CN111233801B - 一种快速检测溶剂成分的比色探针及其制备方法、应用 - Google Patents
一种快速检测溶剂成分的比色探针及其制备方法、应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于分析化学技术领域,具体涉及一种快速检测溶剂成分的比色探针及其制备方法、应用。
背景技术
有机溶剂中水含量会在很大程度上影响化学反应的进行,亦或是影响溶剂的性能,包括水凝胶等一系列物质都会因溶剂的不同而改变其本身的性能。因此,有机溶剂中水含量的测定是最重要也是最常遇见的分析问题之一,水含量的表征也是医药、化工、食品、塑料等产品中一项重要的指标,目前,测定有机溶剂中水含量常用的化学分析方法是卡尔费休法,尽管该方法做了很大的改进,但仍然存在反应速率慢、易受干扰、精密度差、耗时较长、不能实时快速的对其进行定性观察等缺点。目前,应用于有机溶剂中水的测定的化学传感器还很少,而应用于0-100%全范围含量的水检测的探针更是不多。
比色探针因其反应灵敏、裸眼就能识别颜色的变化而不须借助昂贵的仪器而越来越受到人们的青睐。因此,越来越多的人开始追求设计这种新型的传感器,从而大大的提高工作效率,节省不必要的浪费。目前存在的测定有机溶剂中水的探针适应性差,大多针对一种溶剂中的水进行检测,因此,研发一种能够检测多种溶剂的具有高选择性和高灵敏度的比色探针成为了亟待解决的问题。
发明内容
本发明针对现有技术中存在的问题,以及其他一些领域的缺憾,本发明提供了一种快速检测溶剂成分的比色探针
本发明还提供了一种上述比色探针的制备方法,制备得到的比色探针可应用于溶剂成分的快速检测,具精密度高、现象明显易观察、准确度高等优点,设备便捷易操作,可操作性强,特别适合大批量样本组合筛选等大数据研究。
本发明另一目的为提供了一种上述比色探针的应用。
本发明为了实现上述目的所采用的技术方案为:
本发明提供了一种快速检测溶剂成分的比色探针,所述比色探针的结构式如下:
本发明提供的比色探针效果判断指标如下:
检测灵敏度: 0.6%;
吸收波长改变:0-70%,吸收红移动;70%-100%,吸收蓝移;
颜色变化:紫色-蓝色-浅粉色;
双重定量校正:兼具荧光定量功能及吸收峰定量功能;
光学机理指标:兼具荧光淬灭功能及吸收红移动-蓝移功能。
本发明还提供了一种快速检测溶剂成分的比色探针的制备方法,包括以下步骤:
(1)将2-溴-4′-羟基苯乙酮、4-二甲基氨基苯甲醛、碳酸钠溶于乙醇中,然后加入水,60℃搅拌6h,待反应物冷却后,加入盐酸,搅拌至中性,过滤出固体,乙醇洗涤后除去溶液中的不溶性物质,去除溶剂,得橙红色固体产物1(BHDP);
(2)BHDP、4-甲酰基苯硼酸、碳酸钾、乙酸钯(II)、三苯基膦溶于1,4-二氧基和水的混合物中,然后,在氮气保护下,80°C回流6h,去除溶剂,然后洗脱纯化,得红色固体产物2(DPAHB);
(3)将3-羟基-3-甲基-2-丁酮、丙二腈和乙氧基锂溶于乙醇中,混合物在无光的氮气气氛下,在75°C下加热10小时,然后冷却过滤,用去离子水清洗,得绿色产物3(TCF);
(4)DPAHB、TCF、哌啶溶于乙醇中,100℃回流30 min,洗脱纯化,得黑色固体产物4(DHBDY)。
进一步的,步骤(1)中,所述2-溴-4′-羟基苯乙酮、4-二甲基氨基苯甲醛及碳酸钠的摩尔比为1:1:2;所述2-溴-4′-羟基苯乙酮在乙醇中的浓度为0.25mmol/mL;所述乙醇和水的体积比为4:1;所述盐酸的浓度为12mol/L。
进一步的,步骤(2)中,所述BHDP、4-甲酰基苯硼酸、碳酸钾、乙酸钯(II)及 三苯基膦的摩尔比为1:1:14:0.05:0.05;所述BHDP在1,4-二氧基中的浓度为0.05mmol/mL;所述1,4-二氧基和水的体积比为4:1。
进一步的,步骤(3)中,所述3-羟基-3-甲基-2-丁酮、丙二腈及乙氧基锂的摩尔比为5:10:0.01;所述3-羟基-3-甲基-2-丁酮在乙醇中的浓度为0.4mmol/mL。
进一步的,步骤(4)中,所述DPAHB、TCF、哌啶的摩尔比为1:1.15:0.1;所述DPAHB在乙醇中的浓度为0.1mmol/mL。
进一步的,步骤(2)和(4)中,所述洗脱纯化为以体积比20:1组成的石油醚和乙酸乙酯的混合物为洗脱液,在300-400目硅胶上进行柱层析纯化粗品。
本发明还提供了一种上述比色探针的应用,本发明制备的比色探针用于多种有机溶剂和水的定性、定量分析。
进一步的,所述比色探针检测多种溶剂中水的含量的具体步骤如下:将瓶中水的含量分别为90%,80%,60%,40%,20%,0% ,剩余溶剂分别为乙醇、四氢呋喃、1,4二氧六环、二甲基亚砜(DMSO),其中探针浓度为30μM,探针加入时,即可可以看到溶液的颜色变化;
采用比色探针进行水凝胶中水分子检测的具体步骤如下:
1)配制溶液
探针储备液配制: 准确称取水响应的比色探针溶二甲基亚砜,配制浓度为6mM的探针储备液;
待测目标物小分子水含量: 水在有机溶剂的含量采用水和二甲基亚砜不同比例进行混合检测;
2)水凝胶样品中水分子的检测: 配置不同比例的水/二甲基亚砜溶液2ml,将同等大小的水凝胶分别置于溶液中12小时,观察凝胶的颜色与所配溶液的颜色是否一致,并通过PS读取水凝胶的RGB值,建立其相关性方程,从而实现凝胶内的定量分析。
本发明合成 DHBYD探针的合成路线如下:
本发明合成的新型具有高选择性和高灵敏度的比色探针已经能成熟地选择性检测多种溶剂,并且系统地在试管中和凝胶内进行研究。探针设计是将已有探针查尔酮作为母体环,引入一系列官能团。当有机溶剂中加入少量水时,探针会形成分子内氢键,从而导致吸收红移动;而当水含量过多时,会导致酚羟基脱质子引起平面构想的变化从而影响了探针的ICT过程,导致吸收蓝移动。该探针已经成功的应用到了水凝胶中溶剂含量的检测中。这个最新成熟的探针表明了极好的性能包括良好的特异性、超高的灵敏度和较高的紫外吸收度。所有的这些特征都使它尽可能的充当一个有用的对于探索水在个体功能方面差异的工具和在生命系统中探索用于将来的临床研究。
本发明所描述的荧光/紫外分子探针检测水凝胶中水的含量的应用,最优检测范围为荧光0→100%, 紫外0-100%。分别以荧光检测、紫外检测的方法对待测物进行多次平行检测(n=10),并与标准品小分子溶液进行校准,得到荧光/紫外检测的最优检测范围,从而根据不同样品所含待测物的浓度范围来选择最优化的检测手段进行定量。
本发明合成的比色探针适用于多种有机溶剂和水的定性、定量分析,检测灵敏、准确、快捷,并从比色图片中读取的RGB值中建立相关性,从而实现化分析,可应用于分析化学、生命有机分析化学、及工程分析检测等相关领域。本发明比色探针定性定量分析水凝胶样本中水时,适用于检测凝胶内水含量的实时状态。
本发明技术方案有益效果为:
1、提高检测的灵敏性:在不加任何其他附加材料的条件下,提高了检测灵敏性,并且避免了填加附加材料,减少附加材料的消耗以及减少了在检测中的误差来源,线性范围广。
2、样品可视化定量检测:本发明在检测中成功的建立了RGB线性方程,并应用到了实际检测的样品中,成功的建立了一种新的检测方法,实现可视化检测,且可逆性强,能够在线原位检测。
3、提供宽范围检测:本发明具有宽的检测范围,覆盖范围能够达到0-100%,为试验过程提供了更为全面、准确的技术保障。
4、实现多溶剂成分检测:本发明制备的探针可以在多种有机成分中对水含量进行检测,适用溶剂多样,例如乙醇、DMSO、THF、1,4-二氧六环等,且灵敏度高,快速简便。
附图说明
图1为实施例1制备的化合物BHDP的氢谱图(A)、碳谱图(B)。
图2为实施例1制备的化合物DPAHB的氢谱图(A)、碳谱图(B)。
图3为实施例1制备的化合物TCF的氢谱图(A)、碳谱图(B)。
图4为 实施例1制备的化合物DHBDY的氢谱图(A)、碳谱图(B)。
图5为实施例1制备的化合物BHDP(A)、DPAHB(B)、TCF(C)、DHBDY(D)的质谱图。
图6为本发明制备的比色探针检测乙醇中水含量比色图。
图7为本发明制备的比色探针检测1,4二氧六环中水含量比色图。
图8为本发明制备的比色探针检测四氢呋喃中水含量比色图。
图9为本发明制备的比色探针检测DMSO-水体系中的比色图。
图10为DHBYD法检测水凝胶中的水分含量。其中, (B)不同含水量的RGB值;(C)CIE 1931色度图;(D) CIE 1931年色度图的三维散点图;(E)未知水含量的水凝胶照片。
图11为本发明制备的探针在不同温度下的性能曲线图。
图12为本发明制备的探针在不同pH值反应体系中的性能曲线图。
图13为本发明制备的探针对水分子响应的荧光响应图、线性图、CIE色度图(溶液比例:0-95%)。
图 14为本发明制备的探针对待测目标物小分子酶梯度浓度的紫外响应图(比色图)、线性图(0-70%)、线形图(70%-100%)。
具体实施方式
通过结合更加具体实施例子描述本发明的小分子探针,在围绕本发明所描述技术思想情况下,根据一般的技术知识和通常用的技术手段研究的多种方式替换或变更,都属于本发明的范围内。
将本发明实施例中的荧光检测是利用FLS980荧光光谱仪来进行,激发波长为490nm,发射波长为650nm, 激发和发射狭缝宽度均为 10.0 nm,扫描速度1200纳米/分。紫外可见光谱是通过UV2600紫外可见光谱仪来进行,扫描范围为350-700纳米。化合物的分离提纯是采用薄层色谱硅胶柱来实现。
实施例1
(1)将2-溴-4′-羟基苯乙酮(5 mmol, 1.075 g)、4-二甲基氨基苯甲醛(5 mmol,0.745 g)、碳酸钠(10 mmol, 1.060 g)溶于20 ml乙醇中,然后加入5ml水,60℃搅拌6h,待反应物冷却后,加入盐酸(3ml, 12m),搅拌至中性,过滤出固体,乙醇洗涤后除去溶液中的不溶性物质,然后将溶液旋转蒸发以去除溶剂,产品为橙红色固体(1.005 g)(55.2%),得到产物1(BHDP);
(2)BHDP (1 mmol, 0.534 g)、4-甲酰基苯硼酸(1 mmol, 0.149 g)、碳酸钾(14mmol, 1.932 g)、乙酸钯(II) (0.05 mmol, 0.011 g)、三苯基膦(0.05 mmol, 0.013 g)溶于1,4-二氧基(20 mL)和水(5 mL)的混合物中,然后,在氮气保护下,80°C回流6h;溶剂在减压下被除去,然后,以石油醚和乙酸乙酯的混合物为洗脱液(体积比20:1),在硅胶(300-400目)上进行柱层析纯化粗品,产品为红色固体(0.212 g)(31.0%),得到产物2(DPAHB);
(3)将3-羟基-3-甲基-2-丁酮(1.0 g,10 mmol)、丙二腈(1.33 g, 20 mmol)和乙氧基锂(0.001 g, 0.02 mmol)溶于25 mL EtOH中,混合物在无光的氮气气氛下,在75°C下加热10小时,然后冷却过滤,用去离子水清洗三次,产品为绿色(1.35 g, 67.8%)。得到产物3(TCF);
(4)DPAHB (0.37g,1mmol)、TCF (0.23g,1.15mmol)、哌啶(0.008g, 0.1 mmol)溶于10ml EtOH中,100℃回流30 min,粗品硅胶柱层析纯化(PE / EA = 20/1, v / v),产物为黑色固体(0.054 g)(9.0%),得到产物4(DHBDY)。
实施例制备得到的BHDP、DPAHB、TCF、DHBDY的氢谱图、碳谱图及质谱图如图1-5所示。
效果实施例1: 乙醇的检测实验
实际应用:瓶中水的含量分别为90%,80%,60%,40%,20%,0% ,剩余溶剂为乙醇,总体积为2ml,探针浓度为30μM。通过检测,得到的比色图如图6所示。从图中可以看到溶液的颜色由浅灰色变为蓝色最后变为紫色。
效果实施例2:1,4二氧六环的检测实验
实际应用:瓶中水的含量分别为90%,80%,60%,40%,20%,0% ,剩余溶剂为1,4二氧六环,总体积为2ml,探针浓度为30μM。通过检测,得到的比色图如图7所示。从图中可以看到溶剂的颜色从前粉色变为蓝色,然后由开始变为紫色,最后变为粉红色。
效果实施例3:四氢呋喃的检测实验
实际应用:瓶中水的含量分别为90%,80%,60%,40%,20%,0% ,剩余溶剂为四氢呋喃,总体积为2ml,探针浓度为30μM。通过检测,得到的比色图如图8所示。从图中可以看到溶剂的颜色由几乎无色变为蓝色,最后变为紫色。
效果实施例4:DMSO-H2O体系检测
1、首先对DMSO-水体系检测,步骤如下:瓶中水的含量分别为90%-0%,剩余溶剂为二甲基亚砜,总体积为1ml,探针浓度为30μM。通过检测,得到的比色图如图9所示。从图中可以看到溶剂的颜色由几乎无色变为蓝色,最后变为紫色。
2、进一步用于水凝胶中检测
采用已有合成方法的壳聚糖水凝胶为例,以壳聚糖为单体,genipin为化学交联剂,采用热自由基聚合法制备水凝胶。
本发明探针定性定量检测水凝胶样本中水分子时,适用于水含量检测的肉眼观察和可视化检测。
水凝胶样品中水分子的检测,方法为: 配置不同比例的水/二甲基亚砜溶液2ml,将同等大小的水凝胶分别置于溶液中12小时,观察凝胶的颜色与所配溶液的颜色是否一致,并通过PS读取水凝胶的RGB值,建立其相关性方程,从而实现凝胶内的定量分析。
我们将凝胶浸泡到不同比例的溶剂中24h,通过1中我们建立的模型,对7种水凝胶的真实含水量检测(图10)。经计算,7种水凝胶的含水量分别为100%、94.6%、88.7%、86.4%、46.4%、31.6%和25.3%。
探针性能讨论
(1)温度优化
探针分子与水的反应效率与反应程度在一定程度上受到反应温度的影响。因此,在研索出探针检测应用之前,我们就要对反应的温度进行优化。从图11中可以看出,该探针具有很好的耐温性能。
(2)反应体系pH值的优化
一般而言,pH 值影响有机分子探针的光谱性质,因而在反应中一般利用缓冲溶液加以调节pH从而适应实验的要求。我们研究了在不同环境下可能达到的pH值 (2.6;5.8;7;9.16;10.83)。从图12中可见,在酸性、中性和弱碱性环境范围内pH值的波动对于水与探针的混合溶液所表现的紫外吸收响均一致。因此,在一般的环境体系中,该探针与溶剂水响应均可以检测。
(3)光学性质与机理验证
本发明旨在发明一种具备新颖发光机理的多功能分子探针,其对水分子响应的荧光响应图、线性图、CIE色度图(溶液比例:0-95%)如图13所示,此处为该探针的荧光线性检测,从图中我们可以看到,该探针与溶剂检测有一个很好的线性关系,随着水含量的增加,荧光强度趋于淬灭。图 14为 探针对待测目标物小分子酶梯度浓度的紫外响应图(比色图)、线性图(0-70%)、线形图(70%-100%)。此处为该探针的紫外检测,可以看到探针在0-100%范围内分两段线性,0-70%为红移过程,而70%-100%为信号蓝移过程。
Claims (10)
2.根据权利要求1所述的比色探针,其特征在于,所述比色探针效果判断指标如下:
检测灵敏度: 0.6%;
吸收波长改变:0-70%,吸收红移动;70%-100%,吸收蓝移;
颜色变化:紫色-蓝色-浅粉色;
双重定量校正:兼具荧光定量功能及吸收峰定量功能;
光学机理指标:兼具荧光淬灭功能及吸收红移动-蓝移功能。
3.一种如权利要求1或2所述的比色探针的制备方法,其特征在于,包括以下步骤:
(1)将2-羟基-4-溴-苯乙酮、4-二甲基氨基苯甲醛、碳酸钠溶于乙醇中,然后加入水,60℃搅拌6h,待反应物冷却后,加入盐酸,搅拌至中性,过滤出固体,乙醇洗涤后除去溶液中的不溶性物质,去除溶剂,得橙红色固体产物BHDP;
(2)BHDP、4-甲酰基苯硼酸、碳酸钾、乙酸钯(II)、三苯基膦溶于1,4-二氧六环和水的混合物中,然后,在氮气保护下,80°C回流6h,去除溶剂,然后洗脱纯化,得红色固体产物DPAHB;
(3)将3-羟基-3-甲基-2-丁酮、丙二腈和乙氧基锂溶于乙醇中,混合物在无光的氮气气氛下,在75°C下加热10小时,然后冷却过滤,用去离子水清洗,得绿色产物TCF;
(4)DPAHB、TCF、哌啶溶于乙醇中,100℃回流30 min,洗脱纯化,得黑色固体产物DHBDY;
4.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,所述2-羟基-4-溴-苯乙酮、4-二甲基氨基苯甲醛及碳酸钠的摩尔比为1:1:2;所述2-羟基-4-溴-苯乙酮在乙醇中的浓度为0.25mmol/mL;所述乙醇和水的体积比为4:1;所述盐酸的浓度为12mol/L。
5.根据权利要求3或4所述的制备方法,其特征在于,步骤(2)中,所述BHDP、4-甲酰基苯硼酸、碳酸钾、乙酸钯(II)及 三苯基膦的摩尔比为1:1:14:0.05:0.05;所述BHDP在1,4-二氧六环中的浓度为0.05mmol/mL;所述1,4-二氧六环和水的体积比为4:1。
6.根据权利要求3所述的制备方法,其特征在于,步骤(3)中,所述3-羟基-3-甲基-2-丁酮、丙二腈及乙氧基锂的摩尔比为5:10:0.01;所述3-羟基-3-甲基-2-丁酮在乙醇中的浓度为0.4mmol/mL。
7.根据权利要求3所述的制备方法,其特征在于,步骤(4)中,所述DPAHB、TCF、哌啶的摩尔比为1:1.15:0.1;所述DPAHB在乙醇中的浓度为0.1mmol/mL。
8.根据权利要求3所述的制备方法,其特征在于,步骤(2)和(4)中,所述洗脱纯化为以体积比20:1组成的石油醚和乙酸乙酯的混合物为洗脱液,在300-400目硅胶上进行柱层析纯化粗品。
9.一种如权利要求1所述的比色探针的应用,其特征在于,所述比色探针用于多种有机溶剂中水的定性、定量分析。
10.根据权利要求9所述的应用,其特征在于,所述比色探针检测多种溶剂中水的含量的具体步骤如下:瓶中水的含量分别为90%,80%,60%,40%,20%,0% ,剩余溶剂分别为乙醇、四氢呋喃、1,4二氧六环、二甲基亚砜(DMSO),其中探针浓度为30μM,探针加入时,即可看到溶液的颜色变化。
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CN104804723A (zh) * | 2014-01-28 | 2015-07-29 | 中国科学院大连化学物理研究所 | 一类基于dcdhf发色团的溶致变色荧光探针、其制备及应用 |
CN105954242A (zh) * | 2016-04-29 | 2016-09-21 | 武汉理工大学 | 一种基于罗丹明衍生物的聚合物样品及其在水含量分析中的应用 |
CN106187884A (zh) * | 2016-06-24 | 2016-12-07 | 贵州大学 | 2‑[2‑羟基‑5‑(4‑硝基偶氮苯)苯乙烯基]‑8‑羟基喹啉比色试剂及制备和应用 |
KR20180134056A (ko) * | 2017-06-08 | 2018-12-18 | 고려대학교 산학협력단 | 유기용매 내 수분 검출용 형광 프로브 화합물 및 이를 포함하는 수분 검출 형광 센서 |
CN108558801A (zh) * | 2018-05-30 | 2018-09-21 | 济南大学 | 一种长波长超灵敏一氧化碳比色荧光探针 |
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