CN105999305B - 一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料 - Google Patents
一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料 Download PDFInfo
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Abstract
本发明提供了一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料，本发明提供的方法通过将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米粒子；其中，通过选用表面含有双键的纳米粒子和含巯基的功能化试剂为原料，通过形成C‑S实现了纳米粒子表面的功能化，不仅反应条件温和，且反应时间短，进而避免了了纳米粒子表面的破坏。
Description
技术领域
本发明涉及纳米材料领域，尤其涉及一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料。
背景技术
纳米材料的光、电、磁、力、催化等物理学特性展现了不同于本体材料的性质，成为当前材料学研发的热点，无疑纳米材料将会给各个领域带来革命性的影响。比如无机发光量子点材料由于优异的发光性质已经在显示面板、太阳能电池、生物传感器及荧光标记等领域广泛地应用。超顺磁的氧化铁纳米颗粒作为新颖的核磁共振成像造影剂已经获得临床应用，成为肝或脾脏免疫器官有效的影像增强试剂。脂质体和高分子胶束纳米粒由于具有优异的生物相容性作为药物载体已经在临床广泛应用。稀土掺杂的上述转换发光纳米颗粒由于背景荧光低的优点在细菌和病毒等检测方面展示了很大的优点，基于该转换发光材料的检测仪器正在进入市场。
目前高质量的纳米晶体的合成技术通常需要采用高温溶剂热分解技术，该合成方法中，为了防止纳米颗粒团聚表面需要包覆稳定剂，目前最通用的稳定剂为油酸或油胺。油酸或油胺为疏水性烷烃分子，并且没有裸露的活泼的官能团，在许多领域需要进一步修饰才能应用。例如，生物领域纳米药物载体或生物检测等方面要求纳米材料必须具备良好的水分散性，而表面需要引入羧基、胺基、巯基、羟基等官能团，以进一步连接功能性生物分子或进行薄膜制备等。因此，很多研究致力于把疏水性的纳米颗粒转变为亲水性纳米颗粒或在转变为亲水性纳米基团的同时进行表面功能化，如：脂质体和高分子胶束等纳米药物目前在临床医学获得了广泛的应用，通常脂质体等由磷脂这类含有烯键的分子构建，例如：脂质体表面进一步修饰靶向分子对于提高纳米药物在肿瘤部位的累积至关重要。目前，对于纳米粒子的的表面修饰采用的方法主要有表面配体交换、两亲性嵌段共聚物的包裹、强氧化剂氧化油酸等方法，但这些方法仍然具有原材料合成困难、用时冗长、破坏纳米粒子表面使材料性质下降等缺点。因此，提供一种简单、高效、通用的纳米材料的表面修饰方法无疑在上述领域具有重要的应用意义。
发明内容
有鉴于此，本发明所要解决的技术问题在于提供一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料，本发明提供的方法反应条件温和，且反应时间短。
本发明提供了一种纳米粒子的表面修饰方法，包括：
将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料。
优选的，所述表面含有双键的纳米粒子中的纳米粒子为无机纳米粒子、纳米脂质体或纳米囊泡。
优选的，所述表面含有双键的纳米粒子为自身具有双键的纳米粒子；
或者所述表面含有双键的纳米粒子为通过在纳米粒子的表面修饰含有双键的有机配体得到。
优选的，所述含有双键的有机配体为油酸、油胺、磷脂和花生四烯酸中的一种或几种。
优选的，所述含巯基的功能化试剂为含巯基的亲水性小分子、含巯基的疏水性小分子、含巯基的亲水性高分子、含巯基的疏水性高分子、含有官能团的含巯基的小分子或含官能团的含巯基的高分子。
优选的，所述含有官能团的含巯基的小分子或含官能团的含巯基的高分子中的官能团为碳碳双键、碳碳叁键、羟基、羧基、醚键、醛基、羰基、卤素、胺基、硝基或磺酸基。
优选的，所述引发剂为光引发剂、热引发剂或光敏剂。
优选的，所述光引发剂为二苯甲酮、二苯甲酮衍生物、苯偶姻、苯偶姻衍生物、酰基磷氧化物、曙红、二硫酯、和三硫酯衍生物中的一种或几种；
所述光敏剂为酞箐类光敏剂和叶绿素类光敏剂中的一种或几种；
所述热引发剂为偶氮二异丁氰或者偶氮二异丁氰衍生物。
优选的，所述步骤具体为：首先将表面含有双键的纳米粒子溶解于溶剂中，形成溶液；然后在加入含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料。
本发明还提供了一种表面功能化的纳米材料，由本发明提供的制备方法制备得到。
与现有技术相比，本发明提供了一种纳米粒子的表面修饰方法及其一种表面功能化的纳米材料，本发明提供的方法通过将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米粒子；其中，通过选用表面含有双键的纳米粒子和含巯基的功能化试剂为原料，通过形成C-S实现了纳米粒子表面的功能化，不仅反应条件温和，且反应时间短，进而避免了了纳米粒子表面的破坏；实验结果表明，本发明提供的方法，反应温度一般均低于70℃，反应时间可低至10min；大大节约的纳米粒子表面功能化的成本，有利于工业化生产。
附图说明
图1为本发明实施例1提供的纳米材料的制备过程图；
图2为本发明实施例1提供的未接枝纳米晶原料以及接枝聚乙二醇后的纳米晶材料的红外谱图；
图3为本发明实施例1提供的未接枝纳米晶原料的1HNMR谱；
图4为本发明实施例1提供的接枝聚乙二醇后的纳米晶材料的1HNMR谱。
具体实施方式
本发明提供了一种纳米粒子的表面修饰方法，包括：
将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料。
按照本发明，本发明将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料；其中，所述表面含有双键的纳米粒子中的纳米粒子并没有特殊要求，优选为无机纳米粒子、纳米脂质体或纳米囊泡，其中，本发明对无机纳米粒子的种类没有特殊限定，如可以为NaYF4:Yb,Tm上转换纳米晶、Fe3O4超顺磁性纳米晶、CdSe@ZnS发光半导体量子点纳米晶等；本发明对纳米脂质体的种类亦没有特殊要求，如可以为二油酰磷脂酰甘油(DOPG)构成的脂质体；本发明对纳米囊泡的种类也没有特殊要求，本领域公知的需进行表面修饰的纳米囊泡均可。本发明对所述表面含有双键的纳米粒子中的双键的来源也没有特殊要求，如可以是自身具有双键的纳米粒子，如脂质体；也可以是通过在纳米粒子的表面修饰含有双键的有机配体得到，其中，该含有双键的有机配体优选为油酸、油胺、磷脂和花生四烯酸中的一种或几种，更优选为油酸和油胺中的一种或两种。所述含巯基的功能化试剂是指用于修饰纳米粒子以期其能达到特定的功能的试剂，该试剂中，除还有巯基外，还含有特征官能团以使修饰后纳米粒子达到特定的功能；在实际制备中，通过巯基将功能化试剂中的特征官能团引入纳米粒子；具体的，所述含巯基的功能化试剂为含巯基的亲水性小分子、含巯基的疏水性小分子、含巯基的亲水性高分子、含巯基的疏水性高分子、含有官能团的含巯基的小分子或含官能团的含巯基的高分子，所述含有官能团的含巯基的小分子或含官能团的含巯基的高分子中的官能团为碳碳双键、碳碳叁键、羟基、羧基、醚键、醛基、羰基、卤素、胺基、硝基或磺酸基；更具体的如：含巯基的聚乙二醇、含巯基的聚乙二醇修饰的RGD、含巯基的烷基酸或两端分别为巯基和胺基的聚乙二醇。所述引发剂优选为光引发剂、热引发剂或光敏剂，其中，所光引发剂为二苯甲酮、二苯甲酮衍生物、苯偶姻、苯偶姻衍生物、酰基磷氧化物、曙红、二硫酯、和三硫酯衍生物中的一种或几种，更优选为二苯甲酮、安息香、安息香双甲醚、安息香乙醚、安息香异丙醚、安息香丁醚、芳酰基膦氧化物、双苯甲酰基苯基氧化膦、曙红、二硫酯或三硫酯衍生物；所述光敏剂为酞箐类光敏剂和叶绿素类光敏剂中的一种或几种；所述热引发剂为偶氮二异丁氰或者偶氮二异丁氰衍生物。
本发明中，本发明所述反应具体为：首先将表面含有双键的纳米粒子溶解于溶剂中，形成溶液；然后在加入含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料；其中，本发明对溶剂的种类没有特殊要求，只要使纳米粒子溶解在其中，能形成几乎透明的溶液即可，如可以为有机溶剂四氢呋喃、氯仿或环己烷等，也可以为水；本发明对反应的温度和时间也没有特殊要求，本领域技术人员可以根据公知常识调整合适的反应温度和时间。
本发明还提供了一种表面功能化的纳米材料，由本发明所述的制备方法制备得到；该纳米粒子中，所述功能化的基团通过碳硫键与纳米粒子相结合，达到对纳米粒子表面的修饰。
本发明提供的纳米粒子的表面修饰方法通过将表面含有双键的纳米粒子、含巯基的功能化试剂和引发剂混合反应，得到表面功能化的纳米材料；其中，通过选用表面含有双键的纳米粒子和含巯基的功能化试剂为原料，通过形成C-S实现了纳米粒子表面的功能化，不仅反应条件温和，且反应时间短，进而避免了传统的纳米材料修饰方法所需高温和长时间反应进而使得纳米粒子表面的破坏的问题；而且本发明提供的方法，操作步骤简单，原料来源广泛，可以实现批量化生产。
下面将结合本发明实施例的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
100mg NaYF4:Yb,Tm上转换纳米晶，直径60nm，表面为油酸分子，分散于20毫升四氢呋喃中，加入2毫克安息香双甲醚作为光引发剂，100mg端基为巯基的聚乙二醇(SH-PEG，分子量1000道尔顿)，形成透明反应溶液，用紫外灯照射反应体系30分钟后离心分离，用四氢呋喃洗涤2次，分散于水中，得到具有亲水性的纳米材料，其中，实施例1提供的方法的制备过程见图1，图1为本发明实施例1提供的纳米材料的制备过程图；
对得到的纳米粒子的结构进行鉴定，结果见图2～图4，图2为本发明实施例1提供的未接枝纳米晶原料以及接枝聚乙二醇后的纳米晶材料的红外谱图；图3为本发明实施例1提供的未接枝纳米晶原料的1HNMR谱，图4为本发明实施例1提供的接枝聚乙二醇后的纳米晶材料的1HNMR图；其中，
-NaYF4-OA是指未接枝的油酸包覆纳米粒子；-NaYF4-OA-SH-PEG是指接枝后的亲水性纳米粒子；
实施例2
100mg二油酰磷脂酰甘油(DOPG)构成的脂质体负载抗癌药物盐酸阿霉素后分散于水中，加入2mg Irgacure 2959水溶性光引发剂，2mg SH-PEG修饰的RGD作为肿瘤细胞表面和肿瘤血管上皮细胞靶向分子，反应体系置于摇床中并以60rpm速度摇摆，在紫外光照射下反应20分钟，使脂质体表面连接肿瘤靶向分子，离心洗涤出去未连接RGD，得到连接肿瘤靶向分子的纳米材料。
实施例3
400mg Fe3O4超顺磁性纳米晶，直径5nm，表面为油胺分子，分散于100毫升四氢呋喃中，加入10毫克二苯甲酮作为光引发剂，400mg 11-巯基十一烷酸，形成透明反应溶液，用紫外灯照射反应体系2小时后离心分离，用四氢呋喃洗涤2次，分散于水中，表面由于连接巯基十一烷酸分子后变成亲水性，并引入羧基官能团，即得到表面功能化的纳米材料。
实施例4
100mg CdSe@ZnS发光半导体量子点纳米晶，直径12nm，表面为油酸/油胺混合分子，分散于20毫升氯仿中，加入2毫克安息香双甲醚作为光引发剂，100mg两端基分别为巯基和胺基的乙二醇齐聚物(SH-PEG4-NH2)，形成透明反应溶液，用紫外灯照射反应体系10分钟后离心分离，用氯仿洗涤2次，分散于水中，表面由于连接PEG分子后变成亲水性，并引入胺基基团，即得到表面功能化的纳米材料。
实施例5
单层TiO2纳米晶薄膜的制备。
1)500mg TiO2纳米晶，直径10nm，表面为油酸分子，分散于20毫升四氢呋喃中，加入20毫克偶氮二异丁晴(AIBN)作为热引发剂，200mg两端分别为巯基和羧基的聚乙二醇(SH-PEG-COOH，分子量1000)，形成透明反应溶液，体系除氧后加热至60℃，反应4小时后离心分离，用四氢呋喃洗涤2次，分散于水中，表面由于连接PEG分子后变成亲水性，并引入羧基基团。
2)玻璃基底用浓硫酸/30％双氧水煮沸30分钟，表面引入羟基，浸泡于胺丙基三乙氧基硅烷甲苯溶液中反应24小时，使玻璃基底带有胺基。
3)将表面修饰有羧基PEG的TiO2纳米晶和玻璃基底在DMSO溶液中混合，并加入1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)作为催化剂，摇动反应体系过夜后，使TiO2纳米晶连接于玻璃基底表面，形成单层纳米晶薄膜。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (1)
1.一种表面功能化的纳米材料，其特征在于，所述表面功能化的纳米材料为单层TiO2纳米晶薄膜，制备步骤如下：
（1）500mgTiO2纳米晶，直径10nm，表面为油酸分子，分散于20毫升四氢呋喃中，加入20毫克偶氮二异丁腈作为热引发剂，200mg分子量1000的两端分别为巯基和羧基的聚乙二醇(SH-PEG-COOH)，形成透明反应溶液，体系除氧后加热至60℃，反应4小时后离心分离，用四氢呋喃洗涤2次，分散于水中，表面由于连接PEG分子后变成亲水性，并引入羧基基团；
（2）玻璃基底用浓硫酸/30％双氧水煮沸30分钟，表面引入羟基，浸泡于氨丙基三乙氧基硅烷甲苯溶液中反应24小时，使玻璃基底带有胺基；
（3）将表面修饰有羧基PEG的TiO2纳米晶和玻璃基底在DMSO溶液中混合，并加入1-乙基-(3-二甲基氨基丙基)碳二亚胺(EDC)盐酸盐作为催化剂，摇动反应体系过夜后，使TiO2纳米晶连接于玻璃基底表面，形成单层纳米晶薄膜。
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| KR100713745B1 (ko) * | 2006-02-27 | 2007-05-07 | 연세대학교 산학협력단 | 상전이 리간드로 코팅된 수용성 자성 또는 금속 산화물나노입자 및 이의 제조방법 |
| JP4169078B2 (ja) * | 2006-03-24 | 2008-10-22 | Ｔｏｔｏ株式会社 | 酸化チタン複合体粒子、その分散液、およびそれらの製造方法 |
| US20090096136A1 (en) * | 2007-10-12 | 2009-04-16 | The Regents Of The University Of California | Thiol-ene based poly(alkylsiloxane) materials |
| CN101259082B (zh) * | 2008-04-16 | 2011-01-26 | 厦门大学 | 一种根管消炎显影剂及其制备方法 |
| CN101690817B (zh) * | 2009-09-27 | 2011-07-20 | 上海大学 | 聚乙二醇化学接枝修饰二氧化钛纳米管的方法 |
| FR2998179B1 (fr) * | 2012-11-20 | 2015-01-09 | Univ Bourgogne | Nanostructure a base de titanate pour la regeneration et l'ingenierie tissulaire |
| CN105170110A (zh) * | 2015-05-18 | 2015-12-23 | 西北大学 | 一种磁性复合纳米粒子及其制备方法 |
| CN105218741B (zh) * | 2015-11-06 | 2018-03-16 | 武汉理工大学 | 一种温敏性磁性复合微球的制备方法 |
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