CN110499152B - 一种比色和荧光双响应型荧光检测探针及一种传感器 - Google Patents
一种比色和荧光双响应型荧光检测探针及一种传感器 Download PDFInfo
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Abstract
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荧光检测探针及其应用,本发明还涉及一种传感器及其制备方法。
背景技术
挥发性小分子氨/胺类化合物如氨气、二乙胺、三乙胺等被广泛用于化肥、农药、医药、材料及多种精细有机化学品的合成之中。然而,由于该类分子的高挥发性及高水溶性,大量使用会对环境及人类健康造成极大威胁。传统氨/胺类化合物的检测方法包括气相色谱法、气相色谱-质谱连用法、电化学分析法、紫外可见分光光度计法等。
传统仪器分析方法具有分析灵敏度较高、重复性好等优点。然而,该类方法也有其固有缺点如依赖大型检测仪器、待检样品需要较复杂的前处理、检测成本偏高、不适用于实时实地检测等。一种操作简便、携带方便、灵敏度高的挥发性氨/胺检测方法更具可操作性。比色、荧光双响应型探针及其传感器具有响应快速、灵敏度高、可视化检测等优点,可弥补传统检测方法的不足,实现挥发性氨/胺的实时及可视化检测。
发明内容
本发明的目的是提供一种比色和荧光双响应型荧光检测探针,解决了现有技术中挥发性小分子氨/胺类化合物的检测过程复杂的问题。
本发明的另一目的是提供一种传感器,能够降低挥发性氨/胺类化合物的检测成本。
本发明所采用的第一种技术方案是,一种比色和荧光双响应型荧光检测探针,用于检测挥发性胺/氨类化合物,具有以下结构式:
本发明所采用的第二种技术方案是,一种比色和荧光双响应型荧光检测探针在氨基酸检测中的应用。
本发明所采用的第三种技术方案是,一种比色和荧光双响应型荧光检测探针作为荧光墨水的应用。
本发明所采用的第四种技术方案是,一种传感器,包括薄膜类基材,薄膜类基材上覆盖有一种比色和荧光双响应型荧光检测探针。
薄膜类基材为滤纸或者薄膜材料。
本发明所采用的第五种技术方案是,一种传感器的制备方法,具体按照以下步骤实施:将一种比色和荧光双响应型荧光检测探针溶解在以任意比混合的四氢呋喃、二甲基亚砜溶剂中形成探针溶液,取薄膜类基材并浸没于探针溶液后取出,晾干,得用于检测挥发性胺/氨类的传感器。
本发明的有益效果是:
本发明一种比色和荧光双响应型荧光检测探针,弥补了已有氨/胺检测类化合物检测方法的不足,根据探针颜色及荧光强度的变化,定性或定量地检测挥发性氨/胺类化合物;克服了现有氨/胺检测类化合物检测技术中存在的操作复杂、检测成本高、不适于气体及实时检测等技术缺陷;该探针还能够用于信息存储领域如荧光墨水;以该荧光检测探针制备的传感器还具有便于携带、成本低、可视化等特点。
附图说明
图1是本发明中的比色和荧光双响应型检测探针分子的核磁共振氢谱;
图2是本发明中的比色和荧光双响应型检测探针分子核磁共振氢谱在芳香区的放大图;
图3是50μM/L浓度的探针在四氢呋喃中与200μM/L不同胺/氨反应前后紫外吸收谱图;
图4是50μM/L浓度的探针在四氢呋喃中与200μM/L不同胺/氨反应前后荧光谱图;
图5是探针分子附着的滤纸荧光薄膜传感器暴露在不同种类胺(氨)气体中的荧光变化;
图6是探针分子附着的滤纸荧光薄膜传感器暴露在不同浓度氨气气体中的荧光变化图;
图7是探针分子附着的滤纸荧光薄膜传感器暴露在不同浓度氨气氛围中荧光强度随氨气浓度变化的线性拟合图;
图8是探针分子应用在荧光墨水中的实施例演示图;
图9是浓度为20μM/L的探针在二甲基亚砜中与200μM/L不同氨基酸反应前后紫外吸收谱图;
图10是浓度为20μM/L的探针在二甲基亚砜中与200μM/L不同氨基酸反应前后荧光谱图。
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荧光检测探针,用于检测挥发性胺/氨类化合物,具有以下结构式:
制备方法为:
式1为2,4-二羟基苯甲醛,式2为1,4-苯二乙酸,式3为比色和荧光双响应型检测探针;2,4-二羟基苯甲醛与1,4-苯二乙酸在醋酸酐与三乙胺的混合溶剂中反应,可得比色和荧光双响应型荧光检测探针,其中,2,4-二羟基苯甲醛:1,4-苯二乙酸:醋酸酐:三乙胺的摩尔比为2:1:22:24。
在醋酸酐/三乙胺的混合溶剂中反应制备比色和荧光双响应型检测探针。
本发明一种比色和荧光双响应型荧光检测探针用于氨基酸检测。
本发明一种比色和荧光双响应型荧光检测探针作为荧光墨水的应用。
本发明一种传感器,包括薄膜类基材,薄膜类基材上覆盖有一种比色和荧光双响应型荧光检测探针,薄膜类基材为滤纸或者薄膜材料。
本发明一种传感器的制备方法,具体按照以下步骤实施:将一种比色和荧光双响应型荧光检测探针溶解在以任意比混合的四氢呋喃、二甲基亚砜溶剂中形成探针溶液,取薄膜类基材并浸没于探针溶液后取出,晾干,得用于检测挥发性胺/氨类的传感器。
本发明一种比色和荧光双响应型检测探针及传感器的检测原理如下:
本发明利用探针分子中的乙酰氧基与胺/氨类化合物反应,使得探针分子内的乙酰基脱除,导致分子紫外吸收及荧光发射发生变化。上述作用可导致探针溶液或薄膜传感器由无色变为黄色,该变化裸眼可见;同时,该探针的荧光随胺/氨类化合物的浓度增加而显著降低,并在更高波长处出现新的荧光发射峰,该变化在便携式紫外灯下可通过肉眼辨别(探针分子荧光显著猝灭)。
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四氢呋喃、二甲基亚砜等溶剂中,将滤纸等薄膜浸没于探针溶液中,后取出晾干即可得到用于挥发性胺/氨类化合物检测的荧光薄膜传感器。
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。
实施例1
1,4-苯二乙酸(0.97g,5mmol),2,4-二羟基苯甲醛(1.38g,10mmol),三乙胺(5.56g)及乙酸酐(6.12g)加入20mL三颈烧瓶中。混合液在110℃下反应12小时。反应完成后,将反应液倒入水中,有大量固体析出。抽滤、固体干燥,以四氢呋喃为溶剂进行重结晶,得到黄色探针分子1.68g(收率70%)。如图1及图2所示,该探针分子中存在乙酰基氢及芳香氢,产物的结构表征数据如下:m.p.>300℃,1H NMR(DMSO-d6,500MHz)ppm:8.35(s,2H),7.86-7.89(m,6H),7.33(d,J=1.85Hz,2H),7.23(dd,J1=8.45Hz,J2=2.05Hz,2H),2.36(s,6H);MS(ESI)calcd for C28H18O8Na[M+Na]+,found:505.4;FT-IR(KBr)vmax/cm-1 1756,1717,1621,1512,1379,1210,1122,1017,840,632。
实施例2
称取纯化后的荧光检测探针分子,溶于四氢呋喃、配制1mM的探针分子溶液;取上述1mM的探针分子溶液配制50μM/L的探针溶液。分别向50μM/L的探针溶液中加入200μM/L的苯肼、苦味酸、邻硝基苯胺、间硝基苯胺、苯胺、对苯二胺、苄胺、肼、二乙胺、己二胺、氨水、乙二胺及三乙胺。分别测试加入胺/氨前后溶液的紫外光谱,结果如图3所示,由该图可知,脂肪族胺如苄胺、二乙胺、己二胺、氨、乙二胺等与探针分子发生明显反应,紫外吸收光谱发生明显变化,紫外吸收峰从350nm移动到460nm。上述实验证实,该探针分子可用于比色检测脂肪族胺类化合物。
实施例3
称取纯化后的荧光检测探针分子,溶于四氢呋喃、配制1mM的探针分子溶液;取上述1mM的探针分子溶液配制50μM/L的探针溶液。分别向50μM/L的探针溶液中加入200μM/L的苯肼、苦味酸、邻硝基苯胺、间硝基苯胺、苯胺、对苯二胺、苄胺、肼、二乙胺、己二胺、氨水、乙二胺及三乙胺。分别测试加入胺/氨前后溶液的荧光光谱,结果如图4所示。由该图可知,脂肪族胺如苄胺、二乙胺、己二胺、氨、乙二胺等与探针分子发生明显反应,荧光光谱发生明显变化,荧光发射峰从445nm移动到530nm左右。上述实验证实,该探针分子可用于荧光检测脂肪族胺类化合物。
实施例4
将探针分子溶解在二甲基亚砜中,将滤纸等薄膜浸没于探针溶液中,后取出晾干即可得到用于挥发性胺/氨类化合物检测的荧光薄膜传感器。
将上述滤纸荧光薄膜传感器覆盖在盛有相同浓度不同胺/氨类化合物的瓶口,分别记录滤纸荧光薄膜传感器的荧光变化,结果如图5所示(F0表示荧光薄膜传感器的初始荧光,F表示荧光薄膜传感器暴露在不同胺/氨类气体后的荧光强度)。由该图可知,只有暴露在氨气氛围中的荧光薄膜传感器荧光强度发生明显变化,说明该荧光薄膜传感器可用于氨气气体的选择性检测。
实施例5
将探针分子溶解在四氢呋喃中,将滤纸等薄膜浸没于探针溶液中,后取出晾干即可得到用于挥发性胺/氨类化合物检测的荧光薄膜传感器。
将上述滤纸荧光薄膜传感器覆盖在盛有相同浓度不同胺/氨类化合物的瓶口,分别记录滤纸荧光薄膜传感器的荧光变化,结果如图5所示(F0表示荧光薄膜传感器的初始荧光,F表示荧光薄膜传感器暴露在不同胺/氨类气体后的荧光强度)。由该图可知,只有暴露在氨气氛围中的荧光薄膜传感器荧光强度发生明显变化,说明该荧光薄膜传感器可用于氨气气体的选择性检测。
实施例6
探针分子溶解在二甲基亚砜中,将滤纸等薄膜浸没于探针溶液中,后取出晾干即可得到用于挥发性胺/氨类化合物检测的荧光薄膜传感器。
将上述滤纸荧光薄膜传感器暴露在不同浓度的氨气中,分别测试薄膜传感器的荧光强度随氨气浓度的变化,结果如图6所示。由该图可知,在氨气浓度为0-1100ppm范围内,薄膜传感器的荧光强度随着氨气浓的增加逐渐降低。对薄膜传感器的荧光强度与氨气浓度进行线性拟合,结果如图7所示。由该图可知,在浓度范围为0-48ppm的范围内,薄膜传感器荧光强度与氨气浓度间存在线性关系,可用于氨气的定量检测。
实施例7
探针分子溶解在四氢呋喃中,将滤纸等薄膜浸没于探针溶液中,后取出晾干即可得到用于挥发性胺/氨类化合物检测的荧光薄膜传感器。
将上述滤纸荧光薄膜传感器暴露在不同浓度的氨气中,分别测试薄膜传感器的荧光强度随氨气浓度的变化,结果如图7所示。由该图可知,在氨气浓度为0-1100ppm范围内,薄膜传感器的荧光强度随着氨气浓的增加逐渐降低。对薄膜传感器的荧光强度与氨气浓度进行线性拟合,结果如图7所示。由该图可知,在浓度范围为0-48ppm的范围内,薄膜传感器荧光强度与氨气浓度间存在线性关系,可用于氨气的定量检测。
实施例8
称取纯化后的荧光探针分子,溶于四氢呋喃中、配制1mM的探针分子溶液。取上述探针分子溶液,作为荧光墨水在滤纸上书写字母“A”。结果如图8所示,由图8可知以上述溶液写下的字母“A”在日光等下无色,不能被肉眼识别,如图8中(a)所示;该字母经氨气熏蒸,出现黄色字母“A”,肉眼可见如图8中(b)所示;当将上述滤纸暴露在365nm紫外等下时,“A”字母明亮可见如图8中(c)和(d)所示。上述试验证明该探针分子可用在信息存储领域如用作荧光墨水。
实施例9
在二甲基亚砜中配制浓度为20μM/L的探针溶液,分别向上述探针溶液中加入200μM/L的20种编码氨基酸,记录加入氨基酸前探针溶液的紫外吸收光谱,结果如图9所示。由该图可知,探针溶液中加入赖氨酸及精氨酸后,溶液紫外吸收发生明显变化(紫外吸收峰由350nm移动到460nm)。而加入其它氨基酸时,未导致探针溶液紫外吸收发生明显变化。上述实验证实,该探针分子可用于赖氨酸及精氨酸的选择性比色检测。
实施例10
在二甲基亚砜中配制浓度为20μM/L的探针溶液,分别向上述探针溶液中加入200μM/L的20种编码氨基酸,记录加入氨基酸前后探针溶液的荧光光谱,结果如图10所示。由该图可知,探针溶液中加入赖氨酸及精氨酸后,溶液荧光光谱发生明显变化(荧光发射峰由445nm移动到530nm左右)。而加入其它氨基酸时,未导致探针溶液荧光发射峰的明显变化。上述实验证实,该探针分子可用于赖氨酸及精氨酸的选择性荧光检测。
通过上述方式,本发明一种比色和荧光双响应型荧光检测探针,弥补了已有氨/胺检测类化合物检测方法的不足,根据探针颜色及荧光强度的变化,定性或定量地检测挥发性氨/胺类化合物;克服了现有氨/胺检测类化合物检测技术中存在的操作复杂、检测成本高、不适于气体及实时检测等技术缺陷;该探针还能够用于信息存储领域如荧光墨水;以该荧光检测探针制备的传感器还具有便于携带、成本低、可视化等特点。
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