CN111995634B - 一种四配位有机硼化合物、荧光探针及其制备方法与应用 - Google Patents
一种四配位有机硼化合物、荧光探针及其制备方法与应用 Download PDFInfo
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- CN111995634B CN111995634B CN202010886374.3A CN202010886374A CN111995634B CN 111995634 B CN111995634 B CN 111995634B CN 202010886374 A CN202010886374 A CN 202010886374A CN 111995634 B CN111995634 B CN 111995634B
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- organic boron
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- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
本发明公开一种四配位有机硼化合物、荧光探针及其制备方法与应用，所述四配位有机硼化合物的结构式如下所示：
其中，
为取代或未取代的环原子数为5～50的芳香环基或环原子数为5～30的芳香杂环基；
为含有杂原子的给电子基团。本发明提供的四配位有机硼化合物对水氧不敏感，表现出优异的热力学稳定性及突出的光化学稳定性，而且具有很好的溶解性。利用路易斯酸碱相互作用，本发明该四配位有机硼化合物可实现对氟离子的高灵敏、高选择性、可逆识别检测，基本解决了以往方法存在的检测过程不可逆及相应速度慢的问题，并且为性能优异的氟离子荧光探针的设计提供了新的思路。
Description
技术领域
本发明涉及荧光探针技术领域，尤其涉及一种四配位有机硼化合物、荧光探针及其制备方法与应用。
背景技术
氟离子主要以氟化物的形式广泛存在于土壤、自然水、动植物等自然环境中，与人类生产生活过程密切相关。同时，氟离子是生物体中最为重要的阴离子之一，是维持牙齿和骨骼正常生长不可缺少的成分，低浓度的氟离子对牙齿健康和骨质疏松的治疗具有重要作用，然而，当体内氟离子的浓度偏高时，极有可能会导致牙齿变黄、变黑，甚至可能引发氟骨症、骨癌、破坏某些酵素系统导致多器官病变等疾病。近年来，氟离子对人类的影响日益加剧，是因为在我们的日常生活中每天不可避免的都会与氟离子接触，比如我们每天用的牙膏、包括维他命在内的诸多药物以及日常饮用水等都含有大量的氟离子，如在人体内过量蓄积，则会直接危害到人类的身体健康。因此，发展高灵敏、高选择性、快速可逆的氟离子传感检测方法至关重要。
基于上述考虑，到目前为止，人们已经发展了各种各样的检测技术或方法。离子迁移谱、表面增强拉曼、电化学、比色法以及荧光传感器法等都已被成功报道。在众多的检测方法中，荧光传感方法由于具有灵敏度高、选择性强以及易于操作等突出优点越来越受到人们的重视。其中，氢键相互作用、化学反应以及路易斯酸碱相互作用等是实现荧光传感方法的常用策略。然而，基于氢键相互作用和化学反应的荧光传感策略往往存在检测过程不可逆、检测灵敏度低以及响应时间长等不足，这极大地限制了其实际应用。基于此，利用路易斯酸类化合物实现对氟离子的荧光传感则受到大家的关注。
硼元素固有的路易斯酸性可作为氟离子很好的受体材料，近年来，许多研究者证明三配位的有机硼化合物能够用于高选择性的氟离子荧光探针。这是由于硼原子中心具有空的轨道使其作为路易斯酸接受电子从而与氟离子结合，从而破坏整个功能分子体系的pπ-π共轭，进而引起有机硼化合物发光性质的显著变化，最终实现对氟离子的传感检测。但是，由于硼的高的反芳香性使其对水氧极为敏感，因而许多三配位有机硼化合物无法在空气中稳定保存，难以满足现实应用。相较于三芳基硼化合物，四配位有机硼化合物通常对水氧稳定，且表现出优异的光电性能，已在有机发光二极管(OLED)、有机场效应晶体管(OFET)、光伏材料以及荧光成像等领域获得了较为广泛的应用，而基于四配位有机硼的氟离子荧光传感的研究却鲜有报道。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种四配位有机硼化合物、荧光探针及其制备方法与应用，旨在解决现有三配位有机硼化合物无法在空气中稳定保存，难以满足对氟离子的传感检测的问题。
本发明的技术方案如下：
本发明的第一方面，提供一种四配位有机硼化合物，其中，所述四配位有机硼化合物的结构式如下所示：
其中，
为取代或未取代的环原子数为5～50的芳香环基或环原子数为5～30的芳香杂环基；
为含有杂原子的给电子基团。
本发明提供的四配位有机硼化合物均含有主族元素硼和给电子功能片段，硼原子固有的缺电子性(Lewis酸性)使得含硼的有机共轭分子往往都是理想的电子受体材料，因而在有机光电和荧光传感等方面都具有非常广阔的应用前景；通过不同给电子功能基团的引入，可以较大范围的调控所得四配位有机硼化合物的光物理性质，进而产生丰富的光学行为，从而获得性能突出的光电应用。
本发明将具有优异光电性能的主族元素硼及8-羟基喹啉单元同时引入到共轭小分子中，得到一系列四配位有机硼化合物，也可以称为四配位8-羟基喹啉硼化合物。该四配位有机硼化合物具有优良的溶解性、优异的光物理性质和光化学稳定性。本发明四配位有机硼化合物属于荧光化合物，采用该四配位有机硼化合物制备的荧光探针可以实现对氟离子的高灵敏度、高选择性，更为重要的是，可逆地检测识别。
进一步地，所述给电子基团可以为取代或未取代的咔唑基团、9，9-二甲基-9，10-二氢吖啶基团、取代或未取代的10H-吩恶嗪基团、取代或未取代的10H-吩噻嗪基团、取代或未取代的二苯胺基团、取代或未取代的9，9-二苯基-9，10-二氢吖啶基团、取代或未取代的10H-螺[吖啶-9,9'-芴]基团、取代或未取代的10H-螺[吖啶-9,9'-氧杂蒽]基团、取代或未取代的10,11-二氢-5H-二苯并[b,f]氮杂
基团、取代或未取代的5H-二苯并[b,f]氮杂
基团、取代或未取代的9H-三苯并[b,d,f]氮杂
基团等中的一种，但不限于此。
进一步地，
选自如下结构中的一种：
进一步地，
选自如下结构中的一种：
其中，Y1、R3、R4、X1和X2各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代或未取代的C6～C60的芳香环基、取代或未取代的C3～C60的芳杂环基中的一种；
其中，X1、X2能够相互以共价键方式相连成环。
进一步地，所述四配位有机硼化合物选自如下结构中的一种：
本发明的第二方面，提供一种如上所述的四配位有机硼化合物的制备方法，其中，包括步骤：
向装有磁力搅拌和回流冷凝装置的烧瓶中加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环；
加热至110～120℃(如110℃)回流20～24小时(如20小时)后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为10～15％的K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用洗脱剂进行柱色谱分离，得到所述四配位有机硼化合物。
其中，
代表任意基团。
本发明利用一步反应简单高效地制备了一系列四配位有机硼化合物，该四配位有机硼化合物的制备方法具有操作简便、反应条件温和，可以进行大规模生产以及对底物适应性强等突出优点。经实验验证，所制备的四配位有机硼化合物对水氧不敏感，表现出优异的热力学稳定性及突出的光化学稳定性，而且具有很好的溶解性。利用路易斯酸碱相互作用，本发明所制备的四配位有机硼化合物可实现对氟离子的高灵敏、高选择性、可逆识别检测，基本解决了以往方法存在的检测过程不可逆及相应速度慢的问题，并且为性能优异的氟离子荧光探针的设计提供了新的思路。
进一步地，所述8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1:(9～11)：(3～5)：(500～700)。更进一步地，所述8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1：9：3：586。
进一步地，所述洗脱剂由乙酸乙酯与石油醚按照体积比1:9配制而成。即所述洗脱剂采用乙酸乙酯-石油醚体系，所述乙酸乙酯-石油醚体系中乙酸乙酯与石油醚的体积比为1:9。
本发明的第三方面，提供一种荧光探针，其中，包括如上所述的四配位有机硼化合物。
本发明采用如上所述四配位有机硼化合物所制备的荧光探针，具有光化学稳定性好、灵敏度高、选择性好，将这类荧光探针与商品荧光仪器联合使用可以实现对环境氟离子的灵敏快速检测识别。
本发明的第四方面，提供一种采用如上所述的四配位有机硼化合物制备荧光探针的方法，其中，包括以下步骤：
将所述四配位有机硼化合物溶解在溶剂(如四氢呋喃、氯仿、二氯甲烷等)中，制备成1×10-3mol/L～5×10-3mol/L(如1×10-3mol/L)的储备液；
按每30μL储备液加入2970μL溶剂的用量，将储备液稀释为1×10-5mol/L～5×10- 5mol/L(如1×10-5mol/L)溶液，于室温放置2小时，制得荧光探针。
本发明的第五方面，提供一种如上所述的荧光探针在氟离子检测识别中的应用。
附图说明
图1为本发明具体的实施例1～3中所得四配位有机硼化合物的紫外可见吸收和荧光发射光谱图；
图2为本发明具体的实施例1～3中所得四配位有机硼化合物在四氢呋喃溶液和薄膜态的光化学稳定性谱图；
图3为本发明具体的实施例1～3中所得四配位有机硼化合物的聚集诱导发光(AIE)和聚集诱导荧光增强(AIEE)性质研究光谱图；
图4为本发明具体的实施例1～3中所得四配位有机硼化合物在四氢呋喃溶液中对氟离子的荧光传感图；
图5为本发明具体的实施例1～3中荧光探针对氟离子传感的选择性谱图；
图6为本发明具体的实施例1～3中荧光探针对氟离子传感的回复性谱图。
具体实施方式
本发明提供一种四配位有机硼化合物、荧光探针及其制备方法与应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
下面通过具体的实施例对本发明作进一步地说明。
实施例1
化合物1的结构式如下所示：
化合物1的制备步骤如下：
向装有磁力搅拌和回流冷凝装置的圆底烧瓶中以摩尔比1：9：3：586加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环。加热至110℃回流20小时后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为12％K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用体积比为1:9的乙酸乙酯/石油醚体系作为洗脱剂进行柱色谱分离，得到四配位有机硼化合物(即化合物1)。
化合物1通过上述步骤制备得到，所用硼酸衍生物为4-(9H-咔唑-9-基)苯硼酸，产品为黄绿色粉末，产率86％，1H NMR(600MHz,CD2Cl2,25℃):δ8.81(d,1H),8.56(d,1H),8.13(d,4H),7.77(m,6H),7.52(d,4H),7.45(d,4H),7.38(t,5H),7.26(dd,5H)；MS(MALDI-TOF):m/z640.5[M+]。
采用化合物1制备荧光探针的步骤如下：
将化合物1溶解在四氢呋喃中，制备成1×10-3mol/L的储备液；按每30μL储备液加入2970μL四氢呋喃的用量，将储备液稀释为1×10-5mol/L溶液，于室温放置2小时，制得荧光探针，记为探针1。
实施例2
化合物5的结构式如下所示：
化合物5的制备步骤如下：
向装有磁力搅拌和回流冷凝装置的圆底烧瓶中以摩尔比1：9：3：586加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环。加热至120℃回流23小时后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为15％K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用体积比为1:9的乙酸乙酯/石油醚体系作为洗脱剂进行柱色谱分离，得到四配位有机硼化合物(即化合物5)。
化合物5通过上述步骤制备得到，所用硼酸衍生物为4-(9,9-二甲基-9,10二氢吖啶)苯硼酸，产品为黄色粉末，产率55％，1H NMR(600MHz,CDCl3,25℃):δ8.78(d,1H),8.53(d,1H),7.76(dd,6H),7.42(d,4H),7.35(d,1H),7.30(d,1H),7.26(d,4H),6.91(dt,8H),6.32(d,4H),1.67(s,12H)；13C NMR(150MHz,CDCl3,25℃):δ158.6,141.1,140.0,139.5,139.2,137.7,134.4,133.1,130.2,129.8,128.6,126.2,125.0,123.1,120.2,114.2,112.7,110.1,35.9,31.2；MS(MALDI-TOF):m/z 724.6[M+]。
采用化合物5制备荧光探针的步骤如下：
将化合物5溶解在四氢呋喃中，制备成1×10-3mol/L的储备液；按每30μL储备液加入2970μL四氢呋喃的用量，将储备液稀释为1×10-5mol/L溶液，于室温放置2小时，制得荧光探针，记为探针5。
实施例3
化合物9的结构式如下所示：
化合物9的制备步骤如下：
向装有磁力搅拌和回流冷凝装置的圆底烧瓶中以摩尔比1：9：3：586加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环。加热至110℃回流20小时后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为10％K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用体积比为1:9的乙酸乙酯/石油醚体系作为洗脱剂进行柱色谱分离，得到四配位有机硼化合物(即化合物9)。
化合物9通过上述步骤制备得到，所用硼酸衍生物为4-(10H-吩噁嗪-10)苯硼酸，产品为橙色粉末，产率41％，1H NMR(600MHz,CDCl3,25℃):δ8.72(d,J＝4.99Hz,1H),8.53(d,J＝8.29Hz,1H),7.74(ddd,J＝6.47,18.48,36.74Hz,6H),7.35(d,1H),7.28(d,J＝7.65Hz,1H),7.24(s,2H),6.59(m,14H),5.94(d,J＝6.72Hz,4H)；MS(MALDI-TOF):m/z672.6[M+]。
采用化合物9制备荧光探针的步骤如下：
将化合物9溶解在四氢呋喃中，制备成1×10-3mol/L的储备液；按每30μL储备液加入2970μL四氢呋喃的用量，将储备液稀释为1×10-5mol/L溶液，于室温放置2小时，制得荧光探针，记为探针9。
实施例4
化合物11的结构式如下所示：
化合物11的制备步骤如下：
向装有磁力搅拌和回流冷凝装置的圆底烧瓶中以摩尔比1：9：3：586加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环。加热至110℃回流20小时后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为10％K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用体积比为1:9的乙酸乙酯/石油醚体系作为洗脱剂进行柱色谱分离，得到四配位有机硼化合物(即化合物11)。
化合物11通过上述步骤制备得到，所用硼酸衍生物为4-(10H-吩噻嗪-10)苯硼酸，产品为橙色粉末，产率45％，MS(MALDI-TOF):m/z 704.7[M+]。
实施例5
化合物13的结构式如下所示：
化合物13的制备步骤如下：
向装有磁力搅拌和回流冷凝装置的圆底烧瓶中以摩尔比1：9：3：586加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环。加热至110℃回流20小时后，减压除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用质量百分含量为10％K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用体积比为1:9的乙酸乙酯/石油醚体系作为洗脱剂进行柱色谱分离，得到四配位有机硼化合物(即化合物13)。
化合物13通过上述路线制备，所用硼酸衍生物为4-硼酸三苯胺，产品为橙黄色粉末，产率51％，MS(MALDI-TOF):m/z 644.5[M+]。
实施例6
在本实施例中，在四配位有机硼化合物的合成步骤中，8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1：10：3：600，乙酸乙酯-石油醚体系中乙酸乙酯与石油醚的体积比为1:9；其他步骤与实施例1相同。
实施例7
在本实施例中，在四配位有机硼化合物的合成步骤中，8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1：9：4：600，乙酸乙酯-石油醚体系中乙酸乙酯与石油醚的体积比为1:9；其他步骤与实施例1相同。
实施例8
在本实施例中，在四配位有机硼化合物的合成步骤中，8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1：9：3：700，乙酸乙酯-石油醚体系中乙酸乙酯与石油醚的体积比为1:9；其他步骤与实施例1相同。
为了验证本发明的技术效果，发明人对实施例1～3中所合成的四配位有机硼化合物对氟离子的检测识别进行了探索。
参见图1，为四配位有机硼化合物的紫外可见吸收和荧光发射光谱图，其中a为四配位有机硼化合物的四氢呋喃溶液的紫外可见吸收和荧光发射光谱，b为四配位有机硼化合物薄膜态的发射光谱。由紫外可见吸收光谱可以看出，所测试四配位有机硼化合物存在两个特征吸收带，其中，最大吸收波长为400nm的特征吸收带，其为8-羟基喹啉硼结构单元的特征吸收；从溶液态荧光发射光谱可看出其最大发射波长均为500nm，且为没有精细结构的宽峰；从薄膜态荧光发射光谱可看出实施例1～3所得化合物的最大发射波长依次为504、520和556nm，依次表现为绿光发射、黄绿光发射和橙黄光发射，同样为没有精细结构的宽峰。
图2为所得四配位有机硼化合物在四氢呋喃溶液和薄膜态的光化学稳定性谱图，从图中可以看出所得的四配位有机硼化合物均表现出优良的光化学稳定性，成功地规避了“光漂白”现象，为其后续的实际应用奠定了坚实的基础。
图3为所得四配位有机硼化合物的聚集诱导发光(AIE)和聚集诱导荧光增强(AIEE)性质研究光谱图，a为实施例1～3所得四配位有机硼化合物在四氢呋喃/水体系中的AIE性质光谱图，b为实施例1～3所得四配位有机硼化合物作为粘度探针性质谱图。从所得结果可知，实施例1所得四配位有机硼化合物表现为AIEE的特性，而实施例2和3所得四配位有机硼化合物表现为AIE特性，所得四配位有机硼化合物对粘度均有一定程度的响应，可作为粘度探针使用。
图4为实施例1～3所得四配位有机硼化合物在四氢呋喃溶液中对氟离子的荧光传感图。所检测的氟离子浓度分别为0.3μM、0.6μM、2μM、3μM、5μM、8μM、10μM、15μM、25μM、40μM、60μM、80μM、100μM、125μM和150μM。由图表明随着氟离子浓度的增加，实施例1所得四配位有机硼化合物的荧光强度被显著猝灭，当氟离子浓度达到80μM时，荧光强度基本不再降低，猝灭程度达到最大；与之不同的是，实施例2和3所得四配位有机硼化合物的荧光强度随着氟离子的增加显著增强，表现为“点亮型”荧光传感。
图5为上述荧光探针对氟离子传感的选择性谱图，将氯离子(Cl-)、溴离子(Br-)、碘离子(I-)、硝酸根(NO3 -)、高氯酸根(ClO4 -)、四氟硼酸根(BF4 -)、六氟磷酸根(PF6 -)、醋酸根(AcO-)和磷酸二氢跟(H2PO4 -)等作为干扰进行测试。由图中可以看出，该类探针对氟离子的检测具有优良的检测选择性，其他阴离子的存在不会对检测结果造成干扰，为其能够实际应用奠定了基础。
图6为上述探针对氟离子传感的回复性谱图，向含有氟离子的探针溶液中加入三氟化硼乙醚后，其荧光基本可以回复至最初状态，说明其具有良好的检测可逆性，对实际应用无疑具有重要的意义。
综上所述，本发明将具有优异光电性能的主族元素硼及8-羟基喹啉单元同时引入到共轭小分子中，得到一系列四配位有机硼化合物。该四配位有机硼化合物具有优良的溶解性、优异的光物理性质和光化学稳定性。采用该四配位有机硼化合物制备的荧光探针可以实现对氟离子的高灵敏度、高选择性，更为重要的是，可逆地检测识别。本发明该四配位有机硼化合物的制备方法具有操作简便、反应条件温和，可以进行大规模生产以及对底物适应性强等突出优点。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (7)
1.一种四配位有机硼化合物，其特征在于，所述四配位有机硼化合物的结构式如下所示：
其中，
选自如下结构中的一种：
2.一种四配位有机硼化合物，其特征在于，所述四配位有机硼化合物选自如下结构中的一种：
3.一种权利要求1-2任一项所述的四配位有机硼化合物的制备方法，其特征在于，包括步骤：
向装有磁力搅拌和回流冷凝装置的烧瓶中加入8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环；
加热至110～120℃回流20～24小时后，除去溶剂，粗产品溶于乙酸乙酯和水中，分离的有机相用K3PO4溶液和食盐水进行多次洗涤，无水硫酸钠干燥，旋干，用洗脱剂进行柱色谱分离，得到所述四配位有机硼化合物；所述硼酸衍生物选自4-(9H-咔唑-9-基)苯硼酸、4-(9,9-二甲基-9,10二氢吖啶)苯硼酸或4-(10H-吩噁嗪-10)苯硼酸。
4.根据权利要求3所述的四配位有机硼化合物的制备方法，其特征在于，所述8-羟基喹啉、硼酸衍生物、K3PO4和1，4-二氧六环的摩尔比为1:(9～11)：(3～5)：(500～700)；
所述洗脱剂由乙酸乙酯与石油醚按照体积比1:9配制而成。
5.一种荧光探针，其特征在于，包括权利要求1-2任一项所述的四配位有机硼化合物。
6.一种采用权利要求1-2任一项所述的四配位有机硼化合物制备荧光探针的方法，其特征在于，包括以下步骤：
将所述四配位有机硼化合物溶解在溶剂中，制备成1×10-3mol/L～5×10-3mol/L的储备液；
按每30μL储备液加入2970μL溶剂的用量，将储备液稀释为1×10-5mol/L～5×10-5mol/L溶液，于室温放置2小时，制得荧光探针。
7.一种权利要求5所述的所述的荧光探针在氟离子检测识别中的应用。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322007A (ja) * | 2001-04-27 | 2002-11-08 | Shionogi & Co Ltd | 有機ホウ素化合物を含有する植物用殺線虫剤 |
| WO2005123095A1 (en) * | 2004-06-14 | 2005-12-29 | Anacor Pharmaceuticals, Inc. | Anti-parasitic uses of borinic acid complexes |
| CN1972694A (zh) * | 2004-06-14 | 2007-05-30 | 安纳考尔医药公司 | 含二烃基代硼酸络合物的抗生素及使用方法 |
| FR3021050A1 (fr) * | 2014-05-16 | 2015-11-20 | Univ Bordeaux | Procede de preparation d'acide boriniques |
| US20180298034A1 (en) * | 2015-03-10 | 2018-10-18 | Korea Research Institute Of Chemical Technology | Method for Preparing Four-Coordinated Organic Boron Compound |
| CN109608483A (zh) * | 2018-12-17 | 2019-04-12 | 长安大学 | 一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用 |
-
2020
- 2020-08-28 CN CN202010886374.3A patent/CN111995634B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322007A (ja) * | 2001-04-27 | 2002-11-08 | Shionogi & Co Ltd | 有機ホウ素化合物を含有する植物用殺線虫剤 |
| WO2005123095A1 (en) * | 2004-06-14 | 2005-12-29 | Anacor Pharmaceuticals, Inc. | Anti-parasitic uses of borinic acid complexes |
| CN1972694A (zh) * | 2004-06-14 | 2007-05-30 | 安纳考尔医药公司 | 含二烃基代硼酸络合物的抗生素及使用方法 |
| FR3021050A1 (fr) * | 2014-05-16 | 2015-11-20 | Univ Bordeaux | Procede de preparation d'acide boriniques |
| US20180298034A1 (en) * | 2015-03-10 | 2018-10-18 | Korea Research Institute Of Chemical Technology | Method for Preparing Four-Coordinated Organic Boron Compound |
| CN109608483A (zh) * | 2018-12-17 | 2019-04-12 | 长安大学 | 一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用 |
Non-Patent Citations (2)
| Title |
|---|
| "Highly emissive B←N unit containing four-coordinate C,N-Chelated organoboron compound for the detection of fuoride ions";Ni Yan等;《Dyes and Pigments》;20190330;第166卷;第410-415页 * |
| "氟离子荧光探针设计、合成与应用的新进展";张惠敏 等;《有机化学》;20161231;第36卷;第2559-2582页 * |
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