CN108047236B - 一种氨基氧蒽酮改性石墨烯ag及其制备方法与制备肼黄荧光检测试剂上的应用 - Google Patents

一种氨基氧蒽酮改性石墨烯ag及其制备方法与制备肼黄荧光检测试剂上的应用 Download PDF

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CN108047236B
CN108047236B CN201711226274.2A CN201711226274A CN108047236B CN 108047236 B CN108047236 B CN 108047236B CN 201711226274 A CN201711226274 A CN 201711226274A CN 108047236 B CN108047236 B CN 108047236B
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程如梅
于春雷
王狄狮
葛聪聪
戴黎明
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Abstract

一种氨基氧蒽酮改性石墨烯AG及其制备方法与制备肼黄荧光检测试剂上的应用，将发光性强的氧蒽酮衍生物引入到水中分散性强的纳米石墨烯，具体地例如将氨基氧蒽酮引入到氧化石墨烯上，获得了水溶性强、对肼黄选择性高的氨基氧蒽酮改性的氧化石墨烯，其合成方法简单、条件温和、产物易得，将该化合物用于本发明的肼黄检测获得良好效果，受其它常规共存生物分子，例如葡萄糖、氨基葡萄糖、甲硫氨酸、精氨酸、多巴胺、赖氨酸、色氨酸、甘氨酸、亮氨酸、麦芽糖、丙氨酸、苏氨酸、脯氨酸等物质的影响，具有高选择性。由于在水中测试，使用方便。

Description

一种氨基氧蒽酮改性石墨烯AG及其制备方法与制备肼黄荧光 检测试剂上的应用
技术领域
本发明涉及识别结合和用于光学检测肼黄的荧光检测技术领域，特别涉及一种氨基氧蒽酮改性石墨烯AG及其制备方法与制备肼黄荧光检测试剂上的应用。
背景技术
肼黄是一种常见的偶氮类人工合成的食品色素，它具有很强的着色作用以及良好的水溶性，被广泛应用于人们日常食用的面包、饮料、乳制品等多种食物中(Gan T, Sun J,Cao S, et al. Electrochimica Acta 2012,74,151-157. Novellino E, Ritieni A,Rastrelli L. Journal of agricultural and food chemistry 2013,61(8):1599-1603 )。我国《食品添加剂使用卫生标准》中明确规定，肼黄作为食品添加剂的摄入量不得超过0.1g/Kg，当肼黄的摄入过量时，会对人们的身体健康产生多种负面的影响，使人们患有过敏、哮喘、荨麻疹、儿童多动症以及其它等多种疾病，严重时甚至可能会引起癌症的发生(Vidotti EC, Costa WF, Oliveira CC. Talanta 2006,68(3):516-521. Wüthrich B.Annals of allergy 1993,71(4):379-384.)，给人们的身体健康带来了极大地潜在的威胁。传统的检测肼黄的方法有极谱法、高效液相色谱法(HPLC)、液相色谱法、毛细管电泳法和液相-色谱质谱法, 这些方法存在着样品预处理复杂、检测耗时、成本高、检测设备要求精密等诸多缺点。荧光光度法设备操作简单、灵敏度高。然而，由于这些方法中用于识别的小分子水溶性差，选择性低而相应发展缓慢。
发明内容
为了克服以上方法的缺陷，尤其是关于水溶性和选择性的问题，本发明提供了一种氨基氧蒽酮改性石墨烯AG及其制备方法与制备肼黄荧光检测试剂上的应用。
本发明采用的技术解决方案是：一种氨基氧蒽酮改性石墨烯AG，所述的氨基氧蒽酮改性石墨烯AG的结构式如下：
Figure RE-RE-DEST_PATH_IMAGE001
。
一种氨基氧蒽酮改性石墨烯AG的制备方法，包括以下步骤：取浓度为0.2-3.0mg/mL的氧化石墨烯20mL，滴入催化剂1-（3-二甲氨基丙基）-3-乙基碳二亚胺盐酸盐50-100µL，静置30min，称取10-20mg的氨基氧蒽酮溶于10mL的乙醇中，搅拌至完全溶解，将溶解后的氨基氧蒽酮逐滴滴入上述的氧化石墨烯溶液中，40-60 ℃水浴加热3-10h后常温搅拌24h，过滤，用醇水混合溶剂洗涤，即得所述的氨基氧蒽酮改性石墨烯AG。
所述的步骤中氧化石墨烯的浓度为0.5~ 1.5 mg/mL。
一种氨基氧蒽酮改性石墨烯AG在制备肼黄荧光检测试剂上的应用。
所述的肼黄荧光检测试剂通过以下步骤制备：将权利要求1所述的氨基氧蒽酮改性石墨烯AG，溶于水或醇水溶液，配成氨基氧蒽酮改性石墨烯AG浓度为0.01~1.0 mg/mL的肼黄荧光检测试剂溶液。
所述的肼黄荧光检测试剂溶液中氨基氧蒽酮改性石墨烯AG浓度为0.02~0.05mg/mL。
本发明的有益效果是：本发明提供了一种氨基氧蒽酮改性石墨烯AG及其制备方法与制备肼黄荧光检测试剂上的应用，将发光性强的氧蒽酮衍生物引入到水中分散性强的纳米石墨烯，具体地例如将氨基氧蒽酮引入到氧化石墨烯上，获得了水溶性强、对肼黄选择性高的氨基氧蒽酮改性的氧化石墨烯，其合成方法简单、条件温和、产物易得，将该化合物用于本发明的肼黄检测获得良好效果，受其它常规共存生物分子，例如葡萄糖、氨基葡萄糖、甲硫氨酸、精氨酸、多巴胺、赖氨酸、色氨酸、甘氨酸、亮氨酸、麦芽糖、丙氨酸、苏氨酸、脯氨酸等物质的影响，具有高选择性。由于在水中测试，使用方便。
附图说明
图1为实施例1的化合物对不同浓度肼黄的荧光强度响应。
图2为实施例1的化合物在5倍干扰离子存在下对肼黄的荧光响应；其中1为葡萄糖， 2为氨基葡萄糖，3为半乳酸，4为丙氨酸，5为脯氨酸，6为甘氨酸，7为谷氨酸钠，8为甲硫氨酸，9为亮氨酸，10为麦芽糖，11为苏氨酸，12为缬氨酸，13为异亮氨酸，14为蔗糖，15为甜蜜素，16为肼黄，其中图中每组中，棒状标低的为干扰物质的响应，高的为加入肼黄后的响应。
具体实施方式
为了更清楚地说明本发明内容，用具体实施例说明如下，具体实施例不限定本发明内容范围。
实施例1（化合物AG的合成）
取浓度为1.0mg/mL的氧化石墨烯20mL，滴入催化剂1-（3-二甲氨基丙基）-3-乙基碳二亚胺盐酸盐100µL，静置30min。称取20mg的氨基氧蒽酮溶于10mL的乙醇中，搅拌至完全溶解。将溶解后的氨基氧蒽酮逐滴滴入上述的氧化石墨烯溶液中，45 ºC水浴加热3h后常温搅拌24h，过滤，用醇水混合溶剂洗涤，即得化合物AG。
实施例2（化合物AG的合成）
取浓度为2.0mg/mL的氧化石墨烯20mL，滴入催化剂1-（3-二甲氨基丙基）-3-乙基碳二亚胺盐酸盐50µL，静置30min。称取10mg的氨基氧蒽酮溶于10mL的乙醇中，搅拌至完全溶解。将溶解后的氨基氧蒽酮逐滴滴入上述的氧化石墨烯溶液中，55 ºC水浴加热10h后常温搅拌24h，过滤，用醇水混合溶剂洗涤。即得化合物AG。
实施例3（荧光强度工作曲线）
称取实施例1的化合物AG10mg，溶于醇水中，配成25mg/L的标准储备液。称取肼黄5mg，溶于水，配成浓度为5g/L的溶液。量取化合物AG的储备液2.5mL，加入不同浓度的肼黄溶液。在480nm处测试其荧光强度。
实施例4 干扰物质共存检测肼黄实验
荧光实验中化合物AG配成25 mg/L的醇水溶液。肼黄配成5g/L的标准储备液。作为干扰选用葡萄糖，氨基葡萄糖、谷氨酸钠、甘氨酸、麦芽糖、乳糖、蔗糖、果糖等物质。所有实验用的溶液都为新配置，并立即实验。干扰物质实验中，先在25mg/L AG水溶液中加入5倍的干扰物质，测其荧光，再加入5g/L的肼黄, 测其荧光变化。于480 nm处检测荧光变化。
使用本发明的方法测试肼黄，不受其它常规共存生物分子，例如葡萄糖、氨基葡萄糖、甲硫氨酸、精氨酸、多巴胺、赖氨酸、色氨酸、甘氨酸、亮氨酸、麦芽糖、丙氨酸、苏氨酸、脯氨酸等物质的影响，具有高选择性。由于在水中测试，使用方便。综上所述，本发明的技术效果是显著的。
本发明机理：由于肼黄与该化合物形成氢键作用，引起分子中电子分布的变化而发生荧光强度的变化，达到检测肼黄的目的。而氨基葡萄糖、甲硫氨酸、精氨酸、多巴胺、赖氨酸、色氨酸、甘氨酸、亮氨酸、麦芽糖、丙氨酸、苏氨酸等物质不能与其作用产生荧光强度的变化。表明该化合物AG对肼黄具有高选择性。
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。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前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (3)

1.一种氨基氧蒽酮改性石墨烯AG在制备肼黄荧光检测试剂上的应用，其特征在于，所述的氨基氧蒽酮改性石墨烯AG的结构式如下：
Figure DEST_PATH_IMAGE001
。
2.根据权利要求1所述的氨基氧蒽酮改性石墨烯AG在制备肼黄荧光检测试剂上的应用，其特征在于，所述的肼黄荧光检测试剂通过以下步骤制备：将权利要求1所述的氨基氧蒽酮改性石墨烯AG，溶于水或醇水溶液，配成氨基氧蒽酮改性石墨烯AG浓度为0.01~1.0mg/mL的肼黄荧光检测试剂溶液。
3.根据权利要求2所述的氨基氧蒽酮改性石墨烯AG在制备肼黄荧光检测试剂上的应用，其特征在于，所述的肼黄荧光检测试剂溶液中氨基氧蒽酮改性石墨烯AG浓度为0.02~0.05mg/mL。
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