CN116650524A - 近红外光催化具有酸响应的缺陷型铋纳米片的制备方法 - Google Patents
近红外光催化具有酸响应的缺陷型铋纳米片的制备方法 Download PDFInfo
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Abstract
本发明公开了一种近红外光催化具有酸响应的缺陷型铋纳米片的制备方法,是以生物矿化原理为合成基础的新型纳米材料,利用其优良性质用于高效的肿瘤治疗。纳米片合成主要包括氧缺陷BiO2‑x纳米片的制备、原位生长CaCO3薄层及聚乙二醇的修饰,最终合成一种新型的复合纳米片。这种纳米片的具体制备方法包括以下几个步骤:1)氧缺陷结构的BiO2‑x纳米片的制备;2)BiO2‑x表面原位沉积CaCO3薄层;3)复合纳米片BiO2‑x@CaCO3/PEG(BCP)的制备,最终得到的纳米片材料具有良好的生物相容性、肿瘤微环境酸响应性、缓解肿瘤乏氧及良好的肿瘤治疗效果。
Description
技术领域
本发明涉及纳米材料技术领域,具体涉及近红外光催化具有酸响应的缺陷型铋纳米片的制备与应用。
背景技术
癌症是目前世界上最严重的疾病之一,在研究癌症治疗方法方面经历了许多探索和研究,如光动力疗法、化学疗法和光热疗法,随着研究的发展与深入,人们关注到一氧化碳(CO)在癌细胞凋亡中发挥着重要的作用。使用一氧化碳气体治疗癌症,也被认为是一个可行的方案,同时也能减少对正常细胞的毒性。光催化还原二氧化碳在能源领域是一种很有前景的生产化学燃料和减少温室气体的策略,这需要开发设计具有宽波长范围的高效光催化剂。在早期的研究中,只能对紫外(UV)光起反应的光催化剂,如二氧化钛、BaZrO3和NaTaO3等,而目前响应紫外可见近红外光刺激的催化二氧化碳还原的新型光催化剂被广泛研究。比如铋基纳米材料,由于铋的价格低廉、无毒、电子传递效率高,而且关于铋的金属氧化物为代表的研究最多,其中BiO2-x具有窄带隙、富氧空位且宽波长光吸收范围等特点,将其作为光催化剂具有很大的应用潜力。因此,基于以上优势,富氧缺陷的BiO2-x可以作为一种新型光催化剂用于近红外光催化还原CO2,以此高效生产CO。
BiO2-x作为一种有效的人工纳米酶,与天然酶相比,人工纳米酶具有低成本、稳定性高、耐用性等优点在肿瘤微环境下可以催化超氧阴离子(·O2 -)和羟基自由基(·OH)等剧毒自由基的产生,用于肿瘤治疗。为了更好地实现BiO2-x在生命健康学中的应用以及增强其在肿瘤中的治疗效果。研究发现,仿生和矿化材料,如碳酸钙(CaCO3),具有良好的生物相容性,是生物应用中最具有前景的材料之一,同时在肿瘤治疗中的也具备广泛的发展前景和发展潜力。同时,当CaCO3浸没在肿瘤的微酸性环境中,碳酸钙会分解产生二氧化碳气泡和水,为肿瘤提供CO2气体和Ca2+微环境。与此同时,线粒体内的Ca2+过载会引起线粒体的功能障碍,当细胞内Ca2+发生失衡时,线粒体作为传感器和调节器,从细胞质中摄取Ca2+以维持细胞内钙离子稳态。然而,当大量的细胞内Ca2+在线粒体中积累时,过量的Ca2+会引发细胞凋亡,从而起到杀伤肿瘤的作用。
发明内容
癌症是世界上最难攻克的疾病之一,治疗癌症的方式随着研究的深入而不断变得多元化和复杂化,例如光动力疗法、化学疗法和光热疗法等。气体治疗(Gas Therapy)作为一种新兴的治疗策略,在肿瘤治疗中越来越受到重视。许多治疗气体如一氧化碳、一氧化氮、硫化氢、氧气和二氧化硫在细胞、组织或有机体的各种生理过程中发挥重要的调控作用。因此本发明旨在合成一种具有较高生物相容性,酸响应性、近红外光催化还原产生CO用于气体治疗同时缓解肿瘤乏氧的新型药物递送平台。
本发明的技术方案具体如下:
近红外光催化具有酸响应的缺陷型铋纳米片的制备方法,其特征在于:包含以下步骤:
(1)缺陷型结构BiO2-x纳米片的制备:首先将NaBiO3粉末充分溶解于NaOH溶液中,在室温下磁力搅拌2小时,形成均匀悬浮液,再将其转移至50 mL不锈钢高压反应器中,保持180℃加热18小时,冷却至室温,用去离子水多次离心洗涤,得到块状纳米材料,随后制备剥离液(使用一定量体积比的去离子水和无水乙醇溶液),再将上述得到的块状纳米材料分散在剥离液中,冰浴超声8小时,最后离心洗涤5次,获得缺陷型结构BiO2-x纳米片;
(2)BiO2-x@CaCO3纳米片的制备:将CaCl2加入到分散在乙醇溶液中的BiO2-x的容量瓶中,在室温下将该容量瓶与另一个装有固体粉末NH4HCO3的容量瓶同时放入密封容器中,然后对装有分散在乙醇溶液中的BiO2-x的容量瓶剧烈搅拌,反应8小时后,进行多次离心洗涤,获得BiO2-x@CaCO3纳米片;
(3)BiO2-x@CaCO3/PEG(BCP)纳米片的制备:将含有一定量的BiO2-x@CaCO3和NH2-PEG-NH2溶液的分散在50 mL水体系下,进行冰浴超声2 h,然后用去离子水和乙醇洗涤5次后,去除未反应的NH2-PEG-NH2,最后离心干燥,获得具有酸响应和多酶活性用于气体治疗的BCP纳米片。
进一步的,所述步骤(1)中NaBiO3粉末的质量为1.5~2.5 mg; 所述步骤(1)中氢氧化钠的浓度和体积分别为1~1.5 M和30~50 mL;所述步骤(1)中剥离液:无水乙醇和水的体积比为0.8~1.2。
进一步的,所述步骤(2)中CaCl2粉末的质量为15~20 mg;所述步骤(2)中BiO2-x的浓度和体积分别为 10~30 μg/mL和30~50 mL;所述步骤(2)中固体粉末 NH4HCO3质量为5~8g。
进一步的,所述步骤(1)、步骤(2)、步骤(3)中超声的功率为100 W,离心的转速为10000 rpm,离心的时间为8 min。
本发明主要优点有:
针对目前癌症治疗的传统疗法,本发明创造性地制备出一种新型光催化剂用于一氧化碳气体治疗、缓解肿瘤乏氧且生物相容性好,稳定性强的纳米药物递送平台,本发明的创新性在于BiO2-x具有独特的催化活性,其中富氧缺陷型 BiO2-x 的带隙约为 1.35 eV,窄带隙有利于BiO2-x在近红外光辐射下电子和空穴的快速分离,并且通过生物矿化原理在BiO2-x纳米片上稳定形成一层CaCO3薄层,形成的BiO2-x@CaCO3复合物在近红外光照下可以将CO2气体催化还原为CO,并且导致Ca2+在线粒体中超载。同时,制备的BiO2-x@CaCO3/PEG(BCP)富氧缺陷型纳米片具有多种酶活性,如过氧化氢酶、过氧化物酶和超氧化物歧化酶活性,有利于在肿瘤微环境中产生大量ROS物种(如·OH和·O2 -)和氧气。因此该缺陷型复合纳米材料具有很大的应用潜力,在生物应用、疾病治疗等领域具有进一步开发的价值。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚,本发明提供如下附图:
图1为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片的合成,机理及治疗示意图。
图2为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)的TEM图。
图3为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)的高角度环形暗场成像扫描透射电子显微镜(HAADF-STEM)和能量色散 X 射线光谱 (EDX)元素映射。
图4为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)的拉曼光谱。
图5为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)的傅里叶变换红外光谱。
图6为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)在不同浓度的过氧化氢溶液中氧气水平随时间变化图。
图7为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)在光照射处理后的 ESR 光谱。
图8为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)对4T1癌细胞的体外毒性图。
图9为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)的体内抗肿瘤效果图。
图10为本发明实施例1近红外光催化具有酸响应的缺陷型铋纳米片(BCP)在小鼠体内血常规结果图。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
(1)缺陷型结构BiO2-x纳米片的制备:将NaBiO3(2.0 g)粉末溶于NaOH(1.2 M,40mL)中,室温搅拌2小时,形成均匀悬浮液。将其转移至50 mL不锈钢高压反应器中,180℃加热18小时,冷却至室温,离心后得到沉淀,用去离子水洗涤5次以上,得到块状纳米材料后,制备剥离液(去离子水体积比:无水乙醇 = 1:1)。最后将大块材料分散在剥离液中,冰浴超声8小时,最后离心5次;
(2)BiO2-x@CaCO3纳米片的制备:将16 mg CaCl2加入到分散在50 mL乙醇溶液的BiO2-x(20 μg/mL)的容量瓶中,在室温下将该容量瓶与另一个装有固体粉末 NH4HCO3的容量瓶同时放入密封容器中,然后对装有分散在乙醇溶液中的BiO2-x的容量瓶剧烈搅拌,反应8小时后,进行多次离心洗涤,获得BiO2-x@CaCO3纳米片;
(3)BiO2-x@CaCO3/PEG(BCP)纳米片的制备:将含有BiO2-x@CaCO3(0.1 mg/mL)和NH2-PEG-NH2(0.1 mg/mL)溶液的分散在50 mL水体系下,进行冰浴超声2 h,然后用去离子水和乙醇洗涤5次后,去除未反应的NH2-PEG-NH2,最后离心干燥,获得具有酸响应和多酶活性用于气体治疗的BCP纳米片。
BCP纳米片的STEM如图2所示,其粒径在186 nm左右。图3表示BCP纳米片的能量色散X射线光谱(EDX)元素图谱(HAADF-STEM-EDX),证明了BCP纳米片的三种特征元素为铋(Bi)、钙(Ca)和氧(O)。图4显示BCP纳米片的拉曼光谱,从光谱中可得出118 cm−1 处的峰是Bi 原子的振动峰。138 和 154 cm-1 处的峰来自 Bi-O 的伸缩振动峰,而 180-500 cm-1范围内的其他峰来自 O 原子的振动峰。图5 HOOC-PEG-NH2 在 BiO2-x@CaCO3纳米片上的修饰通过傅里叶变换红外(FTIR)光谱证明。HOOC-PEG-NH2在1004~1194 cm-1、2790~2974 cm-1和3366~3611 cm-1处的强吸收峰分别与CH2-O的弯曲振动、C-H和NH2的拉伸振动有关。碳酸钙特征吸收带的在712~875 cm-1是由于碳酸根离子的存在。图6 显示BCP纳米片在不同浓度的过氧化氢溶液中氧气水平随时间变化图,从图中可以看出随着过氧化氢的浓度的提高和时间的延长,氧气水平也逐渐上升,说明了BCP纳米片具有良好的过氧化氢酶的催化效果。图7显示 BCP纳米片在光照射处理后的 ESR 光谱,从图7的a和b图中可看出,在添加 5,5-二甲基-1-吡咯烷-N-氧化物 (DMPO) 作为自旋陷阱以后,分别检测到产生了强度比为1:1:1:1和 1:2:2:1 的四线ESR信号,验证了DMPO/·O2 - 和 DMPO/⋅OH 加合物的生成,说明了BCP纳米片具有良好的过氧化物酶活性和超氧化物歧化酶活性。图8在无光照刺激或有光照刺激条件下BCP纳米片对4T1肿瘤细胞的体外毒性图,从图中可以看出BCP纳米片在光照刺激下对4T1肿瘤细胞具有良好的杀伤效果。图9是不同药物处理下小鼠体内的抑瘤效果图,分组为(1)生理盐水,(2) 生理盐水 + 光照,(3) BCP,(4) BiO2-x + 光照,(5) BCP + 光照,从图中可以看出与BCP纳米片经过光照刺激后与其它组相比,表现出明显的抑瘤效果。图10表示BCP纳米片在小鼠体内血常规的分析图,结果显示其在小鼠体内良好的生物相容性和安全性。
最后说明的是,以上优选实施例仅用以说明本发明的技术方案而非限制,尽管通过上述优选实施例已经对本发明进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其做出各种各样的改变,而不偏离本发明权利要求书所限定的范围。
Claims (5)
1.近红外光催化具有酸响应的缺陷型铋纳米片作为具有产生CO气体能力和多种酶活性功能以及抗肿瘤能力的应用,其特征在于,缺陷型铋纳米片在肿瘤微环境中具有酸响应优势,能将表面的CaCO3分解为CO2,并通过近红外光催化进一步将CO2还原成CO用于气体治疗,同时缺陷型铋纳米片具有多种酶活性,如过氧化氢酶、过氧化物酶和超氧化物歧化酶,有利于肿瘤微环境中产生大量ROS物种和氧气,实现良好的杀伤肿瘤细胞的效果;制备近红外光催化具有酸响应的缺陷型铋纳米片包含以下步骤:
(1)缺陷型结构BiO2-x纳米片的制备:首先将NaBiO3粉末充分溶解于NaOH溶液中,在室温下磁力搅拌2小时,形成均匀悬浮液,再将其转移至50 mL不锈钢高压反应器中,保持180℃加热18小时,冷却至室温,用去离子水多次离心洗涤,得到块状纳米材料,随后制备剥离液(使用一定量体积比的去离子水和无水乙醇溶液),再将上述得到的块状纳米材料分散在剥离液中,冰浴超声8小时,最后离心洗涤5次,获得缺陷型结构BiO2-x纳米片;
(2)BiO2-x@CaCO3纳米片的制备:将CaCl2加入到分散在乙醇溶液中的BiO2-x的容量瓶中,在室温下将该容量瓶与另一个装有固体粉末NH4HCO3的容量瓶同时放入密封容器中,然后对装有分散在乙醇溶液中的BiO2-x的容量瓶剧烈搅拌,反应8小时后,进行多次离心洗涤,获得BiO2-x@CaCO3纳米片;
(3)BiO2-x@CaCO3/PEG(BCP)纳米片的制备:将含有一定量的BiO2-x@CaCO3和NH2-PEG-NH2溶液的分散在50 mL水体系下,进行冰浴超声2 h,然后用去离子水和乙醇洗涤5次后,去除未反应的NH2-PEG-NH2,最后离心干燥,获得具有酸响应和多酶活性用于气体治疗的BCP纳米片。
2.根据权利要求1所述的应用,其特征在于:所述步骤(1)中NaBiO3粉末的质量为1.5~2.5 mg;所述步骤(1)中氢氧化钠的浓度和体积分别为1~1.5 M和30~50 mL;所述步骤(1)中的剥离液:无水乙醇和水的体积比为0.8~1.2。
3. 根据权利要求1所述的应用,其特征在于:所述步骤(2)中CaCl2粉末的质量为15~20mg;所述步骤(2)中BiO2-x的浓度和体积分别为 10~30 μg/mL和30~50 mL;所述步骤(2)中固体粉末 NH4HCO3的质量为5~8 g。
4.根据权利要求1所述的应用,其特征在于:所述步骤(3)中BiO2-x@CaCO3的水溶液浓度为0.05~0.15 mg/mL;所述步骤(3)中NH2-PEG-NH2的浓度为0.05~0.15 mg/mL。
5. 根据权利要求1所述的应用,其特征在于:所述步骤(1)、步骤(2)、步骤(3)中超声的功率为100 W,离心的转速为10000 rpm,离心的时间为8 min。
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