CN110746713B - 一种用于检测次氯酸根比色-荧光纤维膜及其制备方法 - Google Patents

一种用于检测次氯酸根比色-荧光纤维膜及其制备方法 Download PDF

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CN110746713B
CN110746713B CN201911093800.1A CN201911093800A CN110746713B CN 110746713 B CN110746713 B CN 110746713B CN 201911093800 A CN201911093800 A CN 201911093800A CN 110746713 B CN110746713 B CN 110746713B
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蔡珍珍
窦新存
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Abstract

本发明提供一种用于检测次氯酸根比色‑荧光纤维膜及制备方法,该荧光纤维膜是将含双键比色‑荧光探针分子((E)‑((4‑(2‑(4‑氰基‑5‑(二氰基亚甲基)‑2,2‑二甲基‑2,5‑二氢呋喃‑3‑基)乙烯基)苯基)氮烷二基)双(乙烷‑2,1‑二基)二丙烯酸酯)与甲基丙烯酸羟乙酯采用自由基聚合得到改性聚甲基丙烯酸羟乙酯,再将改性聚甲基丙烯酸羟乙酯与聚苯乙烯经研磨制成,所述的检测次氯酸根比色‑荧光纤维膜,其荧光发射峰位在632 nm,紫外吸收峰位在544 nm,用于对次氯酸根的检测时,表现出明显的荧光猝灭和褪色响应,响应速度快,实现对环境中水样及非制式爆炸物原料中的次氯酸根的现场、快速、便捷,可视化检测。

Description

一种用于检测次氯酸根比色-荧光纤维膜及其制备方法
技术领域
本发明涉及静电纺丝技术及环境和非制式爆炸物检测领域,提供了一种用于制备检测次氯酸根比色-荧光纤维膜及其制备方法。
背景技术
静电纺丝法是一种简单、有效制备连续纳米纤维膜的方法,所纺纤维具有直径小、比表面积大、孔隙率高和均一性好等优点,被广泛应用于过滤、防护纺织品、药物输送、组织工程、电子和光子设备、传感器和催化等领域。2007年,李广涛教授(Journal of MaterialsChemistry 2007,17,2730-2736)首次将电纺技术引入到TNT传感领域,可检测到10ppb级的气态TNT分子。Kumar(Technologies for Homeland Security,IEEE Conference on 2008,390-394)等开展了静电纺丝制备荧光高分子纳米纤维膜的工作并将其用于爆炸物检测。自此开启了静电纺丝纤维膜用于爆炸物检测领域。
次氯酸根作为一种非常重要的活性氧,在生物体和饮用水中起到至关重要的作用。但若生物体内积累过多,会引起各种疾病。除此之外,据文献调研发现,目前人们对于非制式爆炸物中氯酸盐、高氯酸盐、硝酸盐和亚硝酸盐等的检测进行了大量研究,而次氯酸盐作为非制式爆炸物中的一种重要原料,还远远没能引起足够的重视。次氯酸钙和刹车油按一定比例混合即可作为爆炸物使用。此外,超市中就能买到的低盐(氯化钾)和消毒水(次氯酸钠)混合在一起就能轻易制备出非制式爆炸物中的氯酸钾。因此,对环境及非制式爆炸物中次氯酸盐的检测是非常有必要的。
目前,检测次氯酸根的方法主要是溶液法,配合分光光度、化学发光等大型仪器。这种分析方法不仅需要预先配制好检测液还需要昂贵的仪器及专业的操作人员。因此,亟需开发可便捷、低成本、快速检测次氯酸根的方法。
本发明从对次氯酸根具有较好检测性能的比色-荧光探针分子((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)(CN201910957006.0)入手,采用自由基聚合与甲基丙烯酸羟乙酯共聚制备改性聚甲基丙烯酸羟乙酯,再与聚苯乙烯混合制备混合物料后溶解,采用静电纺丝技术制备比色-荧光纤维膜,从而实现对次氯酸根的便捷、快速检测。
发明内容
本发明目的在于,针对现有技术中存在的不足,提供一种用于检测次氯酸根比色-荧光纤维膜及其制备方法,该荧光纤维膜是将含双键比色-荧光探针分子((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与甲基丙烯酸羟乙酯采用自由基聚合得到改性聚甲基丙烯酸羟乙酯,再将改性聚甲基丙烯酸羟乙酯与聚苯乙烯经研磨制成,所述的检测次氯酸根比色-荧光纤维膜,其荧光发射峰位在632nm,紫外吸收峰位在544nm,用于对次氯酸根的检测时,表现出明显的荧光猝灭和褪色响应,响应速度快,实现对环境中水样及非制式爆炸物原料中的次氯酸根的现场、快速、便捷,可视化检测。
本发明所述的一种用于检测次氯酸根比色-荧光纤维膜,该荧光纤维膜是由改性聚甲基丙烯酸羟乙酯和聚苯乙烯制成,所述改性聚甲基丙烯酸羟乙酯的化学结构式(1)为:
Figure BDA0002267673610000021
其中:改性聚甲基丙烯酸羟乙酯占混合物料的5-20wt%,聚苯乙烯占混合物料的80-95wt%;
改性聚甲基丙烯酸羟乙酯是由比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与甲基丙烯酸羟乙酯按摩尔比1:100-1:1000采用自由基共聚制备。
所述一种用于检测次氯酸根比色-荧光纤维膜的制备方法,按下列步骤进行:
制备改性聚甲基丙烯酸羟乙酯:
a、按摩尔比1:100-1:1000,将比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与甲基丙烯酸羟乙酯溶于10倍摩尔量的四氢呋喃中,通氮气20min后,加入0.02倍摩尔量的引发剂偶氮二异丁腈,升温至70℃,回流反应12h;冷却至室温,再将反应液于石油醚中沉积,抽滤、洗涤、干燥,即得改性聚甲基丙烯酸羟乙酯;
制备检测次氯酸根比色-荧光纤维膜:
b、将步骤a得到的改性聚甲基丙烯酸羟乙酯与聚苯乙烯置于研钵中研磨至粉末,并混合均匀,得混合物料,其中改性聚甲基丙烯酸羟乙酯占混合物料的5-20wt%,聚苯乙烯占混合物料的80-95wt%;
c、将步骤b得到的含量为10wt%-20wt%混合物料溶于体积比为1:10的四氢呋喃和二甲基亚砜混合溶液中,搅拌至溶解均匀后,过滤料液、消泡后从圆形纤维喷孔中挤出料液,挤出电压为20KV,挤出速率为0.06mL/h,挤出时间为2h,即得检测次氯酸根比色-荧光纤维膜。
本发明所述的一种用于检测次氯酸根比色-荧光纤维膜及其制备方法,该方法的工艺流程为:
Figure BDA0002267673610000031
与现有技术相比,本发明的有益效果是:
本发明所述的一种用于检测次氯酸根比色-荧光纤维膜,可实现对环境中水样及非制式爆炸物原料中的次氯酸根的现场、快速、可视化检测,在632nm处出现荧光猝灭,在544nm处出现褪色变化;无需对待测物进行前处理,操作简单,便捷,高效。具有检测限低、灵敏度高的优点,可实现低成本、快速检测次氯酸根的目的。
附图说明
图1为本发明检测次氯酸根比色-荧光纤维膜扫描电镜图。
具体实施方式
下面通过具体实施例对本发明做进一步的说明,但发明不限制于这些实施例。
实施例1
制备改性聚甲基丙烯酸羟乙酯:
a、将1mmol比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与100mmol甲基丙烯酸羟乙酯溶于1010mmol四氢呋喃中,通氮气20min后,加入2.02mmol引发剂偶氮二异丁腈,升温至70℃,回流反应12h,冷却至室温,再将反应液于5000mL石油醚中沉积,抽滤、洗涤、干燥,即得改性聚甲基丙烯酸羟乙酯80mmol,产率79.2%;
制备检测次氯酸根比色-荧光纤维膜:
b、将步骤a得到的改性聚甲基丙烯酸羟乙酯0.5g与聚苯乙烯9.5g置于研钵中研磨至粉末,并混合均匀,得混合物料10g;
c、将步骤b得到的混合物料1g溶于体积比为1:10的四氢呋喃和二甲基亚砜混合溶液9g中,搅拌至溶解均匀后,过滤料液、消泡后从圆形纤维喷孔中挤出料液,挤出电压为20KV,挤出速率为0.06mL/h,挤出时间为2h,即得检测次氯酸根比色-荧光纤维膜,扫描电镜图如图1所示。
实施例2
制备改性聚甲基丙烯酸羟乙酯:
a、将0.1mmol比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与100mmol甲基丙烯酸羟乙酯溶于1001mmol四氢呋喃中,通氮气20min后,加入2.002mmol引发剂偶氮二异丁腈,升温至70℃,回流反应12h,冷却至室温,反应液于5000mL石油醚中沉积,抽滤、洗涤、干燥,即得改性聚甲基丙烯酸羟乙酯76mmol,产率75.9%;
制备检测次氯酸根比色-荧光纤维膜:
b、将步骤a得到的改性聚甲基丙烯酸羟乙酯2.0g与聚苯乙烯8.0g置于研钵中研磨至粉末,并混合均匀,得混合物料10g;
c、将步骤b得到的混合物料2g溶于体积比为1:10的四氢呋喃和二甲基亚砜混合溶液8g中,搅拌至溶解均匀后,过滤料液、消泡后从圆形纤维喷孔中挤出料液,挤出电压为20KV,挤出速率为0.06mL/h,挤出时间为2h,即得检测次氯酸根比色-荧光纤维膜。
实施例3
制备改性聚甲基丙烯酸羟乙酯:
a、将0.2mmol比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与100mmol甲基丙烯酸羟乙酯溶于1002mmol四氢呋喃中,通氮气20min后,加入2.004mmol引发剂偶氮二异丁腈,升温至70℃,回流反应12h,冷却至室温,反应液于5000mL石油醚中沉积,抽滤、洗涤、干燥,即得改性聚甲基丙烯酸羟乙酯77mmol,产率77.2%;
制备检测次氯酸根比色-荧光纤维膜:
b、将步骤a得到的改性聚甲基丙烯酸羟乙酯1.25g与聚苯乙烯8.75g置于研钵中研磨至粉末,并混合均匀,得混合物料10g;
c、将步骤b得到的混合物料1.5g溶于体积比为1:10的四氢呋喃和二甲基亚砜混合溶液中,搅拌至溶解均匀后,过滤料液、消泡后从圆形纤维喷孔中挤出料液,挤出电压为20KV,挤出速率为0.06mL/h,挤出时间为2h,即得检测次氯酸根比色-荧光纤维膜。
实施例4
取实施例1-3任意一种检测次氯酸根比色-荧光纤维膜,滴加5uM的次氯酸盐溶液5uL,纤维膜的颜色由紫色褪为无色544nm处吸收峰消失,荧光猝灭632nm处荧光发射峰消失。

Claims (2)

1.一种用于检测次氯酸根比色-荧光纤维膜,其特征在于,该荧光纤维膜是由改性聚甲基丙烯酸羟乙酯和聚苯乙烯制成,所述改性聚甲基丙烯酸羟乙酯的化学结构式(1)为:
Figure FDA0003339969590000011
其中:改性聚甲基丙烯酸羟乙酯占混合物料的5-20wt%,聚苯乙烯占混合物料的80-95wt%;
改性聚甲基丙烯酸羟乙酯是由比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与甲基丙烯酸羟乙酯按摩尔比1:100-1:1000采用自由基共聚制备。
2.根据权利要求1所述的一种用于检测次氯酸根比色-荧光纤维膜的制备方法,其特征在于按下列步骤进行:
制备改性聚甲基丙烯酸羟乙酯:
a、按摩尔比1:100-1:1000,将比色-荧光探针分子含双键((E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯)与甲基丙烯酸羟乙酯溶于10倍摩尔量的四氢呋喃中,通氮气20min后,加入0.02倍摩尔量的引发剂偶氮二异丁腈,升温至70℃,回流反应12h;冷却至室温,再将反应液于石油醚中沉积,抽滤、洗涤、干燥,即得改性聚甲基丙烯酸羟乙酯;
制备检测次氯酸根比色-荧光纤维膜:
b、将步骤a得到的改性聚甲基丙烯酸羟乙酯与聚苯乙烯置于研钵中研磨至粉末,并混合均匀,得混合物料,其中改性聚甲基丙烯酸羟乙酯占混合物料的5-20wt%,聚苯乙烯占混合物料的80-95wt%;
c、将步骤b得到的混合物料的10wt%-20wt%溶于体积比为1:10的四氢呋喃和二甲基亚砜混合溶液中,搅拌至溶解均匀后,过滤料液、消泡后从圆形纤维喷孔中挤出料液,挤出电压为20KV,挤出速率为0.06mL/h,挤出时间为2h,即得检测次氯酸根比色-荧光纤维膜。
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