CN111304634B - 一种利用原子层沉积包覆纳米淀粉微球的方法 - Google Patents
一种利用原子层沉积包覆纳米淀粉微球的方法 Download PDFInfo
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Abstract
本发明属于纳米淀粉微球改性技术领域,具体涉及一种利用原子层沉积包覆纳米淀粉微球的方法。本发明通过将纳米淀粉微球置于超声垂直流化原子层沉积设备中,开启超声振动,在适当的反应温度和压力下,选择合适活性与蒸汽压的前驱体交替通入,在纳米淀粉微球表面通过活性官能团的交换形成单层化学吸附并完成自限制化学半反应,生成致密的薄膜,对表面的各个部位进行厚度均匀一致的薄膜包覆。本发明采用原子层沉积技术生成的纳米薄膜包覆均匀性较高,尤其对于颗粒较小的纳米淀粉微球可实现其均匀包覆,形成的纳米薄膜结构致密,具有均匀的厚度、优异的一致性,由于其反应机理的特点,可实现对不同粒径纳米淀粉微球的包覆。
Description
技术领域
本发明属于纳米淀粉微球改性技术领域,涉及一种纳米淀粉微球表面改性的方法,具体涉及一种利用原子层沉积包覆纳米淀粉微球的方法。
背景技术
磁性淀粉微球作为药物载体,可利用外加磁场引导其在体内定向移动、集中,使药物有选择性地分布于特定器官、组织或细胞中,达到定向作用于靶向组织的目的,这不仅可增大病变组织内的药物浓度,提高药物利用率,还可以减少或消除药物对正常组织的毒副作用。但是纳米淀粉微球作为药物载体仍存在药物与淀粉表面吸附力不够,在室温,阳光照射或湿度过高情况下,易被生物污染。目前磁性淀粉微球一般为核壳式结构,淀粉组成壳层,磁性金属氧化物组成核心。但仍存在磁性金属氧化物粒子粒径不一,形状不规则,粒径不易控制,磁核包覆不够密实、易泄露、磁含量较低等问题,同时还存在磁性淀粉微球见光、见水容易被生物感染、磁含量较低、磁性颗粒粒径不易控制、机械强度较差、球形结构欠佳、功能结构单一、等问题等不足,限制了纳米淀粉微球在生物医药方面的应用,且纳米淀粉微球的表面会随着颗粒尺寸的减小急剧的增加,使颗粒之间极易形成软团聚体。
发明内容
本发明所要解决的技术问题在于针对上述现有技术的不足,提供了一种利用原子层沉积包覆纳米淀粉微球的方法。本发明利用原子层沉积设备在适当的反应温度和压力下,选择合适活性与蒸汽压的前驱体交替通入,在纳米淀粉微球表面通过活性官能团的交换形成单层化学吸附并完成自限制化学半反应,可以在纳米级尺度上将被沉积物质以单原子膜的形式一层一层的镀在纳米淀粉微球表面,对表面的各个部位进行厚度均匀一致的薄膜包覆,能够解决目前纳米淀粉微球见光、见水容易被生物感染、磁含量较低、磁性颗粒粒径不易控制等问题,形成的纳米级薄膜不影响纳米淀粉微球的表面吸附性能、生物降解性能。
为解决上述技术问题,本发明采用以下技术方案:一种利用原子层沉积包覆纳米淀粉微球的方法,在纳米淀粉微球表面包覆纳米级薄膜,对纳米淀粉微球进行改性,具体方法如下:
(S1)过筛:首先将纳米淀粉微球通过800-2000目的筛网,除掉团聚的纳米淀粉微球;
(S2)加热等待:将步骤(S1)中经过筛网的纳米淀粉微球置于超声垂直流化原子层沉积设备中,对反应腔进行加热并通入载气对其表面进行清洗,同时打开真空泵对整个超声垂直流化原子层沉积设备进行抽真空直至腔体内压力不大于10Pa;
(S3)超声振动:设定超声振动杆的超声波频率为20-40KHz,超声振动工作时长1s-99h,间歇时长1ms-99s;
(S4)原子层沉积:当温度和压力达到设定值:温度为80-450℃,压力为0.1-10Pa,其后利用低压载气携带前驱体组合进入超声垂直流化原子层沉积设备腔体内,进行氧化物A和氧化物B的原子层沉积,得到改性后的纳米淀粉微球。
步骤(S4)所述原子层沉积过程具体如下:
S4.1 低压载气携带第一前驱体组合进入反应腔并在纳米淀粉微球表面完成化学吸附,得到沉积氧化物A层;
S4.2 通入载气把未被表面吸附、多余的第一前驱体组合和反应副产物带出反应腔;
S4.3低压载气携带第二前驱体组合进入反应腔和第一前驱体组合吸附的表面继续进行原子层沉积,重复多次后得到氧化物B层;
S4.4 利用载气把多余的第二前驱体组合和反应生成的副产物带出反应腔。
所述第一前驱体组合为C10H10Fe/O3 或SiCl4/H2O;第二前驱体组合为能够用于ALD反应的烷基、氨基金属,包括三(二甲胺基)硅烷/O2 等离子气体、四(二甲基氨基)钛/H2O、Ti[OCH(CH3)]4/H2O、二甲基锌/H2O、四(乙基甲基氨基)锆/H2O、三甲基锆/H2O、四(二甲基氨基)铪/H2O、四(乙基甲基氨基)铪/H2O、三甲基铝/H2O或三甲基铝/O3,第一前驱体组合和第二前驱体组合在不构成冲突的情况下可任意组合。
步骤S4.1和S4.3中所述低压载气携带第一前驱体组合或第二前驱体组合以气相形式进入反应腔,其中前驱体通气时长与纳米淀粉微球表面的表面积成正比,反应温度和压力由前驱体组合和纳米淀粉微球对温度的耐受性所决定。
步骤S4.1-S4.4中反应温度为80-120℃,通入载气之前的压力低于1Pa;
所述第一前驱体组合和第二前驱体组合均包括两种前驱体,反应时,通过载气脉冲通入对应前驱体组合中包含的两种前驱体,脉冲时长为60-90s,携带前驱体的载气流量为0.1-100sccm,使两种前驱体分别依次吸附在纳米淀粉微球表面;
每通入下一种前驱体之前通过载气对纳米淀粉微球表面进行清洗,载气流量为100-200sccm,清洗时长为120-150s;
其中,当第一前驱体组合沉积完毕后,通入载气对纳米淀粉微球表面进行清洗,载气流量为100-200sccm,清洗时长为10-30min,而后重复上述步骤进行第二前驱体组合的沉积。
步骤S4.1和S4.3的循环次数为1~800,所述氧化物A或/和氧化物B包覆层的厚度为0.1~50nm,所述被包覆的纳米淀粉微球质量为0.1~100g。
所述载气为惰性气体,惰性气体为高纯氮气或氩气。
所述氧化物A形成的纳米级可控薄膜为Fe2O3涂层或SiO2涂层,氧化物B形成的纳米级可控薄膜为TiO2 涂层、ZnO涂层、ZrO2涂层、HfO2涂层或Al2O3涂层中的一种。
所述纳米淀粉微球替换为聚乳酸纳米颗粒、磷灰石晶体颗粒、金纳米颗粒或生物医药用磁性颗粒。
与现有技术相比,本发明具有以下优点:
1、本发明选取前驱体和沉积反应副产物对于被包覆的纳米淀粉微球饱和度和强度无明显影响的原子层沉积反应,在其表面生成一层或多层厚度可控的、致密均匀的、结合牢固的纳米级薄膜,可实现对不同粒径的纳米淀粉微球的包覆,纳米淀粉磁性物质包覆密实、不容易泄露。
2、原子层沉积工艺中加入过筛步骤,可以提前排除团聚的微纳米粉末,有效提高纳米薄膜的包覆均匀性。在纳米淀粉微球表面包覆铁的纳米级别氧化物薄膜,可利用铁的纳米级别氧化物薄膜具有超顺磁的特性,提高磁性纳米淀粉颗粒的磁含量。在纳米淀粉微球表面包覆铝的氧化物薄膜,有阻水隔氧、防止生物污染的效果。沉积过程中超声振动可实现纳米淀粉微球的解团聚,使纳米淀粉微球的粒径分布范围缩小,更利于药物释放的稳定性。
3、本发明可实现壳核式的磁性纳米淀粉颗粒,即纳米淀粉微球为核,磁性物质为壳;有别于传统的磁性物质为核,纳米淀粉微球为壳。
附图说明
图1是本发明利用原子层沉积包覆纳米淀粉微球的流程图。
图2是本发明实施例1和对比例1中样品的饱和磁化强度。
图3是本发明实施例1和对比例1中样品的水氧渗透率。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
以下通过本发明的具体实施例,进一步说明本发明。
实施例1
一种利用原子层沉积包覆纳米淀粉微球的方法,对粒径为20nm的纳米淀粉微球进行表面改性,包覆5nm的Fe2O3薄膜和1nm的Al2O3薄膜,其中选取C10H10Fe/O3、Al(CH3)3/H2O为前驱体,具体包括如下步骤:
(1)氧化铁包覆:
1.1将纳米淀粉微球通过800目筛网之后,称量5mg将其放置于原子层沉积设备的粉末容器中,将粉末容器放进腔体中,抽真空至10Pa;
1.2 打开超声振动,设置超声频率为20KHz,超声振动工作时长60s,间歇时长5s;
1.3 对腔体进行加热,同时通入载气对纳米淀粉微球进行表面清洗30min并使其分散,选择载气流量为100sccm;
1.4 待反应内腔的温度达到80℃进行第一次沉积反应,具体包括:
1.4.1抽真空,待腔体内的压力抽至<1Pa之后,通入前驱体C10H10Fe脉冲60s;
1.4.2以280L/min的抽气速率以及100sccm的载气除去未吸附在表面的前驱体C10H10Fe;
1.4.3通入前驱体O3脉冲60s,之后通入速率为280L/min、流量为150sccm的载气除去未吸附在表面的前驱体O3;
1.4.4依次交替循环上述步骤 50次,得到厚度为5nm的Fe2O3薄膜。
(2)氧化铝包覆:
2.1以280L/min的抽气速率以及100sccm的载气对反应腔及纳米淀粉微球表面进行清洗30min;
2.2待反应内腔温度达到80℃进行第二次沉积反应,具体包括:
2.2.1以同样的抽真空速率将腔体内的压力抽至<1Pa之后,通入前驱体Al(CH3)3脉冲60s;
2.2.2以150sccm 的载气除去未吸附在表面的前驱体Al(CH3)3;
2.2.3通入前驱体H2O脉冲60s,以100sccm的载气除去未吸附在表面的前驱体 H2O120s;
2.2.4依次交替循环上述步骤10次,得到厚度为10nm的Al2O3薄膜。
两次原子层沉积后,使得纳米淀粉微球表面包覆了一层致密均匀的超薄Fe2O3薄膜和Al2O3薄膜,实现了对纳米淀粉微球的表面改性。其中,Al2O3薄膜具有阻水隔氧抗菌的效果,能够解决纳米淀粉微球见光见水容易被生物感染的问题;Fe2O3薄膜具有超顺磁性,可提高纳米淀粉微球的磁含量;同时原子层沉积形成的Fe2O3薄膜是可控纳米级的,解决纳米淀粉微球磁性颗粒粒径不易控制的问题。
实施例2
一种利用原子层沉积包覆纳米淀粉微球的方法,对粒径为20nm的纳米淀粉微球进行表面改性,包覆5nm的Fe2O3薄膜和1nm的Al2O3薄膜,其中选取C10H10Fe/O3、Al(CH3)3/H2O为前驱体,具体包括如下步骤:
(1)氧化铁包覆:
1.1将纳米淀粉微球通过800目筛网之后,称量100g将其放置于原子层沉积设备的粉末容器中,将粉末容器放进腔体中,抽真空至10Pa;
1.2 打开超声振动,设置超声频率为40KHz,超声振动工作时长5min,间歇时长5s;
1.3 对腔体进行加热,同时通入载气对纳米淀粉微球进行表面进行清洗50min并使其分散,选择载气流量为100sccm;
1.4 待反应内腔的温度达到80℃进行第一次沉积反应,具体包括:
1.4.1抽真空,待腔体内的压力抽至<1Pa之后,通入前驱体C10H10Fe脉冲60s;
1.4.2 以280L/min的抽气速率以及150sccm的载气除去未吸附在表面的前驱体C10H10Fe;
1.4.3 通入前驱体O3脉冲60s,之后以280L/min的抽气速率以及150sccm的载气除去未吸附在表面的前驱体 O3;
1.4.4依次交替循环上述步骤50次,得到厚度为5nm的Fe2O3薄膜。
(2)氧化铝包覆:
2.1以280L/min的抽气速率以及100sccm的载气对反应腔及纳米淀粉微球表面进行清洗30min;
2.2待反应内腔温度达到80℃进行第二次沉积反应,具体包括:
2.2.1以同样的抽真空速率将腔体内的压力抽至<1Pa之后,通入前驱体Al(CH3)3脉冲60s;
2.2.2以150sccm的载气除去未吸附在表面的前驱体Al(CH3)3;
2.2.3通入前驱体H2O脉冲60s,以100sccm的载气除去未吸附在表面的前驱体 H2O120s;
2.2.4依次交替循环上述步骤10次,得到厚度为10nm的Al2O3薄膜。
两次原子层沉积后,使得纳米淀粉微球表面包覆了一层致密均匀的超薄Fe2O3薄膜和Al2O3薄膜,实现了对纳米淀粉微球的表面改性。
实施例3
一种利用原子层沉积包覆纳米淀粉微球的方法,对粒径为10μm的纳米淀粉微球进行表面改性,包覆5nm的Fe2O3薄膜和1nm的SiO2薄膜,其中选取C10H10Fe/ O3、SiCl4/H2O为前驱体,具体包括如下步骤:
(1)氧化铁包覆:
1.1将纳米淀粉微球通过800目筛网之后,称量200g将其放置于原子层沉积设备的粉末容器中,将粉末容器放进腔体中,抽真空至10Pa;
1.2 打开超声振动,设置超声频率为40KHz,超声振动工作时长10min,间歇时长5s;
1.3 对腔体进行加热,同时通入载气对纳米淀粉微球进行表面进行清洗50min并使其分散,选择载气流量为100sccm。
1.4 待反应内腔的温度达到80℃进行第一次沉积反应,具体包括:
1.4.1抽真空,待腔体内的压力<1Pa之后,通入前驱体C10H10Fe脉冲60s;
1.4.2以280L/min的抽气速率以及150sccm的载气除去未吸附在表面的前驱体C10H10Fe;
1.4.3通入前驱体O3脉冲60s,之后以280L/min的抽气速率以及150sccm的载气除去未吸附在表面的前驱体 O3;
1.4.4依次交替循环上述步骤50次,得到厚度为5nm的Fe2O3薄膜。
(2)氧化硅包覆:
2.1以280L/min的抽气速率以及200sccm的载气对反应腔及氧化铁包覆的纳米淀粉微球表面进行清洗30min;
2.2待反应内腔温度达到80℃进行第二次沉积反应,具体包括:
2.2.1以同样的抽真空速率将腔体内的压力抽至<1Pa之后,通入前驱体SiCl4脉冲90s;
2.2.2以200sccm 的载气除去未吸附在表面的前驱体SiCl4;
2.2.3通入前驱体H2O脉冲90s,以200sccm的载气除去未吸附在表面的前驱体 H2O150s;
2.2.4依次交替循环上述步骤10次,得到厚度为1nm的SiO2薄膜。
两次原子层沉积后,使得纳米淀粉微球表面包覆了一层致密均匀的超薄Fe2O3薄膜和SiO2薄膜,实现了对纳米淀粉微球的表面改性。
本实施例中的Fe2O3涂层和SiO2涂层组合,可利用纳米Fe2O3涂层的超顺磁特性,制备出高磁含量的磁性纳米淀粉微球;用原子层沉积实现的致密均匀SiO2涂层,实现对磁性纳米淀粉微球的磁性物质Fe2O3涂层的包覆,避免磁泄露;利用SiO2涂层亲水、良好的生物相容性、抗团聚、悬浮稳定性、表面易修饰等特点,可提高纳米淀粉微球的载药性能,药物释放速度也会更平稳。
本发明原子层沉积过程中利用自行研发的原子层沉积设备—超声流化原子层沉积装置(中国专利CN201811502555.0)将薄膜沉积在软团聚体表面,使得纳米颗粒固化成大的颗粒团聚体,在后续的应用过程中影响纳米淀粉微球的药物释放及应用性能。
对比例1
取与实施例1同一批次纳米淀粉微球,将纳米淀粉微球通过800目筛网之后,与氧化铁和氧化铝颗粒混合。本例除与实施例1中氧化铁和氧化铝的包覆方法不同外,其余条件均相同。
分别测量实施例1和对比例1样品的饱和磁化强度和水氧渗透率,见图2和图3。从图2中磁饱和强度的数据可以看出磁饱和强度与包覆在纳米淀粉微球上氧化铁颗粒的厚度成正相关;但在相同氧化铁的条件下,实施例1中利用ALD在纳米淀粉微球表面包覆氧化铁纳米薄膜的磁饱和强度要比对比例1中氧化铁、氧化铝和纳米淀粉微球的混合样品高出20%。
从图3中水氧渗透率的数据可以看出水氧渗透率与包覆在纳米淀粉微球上氧化铝薄膜的厚度成负相关;但在相同氧化铝的条件下,实施例1中利用ALD在纳米淀粉微球表面包覆氧化铝纳米薄膜的水氧渗透率要比对比例1中氧化铁、氧化铝和纳米淀粉微球的混合样品低30%。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已, 并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,在纳米淀粉微球表面包覆纳米级薄膜,对纳米淀粉微球进行改性,具体方法如下:
(S1)过筛:首先将纳米淀粉微球通过800-2000目的筛网,除掉团聚的纳米淀粉微球;
(S2)加热等待:将步骤(S1)中经过筛网的纳米淀粉微球置于超声垂直流化原子层沉积设备中,对反应腔进行加热并通入载气对其表面进行清洗,同时打开真空泵对整个超声垂直流化原子层沉积设备进行抽真空直至腔体内压力不大于10Pa;
(S3)超声振动:设定超声振动杆的超声波频率为20-40KHz,超声振动工作时长1s-99h,间歇时长1ms-99s;
(S4)原子层沉积:当温度和压力达到设定值:温度为80-450℃,压力为0.1-10Pa,其后利用低压载气携带前驱体组合进入超声垂直流化原子层沉积设备腔体内,进行氧化物A和氧化物B的原子层沉积,得到改性后的纳米淀粉微球;
所述原子层沉积过程具体如下:
S4.1 低压载气携带第一前驱体组合进入反应腔并在纳米淀粉微球表面完成化学吸附,得到沉积氧化物A层;
S4.2 通入载气把未被表面吸附、多余的第一前驱体组合和反应副产物带出反应腔;
S4.3低压载气携带第二前驱体组合进入反应腔和第一前驱体组合吸附的表面继续进行原子层沉积,重复多次后得到氧化物B层;
S4.4 利用载气把多余的第二前驱体组合和反应生成的副产物带出反应腔;
所述第一前驱体组合为C10H10Fe/O3或SiCl4/H2O;第二前驱体组合为能够用于ALD反应的烷基、氨基金属,包括三(二甲胺基)硅烷/O2等离子气体、四(二甲基氨基)钛/H2O、Ti[OCH(CH3)]4/H2O、二甲基锌/H2O、四(乙基甲基氨基)锆/H2O、三甲基锆/H2O、四(二甲基氨基)铪/H2O、四(乙基甲基氨基)铪/H2O、三甲基铝/H2O或三甲基铝/O3,第一前驱体组合和第二前驱体组合在不构成冲突的情况下可任意组合;
所述氧化物A形成的纳米级可控薄膜为Fe2O3涂层或SiO2涂层,氧化物B形成的纳米级可控薄膜为TiO2涂层、ZnO涂层、ZrO2涂层、HfO2涂层或Al2O3涂层中的一种。
2.根据权利要求1所述利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,步骤S4.1和S4.3中所述低压载气携带第一前驱体组合或第二前驱体组合以气相形式进入反应腔,其中前驱体通气时长与纳米淀粉微球表面的表面积成正比,反应温度和压力由前驱体组合和纳米淀粉微球对温度的耐受性所决定。
3.根据权利要求1所述利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,步骤S4.1-S4.4中反应温度为80-120℃,通入载气之前的压力低于1Pa;
所述第一前驱体组合和第二前驱体组合均包括两种前驱体,反应时,通过载气脉冲通入对应前驱体组合中包含的两种前驱体,脉冲时长为60-90s,携带前驱体的载气流量为0.1-100sccm,使两种前驱体分别依次吸附在纳米淀粉微球表面;
每通入下一种前驱体之前通过载气对纳米淀粉微球表面进行清洗,载气流量为100-200sccm,清洗时长为120-150s;
其中,当第一前驱体组合沉积完毕后,通入载气对纳米淀粉微球表面进行清洗,载气流量为100-200sccm,清洗时长为10-30min,而后重复上述步骤进行第二前驱体组合的沉积。
4.根据权利要求1所述利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,步骤S4.1和S4.3的循环次数为1~800,所述氧化物A或/和氧化物B包覆层的厚度为0.1~50nm,所述被包覆的纳米淀粉微球质量为0.1~100g。
5.根据权利要求1所述利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,所述载气为惰性气体,惰性气体为高纯氮气或氩气。
6.根据权利要求1-5任一所述利用原子层沉积包覆纳米淀粉微球的方法,其特征在于,所述纳米淀粉微球替换为聚乳酸纳米颗粒、磷灰石晶体颗粒、金纳米颗粒或生物医药用磁性颗粒。
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