CN113861391A - 一种用于近红外二区成像的双给体共轭聚合物及应用 - Google Patents

一种用于近红外二区成像的双给体共轭聚合物及应用 Download PDF

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CN113861391A
CN113861391A CN202111172322.0A CN202111172322A CN113861391A CN 113861391 A CN113861391 A CN 113861391A CN 202111172322 A CN202111172322 A CN 202111172322A CN 113861391 A CN113861391 A CN 113861391A
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邓卫星
舒琦
刘远立
段炼
徐旭
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Guilin University of Technology
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Abstract

本发明公开了一种用于近红外二区成像的双给体共轭聚合物。分子结构中含有两种不同结构的电子给体单元，和一种电子受体单元。共轭聚合物的光学性质可根据两种电子给体在分子结构中的比例进行调整。此类双给体共轭聚合物吸收波长均大于1100nm，可利用1064nm光源进行成像和治疗，可以实现近红外二区荧光成像，并能有效抑制肿瘤细胞的生长。

Description

一种用于近红外二区成像的双给体共轭聚合物及应用
技术领域
本发明涉及一种用于近红外二区成像的双给体共轭聚合物，属于生物医学成像技术领域。
背景技术
在癌症日益增长的今天，如何对其进行早期预防和诊断变得十分有意义。光热疗法(PTT)将光学成像和激光治疗合二为一，具有高成像灵敏度、低治疗副作用和足够的疗效等特点。目前，荧光成像(FL)以及光热疗法(PTT)已被证明是临床前研究中出色的光疗系统。然而许多生物组织在可见光区(400～700nm)和近红外一区(700～900nm，NIR-Ⅰ)由于内源性物质的吸收和散射，使透光率和灵敏度降低，对可见光波长范围内的荧光成像有不利影响。
而在近红外二区(1000～170nm，NIR-II)，生物组织的吸收、散射和自发荧光相对较低，近红外光可以在生物组织中达到较大的穿透深度和可以进行深层组织成像，因此成为近年来的研究热门。目前报道的基于NIR-Ⅱ荧光成像的PTT材料主要有无机纳米颗粒和有机荧光材料两种。其中有机荧光材料又分为有机小分子和共轭聚合物两种，而共轭聚合物基纳米粒子因为具备优异的光稳定性、强大的光热性能、良好的结构可塑性以及优良的生物相容性等等诸多优秀的光学特征吸引了越来越多的研究者的研究兴趣。但是局限于其发射波长小于900nm，并不适用于NIR-II荧光成像。因此，将其发射波长位移到NIR-II窗口虽是一项挑战性的工作，但对于扩大它们在生物医学成像方面的应用来说是至关重要的。
发明内容
为解决上述技术问题，本发明提供了一种用于近红外二区成像的双给体共轭聚合物。旨在提高共轭聚合物基纳米粒子的水溶性、生物相容性、靶向性以及近红外二区荧光强度和光热转化性质，得以实现近红外二区荧光成像，并能有效抑制肿瘤细胞的生长。
为实现上述目的，本发明所采取的技术方案为：
一种用于近红外二区成像的双给体共轭聚合物，其特征在于，其分子结构中含有两种不同结构的电子给体单元，一种电子受体单元。
所述双给体共轭聚合物的结构式如下：
Figure BDA0003293828080000021
所述双给体共轭聚合物中的供体为(4,8-双(5-(2-丁基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双三甲基锡(BDT)，和2,6-二溴-4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b’]二噻吩(CPDT)，结构式如下：
Figure BDA0003293828080000022
所述电子受体为4,8-二(5-溴-4-(2-辛基十二烷基)噻吩基)-苯并[1,2-c；4,5-c']二[1,2,5]噻二唑(BBT)结构式如下：
Figure BDA0003293828080000023
所述两种电子给体的摩尔比为1:2、1:1、2:1。
本发明还提供用于近红外二区成像的双给体共轭聚合物在近红外二区荧光成像造影剂方面的应用。
本发明还提供用于近红外二区成像的双给体共轭聚合物在作为近红外二区光热治疗试剂方面的应用。
有益效果：本发明公开一种用于近红外二区成像的双给体共轭聚合物，利用两亲性三嵌段聚合物F127形成纳米颗粒水溶液，该纳米颗粒水溶液具有良好的水溶性、生物相容性、靶向性以及出色的近红外二区荧光强度和光热转化性质，可以实现近红外二区荧光成像，并能有效抑制肿瘤细胞的生长。
附图说明
图1为实施例1得到的双给体共轭聚合物纳米颗粒的透射电镜图；
图2为实施例1得到的双给体共轭聚合物纳米颗粒的紫外谱图；
图3为实施例1得到的双给体共轭聚合物纳米颗粒的荧光谱图；
图4为实施例2得到的双给体共轭聚合物纳米颗粒的紫外谱图；
图5为实施例2得到的双给体共轭聚合物纳米颗粒的荧光谱图；
图6为实施例3得到的双给体共轭聚合物纳米颗粒的紫外谱图；
图7为实施例3得到的双给体共轭聚合物纳米颗粒的荧光谱图；
图8为实施例1得到的双给体共轭聚合物纳米颗粒的小鼠血管及肿瘤成像；
图9为实施例1得到的双给体共轭聚合物纳米颗粒的肿瘤小鼠的热成像图；
图10为实施例1得到的双给体共轭聚合物纳米颗粒对肿瘤的治疗效果。
具体实施方式
下面结合实施例对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
近红外二区双给体共轭聚合物的合成路线如下：
Figure BDA0003293828080000041
实施例1：
双给体共轭聚合物一的合成方法如下：
将单体4,8-二(5-溴-4-(2-辛基十二烷基)噻吩基)-苯并[1,2-c；4,5-c']二[1,2,5]噻二唑(BBT)(32.32mg，0.03mmol)、(4,8-双(5-(2-丁基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双三甲基锡(BDT)(91.51mg，0.09mmol)，2,6-二溴-4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b’]二噻吩(CPDT)(33.64mg，0.06mmol)、三二亚苄基丙酮二钯(1.38mg，1.5μmol)、三(邻甲苯基)膦(1.83mg，6μmol)加入希丁克管中，氮气氛围下加入无水甲苯(3mL)，黑暗中加热搅拌(120℃，70min)，反应停止并降至室温后，在甲醇中沉淀，通过离心收集聚合物，在室温下待溶剂挥发完全后得到双给体共轭聚合物一，为红褐色固体。
双给体共轭聚合物一纳米粒子水溶液的制备，方法如下：
称取1mg的双给体共轭聚合物一样品溶于1mL四氢呋喃中，然后在超声条件下将上述溶液迅速加入含有F127(15mg)的5mL超纯水中，再继续超声3min，然后静置待四氢呋喃挥发后用截留分子量30KD的超滤离心管对溶液进行离心去除部分水，最后得到2mg/mL的双给体共轭聚合物一纳米颗粒水溶液。
如图1所示，配置浓度为0.005mg/mL的纳米粒子水溶液，测试其透射电镜图，可得该纳米粒子粒径为30nm-70nm，且都为类球形。
如图2所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其吸收图谱。该双给体共轭聚合物一纳米粒子水溶液的最大吸收峰为945nm，在800-1200nm范围内有较强的吸收。
如图3所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其荧光图谱。该双给体共轭聚合物一纳米粒子水溶液的最大发射峰为1119nm，在100-1400nm范围内有荧光发射。
如图8所示，选用4T1肿瘤小鼠，尾部静脉注射200μL的双给体共轭聚合物一纳米颗粒水溶液(2mg/mL)，用近红外二区成像仪观察小鼠血管和肿瘤部位的荧光信号强度，从图中可知肿瘤部位的近红外二区荧光强度不断增加，在注射后24h达到峰值，随后迅速下降，且身体、腹部和后肢的血管都能观察到，成像清晰。
如图9所示，选用4T1肿瘤小鼠，尾部静脉注射200μL的双给体共轭聚合物一纳米粒子水溶液(2mg/mL)，注射24h后，用激光(1064nm，1W/cm2)持续照射，从图中可知小鼠肿瘤部位温度迅速上升且很快达到62℃左右的平台区，达到对肿瘤细胞消融的温度。
如图10所示，分别选用两组(每组六只)4T1肿瘤小鼠，尾部静脉注射200μL的双给体共轭聚合物一纳米粒子水溶液(2mg/mL)，24h之后，每天分别接受或不接受5min的激光(1064nm，1W/cm2)持续照射，并在15天后处死小鼠，收集肿瘤，从图中可知，肿瘤的生长完全受到了抑制。
实施例2：
双给体共轭聚合物二的合成方法如下：
将单体4,8-二(5-溴-4-(2-辛基十二烷基)噻吩基)-苯并[1,2-c；4,5-c']二[1,2,5]噻二唑(BBT)(32.32mg，0.03mmol)、(4,8-双(5-(2-丁基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双三甲基锡(BDT)(61.01mg，0.06mmol)，2,6-二溴-4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b’]二噻吩(CPDT)(16.82mg，0.03mmol)、三二亚苄基丙酮二钯(1.38mg，1.5μmol)、三(邻甲苯基)膦(1.83mg，6μmol)加入希丁克管中，氮气氛围下加入无水甲苯(3mL)，黑暗中加热搅拌(120℃，70min)，反应停止并降至室温后，在甲醇中沉淀，通过离心收集聚合物，在室温下待溶剂挥发完全后得到双给体共轭聚合物二，为红褐色固体。
双给体共轭聚合物二纳米粒子水溶液的制备，方法如下：
称取1mg的双给体共轭聚合物二样品溶于1mL四氢呋喃中，然后在超声条件下将上述溶液迅速加入含有F127(15mg)的5mL超纯水中，再继续超声3min，然后静置待四氢呋喃挥发后，得到双给体共轭聚合物二纳米颗粒水溶液。
如图4所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其吸收图谱。该双给体共轭聚合物二纳米粒子水溶液的最大吸收峰为959nm，并在800-1200nm范围内有较强的吸收。
如图5所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其荧光图谱。该双给体共轭聚合物二纳米粒子水溶液的最大发射峰为1110nm，并在100-1400nm范围内有荧光发射。
实施例3：
双给体共轭聚合物三的合成方法如下：
将单体4,8-二(5-溴-4-(2-辛基十二烷基)噻吩基)-苯并[1,2-c；4,5-c']二[1,2,5]噻二唑(BBT)(64.64mg，0.06mmol)、(4,8-双(5-(2-丁基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双三甲基锡(BDT)(91.51mg，0.09mmol)，2,6-二溴-4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b’]二噻吩(CPDT)(16.82mg，0.03mmol)、三二亚苄基丙酮二钯(1.38mg，1.5μmol)、三(邻甲苯基)膦(1.83mg，6μmol)加入希丁克管中，氮气氛围下加入无水甲苯(3mL)，黑暗中加热搅拌(120℃，70min)，反应停止并降至室温后，在甲醇中沉淀，通过离心收集聚合物，在室温下待溶剂挥发完全后得到双给体共轭聚合物三，为红褐色固体。
双给体共轭聚合物三纳米粒子水溶液的制备，方法如下：
称取1mg的双给体共轭聚合物三样品溶于1mL四氢呋喃中，然后在超声条件下将上述溶液迅速加入含有F127(15mg)的5mL超纯水中，再继续超声3min，然后静置待四氢呋喃挥发后，得到双给体共轭聚合物三纳米颗粒水溶液。
如图6所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其吸收图谱。该双给体共轭聚合物三纳米粒子水溶液的最大吸收峰为961nm，并在800-1200nm范围内有较强的吸收。
如图7所示，配置浓度为0.025mg/mL的纳米粒子水溶液，测试其荧光图谱。该双给体共轭聚合物三纳米粒子水溶液的最大发射峰为1110nm，并在100-1400nm范围内有荧光发射。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (8)

1.一种用于近红外二区成像的双给体共轭聚合物，其特征在于，其分子结构中含有两种不同结构的电子给体单元，一种电子受体单元。
2.一种用于近红外二区成像的双给体共轭聚合物，其特征在于，其吸收波长大于1100nm，可利用1064nm光源进行成像和治疗。
3.根据权利要求1所述的一种用于近红外二区成像的双给体共轭聚合物，其特征在于，所述双给体共轭聚合物的结构式如下：
Figure FDA0003293828070000011
4.根据权利要求1所述的一种用于近红外二区成像的双给体共轭聚合物，其特征在于，所述双给体共轭聚合物中的电子供体为(4,8-双(5-(2-丁基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双三甲基锡(BDT)，和2,6-二溴-4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b’]二噻吩(CPDT)，结构式如下：
Figure FDA0003293828070000012
5.根据权利要求1所述的一种用于近红外二区成像的双给体共轭聚合物，其特征在于，所述两种电子受体为4,8-二(5-溴-4-(2-辛基十二烷基)噻吩基)-苯并[1,2-c；4,5-c']二[1,2,5]噻二唑(BBT)结构式如下：
Figure FDA0003293828070000021
6.根据权利要求4所述的一种用于近红外二区成像的双给体共轭聚合物，其特征在于，所述两种电子给体的摩尔比为1:2、1:1、2:1。
7.根据权利要求1-5任意一项所述用于近红外二区成像的双给体共轭聚合物在作为肿瘤靶向近红外二窗荧光成像造影剂中的应用。
8.根据权利要求1-5任意一项所述用于近红外二区成像的双给体共轭聚合物在作为肿瘤治疗的光热治疗试剂中的应用。
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