CN111040135B - 具有核磁共振造影功能的共轭聚合物材料及其制备方法 - Google Patents
具有核磁共振造影功能的共轭聚合物材料及其制备方法 Download PDFInfo
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- CN111040135B CN111040135B CN201911264177.1A CN201911264177A CN111040135B CN 111040135 B CN111040135 B CN 111040135B CN 201911264177 A CN201911264177 A CN 201911264177A CN 111040135 B CN111040135 B CN 111040135B
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Abstract
本发明属于生物医学材料技术领域，具体为一种具有核磁共振造影功能的共轭聚合物纳米材料及其制备方法。本发明使用含有邻二酚单元的小分子调控共轭聚合物单体的聚合过程，从而调控材料的光学和顺磁性能；制备得到一系列具有磁共振造影功能和第二近红外诊疗功能的纳米材料，拓展了共轭聚合物纳米材料的应用范围。
Description
技术领域
本发明属于生物医学材料技术领域，具体涉及一种具有核磁共振造影功能的共轭聚合物纳米材料及其制备方法。
背景技术
纳米材料由于其小尺寸、高负载量以及自身特有的物理化学性能等特点被广泛用于肿瘤诊疗上。这些纳米材料可以按照其构成组份分为无机和有机两类。其中无机纳米材料自身特殊的理化性能，能被用于光学、磁学、核医学相关的诊疗技术上。然而在体内应用时，无机纳米材料需要较长的代谢时间，容易引起全身性的毒性和免疫反应，并且也会对癌细胞的转移有促进作用。相对于无机材料，有机纳米材料具有良好的生物相容性和可降解性，因此常被用在纳米载药领域。这一类纳米材料的缺点在于，作为功能单元，有机纳米材料（可分为小分子聚集体和共轭聚合物纳米材料）仅能被用于光学相关的诊疗技术上，光学诊疗技术受限于其较低的组织穿透深度（紫外-可见区，范围：700nm以下，组织穿透深度通常只有几个微米，第一近红外区，范围：700～1000 nm，组织穿透深度为几个毫米），实际应用价值有限。
本发明提出一种具有超顺磁性以及第二近红外吸收性能的共轭聚合物纳米材料及其制备方法。首先，本发明突破了共轭聚合物纳米材料仅能用于光学诊疗的限制，将其应用范围扩展到磁共振成像领域。核磁共振成像是一种适用于软组织的高精度成像模式，其在临床上的使用已经十分成熟，且不受组织穿透深度的限制。因此本发明得到的聚合物纳米材料具有良好的实际应用价值。其次，这类聚合物材料的第二近红外吸收性能使其还具备了这一区域的光热治疗和光声成像功能。光热治疗和光声成像功能等光学诊疗功能本身具有超高的精度和良好的时/空分辨率，但由于组织穿透深度较低（毫米级别），故实际效果有限。当进入第二近红外窗口后（范围：1000 nm～1700 nm），由于组织穿透深度的提升（达到厘米级别），这一区域的光学诊疗功能效果均能够大幅提高。因此，本发明制备得到的光学-核磁共振诊疗功能结合的纳米平台能够同时实现高精度、高时空分辨率和高组织穿透深度，对肿瘤的有效治疗有重要作用。
除以上两点，本发明提供的是针对一系列共轭聚合物纳米材料的制备方法。目前对于共轭聚合物纳米材料的性能调节主要是通过设计化学结构实现的，不仅过程繁琐，而且其化学结构与理化性能一一对应，并不具有普适性。而本发明提出利用含有邻苯二酚单元的小分子调控共轭聚合物纳米材料的光学和顺磁性能，能够适用于不同的共轭聚合物以制备一系列具有磁共振造影功能和第二近红外诊疗功能的纳米材料，由此对共轭聚合物纳米材料在诊疗平台上的开发具有指导意义。
发明内容
本发明的目的在于提供一种具有核磁共振造影功能的共轭聚合物纳米材料及其制备方法。
本发明提供的共轭聚合物纳米材料（粒子）的制备方法，对于聚吡咯、聚噻吩、聚苯胺和它们的衍生物均有效。
本发明提供的具有核磁共振造影功能的共轭聚合物纳米材料的制备方法，使用含有邻二酚单元的小分子调控共轭聚合物单体的聚合过程，从而调控材料的光学和顺磁性能；具体步骤如下（具体制备时可按照产量需求进行同比例放大）：
（1）配置4—10 mL pH为0—5的盐酸水溶液，将离子型表面活性剂溶解于盐酸溶液中，使其终浓度为0.4—0.6 mol/L；
其中，所述表面活性剂选择正辛基三甲基溴化铵、十八烷基三甲基溴化铵和十二烷基磺酸钠等；
（2）将0.5—2 mmol共轭聚合物的单体缓慢滴加至上述溶液中；所述单体为吡咯、噻吩或苯胺，或其衍生物；
（3）配置1 mL含有氧化剂氯化铁和邻二酚的混合溶液，记为溶液A，以及0.5 mL为氯化铁溶液、0.5 mL为氯化铁和邻二酚的混合液,记为溶液B；其中，氯化铁和单体的摩尔比（此处为单体完全转化为聚合物所需的氯化铁最低比例）：n氯化铁/n吡咯≥2.3, n氯化铁/n噻吩≥2，n氯化铁/n苯胺≥2，n为其下标所示化合物的摩尔数；单体与邻二酚的摩尔比范围为40—2.5；
其中，优选氯化铁和单体的摩尔比为：2.8≥ n氯化铁/n吡咯≥2.3，2.5≥ n氯化铁/n噻吩≥2，2.5≥n氯化铁/n苯胺≥2，
（4）共轭聚合物纳米粒子的合成
聚吡咯的合成，在冰水浴中进行，将步骤（3）中配置的溶液A缓慢滴加入步骤（2）中配置的含有对应单体的溶液中，保持0—8℃下反应3小时以上，优选反应时间3--5小时；
聚噻吩的合成，在室温下进行，首先对步骤（3）配置的溶液进行超声，使其形成均一的乳液，然后在超声下将步骤（3）中配置的溶液A缓慢滴入步骤（2）中配置的含有对应单体的溶液，室温反应24小时以上，优选反应时间24--30小时；
聚苯胺的合成，在室温下进行，首先加入溶液B中的氯化铁溶液0.5 mL，室温下反应15分钟—1小时，随后加入溶液B中邻二酚和氯化铁的混合溶液0.5 mL，室温下继续反应48小时以上，优选反应时间48--60小时；
对于吡咯、噻吩或苯胺的衍生物的聚合物的合成，与对应聚合物的合成方法相同；
（5）将上述制备的纳米粒子离心分离，并用乙醇洗涤数次，干燥（干燥温度不得高于40℃）。
上述方法制备所得共轭聚合物纳米粒子材料均具有顺磁性，能够缩短附近水分子的T2弛豫时间，在组织内，纳米粒子周围的水分子和其他部位的水分子T2弛豫时间不同，因此制备得到的纳米粒子可以用于T2加权的核磁共振造影。
本发明中，所述邻二酚单元的小分子可以为苯酚、多巴胺、左旋多巴或单宁酸等。
对于某些聚吡咯、聚噻吩、聚苯胺的衍生物，其氧化态对应的紫外吸收峰高于1000nm。用这种方法制备得到的纳米粒子同时具有第二近红外区域的光吸收，因此能够用于这一范围的光声成像和光热治疗方面。
本发明得到的共轭聚合物纳米粒子能够通过物理化学作用负载化疗药物、靶向配体、造影剂等等一系列功能分子，能够对其进行进一步的功能拓展，包括T1加权的磁共振成像、PET成像、化疗、放疗等，在构建多功能诊疗一体化纳米平台上有重要贡献。
附图说明
图1为实施例1所得的聚吡咯纳米粒子的透射电子显微镜照片。
图2为实施例1所得的聚吡咯纳米粒子在300—1100 nm波段的吸收光谱图。
图3为实施例2所得的聚（3,4-乙烯二氧）噻吩纳米粒子的透射电子显微镜照片。
图4为实施例2所得聚（3,4-乙烯二氧）噻吩纳米粒子在400—1100 nm波段的吸收光谱图。
图5为实施例3所得的浓度为100 μg/mL聚吡咯纳米粒子，在功率密度为1 W/cm2的激光器照射下，溶液温度随时间变化曲线（即实施例5）。
图6为实施例3所得聚吡咯纳米粒子材料的体外光声信号~激发波长曲线。
图7为实施例3所得的聚吡咯纳米粒子体外1/T2~浓度曲线图（即实施例6）。
图8为实施例4所得聚（3,4-乙烯二氧）噻吩纳米粒子体外1/T2~浓度曲线图（即实施例7）。
具体实施方式
以下结合具体实施例和附图对本发明进行进一步的详细描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1：
将正辛基三甲基溴化铵以终浓度为0.5 M的浓度溶于3.5 mL 1 M 盐酸，溶解后将0.745 mmol吡咯缓慢滴入溶液中。将0.463 g 三氯化铁溶于1 mL1 M盐酸，加入0.0745mmol邻苯二酚，溶解后，在冰浴下缓慢滴入含有吡咯单体的溶液。保持低温，反应三小时以上。用去离子水洗涤数次，真空干燥。
实施例2：
将0.265g十八烷基溴化铵溶于4.5 mL 1 M 盐酸，溶解后加入75 μL 3,4-乙烯二氧噻吩缓慢滴入溶液中。将0.381 g 三氯化铁溶于0.5 mL 1 M盐酸，加入12.5 mg多巴胺盐酸盐，溶解后，在冰浴下缓慢滴入含有噻吩衍生物单体的溶液。保持低温，反应48小时以上。用去离子水洗涤数次，真空干燥。
实施例3：
将10 mg实施例1中制备得到的纳米粒子分散在去离子水中，随后加入30 mg二硬脂酰磷脂酰乙醇胺修饰的聚乙二醇，分子量为2000。超声30分钟，室温下放置过夜后离心，用去离子水和PBS洗涤数次，待用。
实施例4：
将10 mg实施例2中制备得到的纳米粒子分散在去离子水中，随后加入30 mg二硬脂酰磷脂酰乙醇胺修饰的聚乙二醇，分子量为2000。超声30分钟，室温下放置过夜后离心，用去离子水和PBS洗涤数次，待用。
以下具体实验对于实施例3和实施例4制备出的聚吡咯纳米粒子进行检测。
实施例5：
使用实施例3所制备得到的纳米粒子，配置浓度为100μg/mL的PBS分散液，使用波长为1064nm，能量密度为1 W/cm2激光照射，并测定不同时间段的温度变化，观察到纳米粒子的PBS溶液在激光照射下迅速从室温开始上升，最终升至55℃。这一体外升温实验表明纳米粒子在激光照射下能够迅速加热周边环境，在体内应用时能够利用这一升温效果杀伤对温度敏感的肿瘤细胞。
实施例6：
使用实施例3所制备得到的纳米粒子，分别配置浓度为0.5 mg/mL, 1 mg/mL, 1.5mg/mL, 2.0 mg/mL, 2.5 mg/mL溶液，放置于0.5 T的磁场下得到T2加权的核磁共振成像照片。对比去离子水的T2加权核磁共振成像照片，纳米粒子溶液照片明显变暗，T2弛豫时间与浓度成线性关系。在体内应用时，纳米粒子能够缩短周围水分子的T2弛豫时间，在核磁共振成像上表现为变暗，以此实现体内成像功能。
实施例7：
使用实施例4所制备得到的纳米粒子，分别配置浓度为0.5 mg/mL, 1 mg/mL, 1.5mg/mL, 2.0 mg/mL, 2.5 mg/mL溶液，放置于0.5 T的磁场下得到的1/T2弛豫时间与纳米粒子浓度的关系图。与实施例5相似，实施例4制备得到的纳米粒子同样能够缩短周围水分子的T2弛豫时间，因此也具备T2加权的核磁共振成像造影功能。
Claims (6)
1.一种具有核磁共振造影功能的共轭聚合物纳米材料的制备方法，其特征在于，使用含有邻二酚单元的小分子调控共轭聚合物单体的聚合过程，从而调控材料的光学和顺磁性能；具体步骤如下：
（1）配置4—10 mL pH为0—5的盐酸水溶液，将离子型表面活性剂溶解于盐酸溶液中，使其终浓度为0.4—0.6 mol/L；
（2）将0.5—2 mmol共轭聚合物的单体缓慢滴加至上述溶液中；所述单体为吡咯、噻吩或苯胺，或其衍生物；
（3）配置1 mL含有氧化剂氯化铁和邻二酚的混合溶液，记为溶液A，以及0.5 mL为氯化铁溶液、0.5 mL为氯化铁和邻二酚的混合液,记为溶液B；其中，氯化铁和单体的摩尔比：n氯化铁/n吡咯≥2.3, n氯化铁/n噻吩≥2，n氯化铁/n苯胺≥2，n为其下标所示化合物的摩尔数；单体与邻二酚的摩尔比范围为40—2.5；
（4）共轭聚合物纳米粒子的合成
聚吡咯的合成，在冰水浴中进行，将步骤（3）中配置的溶液A缓慢滴加入步骤（2）中配置的含有对应单体的溶液中，在0—8℃下反应3小时以上；
聚噻吩的合成，在室温下进行，首先对步骤（3）配置的溶液进行超声，使其形成均一的乳液，然后在超声下将步骤（3）中配置的溶液A缓慢滴入步骤（2）中配置的含有对应单体的溶液，室温反应24小时以上；
聚苯胺的合成，在室温下进行，首先加入溶液B中的氯化铁溶液0.5 mL，室温下反应15分钟—1小时，随后加入溶液B中邻二酚和氯化铁的混合溶液0.5 mL，室温下继续反应48小时以上；
对于吡咯、噻吩或苯胺的衍生物的聚合物的合成，与对应聚合物的合成方法相同；
（5）将上述制备的纳米粒子离心分离，并用乙醇洗涤数次，干燥，干燥温度不高于40℃。
2.根据权利要求1所述的共轭聚合物纳米材料的制备方法，其特征在于，所述表面活性剂选自正辛基三甲基溴化铵、十八烷基三甲基溴化铵和十二烷基磺酸钠。
3.根据权利要求1所述的共轭聚合物纳米材料的制备方法，其特征在于，所述邻二酚单元的小分子选自多巴胺、左旋多巴或单宁酸。
4.由权利要求1-3之一所述制备方法得到的共轭聚合物纳米材料。
5.由权利要求4所述的共轭聚合物纳米材料在制备T2加权核磁共振造影剂中的应用。
6.由权利要求4所述的共轭聚合物纳米材料在制备光声成像和光热治疗材料方面的应用。
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| US20110212032A1 (en) * | 2007-08-29 | 2011-09-01 | Korea Research Institute Of Bioscience And Biotechnology | Polymer particles for nir/mr bimodal molecular imaging and method for preparing the same |
| CN104072736A (zh) * | 2014-06-24 | 2014-10-01 | 首都师范大学 | 一种共轭聚合物纳米材料的制备方法 |
| CN105153418A (zh) * | 2015-09-30 | 2015-12-16 | 华南理工大学 | 一种聚苯乙烯磺酸分散聚多巴胺—聚3,4-乙撑二氧噻吩复合导电聚合物的制备与应用 |
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| US20110212032A1 (en) * | 2007-08-29 | 2011-09-01 | Korea Research Institute Of Bioscience And Biotechnology | Polymer particles for nir/mr bimodal molecular imaging and method for preparing the same |
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