CN114906856B - 一种可释放h2s/co的纳米介孔二氧化硅球及其制备方法与应用 - Google Patents
一种可释放h2s/co的纳米介孔二氧化硅球及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种可释放H2S/CO的纳米介孔二氧化硅球及其制备方法与应用,该制备方法包括:将两种有机硅源加入到含有致孔剂、催化剂的水溶液中,经过搅拌加热、离心洗涤、冷凝回流得到S4‑MSN,再将S4‑MSN加入含有十二羰基三铁的四氢呋喃溶液中,经过搅拌加热、离心洗涤即得可释放H2S/CO的纳米介孔二氧化硅球FeCO‑S4‑MSN。所制得的样品能应用于药物负载中,其介孔结构的存在有利于药物的负载、增强疏水性药物的溶解度,并有望实现肿瘤治疗性气体和化疗药物共递送纳米体系。本发明所提供的制备方法材料简单易得、设备要求低、生产效率高,有利于实现工业化生产。
Description
技术领域
本发明属于药物负载用纳米材料技术领域,具体涉及到一种可释放H2S/CO的纳米介孔二氧化硅球及其制备方法与应用。
背景技术
目前主要通过外科手术、放疗和化疗等方式医治癌症,然而它们都存在一定的局限性,如当癌症晚期病人肿瘤发生转移后,手术切除无法根除所有的病灶;大多数现有的化疗和放射治疗药物对正常细胞有相当大的毒性,或者缺乏特异性和选择性从而降低治疗效果。因此,开发一种低毒性或无毒性的可控给药系统是医学、药理学、药物化学等健康相关学科研究人员的主要目标。近年来,纳米药物递送体系得到人们的广泛关注。纳米药物不仅可以增加药物溶解度、特异性肿瘤靶向性、增强在肿瘤组织和肿瘤细胞中的积累、还可以降低全身毒性和增加最大耐受剂量。
气体治疗是一种新型高效,并且具有较好应用前景的治疗手段。研究发现,一些GSMs(Gaseous signaling molecules,气体信号分子)如CO、NO和H2S可以选择性地诱导癌细胞凋亡,并在适当的浓度范围内保护正常细胞,同时也对许多疾病表现出独特的治疗优势,这类抗癌药物的选择性明显优于传统的化疗/放疗药物。迄今为止,科学家们已经开发出大量能够释放NO、CO和H2S的供体,在治疗癌症、类风湿性关节炎等方面显示出巨大的潜力。有研究人员使用纳米介孔二氧化硅球(MSN)大量装载CO前药(FeCO-TPP@MSN),进一步包裹肿瘤细胞靶向分子透明质酸(HA),构建了一种具有靶向肿瘤细胞线粒体并原位控释CO功能的新型智能纳米药物(FeCO-TPP@MSN@HA)。尽管不同的GSMs之间存在微妙的相互作用,能够在真正的生理条件下最大限度地发挥调节作用,但对同时递送两个或更多GSMs的报道却很少。同时,相对于单一的治疗手段,多种药物或治疗方法的联合治疗可以有效的提高治疗效果,延长患者的寿命。
发明内容
本发明的目的是提供一种可释放H2S/CO的纳米介孔二氧化硅球及其制备方法与应用,该纳米介孔二氧化硅球可以释放两种肿瘤治疗性气体(H2S/CO),且硅球粒径均一,原材料简单易得,设备要求低,生产效率高,有利于连续生产,实现工业化生产。
为达上述目的,本发明提供了一种可释放H2S/CO的纳米介孔二氧化硅球的制备方法,包括以下步骤:
(1)制备S4-MSN
将两种有机硅源溶液加入到含有致孔剂、催化剂的水溶液中,经搅拌加热、离心洗涤后制得含四硫的介孔二氧化硅球,即为S4-MSN;
两种有机硅源为体积比为1.5-3:3的硅酸四乙酯溶液和双[3-(三乙氧基硅)丙基]-四硫化物溶液;
(2)制备可释放H2S/CO的纳米介孔二氧化硅球
将步骤(1)制得的含四硫的介孔二氧化硅球加入到含金属羰基配合物的有机溶液中,经搅拌加热、离心洗涤后烘干制得可释放H2S/CO的纳米介孔二氧化硅球,即为FeCO-S4-MSN。
进一步地,硅酸四乙酯溶液与致孔剂水溶液的比例关系为1.5-3mL:20g。
进一步地,致孔剂为十六烷基三甲基氯化铵,十六烷基三甲基氯化铵的水溶液浓度为10wt%。催化剂为三乙醇胺,三乙醇胺的水溶液浓度为10wt%。
进一步地,含金属羰基配合物的有机溶液为0.8mM的十二羰基三铁的四氢呋喃溶液,含四硫的介孔二氧化硅球与金属羰基配合物的质量比为15-20:4。
进一步地,步骤(1)具体包括以下过程:
将致孔剂水溶液与催化剂水溶液混合后于90-100℃条件下加热,然后加入两种有机硅源反应4-5h,离心后收集产品;
将产品用乙醇洗涤2-3次后分散于含有浓盐酸的乙醇溶液中,并于75-80℃条件下冷凝回流10-15h,之后,再次离心收集产品并分散于含有浓盐酸的乙醇溶液中冷凝回流,除去致孔剂后于55-65℃条件下烘干即可;
浓盐酸的浓度为37%,含有浓盐酸的乙醇溶液中的浓盐酸与乙醇溶液的体积比为1:9。
进一步地,步骤(2)中加热的温度为50-60℃,加热的时间为4h以上。
进一步地,本发明还提供了采用可释放H2S/CO的纳米介孔二氧化硅球的制备方法制备得到的可释放H2S/CO的纳米介孔二氧化硅球。
进一步地,该纳米介孔二氧化硅球的粒径为50-100nm,比表面积为448-465m2/g,Zeta电势为负值。
进一步地,本发明还提供了可释放H2S/CO的纳米介孔二氧化硅球在药物负载中的应用,介孔结构的存在,有利于药物的负载、增强疏水性药物的溶解度,并有望实现肿瘤治疗性气体和化疗药物共递送纳米体系。
综上所述,本发明具有以下优点:
1、本发明仅通过将两种有机硅源加入到含有致孔剂、催化剂的水溶液中,其中双[3-(三乙氧基硅)丙基]-四硫化物硅源提供四硫键,经过搅拌加热、离心洗涤、冷凝回流得到可释放肿瘤治疗性H2S气体的含四硫的介孔二氧化硅球(S4-MSN),再将S4-MSN加入含有十二羰基三铁(Fe3CO12)的四氢呋喃(THF)溶液中,经过搅拌加热、离心洗涤即得可释放H2S/CO的纳米介孔二氧化硅球的FeCO-S4-MSN。制备过程工艺简单,环境友好,重复性好。
2、本发明所提供的可释放H2S/CO的纳米介孔二氧化硅球的制备方法,原材料简单易得,设备要求低,生产效率高,有利于实现工业化生产。
3、本发明首次提出使用介孔二氧化硅纳米球作为载体来共递送H2S/CO两种肿瘤治疗性气体,并且双[3-(三乙氧基硅)丙基]-四硫化物硅源提供了稳定的H2S释放供体,介孔结构的存在也为负载CO释放供体的十二羰基三铁提供可能,同时也有利于进一步负载盐酸阿霉素、喜树碱等抗肿瘤化疗药物,有希望实现肿瘤治疗性气体和化疗药物共递送纳米体系,为纳米给药系统提供了新的策略,具有良好的应用前景且实际意义重大。
附图说明
图1是本发明实施例1制备的S4-MSN的扫描电镜图;
图2是本发明实施例1制备的S4-MSN的透射电镜图;
图3是本发明实施例1制备的FeCO-S4-MSN的透射电镜图;
图4是本发明实施例1制备的S4-MSN的氮气吸附-脱附曲线图;
图5是本发明实施例1制备的S4-MSN的孔径分布图;
图6是本发明实施例1制备的FeCO-S4-MSN的氮气吸附-脱附曲线图;
图7是本发明实施例1制备的FeCO-S4-MSN的孔径分布图;
图8是本发明实施例1制备的FeCO-S4-MSN负载盐酸阿霉素的透射电镜图;
图9是本发明实施例1制备的FeCO-S4-MSN在不同浓度羟基自由基(.OH)作用下的CO释放结果;
图10是本发明实施例1制备的S4-MSN、FeCO-S4-MSN以及FeCO的红外谱图;
图11是本发明实施例2制备的S4-MSN的氮气吸附-脱附曲线图;
图12是本发明实施例2制备的S4-MSN的孔径分布图;
图13是本发明实施例2制备的FeCO-S4-MSN的氮气吸附-脱附曲线图;
图14是本发明实施例2制备的FeCO-S4-MSN的孔径分布图;
图15是本发明实施例1和实施例2所制备的S4-MSN利用醋酸铅试纸测试结果。
具体实施方式
本发明提供了一种可释放H2S/CO的纳米介孔二氧化硅球的制备方法,包括以下步骤:
(1)将十六烷基三甲基氯化铵(CTAC)水溶液和三乙醇胺水溶液混合并在90-100℃下搅拌加热,然后加入硅酸四乙酯(TEOS)和双[3-(三乙氧基硅)丙基]-四硫化物(BTES)的混合溶液,再反应4-5h。离心后收集产品,然后用乙醇洗涤数次(2-3次),直到洗出的上清液没有黄色,再将其分散于含有浓HCL(37%,10mL)的乙醇溶液(100mL)中并在75-80℃下加热冷凝回流10-15h以去除CTAC。重复冷凝回流过程数次(2-3次),直到彻底去除CTAC,将产物66-65℃下烘干备用,所得到的白色粉末就是含四硫的介孔二氧化硅球(S4-MSN)。
(2)将步骤(1)中所制得的S4-MSN加入到100mL含十二羰基三铁的四氢呋喃溶液中,并在50-60℃下加热搅拌冷凝回流,4h后观察其颜色变化,待溶液颜色从深绿色变成红褐色,则证明负载成功,之后再离心取沉淀并洗涤两次,将产物在60℃下烘干,即得可释放H2S/CO的纳米介孔二氧化硅球的FeCO-S4-MSN。
本发明中的TEOS和BTES为两种有机硅源,其中BTES含有四硫键,是H2S气体的释放供体。
本发明制备的可释放H2S/CO的纳米介孔二氧化硅球,粒径为50-100nm,比表面积为448-465m2/g,Zeta电势为负值。
本发明还提供了可释放H2S/CO的纳米介孔二氧化硅球在药物负载中的应用。本发明中药物为抗肿瘤化疗药物,应用包括实现了药物的纳米化、增强了疏水性药物的溶解度,并有望实现肿瘤治疗性气体和化疗药物共递送纳米体系的应用。
具体的,抗肿瘤化疗药物可以为盐酸阿霉素、喜树碱和其他化疗药物。当通过将盐酸阿霉素和喜树碱分别负载到可释放H2S/CO的纳米介孔二氧化硅球FeCO-S4-MSN上时,可以实现盐酸阿霉素和喜树碱的纳米化,并且可提高疏水性喜树碱化疗药物的溶解度。经计算,盐酸阿霉素的载药量为14.2%,包封率为38.85%,喜树碱的载药率为2.96%,包封率为17.55%。
本发明在实施例1中验证了盐酸阿霉素、喜树碱的负载效果,其中用到了化疗药物载药量和包封率的测试,具体包括以下步骤:
S1盐酸阿霉素
配制具有不同浓度梯度的盐酸阿霉素溶液,使用LCMS(高效液相色谱-质谱联用)方法,依据不同浓度梯度盐酸阿霉素溶液的紫外吸收峰面积,绘制盐酸阿霉素紫外吸收峰面积-浓度的标准曲线。
称取FeCO-S4-MSN硅球40mg,将其加入到2mL的盐酸阿霉素水溶液(10mg/mL)中,超声后震荡混匀24h,离心水洗3遍,收集上清液,使用LCMS测出上清液的紫外吸收峰面积。通过计算得载药率为14.2%,包封率为38.85%。
S2喜树碱
配制具有不同浓度梯度的喜树碱溶液,使用LCMS(高效液相色谱-质谱联用)方法,依据不同浓度梯度喜树碱溶液的紫外吸收峰面积,绘制喜树碱紫外吸收峰面积-浓度的标准曲线。称取8mg喜树碱,溶于4mL N,N-二甲基甲酰胺(DMF),再加入上述FeCO-S4-MSN硅球40mg,振荡24h,离心并用甲醇洗两遍,收集上清液,液质联用系统(HPLC-MS),测出上清液的紫外吸收峰面积。计算得载药率为2.96%,包封率为17.55%。
用醋酸铅试纸法判断实施例1和实施例2中的H2S释放的测试方法包括以下步骤:
分别称取6mg实施例1和实施例2中的FeCO-S4-MSN,放入玻璃瓶中,加入1mL的pH为5.4的PBS缓冲液,再将300μL的10mM半胱氨酸溶液加入瓶中,封住瓶口,37℃反应1h后利用醋酸铅试纸测试,观察颜色变化判断是否有H2S释放。
以下结合实施例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
本实施例提供了一种可释放H2S/CO的纳米介孔二氧化硅球的制备方法,包括以下步骤:
(1)首先将20g CTAC水溶液(10wt%)和1g三乙醇胺水溶液(10wt%)混合并在95℃搅拌加热,然后加入TEOS(3mL)和BTES(3mL)的混合溶液,再反应4h。离心后收集产品,然后用乙醇洗涤3次,直到洗出的上清液没有黄色,再将其分散于含有浓HCl(37%,10mL)的乙醇溶液(100mL)中并在78℃下加热冷凝回流12h以去除CTAC。重复冷凝回流过程3次,直到彻底去除CTAC,将产物60℃下烘干备用,所得到的白色粉末就是含四硫的介孔二氧化硅球(S4-MSN)。
(2)称取170mg的S4-MSN,将其与40mg十二羰基三铁混合在100mL的四氢呋喃(THF)溶液中,并在55℃下加热搅拌冷凝回流,4h后观察其颜色变化,待溶液颜色从深绿色变成红褐色,则证明负载成功,之后再离心取沉淀并洗涤两次,将产物在60℃下烘干,即得可释放H2S/CO的纳米介孔二氧化硅球FeCO-S4-MSN。
实施例1制备得到的可释放H2S/CO的纳米介孔二氧化硅球在药物负载上的应用,包括以下步骤:
a:称取实施例1制备得到的纳米介孔二氧化硅球40mg,将其加入到2mL的盐酸阿霉素水溶液(10mg/mL)中,超声后震荡混匀24h,离心并水洗3遍去除没有载入的盐酸阿霉素,收集产物在40℃烘干备用。
计算得载药率为14.2%,包封率为38.85%。
b:称取8mg喜树碱,溶于4mL N,N-二甲基甲酰胺(DMF),再加入40mg实施例1制备的FeCO-S4-MSN硅球,振荡24h,离心并用甲醇洗两遍。
计算得载药率为2.96%,包封率为17.55%。
从图1和图2中可以看出S4-MSN粒径为50-60nm,且具有从球心向外表面的连通孔道结构。
从图4和图5可以看出:本发明实施例1制备的S4-MSN的比表面积为554.64m2/g。
从图6和图7可以看出:本发明实施例1制备的FeCO-S4-MSN的比表面积为464.76m2/g。
从图10可以看出:由FeCO-S4-MSN中2060处的C=O峰表明FeCO成功负载在S4-MSN上。
实施例2
本实施例提供了一种可释放H2S/CO的纳米介孔二氧化硅球的制备方法,包括以下步骤:
(1)首先将20g CTAC水溶液(10wt%)和1g三乙醇胺水溶液(10wt%)混合并在95℃搅拌加热,然后逐滴添加TEOS(1mL)。反应1h后,加入TEOS(0.5mL)和BTES(1mL)的混合溶液,再反应4h。离心后收集产品,然后用乙醇洗涤3次,直到洗出的上清液没有黄色,再将其分散于含有浓盐酸(37%,10mL)的乙醇溶液(100mL)中并在78℃下加热冷凝回流12h以去除CTAC。重复冷凝回流过程3次,直到彻底去除CTAC,将产物60℃下烘干备用,所得到的白色粉末就是含四硫的介孔二氧化硅球(S4-MSN)。
(2)称取170mg的S4-MSN,将其与40mg十二羰基三铁混合在100mL的四氢呋喃(THF)溶液中,并在55℃下加热搅拌冷凝回流,4h后观察其颜色变化,待溶液颜色从深绿色变成红褐色,则证明负载成功,之后再离心取沉淀并洗涤两次,将产物在60℃下烘干,即得可释放H2S/CO的纳米介孔二氧化硅球的FeCO-S4-MSN。
由图11和图12可知,本发明实施例2制备的S4-MSN的比表面积为641.21m2/g。
由图13和图14可知,本发明实施例2制备的FeCO-S4-MSN的比表面积为448.52m2/g。
由图15(左为实施例1,右为实施例2)可以看出,在半胱氨酸的作用下,四硫键发生断裂并释放出了H2S气体。
虽然对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (9)
1.一种可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述可释放H2S/CO的纳米介孔二氧化硅球的通过下述制备获得,包括以下步骤:
(1)制备S4-MSN
将两种有机硅源溶液加入到含有致孔剂、催化剂的水溶液中,经搅拌加热、离心洗涤后制得含四硫的介孔二氧化硅球,即为S4-MSN;
其中所述有机硅源为体积比为1.5-3:3的硅酸四乙酯溶液和双[3-(三乙氧基硅)丙基]-四硫化物溶液;
(2)制备可释放H2S/CO的纳米介孔二氧化硅球
将步骤(1)制得的含四硫的介孔二氧化硅球加入到含金属羰基配合物的有机溶液中,经搅拌加热、离心洗涤后烘干制得可释放H2S/CO的纳米介孔二氧化硅球,即为FeCO-S4-MSN;
所述可释放H2S/CO的纳米介孔二氧化硅球同时释放出H2S和CO,其中,在半胱氨酸的作用下释放出H2S。
2.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述硅酸四乙酯溶液与所述致孔剂水溶液的比例关系为1.5-3mL:20g。
3.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述致孔剂为十六烷基三甲基氯化铵,所述十六烷基三甲基氯化铵的水溶液浓度为10wt%。
4.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述催化剂为三乙醇胺,所述三乙醇胺的水溶液浓度为10wt%。
5.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述含金属羰基配合物的有机溶液为浓度为0.8mM的十二羰基三铁的四氢呋喃溶液,所述含四硫的介孔二氧化硅球与所述金属羰基配合物的质量比为15-20:4。
6.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述步骤(1)具体包括以下过程:
将致孔剂水溶液与催化剂水溶液混合后于90-100℃条件下加热,然后加入两种有机硅源反应4-5h,离心后收集产品;
将产品洗涤2-3次后分散于含有浓盐酸的乙醇溶液中,并于75-80℃条件下冷凝回流10-15h,除去致孔剂后于55-65℃条件下烘干即可;
所述浓盐酸的浓度为37%,所述含有浓盐酸的乙醇溶液中的浓盐酸与乙醇溶液的体积比为1:9。
7.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,所述步骤(2)中加热的温度为50-60℃,加热的时间为4h以上。
8.如权利要求1所述的可释放H2S/CO的纳米介孔二氧化硅球,其特征在于,粒径为50-100nm,比表面积为448-465m2/g,Zeta电势为负值。
9.如权利要求1~8任一项所述的可释放H2S/CO的纳米介孔二氧化硅球在药物负载中的应用。
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