CN107417694B - 一种比色和荧光双响应型铋离子检测探针及其制备方法 - Google Patents
一种比色和荧光双响应型铋离子检测探针及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种比色和荧光双响应型铋离子检测探针，具有以下化学式组成：本发明还公开了比色和荧光双响应型铋离子检测探针的制备方法，步骤1、将罗丹明6G与乙二胺反应制备罗丹明6G乙二胺中间体；步骤2、将步骤1得到的罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应，得到中心对称的探针分子产物；步骤3、将步骤2得到的探针分子产物经过滤，然后采用有机溶剂重结晶得到淡红色固体探针分子，即比色和荧光双响应型铋离子检测探针，本发明解决了现有技术中Bi3+检测技术存在的空白，提供一种具有选择性好、灵敏度高、响应速度快等特点的有机小分子类Bi3+比色/荧光探针。
Description
技术领域
本发明属于化学传感技术领域，具体涉及一种比色和荧光双响应型铋离子检测探针，本发明还涉及比色和荧光双响应型铋离子检测探针的制备方法。
背景技术
铋金属化合物具有多样而有趣的生物活性，特别是在治疗消化系统疾病领域已获得实际临床应用。例如：碱式硝酸铋(次硝酸铋)，从中世纪开始已被用于治疗胃肠道不适；碱式水杨酸铋(Pepto-Bismol)被广泛用于治疗腹泻和消化不良；胶体次枸橼酸铋(De-Nol)已成功用于治疗十二指肠溃疡等。此外，铋离子与特殊有机配体形成的配合物，有望在癌症的放疗治疗中获得应用；而掺杂铋离子的单分散NaGdF4有望应用于CT生物成像之中。
然而，事实证明铋离子(以下采用Bi3+)对生物体并非完全无害。Bi3+在大脑及肾脏中富集，会导致神经中毒及肾脏损伤。
目前已经报道的Bi3+的检测方法多为通用型检测方法：如电感耦合等离子发射光谱法、原子荧光光谱法以及电化学方法等。然而，更为简便、高效、专一的有机小分子类Bi3+探针尚未见报道。
发明内容
本发明的目的是提供一种比色和荧光双响应型铋离子检测探针，解决了现有技术中Bi3+检测技术存在的空白，提供一种具有选择性好、灵敏度高、响应速度快等特点的有机小分子类Bi3+比色/荧光探针。
本发明所采用的第一技术方案是，一种比色和荧光双响应型铋离子检测探针，具有以下结构式：
本发明所采用的第二技术方案是，一种比色和荧光双响应型铋离子检测探针的制备方法，具体按照以下步骤实施：
步骤1、将罗丹明6G与乙二胺反应制备罗丹明6G乙二胺中间体；
步骤2、将步骤1得到的罗丹明6G乙二胺中间体与均苯四甲酸酐于有机溶剂中、加热条件下发生双分子胺解反应，合成中心对称的探针分子，反应液经过滤得到粗产物，粗产物采用有机溶剂重结晶得到淡红色探针分子。
本发明第二技术方案的特点还在于，
步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐的摩尔比为2.0:(0.9～1.1)。
步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的反应温度为10～100℃。
步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的加热方法采用微波加热或者常规加热。
步骤2中的有机溶剂为乙腈、四氢呋喃、N,N-二甲基甲酰胺或N-甲基吡咯烷酮中的一种。
步骤3中重结晶采用溶剂为乙醇、乙腈、二氯甲烷中的一种。
本发明的有益效果是，一种比色和荧光双响应型铋离子检测探针，填补了该类型Bi3+检测方法的空白，可根据探针溶液颜色的变化，定性地鉴别Bi3+；使用荧光光谱仪及紫外可见光谱仪可定量地测定Bi3+浓度，解决了现有Bi3+检测技术中存在的无法特异性识别、检测操作复杂、检测灵敏度低等技术缺陷。
附图说明
图1是探针分子的核磁共振氢谱图；
图2是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应曲线图，横坐标为波长、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对荧光强度；
图3是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应拟合曲线图，横坐标为浓度、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对荧光强度；
图4是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应曲线图，横坐标为波长、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对紫外吸收强度；
图5是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应拟合曲线，横坐标为浓度、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对紫外吸收强度；
图6是20μM/L探针溶液对同等浓度(20μM)不同离子的响应图，横坐标为离子种类、纵坐标为探针溶液加入同等浓度不同离子后(PH约为7.0)的相对荧光强度；
图7是其它离子对Bi3+检测的干扰测试图；
图8是Bi3+检测响应时间测试图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明一种比色和荧光双响应型铋离子检测探针，具有以下结构式：
一种比色和荧光双响应型铋离子检测探针的制备方法，具体按照以下步骤实施：
步骤1、将罗丹明6G与乙二胺反应制备罗丹明6G乙二胺中间体；
步骤2、将所述步骤1得到的罗丹明6G乙二胺中间体与均苯四甲酸酐于有机溶剂中、加热条件下发生双分子胺解反应，合成中心对称的探针分子，反应液经过滤得到粗产物，粗产物采用有机溶剂重结晶得到淡红色探针分子，其中，罗丹明6G乙二胺中间体与均苯四甲酸酐的摩尔比为2.0:0.9～1.1，罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的反应温度为10～100℃，罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的加热方法采用微波加热或者常规加热，采用的有机溶剂为乙腈、四氢呋喃、N,N-二甲基甲酰胺或N-甲基吡咯烷酮中的一种，重结晶采用溶剂为乙醇、乙腈、二氯甲烷中的一种。
一种比色和荧光双响应型铋离子检测探针的制备方法如下：
式1为罗丹明6G乙二胺中间体，式2为均苯四甲酸酐，式3为比色和荧光双响应型铋离子检测探针。
本发明一种比色和荧光双响应型铋离子检测探针的检测原理如下：
本发明利用探针分子与铋离子(以下采用Bi3+)特异性的螯合反应，打开探针分子中螺环，而导致探针分子共轭体系发生变化，使其在紫外和荧光光谱上产生显著地变化，且该变化可通过肉眼辨别(探针溶液由无色变为红色)。
本发明所述探针的使用方法并无特殊限制，通常可以在室温下将探针分子溶解在乙醇和乙腈混合溶液(1:4，v/v)中进行测试。配置浓度为20μM/L的探针溶液；采用去离子水配置10mM/L的待测离子硝酸盐水溶液(硝酸钠、硝酸银、硝酸铅、硝酸钾、三水合硝酸铜、六水合硝酸镍、六水合硝酸锌、四水合硝酸镉、硫酸铁、六水合硝酸钴、一水合硝酸汞2mM/L、五水合硝酸铋2mM/L)；探针溶液中加入离子溶液后PH值约为7.0。
该探针对于不同浓度的Bi3+产生响应，呈现良好的线性关系。在Bi3+浓度为10-35μM范围内可采用荧光检测方法对Bi3+进行定量检测，Bi3+最低检测浓度为2.69nM/mL(激发波长为500nm)；在Bi3+浓度为15-45μM范围内，可采用紫外可见吸收检测方法对Bi3+进行定量检测，Bi3+最低检测浓度为0.69nM/mL；此外，除Bi3+外其它金属离子对Bi3+的测定结果几乎无干扰，检测方法可靠稳定。
为了更清楚地说明本发明所述探针的检测性能、特点及实施例，下面对所需附图作简要地介绍。值得指出的是，以下附图仅仅是本发明的实施例，对于本领域普通技术人员无需付出创造性劳动，也能根据提供的附图和数据获得其它类似附图。
附图中，图1是探针分子的核磁共振氢谱，从该谱图可以看出该分子为一中心对称分子，化学位移δ＝7.603处的氢核磁信号为均苯四甲酸酐上a氢的信号峰,，其它各信号峰归属明确。
实施例1
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，0.218mg，1.0mmol)及预先干燥的乙腈(10ml)于双颈反应瓶中，油浴加热下60℃反应24小时，反应瓶中有大量淡红色固体生成。TLC监测反应，反应完毕后，冷却、抽滤，滤饼用少量乙腈和水的混合溶剂洗涤两次。滤液旋蒸除去溶剂，固体用乙醇重结晶得到淡红色探针分子固体0.92g，收率81％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例2：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，196mg，0.9mmol)及预先干燥的乙腈(10ml)于双颈反应瓶中，油浴加热下60℃反应24小时，反应瓶中有大量淡红色固体生成。TLC监测反应，反应完毕后，冷却、抽滤，滤饼用少量乙腈和水的混合溶剂洗涤两次。滤液旋蒸除去溶剂，固体用乙醇重结晶得到淡红色探针分子固体0.85g，收率75％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例3：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，239mg，1.1mmol)及预先干燥的乙腈(10ml)于双颈反应瓶中，油浴加热下60℃反应24小时，反应瓶中有大量淡红色固体生成。TLC监测反应，反应完毕后，冷却、抽滤，滤饼用少量乙腈和水的混合溶剂洗涤两次。滤液旋蒸除去溶剂，固体用乙醇重结晶得到淡红色探针分子固体0.88g，收率78％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例4：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，0.218mg，1.0mmol)及预先干燥的乙腈(10ml)于双颈反应瓶中，油浴加热下80℃反应24小时，反应瓶中有大量淡红色固体生成。TLC监测反应，反应完毕后，冷却、抽滤，滤饼用少量乙腈和水的混合溶剂洗涤两次。滤液旋蒸除去溶剂，固体用乙醇重结晶得到淡红色探针分子固体0.81g，收率72％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例5：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，0.218mg，1.0mmol)及预先干燥的乙腈(10ml)于双颈反应瓶中，10℃条件下反应24小时，反应瓶中有淡红色固体生成。反应液抽滤，滤饼用少量乙醇和水的混合溶剂洗涤两次。滤液旋蒸除去溶剂，固体用乙腈重结晶得到淡红色探针分子固体0.62g，收率55％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例6：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，0.218mg，1mmol)及预先干燥的N,N-二甲基甲酰胺(8ml)于双颈反应瓶中，100℃条件下反应12小时。TLC监测反应，反应完毕后，抽滤，滤饼用少量乙醇和水的混合溶剂洗涤两次。滤液中加入50ml饱和食盐水，有大量固体析出，抽滤，滤饼用少量乙醇和水的混合溶剂洗涤两次。固体用二氯甲烷重结晶得到淡红色探针分子固体0.69g，收率61％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例7：
称取罗丹明6G乙二胺中间体(式1，912mg，2.0mmol)，均苯四甲酸酐(式2，0.218mg，1mmol)及预先干燥的N-甲基吡咯烷酮(8ml)于双颈反应瓶中，100℃条件下反应12小时。TLC监测反应，反应完毕后，抽滤，滤饼用少量乙醇和水的混合溶剂洗涤两次。滤液中加入50ml饱和食盐水，有大量固体析出，抽滤，滤饼用少量乙醇和水的混合溶剂洗涤两次。固体用二氯甲烷重结晶得到淡红色探针分子固体0.73g，收率65％。
产物的结构表征数据如下：1H NMR(400MHz,DMSO-d6)(T＝298K)δ:ppm13.18(s,2H,COOH),8.33(s,2H,-CONHR),7.79(m,2H),7.60(s,2H),7.50(m,4H),6.94(t,J＝3.6Hz,2H),6.26(s,4H),6.13(s,4H),5.10(s,4H,ArNH-R),3.14(m,12H),2.87(s,4H),1.86(s,12H),1.20(t,J＝7.2Hz,12H)；IR(KBr)vmax/cm-13428,2951,1687,1673,1640,1620,1517,1468,1420,1380,1270；MS(ESI)calcd.for C66H67N8O10[M+H]+1131.5,found:1131.5。
实施例8：
本实施例为实施例1～7制得的探针分子，对不同浓度Bi3+的荧光响应。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为20μM的探针分子溶液，再分向探针溶液中加入Bi3+，使得Bi3+浓度分别为0μM、10μM、15μM、20μM、25μM、30μM、35μM、40μM、45μM、50μM、55μM、60μM，并且探针溶液体积变化可以忽略。以波长为500nm的激发光，测定加入Bi3+前后探针溶液的荧光光谱变化，结果如图2所示。
图2是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应，横坐标为波长、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对荧光强度，从图中可以看出，随着Bi3+离子浓度的增加，该探针分子在560nm处的荧光强度逐渐增强，Bi3+浓度为40μM时接近饱和。以不同浓度Bi3+对应的相对荧光强度作图，根据拟合曲线可知，Bi3+浓度在10-35μM范围内时与荧光强度成线性关系，R2＝0.9864，检出限为2.69nM/mL。本实施例所得实验结果显示，该探针分子可以用于定量检测Bi3+，且有较高的灵敏度。
实施例9
本实施例为实施例1～7制得的探针分子，对不同浓度Bi3+的紫外可见吸收响应。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为20μM的探针分子溶液，再分向探针溶液中加入Bi3+，使得Bi3+浓度分别为0μM、10μM、15μM、20μM、25μM、30μM、35μM、40μM、45μM、50μM、55μM、60μM，并且探针溶液体积变化可以忽略。测定加入Bi3+前后探针溶液的紫外可见吸收光谱变化，结果如图4所示。
图4是20μM/L探针溶液对不同浓度Bi3+(0-60μM)的响应，横坐标为波长、纵坐标为探针溶液加入Bi3+溶液后(PH约为7.0)的相对紫外吸收强度，从图中可以看出，随着Bi3+离子浓度的增加，该探针分子在523nm处的吸收逐渐增强，Bi3+浓度为40μM时接近饱和。以不同浓度Bi3+对应的相对吸收强度作图得到图5，根据拟合曲线可知，Bi3+浓度在15-45μM范围内时与紫外吸收强度成线性关系，R2＝0.9955，检出限为0.69nM/mL。本实施例所得实验结果显示，该探针分子可以采用紫外可见吸收光谱法定量检测Bi3+，且有较高的灵敏度。
实施例10
本实施例为实施例1～7制得的探针分子，对相同浓度的不同离子的荧光响应测试。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为20μM的探针分子溶液，再分向探针溶液中加入Na+、Ag+、K+、Cu2+、Pb2+、Ni2+、Zn2+、Cd2+、Fe3+、Co2+、Hg2+、Bi3+等离子，使得离子浓度均为20μM并且保持探针溶液体积变化可忽略。测定探针溶液加入不同离子后的相对荧光强度，结果如图6所示。从图6中可以看出，仅有加入Bi3+的探针溶液，荧光显著增强。其它离子与探针分子均无明显作用。本实施例所得实验结果显示，该探针分子可以特异性地识别并检测出Bi3+。
实施例11
本实施例为实施例1～7制得的探针分子，进行Bi3+检测时，其它离子对Bi3+荧光响应的干扰测试。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为20μM的探针分子溶液，再分别向探针溶液中加入60μM Bi3+进行荧光测试，而后分别加入60μM的Na+、Ag+、K+、Cu2+、Pb2+、Ni2 +、Zn2+、Cd2+、Fe3+、Co2+、Hg2+等离子，并且保持探针溶液体积变化可忽略。采用荧光光谱仪测试加入其它离子前后荧光变化，结果如图7所示。图7是其它离子对Bi3+检测的干扰测试，20μM/L探针溶液中加入Bi3+(60μM)和其它离子(60μM)；横坐标为加入其它离子的情况，纵坐标为相对荧光强度，从图7可以看出，其它离子的加入对Bi3+导致的荧光增强无明显影响。本实施例所得实验结果表明，该探针分子可以特异性地识别并检测出Bi3+，其它离子的干扰可忽略不计。
实施例12
本实施例为实施例1～7制得的探针分子，对Bi3+荧光测试响应时间。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为20μM的探针分子溶液。室温下，向探针溶液中加入60μM Bi3+进行荧光测试，分别记录加入Bi3+后每隔10秒的荧光强度，结果如图8所示，图8是Bi3+检测响应时间测试，20μM/L探针溶液中加入Bi3+(60μM)，横坐标为加入离子的时间，纵坐标为相对荧光强度，从图8可以看出：加入Bi3+后，10秒已经开始响应，到300秒已经接近完全响应。本实施例所得实验结果表明，该探针分子可以快速地与Bi3+发生作用，给出荧光信号，完全响应时间约为5分钟；探针溶液颜色由无色透明逐渐变为红色，可进行可视化检测。
实施例13
本实施例为实施例1～7制得的探针分子，在检测含铋药物中的应用实例。
采用体积比为1:4的乙醇-乙腈混合溶液配制浓度为100μM的探针分子溶液。室温下，加入到枸橼酸铋钾溶液中，溶液在556nm处出现一荧光信号，溶液颜色由无色快速变成粉红色。本实施例所得实验结果表明，该探针分子可以快速地与含Bi3+药物发生作用，进行荧光及可视化检测。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种比色和荧光双响应型铋离子检测探针，其特征在于，具有以下结构式：
2.一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，具体按照以下步骤实施：
步骤1、将罗丹明6G与乙二胺反应制备罗丹明6G乙二胺中间体；
步骤2、将所述步骤1得到的罗丹明6G乙二胺中间体与均苯四甲酸酐于有机溶剂中、加热条件下发生双分子胺解反应，合成中心对称的探针分子，反应液经过滤得到粗产物，粗产物采用有机溶剂重结晶得到淡红色探针分子；
所述罗丹明6G乙二胺中间体的结构式为：
所述比色和荧光双响应型铋离子检测探针的结构式为：
3.根据权利要求2所述的一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，所述步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐的摩尔比为2.0:0.9～1.1。
4.根据权利要求2所述的一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，所述步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的反应温度为10～100℃。
5.根据权利要求2所述的一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，所述步骤2中罗丹明6G乙二胺中间体与均苯四甲酸酐发生双分子胺解反应时的加热方法采用微波加热或者常规加热。
6.根据权利要求2所述的一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，所述步骤2中的有机溶剂为乙腈、四氢呋喃、N,N-二甲基甲酰胺或N-甲基吡咯烷酮中的一种。
7.根据权利要求2所述的一种比色和荧光双响应型铋离子检测探针的制备方法，其特征在于，所述步骤2中重结晶采用溶剂为乙醇、乙腈、二氯甲烷中的一种。
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