CN111467490A - 一种二氧化钛纳米复合材料的制备方法和应用 - Google Patents
一种二氧化钛纳米复合材料的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种二氧化钛纳米复合材料的制备方法，属于纳米医学材料技术领域。本发明提供了具有广泛的抗病毒活性、抗菌活性和抗癌活性的医用复合材料，提供一种二氧化钛纳米复合材料的制备方法。本发明将二氧化钛为无机半导体纳米材料为载体，进行有机光敏分子的封装，并使用生物相容性高分子进行表面修饰，制得材料具有广泛的抗病毒活性、抗菌活性和抗癌活性，其生物活性基于光催化产生的活性氧破坏病毒、细菌及感染细胞的核酸、蛋白质、溶酶体、线粒体等，导致病毒、细菌、癌细胞无法复制和组织养料供给，从而杀死病毒、细菌和癌细胞。本发明所提供的纳米复合材料还可用作医疗卫生的防护材料，包括医用口罩、防护服、手套、消毒液等。
Description
技术领域
本发明涉及一种二氧化钛纳米复合材料的制备方法和应用，属于纳米医学材料技术领域。
背景技术
病毒的核心是核糖核酸(RNA)或脱氧核糖核酸(DNA)，外壳是蛋白质，寄生于宿主细胞内，如SARS病毒、新型冠状病毒、埃博拉病毒等寄宿在某些动物细胞内，通过人与动物接触而被感染，直至发生人传染人的后果。病毒依赖宿主细胞代谢系统进行增殖复制。病毒在宿主细胞内合成病毒核酸和蛋白质，组装成感染性病毒体，从细胞释出而感染其他细胞。病毒病是人类的主要传染病，由病毒引起的常见疾病有流行性感冒、普通感冒、肺炎、麻疹、腮腺炎、小儿麻痹症、传染性肝炎、乙型肝炎、艾滋病、疱疹性角膜炎、性病疱、某些肿瘤。多数病毒缺乏酶系统，不能独立自营生活，必须依靠宿主的酶系统才能使其本身繁殖(复制)，病毒核酸有时整合于细胞，不易消除，不同的病毒作用机制不同，因此抗病毒药研究发展缓慢。癌症是威胁人类健康的重大疾病，常规的化疗、放疗和手术有很大的毒副作用、耐药性和较大创伤，开发无耐药性、微创和低毒副作用的抗癌药物具有重要意义。细菌感染是致病菌或条件致病菌侵入血循环中生长繁殖，产生毒素和其他代谢产物所引起的全身性感染，尤其是老人、儿童、有慢性病或免疫功能低下者可发展为败血症或者脓毒血症,用抗菌素治疗细菌感染往往引起细菌的耐药性，使抗生素无效，导致耐药细菌二重感染。提供一种具有广泛的抗病毒活性、抗菌活性和抗癌活性的医用复合材料是十分必要的。
发明内容
本发明提供了具有广泛的抗病毒活性、抗菌活性和抗癌活性的医用复合材料，提供一种二氧化钛纳米复合材料的制备方法和应用。
本发明的技术方案：
一种二氧化钛纳米复合材料的制备方法，该方法包括以下步骤：
步骤一，在二氧化钛纳米粒子表面修饰上介孔二氧化硅，获得TiO2@SiO2；
步骤二，将光敏剂封装在TiO2@SiO2的二氧化硅介孔中，获得TiO2@SiO2/Ps；
步骤三，在TiO2@SiO2/Ps的二氧化硅表面修饰生物相容性高分子物质，获得TiO2@SiO2/Ps@P。
进一步限定，步骤一的具体操作过程为：
Step1，将抗坏血酸在室温下搅拌10min后，加入TiCl3溶解后，加入NaOH溶液调节pH值至1～10，在室温下搅拌5～60min后，在80～250℃下加热1～24h，离心弃上清液，使用去离子水和乙醇洗涤后，60～120℃下干燥，获得TiO2纳米粒子；
Step2，将TiO2NPs超声分散在无水乙醇中，加入3-氨基丙基-三乙氧基硅烷溶液，搅拌2～48h，使用去离子水和乙醇洗涤，干燥，获得TiO2@SiO2纳米粒子。
更进一步限定，抗坏血酸与TiCl3的质量比为1：(1～20)。
更进一步限定，3-氨基丙基-三乙氧基硅烷溶液的体积与TiO2的质量比为1mL：(10～60)mg。
更进一步限定，3-氨基丙基-三乙氧基硅烷溶液的溶剂为乙酸、去离子水和乙醇，其中乙酸体积浓度为0.1～10％，去离子水体积浓度为1～20％，乙醇的体积浓度为1～20％。
进一步限定，步骤二的具体操作过程为：将步骤一获得的TiO2@SiO2纳米粒子分散在无水乙醇中，超声振动5min后，加入光敏剂，磁力搅拌30min，将加入正己烷，离心弃上清液，在50℃下干燥，获得TiO2@SiO2/Ps。
进一步限定，光敏剂包括卟啉类化合物、酞菁类化合物和叶绿素降解产物。
更进一步限定，TiO2@SiO2纳米粒子和光敏剂的质量比为1：(0.5～20)。
进一步限定，步骤三的具体操作过程为：将生物相容性高分子分散在二甲亚砜溶剂中，加入碳二亚胺和N-羟基硫代琥珀酰亚胺，室温搅拌0.5～24h，加入使用无水乙醇溶解的TiO2@SiO2/Ps，搅拌1～24h，加入正己烷沉化，获得TiO2@SiO2/Ps@P。
更进一步限定，生物相容性高分子包括聚乙烯醇、脂质体、蛋白质和壳聚糖。
进一步限定，二氧化钛纳米复合材料用于因病毒感染引起的疾病、细菌感染引起的疾病和癌症的光动力治疗；或用作医疗卫生的防护材料，包括医用商用的口罩、防护服、手套和消毒液。
本发明具有以下有益效果：本发明所涉及的新型纳米药物具有广泛的抗病毒活性、抗菌活性和抗癌活性，其生物活性基于光催化产生的活性氧破坏病毒、细菌及感染细胞的核酸、蛋白质、溶酶体、线粒体等，导致病毒、细菌、癌细胞无法复制和组织养料供给，从而杀死病毒、细菌、癌细胞。本发明所提供的纳米复合材料可以用于光动力治疗因病毒感染、细菌感染引起的各种疾病和各种癌症，还可以用作医疗卫生的防护材料，包括医用商用的口罩、防护服、手套、消毒液等。
附图说明
图1为本发明纳米复合材料的结构和合成路线示意图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器，未经特殊说明，均为本领域常规材料、试剂、方法和仪器，本领域技术人员均可通过商业渠道获得。
具体实施方式1
本实施例以叶绿素降解产物叶绿素-a(PPa)为有机光敏分子，二氧化钛为无机半导体纳米材料为载体，聚乙二醇修饰，得到TiO2@SiO2/PPa@PEG纳米复合材料。
如图1所示，具体操作过程如下：
(1)TiO2纳米颗粒制备：将0.5g L-抗坏血酸加入到有70mL二次蒸馏水的烧杯中，室温搅拌10min。随后加入6g三氯化钛TiCl3，形成紫色溶液。然后加入NaOH溶液(1mol/L)至pH为4。在室温下再搅拌30min后，将混合物转移到100mL特氟龙内衬的不锈钢高压釜中，在180℃下加热12h。所得的沉淀物通过离心收集，用水和乙醇清洗，然后子啊80℃干燥过夜，得到TiO2纳米粒子。
(2)TiO2@SiO2制备：将20mg TiO2NPs超声分散在10mL无水乙醇中。加入1mL3-氨基丙基-三乙氧基硅烷(APTES)溶液(0.1％乙酸、4％去离子水、2％乙醇)，搅拌24h，用乙醇和去离子水反复离心洗涤得到TiO2@SiO2纳米粒子。
(3)TiO2@SiO2纳米加载PPa：将10mg TiO2@SiO2分散在10mL无水乙醇中，超声振荡5min，加入10mgPPa，磁力搅拌30min，加入20mL正己烷，高速离心，去掉上清液，沉淀在50℃真空干燥得到PPa加载的TiO2@SiO2/PPa纳米粒子。
(4)TiO2@SiO2/PPa纳米粒子PEG修饰：将20mg羧基聚乙二醇(PEG-COOH)分散在5mL二甲亚砜中，加入5mg EDC，加入5mg NHS，室温搅拌1h，加入10mg TiO2@SiO2/PPa(溶于10mL无水乙醇中)，搅拌过夜，加入30ml正己烷沉化，得到TiO2@SiO2/PPa@PEG。
TiO2@SiO2/PPa@PEG乙醇溶液为药物工作液进行抗菌实验和抗病毒实验。
(1)抗菌试验：肠杆菌、沙门氏菌、金黄色葡萄球菌、黄曲霉菌菌株制成浓度104mL-1的菌悬液。TiO2@SiO2/PPa@PEG用50％乙醇配制浓度几何级数的药物工作液，浓度分别为：100μg/mL、50μg/mL、25μg/mL、12.5μg/mL、6.25μg/mL、3.13μg/mL、1.56μg/mL和0.78μg/mL。分别取不同浓度的药物工作液加入到菌悬液中，孵育4h，然后用模拟可见光源照射20min(0.5w/cm2)，再孵育3h后观察细菌生长情况，药物工作液对四种细菌的最低杀菌浓度为0.78μg/mL。
(2)抗病毒试验：将TiO2@SiO2/PPa@PEG溶于50％乙醇中配制浓度几何级数的药物工作液，浓度分别为：50μg/mL、25μg/mL、12.5μg/mL、6.25μg/mL、3.13μg/mL和1.56μg/mL。在96孔板单层培养Vero细胞，在每孔中加入0.1mLHSV-2病毒原液，培养48h，加入各药物工作液10μL在暗处继续孵育4h，用模拟可见光照射20min(0.5w/cm2)，继续孵育3h。用MTT法计算细胞致死率。IC50为6.26μg/mL。
将HSV-2病毒感染的Vero细胞置于96孔板中，细胞浓度为104/mL，加入双染色剂，孵育4h后在荧光显微镜下细胞全部为绿色，显示全部为活细胞。加入10μL 12.5μg/mL的TiO2@SiO2/PPa@PEG孵育4h，然后模拟可见光照射20min(0.5w/cm2)，继续孵育3h后在荧光显微镜下观察细胞全部为红色，表明细胞100％死亡。
(3)抗癌活性实验：将Hela细胞接种在90孔板，分为两组，一组为实验组，另一组为空白对照组。将实验组分为6个样品，分别加入10μL不同浓度的TiO2@SiO2/PPa@PEG药物工作液(浓度分别为：50μg/mL、25μg/mL、12.5μg/mL、6.25μg/mL、3.13μg/mL和1.56μg/mL)。避光孵育4h模拟可见光照20min(0.5w/cm2)后孵育3h。用MTT法计算细胞致死率，IC50为6.25μg/mL。空白对照组不加TiO2@SiO2/PPa@PEG药物工作液，其他条件与实验组相同，细胞致死率0％。
Claims (10)
1.一种二氧化钛纳米复合材料的制备方法，其特征在于，该方法包括以下步骤：
步骤一，在二氧化钛纳米粒子表面修饰上介孔二氧化硅，获得TiO2@SiO2；
步骤二，将光敏剂封装在TiO2@SiO2的二氧化硅介孔中，获得TiO2@SiO2/Ps；
步骤三，在TiO2@SiO2/Ps的二氧化硅表面修饰生物相容性高分子物质，获得TiO2@SiO2/Ps@P。
2.根据权利要求1所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的步骤一的具体操作过程为：
Step1，将抗坏血酸在室温下搅拌10min后，加入TiCl3溶解后，加入NaOH溶液调节pH值至1～10，在室温下搅拌5～60min后，在80～250℃下加热1～24h，离心弃上清液，使用去离子水和乙醇洗涤后，60～120℃下干燥，获得TiO2纳米粒子；
Step2，将TiO2NPs超声分散在无水乙醇中，加入3-氨基丙基-三乙氧基硅烷溶液，搅拌2～48h，使用去离子水和乙醇洗涤，干燥，获得TiO2@SiO2纳米粒子。
3.根据权利要求2所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的抗坏血酸与TiCl3的质量比为1：(1～20)。
4.根据权利要求2所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的3-氨基丙基-三乙氧基硅烷溶液的体积与TiO2的质量比为1mL：(10～60)mg。
5.根据权利要求2所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的3-氨基丙基-三乙氧基硅烷溶液的溶剂为乙酸、去离子水和乙醇，其中乙酸体积浓度为0.1～10％，去离子水体积浓度为1～20％，乙醇的体积浓度为1～20％。
6.根据权利要求1所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的步骤二的具体操作过程为：将步骤一获得的TiO2@SiO2纳米粒子分散在无水乙醇中，超声振动5min后，加入光敏剂，磁力搅拌30min，将加入正己烷，离心弃上清液，在50℃下干燥，获得TiO2@SiO2/Ps。
7.根据权利要求1或6所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的光敏剂包括卟啉类化合物、酞菁类化合物和叶绿素降解产物。
8.根据权利要求6所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的TiO2@SiO2纳米粒子和光敏剂的质量比为1：(0.5～20)。
9.根据权利要求2所述的一种二氧化钛纳米复合材料的制备方法，其特征在于，所述的步骤三的具体操作过程为：将生物相容性高分子分散在二甲亚砜溶剂中，加入碳二亚胺和N-羟基硫代琥珀酰亚胺，室温搅拌0.5～24h，加入使用无水乙醇溶解的TiO2@SiO2/Ps，搅拌1～24h，加入正己烷沉化，获得TiO2@SiO2/Ps@P；其中，所述的生物相容性高分子包括聚乙烯醇、脂质体、蛋白质和壳聚糖。
10.权利要求1所述方法制得的二氧化钛纳米复合材料的应用，其特征在于，该材料用于因病毒感染引起的疾病、细菌感染引起的疾病和癌症的光动力治疗；或用作医疗卫生的防护材料，包括医用商用的口罩、防护服、手套和消毒液。
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| CN114796486A (zh) * | 2022-03-21 | 2022-07-29 | 华南理工大学 | 一种铂/二氧化钛@二氧化锰-聚乙烯亚胺复合抗癌纳米材料的制备方法及其应用 |
| CN114796486B (zh) * | 2022-03-21 | 2023-03-21 | 华南理工大学 | 一种铂/二氧化钛@二氧化锰-聚乙烯亚胺复合抗癌纳米材料的制备方法及其应用 |
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