CN104098500B - 基于花青的有机化合物及其应用 - Google Patents
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Abstract
本发明涉及用于检测己烯雌酚的探针，具体的说是一种基于花菁的有机化合物及其应用。此化合物结构如式Ⅰ所示，以所述化合物作为检测己烯雌酚的探针。本发明己烯雌酚荧光探针的这类化合物，在己烯雌酚存在下对应的荧光强度发生明显变化，可用于己烯雌酚的检测，并可大大降低外部检测条件的干扰，提高检测精度。此外，该发明己烯雌酚荧光探针的这类化合物，在己烯雌酚存在时紫外吸收亦发生明显变化，可同时用紫外分光光度计及肉眼进行检测。本发明的优点：操作简单方便、快速、肉眼可视、费用低，应用范围广泛等。
Description
技术领域
本发明涉及用于检测己烯雌酚的探针，具体的说是一种基于花菁的有机化合物及其应用。
背景技术
己烯雌酚是人工合成的非甾体雌激素的一种，目前在临床上主要用于治疗卵巢功能不全或垂体功能异常引起的各种疾病或作为女用口服避孕药，还可用来治疗乳腺癌和前列腺癌。其口服作用为雌二醇的2-3倍。它的主要作用为促使女性性器官及副性征正常发育；促使子宫内膜增生和阴道上皮角化；减轻妇女更年期或妇科手术后因性腺功能不足而产生的全身性紊乱；增强子宫收缩，提高子宫对催产素的敏感性；小剂量刺激、而大剂量抑制垂体前叶促性腺激素及催乳激素的分泌；抗雄激素作用。在兽医临床上，己烯雌酚主要用于不明显发情动物的催情，还可用来治疗胎衣不下、排出死胎、治疗子宫炎等。但是，人们通过实验发现，己烯雌酚具有致畸和致癌的毒性，使用了己烯雌酚的妇女得乳腺癌的几率比正常的高25-35％此外，己烯雌酚还具有明显的生殖毒性。对于男性而言，接触己烯雌酚会降低精液的品质、增加泌尿生殖系统缺陷的发生概率。妊娠期应用己烯雌酚治疗疾病，会影响后代雄性个体精子的数量和质量。从细胞生物学角度分析，己烯雌酚对生物体的破坏作用具体表现为：改变DNA的合成时间；增加或诱导姊妹染色单体的交换；抑制依赖于GTP的微管蛋白的自组装，通过与微管蛋白的特异结合，阻止微管和纺锤体的形成，从而阻碍有丝分裂过程中染色体的分离，引起细胞形变；抑制细胞增殖，诱导产生非整倍体和多倍体。由于己烯雌酚在促进动物蛋白质的合成代谢、提高动物日增重和减少脂肪等方面效果明显，因此尽管DES残留严重威胁着人体健康，但是在畜牧养殖业上仍然有着广泛的使用。己烯雌酚类激素生长促进剂仍然有着较高的检出率因此有必要加强DES残留的监测工作，强化监督管理。因此,实现快速、灵敏的己烯雌酚检测具有十分重要的意义。
目前，己烯雌酚的检测方法主要有气相色谱法、液相色谱法、气质联用法、液质联用法、毛细管电泳法、化学发光法、循环伏安法和酶联免疫法等，然而这些方法大多需要样品的预处理，需要复杂的操作手段及大型仪器。因此，寻找一种方便快捷检测己烯雌酚的方法迫在眉睫。
发明内容
本发明的目的在于提供一种基于花菁的有机化合物及其应用。
为实现上述目的，本发明采用的技术方案为：
一种基于花菁的有机化合物，有机化合物的结构如式Ⅰ所示，
一种基于花菁的有机化合物的应用，所述基于花菁的有机化合物作为制备己烯雌酚的探针的应用中。
所述式Ⅰ所示的基于花青的有机化合物作为探针用于定性/定量的检测水体、模拟生理环境或生物体内外中的己烯雌酚。
所述式Ⅰ所示的基于花青的有机化合物作为探针用于定性/定量的检测水环境中的己烯雌酚。
本发明的有益效果：
本发明用于作为检测己烯雌酚的化合物，其在己烯雌酚存在下对应的荧光强度发生变化，同时紫外吸收也对应发生改变，进而可用于水体系、人体尿液中己烯雌酚水平的检测，并可大大降低外部检测条件的干扰，提高检测精度。本发明化合物用作检测探针，可用于水环境中己烯雌酚的检测，用于判断饮用水的安全。本发明具有操作简单方便、快速肉眼可视、费用低等优点。
附图说明
图1为本发明实施例提供的探针在不同己烯雌酚浓度下的反应图及肉眼观测图。
图2为本发明实施例提供的不同pH下实施例所采用的探针的稳定性图谱。
图3为本发明实施例提供的不同pH下实施例所采用的探针与己烯雌酚作用后紫外吸收变化曲线图。
图4为本发明实施例提供的采用的探针对己烯雌酚的选择性示意图；其中，横坐标从左至右依次为空白、己烯雌酚、双酚A、雌二醇、雌三醇、半胱氨酸、高半胱氨酸、谷胱甘肽。
图5为本发明实施例提供的采用的探针紫外吸收强度值与己烯雌酚浓度变化的线性拟合曲线。
具体实施方式
基于花菁的有机化合物结构式为：
式Ⅰ化合物与待测定水体、模拟生理环境或生物体内外中的己烯雌酚结合，得结构式II所示的化合物从而导致式Ⅰ化合物的荧光强度和波长的改变，以及紫外吸收的改变，进而利用式Ⅰ化合物可对己烯雌酚进行定性、定量的检测。实施例用于进一步说明本发明，但本发明不限于实施例。
实施例1.基于花菁的有机化合物的制备：
(1)化合物一的制备
量筒量取20-50mLDMF溶于20-40mL二氯甲烷，倒入250mL三口烧瓶中(放磁子搅拌)，冰水浴中冷却。量取20-40mL三氯氧磷溶入20-40mL二氯甲烷，倒入恒压漏斗中滴加入上述冷却后溶液中，并用磁搅拌仪不断搅拌。
滴加完毕，称取5-10g环己酮倒入上述恒压漏斗滴加。此时溶液颜色由无色逐渐变为黄色。然后撤去冰水浴，加热回流3小时。反应结束后，将反应液倒入装满碎冰中。置于通风橱中静置过夜。水槽内上层为黄色液体底部为黄色絮状沉淀且有少许红色油状物。用布氏漏斗减压抽滤，母液洗涤，得黄色固体化合物一。将固体转移到小烧杯中，在真空干燥箱中干燥。熔点：130～131℃，元素分析结果(理论值)：C,55.4(55.7)；H5.4(5.3)；Cl,20.4(20.6)；O，18.8(18.4)。LC-MS(API-ES):m/zC8H9ClO2Calcd172,found[M+]173.
(2)化合物二的制备
将100-150mL碘乙烷，20-30mL2,3,3-三甲基吲哚啉，10-20mL甲苯三者加入250mL圆底烧瓶中，加热回流10-15h反应。完后在旋转蒸发仪上将溶剂旋干，旋干后得深紫红色固体化合物二。往烧瓶中加甲醇加热使固体溶解后，转移到烧杯中滴加乙醚将固体沉淀出。抽滤，用乙醚洗涤沉淀，得浅粉红色粉末状固体。将固体干燥后转移到广口瓶中待用。元素分析结果(理论值)：C,82.9(82.9)；H9.7(9.6)；N,7.4(7.5)。LC-MS(API-ES):m/zC13H18N+Calcd188,found[M+]189.
(3)化合物三的制备
0.5-1g化合物一和0.2-0.5g化合物二溶解在100-150mL正丁醇和苯的混合溶剂中(7:3v/v)，在反应器上装一水分离器，分出反应生成的水，使反应能够向正反应方向进行。混合物加热回流，并不断搅拌。反应2-4h后，冷却到室温，减压蒸馏除去溶剂。沉淀用乙醚洗涤，得深紫红色固体粗产物，柱色谱分离纯化，洗脱剂为甲醇－乙酸乙酯(7:12V/V)，得到绿色产物化合物三。元素分析结果(理论值)：C,79.8(79.7)；H,7.8(7.9)；Cl,6.9(6.9)；N,5.5(5.5)。LC-MS(API-ES):m/zC34H40ClN2 +Calcd511,found[M+]512.
(4)化合物四的制备
在氮气保护下，0.3-0.5g化合物三和0.1-0.3g醋酸钠在10-20ml无水N,N-二甲基甲酰胺中于80-90℃下反应5-8小时。冷却后，用石英砂终止反应并过滤。硅胶柱色谱分离纯化，洗脱剂为甲醇－乙酸乙酯(7:12V/V)，接收红色组分，得到红色产物化合物四。元素分析结果(理论值)：C,82.8(82.9)；H,8.3(8.2)；N,5.8(5.7)；O,3.1(3.2)。LC-MS(API-ES):m/zC34H40N2OCalcd492,found[M+]493.
(5)式Ⅰ的制备
将0.2-0.5g化合物四，0.1-0.3g丙酰氯及150-200μL无水的乙二胺在20-30ml无水N,N-二甲基甲酰胺中于冰浴条件下反应0.5-2h。硅胶柱色谱分离纯化，洗脱剂为甲醇－乙酸乙酯(1:3V/V)，接收绿色组分得到绿色产物式Ⅰ化合物。元素分析结果(理论值)：C,80.6(80.8)；H,8.4(8.3)；N,5.2(5.1)；O,5.8(5.8)。LC-MS(API-ES):
m/zC41H44N3O4 +Calcd535,found[M+]536.
实施例2
将制备所得式Ⅰ化合物作为探针应用于水体中，进行对己烯雌酚的检测，以下各项实验均在pH5.0-11.0条件下进行(B-R缓冲溶液，浓度为1-30mM)，探针浓度采用0.5-10μM。
上述制备所得探针对己烯雌酚响应的pH效应：
pH梯度采用B-R缓冲溶液控制。于1.5ml比色管中加入0.8-1mL不同pH梯度的1-10mMB-R缓冲液，再加入1-10μL100μM探针，摇匀溶液，25-40℃下平衡10-30min后，将上述混合后的工作液加入比色皿中测定紫外光谱。紫外吸收值随pH的变化如图1所示。由图1所示在pH5.0～11.0的范围内紫外吸收值没有明显变化，即在pH5.0～11.0的体系中，探针都是稳定的，都可以用于检测己烯雌酚。于1.5mL比色管中加入0.8-1mL1-10mMB-R缓冲液，再加入1-10μL100μM探针，然后加入50-100μL200μM己烯雌酚，摇匀溶液，25-40℃下平衡10-30min后，将上述工作液加入荧光皿中测定荧光光谱。荧光比率随pH的变化如图2所示。可以发现在pH8.0～11.0的体系，探针己烯雌酚都有相应，在pH9左右，响应最好，所以，在pH为9.0时，探针既稳定，又对己烯雌酚灵敏响应，可实现实际样品的检测。
实施例3
探针对己烯雌酚的选择性
pH采用B-R缓冲溶液控制。取多个1.5ml比色管，于每个比色管中加入0.9-1mL1-10mMB-R缓冲液，pH9-10，再加入1-10μL100μM式Ⅰ所示的探针作为的工作液，然后分别加入待测物如图2所示，待测物工作液依次为：空白(无其他加入物)、己烯雌酚、双酚A、雌二醇、雌三醇、半胱氨酸、高半胱氨酸，谷胱甘肽，其中己烯雌酚与双酚A的终浓度是5μM，其他终浓度为50μM。摇匀溶液，25-40℃下平衡10-30min后，将各个比色管中工作液分别倒入到比色皿中测定紫外光谱。探针对己烯雌酚的选择性如图4所示。并由图可知探针对己烯雌酚具有很好的选择性，与己烯雌酚作用后，770nM处紫外吸收值明显减弱。在测定条件下双酚A、雌二醇、雌三醇、半胱氨酸、高半胱氨酸，谷胱甘肽使探针770nM处紫外吸收值发生变化。
实施例4
探针对己烯雌酚的定量检测
取多个1.5ml比色管，于每个比色管中加入0.9-1mL1-10mMB-R缓冲液，pH9-10,再加入1-10μL100μM式Ⅰ所示的探针作为的工作液，然后分别加入不同终浓度的己烯雌酚，终浓度分别为2,4,6,8,10,12μM，摇匀溶液，25-40℃下平衡10-30min后，将各个比色管中的工作液分别倒进荧光皿测定荧光光谱，取各770nm处紫外吸收值，输入软件OriginPro8.0,得到线性工作曲线如图5所示，其中线性拟合曲线的线性回归常数为0.999，表明探针能定量的测定己烯雌酚的浓度。
由图3表示随己烯雌酚浓度的变化体系紫外吸收强度的变化，表明随己烯雌酚浓度的增加，770nm处紫外吸收强度在明显减弱。
实施例5
探针对饮用水中己烯雌酚的定量检测
取多个1.5ml比色管，于每个比色管中加入0.9-1mL1-10mM饮用水，pH9-10,再加入1-10μL100μM式Ⅰ所示的探针作为的工作液，然后分别加入终浓度为5,10μM己烯雌酚，摇匀溶液，25-40℃下平衡10-30min后，将各个比色管中的工作液分别倒进比色皿测定紫外光谱，获取770nm处紫外吸收值，并将所得数值与实施例7中所得到线性工作曲线中数值相比较，发现重合性较好(参见表1)，表明探针能在饮用水中定量的测定己烯雌酚的浓度。
表1为本发明实施例提供的采用的探针用于检测实际样中的己烯雌酚。
| 样品 | 加标(μM) | 检出浓度(μM) | 回收率(100％) |
| 饮用水 | 5 | 4.91±0.42 | 89.8-106.6 |
| 10 | 9.95±0.61 | 93.4-105.6 | |
| 湖水 | 5 | 5.08±0.41 | 93.4-109.8 |
| 10 | 10.68±0.71 | 99.7-114 |
实施例6
探针对湖水中己烯雌酚的定量检测
取多个1.5ml比色管，于每个比色管中加入0.9-1mL1-10mM湖水，pH9-10,再加入1-10μL100μM式Ⅰ所示的探针作为的工作液，然后分别加入终浓度为5,10μM己烯雌酚，摇匀溶液，25-40℃下平衡10-30min后，将各个比色管中工作液分别倒进比色皿测定紫外光谱，获取770nm处紫外吸收值，并将所得数值与实施例7中所得到线性工作曲线中数值相比较，发现重合性较好(参见表1)，表明探针能在湖水中定量的测定己烯雌酚的浓度。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。作为荧光染料是本发明新化合物的一种用途，不能认定本发明的化合物仅用于荧光染料，对于本发明所属技术领域的普通技术人员来说，在基于本发明化合物用作荧光染料的相同作用机理的考虑下，还可以做出若干简单推理，得出本发明的化合物的其他应用用途，都应当视为属于本发明的保护范围。
Claims (2)
1.一种基于花菁的有机化合物，其特征在于：有机化合物的结构如式Ⅰ所示，
2.一种权利要求1所述的基于花菁的有机化合物的应用，其特征在于：所述式Ⅰ所示的基于花菁的有机化合物作为探针用于定性/定量的检测水体中的己烯雌酚。
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