CN110279874A - 一种核磁共振成像引导肿瘤光热疗材料及其制备方法 - Google Patents
一种核磁共振成像引导肿瘤光热疗材料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种核磁共振成像引导肿瘤光热疗材料及其制备方法，采用碳酸钆纳米球和葡萄糖为原料，通过水热法制备得到纳米空心球壳结构，其成份为碳酸钆和无定形碳，其外径为60～100纳米，壳厚为10～25纳米，球壳结构具有介孔通道可供药物分子进出。该材料同时具有核磁共振成像、肿瘤光热治疗以及载药释放的功能，在肿瘤治疗领域具有良好的应用前景。
Description
技术领域
本发明涉及新材料领域，具体涉及一种具有核磁共振成像、肿瘤光热治疗和载药功能的纳米材料。
背景技术
在医疗技术飞速发展的今天，癌症仍然是困扰着人们的健康、生存问题的重要原因。目前，临床上癌症治疗的主要方法包括手术，放疗和化疗。然而，在大多数情况下，手术并不能完全清除所有的癌细胞组织，而放疗和化疗通常会导致严重的毒副作用，因为化学疗法的一般所需的抗癌药物剂量很高。显而易见，他们不是理想的选择，开发新的肿瘤治疗方法/药物是十分必要的。在过去的十年期间，随着纳米技术的进步，光热疗法引起了极大的关注。由于癌细胞的耐热性差，光热疗法采用近红外区域光吸收纳米材料，在肿瘤区域内将近红外激光的能量转化为热能，造成恶性癌组织/细胞的热消融，从而抑制肿瘤生长。
贵金属如金、银、铂的纳米颗粒是研究最广泛的肿瘤光热治疗材料，其光热转换原理是基于表面等离子体共振，吸收光子能量转换成热量。然而，金属的表面等离子体共振吸收波长普遍处于可见光波段，必须经由特殊而复杂的调控手段来改变贵金属纳米颗粒的尺寸形貌，使其共振吸收波长转移到近红外波段。半导体材料如硫化铜系列纳米结构也是研究比较多的肿瘤光热治疗材料。碳基材料如碳纳米管、石墨烯、氧化石墨烯等由于具有很宽的吸收波段，在近红外区域也有很好的光吸收和光热转换特性。相比较而言，碳基材料原料来源丰富，和人体的相容性好，因而是很有潜力的肿瘤光热治疗材料。
采用光热疗法杀灭癌细胞时，先让肿瘤光热治疗材料靶向附着在肿瘤组织上，然后用近红外激光定点照射肿瘤组织。因而，要有效实施光热疗法，前提条件是准确定位肿瘤组织，实现成像引导的肿瘤光热治疗。目前，有效的定位方法是利用医学成像技术实现肿瘤组织的可视化。在各种医学成像技术中，核磁共振成像技术具有分辨率高和软组织对比度强的主要优点。
在肿瘤治疗的实践中，单一的治疗手段往往难以得到理想的治疗效果，需要不同的治疗方法配合使用。比如，靶向药物治疗配合靶向光热治疗。因此，研究一种纳米材料使其既能够作为核磁共振成像造影剂使用，又能作为光热治疗试剂使用，同时还具有载药释放的功能，这对肿瘤成像及治疗的研究和发展具有极大的理论意义和实际意义。
在此，我们采用碳酸钆纳米球和葡萄糖为原料，通过水热法制备得到纳米空心球壳结构，其成份为碳酸钆和无定形碳，该材料同时具有核磁共振成像、肿瘤光热治疗以及载药释放的功能。
发明内容
针对上述问题，本发明提供了一种核磁共振成像引导肿瘤光热疗材料及其制备方法，以碳酸钆纳米球和葡萄糖为原料，通过水热法制备主要成分为碳酸钆和无定形碳的纳米空心球壳结构，其外径为60～100纳米，壳厚为10～20纳米，壳层具有介孔通道。该材料同时具有核磁共振成像、肿瘤光热治疗以及载药释放的功能。
制备过程中使用的碳酸钆纳米球的直径为60～100纳米，是以氯化钆和尿素为原料，在十六烷基三甲基溴化铵存在下，在水溶液中通过均匀沉淀法制得。在水热条件下，葡萄糖逐步脱水缩合生成无定形碳，附着在碳酸钆纳米球的表面，同时碳酸钆成分不断向外扩散，最终形成含有碳酸钆和无定形碳的空心球壳，并在球壳上留下大量的介孔通道。所制备的纳米空心球壳结构的外径可以通过碳酸钆纳米球的直径来调控，壳厚可以通过水热反应温度和水热反应时间来调控。在这个新颖的纳米结构中，碳酸钆赋予材料优异的核磁共振成像性能；无定形碳具有良好的近红外光吸收及光热转换特性，赋予材料显著的光热治疗特性；内部的空腔可以装载药物，壳层上的介孔通道为药物分子的进出提供了路径。综合上述三方面的因素，本发明制备的纳米空心球壳结构同时具有核磁共振成像、肿瘤光热治疗以及载药释放的功能。
具体实施方式
以下将结合实施例对本发明作进一步说明。
实例1
称取1.859g GdCl3·6H2O溶解于250mL水中配制成溶液，加入1.822g十六烷基三甲基溴化铵搅拌1h，最后加入0.9010g的尿素搅拌1h。将溶液转移到三口烧瓶中，于80℃下油浴加热5h。离心分离收集沉淀，用去离子水洗涤，重复三次得到直径为100纳米的碳酸钆纳米球。取0.6g上述碳酸钆纳米球分散到10mL去离子水中，加入0.8g葡萄糖，再加入30mL去离子水搅拌均匀之后，转移到高压水热反应釜中，于200℃下反应4h。待上述高压釜冷却至室温之后，收集沉淀物，离心分离，用去离子水洗涤，重复三次得到碳酸钆/碳纳米空心球壳结构，外径100纳米，壳厚15纳米，壳层具有介孔通道。经过核磁共振成像、光热转换以及载药释放实验检验，证实该材料同时具有上述三方面的功能。
实例2
称取1.859g GdCl3·6H2O溶解于250mL水中配制成溶液，加入1.822g十六烷基三甲基溴化铵搅拌1h，最后加入0.9010g的尿素搅拌1h。将溶液转移到三口烧瓶中，于80℃下油浴加热2h。离心分离收集沉淀，用去离子水洗涤，重复三次得到直径为80纳米的碳酸钆纳米球。取0.6g上述碳酸钆纳米球分散到10mL去离子水中，加入0.8g葡萄糖，再加入30mL去离子水搅拌均匀之后，转移到高压水热反应釜中，于200℃下反应2h。待上述高压釜冷却至室温之后，收集沉淀物，离心分离，用去离子水洗涤，重复三次得到碳酸钆/碳纳米空心球壳结构，外径80纳米，壳厚10纳米，壳层具有介孔通道。经过核磁共振成像、光热转换以及载药释放实验检验，证实该材料同时具有上述三方面的功能。
Claims (7)
1.一种核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，采用碳酸钆纳米球和葡萄糖为原料，通过水热法制备得到纳米空心球壳结构，其成份为碳酸钆和无定形碳，该材料同时具有核磁共振成像、肿瘤光热治疗以及载药释放的功能。
2.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，所述的纳米空心球壳结构，其外径为60～100纳米，壳厚为10～25纳米，球壳结构具有介孔通道可供药物分子进出。
3.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，所述的碳酸钆纳米球的直径为60～100纳米，是以氯化钆和尿素为原料，在十六烷基三甲基溴化铵存在下，在水溶液中通过均匀沉淀法制得。
4.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，作为原料的葡萄糖和碳酸钆纳米球的质量比为1～4，水热反应温度为180～220℃，水热反应时间为1～4小时。
5.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，所制备的纳米空心球壳结构的外径可以通过碳酸钆纳米球的直径来调控，壳厚可以通过水热反应温度和水热反应时间来调控。
6.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，该材料具有显著的核磁共振成像增强效果，可用作核磁共振成像剂。
7.如权利要求1所述的核磁共振成像引导肿瘤光热疗材料及其制备方法，其特征在于，该材料在780～1400纳米波段具有良好的光吸收及光热转换特性，可用作肿瘤光热治疗剂。
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