CN114524896A - 一种表面褶皱微球的制备方法 - Google Patents
一种表面褶皱微球的制备方法 Download PDFInfo
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- CN114524896A CN114524896A CN202111566184.4A CN202111566184A CN114524896A CN 114524896 A CN114524896 A CN 114524896A CN 202111566184 A CN202111566184 A CN 202111566184A CN 114524896 A CN114524896 A CN 114524896A
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Abstract
本发明涉及高分子材料技术领域,提供一种表面褶皱微球的制备方法,包括以下步骤:(1)纳米颗粒的制备;(2)稳定相的制备;(3)聚合等过程。此法利用纳米颗粒在单体及交联剂聚合过程中,通过物理性方法占据微球乳液表面的区域,形成凹凸褶皱,具有合成方法简单,容易控制、便于放大生产等优点。
Description
技术领域
本发明涉及高分子材料技术领域,尤其涉及一种表面褶皱微球的制备方法。
背景技术
具有不同组成和形态的聚合物微球近年来受到越来越多的科学家的关注,且可以根据其 自身材料的不同性质制备出不同尺寸、不同结构、不同形态的微球:如无孔、多孔微球,表 面光滑微球,表面褶皱微球,红细胞状微球,洋葱型微球,哑铃型微球等。其中表面褶皱微 球在调节生物材料和生物体系之间的相互作用方面起着十分重要的作用,如:表面褶皱结构 的微球因其表面粗糙与具有特定的形状、表面的细胞及微生物在结构上有相似之处,所以会 对细胞的吸附、增长等方面具有特殊的益处。但,目前很少有相关专利报道。
本发明专利,选用悬浮聚合方法,采用含有纳米颗粒的稳定剂作为稳定相,合成出一种表面 褶皱的聚合物微球。
发明内容
针对特殊使用要求,本专利发明一种表面不光滑,含有褶皱形状的聚合物微球。
本发明提供一种表面褶皱微球的制备方法。
为达到上述目的,本发明是通过以下技术方案实现的:
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备:
称取0.5-20份的物质W1于容器中混合均匀,加入一定量的浓度为20-40%的氢氧化钠溶 液,剧烈搅拌混合均匀;将此转移至研磨器中,研磨30min;
(2)稳定相的制备:
将0.5-5份的稳定剂P1加入到20份的去离子水,升温至50~80℃,待稳定剂完全溶解后, 即得到含稳定剂P1的水相溶液;
将(1)中得到的的纳米颗粒加入到含有P1的稳定剂水相中;搅拌均匀,即得到稳定相。
(3)聚合及清洗
称取2-100份的可聚合单体M1,2-100份的交联剂M2,0.5-5份的引发剂I1于烧杯中, 混合均匀,备用;称取5-20份盐S1,0.01-0.1份的阻聚剂Z1于烧杯中,加入300份的去离子水, 溶解完全;加入0.5-5份的乳化剂S2,分散均匀,转移至反应瓶中;将(2)中得到的稳定性 转移至反应瓶中;搅拌均匀;将含有M1、M2、I1的油相转移至反应瓶中,50-1000rpm搅拌转 速下,升温至65-90℃,保温反应8-18h;反应结束后,降至室温,抽滤掉反应液,依次用含 有0.1-5%稀盐酸水溶液清洗,去离子水清洗,即可得到表面含有褶皱的聚合物微球。
进一步的改进是:所述物质W1为硬脂酸钙或十八烷基磷酸钙与磷酸氢钙、或氯化镁、或 碳酸钙、或碳酸氢钙或其任意组合。
进一步的改进是:所述稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维 素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精中的任意一 种或两种以上的混合物。
进一步的改进是:所述可聚合单体M1为苯乙烯、甲基苯乙烯、乙基苯乙烯、氯甲基苯乙 烯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸季戊四醇酯、甲 基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、甲基丙烯酸丁酯、丙烯酰胺、甲基丙烯酸羟乙酯、 丙烯酸羟乙酯、甲基丙烯酰胺中的任意一种或两种以上的混合物。
进一步的改进是:所述交联剂M2为二乙烯基苯、二丙烯苯、双甲基丙烯酸乙二醇酯、三 乙烯酸甘油酯、三羟甲基丙基三甲基丙烯酸、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸 酯、二缩三乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯 酸酯、1,4-丁二醇二甲基丙烯酸酯六亚甲基双甲基丙烯酰胺、二乙烯基苯基甲烷、三甲基丙 烯酸甘油酯、亚甲基丙烯酰胺中的任意一种或两种以上的混合物。
进一步的改进是:所述乳化剂S1为离子型乳化剂、非离子型乳化剂中的任意一种或二者 以任意比混合而成。所述离子型乳化剂为烷基苯磺酸盐、烷基磺酸盐、烷基丁二酸酯磺酸盐 或烷基联苯基醚磺酸盐。所述非离子型乳化剂为烷基酚聚氧乙烯醚、苄基酚聚氧乙烯醚、苯 乙基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚或脂肪胺聚氧乙烯醚。
进一步的改进是:所述的阻聚剂Z1为亚硝酸钠、对苯二酚、对硝基苯酚钠中的一种或两 种以上的混合物。
进一步的改进是:所述的盐S2为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸 二氢钠中的任意一种或两种以上的混合物。
进一步的改进是:所述引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、 偶氮二异丁基脒中的任意一种或两种以上的混合物。
本发明的特点:
通过采用前述技术方案,本发明的有益效果是:
本发明制备一种表面褶皱的微球,首先合成纳米颗粒,其次将纳米颗粒与稳定剂混合, 形成复合型稳定相,即稳定剂的水溶液包裹此纳米颗粒;油相在复合型稳定相中,在搅拌情 况下,形成水包油乳液;纳米颗粒均匀分散于稳定剂水溶液中,因此纳米颗粒表面含有烷基, 增加了其表面的疏水、亲油性,可与水包油乳液接触,占据乳液表面的位置,单体及交联剂 经过聚合后,在乳液表面形成凹凸褶皱。
此法具有如下优点:利用纳米颗粒在单体及交联剂聚合过程中,通过物理性方法占据微 球乳液表面的区域,形成凹凸褶皱,合成方法简单,容易控制、便于放大生产等优点,在生 物医药及体外诊断方面具有潜在的应用价值。
附图说明
图1是实施例2中的得到的表面褶皱微球扫描电子显微镜图。
具体实施方式
以下将结合具体实施例来详细说明本发明的实施方式,借此对本发明如何应用技术手段 来解决技术问题,并达成技术效果的实现过程能充分理解并据以实施。
若未特别指明,实施例中所采用的技术手段为本领域技术人员所熟知的常规手段,所采 用的试剂和产品也均为可商业获得的。所用试剂的来源、商品名以及有必要列出其组成成分 者,均在首次出现时标明。
实施例一
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取0.45g硬脂酸钙,7.5g 20%的氢氧化钠溶液,剧烈搅拌后,转移至研磨器中,研磨 30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.2g的聚乙烯醇,升温至80℃,搅拌至聚乙烯 醇完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀,备用。
(3)聚合
称取20g苯乙烯,2.5g的二乙烯基苯,0.19g的过氧化苯甲酰于烧杯中,搅拌至过氧化 苯甲酰完全溶解;称取10g的氯化钠、0.05的亚硝酸钠于烧杯中,加入100g的去离子水,加入 0.37g的SDS,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均 匀;继续将上述的油性单体转移至反应瓶中,在搅拌220rpm下,体系升温至80℃,保温反应 8h;反应结束后,降至室温,滤布过滤,分别用10倍量的12%的盐酸水溶液,去离子水清洗, 即得平均粒径为40.8μm的表面褶皱微球。
实施例二
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取6g十八烷基磷酸钙,60g 30%的氢氧化钠溶液,剧烈搅拌后,转移至研磨器中,研 磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.83g的羟丙基纤维素,升温至80℃,搅拌 至羟丙基纤维素完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分 散均匀,备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯,10g的二乙二醇二甲基丙烯酸酯,0.2g的过氧化苯甲 酰于烧杯中,搅拌至过氧化苯甲酰完全溶解;称取1g的氯化钠、0.008的对苯二酚于烧杯中, 加入280g的去离子水,加入0.9g的SDBS,搅拌至完全溶解,转移至反应瓶中;将上述的稳 定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌320rpm 下,体系升温至80℃,保温反应8h;反应结束后,降至室温,滤布过滤,分别用10倍量的 12%的盐酸水溶液,去离子水清洗,即得平均粒径为2.5μm的表面褶皱微球。
实施例三
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取10.5g硬脂酸钙,2.1g的碳酸氢钙及105g的35%的氢氧化钠溶液,剧烈搅拌后, 转移至研磨器中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.75g的β-环糊精,升温至80℃,搅拌至β-环糊精完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀,备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯,25g的二乙二醇二甲基丙烯酸酯,0.18g的偶氮二异 丁腈于烧杯中,搅拌至偶氮二异丁腈完全溶解;称取3.5g的氯化钠、0.002的对苯二酚于烧 杯中,加入300g的去离子水,加入0.35g的曲拉通X-104,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌180rpm下,体系升温至70℃,保温反应12h;反应结束后,降至室温,滤布过滤, 分别用10倍量的12%的盐酸水溶液,去离子水清洗,即得平均粒径为28.8μm的表面褶皱微 球。
实施例四
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取12.6g硬脂酸钙,2.1g碳酸氢钙及138.6g的35%的氢氧化钠溶液,剧烈搅拌后, 转移至研磨器中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.315g的聚乙烯醇,升温至80℃,搅拌至 聚乙烯醇完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀, 备用。
(3)聚合
称取10g苯乙烯,32g的二乙烯基苯,1.23g的偶氮二异丁基脒于烧杯中,搅拌至偶氮 二异丁基脒完全溶解;称取10.5g的氯化钠、0.28g的磷酸二氢钠、0.036g的对硝基苯酚钠 于烧杯中,加入600g的去离子水,加入0.21g的SDS,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌180rpm下,体系升温至70℃,保温反应12h;反应结束后,降至室温,滤布过滤,分别 用10倍量的12%的盐酸水溶液,去离子水清洗,即得平均粒径为64.1μm的表面褶皱微球。
实施例五
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取4.5g硬脂酸钙,1.1g碳酸钙及81.6g的30%的氢氧化钠溶液,剧烈搅拌后,转移 至研磨器中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.75g的聚乙烯吡咯烷酮,升温至80℃,搅拌至聚乙烯吡咯烷酮完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀,备用。
(3)聚合
称取10g丙烯酸缩水甘油酯,5g的季戊四醇三丙烯酸酯,0.08g的偶氮二异丁腈于烧杯 中,搅拌至偶氮二异丁腈完全溶解;称取3.3g的硫酸钠、0.03g的对硝基苯酚钠于烧杯中, 加入100g的去离子水,加入0.15g的曲拉通X-104,搅拌至完全溶解,转移至反应瓶中;将 上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌 160rpm下,体系升温至70℃,保温反应12h;反应结束后,降至室温,滤布过滤,分别用10倍量的12%的盐酸水溶液,去离子水清洗,即得平均粒径为58.4μm的表面褶皱微球。
实施例六
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取3.0g硬脂酸钙,54g的30%的氢氧化钠溶液,剧烈搅拌后,转移至研磨器中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.3g的聚乙烯醇,升温至80℃,搅拌至聚 乙烯醇完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀, 备用。
(3)聚合
称取10g丙烯酸缩水甘油酯,10g的二乙烯基苯,0.1g的偶氮二异丁腈于烧杯中,搅拌 至偶氮二异丁腈完全溶解;称取2.3g的氯化钠、0.02g的亚硝酸钠于烧杯中,加入100g的去离子水,加入0.2g的曲拉通X-104,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌160rpm下, 体系升温至70℃,保温反应12h;反应结束后,降至室温,滤布过滤,分别用10倍量的12% 的盐酸水溶液,去离子水清洗,即得平均粒径为62.4μm的表面褶皱微球。
实施例七
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取3.78g硬脂酸钙,68g的25%的氢氧化钠溶液,剧烈搅拌后,转移至研磨器中,研 磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.9g的聚乙烯基吡咯烷酮,升温至80℃, 搅拌至聚乙烯基吡咯烷酮完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌 至完全分散均匀,备用。
(3)聚合
称取10g苯乙烯,8g的二乙烯基苯,0.09g的偶氮二异丁基脒于烧杯中,搅拌至偶氮二 异丁基脒完全溶解;称取5.4g的硝酸钠、0.03g的亚硝酸钠于烧杯中,加入120g的去离子水,加入0.18g的曲拉通X-104,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移 至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌80rpm下,体系升 温至65℃,保温反应18h;反应结束后,降至室温,滤布过滤,分别用10倍量的12%的盐酸 水溶液,去离子水清洗,即得平均粒径为84.7μm的表面褶皱微球。
实施例八
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取4.68g十八烷基磷酸钙,84.3g的25%的氢氧化钠溶液,剧烈搅拌后,转移至研磨 器中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入0.78g的聚乙烯醇,升温至80℃,搅拌至聚乙烯醇完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀, 备用。
(3)聚合
称取10g甲基丙烯酸缩水甘油酯,16g的二缩三乙二醇二甲基丙烯酸酯,0.13g的过氧 化苯甲酰于烧杯中,搅拌至过氧化苯甲酰完全溶解;称取2.08g的氯化钠、0.036g的亚硝酸 钠于烧杯中,加入180g的去离子水,加入0.18g的SDBS,搅拌至完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌380rpm下,体系升温至75℃,保温反应12h;反应结束后,降至室温,滤布过滤, 分别用10倍量的12%的盐酸水溶液,去离子水清洗,即得平均粒径为24.4μm的表面褶皱微 球。
实施例九
一种表面褶皱微球的制备方法,包括以下步骤:
(1)纳米颗粒的制备
称取40.g十八烷基磷酸钙,700g的25%的氢氧化钠溶液,剧烈搅拌后,转移至研磨器 中,研磨30min;
(2)稳定相的制备:
称取20g的去离子水于反应瓶中,继续加入48g的聚乙烯醇,升温至80℃,搅拌至聚乙烯醇完全溶解;将上述(1)中的纳米颗粒加上上述反应瓶中,继续搅拌至完全分散均匀,备用。
(3)聚合
称取10g丙烯酸缩水甘油酯,90g的二缩三乙二醇二甲基丙烯酸酯,0.5g的过氧化苯甲 酰于烧杯中,搅拌至过氧化苯甲酰完全溶解;称取6.0g的氯化钠、0.24g的亚硝酸钠于烧杯 中,加入920g的去离子水,加入58g的曲拉通X-104,搅拌至完全溶解,转移至反应瓶中; 将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅 拌460rpm下,体系升温至75℃,保温反应12h;反应结束后,降至室温,滤布过滤,分别用10倍量的12%的盐酸水溶液,去离子水清洗,即得平均粒径为8.3μm的表面褶皱微球。
Claims (4)
1.一种表面褶皱微球的制备方法,其特征在于:包括以下步骤:
(1)纳米颗粒的制备:
称取0.5-20份的物质W1于容器中混合均匀,加入一定量的浓度为20-40%的氢氧化钠溶液,剧烈搅拌混合均匀;将此转移至研磨器中,研磨30min;
(2)稳定相的制备:
将0.5-5份的稳定剂P1加入到20份的去离子水,升温至50~80℃,待稳定剂完全溶解后,即得到含稳定剂P1的水相溶液;
将(1)中得到的的纳米颗粒加入到含有P1的稳定剂水相中;搅拌均匀,即得到稳定相。
(3)聚合及清洗
称取2-100份的可聚合单体M1,2-100份的交联剂M2,0.5-5份的引发剂I1于烧杯中,混合均匀,备用;称取5-20份盐S1,0.01-0.1份的阻聚剂Z1于烧杯中,加入300份的去离子水,溶解完全;加入0.5-5份的乳化剂S2,分散均匀,转移至反应瓶中;将(2)中得到的稳定相转移至上述反应瓶中;搅拌均匀;将含有M1、M2、I1的油相转移至反应瓶中,50-1000rpm搅拌转速下,升温至65-90℃,保温反应8-18h;反应结束后,降至室温,抽滤掉反应液,依次用含有0.1-5%稀盐酸水溶液清洗,去离子水清洗,即可得到表面含有褶皱的聚合物微球。
2.根据权利要求书1所述的制备方法,其特征在于:所述的步骤(1)中W1为硬脂酸钙或十八烷基磷酸钙与磷酸氢钙、或氯化镁、或碳酸钙、或碳酸氢钙或其任意组合;所述步骤(2)中稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精中的任意一种或两种以上的混合物;所述步骤(3)中可聚合单体M1为苯乙烯、甲基苯乙烯、乙基苯乙烯、氯甲基苯乙烯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸季戊四醇酯、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、甲基丙烯酸丁酯、丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酰胺中的任意一种或两种以上的混合物;所述步骤(3)中交联剂M2为二乙烯基苯、二丙烯苯、双甲基丙烯酸乙二醇酯、三乙烯酸甘油酯、三羟甲基丙基三甲基丙烯酸、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯六亚甲基双甲基丙烯酰胺、二乙烯基苯基甲烷、三甲基丙烯酸甘油酯、亚甲基丙烯酰胺中的任意一种或两种以上的混合物;所述步骤(3)中乳化剂S2为离子型乳化剂、非离子型乳化剂中的任意一种或二者以任意比混合而成;所述步骤(3)中离子型乳化剂为烷基苯磺酸盐、烷基磺酸盐、烷基丁二酸酯磺酸盐或烷基联苯基醚磺酸盐。所述非离子型乳化剂为烷基酚聚氧乙烯醚、苄基酚聚氧乙烯醚、苯乙基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚或脂肪胺聚氧乙烯醚;所述步骤(3)中盐S1为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸二氢钠中的任意一种或两种以上的混合物。所述步骤(3)中引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒中的任意一种或两种以上的混合物;所述步骤(3)中阻聚剂Z1为亚硝酸钠、对苯二酚、对硝基苯酚钠中的一种或两种以上的混合物。
3.根据权利要求书1所述的制备方法,其特征在于:所述的步骤(1)中,所述的W1与氢氧化钠质量比为1∶10-30;所述的W1与M1及M2的总质量的比为0.5-5∶100;所述的步骤(2)中P1与M1及M2的总质量的比为0.5-5∶100;所述的步骤(3)中的M1与M2的质量比为2-90∶10;所述步骤(3)中的引发剂I1与M1及M2的总质量的比为0.5-5∶100;所述步骤(3)中的盐S1与M1及M2的总质量的比为5-30∶100;所述步骤(3)中的阻聚剂Z1与M1及M2的总质量的比为0.01-0.3∶100;所述步骤(3)中的乳化剂S2与M1及M2的总质量的比为0.5-5∶100;所述的M1及M2的总质量与水的比为5-25∶100。
4.根据权利要求1所述的一种表面褶皱微球的制备方法,其特征在于得到的微球的粒径为:0.5um~100um间。
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