CN107857303A - 基于双氧水和peg修饰的亲水铁碳复合纳米颗粒及其制备方法 - Google Patents
基于双氧水和peg修饰的亲水铁碳复合纳米颗粒及其制备方法 Download PDFInfo
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- CN107857303A CN107857303A CN201711086985.4A CN201711086985A CN107857303A CN 107857303 A CN107857303 A CN 107857303A CN 201711086985 A CN201711086985 A CN 201711086985A CN 107857303 A CN107857303 A CN 107857303A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical class ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 52
- 229920001223 polyethylene glycol Polymers 0.000 description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000010148 water-pollination Effects 0.000 description 18
- 235000013339 cereals Nutrition 0.000 description 13
- 238000002595 magnetic resonance imaging Methods 0.000 description 10
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- 230000015572 biosynthetic process Effects 0.000 description 5
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 239000002616 MRI contrast agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- QUTGXAIWZAMYEM-UHFFFAOYSA-N 2-cyclopentyloxyethanamine Chemical compound NCCOC1CCCC1 QUTGXAIWZAMYEM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 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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- A61K49/1824—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles
- A61K49/1827—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle
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Abstract
本发明涉及一种基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒及其制备方法，先将铁盐和碳源加入水中，采用水热反应合成Fe3O4@C颗粒；使用双氧水氧化处理Fe3O4@C颗粒；使用PEG接枝经双氧水氧化处理后的Fe3O4@C，接枝反应结束后，对反应液进行透析、分离、洗涤和干燥，得到基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒。本发明通过水热条件下自组装合成具有核壳结构的Fe3O4@C磁性纳米粒，接着利用双氧水氧化和PEG接枝两种后期修饰手段，改变Fe3O4@C碳壳表面官能团种类和数目，成功将大量PEG修饰在碳壳上，从而获得具有高度亲水性和生物相容性的Fe3O4@C纳米颗粒。
Description
技术领域
本发明属于核磁共振成像造影剂领域，特别涉及一种基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒及其制备方法。
背景技术
磁共振成像(MRI)是一种收集核磁共振现象产生的信号，再重建图像的成像技术，它具有最高的软组织分辨率，被广泛用于医学诊断和各种病理研究。在应用中常常需要造影剂改变周围环境中氢质子的弛豫时间，从而增强核磁共振成像的对比度，以利于病灶组织与正常组织之间结构区分，进而提高诊断能力。因此，开发核磁共振成像造影剂成为了医学界的热点问题。依据改变弛豫时间的不同可以分为两类：一类是钆螯合剂为代表的T1造影剂，特异性影响氢质子的纵向弛豫时间，使核磁共振成像信号正增强。另一类是以四氧化三铁(Fe3O4)纳米粒为代表的T2造影剂，特异性影响氢质子的横向弛豫时间，使核磁共振成像信号负增强。
与钆配位化合物相比，Fe3O4纳米粒子的优点在于无毒以及磁学性质较强。然而，Fe3O4纳米颗粒直接用于造影剂具有以下缺点：①在水溶液中极易被氧化和发生团聚；②某些化学方法制备的Fe3O4纳米粒表面含有大量的有机溶剂，不适合直接在生物体内使用；③粒径较大、水溶性差。因此，提高Fe3O4纳米粒的抗氧化性、生物相容性及在水中的分散稳定性，是其成功用作MRI造影剂的关键。
碳元素是构成生命体的重要元素之一，碳材料具有良好的生物相容性和化学稳定性，如在纳米颗粒的外周紧密包覆而形成碳壳层，则可大幅提高纳米颗粒的化学稳定性，也有望降低潜在的生物毒性。由此产生的问题是碳包覆的纳米颗粒表面有很强的疏水性，不利于MRI成像应用。因此，需要后期修饰手段提高铁碳纳米颗粒的亲水性。
聚乙二醇(PEG)是高亲水性聚合物，它对纳米颗粒的修饰可以提高纳米颗粒的水溶性和生物相容性，并延长其在体内的血液循环时间(Peng et al.,Biomaterials 2012,33,1107-1119)。这是由于PEG本身具备大量亲水性的醚键，并且PEG的毛刷作用可以有效屏蔽体内蛋白与纳米颗粒作用。但是，由于铁碳纳米粒中碳壳的化学稳定性高，不易再外接修饰基团，从而限制了铁碳纳米材料的应用。
发明内容
本发明的目的在于克服现有技术中存在的问题，提供一种基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒及其制备方法，制得的铁碳复合纳米颗粒化学稳定性高、不易团聚，且核磁共振响应信号强。
为了达到上述目的，本发明采用如下技术方案：
包括以下步骤：
(1)将铁盐和碳源加入水中，采用水热反应合成Fe3O4@C颗粒；
(2)使用双氧水氧化处理Fe3O4@C颗粒；
(3)使用PEG接枝经双氧水氧化处理后的Fe3O4@C，接枝反应结束后，对反应液进行透析、分离、洗涤和干燥，得到基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒。
进一步地，步骤(1)中，铁盐包括三氯化铁、硝酸铁或硫酸铁；碳源包括葡萄糖、蔗糖、果糖或淀粉。
进一步地，步骤(1)中，铁盐和碳源之间的摩尔比为0.1～1；每0.01mol的碳源加入0.04～0.4L的去离子水中。
进一步地，步骤(1)中在水热反应之前，水中还加入有尿素，尿素和碳源之间的摩尔比例为5～50。
进一步地，步骤(1)的水热反应是在180～300℃反应10～24h。
进一步地，步骤(1)的水热反应结束后，冷却并收集沉淀，将沉淀洗涤干燥后得到Fe3O4@C颗粒。
进一步地，步骤(2)中，双氧水氧化处理Fe3O4@C颗粒的具体步骤是：将Fe3O4@C颗粒和双氧水按质量比为0.01～0.1混合，在20～100℃搅拌1～12h，分离后洗涤干燥，完成氧化处理；其中双氧水的质量分数为30％。
进一步地，步骤(3)中，使用PEG接枝经双氧水氧化处理后的Fe3O4@C的具体步骤包括：先将双氧水氧化处理后的Fe3O4@C加入到含有1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基丁二酰亚胺的超纯水中，在10～100℃搅拌均匀，得到混合液A；再向混合液A中加入PEG，搅拌反应2～48h，完成接枝；其中，双氧水氧化处理后的Fe3O4@C、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐、N-羟基丁二酰亚胺、超纯水和PEG之间的比例为(0.1～1)g：(20～400)mg：(10～200)mg：(5～50)ml：(0.1～1)g。
进一步地，步骤(3)中，PEG包括氨基PEG或羟基PEG，其分子量为100～10000。
进一步地，该纳米颗粒是以纳米四氧化三铁颗粒为核心，纳米四氧化三铁颗粒上包裹碳壳层，碳壳层上连接PEG；碳壳包覆的纳米四氧化三铁的粒径在20～300nm之间，碳壳厚度在5～100nm之间。
与现有技术相比，本发明具有以下有益的技术效果：
本发明首先以水热法合成碳层包裹的Fe3O4纳米颗粒；再利用简单的双氧水氧化处理，使碳层暴露羧基基团，可有效提高Fe3O4@C纳米粒碳壳表面-COOH基团数量，为下一步PEG接枝提供更多的结合位点，增强修饰效果。使用PEG与碳层上羧基基团反应，通过化学键接枝修饰在Fe3O4@C表面，实现纳米颗粒的亲水改性。其中碳铁核壳结构为MRI成像功能基团，聚乙二醇为亲水基团。本发明通过水热条件下自组装合成具有核壳结构的Fe3O4@C磁性纳米粒，接着利用双氧水氧化和PEG接枝两种后期修饰手段，改变Fe3O4@C碳壳表面官能团种类和数目，成功将大量PEG修饰在碳壳上，从而获得具有高度亲水性和生物相容性的Fe3O4@C纳米颗粒。本发明方法工艺简单，反应条件温和，易于操作，成本较低，经“双氧水+PEG”修饰后的Fe3O4@C纳米粒亲水性和生物相容性显著提高，可长时间在水中均匀稳定分散，具备增强的核磁共振成像性能，。检索国内外文献，尚没有发现基于"双氧水+PEG"修饰的高度亲水的Fe3O4@C纳米颗粒的制备方法，及其用于MRI造影剂研究的相关报道。
本发明纳米颗粒具有以下优点：
(1)其结构是以纳米四氧化三铁颗粒为核心，外围包裹碳壳层，碳壳层上连接PEG，借助于碳的包裹，Fe3O4@C的稳定性和分散性要好于无包碳的Fe3O4纳米粒子，并且本发明制备的Fe3O4@C粒径分布较窄，碳层厚度均匀。
(2)本发明制备的亲水Fe3O4@C磁性纳米颗粒粒径较小、弛豫率高、造影效果显著，同时具有良好的水溶性、胶体稳定性、生物相容性，对生物体无不良影响，在核磁共振成像诊断领域有潜在的应用价值。
(3)本发明碳壳包覆的纳米四氧化三铁的整体粒径在20～300nm之间，碳壳厚度在5～100nm之间；经超声分散后静置1h仍均匀分散，无聚集沉淀；应用于T2及T2*的核磁共振成像模式，成像TR时间在50～200ms之间，成像TE时间在1000～3500ms之间。
附图说明
图1是本发明Fe3O4@C纳米颗粒的结构图。
图2是本发明Fe3O4@C的透射电镜图像。
图3是Fe3O4@C(右)和商用Fe3O4纳米粒(左)的不同浓度的核磁共振T2成像结果。
图4是Fe3O4@C的横向弛豫计算。
具体实施方式
下面结合附图对本发明做进一步详细说明。
本发明是以碳水化合物为碳源合成具有核壳结构的磁性铁碳纳米粒，利用双氧水氧化和PEG接枝修饰两个步骤提高Fe3O4@C的亲水性，得到亲水核壳型Fe3O4@C纳米粒，用于核磁共振成像造影剂。其制备方法具体步骤如下：
(1)以水热法合成碳层包裹的Fe3O4纳米颗粒：将作为铁源的铁盐和作为碳源的碳水化合物按照摩尔比0.1～1溶解于去离子水中，并加入与碳源的摩尔比为5～50的尿素，完全溶解后将混合溶液转移入高压反应釜中，于180～300℃反应10～24h。其中，铁盐包括三氯化铁、硝酸铁或硫酸铁；碳源包括葡萄糖、蔗糖、果糖或淀粉，每0.01mol的碳源溶解于0.04～0.4L的去离子水中。
(2)冷却后将反应器内的溶液倒出，收集不溶物，乙醇和水洗涤干燥，得到纳米级Fe3O4@C颗粒。
(3)利用双氧水氧化处理Fe3O4@C，提高碳壳表面羧基基团数量。将Fe3O4@C和双氧水的按照质量比为0.01～0.1加入烧杯中，20～100℃机械搅拌，反应时间1～12h，离心分离，乙醇洗涤后干燥。
(4)利用PEG接枝经双氧水氧化后的Fe3O4@C，提高其亲水性。将0.1～1g双氧水处理后的Fe3O4@C加入到含有20～400mg 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和10～200mg N-羟基丁二酰亚胺的5～50ml超纯水中，10～100℃机械搅拌0.5～5h；再加入0.1～1g PEG，继续搅拌反应2～48h。PEG的种类包括氨基PEG或羟基PEG；PEG分子量100～10000；Fe3O4@C与PEG的质量比为0.1～1。使用透析袋透析反应液，离心分离，乙醇洗涤后干燥，最终获得高度亲水Fe3O4@C纳米颗粒。
本发明提供了一种基于双氧水和PEG修饰的化学稳定性高、不易团聚，且核磁共振响应信号强的Fe3O4@C纳米粒及制备方法。该方法工艺简单，反应条件温和，易于操作，成本较低，具有良好的核磁共振成像能力。本发明的核磁共振成像造影剂由纳米四氧化三铁、碳和PEG组成，其结构如图1所示，是纳米四氧化三铁颗粒为核心，外围包裹碳壳层，碳壳层上连接PEG。
实施例1
一、亲水性Fe3O4@C的制备方法：
(1)Fe3O4@C的合成
0.01mol葡萄糖，0.006mol三氯化铁，0.1mol尿素溶解在40ml水中，搅拌均匀后置于密封反应釜中。反应温度180℃，反应20小时。冷却后过滤分离磁性纳米粒子Fe3O4@C，分别用去离子水和乙醇冲洗至滤液中性。100度干燥Fe3O4@C。
(2)Fe3O4@C的亲水性修饰
利用双氧水处理Fe3O4@C，提高纳米粒子表面炭层上羧基数量，以增加用于PEG修饰位点。将300mg干燥的Fe3O4@C加入10g 30wt％的H2O2溶液中，于60℃下机械搅拌1h，转速1000rmp。将处理后的Fe3O4@C从溶液中离心分离，转速4000rpm持续5min，并用乙醇离心冲洗三次，真空干燥。干燥后的Fe3O4@C进一步通过接枝氨基聚乙二醇(NH2-PEG)以提高其亲水性。将300mg双氧水处理后的Fe3O4@C加入到20ml超纯水中混入197mg1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和115mg N-羟基丁二酰亚胺，在50℃反应0.5h使羧基活化，再加入300mg的NH2-PEG(分子量5000MW)，室温搅拌反应24h。使用截留分子量10000MW的透析袋透析，纯化纳米粒，最终获得高度亲水Fe3O4@C纳米颗粒。
二、亲水性Fe3O4@C的性质表征：
(1)亲水性Fe3O4@C的形态及大小尺寸
图2是亲水性Fe3O4@C的高分辨透射电子显微镜照片，照片显示亲水性Fe3O4@C为核壳结构，Fe3O4球形壳外均匀包裹修饰PEG的碳层，粒径为100nm±10nm，碳壳厚度在5～15nm。
(2)亲水性Fe3O4@C的亲水性能评价
将亲水性Fe3O4@C与商品化100nm Fe3O4纳米粒超声分散后静置1h后进行对比。结果显示，静止后亲水性Fe3O4@C在水相仍然均匀分散，无聚集沉淀，较商品化100nm Fe3O4纳米粒亲水性提升。而商品化100nm Fe3O4纳米粒基本完全沉淀，固液分离明显。
三、亲水性Fe3O4@C的核磁共振成像性能评价：
图3为Fe3O4@C浓度分别为100/50/25/12.5/6.25/3.125mg/L与同浓度商品化100nm四氧化三铁纳米粒对比的核磁共振成像结果对比，成像条件为T2成像条件(TR＝100ms,TE＝1500ms)。结果显示，未亲水性修饰的四氧化三铁纳米粒由于无法在水相中长时间稳定分散，因此T2成像能力弱，并且无法显示浓度依赖的信号改变；而亲水性Fe3O4@C由于可以长时间稳定分散在水相，因此具备优异的核磁共振成像能力，表现出明显的信号强度具有浓度依赖。图4显示，通过将弛豫时间倒数与铁元素浓度拟合，获得7T的横向弛豫率为122.8mM-1*s-1。
实施例2
(1)Fe3O4@C的合成
0.01mol蔗糖，0.01mol三氯化铁，0.5mol尿素溶解在400ml水中，搅拌均匀后置于密封反应釜中。反应温度220℃，反应24小时。冷却后过滤分离磁性纳米粒子Fe3O4@C，分别用去离子水和乙醇冲洗至滤液中性。100℃干燥Fe3O4@C。
(2)Fe3O4@C的亲水性修饰
利用双氧水处理Fe3O4@C，提高纳米粒子表面炭层上羧基数量，以增加用于PEG修饰位点。将300mg干燥的Fe3O4@C加入30g 30wt％的H2O2溶液中，于80℃下机械搅拌3h。将处理后的Fe3O4@C从溶液中离心分离，并用乙醇离心冲洗三次，真空干燥。干燥后的Fe3O4@C进一步通过接枝氨基聚乙二醇(NH2-PEG)以提高其亲水性。将100mg双氧水处理后的Fe3O4@C加入到30ml超纯水中混入300mg1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和200mg N-羟基丁二酰亚胺，在10℃反应0.5h使羧基活化，再加入1000mg的NH2-PEG(分子量10000MW)，室温搅拌反应2h。使用截留分子量10000MW的透析袋透析，纯化纳米粒，最终获得高度亲水Fe3O4@C纳米颗粒。所得纳米颗粒Fe3O4球形壳外均匀包裹修饰PEG的碳层，粒径为50～80nm，碳壳厚度在20～30nm；T2成像条件TR＝50ms，E＝1000ms。
实施例3
(1)Fe3O4@C的合成
0.01mol果糖，0.004mol硝酸铁，0.1mol尿素溶解在100ml水中，搅拌均匀后置于密封反应釜中。反应温度260℃，反应15小时。冷却后过滤分离磁性纳米粒子Fe3O4@C，分别用去离子水和乙醇冲洗至滤液中性。100℃干燥Fe3O4@C。
(2)Fe3O4@C的亲水性修饰
利用双氧水处理Fe3O4@C，提高纳米粒子表面炭层上羧基数量，以增加用于PEG修饰位点。将300mg干燥的Fe3O4@C加入10g 30wt％的H2O2溶液中，于20℃下机械搅拌12h。将处理后的Fe3O4@C从溶液中离心分离，并用乙醇离心冲洗三次，真空干燥。干燥后的Fe3O4@C进一步通过接枝氨基聚乙二醇(NH2-PEG)以提高其亲水性。将500mg双氧水处理后的Fe3O4@C加入到5ml超纯水中混入20mg1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和10mg N-羟基丁二酰亚胺，在80℃反应3h使羧基活化，再加入800mg的羟基PEG(分子量2000MW)，室温搅拌反应15h。使用截留分子量10000MW的透析袋透析，纯化纳米粒，最终获得高度亲水Fe3O4@C纳米颗粒。所得纳米颗粒Fe3O4球形壳外均匀包裹修饰PEG的碳层，粒径为120～140nm，碳壳厚度在50～60nm；T2成像条件TR＝120ms，E＝2000ms。
实施例4
(1)Fe3O4@C的合成
0.01mol淀粉，0.001mol硫酸铁，0.05mol尿素溶解在40ml水中，搅拌均匀后置于密封反应釜中。反应温度300℃，反应10小时。冷却后过滤分离磁性纳米粒子Fe3O4@C，分别用去离子水和乙醇冲洗至滤液中性。100℃干燥Fe3O4@C。
(2)Fe3O4@C的亲水性修饰
利用双氧水处理Fe3O4@C，提高纳米粒子表面炭层上羧基数量，以增加用于PEG修饰位点。将300mg干燥的Fe3O4@C加入3g 30wt％的H2O2溶液中，于100℃下机械搅拌1.5h。将处理后的Fe3O4@C从溶液中离心分离，并用乙醇离心冲洗三次，真空干燥。干燥后的Fe3O4@C进一步通过接枝氨基聚乙二醇(NH2-PEG)以提高其亲水性。将1000mg双氧水处理后的Fe3O4@C加入到50ml超纯水中混入400mg1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和150mgN-羟基丁二酰亚胺，在100℃反应5h使羧基活化，再加入1000mg的羟基PEG(分子量100MW)，室温搅拌反应48h。使用截留分子量10000MW的透析袋透析，纯化纳米粒，最终获得高度亲水Fe3O4@C纳米颗粒。所得纳米颗粒Fe3O4球形壳外均匀包裹修饰PEG的碳层，粒径为190～300nm，碳壳厚度在80～100nm；T2成像条件TR＝200ms，E＝3500ms。
Claims (10)
1.基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：包括以下步骤：
(1)将铁盐和碳源加入水中，采用水热反应合成Fe3O4@C颗粒；
(2)使用双氧水氧化处理Fe3O4@C颗粒；
(3)使用PEG接枝经双氧水氧化处理后的Fe3O4@C，接枝反应结束后，对反应液进行透析、分离、洗涤和干燥，得到基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒。
2.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(1)中，铁盐包括三氯化铁、硝酸铁或硫酸铁；碳源包括葡萄糖、蔗糖、果糖或淀粉。
3.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(1)中，铁盐和碳源之间的摩尔比为0.1～1；每0.01mol的碳源加入0.04～0.4L的去离子水中。
4.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(1)中在水热反应之前，水中还加入有尿素，尿素和碳源之间的摩尔比例为5～50。
5.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(1)的水热反应是在180～300℃反应10～24h。
6.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(1)的水热反应结束后，冷却并收集沉淀，将沉淀洗涤干燥后得到Fe3O4@C颗粒。
7.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(2)中，双氧水氧化处理Fe3O4@C颗粒的具体步骤是：将Fe3O4@C颗粒和双氧水按质量比为0.01～0.1混合，在20～100℃搅拌1～12h，分离后洗涤干燥，完成氧化处理；其中双氧水的质量分数为30％。
8.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(3)中，使用PEG接枝经双氧水氧化处理后的Fe3O4@C的具体步骤包括：先将双氧水氧化处理后的Fe3O4@C加入到含有1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和N-羟基丁二酰亚胺的超纯水中，在10～100℃搅拌均匀，得到混合液A；再向混合液A中加入PEG，搅拌反应2～48h，完成接枝；其中，双氧水氧化处理后的Fe3O4@C、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐、N-羟基丁二酰亚胺、超纯水和PEG之间的比例为(0.1～1)g：(20～400)mg：(10～200)mg：(5～50)ml：(0.1～1)g。
9.根据权利要求1所述的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒的制备方法，其特征在于：步骤(3)中，PEG包括氨基PEG或羟基PEG，其分子量为100～10000。
10.如权利要求1所述制备方法制得的基于双氧水和PEG修饰的亲水铁碳复合纳米颗粒，其特征在于：该纳米颗粒是以纳米四氧化三铁颗粒为核心，纳米四氧化三铁颗粒上包裹碳壳层，碳壳层上连接PEG；碳壳包覆的纳米四氧化三铁的粒径在20～300nm之间，碳壳厚度在5～100nm之间。
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