CN104607152A - 罗丹明衍生物修饰的磁性壳聚糖吸附剂用于Hg(Ⅱ)的检测及吸附 - Google Patents

罗丹明衍生物修饰的磁性壳聚糖吸附剂用于Hg(Ⅱ)的检测及吸附 Download PDF

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CN104607152A
CN104607152A CN201410776340.3A CN201410776340A CN104607152A CN 104607152 A CN104607152 A CN 104607152A CN 201410776340 A CN201410776340 A CN 201410776340A CN 104607152 A CN104607152 A CN 104607152A
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magnetic
chitosan
rhodamine
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颜范勇
史德超
郑坦诚
张生兰
韩子怡
周旭光
陈莉
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Tianjin Polytechnic University
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Abstract

本发明公开了一种罗丹明衍生物修饰的荧光磁性吸附剂。该荧光磁性吸附剂的合成方法为：以戊二醛为交联剂，使壳聚糖包覆四氧化三铁纳米微粒制备磁性壳聚糖微球，通过环氧氯丙烷的作用，将带有氨基的罗丹明类衍生物分子“粘附”到磁性壳聚糖表面得到荧光磁性复合吸附剂。与传统吸附剂相比，该吸附剂不仅对Hg(II)有很强的吸附性能，而且在吸附过程中能够实现Hg(II)的荧光检测及肉眼识别。在该吸附剂的悬浮液中加入Hg(II)后，荧光强度明显增强，同时溶液的颜色由无色变为粉红色。此外还对该吸附剂的吸附动力学和热力学进行了研究，为以后荧光吸附剂的设计及未来的综合研究提供了重要的参考依据。

Description

罗丹明衍生物修饰的磁性壳聚糖吸附剂用于Hg(Ⅱ)的检测及吸附
技术领域
本发明涉及一种壳聚糖吸附剂，特别是一种罗丹明衍生物修饰的磁性壳聚糖吸附剂的制备方法，本发明还涉及该荧光吸附剂在检测及吸附水体汞离子中的应用。
背景技术
众所周知，汞是一种危害人体健康的重金属，由于其具有持久性、易迁移性和高度的生物富集性，使其成为目前全球最引人关注的环境污染物之一。重金属汞进入环境后不能被生物降解，并参与食物链循环，最终在生物体内积累，破坏生物体正常生理代谢，由此引发许多环境问题。目前含汞废水处理的方法有化学沉淀、膜技术、离子交换及生物法等。但这些方法存在很多缺点，如成本高、二次污染及去除率低等。而目前吸附被认为是最经济环保有效的去除重金属污染的途径。因此，很多吸附剂如活性炭、硅胶和树脂被广泛用于生活废水及工业废水中汞离子的去除。壳聚糖(chitosan)是甲壳素脱乙酰基的产物，在自然界的含量仅次于纤维素，具有良好的生物降解性和组织相容性。此外，分子链中所含的-NH2、-OH具有良好的络合作用，能与水中的过渡金属离子和腐殖酸类物质等进行络合，从而实现对水中污染物的吸附分离，而且易于成膜，是当前水处理领域重要的材料之一。
对于上述吸附剂，均存在一个缺陷就是这些吸附剂只能达到吸附的目的，而不能达到检测的效果。荧光分子探针在重金属离子识别方面选择性高、灵敏度高、过程可视化、实时便捷和生物应用强，是目前环境、医药和生命科学等领域的研究热点。若将小分子荧光物质固载到能够吸附重金属离子的壳聚糖载体材料上，即可实现荧光检测重金属离子及吸附的双重目的。
发明内容
本发明的目的在于改进现有的用于汞离子去除的吸附剂在性能和结构上的不足，设计合成出性能优良、可同时检测和吸附汞离子的基于罗丹明染料的荧光吸附剂。提供了此荧光磁性吸附剂的制备方法及检测吸附水体中汞离子的应用。
本发明所述的荧光磁性吸附剂，可通过如下技术措施来实现：
(1)将三氯化铁溶液(0.02mol)与氯化亚铁溶液(0.01mol)，混匀后加入到0.7mol/L的氨水溶液中得到黑褐色四氧化三铁纳米粒子沉淀。
(2)以戊二醛作交联剂，将磁性四氧化三铁纳米粒子加入到溶于2％乙酸的壳聚糖溶液中得到磁性壳聚糖微球。
(3)磁性壳聚糖与环氧氯丙烷在高氯酸的催化下反应生成羟丙基氯壳聚糖，用乙二胺进行氨化得到胺化磁性微球。
(4)罗丹明B酰肼由罗丹明B与水合肼回流反应得到。
(5)乙二醛将胺化磁性壳聚糖与罗丹明B水合肼进行桥联。
此外，本发明还提供了该荧光磁性吸附剂在检测吸附水体汞离子中的应用。
本发明的吸附剂，制备方法简单，容易实现，原料易得，成本低廉；具有非常高的检测灵敏度，适合微量检测，有良好的应用前景；可以实现Hg(II)的同时检测及吸附。
附图说明
图1本发明中的荧光磁性吸附剂对Hg(II)的选择性；横坐标为波长(nm)，纵坐标为荧光强度。
图2本发明中的吸附剂加入各种离子的颜色变化
图3磁性分离性能
图4吸附热力学，吸附温度对Hg(II)吸附以及离子去除百分比的影响
图5吸附剂的可再生性
具体实施例：
参照附图1-5对本发明做进一步的说明
实施例1：吸附剂对汞离子的选择性
使用合成的荧光磁性吸附剂评价对汞离子的选择性。将吸附剂加到各种金属离子pH7.4的C2H5OH-HEPES缓冲溶液(pH＝7.40，EtOH-H2O＝1∶1，v/v)，测试结果显示于图1中。可以看出化合物对汞离子具有很高的灵敏度，汞离子的加入产生很大的荧光增强，对汞离子有很好的选择性。
实施例2：
在吸附剂的悬浮液中加入各种金属离子，放置一段时间后，可观察到只有加入Hg(II)的有颜色变化，由图2显示。
实施例3
在外加磁场的作用下，可以看到吸附剂迅速向只有磁铁一侧聚集。
实施例4
在不同温度下进行Hg(II)吸附实验，吸附达到平衡后测量吸附量。
实施例5
用EDTA对吸附过Hg(II)的吸附剂进行洗脱得到再生吸附剂，然后重复进行吸附实验。

Claims (5)

1.一种用于Hg(II)的检测及吸附的荧光磁性吸附剂，其特征在于该荧光磁性吸附剂为罗丹明衍生物修饰的磁性壳聚糖复合物，其演示结构式为：
2.如权利要求1所述的罗丹明衍生物修饰的磁性壳聚糖复合物吸附剂的制备方法，其特征在于：
(1)将三氯化铁溶液(0.02mol)与氯化亚铁溶液(0.01mol)，混匀后加入到0.7mol/L的氨水溶液中得到黑褐色四氧化三铁纳米粒子沉淀。
(2)以戊二醛作交联剂，将磁性四氧化三铁纳米粒子加入到溶于2％乙酸的壳聚糖溶液中得到磁性壳聚糖微球。
(3)磁性壳聚糖与环氧氯丙烷在高氯酸的催化下反应生成羟丙基氯壳聚糖，用乙二胺进行氨化得到胺化磁性微球。
(4)罗丹明B酰肼由罗丹明B与水合肼回流反应得到。
(5)乙二醛将胺化磁性壳聚糖与罗丹明B水合肼进行桥联。
3.如权利要求1所述荧光磁性壳聚糖吸附剂在检测汞离子方面的应用。
4.如权利要求1所述该吸附剂在吸附水体中汞离子中的应用。
5.如权利要求1，该磁性吸附剂在外磁场的作用下可以被很好的分离。
CN201410776340.3A 2014-12-16 2014-12-16 罗丹明衍生物修饰的磁性壳聚糖吸附剂用于Hg(Ⅱ)的检测及吸附 Pending CN104607152A (zh)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105817208A (zh) * 2016-05-06 2016-08-03 福州大学 一种罗丹明b接枝壳聚糖吸附剂及其制备和应用
CN106076295A (zh) * 2016-07-01 2016-11-09 四川大学 一种可荧光探测水体中三价铬并将其快速移除的磁性纳米吸附剂的制备方法
CN106268673A (zh) * 2016-09-06 2017-01-04 河海大学 一种氨基改性壳聚糖复合吸附材料的制备方法
CN108636387A (zh) * 2018-07-13 2018-10-12 武汉工程大学 一种铁离子吸附海绵及其制备方法和应用
CN109439314A (zh) * 2018-12-07 2019-03-08 武汉工程大学 特异性识别Fe(III)的磁性纳米荧光探针的制备方法
CN109596586A (zh) * 2018-12-07 2019-04-09 武汉工程大学 一种基于罗丹明b的磁性纳米探针的制备方法
CN113070050A (zh) * 2021-04-28 2021-07-06 山东大学 一种能可视化识别并除去汞离子的壳聚糖基水凝胶吸附剂及其制备方法与应用

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105817208A (zh) * 2016-05-06 2016-08-03 福州大学 一种罗丹明b接枝壳聚糖吸附剂及其制备和应用
CN106076295B (zh) * 2016-07-01 2018-08-21 四川大学 一种可荧光探测水体中三价铬并将其快速移除的磁性纳米吸附剂的制备方法
CN106076295A (zh) * 2016-07-01 2016-11-09 四川大学 一种可荧光探测水体中三价铬并将其快速移除的磁性纳米吸附剂的制备方法
CN106268673B (zh) * 2016-09-06 2019-03-12 河海大学 一种氨基改性壳聚糖复合吸附材料的制备方法
CN106268673A (zh) * 2016-09-06 2017-01-04 河海大学 一种氨基改性壳聚糖复合吸附材料的制备方法
CN108636387A (zh) * 2018-07-13 2018-10-12 武汉工程大学 一种铁离子吸附海绵及其制备方法和应用
CN108636387B (zh) * 2018-07-13 2021-01-05 武汉工程大学 一种铁离子吸附海绵及其制备方法和应用
CN109439314A (zh) * 2018-12-07 2019-03-08 武汉工程大学 特异性识别Fe(III)的磁性纳米荧光探针的制备方法
CN109596586A (zh) * 2018-12-07 2019-04-09 武汉工程大学 一种基于罗丹明b的磁性纳米探针的制备方法
CN109596586B (zh) * 2018-12-07 2022-03-15 武汉工程大学 一种基于罗丹明b的磁性纳米探针的制备方法
CN109439314B (zh) * 2018-12-07 2022-05-10 武汉工程大学 特异性识别Fe(III)的磁性纳米荧光探针的制备方法
CN113070050A (zh) * 2021-04-28 2021-07-06 山东大学 一种能可视化识别并除去汞离子的壳聚糖基水凝胶吸附剂及其制备方法与应用
CN113070050B (zh) * 2021-04-28 2022-06-21 山东大学 一种能可视化识别并除去汞离子的壳聚糖基水凝胶吸附剂及其制备方法与应用

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