CN114105928B - 一种香豆素型荧光离子液体及其合成方法与在低浓度二氧化硫检测中的应用 - Google Patents
一种香豆素型荧光离子液体及其合成方法与在低浓度二氧化硫检测中的应用 Download PDFInfo
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Abstract
本发明公开了一种香豆素型荧光离子液体及其合成方法与在低浓度二氧化硫检测中的应用，所述香豆素型荧光离子液体化学式为[P66614][7‑HDC]，结构式如下式所示；本发明以离子交换法合成具有蓝色荧光发射的离子液体，该方法合成步骤简单、合成产率高；合成的[P66614][7‑HDC]荧光离子液体热稳定性好、不易挥发、对环境污染性小；对SO2有较强的特异性、灵敏度，可实现线性范围内SO2的定量检测；该探针可以制备到乙基纤维素薄膜上，实现对SO2的可视化便携式检测，检测限低至2.1ppm，该膜具有可循环性、防水性等优点，为实际环境中实时检测低浓度SO2提供了可能性；
Description
技术领域
本发明属于材料制备及分析检测领域，具体涉及一种香豆素型荧光离子液体及其合成方法，以及在低浓度SO2的便携式检测中的应用。
背景技术
SO2是一种主要由化石燃料燃烧排放产生的污染性气体，引起了大量环境和社会问题，例如酸雨、建筑物腐蚀和公共卫生威胁等。几项基于人体的研究表明，反复接触低水平的SO2(<5ppm)会导致永久性肺损伤。而SO2气体的长期和短期暴露限值分别为2ppm和5ppm，对人类的健康具有极大的威胁。目前已采用分光光度法、表面增强拉曼法、滴定法、电化学法等多种分析方法对SO2进行检测。这些方法往往存在成本高、耗时长的问题，限制了它们的实际应用。因此建立一种可以快速、准确、灵敏的检测低浓度SO2的检测方法对人类健康和环境安全至关重要。
在此，本发明设计并制备了一种新型阴离子功能化荧光离子液体，用于实现可视化检测低浓度SO2。[P66614][7-HDC]探针即使在ppm浓度水平对气态SO2也具有荧光比色信号。此外，[P66614][7-HDC]可制备到薄膜中，以获得一种方便、简单、可重复使用和防水的纤维素薄膜设备，用于灵敏检测SO2。IL薄膜提供信号输出，可直接用肉眼观察，为实际环境中对低浓度SO2的便携式检测提供了可能。
发明内容
本发明设计合成了一种新型的高特异性和可逆性的离子液体型荧光探针，通过使用该探针，实现了低浓度SO2的可视化检测。该探针可组装成薄膜，达到便携式、实时检测SO2的目的。基于羟基香豆素离子液体具有良好的选择性、灵敏度和重复使用性，为检测低浓度SO2提供了一种新方法。
本发明以荧光离子液体[P66614][7-HDC]为荧光/比色探针，以低浓度SO2为待测物，通过SO2与[P66614][7-HDC]特异性结合使探针的荧光猝灭，根据以反应前后的荧光强度之差为纵坐标，SO2浓度为横坐标拟合的线性曲线进行定量分析，实现对实际环境中SO2的准确识别和定量检测。
此外，将[P66614][7-HDC]制备到薄膜中，获得了一种方便、简单、可重复使用和防水的薄膜设备，用于特异性检测SO2。
本发明的技术方案如下：
一种香豆素型荧光离子液体，化学式为[P66614][7-HDC]，结构式如下所示：
本发明香豆素型荧光离子液体[P66614][7-HDC]的制备方法为：
在[P66614][OH]的乙醇溶液中加入7-羟基香豆素(7-HDC)，20～100℃搅拌1～24h，之后经旋蒸、干燥(60～100℃)，得到香豆素型荧光离子液体[P66614][7-HDC]；
所述[P66614][OH]与7-羟基香豆素的物质的量之比为0.8～1.2：1；
所述[P66614][OH]的乙醇溶液按如下方法制备得到：
将三己基(十四烷基)氯化膦([P66614][Cl])的乙醇溶液加入到装有强碱性阴离子交换树脂的层析柱中，收集流出液，即得[P66614][OH]的乙醇溶液；
所述强碱性阴离子交换树脂使用前经过如下预处理：用2mol/L NaOH水溶液将717强碱性I型阴离子交换树脂中的Cl-通过层析柱交换出来(直至用硝酸酸化的硝酸银溶液检测得到澄清透明的溶液，证明无Cl-存在)，再用乙醇处理得到无水的强碱性阴离子交换树脂。
本发明香豆素型荧光离子液体[P66614][7-HDC]可用于检测SO2。具体的检测方法如下：
将[P66614][7-HDC]用无水乙醇溶解并用去离子水稀释至当激发波长为365nm时，[P66614][7-HDC]在452nm处的荧光强度在3000～3500a.u.，得到反应前[P66614][7-HDC]溶液，将其置于SO2气体环境下，静置反应3～60s，在激发波长为365nm，激发与发射狭缝宽度分别为5～20nm和5～20nm下，采集反应前、反应后荧光光谱数据，以SO2的浓度为横坐标，反应前后[P66614][7-HDC]溶液的荧光强度之差为纵坐标，绘制得到标准拟合曲线；
通过将反应前[P66614][7-HDC]溶液置于实际待测环境中，静置反应3～60s之后，采集反应后荧光光谱数据，代入标准拟合曲线，即可获得实际待测环境中SO2的浓度信息；
本发明香豆素型荧光离子液体[P66614][7-HDC]的激发波长为365nm，发射波长为378～550nm。
本发明还涉及一种可用于检测SO2的薄膜设备，该薄膜设备是将[P66614][7-HDC]制备到乙基纤维素膜里面，具体的制备方法为：
将0.2～0.8重量份的乙基纤维素加入5～15体积份乙醇中，在40～120℃下搅拌0.2～1.8h，再加入0.2～0.8体积份10-3M的[P66614][7-HDC]乙醇溶液，继续搅拌0.2～0.8h后，得到均匀的混合液；取所得混合液加入培养皿中，在20～100℃烘箱中放置1～5h，得到含有[P66614][7-HDC]的乙基纤维素薄膜，在紫外灯下具有蓝色荧光，厚度约为0.04～0.1mm；
其中，重量份以g为单位，体积份以mL为单位。
将含有[P66614][7-HDC]的乙基纤维素薄膜置于不同浓度的SO2气体环境中，薄膜的荧光会发生不同程度的猝灭。该乙基纤维素膜对SO2的检测具有可逆性，将其置于SO2环境中，薄膜荧光会发生猝灭，在50～90℃加热处理1～15min，薄膜的荧光又可以恢复。
因此，本发明还获得了一种方便、简单、可重复使用和防水的薄膜设备，用于特异性检测SO2。该乙基纤维素薄膜对SO2的检测表现出优异的选择性。将其置于N2O、HCl、CO2、COS、NH3、N2、H2O、O2、o-DCB、Me2CO、CHCl3、AcOEt、PhMe这些气体环境中，膜的荧光不会发生猝灭。
与现有技术相比，本发明具有以下有益效果：
(1)以离子交换法合成具有蓝色荧光发射的离子液体，该方法合成步骤简单、合成产率高；
(2)合成的[P66614][7-HDC]荧光离子液体热稳定性好、不易挥发、对环境污染性小；
(3)制备的离子液体[P66614][7-HDC]对SO2有较强的特异性、灵敏度，可实现线性范围内SO2的定量检测；
(4)该探针可以制备到乙基纤维素薄膜上，实现对SO2的可视化便携式检测，检测限低至2.1ppm，该膜具有可循环性、防水性等优点，为实际环境中实时检测低浓度SO2提供了可能性。
附图说明
图1为本发明在不同SO2浓度下(9ppm，19ppm，28ppm，34ppm，41ppm，60ppm，90ppm，135ppm)反应后的[P66614][7-HDC]在紫外灯下拍摄的可视化照片。
图2为本发明在不同SO2浓度下(9ppm，19ppm，28ppm，34ppm，41ppm，60ppm，90ppm，135ppm)反应后的[P66614][7-HDC]的荧光发射光谱图。
图3为本发明以与SO2反应前后的[P66614][7-HDC]的荧光强度之差(ΔF)为纵坐标，SO2浓度(9～150nM)为横坐标的荧光变化趋势，插图显示了ΔF和SO2浓度之间的线性关系。
图4为本发明将[P66614][7-HDC]制备到乙基纤维素薄膜中的制备流程。
图5中(a)为本发明制备的乙基纤维素薄膜在日照下和紫外灯下拍摄的照片，(b)为将该薄膜应用于检测不同浓度的SO2后在紫外灯下的可视化照片。
图6中(a)为本发明中乙基纤维素薄膜在浓度为5000ppm时的视觉循环图，(b)为将[P66614][7-HDC]薄膜置于5000ppm浓度的SO2中并加热后，λem＝452nm处发射峰的荧光增强和猝灭循环。
图7为本发明在不同气体下的检测图(SO2、N2O、HCl、CO2、COS、NH3、N2、H2O、O2、o-DCB、Me2CO、CHCl3、AcOEt、PhMe)。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例，不应理解以下内容是对本发明的权利要求书请求保护范围的限制。
实施例中所使用的化学试剂和溶剂均为分析纯。所述的荧光光谱测定条件均为激发波长为365nm，发射波长378～550nm，激发和发射狭缝宽度分别为5nm和5nm。
实施例1：一种荧光离子液体的合成，具体合成方法如下：
(1)[P66614][Cl]的脱氯处理：
用2mol/L的氢氧化钠溶液将717强碱性I型阴离子交换树脂(购自阿拉丁化学有限公司)中的Cl-通过层析柱交换出来，直至用硝酸酸化的硝酸银溶液检测得到澄清透明的溶液，证明无Cl-存在，再用乙醇处理得到无水的强碱性阴离子交换树脂。
将[P66614][Cl]的乙醇溶液缓缓加入到装有经过上述预处理的强碱性阴离子交换树脂的层析柱中，收集流出液[P66614][OH]。
(2)荧光离子液体[P66614][7-HDC]的合成：
在[P66614][OH]的乙醇溶液中加入等摩尔7-HDC，60℃油浴搅拌12h。将所得产物用旋转蒸发干燥，然后在60℃烘箱中再干燥24h。最终得到棕色的粘稠状液体，室温密封保存。反应式如下：
实施例2：离子液体作为比色/荧光探针用于低浓度SO2的检测，具体步骤包括：
(1)荧光/比色探针对SO2气体的检测：
取0.0322g离子液体溶于50mL乙醇中，配置为1mM的储备液。取一定量的储备液，将其置于SO2气氛下，静置12s，在紫外灯下拍摄可视图，如图1所示。在激发波长为365nm，激发与发射狭缝宽度分别为5nm和5nm，将反应后的离子液体用去离子水稀释10倍，再进行荧光光谱数据的采集，结果如图2所示。
从图1中可以看到[P66614][7-HDC]在紫外灯下呈现亮蓝色，当SO2浓度逐渐增大，蓝色荧光慢慢被猝灭。从图2中可以看出，荧光光谱也呈现出同样的变化，[P66614][7-HDC]的荧光随着SO2浓度的增大而减小。
(2)标准曲线的绘制
以反应前后[P66614][7-HDC]的荧光强度之差为纵坐标，SO2浓度为横坐标拟合的线性曲线进行定量分析结果如图3所示。当SO2浓度为0～40ppm时，线性拟合得到的方程为y＝54.93x-17.54(R2＝0.996)。
(3)将[P66614][7-HDC]制备到乙基纤维素膜上
将0.5g乙基纤维素溶于10mL乙醇中，80℃搅拌1h。然后加入500μL 10-3M的[P66614][7-HDC]乙醇溶液，室温搅拌30min后，取一定量的混合溶液置于培养皿中，置于60℃烘箱中3h，制备所需的[P66614][7-HDC]薄膜(厚度约为0.06mm)，如图4所示。
(4)将薄膜应用于SO2的检测
制备好的薄膜在日光下呈现出透明色，在365nm的紫外灯下具有蓝色的荧光，如图5中(a)。将薄膜置于3ppm，120ppm，600ppm，1200ppm的SO2环境中，放置一定的时间，膜的荧光发生猝灭，当SO2浓度增大时，荧光猝灭更加明显，如图5中(b)。
(5)薄膜的循环实验
该离子液薄膜可以循环使用。在高浓度气态SO2中，薄膜的荧光迅速猝灭，在紫外光下薄膜由亮蓝色变为深蓝色，70℃加热10分钟后荧光恢复原状，如图6中(a)。记录薄膜在SO2处理前后442nm处的荧光，从初始荧光强度4325a.u.下降到2500a.u.，如图6中(b)所示。在13个循环内，荧光强度几乎没有变化，表明薄膜可以用于SO2检测。
(6)薄膜对常见气体的响应
将荧光膜放入含有不同气体(如SO2、N2O、HCl、CO2、COS、NH3、N2、H2O、O2、o-DCB、Me2CO、CHCl3、AcOEt、PhMe等)的气氛中，然后在紫外灯(λex＝365nm)下观察薄膜的变化。将薄膜置于2000ppm浓度的SO2中10分钟，1000ppm浓度的COS中10分钟，0.26vol％的N2O中20分钟，1vol％的HCl中3分钟。同时，将薄膜置于纯NH3、H2O、o-DCB、Me2CO、CHCl3、AcOEt、PhMe中3分钟，反应后的薄膜在紫外灯下照片如图7所示。
Claims (8)
1.一种香豆素型荧光离子液体，化学式为[P66614][7-HDC]，结构式如下所示：
2.一种如权利要求1所述香豆素型荧光离子液体的制备方法，其特征在于，所述制备方法为：
在[P66614][OH]的乙醇溶液中加入7-羟基香豆素，20～100℃搅拌1～24h，之后经旋蒸、干燥，得到香豆素型荧光离子液体[P66614][7-HDC]。
3.如权利要求2所述香豆素型荧光离子液体的制备方法，其特征在于，所述[P66614][OH]与7-羟基香豆素的物质的量之比为0.8～1.2：1。
4.如权利要求2所述香豆素型荧光离子液体的制备方法，其特征在于，所述[P66614][OH]的乙醇溶液按如下方法制备得到：
将三己基(十四烷基)氯化膦的乙醇溶液加入到装有强碱性阴离子交换树脂的层析柱中，收集流出液，即得[P66614][OH]的乙醇溶液；
所述强碱性阴离子交换树脂使用前经过如下预处理：用2mol/L NaOH水溶液将717强碱性I型阴离子交换树脂中的Cl-通过层析柱交换出来，再用乙醇处理得到无水的强碱性阴离子交换树脂。
5.如权利要求1所述香豆素型荧光离子液体在检测SO2中的应用。
6.如权利要求5所述的应用，其特征在于，所述应用的方法为：
将[P66614][7-HDC]用无水乙醇溶解并用去离子水稀释至当激发波长为365nm时，[P66614][7-HDC]在452nm处的荧光强度在3000～3500a.u.，得到反应前[P66614][7-HDC]溶液，将其置于SO2气体环境下，静置反应3～60s，在激发波长为365nm，激发与发射狭缝宽度分别为5～20nm和5～20nm下，采集反应前、反应后荧光光谱数据，以SO2的浓度为横坐标，反应前后[P66614][7-HDC]溶液的荧光强度之差为纵坐标，绘制得到标准拟合曲线；
通过将反应前[P66614][7-HDC]溶液置于实际待测环境中，静置反应3～60s之后，采集反应后荧光光谱数据，代入标准拟合曲线，即可获得实际待测环境中SO2的浓度信息。
7.一种薄膜设备，其特征在于，该薄膜设备是将[P66614][7-HDC]制备到乙基纤维素膜里面。
8.如权利要求7所述薄膜设备在检测SO2中的应用。
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| Highly Efficient and Reversible SO2 Capture by Tunable Azole-Based Ionic Liquids through Multiple-Site Chemical Absorption;Congmin Wang 等;《Journal of the American Chemical Society》;20110713;第133卷;全文 * |
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