggressive malignant brain tumor and has a high mortality *** therapy(PDT)has emerged as a promising approach for the treatment of malignant brain ***,the use of PDT for the treatment of GBM has been limited by its low blood-brain barrier(BBB)permeability and lack of cancer-targeting ***,brain endothelial cell-derived extracellular vesicles(beVs)were used as a biocompatible nanoplatform to transport photosensitizers into brain tumors across the *** enhance PDT efficacy,the photosensitizer chlorin e6(Ce6)was linked to mitochondria-targeting triphenylphosphonium(TPP)and entrapped into *** Ce6(TPP-Ce6)selectively accumulated in the mitochondria,which rendered brain tumor cells more susceptible to reactive oxygen species-induced apoptosis under light ***,the encapsulation of TPP-Ce6 into b eVs markedly improved the aqueous stability and cellular internalization of TPP-Ce6,leading to significantly enhanced PDT efficacy in U87MG GBM *** in vivo biodistribution study using orthotopic GBM-xenografted mice showed that b eVs containing TPP-Ce6[b eV(TPP-Ce6)]substantially accumulated in brain tumors after BBB penetration via transferrin receptor-mediated *** such,b eV(TPP-Ce6)-mediated PDT considerably inhibited the growth of GBM without causing adverse systemic toxicity,suggesting that mitochondria are an effective target for photodynamic GBM therapy.

关键词： extracellular vesicle chlorin e6 Triphenylphosphonium Mitochondria-targeting photosensitizer Photodynamic therapy Blood-brain barrier Glioblastoma Transferrin receptor

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Mesoporous silica nanorods intrinsically doped with photosensitizers as a multifunctional drug carrier for combination therapy of cancer

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Nano Research 2015年第3期8卷 751-764页

作者： Guangbao Yang Hua Gong Xiaoxin Qian Pengli Tan Zhiwei Li Teng Liu Jingjing Liu Youyong Li Zhuang Liu Institute of Functional Nano and Soft Materials (FUNSOM) Collaborative Innovation Center of Suzhou Nano Science and TechnologySoochow University Suzhou Jiangsu 215123 China

Mesoporous silica nanoparticles （MSNs） have attracted tremendous attention in recent years as drug delivery carriers due to their large surface areas, tunable sizes, facile modification and considerable biocompatibility. In this work, we fabricate an interesting type of MSNs which are intrinsically doped with photosensitizing molecules, chlorin e6 （Ce6）. By increasing the amount of Ce6 doped inside the silica matrix, it is found that the morphology of MSNs changes from spheres to rod-like shapes. The obtained Ce6-doped mesoporous silica nanorods （CMSNRs） are not only able to produce singlet oxygen for photodynamic therapy, but can also serve as a drug delivery platform with high drug loading capacity by utilizing their mesoporous structure. Compared to spherical nano- particles, it is found that CMSNRs with a larger aspect ratio show much faster uptake by cancer cells. With doxorubicin （DOX） employed as a model drug, the combined photodynamic and chemotherapy is carried out, achieving synergistic anti-tumor effects both in vitro and in vivo. Our study presents a new design of an MSN-based drug delivery platform, which intrinsically is fluorescent and able to serve as a photodynamic agent, promising for future imaging-guided combination therapy of cancer.

关键词： mesoporous silicananorods chlorin e6 photodynamic therapy drug delivery combination therapy

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New approaches to diagnostics and treatment of cholangiocellular cancer based on photonics methods

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Frontiers of Optoelectronics 2020年第4期13卷 352-359页

作者： Dmitry V.YAKOVLeV Dina S.FARRAKHOVA Artem A.SHIRYAeV Kanamat T.eFeNDIeV Maxim V.LOSCHeNOV Liana M.AMIRKHANOVA Dmitry O.KORNeV Vladimir V.LeVKIN Igor V.ReSHeTOV Victor B.LOSCHeNOV Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry Russian Academy of SciencesMoscow 117997Russia Prokhorov General Physics Institute of Russian Academy of Sciences Moscow 119991Russia University Clinical Hospital No.1 Oncology CenterI.M.Sechenov First Moscow State Medical University(Sechenov University)Ministry of Health of the Russian FederationMoscow 119991Russia Department of Laser Micro- Nano-and BiotechnologyInstitute of Engineering Physics for BiomedicineNational Research Nuclear University MEPhIMoscow 115409Russia

Cholangiocellular cancer(CCC)is an oncological disease of the bile ducts characterized by a high mortality *** date,the use of standard methods for the diagnosis and treatment of CCC has not been able to reduce mortality from this *** work presents the results of fluorescence diagnostics(FD),which consists in using a modified optical fiber and photodynamic therapy(PDT)using a therapeutic laser instead of a low-intensity *** technique was tested on 43 patients in a clinical *** results obtained indicate a direct correlation between spectroscopic and video FD ***,a direct correlation was found between the photobleaching of a chlorin e6-based photosensitizer,with the commercial names of PhotoIon Radachlorin and Photoran and stricture *** findings demonstrate the possibility of using a therapeutic laser with a wavelength of 660 nm for both diagnosis and treatment of bile ducts cancer,which results in a significant reduction of the operation time without decreasing its effectiveness.

关键词： cholangiocellular cancer(CCC) fluorescent diagnostics(FD) photodynamic therapy(PDT) chlorin e6 PhotoIon spectroscopic method video fluorescent method photobleaching cancer bile ducts tumor intraoperation diagnostics photosensitizer(PS)

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内在掺杂光敏剂的介孔二氧化硅纳米棒作为多功能药物载体用于癌症的联合治疗

内在掺杂光敏剂的介孔二氧化硅纳米棒作为多功能药物载体用于癌症...

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中国化学会第29届学术年会

作者：杨光保龚华钱孝鑫谭朋利李有勇刘庄苏州大学功能纳米与软物质研究院

近年来,介孔二氧化硅作为药物运输载体引起了极大的关注,我们合成了一种有趣的介孔硅材料,在介孔二氧化硅形成过程中,把光敏分子chlorin e6（Ce6）掺杂到介孔硅硅层中。我们进一步发现当掺杂到介孔硅骨架中的Ce6含量增加时,介孔硅的形... 详细信息

近年来,介孔二氧化硅作为药物运输载体引起了极大的关注,我们合成了一种有趣的介孔硅材料,在介孔二氧化硅形成过程中,把光敏分子chlorin e6（Ce6）掺杂到介孔硅硅层中。我们进一步发现当掺杂到介孔硅骨架中的Ce6含量增加时,介孔硅的形貌从球形逐渐地变为棒状。得到了掺杂Ce6的介孔硅纳米棒,不仅可以产生用于光动力治疗的单线态氧,而且可以利用其介孔的结构,作为高装载率的药物载体。和球状的颗粒相比,更大长径比的棒状颗粒可以更快地被癌细胞吸收。我们选择DOX作为装载的药物,这样光动力治疗和化疗可以作为治疗癌症的手段,我们在体外和活体水平同时实现了协同治疗肿瘤的作用。

关键词：介孔硅纳米棒 chlorin e6 光动力治疗药物传输联合治疗

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