CN107722286B - 一种irmof3合成后修饰产物及其应用 - Google Patents
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Abstract
本发明涉及一种IRMOF3合成后修饰产物及其应用，该IRMOF3合成后修饰产物为IRMOF3微晶经CM‑PEG‑NH2合成后修饰得到的IRMOF3‑PEG‑NH2微晶。该应用是将合成后修饰产物IRMOF3‑PEG‑NH2微晶用于对市售蔬菜中微量氨基甲酸酯农药的检测。本发明将IRMOF3微晶经CM‑PEG‑NH2合成后修饰，得到IRMOF3‑PEG‑NH2微晶，结果表明PEG化修饰成功，得到的IRMOF3‑PEG‑NH2微晶用于SPE小柱制备，可将其用于市售蔬菜中氨基甲酸酯农药的富集，可对极微量氨基甲酸酯农药含量的市售蔬菜进行有效测定。
Description
技术领域
本发明属于材料科学中金属有机框架技术领域，具体涉及一种IRMOF3合成后修饰产物及其应用。
背景技术
金属有机框架(Metal-Organic Frameworks，MOFs)是材料学研究的一个热点领域.MOFs多在溶剂热条件下由配体和金属离子构筑而成，与其它无机材料相比，配体的存在使金属有机框架导入不同的功能基团相对简单.然而，溶剂热合成方法是有局限性的，在这个条件下，很多配体的功能基团对热不稳定或者与金属离子配位，这就使得高度功能化配合物的制备成为一个难题。2007年，相关报道给出配合物IRMOF3(以2-氨基对苯二甲酸，即NH2-bdc为配体)上未配位氨基与乙酸酐的反应，创建了术语post-syntheticmodification，即合成后修饰(PSM).而PSM是由翻译后修饰(即post-translationalmodification)转化而来，后者是用来描述在多肽合成中蛋白质和氨基酸残基化学修饰过程的。
发明内容
本发明的目的在于克服现有技术的溶剂热合成方法中很多配体的功能基团对热不稳定或者与金属离子配位，使得高度功能化配合物制备成为难题的不足，提供一种IRMOF3合成后修饰产物及其应用。
本发明解决其技术问题而采用的技术方案如下：
一种IRMOF3合成后修饰产物，该IRMOF3合成后修饰产物为IRMOF3微晶经CM-PEG-NH2合成后修饰得到的IRMOF3-PEG-NH2微晶。
而且，所述经CM-PEG-NH2合成后修饰的制备过程为：将CM-PEG-NH2(0.2g，0.1mmol)溶于5mL MES buffer(0.1M，pH6)中，加入EDC·HCl(0.0383g，0.2mmol)超声活化30min，再向其中加入NHS(0.023g，0.2mmol)超声活化30min，摇床140rpm过夜活化，将IRMOF3微晶(0.0246g)浸入其中，超声反应30min后，摇床140rpm 25℃振荡反应过夜，10000rpm离心5min，弃上清，超纯水洗涤一次，80℃真空干燥，即得IRMOF3-PEG-NH2微晶。
一种如权利要求1所述的IRMOF3合成后修饰产物的应用，该应用是将合成后修饰产物IRMOF3-PEG-NH2微晶用于对市售蔬菜中微量氨基甲酸酯农药的检测。
本发明的优点及效果：
本发明将IRMOF3微晶经CM-PEG-NH2合成后修饰，得到IRMOF3-PEG-NH2微晶，结果表明PEG化修饰成功.得到的IRMOF3-PEG-NH2微晶用于SPE小柱制备，可将其用于氨基甲酸酯农药的富集，对低氨基甲酸酯农药含量的市售蔬菜进行测定。
附图说明
图1为IRMOF3的高分辨C1s谱图；
图2为IRMOF3的高分辨O1s谱图；
图3为IRMOF3-PEG-NH2的高分辨C1s谱图；
图4为IRMOF3-PEG-NH2的高分辨O1s谱图；
图5为0.78125μg/mL到25μg/mL之间混合标品的色谱图；
图6为样品与12.5μg/mL混标的比较色谱图；
图7为样品与3.125μg/mL混标的比较色谱图；
图8为样品+12.5μg/mL混标与12.5μg/mL混标的比较色谱图；
图9为空白基质与12.5μg/mL混标的比较色谱图。
具体实施方式
下面结合具体实施方案对本发明进一步说明，其具体实施方案应该理解为仅为举例说明，不是限定性的，不能以下述举例说明来限定本发明的保护范围。
一种IRMOF3合成后修饰产物，该IRMOF3合成后修饰产物为：IRMOF3微晶经CM-PEG-NH2合成后修饰得到的IRMOF3-PEG-NH2微晶，
IRMOF3合成后修饰的具体实施过程包括步骤内容如下：
(1)试剂和仪器准备
所用试剂均为市售分析纯.N-羟基琥珀酰亚胺(NHS)、1-(3-二甲氨基丙基)-3-乙基-碳二亚胺盐酸盐(EDC)、CM-PEG-NH2(MW:2000)、灭多威、涕灭威和甲萘威标准品(100μg/mL甲醇溶液)、XPS由X射线光电子能谱仪(Thermol scientific,Escalab 250Xi)测定。
(2)IRMOF3的制备
根据文献报道，2-氨基对苯二酸(NH2BDC，0.75g，4.1mmol)，Zn(NO3)2·6H2O(3.0g，11mmol)溶于100mL DMF中，100℃搅拌回流18h，得到IRMOF3微晶粗品，离心，弃上清，DMF洗涤3次(1time/1day)，CH2Cl2洗涤3次(1time/1day)，于45℃条件下真空干燥8h后，仔细研磨即得IRMOF3微晶。
(3)IRMOF3的修饰及表征
CM-PEG-NH2(0.2g，0.1mmol)溶于5mL MES buffer(0.1M，pH6)，加入EDC·HCl(0.0383g，0.2mmol)超声活化30min，再向其中加入NHS(0.023g，0.2mmol)超声活化30min，摇床140rpm过夜活化，将IRMOF3微晶(0.0246g)浸入其中，超声反应30min后，摇床140rpm25℃振荡反应过夜.10000rpm离心5min，弃上清，超纯水洗涤一次，80℃真空干燥，即得IRMOF3-PEG-NH2微晶，留样用于XPS表征。
一种上述IRMOF3合成后修饰产物IRMOF3-PEG-NH2的应用，该应用是将IRMOF3-PEG-NH2微晶用于对市售蔬菜中微量氨基甲酸酯农药的检测；
用于检测的具体实施过程如下：
(1)IRMOF3-PEG-NH2氨基化小柱的制备：
称取100mg IRMOF3-PEG-NH2微晶加入购买的空塑料小柱中(3mL)，用注射器内塞将其压实，4℃冰箱保存备用。
(2)提取与净化:
称取10.0g经粉碎均质后的蔬菜，加入混合标准品(1.25μg/mL×1mL)，超声1h，加入20mL乙腈，涡旋2min后离心，取上清，过0.22μm滤膜，加入2g氯化钠振荡1min，室温静置30min.吸上清10.0mL，80℃吹至近干，用2.0mL丙酮溶解，待净化.加样前将自行制备的氨基柱用4.0mL甲醇+二氯甲烷(1:99，V/V)预洗活化，当溶剂液面到达柱吸附层表面时，立即加入提取液，用15mL离心管收集洗脱液.用2.0mL甲醇+二氯甲烷(1:99，V/V)冲洗残留物后过柱，并重复1次，50℃氮吹至近干，甲醇溶解定容至200μL，过0.22μm滤膜备用。
(3)色谱条件：
C18柱(250mm×4.6mm，5.0μm)，柱温40℃，流动相为(乙腈:甲醇＝8:3，V/V)和水，梯度洗脱见表1，流速1.0mL/min，检测波长220nm。
(4)混合标准品标准曲线的绘制:由高浓度逐级稀释配制灭多威、涕灭威和甲萘威混合标准品:首先各取50μL所购标品，另外补充50μL色谱纯甲醇，即得25μg/mL混合标准品溶液,逐级稀释得到12.5，6.25，3.125，1.5625和0.78125μg/mL的混合标准品.
表1梯度洗脱程序
(5)XPS表征
如图1或2或3或4所示，IRMOF3样品的XPS谱显示出N1s和C1s的表达比率为0.085，而IRMOF3-PEG-NH2样品经观察，发现N1s﹕C1s的比率为0.107，这表明CM-PEG-NH2的引入改变了IRMOF3样品表面化学组成和更多的N元素被介入，如表2所示，表3结合C1s谱，285.594eV峰的增强(C-N/C-O)，原子百分含量为26.16％，CM-PEG-NH2的修饰增加了样品表面的C-N/C-O比例，说明修饰成功。表3结合O1s谱，532.253eV峰的增强(C-OH/C-O-C)同样意味着CM-PEG-NH2的修饰是成功的.
表2每步修饰过程的元素含量
表3修饰前后的结合能和元素比例
(6)氨基甲酸酯的SPE-HPLC分析
固相萃取法是一种基于液相色谱分离机制的前处理方法，已广泛应用于氨基甲酸酯类农药残留检测工作.根据文献报道，对比C18、苯基柱和氨基固相柱净化除杂效果，本文选用自制氨基化SPE小柱代替市售的成品氨基固相小柱，用于氨基甲酸酯类农药的提取和净化.由于乙腈提取效果好、干扰少、操作简单，本试验先用乙腈提取所需组分，再加入过量氯化钠盐析，使水相和有机相充分分离，从而使氨基甲酸酯农药进入乙腈相.因此，本试验选取乙腈作为提取液.
从图5分析，三种氨基甲酸酯类农药UV检测器下，从0.78125μg/mL到25μg/mL之间不能绘制出标准曲线，鉴于此，加标样品与各混标的色谱图直接进行对比，从图6和图7可见灭多威过柱后富集，样品中含量与12.5μg/mL混标中灭多威含量接近，从图8可见，甲萘威过柱发生吸附，12.5μg/mL混标图谱中比样品+12.5μg/mL混标中甲萘威含量还要高，从图9可见，空白基质中不含甲萘威，说明市售蔬菜中不含甲萘威。
Claims (2)
1.一种IRMOF3合成后修饰产物，其特征在于：该IRMOF3合成后修饰产物为IRMOF3微晶经CM-PEG-NH2合成后修饰得到的IRMOF3-PEG-NH2微晶；
所述经CM-PEG-NH2合成后修饰的制备过程为：将0.2g、0.1mmol CM-PEG-NH2溶于5mL0.1M、pH6 MES buffer中，加入0.0383g、0.2mmol EDC·HCl超声活化30min，再向其中加入0.023g、0.2mmol NHS超声活化30min，摇床140rpm过夜活化，将0.0246g IRMOF3微晶浸入其中，超声反应30min后，摇床140rpm 25℃振荡反应过夜，10000rpm离心5min，弃上清，超纯水洗涤一次，80℃真空干燥，即得IRMOF3-PEG-NH2微晶。
2.一种如权利要求1所述的IRMOF3合成后修饰产物的应用，其特征在于：该应用是将合成后修饰产物IRMOF3-PEG-NH2微晶用于对市售蔬菜中微量氨基甲酸酯农药的检测。
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