CN104140431B - 一种可检测、分离重金属离子的罗丹明类荧光探针及其制备方法 - Google Patents

一种可检测、分离重金属离子的罗丹明类荧光探针及其制备方法 Download PDF

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CN104140431B
CN104140431B CN201410306144.XA CN201410306144A CN104140431B CN 104140431 B CN104140431 B CN 104140431B CN 201410306144 A CN201410306144 A CN 201410306144A CN 104140431 B CN104140431 B CN 104140431B
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rhodamine
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施冬健
倪明
曾金凤
叶瑾
陈明清
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Abstract

一种可检测、分离重金属离子的罗丹明类荧光探针及其制备方法，属于功能材料领域。本发明的荧光探针以罗丹明B(RhB)为原料，通过修饰改性使其末端带有偶氮苯基团，制备得到可检测金属汞离子的罗丹明类荧光探针，且具有较低的检测极限。利用偶氮苯与环糊精的主客体包合作用，将预先制备得到的环糊精磁性纳米粒子作为吸附剂，使被包合的荧光探针与检测到的金属离子在外加磁场的作用下从溶液中分离；进而利用偶氮苯基团的光反应性，可实现重金属离子的脱除及环糊精磁性纳米粒子的多次重复使用。本发明所得的罗丹明衍生物对水溶液中汞离子具有较好的识别能力可以作为汞离子的检测与去除剂。本发明所制得的罗丹明衍生物可作为荧光探针广泛应用于环境工程、分析检测等领域。

Description

一种可检测、分离重金属离子的罗丹明类荧光探针及其制备 方法
技术领域
本发明涉及罗丹明荧光探针分子的设计、制备及应用，属于功能材料领域。
背景技术
铜(Cu)、汞(Hg)、铅(Pb)等一系列剧毒重金属已被广泛用于各工业生产流程中，它们中的大多数最终转化成为阳离子而被排放到自然界，从而重金属对水和大气的污染越发严重和频繁。而一些重金属离子具有较强的毒性或对生命过程具有非常重要的影响。如汞离子在水溶液中容易被氧化为甲基汞，通过食物链对人类和自然生态系统存在潜在的危害，长时间接触高浓度的汞离子会对中枢神经系统和其它器官比如心脏，肾脏，肺等造成严重的损害；因而，建立快速、高效的重金属离子检测和有效脱除分离的方法对于生命、环境和医药科学都具有非常重要的意义。
罗丹明是一种性能优越的染料，其系列衍生物通常具有较大的摩尔吸光系数及较高的量子产率，在可见光区具有较长的发射和吸收波长；螺旋状罗丹明内酰胺化合物本身具有一定的结构张力，在与重金属粒子结合后，内酰胺氮原子的质子化将导致氮原子电荷密度减少，从而引发螺旋中心C-N键的开裂，同时，断键后原本富电子的螺旋环将进行电荷重排，形成更稳定的刚性平面大π键结构，从而产生荧光变化和颜色变化；因而罗丹明类化合物作为荧光标记物，在分析化学及分子生物学领域有广泛的应用。目前已有众多的研究者设计合成一系列含有O、N、S等原子的罗丹明衍生物，使其与Hg2+，Cu2+等配位络合，利用配位前后罗丹明结构的变化而发出荧光，从而实现对重金属离子检测。尽管已有较多的研究工作报道了对重金属离子的检测，但是还没有在检测的同时实现重金属离子脱除分离的研究。
环糊精(Cyclodextrin，简称CD)是直链淀粉在由芽孢杆菌产生的D-吡喃葡萄糖基转移酶作用下生成的一系列环状低聚糖的总称。CD最显著的特点是外亲水内疏水，因而CD可与适当大小和形状的分子(如金属配合物、无机物、有机物及高分子聚合物等)，通过疏水相互作用、主客体相互作用等形成稳定的包合物。利用环糊精的这一特性可以将环糊精广泛应用于污水处理、催化剂、化妆品、食品、制药等领域。另一方面，Fe3O4磁性纳米粒子是常用的磁性纳米材料之一，它集纳米性质和磁学特性于一体，不仅具有纳米材料的一般性质即小尺寸效应、量子效应、表面效应和宏观量子隧道效应，同时还呈现出独特的磁学性能。
本发明制备的一类新型罗丹明衍生物，使其与重金属离子(Hg2+)发生配位络合，实现对Hg2+检测；同时利用罗丹明衍生物中的偶氮苯功能基团与环糊精的包合作用，将其和环糊精磁性纳米粒子形成包合物，进而利用磁场的作用将罗丹明-Hg2+的络合物脱除分离；进一步通过偶氮苯的光响应特性，将环糊精磁性纳米粒子与络合物解包合，可实现脱除重金属离子及对环糊精磁性纳米粒子的多次重复利用。本发明的研究将对环境、生命和医药科学具有很重要的理论意义和实际应用价值。
发明内容
本发明的目的是提供一种可检测、分离重金属离子的罗丹明类荧光探针及其制备方法，实现同时检测和脱除分离重金属离子的荧光探针。
本发明的技术方案：一种新型罗丹明类荧光探针，该荧光探针是以罗丹明B(RhB)为原料，用二元胺修饰改性RhB制备罗丹明内酰胺(SRhB)，进而与马来酸酐(MAH)和偶氮苯(Azo)反应，得到罗丹明类荧光探针分子；所用的二元胺可以为乙二胺、丙二胺、己二胺等，所得产物的结构为：
n＝2，3，6，表示成SRhB-Azo。
利用偶氮苯与环糊精的主客体包合作用以及偶氮苯的结构特异性，使荧光探针在检测的同时可以利用磁性纳米粒子的顺磁性分离重金属离子，且磁性纳米粒子可以多次使用。
该类荧光探针的特征步骤是：
(1)罗丹明内酰胺(SRhB)的制备：RhB(10.46mmol)溶于180ml无水乙醇中，N2氛围下快速加入40.23mL乙二胺(或丙二胺，己二胺)后，温度缓慢加到85℃，反应24h，再减压蒸馏，得到的粉末用CH2Cl2(100mL)溶解，用水(200mL)萃取，分离出有机层，再用水洗5次，减压蒸馏得橙色粉末。用硅胶色谱法(CH2Cl2/EtOH/Et3N＝5∶1∶0.1)提纯。
(2)偶氮苯-罗丹明(SRhB-Azo)的制备：在50mL单口烧瓶中加入100mg马来酸酐(MAH)，516mg SRhB，20mg4-二甲氨基吡啶(DMAP)，5mL DMSO，室温反应12h后加入191mg1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)，137mg1-羟基-苯并-三氮唑(HOBt)，活化1h后，加入197.24mg偶氮苯(Azo)室温反应12h。得到的粉末用CH2Cl2(100mL)溶解，用水(200mL)萃取，分离出有机层，减压蒸馏得粉红色粉末，用硅胶色谱法提纯(CH2Cl2)。
(3)环糊精磁性纳米粒子的制备：
在500mL三颈烧瓶中加入3g FeCl2·4H2O，8.1g FeCl3·6H2O，溶于200mL水中，N2氛围下机械搅拌10min，将40mL氨水逐滴加入其中，在室温下搅拌30min，加热到70℃，持续搅拌1h。将产物冷却到室温后，磁铁分离，用无水乙醇洗涤3次，真空干燥得到MNP。1.91gMNPs，1.5mL干燥甲苯，超声得到均相溶液后，加入6mL硅烷偶联剂，在N2氛围，室温条件下剧烈搅拌6h，得到MNP-NH2。先用磁铁分离，再用二氯甲烷和乙醇交替洗涤，除去没有反应的硅烷偶联剂，真空干燥。
称取5gβ-CD(4mmol)溶于150mL浓度为0.4mol·L-1的NaOH溶液中，把三口烧瓶放在0℃冰水浴中，缓慢加入3.6g对甲苯磺酰氯(Ts，19.0mmol)，(控制时间10min以上)，在室温下机械搅拌2h。得到白色沉淀，过滤得到滤液，加入HCl溶液调节PH至6，搅拌1h，将得到的悬浮液放在冰箱冷藏过夜，重结晶3次，得到产物β-CD-OTs。称取0.473g的β-CD-OTS和0.302gAPTES-MNPs分散于15mL干燥的吡咯烷酮中，超声震荡20min，然后加入0.01gKI，加热到70℃，在N2氛围下，机械搅拌6h。反应结束后，冷却至室温，加入50mL乙醇，洗涤3次，干燥，得到MNP-CD。
本发明的有益效果：本发明通过用二元胺(乙二胺，丙二胺，己二胺等)修饰改性罗丹明B(RhB)制备罗丹明内酰胺(SRhB)，进而与马来酸酐(MAH)和偶氮苯(Azo)反应，得到罗丹明类荧光探针分子；所得的结构中含有可与金属离子发生作用的多个胺基功能团和可与Hg作用的碳碳双键；该荧光探针能够在水溶液中检测汞离子，检测极限约为3ppm；以环糊精磁性纳米粒子为吸附剂，利用罗丹明衍生物中的偶氮苯等功能基团与环糊精的包合作用，将其和环糊精磁性纳米粒子形成包合物，从而利用磁场的作用将罗丹明-重金属离子的络合物从污水中脱除分离；进一步通过光响应等特异响应性，将环糊精磁性纳米粒子与络合物解包合，实现分离金属离子及环糊精磁性纳米粒子的多次重复利用；本发明所制得的罗丹明衍生物可作为荧光探针广泛应用于环境工程、检测等领域。
附图说明
图1罗丹明类荧光探针对重金属离子检测和分离的示意图。
图2荧光探针金刚烷-罗丹明(SRhB-Azo)的1H-NMR谱图。
图3荧光探针SRhB-Azo对不同汞离子浓度的荧光光谱。
图4 SRhB-Azo对各种金属离子的紫外吸收光谱。
图5磁性纳米粒子对SRhB-Azo的吸附与解吸附照片
具体实施方式
实施例1、罗丹明内酰胺(SRhB)的合成
将RhB(10.46mmol)溶于180ml无水乙醇中，N2氛围下快速加入40.23mL乙二胺，温度缓慢加到85℃，反应24h，减压蒸馏，得到的粉末用CH2Cl2(100mL)溶解，用水(200mL)萃取，分离出有机层，再用水洗5次，减压蒸馏得橙色粉末。用硅胶色谱法(CH2Cl2/EtOH/Et3N＝5∶1∶0.1)提纯，产率90％。
实施例2、偶氮苯-罗丹明(SRhB-Azo)的制备
在50mL单口烧瓶中加入100mg马来酸酐(MAH)，516mg SRhB，20mg DMAP，5mL DMSO，室温反应12h后加入191mg EDC，137mg HOBt，活化1h后，加入197.24mg偶氮苯(Azo)室温反应12h。得到的粉末用CH2Cl2(100mL)溶解，用水(200mL)萃取，分离出有机层，减压蒸馏得粉红色粉末，用硅胶色谱法提纯(CH2Cl2)。
实施例3、检测汞离子
在100mL的容量瓶中分别配置2.5×10-3M的SRhB-MAH-A2O乙醇标准液，1×10-4M的汞离子标准溶液。分别取1mLSRhB-Azo标准液与0.1mL，0.2mL，0.4mL，0.6mL，0.8mL，1.0mL汞离子标准液于离心管，用乙醇稀释至5mL，于492nm处测荧光强度，于563nm处进行光度测定。
实施例4、环糊精磁性纳米粒子(MNP-CD)的制备
在500mL三颈烧瓶中加入3g FeCl2·4H2O，8.1g FeCl3·6H2O，溶于200mL水中，N2氛围下机械搅拌10min，将40mL氨水逐滴加入其中，在室温下搅拌30min，加热到70℃，持续搅拌1h。将产物冷却到室温后，磁铁分离，用无水乙醇洗涤3次，真空干燥得到MNP。1.91gMNPs，1.5mL干燥甲苯，超声得到均相溶液后，加入6mL硅烷偶联剂，在N2氛围，室温条件下剧烈搅拌6h，得到MNP-NH2。先用磁铁分离，再用二氯甲烷和乙醇交替洗涤，除去没有反应的硅烷偶联剂，真空干燥。
称取5gβ-CD(4mmol)溶于150mL浓度为0.4mol·L-1的NaOH溶液中，把三口烧瓶放在0℃冰水浴中，缓慢加入3.6g对甲苯磺酰氯(Ts，19.0mmol)，(控制时间10min以上)，在室温下机械搅拌2h。得到白色沉淀，过滤得到滤液，加入HCl溶液调节PH至6，搅拌1h，将得到的悬浮液放在冰箱冷藏过夜，重结晶3次，得到产物β-CD-OTs。称取0.473g的β-CD-OTS和0.302gAPTES-MNPs分散于15mL干燥的吡咯烷酮中，超声震荡20min，然后加入0.01gKI，加热到70℃，在N2氛围下，机械搅拌6h。反应结束后，冷却至室温，加入50mL乙醇，洗涤3次，干燥，得到MNP-CD。
实施例5、磁性纳米粒子对SRhB-Azo的吸附
分别取10，20，40，60，80mg MNP-CD于样品瓶中，分别各取5ml SRhB-A2O(1×10-3M)标准液和1ml Hg2+标准液(1×10-3)加入其中，使其显色且振荡4天。定量测定溶液中残留的SRhB-Azo的含量，根据标准曲线算出包合率。
实施例5、磁性纳米粒子对SRhB-Azo的解吸附
用乙醇把包结后的MNP-CD洗三次出去表面附着的SRhB-Azo，各加入5ml的乙醇溶液，在波长为302nm的紫外灯照射三天后，定量测定溶液中脱包合后的SRhB-Azo。
以上吸附与解吸附步骤重复5次。

Claims (1)

1.一种可检测、分离重金属离子的罗丹明类荧光探针，其特征在于，所述罗丹明类荧光探针分子的结构为：
n＝1或3；表示成SRhB-Azo。
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