CN111233882B - 几种4-（5-四唑巯丙氧基）土甘草a型荧光探针及其制备方法 - Google Patents
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Abstract
本发明公开了六种具有不同取代基的4‑(5‑四唑巯丙氧基)土甘草A型荧光探针及其制备方法和应用，其结构式为
本发明的土甘草A‑1，2，3，4‑巯基四唑型荧光探针结合了香豆素类以及四唑衍生物优良荧光特性，在DMSO/H2O溶液中对铅离子表现出较高的选择性和灵敏度，出现明显的增色效应，能够达到微量检测铅离子的目的。
Description
技术领域
本发明涉及荧光探针技术领域，更具体地说，本发明涉及几种具有不同取代基的4-(5-四唑巯丙氧基)土甘草A型荧光探针及其制备方法和应用。
背景技术
有机荧光探针与特定客体离子或分子相互作用后，可以产生显著的荧光变化，具有高选择性和高灵敏度的特点，现在已被广泛应用于各类离子和小分子的传感与检测。通过对有较好发光能力的有机探针骨架进行适当的化学官能团修饰，可以得到对特定底物高选择性和高灵敏性的探针。香豆素类衍生物荧光特性优良，具有大的斯托克斯位移和高的荧光量子产率、光稳定性好等诸多优点，以香豆素为荧光团的小分子荧光探针近年来逐渐成为一个新兴的研究热点，在离子检测、生物分子探针等领域展现出很好的应用前景。
铅是一种常见环境污染物。其主要来源为汽车尾气、蓄电池、冶炼、五金、电镀等行业的废物废水排放。铅生物半衰期长，在人体中容易积聚，对人体的血液系统、消化系统、生殖系统、泌尿系统均有较大损害。高浓度铅还可造成儿童脊髓运动细胞损害，导致运动机能下降。因此，建立痕量铅离子分析技术对环境保护十分重要。
因此，亟需设计一种能用于痕量铅离子浓度检测的荧光探针，达到微量检测铅离子的目的。
发明内容
本发明的一个目的是解决上述缺陷，并提供至少后面将说明的优点。
本发明的另一个目的是提供一种结构简单、易于合成，且具有良好荧光性能的4-(5-四唑巯丙氧基)土甘草A型荧光探针。
本发明的另一个目的是提供一种4-(5-四唑巯丙氧基)土甘草A型荧光探针的制备方法。
本发明的另一个目的是提供一种4-(5-四唑巯丙氧基)土甘草A型荧光探针作为探针进行铅离子检测的应用。
为了实现本发明的这些目的和其它优点，本发明提供4-(5-四唑巯丙氧基)土甘草A型荧光探针，其中，结构式如下：
其中，R1为
对应的，化学名分别为：
4-[6’-(1-甲基-5’-四唑巯基)丙氧基]土甘草A衍生物；
4-[6’-(1-苯基-5-四唑巯基)丙氧基]土甘草A衍生物；
4-[6’-(1-对甲氧基苯基-5’-四唑巯基)丙氧基]土甘草A衍生物；
4-[6’-(1-对乙基苯基-5’-四唑巯基)丙氧基]土甘草A衍生物；
4-[6’-(1-对氯苯基-5’-四唑巯基)丙氧基]土甘草A衍生物；
4-[6’-(1-间硝基苯基-5’-四唑巯基)丙氧基]土甘草A衍生物。
上述化合物以吡喃香豆素土甘草A为荧光基团，结合了香豆素类以及四唑衍生物优良荧光特性，在DMSO/H2O溶液中对铅离子表现出较高的选择性和灵敏度，出现明显的增色效应，能够达到微量检测铅离子的目的。
一种4-(5-四唑巯丙氧基)土甘草A型荧光探针的制备方法，其中，包括：
步骤一、以土甘草A、1，3-二溴丙烷和碳酸钾为原料，在溶剂中进行回流反应，反应结束后，趁热过滤，滤液静置析晶，抽滤，无水乙醇洗涤，得到中间产物4-(3-溴丙氧基)土甘草A；
步骤二、在反应溶剂和催化剂存在的条件下，将中间产物4-(3-溴丙氧基)土甘草A分别和不同取代基的巯基四唑衍生物经回流反应，重结晶，即分别得到相应的目标产物。
具体的合成路线如下：
上述方法原料易得，合成简单，便于量产。
优选的是，所述的4-(5-四唑巯丙氧基)土甘草A型荧光探针的制备方法中，所述不同取代基的巯基四唑衍生物的制备方法为：
取异硫氰酸苯酯衍生物溶于纯水中，加入叠氮化钠，回流反应，利用薄层色谱法(TLC)跟踪反应，用体积比＝2：1及4：1的石油醚和乙酸乙酯为展开剂，苯酯层消失时停止反应，冷却至室温时逐滴滴加浓盐酸并搅拌至pH 为3，析出大量白色沉淀，抽滤，取滤饼加入纯水至pH 4～5，抽滤，滤饼用无水乙醇重结晶，即得到相应的巯基四唑衍生物；
合成途径如下：
其中，所述R1分别为-CH2，-C6H5，-OCH3，-C2H5，-Cl，-NO2中的一种。
优选的是，所述的4-(5-四唑巯丙氧基)土甘草A型荧光探针的制备方法中，所述步骤一中的溶剂为乙腈，使用乙醇进行洗涤。
优选的是，所述的4-(5-四唑巯丙氧基)土甘草A型荧光探针的制备方法中，所述步骤二中，使用四氢呋喃为反应溶剂，三乙胺(TEA)为催化剂，使用乙酸乙酯进行重结晶。
一种4-(5-四唑巯丙氧基)土甘草A型荧光探针作为荧光探针检测铅离子的应用。该类化合物在水、DMSO、缓冲液等溶剂中选择性的结合金属铅离子，其紫外-可见光出现较大程度增色效应或者最大吸收峰出现变化。
作为羧基的生物等电体，四唑具有较低的毒性和生物兼容性，在化学、生物等领域中都有广泛的应用。
本发明至少包括以下有益效果：
本发明的4-(5-四唑巯丙氧基)土甘草A型荧光探针结合了香豆素类衍生物荧光特性，结合了香豆素类以及四唑衍生物优良荧光特性，在DMSO/H2O 溶液中对铅离子表现出较高的选择性和灵敏度，出现明显的增色效应，能够达到微量检测铅离子的目的。
本发明的制备方法原料易得，合成简单，便于量产。
本发明的4-(5-四唑巯丙氧基)土甘草A型荧光探针结构相对简单，易于合成，在DMSO/H2O溶液中对铅离子表现出很高的选择性和灵敏度，较其他离子对铅离子出现明显的增色效应，并且最大吸收峰出现变化，可用作一种铅离子荧光探针使用。
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为本发明所述的4-(5-四唑巯丙氧基)土甘草A型荧光探针4a-4f对铅离子的选择性。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
实施例1
4-(5-四唑巯丙氧基)土甘草A型荧光探针制备步骤如下：
一、中间产物4-(3-溴丙氧基)土甘草A的制备
在100mL三颈圆底烧瓶中加入土甘草A 0.1250g(0.25mmol)及5.0mL 乙腈溶剂，在一定温度下溶解，加入1，3-二溴丙烷0.334mL(3.30mmol)，再加入无水碳酸钾0.0909g(0.66mmol)，80℃下回流近10h，利用薄层色谱法(TLC)跟踪反应，反应结束后，趁热过滤，滤液静置析晶，抽滤，无水乙醇洗涤，得到4-(3-溴丙氧基)土甘草A 0.034g(0.067mmol)，20.26％。
二、巯基四唑衍生物的制备
取不同取代基的异硫氰酸苯酯衍生物3.0mmol溶于纯水中，加入4.5 mmol叠氮化钠，回流2.5-9h，利用薄层色谱法(TLC)跟踪反应，用体积比＝2：1及4：1的石油醚和乙酸乙酯为展开剂，苯酯层消失时停止反应，反应液冷却至室温时逐滴滴加浓盐酸并搅拌至pH为3，析出大量白色沉淀，抽滤，取滤饼加入纯水至pH 4～5，抽滤，滤饼用无水乙醇重结晶，得到相应的巯基四唑衍生物。
合成如下：
其中，R1分别为-CH2，-C6H5，-OCH3，-C2H5，-Cl，-NO2；对应的巯基四唑衍生物分别标记为3a、3b、3c、3d、3e、3f。
三、4-(5-四唑巯丙氧基)土甘草A型荧光探针(4a-4f)的制备
在50mL三颈圆底烧瓶中加入4-(3-溴丙氧基)土甘草A0.125g(0.25 mmol)及四氢呋喃5.0mL，油浴加热，溶解后，加入对应的巯基四唑衍生物(3a-3f)0.375mmol，三乙胺0.052mL(0.375mmol)，于62℃下回流反应，利用薄层色谱法(TLC)跟踪反应，趁热过滤，滤液旋干，乙酸乙酯重结晶，得到对应的目标产物4-(5-四唑巯丙氧基)土甘草A型荧光探针(4a-4f)。
目标产物4-(5-四唑巯丙氧基)土甘草A型荧光探针(4a-4f)的物理性质表征如下表1所示：
表1化合物(4a-4f)的产率、熔点以及光谱数据
实施例2
S1、准确称取实施例1制备的4-(5-四唑巯丙氧基)土甘草A型荧光探针4a-4f，以DMSO和3-吗啉丙磺酸缓冲溶液(MOPS,10mM,pH＝7.0).(8:2， v/v)为溶剂溶解前述4a-4f，分别配制100mL的探针储备液(0.6667× 10-4mol/L)；
S2、以去离子水为溶剂，配制0.01mol/L的Cu2+、Fe3+、Zn2+、Na+、Cd2+、 Ca2+、Mg2+、Mn2 +、Pb2+、Ni2+、Co2+、Ag+(均为高氯酸盐)金属阳离子储备液，分别置于10mL容量瓶中。
S3、取多个样品瓶，操作如下：
对照组：在其中一个样品瓶中加入(2mL+20uL)的上述探针储备液；
实验组：在剩余每一个样品瓶中分别加入2mL上述探针储备液、再加入一种上述的金属阳离子储备液20uL，混合均匀；
待对照组和实验组稳定10min之后，分别转移至比色皿中，依次测定紫外-可见光光谱，见图1。
由图1可知，六种荧光探针对Pb2+具有选择性识别作用，各化合物和Pb+ 结合后均有明显的增色效应，特别是化合物4a，4b，和4e，吸光度明显变大，这三个化合物化合物的最大吸收峰均处于352、268，259，和235cm-1，未加金属时吸光度0.5539，加了铅离子后其吸光度分别增加到了0.9936、0.7976、 0.8906。化合物4f虽吸光度变化不大，但最大吸收峰发生改变，352cm-1的吸收峰消失，235cm-1的吸收峰明显增大，说明可能形成了新的物质。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用。它完全可以被适用于各种适合本发明的领域。对于熟悉本领域的人员而言，可容易地实现另外的修改。
Claims (6)
1.具有不同取代基的4-（5-四唑巯丙氧基）土甘草A型荧光探针，其中，结构式如下：
其中，R1为
或
或
或
或
或
。
2.一种如权利要求1所述的4-（5-四唑巯丙氧基）土甘草A型荧光探针的制备方法，其中，包括：
步骤一、以土甘草A和1，3-二溴丙烷为原料，碳酸钾为催化剂，在溶剂中进行回流反应，滤液静置析晶，抽滤，洗涤得到中间产物4-（3-溴丙氧基）土甘草A；
步骤二、在反应溶剂和催化剂存在的条件下，将中间产物4-（3-溴丙氧基）土甘草A分别和不同取代基的巯基四唑衍生物经回流反应，重结晶，即分别得到相应的4-（5-四唑巯丙氧基）土甘草A型荧光探针；
所述不同取代基的巯基四唑衍生物为： 
，其中，R1为
或
或
或
或
或
。
3.如权利要求2所述的4-（5-四唑巯丙氧基）土甘草A型荧光探针的制备方法，其中，当所述不同取代基的巯基四唑衍生物的R1为
或
或
或
时，制备方法为：
取异硫氰酸苯酯衍生物溶于纯水中，加入叠氮化钠，回流反应，利用薄层色谱法跟踪反应，用体积比=2：1及4：1的石油醚和乙酸乙酯为展开剂，苯酯层消失时停止反应，冷却至室温时逐滴滴加浓盐酸并搅拌至pH为3，析出大量白色沉淀，抽滤，取滤饼加入纯水至pH 4~5，抽滤，滤饼用无水乙醇重结晶，即得到相应的巯基四唑衍生物；
合成途径如下：
其中，化学式中的R2对应为-OCH3，-C2H5，-Cl，-NO2中的一种。
4.如权利要求3所述的4-（5-四唑巯丙氧基）土甘草A型荧光探针的制备方法，其中，所述步骤一中的溶剂为乙腈，使用无水乙醇洗涤。
5.如权利要求4所述的4-（5-四唑巯丙氧基）土甘草A型荧光探针的制备方法，其中，所述步骤二中，使用四氢呋喃为反应溶剂，三乙胺为催化剂，使用乙酸乙酯进行重结晶。
6.一种如权利要求1所述的4-（5-四唑巯丙氧基）土甘草A型荧光探针在制备检测铅离子探针的应用。
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