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Largeπ-extended donor-acceptor polymers for highly efficient in vivo near-infrared photoacoustic imaging and photothermal tumor therapy

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Science China Chemistry 2021年第12期64卷 2180-2192页

作者： jiangao li Hanlin Ou Jing li Xiaodi Yang Congwu Ge Dan Ding Xike Gao Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules Shanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesChinese Academy of SciencesShanghai200032China State Key Laboratory of Medicinal Chemical Biology Key Laboratory of Bioactive MaterialsMinistry of EducationCollege of Life SciencesNankai UniversityTianjin300071China China Innovation Research Institute of Traditional Chinese Medicine Shanghai University of Traditional Chinese MedicineShanghai201203China

Semiconducting polymers(SPs)with intensive near-infrared(NIR)absorption and high photothermal conversion efficiencies have been employed as a new generation of photothermal agents(PTAs)for“all-in-one”theranostic nanoplatforms with integrated photoacoustic imaging(PAI)and photothermal therapy(PTT)***,the lack of facile molecular design principles impedes the development of highly efficient NIR ***,a facile molecular design strategy based on largeπ-extended donor-acceptor(L-π-D-A)structure is reported for achieving SPs(SP1-SP3)with highly efficient in vitro and in vivo PAI and PTT *** adjusting the conjugation length and planarity of the donor units,both SP3 and corresponding nanoparticle(SPN)SPN3 exhibit stronger D-A strength,intensive NIR absorption,enhanced absorption coefficient,and higher photothermal conversion efficiency(up to 61.8%).The excellent photothermal conversion efficiencies make SPN1-SPN3 produce efficient inhibition of tumor growth with excellent biocompatibility and prominent PAI performance with a high contrast manner in living mice at a low systemic injection *** research highlights that the new L-π-D-A molecular design is an effective strategy to obtain highly efficient polymeric NIR PTAs for high desirable cancer phototheranostic nanoplatforms.

关键词： D-A polymers near-infrared photothermal agents photoacoustic imaging photothermal therapy

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light-driven sextuple theranostics:nanomedicine involving second near-infrared AIE-active Ir(Ⅲ)complex for prominent cancer treatment

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Science China Chemistry 2024年第7期67卷 2314-2324页

作者： Xue liu jiangao li Fei Zhang Dingyuan Yan Lei Wang Dong Wang Ben Zhong Tang Center for AIE Research Shenzhen Key Laboratory of Polymer Science and TechnologyGuangdong Research Center for Interfacial Engineering of Functional MaterialsCollege of Material Science and EngineeringShenzhen UniversityShenzhen 518060China College of Physics and Optoelectronic Engineering Shenzhen UniversityShenzhen 518060China School of Science and Engineering Shenzhen Institute of Aggregate Science and TechnologyThe Chinese University of Hong KongShenzhen(CUHK-Shenzhen)Shenzhen 518172China

light-driven cancer theranostics has shown inexhaustible and vigorous vitality by virtue of its high efficacy,prominent controllability and *** of an all-round theranostic material simultaneously affording both multimodal diagnosis imaging and synergistic phototherapy would be an appealing yet significantly challenging ***,a novel nanomedicine Ir@PPEG-MeEPO was ingeniously constructed by integrating beforehand1O2-charged amphiphilic polymer and well-tailored Ir(Ⅲ)complex IrDPTP,which was featured by second near-infrared(NIR-Ⅱ)aggregation-induced emission(AIE)tendency,efficient reactive oxygen species(ROS)generation,good photothermal conversion efficiency and high-performance hydrogen gas *** the best of our knowledge,IrDPTP held the longest emission wavelength among all reported AIE Ir(Ⅲ)***,Ir@PPEG-MeEPO was capable of controllably releasing ROS via triggered photothermal effect upon NIR irradiation,making it well-adapted to hypoxic environment of *** distinctive characteristics of Ir@PPEG-MeEPO endowed it with unprecedented performance on sextuple theranostics comprised of NIR-Ⅱfluorescence-photoacoustic-photothermal trimodal imaging and photodynamic-photothermal-hydrogen trimodal therapy,witnessed by the precise tumor diagnosis and complete tumor *** study would open up new perspectives for the exploration of superior nanomedicine for practical cancer theranostics.

关键词： aggregation-induced emission NIR-II emission cancer theranostics multimodal diagnosis imaging multimodal therapy

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Acceptor-engineering tailored type-Ⅰ photosensitizer with aggregation-induced NIR-II emission for cancer multimodal phototheranostics

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Science China Chemistry 2024年第8期67卷 2647-2660页

作者： jiangao li Niu Niu Deliang Wang Xue liu Yi Qin Lei Wang Ben Zhong Tang Dong Wang Center for AIE Research Shenzhen Key Laboratory of Polymer Science and TechnologyGuangdong Research Center for Interfacial Engineering of Functional MaterialsCollege of Materials Science and EngineeringShenzhen UniversityShenzhen 518060China Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target Clinical Pharmacologythe State Key Laboratory of Respiratory DiseaseSchool of Pharmaceutical Sciences and the Fifth Affiliated HospitalGuangzhou Medical UniversityGuangzhou 511436China School of Science and Engineering Shenzhen Institute of Aggregate Science and TechnologyThe Chinese University of Hong KongShenzhen(CUHK-Shenzhen)Shenzhen 518172China

Exploration of single molecular species synchronously featured by long excitation/emission wavelength, accurate diagnosis, and effective therapy, remains supremely appealing to implement high-performance cancer phototheranostics. However, those previously established phototheranostic agents are undiversified and stereotyped in terms of structural skeleton, and generally exhibit insufficient phototheranostic outcomes. Herein, we innovatively utilized indanone-condensed thiadiazolo[3,4-g]quinoxaline(ITQ) as electron acceptor to construct novel photosensitizer with second near-infrared(NIR-II) emission. Experimental study and theoretical calculation demonstrated that comparing with the counterparts constituting by widely employed NIR-II building block benzobisthiadiazole(BBTD) and 6,7-diphenylthiadiazoloquinoxaline(DPTQ), ITQ-based photosensitizer(TITQ) showed superior aggregation-induced emission(AIE) characteristics, much stronger type-I reactive oxygen species(ROS) production, and prominent photothermal conversion capacity. Furthermore, TITQ nanoparticles with excellent biocompatibility were capable of effectively accumulating in the tumor site and visualizing tumor through fluorescence-photoacoustic-photothermal trimodal imaging with highly spatiotemporal resolution, and completely eliminating tumor by type-I photodynamic-photothermal therapy.

关键词： phototheranostics aggregation-induced emission NIR-Ⅱfluorescence acceptor engineering photodynamic-photothermal therapy

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Tunable oxygen defect density and location for enhancement of energy storage

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Journal of Energy Chemistry 2021年第8期30卷 736-747,I0015页

作者： Jun Chen jiangao li ling Sun Zhong lin Zhengguang Hu Hongtao Zhang Xiaoling Wu Dongbo Zhang Guoan Cheng Ruiting Zheng Key Laboratory of Radiation Beam Technology and Materials Modification of the Ministry of Education College of Nuclear Science and TechnologyBeijing Normal University100875 BeijingChina Department of Physics Nanchang UniversityNanchang 330031China Department of Materials Loughborough UniversityLE113TU LeicestershireUK Beijing Computational Science Research Center 100193 BeijingChina

Defect engineering is in the limelight for the fabrication of electrochemical energy storage ***,determining the influence of the defect density and location on the electrochemical behavior remains ***,self-organized TiO_(2)nanotube arrays(TNTAs)are synthesized by anodization,and their oxygen defect location and density are tuned by a controllable post-annealing *** annealed at 600℃ in N2 exhibit the highest capacity(289.2 m Ah g^(-1)at 0.8 C)for lithium-ion storage,while those annealed at 900℃ in N2 show a specific capacitance of 35.6 m F cm^(-2)and stability above96%after 10,000 cycles for *** situ electron paramagnetic resonance spectra show that the surface-exposed oxygen defects increase,but the bulk embedded oxygen defects decrease with increasing annealing *** functional theory simulations reveal that a higher density of bulk oxygen defects corresponds to higher localized electrons states,which upshift the Fermi level and facilitate the lithium intercalation kinetic ***,differential charge density calculation indicates that the increase of surface oxygen defects in the anatase(101)plane leads to higher density excess electrons,which act as negative charge centers to enhance the surface potential for ion *** oxygen-deficient location and density tunable strategy introduce new opportunities for high-energy and high-power-density energy storage systems.

关键词： Oxygen defects Excess electrons Supercapacitors lithium-ion batteries DFT calculations

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light-driven sextuple theranostics: nanomedicine involving second near-infrared AIE-active Ir(III) complex for prominent cancer treatment

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Science China Chemistry 2024年

作者： Xue liu jiangao li Fei Zhang Dingyuan Yan Lei Wang Dong Wang Ben Zhong Tang Center for AIE Research Shenzhen Key Laboratory of Polymer Science and Technology Guangdong Research Center for Interfacial Engineering of Functional Materials College of Material Science and Engineering Shenzhen University College of Physics and Optoelectronic Engineering Shenzhen University School of Science and Engineering Shenzhen Institute of Aggregate Science and Technology The Chinese University of Hong Kong

light-driven cancer theranostics has shown inexhaustible and vigorous vitality by virtue of its high efficacy, prominent controllability and noninvasiveness. Exploration of an all-round theranostic material simultaneously affording both multimodal diagnosis imaging and synergistic phototherapy would be an appealing yet significantly challenging task. Herein, a novel nanomedicine Ir@PPEG-MeEPO was ingeniously constructed by integrating beforehand1O2-charged amphiphilic polymer and well-tailored Ir（III） complex IrDPTP, which was featured by second near-infrared（NIR-II） aggregation-induced emission（AIE）tendency, efficient reactive oxygen species（ROS） generation, good photothermal conversion efficiency and high-performance hydrogen gas production. To the best of our knowledge, IrDPTP held the longest emission wavelength among all reported AIE Ir（III） complexes. Moreover, Ir@PPEG-MeEPO was capable of controllably releasing ROS via triggered photothermal effect upon NIR irradiation, making it well-adapted to hypoxic environment of tumor. Those distinctive characteristics of Ir@PPEG-MeEPO endowed it with unprecedented performance on sextuple theranostics comprised of NIR-II fluorescence-photoacoustic-photothermal trimodal imaging and photodynamic-photothermal-hydrogen trimodal therapy, witnessed by the precise tumor diagnosis and complete tumor elimination. The study would open up new perspectives for the exploration of superior nanomedicine for practical cancer theranostics.

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复杂条件下超深地下连续墙泥浆的使用及性能

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现代隧道技术 2013年第1期50卷 166-170,176页

作者：张海波柳伟李建高中铁隧道集团三处有限公司深圳518052 江西交通职业技术学院路桥工程系南昌330013

天津文化中心交通枢纽工程地铁Z1线,采用地下连续墙围护结构,最大墙深67m,在开挖过程中需穿越最大厚度达18m的粉砂层,且需在寒冷的冬季施工,科学地配置和正确地使用泥浆是保证成槽的关键。根据技术规范和工程经验,设定了本项目地下连续... 详细信息

天津文化中心交通枢纽工程地铁Z1线,采用地下连续墙围护结构,最大墙深67m,在开挖过程中需穿越最大厚度达18m的粉砂层,且需在寒冷的冬季施工,科学地配置和正确地使用泥浆是保证成槽的关键。根据技术规范和工程经验,设定了本项目地下连续墙施工中泥浆的性能指标,采取多种措施实现了对泥浆质量的严格控制,从而有效地保证了后续施工工艺的顺利进行。

关键词：泥浆性能劣化再生保温

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深埋隧道岩爆特征分析与综合防治技术--以成兰铁路平安隧道为例

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隧道建设（中英文） 2020年第12期40卷 1781-1790页

作者：李建高唐泽林中铁隧道集团三处有限公司广东深圳518000

为有效控制高地应力影响下深埋隧道岩爆段围岩发生动力失稳及持续性岩爆,保证围岩稳定、支护结构有效、施工人员安全,顺利、快速地通过高地应力岩爆段,依托成兰铁路平安隧道岩爆现场施工,对隧道现场发生的岩爆特征进行总结,分析不同时... 详细信息

为有效控制高地应力影响下深埋隧道岩爆段围岩发生动力失稳及持续性岩爆,保证围岩稳定、支护结构有效、施工人员安全,顺利、快速地通过高地应力岩爆段,依托成兰铁路平安隧道岩爆现场施工,对隧道现场发生的岩爆特征进行总结,分析不同时段、不同隧道部位、不同等级、不同洞段的岩爆发生特征;同时,从工艺工法、爆破参数、支护结构、变形监测等方面,提出"防、治、监"相结合的岩爆综合防治处理技术,有效控制高地应力深埋隧道岩爆段施工风险,实现岩爆段的安全快速施工。

关键词：深埋隧道高地应力岩爆特征防治措施优化施工

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富水软弱地层中麻花型盾构隧道群施工关键技术

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隧道建设（中英文） 2019年第10期39卷 1678-1689页

作者：李建高王长虹中铁隧道集团三处有限公司广东深圳518000 上海大学土木工程系上海200444

为解决富水软弱地层中上下重叠、麻花交叉型盾构隧道群施工的关键技术难题,根据工程地质条件、周边工作环境和4条隧道空间位置关系进行理论分析,确定隧道群最优施工顺序,并通过信息化监测手段进行验证控制。通过控制施工时间,采用自行... 详细信息

为解决富水软弱地层中上下重叠、麻花交叉型盾构隧道群施工的关键技术难题,根据工程地质条件、周边工作环境和4条隧道空间位置关系进行理论分析,确定隧道群最优施工顺序,并通过信息化监测手段进行验证控制。通过控制施工时间,采用自行式智能支撑台车,注浆加固技术等措施确保了重叠、交叉段隧道施工安全;采用注浆预加固和克泥效技术保证了周边建筑物的安全。上下重叠、麻花交叉型隧道群施工技术对于类似空间交叠、始发/接收风险较大隧道、近距离下穿重要建构筑隧道的施工有较强的指导和借鉴意义。

关键词：富水软弱地层重叠交叉盾构隧道自行式智能支撑台车注浆加固

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基于硫杂萘二酰亚胺的席夫碱型聚合物电子传输材料

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功能高分子学报 2020年第2期33卷 148-156页

作者：李建高李晶高希珂中国科学院上海有机化学研究所中国科学院大学上海200032

将苯甲醛基团引入到硫杂萘二酰亚胺共轭骨架中,与不同共轭程度和刚性的芳香二胺进行缩合反应,构筑了一类基于硫杂萘二酰亚胺的席夫碱型聚合物P1、P2、P3。采用紫外-可见吸收光谱(UV-Vis)、循环伏安等研究了材料的基本物理化学性质。这... 详细信息

将苯甲醛基团引入到硫杂萘二酰亚胺共轭骨架中,与不同共轭程度和刚性的芳香二胺进行缩合反应,构筑了一类基于硫杂萘二酰亚胺的席夫碱型聚合物P1、P2、P3。采用紫外-可见吸收光谱(UV-Vis)、循环伏安等研究了材料的基本物理化学性质。这类聚合物具有良好的成膜性和较低的最低未占分子轨道能级(-4.07^-4.19 eV)。聚合物P3含有刚性萘单元,其UVVis的最大吸收波长(λmax)为754 nm,比P1和P2分别红移了约76 nm和75 nm。X射线衍射(XRD)表明,聚合物P1、P2、P3的薄膜均呈现无定形的特征。以溶液甩膜法制备了此类聚合物的有机场效应晶体管(OFET)器件,其中聚合物P3的薄膜经300℃热退火,其OFET器件的电子迁移率可达2.47×10^-3 cm^2/(V·s),开关比为105,表明聚合物P3是一种可耐高温处理的n-型半导体材料。在聚合物共轭骨架中引入刚性的结构单元,可以有效调控吸收光谱、能级结构和薄膜形貌,进而提升OFET器件性能。

关键词：席夫碱硫杂萘二酰亚胺聚合物有机场效应晶体管

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高黎贡山隧道1^#高地温斜井降温处理技术研究及比选

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隧道建设（中英文） 2020年第10期40卷 1498-1505页

作者：李建高刘亚飞中铁隧道集团三处有限公司广东深圳518000

为解决高地温隧道工程中存在的作业环境差、机械设备故障多、劳动生产率低等高温热害问题,以大瑞铁路高黎贡山隧道1^#长大斜井为背景,进行技术研究和降温方案比选。首先,分析热水源、监测隧道洞内外气象条件,通过加强通风措施改善人体... 详细信息

为解决高地温隧道工程中存在的作业环境差、机械设备故障多、劳动生产率低等高温热害问题,以大瑞铁路高黎贡山隧道1^#长大斜井为背景,进行技术研究和降温方案比选。首先,分析热水源、监测隧道洞内外气象条件,通过加强通风措施改善人体的舒适度。其次,采用注浆封堵热水源,减少热水流量,控制施工环境的湿度和温度;采用冰块+射流风机+快热交换的处理措施,冰块吸收隧道内热量,降低局部环境温度;采用机械制冷设备进行强制降温,改善热害隧道施工环境;综合优化资源配置,采用增加作业人员和设备数量,倒班作业,缩短人员和设备作业时长等多种处理措施。最后,分析各种降温措施能够达到的施工效果。结果证明,针对以围岩、热水为主要热源的高地温隧道施工,采用"通风降温+注浆堵水+机械降温+合理施工组织"的处理方案,符合高地温隧道施工的技术要求。

关键词：高黎贡山隧道长大斜井降温措施热源分析高地温监测

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