CN112961671B - 一类多目标同时检测的荧光/磷光发光寿命聚合物探针及其应用 - Google Patents

一类多目标同时检测的荧光/磷光发光寿命聚合物探针及其应用 Download PDF

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CN112961671B
CN112961671B CN202110159473.6A CN202110159473A CN112961671B CN 112961671 B CN112961671 B CN 112961671B CN 202110159473 A CN202110159473 A CN 202110159473A CN 112961671 B CN112961671 B CN 112961671B
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张寅�
王云
吴琦
刘淑娟
赵强
黄维
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Nanjing University of Posts and Telecommunications
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Abstract

本发明公开了一类多目标同时检测的荧光/磷光发光寿命聚合物探针，该类探针通过聚合反应将各响应端连接起来，并利用各响应端发光寿命的变化实现两种或多种目标的同时检测。相对于现有检测方法，本发明结构新颖，为实现单个探针对多种分析目标的同时检测提供了新的思路。

Description

一类多目标同时检测的荧光/磷光发光寿命聚合物探针及其 应用
技术领域
本发明属于有机光电半导体材料技术领域，具体涉及一类可同时检测多目标的荧光/磷光发光寿命聚合物探针及其在多种分析物同时检测方面的应用。
背景技术
有机光电半导体材料在生物医学光子学领域具有广泛的应用前景，长期以来，以激光共聚焦显微术为代表的生物医学光学成像技术一直都是以探针材料的发光强度或是发射波长的改变为分析信号，这种方法能够简单有效的反映细胞、组织或器官中目标分析物的空间分布以及局部浓度。目前研究并开发的有机光电半导体探针大多是只针对单一目标分析物的检测，但是无论是生命活动过程的研究还是一些疾病的诊断，单一分析物的变化则不足以反映问题，可能会造成检测结果的假阳性，因此需要多种参数联合判断，以增加检测的准确性，提高检测效率。但是，由于有机光电半导体探针材料的半峰宽较宽，当不同材料的光谱发生重叠时，想要通过波长进行分离是不可能实现的，同时生物体中也含有大量的荧光物质，这会很大程度上造成高的检测信噪比。
除了发光强度和波长以外，发光寿命则是有机光电半导体材料另一种重要的发射信号的参数之一。发光寿命是一种状态函数，它不随激发光源功率的改变而发生变化，亦与探针自身的浓度无关系，其灵敏度高，可实现更低材料浓度的检测。相比发光强度和波长，发光寿命是一种在时间维度上的参数，因此发光波长重叠的信号则可以通过发光寿命在时间维度上进行区分。故可利用时间分辨技术，通过对发光寿命的测量，检测pH值、离子浓度、氧压、极性和粘度等生理参数。
发明内容
本发明的目的在于提供一类多分析目标同时检测的荧光/磷光发光寿命聚合物探针，该类探针利用各响应端发光寿命的变化以实现多个目标分析物的同时检测，能兼顾多个参数的变化，提高检测效率。相对于现有检测方法，本发明结构新颖，为实现单个探针对多种目标分析物的同时检测提供了新方法。
本发明的目的可以通过以下技术方案来实现：
本发明提供的多种分析目标同时检测的荧光/磷光发光寿命聚合物探针具有如下结构通式：
Figure BDA0002935766880000021
其中，a、b、c…n为聚合度；
其中，通式中A为一类可增加聚合物水溶性的基团单体，为下列结构中的任意一种：
Figure BDA0002935766880000022
其中，通式中B、C、D…N为一类可作为ClO-响应端的有机荧光小分子化合物单体，为下列结构中的任意一种：
Figure BDA0002935766880000023
或B、C、D…N为一类可作为氧气响应端的磷光金属配合物单体，配合物具有如下结构：
Figure BDA0002935766880000024
N^C配体为下列结构中的任意一种：
Figure BDA0002935766880000025
Figure BDA0002935766880000031
本发明所述的聚合物探针的ClO-响应端均具备吩噻嗪基团，将聚合物放置在ClO-环境条件下，ClO-可以将化合物中吩噻嗪基团上的S氧化，从而实现ClO-的检测；本发明所述的聚合物探针的氧气响应端包含铱配合物，将聚合物放置在氧气环境条件下，氧气分子可以淬灭铱配合物的三重态磷光，从而实现氧气的检测，因而本发明提供的聚合物探针可通过各个响应端发光寿命的变化检测多种目标分析物，且通过测试结果发现本发明所述的聚合物探针可以实现对ClO-和O2的同时检测且互不影响；
本发明提供的聚合物探针的各响应端发光寿命具有明显的差异，避免了利用发光波长检测时因波长信号重叠而造成的干扰，各响应端发光寿命的变化能较好的区分。
本发明的有益效果在于：提供一类多种分析目标同时检测的荧光/磷光发光寿命聚合物探针的设计新思路；本发明提供的多种分析目标同时检测的荧光/磷光发光寿命聚合物探针通过聚合反应将各响应端单体连接在一起制备成探针，该类探针结合时间分辨技术检测其发光寿命的变化，突破发光波长的限制，可实现多种分析目标的同时检测，且各分析物响应端能同时使用，互不影响，检测灵敏度高。
附图说明
图1a为本发明实施例1和测试例1中所述ClO-响应端单体对ClO-的发射光谱测试；
图1b为本发明实施例1和测试例1中所述探针P1对ClO-的发射光谱测试；
图2a为本发明实施例1和测试例2中所述探针P1及O2响应端单体对O2的发射光谱测试；
图2b为本发明实施例1和测试例2中所述O2响应端单体对O2的发射光谱测试；
图3a为本发明实施例1和测试例3中所述探针P1在N2条件下加或不加ClO-的发光寿命衰减曲线；
图3b为本发明实施例1和测试例3中所述探针P1在空气(Air)条件下加或不加ClO-的发光寿命衰减曲线；
图3c为本发明实施例1和测试例3中所述探针P1在O2条件下加或不加ClO-的发光寿命衰减曲线；
图4a为本发明实施例1和测试例3中所述探针P1在不加ClO-时不同O2含量条件下的发光寿命衰减及相应的拟合曲线；
图4b为本发明实施例1和测试例3中所述探针P1在加ClO-时不同O2含量条件下的发光寿命衰减及相应的拟合曲线。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实例。
实施例1：聚合物探针P1化学结构
先合成ClO-响应端的具有短发光寿命的有机荧光小分子单体(以下简称ClO-响应端单体)，再合成O2响应端的具有长发光寿命的磷光金属配合物单体(以下简称O2响应端单体)，最后通过聚合反应将ClO-响应端单体、O2响应端单体与水溶性的基团单体聚合在一起制备成聚合物探针P1；聚合物探针P1可用于O2和ClO-同时检测；聚合物探针P1化学结构式如下所示：
Figure BDA0002935766880000051
其中，a、b、c≥55，化学结构式
Figure BDA0002935766880000052
为ClO-响应端的具有短发光寿命的有机荧光小分子单体，化学结构式
Figure BDA0002935766880000053
为O2响应端的具有长发光寿命的磷光金属配合物单体，化学结构式
Figure BDA0002935766880000054
为水溶性的基团单体。
实施例2：ClO-响应端单体即化合物S1的制备
Figure BDA0002935766880000055
将吩噻嗪(1.0g，5mmol)和KOH(1.1g，20mmol)加入到10mLDMSO中，在0℃下滴加溴乙烷(0.54g，5mol)，然后室温下搅拌过夜后。反应结束后将反应物倒入20ml水中，过滤后再通过柱层析法提纯得到淡黄色固体产物10-乙基吩噻嗪1.05g(产率90％)；
在N2保护下，将POCl3(0.47mL，5mmol)在01C下加入到无水DMF(0.39mL，5mmol)中搅拌1h。然后将10-乙基吩噻嗪(227mg，1mmol)溶于8mL的CH3CHCl2后加入上述溶液中，902C回流过夜。反应结束后冷却至室温，用CH2Cl2萃取并通过柱层析法提纯得到黄色产物10-乙基吩噻嗪-3-甲醛178.5mg(产率70％)；
在N2条件下，将10-乙基吩噻嗪-3-甲醛(127.5mg，0.5mmol)和对甲基吡啶(55.8mg，0.6mmol)溶解在无水乙腈(10mL)中，然后加入叔丁醇钾(56mg，0.5mmol)，40℃下搅拌反应12h。反应结束后，用二氯甲烷萃取，之后通过柱层析法提纯得到深红色固体产物S1178.5 mg(产率73％)。
1H NMR(400MHz,Chloroform-d)δ(ppm):8.46(d,J＝4.8Hz,2H),7.28–7.19(m,4H),7.13–7.03(m,3H),6.85(t,J＝7.2Hz,1H),6.81–6.72(m,3H),3.86(dd,J＝7.11,6.5Hz,2H),1.36(t,J＝6.8Hz,3H).
实施例3：O2响应端单体即化合物S2的制备
Figure BDA0002935766880000061
将苯并噻吩-2-硼酸(356mg，2mmol)，2-溴吡啶(316mg，2mmol)和四(三苯基膦)钯(115.5mg，0.1mmol)溶解在10mL甲苯、饱和K2CO3和乙醇(2:1:1)的混合溶液中80℃下反应8h。反应结束后，用二氯甲烷萃取，之后用柱层析分离提纯得2-(2-吡啶基)苯并噻吩388mg(产率92％)。
将2-(2-吡啶基)苯并噻吩和IrCl3·3H2O(353mg，1mmol)溶解在15mL水与乙二醇乙醚(1:3)的混合溶液中110`C反应12h。反应结束后加水抽滤，干燥得黄色固体产物2-(2-吡啶基)苯并噻吩铱二氯桥配合物。
将2-(2-吡啶基)苯并噻吩铱二氯桥配合物(193.5mg，0.15mmol)，3-羟基-2-吡啶甲酸(43.8mg，0.32mmol)和K2CO3(83mg，0.6mmol)溶解在乙二醇乙醚溶液中110℃反应12h。将反应液冷却至室温，加入10倍当量的六氟磷酸钾，继续搅拌5h。反应结束后，用二氯甲烷萃取，之后柱层析分离提纯得3-羟基-2-吡啶甲酸铱2-(2-吡啶基)苯并噻吩。
将3-羟基-2-吡啶甲酸铱2-(2-吡啶基)苯并噻吩(187.7mg，0.25mmol)与3-溴丙烯(0.03mL，0.3mmol)溶解在DMF和NaOH的饱和溶液中室温继续反应12h。反应结束，用二氯甲烷萃取，之后柱层析分离提纯得S2共158mg(产率80％)。1H NMR(400MHz,Chloroform-d)δ(ppm):8.89(d,1H),7.8-7.58(m,6H),7.46-7.31(m,3H),7.16(m,2H),7.06(m,2H),6.9-6.72(m,3H),6.30(d,1H),6.09(m,1H),5.98(d,1H),5.57(d,1H),5.36(d,1H),4.75(s,2H).
实施例4：聚合物探针P1的制备
Figure BDA0002935766880000071
其中a、b、c≥55；
N-乙烯基吡咯烷酮(1mL，10mol)、AIBN(30mg，0.2mmol)、4-氯甲基苯乙烯(7.6mg，0.05mmol)和S2(39.5mg，0.05mmol)溶解在严格除水除氧的四氢呋喃中，在氮气氛围中80℃下搅拌反应24h。反应结束后冷却至室温，分别用二氯甲烷、甲醇和水各透析12h得S3；
将S3(21mg)和S1(16.5mg，0.05mmol)加入到乙腈溶液中，然后在25℃下反应12h。反应结束后用二氯甲烷、甲醇和水各透析12h得产物P1，P1的产率在44％以上。
测试例1：聚合物探针P1及ClO-响应端单体对ClO-响应的发射光谱测试
ClO-响应端单体(ClO-sensor unit)化学式为：
Figure BDA0002935766880000072
聚合物探针P1及单体测试浓度均为10μM，测试溶剂为甲醇/水＝1/1(v/v)，激发波长为405nm。测试结果见图1，其中，如图1a所示，从ClO-响应端单体的ClO-滴定图可以观察出，随着加入NaClO浓度的增加，单体在600nm处的发光逐渐增强，说明单体对ClO-具有很好的响应性。同样，对聚合物探针P1的测试中也可以观察到相同的现象，如图1b所示，随着加入NaClO浓度的增加，聚合物探针P1在600nm处的发光亦逐渐增强，表明聚合物探针P1对有机荧光小分子单体的发光无明显影响，且对ClO-具有较好的响应性。
测试例2：聚合物探针P1及O2响应端单体对O2响应的发射光谱测试
O2响应端单体(O2 sensor unit)化学式为：
Figure BDA0002935766880000081
聚合物探针P1及单体测试浓度均为10μM，测试溶剂为甲醇/水＝1/1(v/v)，激发波长为405nm。测试结果见图2，其中如图2a对O2响应端单体的测试结果可以看出，随着氧气浓度的增加，由于氧气对O2响应端单体的猝灭作用，其在600nm处的发射逐渐减弱，说明O2响应端单体对氧气具有很好的响应性；如图2b在聚合物探针P1的氧气测试中也观察到，随着氧气浓度的增加，聚合物探针P1在660nm处的发光减弱的现象，说明聚合物探针P1对氧气也具有良好的响应性。
测试例3：聚合物探针P1在不同条件下的发光寿命衰减测试
聚合物探针P1测试浓度为10μM，测试溶剂为甲醇/水＝1/1(v/v)；分别在N2、空气(Air)和O2条件下，检测聚合物加或不加ClO-时的发光寿命。
如图3a、3b、3c所示，无论在N2、空气(Air)亦或O2条件下，随着NaClO的加入，聚合物探针P1的O2响应端长的磷光发光寿命不变，聚合物探针P1的ClO-响应端短的荧光发光寿命均明显增强，说明探针P1对ClO-有较好的响应效果，且氧气对探针P1中ClO-的检测无明显影响。
如图4a所示，在不加ClO-时，随着氧气浓度的增大，聚合物探针P1的O2响应端长的磷光发光寿命均逐渐缩短；如图4b所示，在加ClO-时，聚合物探针P1的O2响应端长的磷光发光寿命也随着氧气浓度的增大而逐渐缩短，说明无论是否存在ClO-，聚合物探针P1对O2均有较好的响应效果，且ClO-对聚合物探针P1中O2含量的检测无明显影响。同时，结合图4a和4b可以得出，在同时改变O2和ClO-含量时，聚合物探针P1上的ClO-响应端短的荧光发光寿命和O2响应端长的磷光发光寿命均发生相应改变，说明聚合物探针P1可以实现对ClO-和O2的同时检测。由此可以推断，聚合物探针P1可以实现对ClO-和O2的同时检测，且各分析物响应端之间互不影响。
以上所述仅为本发明的较佳实施例，并不以上述实施方式为限，但凡本领域普通技术人员根据本发明所揭示内容所作的等效修饰、等同替换和改进等，皆应纳入权利要求书中记载的保护范围。

Claims (5)

1.一类多目标同时检测的荧光/磷光发光寿命聚合物探针，其特征在于，所述聚合物探针具有如下结构通式：
Figure DEST_PATH_IMAGE002A
，
其中，a、b、c为聚合度；
其中，A为一类可增加聚合物水溶性的基团；
其中，B、C中至少一者为可作为ClO-响应端的有机荧光小分子化合物基团且B、C中至少一者为可作为氧气响应端的磷光金属配合物基团；
所述可作为ClO-响应端的有机荧光小分子化合物基团单体为下列结构中的任意一种：
Figure DEST_PATH_IMAGE004A
，
所述可作为氧气响应端的磷光金属配合物基团单体化学结构如下：
Figure 984406DEST_PATH_IMAGE005
，
所述配合物基团单体化学结构中的N^C配体为下列结构中的任意一种：
Figure DEST_PATH_IMAGE007A
Figure DEST_PATH_IMAGE009A
Figure DEST_PATH_IMAGE011
。
2.如权利要求1所述的一类多目标同时检测的荧光/磷光发光寿命聚合物探针，其特征在于，所述可增加聚合物水溶性的基团单体为下列结构中的任意一种：
Figure DEST_PATH_IMAGE013
。
3.一类多目标同时检测的荧光/磷光发光寿命聚合物探针，所述聚合物探针化学结构式如下所示，标记为聚合物探针P1：
Figure 295343DEST_PATH_IMAGE014
，其中，a、b、c≥55。
4.如权利要求1或3所述的一类多目标同时检测的荧光/磷光发光寿命聚合物探针的应用，其特征在于，所述聚合物探针通过各个响应端发光寿命的变化检测多种目标分析物。
5.如权利要求4所述的一类多目标同时检测的荧光/磷光发光寿命聚合物探针的应用，其特征在于，所述聚合物探针利用各响应端发光寿命的明显的差异，避免发光波长检测时因波长信号重叠而造成的干扰，实现各响应端发光寿命的变化的区分。
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