CN107235514A - 具吡啶二硫功能基的磁性纳米粒子Fe3O4@SiO2@S-S-Py的制备及生物医药中的应用 - Google Patents
具吡啶二硫功能基的磁性纳米粒子Fe3O4@SiO2@S-S-Py的制备及生物医药中的应用 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 58
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
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- 229910052681 coesite Inorganic materials 0.000 claims abstract description 54
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- -1 3- mercapto propyl group Ethoxysilanes Chemical class 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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Abstract
本发明属于磁性功能材料制备技术领域,具体为一种含吡啶二硫功能基的磁性纳米粒子的制备及应用。本发明以具有磁性四氧化三铁为纳米核载体通过表面修饰,制备具吡啶二硫功能基的磁性纳米粒子。所述方法包括磁性Fe3O4@S‑S‑Py纳米粒子、Fe3O4@SiO2@S‑S‑Py的制备。该粒子具有良好的热稳定性和独特的磁性性能,可应用于生物技术和材料学科的许多领域,如蛋白、细胞代谢物分离纯化、酶固定化和氧化还原反应的催化和吸附分离等。
Description
技术领域
本发明涉及磁性纳米材料的领域,特别涉及到一种磁性纳米粒子Fe3O4@SiO2@S-S-Py的制备,及该材料在特殊磁响应性及吡啶二硫功能基的氧化性在生物医学领域和催化材料领域实际研究中的开发和应用。
背景技术
磁性纳米粒子作为一种新型的纳米材料,具备纳米粒子的化学和物理性能,并且有着独特的磁学性质,能在外加磁场下迅速分离,已应用于催化材料、生物工程和生物医学、磁共振成像和环境保护等多方面;且磁性纳米粒子表面能进行各种修饰,在粒子表面进行包裹或修饰能避免Fe3O4的氧化并保持磁性能、提高粒子的稳定性和增加其水分散性的同时,还能调节并丰富粒子各种性能,获得多功能磁性纳米粒子拓宽其应用范围。表面修饰后的磁性纳米粒子同时兼具无机纳米粒子的磁响应性和表面修饰剂的化学物理特性。
吡啶二硫基能与自由巯基发生交换且离去基团反应后的产物不含巯基,是普遍使用的交联剂的功能基团。将吡啶二硫功能基固定在磁性纳米粒子上能利用粒子的磁性,能结合二者之间的优势。
该类吡啶二硫功能基化的磁性纳米粒子的结构通式如图1.
发明内容
本发明所要解决的技术问题是克服现有技术的不足,开发提供一种具有独特磁性性能,独特功能基团且有在生物医药领域,和催化材料领域潜在应用价值的磁性材料。
本发明的提供的磁性Fe3O4@SiO2@S-S-Py纳米粒子的制备包括以下方案:
方案一:
工艺步骤为:
(1)磁性纳米粒子的合成:共沉淀法合成磁性纳米粒子;
(2)合成吡啶二硫功能基的硅烷硅烷偶联剂,该类分子的结构通式如图2;
(3)表面吡啶二硫功能基修饰的磁性纳米粒子的制备:用步骤1所得的磁性纳米粒子及步骤2合成的含吡啶二硫功能基德硅烷偶联剂对粒子表面进行功能化。
方案二:
工艺步骤为:
(1)磁性纳米粒子的合成:共沉淀法合成磁性纳米粒子;
(2)Fe3O4-SiO2包裹磁性纳米粒子:利用步骤1得到的磁性纳米粒子,反相微乳液法,在油包水的环境里合成Fe3O4-SiO2核壳结构;
(3)表面吡啶二硫功能基修饰的磁性纳米粒子的制备:用步骤2所得的磁性纳米粒子及合成的含吡啶二硫功能基德硅烷偶联剂对粒子表面进行功能化。
方案三:
工艺步骤为:
(1)磁性纳米粒子的合成:共沉淀法合成磁性纳米粒子;
(2)Fe3O4-SiO2包裹磁性纳米粒子:利用步骤1得到的磁性纳米粒子,反相微乳液法,在油包水的环境里合成Fe3O4-SiO2核壳结构;
(3)表面硫基功能化磁性纳米粒子的制备:用步骤1或步骤2所得的磁性纳米粒子与γ巯丙基三乙氧基硅烷对粒子表面进行巯基化;
(4)表面吡啶二硫功能基修饰的磁性纳米粒子的制备:用步骤3所得的磁性纳米粒子及与二吡啶二硫反应,将巯基转化为吡啶二硫功能基
本发明制备的磁性Fe3O4@SiO2@S-S-Py纳米粒子的制备方法中,磁性Fe3O4纳米粒子的合成中,以氯化铁、氯化亚铁和氨水为主要原料,采用化学共沉淀法制备Fe3O4磁性纳米粒子,磁性Fe3O4纳米粒子的结构和形态由TEM图3可以看出,所得的磁性纳米粒子Fe3O4纳米粒子形貌为球形,粒度均一,分散性良好,粒径为~10nm。说明制备的粒子为纳米级材料并具有良好的热稳定性。图4磁性Fe3O4纳米粒子的红外光谱图在579cm-1有强烈的吸收峰,此处对应为Fe3O4中的Fe-O特征伸缩振动吸收峰,峰型完整。从图5磁性Fe3O4纳米粒子的XRD谱图可以看出,磁性Fe3O4纳米粒子在2θ 为220,311,400,511和440出现衍射峰,这些衍射峰和标准的Fe3O4谱图中的相应峰相符,表明所得样品为纯净的尖晶石结构的Fe3O4。从图6磁性Fe3O4纳米粒子的磁性能分析看可以看出,室温下测量的磁性Fe3O4纳米粒子的饱和磁化强度为36emu/g。
本发明对磁性Fe3O4纳米粒子进行了表面改性,先选择正硅酸乙酯(TEOS)与磁性Fe3O4纳米粒子反应,在表面用SiO2进行包裹,然后选择硅烷偶联剂与SiO2包裹的磁性纳米粒子反应,并最终得到吡啶二硫功能基化的磁性Fe3O4@SiO2@S-S-Py纳米粒子。
吡啶二硫功能基的硅烷硅烷偶联剂的合成反应式如图7。
磁性纳米粒子二硫键含量的测定
磁性纳米Fe3O4@SiO2 @S-S-Py粒子的TEM分析
用TEM分别对制备的Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子进行形貌和粒径分析图8, 由图可知,Fe3O4@ @SiO2@S-S-Py粒子的粒子的平均粒径分别约为~200nm。
磁性纳米Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子的傅里叶红外变换光谱图分析
图9中磁性纳米Fe3O4,Fe3O4@SiO2中3426 和1616分别对应于-OH的伸缩振动峰,791和1087处分别为Si-O-Si的对称和不对称的伸缩振动吸收峰,967和460处分别为Si-OH和Si-O-Si的弯曲振动吸收峰,表面Fe3O4@SiO2修饰成功,3000,1087,579处为吡啶环的吸收峰。
磁性磁性纳米Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子的XRD分析
由图10和表可以看出磁性纳米Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子的衍射峰的出现位置及强度和标准的Fe3O4基本一致,一次对应于Fe3O4的(220), (311), Fe3O4晶体的结构未发生变化,粒子物相为反式尖晶石结构,峰行窄,晶体完整。在对磁性Fe3O4纳米粒子进行表面功能化的过程中,Fe3O4的晶体结构未有变化,粒子物相为反式尖晶石结构,峰型窄且尖锐,晶体完整。另外磁性纳米Fe3O4@SiO2,e3O4@SiO2@S-S-Py粒子在2θ为20, 25附近出现了宽化的衍射峰,强度不大,这是非晶态的SiO2的衍射峰。
磁性纳米Fe3O4@SiO2@S-S-Py粒子的磁性能分析
磁性纳米Fe3O4@SiO2@S-S-Py粒子的磁滞曲线见图11,这种磁性纳米粒子的剩余磁化强度和矫顽力都几乎为零,接近超顺磁性。
磁性纳米Fe3O4 粒子的饱和磁化强度为38emu/g,没减弱。
对磁性纳米Fe3O4粒子的的改性,在其表面连接吡啶二硫键,得到吡啶二硫键包覆的磁性纳米Fe3O4@SiO2@S-S-Py粒子,通过投射电镜,傅立叶变换红外光谱,X-射线衍射,热重分析仪等表征方法对制得的纳米微球进行表征,结果表明,磁性纳米Fe3O4@SiO2@S-S-Py粒子的粒径约为~200nm,吡啶二硫功能基修饰成功,吡啶二硫键的含量为55.22umol/g ,晶型结构良好,饱和磁化强度为40.5,能在外在磁场作用下进行有效分离。
将本发明的方法制备的磁性纳米Fe3O4@SiO2@S-S-Py粒子的用于木瓜蛋白酶的的富集分离研究。
本发明提供的磁性纳米Fe3O4@SiO2@S-S-Py粒子的制备方法特点为:
1)磁性纳米Fe3O4@SiO2@S-S-Py粒子的形貌为球形,粒度均一,分散性好,粒径为,具有吡啶二硫功能基,含量为55.22umol/g,具有良好的热稳定性,晶型结构良好。
2)具吡啶二硫功能基的硅烷偶联试剂的合成
3)用于含巯基蛋白或其他生物分子的富集分离或固化。如含巯基的蛋白-木瓜蛋白酶的富集和分离。
本发明提供的磁性纳米Fe3O4@SiO2@S-S-Py粒子可应用于催化领域或生物医药技术领域,如蛋白分离纯化、酶的固化、生物传感和药物传递等领域。
附图说明
图1 吡啶二硫功能基的硅烷硅烷偶联剂的结构通式
图2吡啶二硫功能基化的磁性纳米粒子的结构通式
图3 磁性纳米粒子Fe3O4的TEM表征图
图4 磁性纳米粒子Fe3O4的红外表征图
图5磁性纳米粒子Fe3O4的XRD表征图
图6磁性纳米粒子Fe3O4的磁学性能图
图7吡啶二硫功能基的硅烷偶联剂的合成反应式
图8 磁性纳米粒子Fe3O4@SiO2@S-S-Py的TEM表征图
图9 磁性纳米粒子Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子的红外表征图
图10磁性纳米粒子Fe3O4,Fe3O4@SiO2,@SiO2@S-S-Py粒子的XRD表征图
图11磁性纳米粒子Fe3O4@SiO2@S-S-Py的磁学性能图
图12 利用含吡啶二硫功能基磁性纳米粒子对木瓜蛋白酶的选择性分离
图13 分离后木瓜蛋白酶的LC/MS/MS分析图
具体实施方式
本发明用下列实施方式来进一步说明本发明,但本发明的保护范围并不限于下列实例。
实例1
1) 磁性纳米Fe3O4粒子的合成:
在三口烧瓶内加入一定量水,加入3.5g FeCl2·4H2O和7gFeCl3· 6H2O与烧瓶中,通高纯氮半小时,除去溶液中的氧气,加热至90︒C,待反应体系均一后,逐滴加入35ml氨水,溶液变为黑色,继续加热1小时,后降温,室温静置5小时,磁性吸附,去溶液,分别用蒸馏水反复洗涤5次,至中性,冷冻干燥,得黑色产品磁性Fe3O4纳米粒子。
2) 磁性Fe3O4@SiO2纳米粒子的合成
将步骤1)的磁性纳米粒子0.1g,于250ml三口烧瓶中,加入125ml无水乙醇,及20ml水,超声30min,在高纯氮气保护下搅拌至体系均匀,逐滴加入氨水至pH9.0,加入正硅酸乙酯(TEOS)1ml,室温反应12h,磁性吸附,分别用水和无水乙醇洗涤数次,冷冻干燥得到产品Fe3O4@SiO2纳米粒子。
3)磁性纳米Fe3O4@SiO2@S-S-Py粒子的合成:
将步骤2)得到的磁性纳米Fe3O4@SiO2粒子0.1g,于三口烧瓶中,加入20ml甲苯,高纯氮气保护,剧烈磁力搅拌,是粒子分散均匀,逐滴加入0.1g合成的硅烷偶联剂,磁性搅拌反应5h,磁性吸附,用无水乙醇洗涤产品数次,冷冻干燥得到Fe3O4@SiO2@S-S-Py纳米粒子
实例2
含可吡啶二硫功能基的硅烷偶联剂的合成:
称取3-巯丙基乙氧基硅烷1g与5g二吡啶二硫与100ml乙腈中,搅拌,室温反应过夜,柱层析得到产物。
实例3
1) 磁性纳米Fe3O4粒子的合成:
在三口烧瓶内加入一定量水,加入3.5g FeCl2·4H2O和7gFeCl3·6H2O与烧瓶中,通高纯氮半小时,除去溶液中的氧气,加热至80︒C,待反应体系均一后,逐滴加入35ml氨水,溶液变为黑色,继续加热50min,后降温,室温静置5小时,磁性吸附,去溶液,分别用蒸馏水反复洗涤5次,至中性,冷冻干燥,得黑色产品磁性Fe3O4纳米粒子。
2)磁性Fe3O4@SiO2纳米粒子的合成
将步骤1)的磁性纳米粒子0.1g,于250ml三口烧瓶中,加入125ml无水乙醇,及20ml水,超声30min,在高纯氮气保护下搅拌至体系均匀,逐滴加入氨水至pH9.0,并加入正硅酸乙酯(TEOS)0.3ml,40OC度反应2h,磁性吸附,分别用水和无水乙醇洗涤数次,冷冻干燥得到产品Fe3O4@SiO2纳米粒子。
3)磁性纳米Fe3O4@SiO2@SH粒子的合成:
将步骤2)得到的磁性纳米Fe3O4@SiO2粒子0.1g,于三口烧瓶中,加入20ml甲苯,高纯氮气保护,剧烈磁力搅拌,是粒子分散均匀,逐滴加入0.1g 3-巯丙基乙氧基硅烷,磁性搅拌反应5h,磁性吸附,用无水乙醇洗涤产品数次,冷冻干燥得到Fe3O4@SiO2@S-S-Py纳米粒子。
4)磁性纳米粒子Fe3O4@SiO2@S-S-Py
将步骤3)得到的磁性纳米Fe3O4@SiO2粒子0.1g,于三口烧瓶中,加入20ml甲苯,高纯氮气保护,剧烈磁力搅拌,是粒子分散均匀,逐滴加入0.1g二硫二吡啶,磁性搅拌反应5h,磁性吸附,用无水乙醇洗涤产品数次,冷冻干燥得到Fe3O4@SiO2@S-S-Py纳米粒子。
实例4
磁性纳米粒子对含自由巯基蛋白(木瓜蛋白酶)的富集
1.5ml试管加入PBS缓冲液100ul,木瓜蛋白酶和卵清白蛋白各100ug,加入超声分散好的2mg吡啶二硫功能基化的磁性纳米粒子,室温反应2小时;磁性分离,用含0.1%SDS,8M尿素的PBS缓冲液洗磁性纳米粒子30分钟;磁性分离,用PBS洗3-5遍;用上样缓冲液处理磁性纳米粒子10分钟,SDS-PAGE检测分离的蛋白。分离后的结果如图12。图中显示磁性纳米材料能从蛋白混合液中分离带自由巯基的木瓜蛋白酶。
实例5
分离后的木瓜蛋白酶的LC/MS/MS分析
将分离后带自由巯基的木瓜蛋白酶利用胰酶进行酶解,利用LC/MS/MS对其进行分析,得到的质谱图如13. 图中的四个肽段通过MS/MS进行了分析鉴定为木瓜蛋白酶。
Claims (10)
1.具吡啶二硫功能基修饰的磁性纳米粒子的制备。
2.Fe3O4@S-S-Py磁性纳米材料的制备。
3.Fe3O4@SiO2@S-S-Py磁性纳米材料的制备。
4.权利要求1所述的材料,其中所述的材料具有磁性。
5.权利要求1或2所述的材料,其中包含吡啶二硫功能基。
6.权利要求1至3所述的材料,含吡啶二硫功能基的硅烷偶联试剂,选自图1。
7.权利要求1至4所述的材料,吡啶二硫功能基修饰的磁性纳米材料在催化/吸附分离方面的应用。
8.权利要求1至4所述的材料,在生物分子进行分离中的应用。
9.权利要求1至4所述的材料,在含巯基的药物传递中的应用。
10.权利要求1至4所述的材料,在生物医药领域的其它应用。
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CN111100840A (zh) * | 2019-12-23 | 2020-05-05 | 湖北工业大学 | 特异性捕获和有效释放循环肿瘤细胞的磁性纳米复合物及其制备方法 |
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