CN109970912A - 黄酮类磁性分子印迹聚合物的制备方法 - Google Patents
黄酮类磁性分子印迹聚合物的制备方法 Download PDFInfo
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- CN109970912A CN109970912A CN201910212099.4A CN201910212099A CN109970912A CN 109970912 A CN109970912 A CN 109970912A CN 201910212099 A CN201910212099 A CN 201910212099A CN 109970912 A CN109970912 A CN 109970912A
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- magnetic
- molecularly imprinted
- imprinted polymer
- flavonoids
- reaction
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Classifications
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
本发明公开了黄酮类磁性分子印迹聚合物的制备方法,属于药物分析技术领域;本发明方法采用表面分子印迹技术制备对槲皮素具有吸附能力的磁性分子印迹纳米材料;制备获得的磁性分子印迹聚合物呈规则的球形,在聚合物表面含有多个模板分子留下的特定形状和大小的孔穴,孔穴内具有特定排列的结合位点;本发明制备的磁性分子印迹纳米材料性能显著优于传统富集材料,且制备简单,廉价易得,对模板分子具有优异的选择性和吸附能力。
Description
技术领域
本发明属于药物分离技术领域,具体涉及一种黄酮类磁性分子印迹聚合物的制备方法,以及利用磁性分子印迹聚合物作为吸附剂,选择性的分离富集天然产物中的槲皮素及其结构类似物。
背景技术
槲皮素(Quercetin) 是一种多羟基黄酮类化合物,广泛存在于中草药的花、叶、果实中,具有抗癌、抗炎、抗菌、抗病毒、降糖降压、调节免疫功能和保护心血管的功效,因此可用于功能性食品和制药行业;但是自然条件下存在的槲皮素样品基质较为复杂,含量较低,且与其他黄酮类化合物具有相似的结构。因此探索一种快速提取、分离和富集槲皮素的新方法是分析研究人员的一项紧迫任务。
自从1972年Wulff研究小组报道了人工合成的分子印迹聚合物之后,分子印迹这一概念引起了许多学者的兴趣。分子印迹技术的原理是模板分子与功能单体在合适的溶剂中依靠两者之间的相互作用力(共价键或非共价键)形成可逆的复合物,然后加入交联剂和引发剂,在一定条件下由自由基引发,交联剂和功能单体共聚合成具有一定刚性和柔性的高分子聚合物;然后用合适的洗脱剂将合成的聚合物中的模板分子洗脱,使聚合物分子上留下与模板分子三维空间匹配、官能团完全互补的孔穴,这些空穴具有特异识别模板分子的功能,被称为结合位点,它可以选择性的结合混合物中的模板分子,从而达到分离纯化和富集模板分子的目的。
磁性分子印迹聚合物由于其具有超顺磁性和特异性识别等优点,在化学分析、生物分离、靶向给药等领域有着广泛的应用。与传统聚合法制备的分子印迹聚合物相比,传统聚合法制备的分子印迹聚合物中模板分子被包埋在聚合物中难以被洗脱;块状物的研磨、筛分等工序繁琐耗时;在研磨和筛分过程中聚合物的损失、活性位点被破坏等缺点,进而使其吸附效率降低。并且由于样品基质成分复杂,检测前一般需采用适当的样品前处理方法对其进行净化、分离和富集。而传统的样品前处理方法索氏提取、液-液萃取、液相微萃取、固相微萃取等操作繁琐,有机溶剂消耗大,选择性差,常常导致分析流程长、灵敏度不高。因此,建立高选择性、高特异性识别、简便快速的样品前处理方法非常重要。
发明内容
本发明提供了一种黄酮类磁性分子印迹聚合物的制备方法,本发明方法制得的磁性分子印迹聚合物具有良好的超顺磁性,高选择性,高特异性吸附能力;能够利用磁性分子印迹聚合物作为吸附剂,对天然产物中的目标分子槲皮素进行分离、富集和纯化。
本发明黄酮类磁性分子印迹聚合物的制备方法步骤如下:
(1)将FeCl2·4H2O和FeCl3·6H2O溶于去离子水中,于75~85℃、氮气保护下搅拌30~60min;然后在每100mL混合溶液中滴加1~5mL油酸反应30~60min后,再在每100mL混合溶液中滴加10~15mL氢氧化铵反应30~60min,反应完成后,将产物自然冷却至室温,在外加磁场作用下进行分离,固体依次用乙醇和去离子水洗涤,40~60℃下真空干燥,制得Fe3O4磁性纳米颗粒,其中FeCl2·4H2O和FeCl3·6H2O的质量比为1:2~1:4,Fe2+在去离子水中的浓度为4mmol/L~6mmol/L,Fe3+在去离子水中的浓度为10mmol/L~12mmol/L;
(2)将步骤(1)Fe3O4磁性纳米颗粒超声分散于质量浓度80~90%乙醇溶液中,Fe3O4磁性纳米颗粒在乙醇溶液中浓度为1.5g/L~3g/L,在每200mL的分散液中依次加入氢氧化铵1~5mL和正硅酸乙酯1~2mL,混匀后置于40~50℃下搅拌反应12~24h,反应结束后,在外加磁场作用下进行分离,固体水洗至洗液透明,并于40~60℃下真空干燥,制得Fe3O4@SiO2复合粒子;
(3)将Fe3O4@SiO2复合粒子搅拌分散于无水甲苯中,然后加入硅胶改性剂,超声分散10~30min去除溶液中的氧气,混合物于60~80℃、氮气保护下回流反应12~24h,反应完成后,在外加磁场的作用下进行分离,固体依次用乙醇和去离子水洗涤,冷冻干燥,得到改性的磁性硅胶纳米颗粒,其中Fe3O4@SiO2复合粒子与硅胶改性剂的质量比为1:25~1:5;
所述硅胶改性剂为3-(异丁烯酰氧)丙基三甲氧基硅烷、聚乙二醇或3-氨丙基三乙氧基硅烷;
(4)将模板分子和功能单体按摩尔比1:4~1:8的比例分散在乙腈中反应5~10h得到预聚合物,然后加入改性的磁性硅胶纳米颗粒和交联剂,模板分子与交联剂的摩尔比为1:10~1:30,在氮气保护下加入引发剂,模板分子与引发剂的摩尔比为1:1~1:3,混匀后在50~70℃下聚合反应,反应完成后,反应产物冷却至室温,在外加磁场的作用下进行分离,固体用甲醇-乙酸混合液洗涤,直到采用高效液相色谱未检测到模板分子,然后在40~60℃下真空干燥,制得黄酮类磁性分子印迹聚合物。
所述模板分子为模板分子为槲皮素、芦丁、水飞蓟素或山奈酚,槲皮素分子结构为:。
所述功能单体为丙烯酰胺或甲基丙烯酸。
所述交联剂为乙二醇二甲基丙烯酸酯。
所述引发剂为偶氮二异丁腈。
所述甲醇-乙酸混合液是甲醇和乙酸按体积比9:1~8:2的比例混合制得。
本发明与现有技术相比,其显著特点如下:
(1)磁性分子印迹聚合物作为有效合成的吸附剂,具有优异的选择性,化学稳定性和易于制备的特点,聚合物分子上留下与模板分子三维空间结构匹配、官能团完全互补的孔穴,可以富集模板化合物;
(2)磁性分子印迹聚合物具有较高的特异性识别能力,且颗粒粒径小,实现纳米级,可以通过外加磁场快速方便的将聚合物从复杂基质中分离出来;
(3)磁性分子印迹聚合物具有超顺磁性,吸附能力强,结合动力学快,不需要额外的离心或过滤过程,在分离、检测、和鉴定模板分子具有很大的优势;
(4)本发明的磁性分子印迹聚合物制备简单,廉价易得,重复性高。因此,本发明用于从天然产物中提取分离槲皮素具有良好的经济效益和应用前景,可以很好地替代传统方法。
附图说明
图1为Fe3O4(a)、Fe3O4@SiO2(b)、Fe3O4@SiO2-CH=CH2(c)、磁性分子非印迹聚合物(d)和磁性分子印迹聚合物(e)的FT-IR光谱图;
图2为Fe3O4和磁性分子印迹聚合物的X射线衍射图(XRD);
图3为Fe3O4和磁性分子印迹聚合物的透射电子显微镜图(TEM);
图4为本发明制备的磁性分子印迹聚合物和磁性分子非印迹聚合物对槲皮素的吸附动力学曲线;
图5为本发明制备的磁性分子印迹聚合物和磁性分子非印迹聚合物对槲皮素和其他竞争化合物的选择性吸附结果示意图。
具体实施方式
下面通过实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1:本黄酮类磁性分子印迹聚合物的制备方法如下:
(1)将FeCl2·4H2O和FeCl3·6H2O溶于去离子水中,于75℃、氮气保护下搅拌60min;然后在每100mL混合溶液中滴加1mL油酸反应30min后,再在每100mL混合溶液中滴加10mL氢氧化铵反应30min,反应完成后,将产物自然冷却至室温,在外加磁场作用下进行分离,固体依次用乙醇和去离子水分别洗涤3次,40℃下真空干燥,制得Fe3O4磁性纳米颗粒,其中FeCl2·4H2O和FeCl3·6H2O的质量比为1:2.5,Fe2+在去离子水中的浓度为4mmol/L;
(2)将步骤(1)Fe3O4磁性纳米颗粒超声分散于质量浓度80%乙醇溶液中,Fe3O4磁性纳米颗粒在乙醇溶液中浓度为1.5g/L,在每200mL的分散液中依次加入氢氧化铵5mL和正硅酸乙酯1mL,混匀后置于40℃下搅拌反应24h,反应结束后,在外加磁场作用下进行分离,固体水洗至洗液透明,并于40℃下真空干燥,制得Fe3O4@SiO2复合粒子;
(3)将Fe3O4@SiO2复合粒子搅拌分散于无水甲苯中,然后加入3-(异丁烯酰氧)丙基三甲氧基硅烷,超声分散10min去除溶液中的氧气,混合物于70℃、氮气保护下回流反应18h,反应完成后,在外加磁场的作用下进行分离,固体依次用乙醇和去离子水分别洗涤3次,冷冻干燥,得到改性的磁性硅胶纳米颗粒,其中Fe3O4@SiO2复合粒子与3-(异丁烯酰氧)丙基三甲氧基硅烷的质量比为1:5;
(4)将槲皮素和丙烯酰胺按摩尔比1:4的比例分散在乙腈中反应5h得到预聚合物,然后加入改性的磁性硅胶纳米颗粒和乙二醇二甲基丙烯酸酯,槲皮素与乙二醇二甲基丙烯酸酯的摩尔比为1:10,在氮气保护下加入偶氮二异丁腈,槲皮素与偶氮二异丁腈的摩尔比为1:1,混匀后在50℃下聚合反应,反应完成后,反应产物冷却至室温,在外加磁场的作用下进行分离,固体用甲醇-乙酸混合液(甲醇和乙酸按体积比8:2的比例混合制得)洗涤,直到采用高效液相色谱未检测到模板分子,然后在40℃下真空干燥,制得黄酮类磁性分子印迹聚合物。
与此同时,在缺乏模板分子槲皮素的前提下,使用相同的制备方法制备磁性非印迹聚合物;
本实施例制得的黄酮类磁性分子印迹聚合物的结构表征,结果如下:
1、傅里叶变换红外光谱图(FT-IR)
结果见图1由图1a可知,580cm-1处的强峰为Fe3O4磁性纳米颗粒Fe-O的伸缩振动峰,并且在其他图谱中都出现了这个峰,只是强度有所减弱;在图1b中,1092cm-1为Si-O的不对称伸缩振动,800cm-1为Si-O的对称伸缩振动,462cm-1为Si-O的弯曲振动,在3418 cm-1处较强且宽的吸收峰为Fe3O4表面上-OH的吸收峰,表明SiO2已成功包裹在Fe3O4磁性纳米颗粒表面;由图1c可知,1440cm-1为亚甲基中的C-H伸缩振动吸收峰,1637cm-1为C=O的伸缩振动特征峰并且在3410cm-1附近的Si-OH吸收峰有所减弱,表明3-(异丁烯酰氧)丙基三甲氧基硅烷与Fe3O4磁性纳米颗粒表面的羟基发生反应,双键成功接枝到Fe3O4@SiO2表面,进一步表明Fe3O4@SiO2已被MPS成功改性;由图1d和1e可知,槲皮素磁性分子印迹聚合物(MMIPs)和槲皮素磁性分子非印迹聚合物(MNIPs)的红外图谱差异较小,这主要是由于在洗脱模板分子槲皮素的前提下,MMIPs和MNIPs所含化学成分完全相似;MMIPs和MNIPs在1726cm-1处出现N-H特征吸收峰,表明MMIPs和MNIPs通过功能单体(AM)和交联剂(EGDMA)制备成功。
2、X射线衍射图(XRD)
结果见图2,从图2我们可以清楚地看到Fe3O4的六个相对较强的特征衍射峰(2θ=30.09°, 35.53°, 43.09°, 53.49°, 57.09°, 62.52°),与JCPDS标准谱图进行比对可知,其对应的晶面指数分别为(220),(311),(400),(422),(511)和(440)。从图3b可知,Fe3O4磁性纳米颗粒经过修饰和表面分子印迹聚合后,其特征峰强度明显降低,表明合成的磁性分子印迹聚合物(MMIPs)不改变Fe3O4的晶型。
3、透射电子显微镜图(TEM)
结果见图3,由图3a可知,通过化学共沉淀法制备的Fe3O4磁性纳米颗粒形状规则,粒径分布均匀,平均粒径在10nm左右,但也存在明显的团聚现象。由图3b可知,与Fe3O4磁性纳米颗粒相比,MMIPs颗粒粒径有所增加,分散性明显改善,表明在Fe3O4颗粒表面包覆了一层印迹聚合物,进一步证明黄酮类磁性分子印迹聚合物制备成功。
实施例2:本黄酮类磁性分子印迹聚合物的制备方法如下:
(1)将FeCl2·4H2O和FeCl3·6H2O溶于去离子水中,于80℃、氮气保护下搅拌45min;然后在每100mL混合溶液中滴加3mL油酸反应40min后,再在每100mL混合溶液中滴加15mL氢氧化铵反应40min,反应完成后,将产物自然冷却至室温,在外加磁场作用下进行分离,固体依次用乙醇和去离子水分别洗涤4次,60℃下真空干燥,制得Fe3O4磁性纳米颗粒,其中FeCl2·4H2O和FeCl3·6H2O的质量比为1:3,Fe2+在去离子水中的浓度为5mmol/L;
(2)将步骤(1)Fe3O4磁性纳米颗粒超声分散于质量浓度85%乙醇溶液中,Fe3O4磁性纳米颗粒在乙醇溶液中浓度为2g/L,在每200mL的分散液中依次加入氢氧化铵3mL和正硅酸乙酯2mL,混匀后置于50℃下搅拌反应12h,反应结束后,在外加磁场作用下进行分离,固体水洗至洗液透明,并于60℃下真空干燥,制得Fe3O4@SiO2复合粒子;
(3)将Fe3O4@SiO2复合粒子搅拌分散于无水甲苯中,然后加入3-(异丁烯酰氧)丙基三甲氧基硅烷,超声分散20min去除溶液中的氧气,混合物于80℃、氮气保护下回流反应12h,反应完成后,在外加磁场的作用下进行分离,固体依次用乙醇和去离子水分别洗涤4次,冷冻干燥,得到改性的磁性硅胶纳米颗粒,其中Fe3O4@SiO2复合粒子与3-(异丁烯酰氧)丙基三甲氧基硅烷的质量比为1:15;
(4)将槲皮素和丙烯酰胺按摩尔比1:6的比例分散在乙腈中反应8h得到预聚合物,然后加入改性的磁性硅胶纳米颗粒和乙二醇二甲基丙烯酸酯,槲皮素与乙二醇二甲基丙烯酸酯的摩尔比为1:20,在氮气保护下加入偶氮二异丁腈,槲皮素与偶氮二异丁腈的摩尔比为1:2,混匀后在70℃下聚合反应,反应完成后,反应产物冷却至室温,在外加磁场的作用下进行分离,固体用甲醇-乙酸混合液(甲醇和乙酸按体积比6:1的比例混合制得)洗涤,直到采用高效液相色谱未检测到模板分子,然后在50℃下真空干燥,制得黄酮类磁性分子印迹聚合物。
实施例3:本黄酮类磁性分子印迹聚合物的制备方法如下:
(1)将FeCl2·4H2O和FeCl3·6H2O溶于去离子水中,于85℃、氮气保护下搅拌30min;然后在每100mL混合溶液中滴加5mL油酸反应55min后,再在每100mL混合溶液中滴加12mL氢氧化铵反应50min,反应完成后,将产物自然冷却至室温,在外加磁场作用下进行分离,固体依次用乙醇和去离子水分别洗涤3次,50℃下真空干燥,制得Fe3O4磁性纳米颗粒,其中FeCl2·4H2O和FeCl3·6H2O的质量比为1:4,Fe2+在去离子水中的浓度为6mmol/L;
(2)将步骤(1)Fe3O4磁性纳米颗粒超声分散于质量浓度90%乙醇溶液中,Fe3O4磁性纳米颗粒在乙醇溶液中浓度为3g/L,在每200mL的分散液中依次加入氢氧化铵1mL和正硅酸乙酯1.5mL,混匀后置于45℃下搅拌反应15h,反应结束后,在外加磁场作用下进行分离,固体水洗至洗液透明,并于50℃下真空干燥,制得Fe3O4@SiO2复合粒子;
(3)将Fe3O4@SiO2复合粒子搅拌分散于无水甲苯中,然后加入3-氨丙基三乙氧基硅烷,超声分散30min去除溶液中的氧气,混合物于60℃、氮气保护下回流反应24h,反应完成后,在外加磁场的作用下进行分离,固体依次用乙醇和去离子水分别洗涤3次,冷冻干燥,得到改性的磁性硅胶纳米颗粒,其中Fe3O4@SiO2复合粒子与3-氨丙基三乙氧基硅烷的质量比为1:20;
(4)将芦丁和甲基丙烯酸按摩尔比1:8的比例分散在乙腈中反应9h得到预聚合物,然后加入改性的磁性硅胶纳米颗粒和乙二醇二甲基丙烯酸酯,芦丁与乙二醇二甲基丙烯酸酯的摩尔比为1:30,在氮气保护下加入偶氮二异丁腈,芦丁与偶氮二异丁腈的摩尔比为1:3,混匀后在60℃下聚合反应,反应完成后,反应产物冷却至室温,在外加磁场的作用下进行分离,固体用甲醇-乙酸混合液(甲醇和乙酸按体积比9:1的比例混合制得)洗涤,直到采用高效液相色谱未检测到模板分子,然后在60℃下真空干燥,制得黄酮类磁性分子印迹聚合物。
上述实施例1、2中黄酮类磁性分子印迹聚合物的吸附性能评价按下述方法进行,利用动力学吸附实验完成;根据吸附前后溶液中槲皮素浓度的变化,计算在不同时间内MMIPs和MNIPs对槲皮素的吸附量,然后计算平衡吸附容量Qt(µmol/g),;
其中Qt为MMIPs或MNIPs的吸附量(µmol/g);Ct为检测时溶液中槲皮素的浓度(µg/mL)。
分别准确称取50mg MMIPs和MNIPs于50mL离心管中,然后分别加入5mL槲皮素乙腈溶液(初始浓度是10µg/mL),室温下振荡5、10、15、20、30min,在外加磁场作用下分离MMIPs和MNIPs;上清液用0.45µm的微孔滤膜过滤,然后用高效液相色谱检测吸附前后溶液中槲皮素浓度的变化;由图4可知,MMIPs和MNIPs的吸附容量随着时间的增加而增加,但吸附速率逐渐减小,20min后达到吸附平衡,在吸附过程中,MMIPs对槲皮素的吸附量始终大于MNIPs的吸附量,表现出优异的吸附动力学性能。
上述实施例1、2中黄酮类磁性分子印迹聚合物的选择性吸附性能评价按下述方法进行,利用特异性实验评价MMIPs和MNIPs在不同化合物中的选择性识别特性,选择木犀草素、芦丁、对香豆酸为竞争吸附的化合物,根据吸附前后溶液中样品浓度的变化,计算MMIPs和MNIPs对各化合物的吸附容量Q(µmol/g),;
其中Q为MMIPs或MNIPs的吸附量(µmol/g);C1为检测时溶液中样品的浓度(µg/mL)。
分别准确称取50mg MMIPs和MNIPs于50mL离心管中,然后分别加入5mL 10µg/mL的槲皮素、木犀草素、芦丁和对香豆酸的乙腈标准溶液,室温下摇床缓慢振荡1h;然后在外加磁场作用下分离MMIPs和MNIPs,溶液过滤,最后用HPLC测定溶液中各样品的浓度;从图5可以看出,与其他竞争化合物相比,MMIPs表现出对槲皮素具有显著的特异性识别,且吸附容量明显高于其他竞争化合物。
Claims (7)
1.一种黄酮类磁性分子印迹聚合物的制备方法,其特征在于,步骤如下:
(1)将FeCl2·4H2O和FeCl3·6H2O溶于去离子水中,于75~85℃、氮气保护下搅拌30~60min;然后在每100mL混合溶液中滴加1~5mL油酸反应30~60min后,再在每100mL混合溶液中滴加10~15mL氢氧化铵反应30~60min,反应完成后,将产物自然冷却至室温,在外加磁场作用下进行分离,固体依次用乙醇和去离子水洗涤,40~60℃下真空干燥,制得Fe3O4磁性纳米颗粒,其中FeCl2·4H2O和FeCl3·6H2O的质量比为1:2~1:4,Fe2+在去离子水中的浓度为4mmol/L~6mmol/L;
(2)将步骤(1)Fe3O4磁性纳米颗粒超声分散于质量浓度80~90%乙醇溶液中,Fe3O4磁性纳米颗粒在乙醇溶液中浓度为1.5g/L~3g/L,在每200mL的分散液中依次加入氢氧化铵1~5mL和正硅酸乙酯1~2mL,混匀后置于40~50℃下搅拌反应12~24h,反应结束后,在外加磁场作用下进行分离,固体水洗至洗液透明,并于40~60℃下真空干燥,制得Fe3O4@SiO2复合粒子;
(3)将Fe3O4@SiO2复合粒子搅拌分散于无水甲苯中,然后加入硅胶改性剂,超声分散10~30min去除溶液中的氧气,混合物于60~80℃、氮气保护下回流反应12~24h,反应完成后,在外加磁场的作用下进行分离,固体依次用乙醇和去离子水洗涤,冷冻干燥,得到改性的磁性硅胶纳米颗粒,其中Fe3O4@SiO2复合粒子与硅胶改性剂的质量比为1:25~1:5;
(4)将模板分子和功能单体按摩尔比1:4~1:8的比例分散在乙腈中反应5~10h得到预聚合物,然后加入改性的磁性硅胶纳米颗粒和交联剂,模板分子与交联剂的摩尔比为1:10~1:30,在氮气保护下加入引发剂,模板分子与引发剂的摩尔比为1:1~1:3,混匀后在50~70℃下聚合反应,反应完成后,反应产物冷却至室温,在外加磁场的作用下进行分离,固体用甲醇-乙酸混合液洗涤,直到采用高效液相色谱未检测到模板分子,然后在40~60℃下真空干燥,制得黄酮类磁性分子印迹聚合物。
2.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:硅胶改性剂为3-(异丁烯酰氧)丙基三甲氧基硅烷、聚乙二醇或3-氨丙基三乙氧基硅烷。
3.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:模板分子为槲皮素、芦丁、水飞蓟素或山奈酚。
4.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:功能单体为丙烯酰胺或甲基丙烯酸。
5.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:交联剂为乙二醇二甲基丙烯酸酯。
6.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:引发剂为偶氮二异丁腈。
7.根据权利要求1所述的黄酮类磁性分子印迹聚合物的制备方法,其特征在于:甲醇-乙酸混合液是甲醇和乙酸按体积比9:1~8:2的比例混合制得。
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