【作者】 李艳；

【导师】 韩秋霞； 孙记夫；

【作者基本信息】 山东科技大学 ， 材料与化工（专业学位）， 2025， 硕士

【摘要】 氟硼二吡咯(BODIPY)具有结构稳定、易于修饰性、荧光量子产率高以及良好的光稳定性等。目前已被广泛应用于光动力治疗(PDT)、荧光成像等领域。然而,其固有的刚性共轭平面结构所带来的水溶性、生物相容性差和在水相和固态下容易聚集等问题严重限制了其在PDT中的应用。本文通过合成一系列含不同比例BODIPYs的聚合物并与葫芦脲[7](CB[7])组装构筑主客体体系,成功解决了以上问题,并研究了不同聚合物体系中BODIPYs的含量对其荧光发射、紫外吸收、三线态寿命以及产生单线态氧能力的影响规律。具体研究内容如下:(1)合成了两种高分子聚合物:(1)含BODIPY单体的聚合物MPPBDP;(2)含不同比例碘代BODIPY单体的聚合物2IMPPBDP(2IMPPBDP-1、2IMPPBDP-2、2IMPPBDP-3、2IMPPBDP-4)。通过核磁共振氢谱、碳谱、高分辨质谱以及凝胶渗透色谱(GPC)对化合物结构进行了表征。经过计算确定MPPBDP中各单体的聚合比例为19/2/24;2IMPPBDP-1、2IMPPBDP-2、2IMPPBDP-3、2IMPPBDP-4中各单体的聚合比例分别为18/1/18、16/2/19、14/3/16、20/4/24。(2)将MPPBDP、2IMPPBDP作为客体分子分别与CB[7]组装,并探究不同组装体系中BODIPYs的含量对其荧光发射、紫外吸收、三线态寿命及单线态氧产生效率的影响规律。研究结果表明:随着聚合物中碘代BODIPY含量增大,其荧光发射强度和紫外吸收强度也变大、单线态氧的产生效率也增高。此外,测得2IMPPBDP-1/CB[7]、2IMPPBDP-2/CB[7]、2IMPPBDP-3/CB[7]和2IMPPBDP-4/CB[7]体系的三线态寿命分别为501、507、694和528μs。随着碘代BODIPY的含量越高,2IMPPBDP/CB[7]组装体系的三线态寿命呈现出先上升后下降的趋势,其中2IMPPBDP-3/CB[7]体系表现出最长的三线态寿命(694μs)。聚合物中碘代BODIPY含量最高的2IMPPBDP-4,三线态寿命却出现缩短现象,推测是由于2IMPPBDP-4/CB[7]组装体系中过多的碘代BODIPY发生了聚集淬灭,最终导致三线态寿命降低。综上所述,本文通过将BODIPY光敏剂进行高分子共聚并与CB[7]组装,成功构建了性质更为稳定的PDT光敏剂。解决了BODIPY在PDT应用中存在的水溶性、生物相容性差等问题,并研究了聚合体系中BODIPY单体的含量对组装体系PDT性能的影响规律。本研究有望为荧光分子在PDT等光疗领域的应用提供坚实的理论基础,推动相关领域的进一步发展。更多还原

【Abstract】 Fluoroboron dipyrrole（BODIPY）has characteristics such as stable structure,easy modifiability,high fluorescence quantum yield,and good photostability.Currently,it has been widely applied in fields such as photodynamic therapy（PDT）and fluorescence imaging.However,problems such as poor water solubility,poor biocompatibility,and easy aggregation in the aqueous phase and solid state,which are caused by its inherent rigid conjugated planar structure,severely limit its application in PDT.In this thesis,a series of polymers containing BODIPYs in different proportions were synthesized and assembled with cucurbituril[7]（CB[7]）to construct a host-guest system,successfully solving the above problems.Moreover,the influence laws of the content of BODIPYs in different polymer systems on their fluorescence emission,ultraviolet absorption,triplet state lifetime,and the ability to generate singlet oxygen were studied.The specific research contents are as follows:（1）Two kinds of high molecular polymers were synthesized:（1）the polymer MPPBDP containing BODIPY monomer;（2）the polymers 2IMPPBDP（2IMPPBDP-1,2IMPPBDP-2,2IMPPBDP-3,2IMPPBDP-4）containing iodinated BODIPY monomers in different proportions.The structures of the compounds were characterized by proton nuclear magnetic resonance（¹H NMR）,carbon nuclear magnetic resonance(¹³C NMR),high-resolution mass spectrometry（HRMS）and gel permeation chromatography（GPC）.Through calculation,it was determ-ined that the polymerization ratios of each monomer in MPPBDP were 19/2/24;and the polymerization ratios of each monomer in 2IMPPBDP-1,2IMPPBDP-2,2IMPPBDP-3 and2IMPPBDP-4 were 18/1/18,16/2/19,14/3/16 and 20/4/24 respectively.（2）MPPBDP and 2IMPPBDP were used as guest molecules to assemble with CB[7]respectively,and the influence rules of the content of BODIPYs in different assembly systems on their fluorescence emission,ultraviolet absorption,triplet state lifetime and singlet oxygen generation efficiency were explored.The research results show that:with the increase of the content of iodinated BODIPY in the polymer,the fluorescence emission intensity,ultraviolet absorption intensity and the generation efficiency of singlet oxygen also increase.In addition,the triplet state lifetimes of the 2IMPPBDP-1/CB[7],2IMPPBDP-2/CB[7],2IMPPBDP-3/CB[7]and2IMPPBDP-4/CB[7]systems were measured to be 501,507,694 and 528μs respectively.With the increase of the content of io-dinated BODIPY,the triplet state lifetime of the2IMPPBDP/CB[7]assembly system shows a trend of first increasing and then decreasing,among which the 2IMPPBDP-3/CB[7]system exhibits the longest triplet state lifetime（694μs）.For 2IMPPBDP-4 with the highest content of iodinated BODIPY in the polymer,the triplet state lifetime is shortened.It is speculated that this is because excessive iodinated BODIPY in the2IMPPBDP-4/CB[7]assembly system undergoes aggregation quenching,ultimately leading to a decrease in the triplet state lifetime.In conclusion,in this thesis,by conducting high molecular copolymerization of the BODIPY photosensitizer and assembling it with CB[7],a more stable PDT photosensitizer with better properties has been successfully constructed.The problems such as poor water solubility and biocompatibility of BODIPY in PDT applications have been solved,and the influence laws of the content of BODIPYs monomers in the polymerization system on the PDT performance of the assembled system have been studied.This research is expected to provide a solid theoretical foundation for the application of fluorescent molecules in phototherapy fields such as PDT,and to promote the further development of related fields.更多还原