CN109134383B - 一种苯并咪唑鎓盐及其超分子水凝胶的制备和应用 - Google Patents
一种苯并咪唑鎓盐及其超分子水凝胶的制备和应用 Download PDFInfo
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Abstract
本发明公开了一种苯并咪唑鎓盐BI,是以乙腈为溶剂,2‑十一烷基‑1‑H‑苯并咪唑‑3‑乙酸甲酯和碘甲烷为底物,于85~90℃下反应30~32h;反应结束后冷却至室温,抽滤除溶剂,重结晶而得。将苯并咪唑鎓盐加热溶解于有机溶剂‑水混合溶剂中,冷却至室温后形成稳定的超分子有机水凝胶BI‑G。在BI‑G中分别加入NaCl,Na2SO4,NaClO4,NaNO2,NaNO3,Na3PO4,NaH2PO4,NaHSO3,Na2S2O3,Na2HPO4的水溶液时,只有NaNO2的加入能够引起超分子有机水凝胶荧光猝灭。因此,超分子水凝胶BI‑G对NaNO2具有单一选择性荧光响应性能,能实现对水体中的NO2 ‑的荧光识别。
Description
技术领域
本发明涉及一种苯并咪唑鎓盐类化合物及其制备方法;本发明还涉及一种基于苯并咪唑鎓盐的超分子水凝胶;本发明同时涉及该超分子水凝胶高灵敏度比色-荧光识别亚硝酸离子的应用,属于化合物和成领域和阴离子检测领域。
背景技术
亚硝酸盐对人类和整个生态系统都是一种令人担忧的污染物,但也是很受欢迎的可以改善的食品添加剂颜色、纹理和存储稳定性,被广泛用作腐蚀抑制剂,食品防腐剂和化学肥料。NO2 -对微生物和高级动物有毒性。世界卫生组织已经宣布了NO2 -的致命水平被认为是在8.7~28.3μM-1。在生态系统中,多余的亚硝酸盐存在于我们的身体会氧化血红蛋白,人体内亚硝酸盐的长期和过量积累会引起一种俗称“蓝婴综合症”的疾病。此外,亚硝酸盐也可以与酰胺/胺结合产生有害的N-亚硝胺化合物,导致癌症和高血压。主要是因为亚硝酸盐是NO的主要氧化产物之一,其通过NO合成在不同类型的细胞中产生。而NO2 -沉积在人体系统中导致高铁血红蛋白血症并成为致癌亚硝胺的主要来源。因此,开发一种可行的环境监测方法检测亚硝酸盐是至关重要的,并且亚硝酸的检测在环境检测和生命科学等领域有着重要意义。
目前,人们已经研发出多种离子/分子检测的方法,并且由于荧光法具有操作简便、快捷、灵敏度高等优点,已经发展为离子/分子识别的主要检测手段。化学传感器的设计合成愈发受到人们的关注。然而,在现实生活中,各种对人体有益或有害的离子/分子大都存在于水相中,而所报道的可以对离子进行检测的方法大多是在溶液中进行,对离子/分子的检测也比较局限。另外,离子响应型超分子有机水凝胶由于其易于制备、使用方便,成为了离子识别领域的研究热点。
发明内容
本发明的目的是提供一种能够识别亚硝酸离子的苯并咪唑鎓盐及其合成方法;
本发明的另一目的是提供一种基于所述苯并咪唑鎓盐的超分子有机水凝胶;
本发明还有一个目的,就是提供一种基于所述苯并咪唑鎓盐类的超分子有机水凝胶在比色-荧光识别水体中亚硝酸离子的具体应用。
一、苯并咪唑鎓盐
本发明苯并咪唑鎓盐的分子式为:C22H35N2O2I,命名为:N-甲氧基羰甲基-2-十一烷基苯并咪唑碘鎓盐,标记为:BI,其结构式为:
苯并咪唑鎓盐BI的制备:以乙腈为溶剂,2-十一烷基-1H-苯并咪唑-3-乙酸甲酯和碘甲烷的摩尔比为1:1~1:3,于85~90℃下反应30~32h;反应结束后冷却至室温,抽滤除溶剂,用DMF/ EtOH /H2O重结晶,得白色固体产物即为目标化合物——苯并咪唑鎓盐BI。苯并咪唑鎓盐BI的氢谱见图1。
苯并咪唑鎓盐BI的结构中,咪唑作为一荧光信号基团,长烷基链作为范德华驱动力,在苯并咪唑骨架上1位的N原子上引入甲基,形成功能化的苯并咪唑鎓盐后,其表现出很好的水溶性和配位能力。因此,以苯并咪唑鎓盐BI为凝胶因子,在有机溶剂与水的二元混合溶剂中能形成稳定的有机水凝胶。
二、基于苯并咪唑鎓盐的超分子有机水凝胶
基于苯并咪唑鎓盐的超分子有机水凝胶,是将苯并咪唑鎓盐BI加热溶于有机溶剂-水的混混合溶剂中,形成均匀的质量体积比为1mg/mL的溶液,冷却至室温后形成稳定的超分子有机水凝胶,记为BI-G。
其中,有机溶剂-水的混合溶剂中,有机溶剂为乙腈、二甲基亚砜、N,N-二甲基甲酰胺或乙二醇,有机溶剂与水的体积比为1:1~1:9。由于苯并咪唑鎓盐在乙二醇/水(v/v=1:9)中具有较高的转熔温度(46℃),在后续的一系列实验中,选用在乙二醇/水(v/v=1:9)中形成质量体积比为1mg/mL的超分子有机水凝胶BI-G进行性能研究。
三、超分子有机水凝胶BI-G在离子检测中的应用
1、有机水凝胶BI-G对不同钠盐的荧光性能
由于苯并咪唑鎓盐BI的分子中引入羰基作为金属离子的结合位点,其次以长烷基链的缠绕作用,刚性结构基团苯并咪唑间的π-π堆积作为成凝胶的驱动力,致使凝胶因子具有良好的荧光性能。图2为凝胶因子BI在乙二醇/水(v/v=1:9)中形成的超分子有机水凝胶BI-G的荧光发射光谱。
在超分子有机水凝胶BI-G中分别加入2倍摩尔量(相对于传感器分子BI)的NaCl,Na2SO4,NaClO4,NaNO2,NaNO3,Na3PO4,NaH2PO4,NaHSO3,Na2S2O3,Na2HPO4的钠盐水溶液(浓度为0.1M),发现,只有NaNO2的加入能够引起超分子有机水凝胶BI-G荧光猝灭(见图2),而其他钠盐的加入不能产生类似的荧光猝灭性能。因此,超分子水凝胶BI-G对NaNO2具有单一选择性荧光响应性能,能实现对水体中的NO2 -的荧光识别。
2、超分子有机水凝胶BI-G对亚硝酸根离子的荧光滴定响应
在超分子有机水凝胶BI-G中加入不同倍摩尔量(相对于传感器分子BI)的NaNO2的水溶液。发现,随着NO2 -量从0倍当量逐渐增加,有机水凝胶的荧光强度逐渐减弱,当NO2 -量增加到2倍当量时,超分子有机水凝胶的荧光强度不再发生变化,即荧光达到猝灭。在相应的荧光光谱中,当NO2 -量增加到2倍当量时,荧光光谱发生红移(见图3),说明NO2 -与该有机水凝胶发生了配位作用。滴定实验还表明,超分子有机水凝胶BI-G对NO2 -的最低检测限为2.75 × 10-8 M。
图4为超分子有机水凝胶BI-G中加入2倍摩尔量亚硝酸钠时的线性拟合。线性拟合曲线说明了利用滴定得到的数据的置信度高,误差相对较小。
3、超分子有机水凝胶BI-G裸眼测试
在超分子有机水凝胶BI-G中分别加入2倍摩尔量(相对于BI)的NaNO2钠盐,观察超分子有机水凝胶BI-G。结果发现,随着时间的变化,NaNO2钠盐缓慢渗透,超分子有机水凝胶BI-G被破坏,超分子有机水凝胶的颜色由白色转变为浅黄色,同时荧光猝灭。因此,超分子有机水凝胶BI-G能实现对NO2 -的裸眼检测。
综上所述,本发明设计合成了一种基于苯并咪唑鎓盐类凝胶因子,在该凝胶因子的分子中,引入羰基作为金属离子的结合位点,其次以长烷基链的缠绕作用,苯并咪唑间的π-π堆积作为成凝胶的驱动力,同时苯并咪唑作为一个刚性结构稳定的体系,致使凝胶因子具有良好的荧光性能。该凝胶因子在有机溶剂与水中形成的超分子有机水凝胶对NO2 -具有单一选择性荧光识别性能。超分子有机水凝胶与亚硝酸根离子结合后荧光猝灭,凝胶状态破坏,且发生了红移,实现了传感器分子“ON-OFF”荧光信号体现。这种“ON-OFF”类型传感器分子的合成实现了对亚硝酸根的灵敏检测。
附图说明
图1为本发明制备的苯并咪唑鎓盐BI的氢谱图。
图2为本发明超分子有机水凝胶BI-G在乙二醇/水(v/v=1:9)中加入不同钠盐时的荧光光谱(激发波长280 nm)。
图3为超分子有机水凝胶BI-G中加入2倍摩尔摩尔量的亚硝酸钠时的荧光滴定光谱(激发波长280nm)。
图4为超分子有机水凝胶BI-G中加入2倍摩尔量亚硝酸钠时荧光滴定光谱的线性拟合。
具体实施方式
下面通过具体实施例对本发明凝胶因子BI的合成、超分子有机水凝胶及其在比色/荧光识别亚硝酸根离子的应用做进一步说明。
实施例1、苯并咪唑鎓盐BI的制备
称取1.03 g(3.0 mmol)2-十一烷基-1-H-苯并咪唑-3-乙酸甲酯,1.27 g(9.0mmol)碘甲烷,加入到1ml乙腈中,于85~90℃下反应30~32 h;反应结束后冷却至室温,抽滤除溶剂,用DMF/EtOH/H2O重结晶,得白色固体产物即为苯并咪唑鎓盐BI,产率为53.9%。
实施例2、超分子有机水凝胶BI-G的制备
取实施例1制备的于苯并咪唑鎓盐BI 0.001 g,加入1.00 mL乙二醇/水(v/v=1:9),加热使其充分溶解,静置,冷却至室温后形成质量体积比为1mg/mL的超分子有机水凝胶BI-G。该凝胶BI-G为白色,转熔温度为46℃。
实施例3、超分子有机水凝胶BI-G比色-荧光识别亚硝酸离子
移取超分子有机水凝胶BI-G于一系列点滴板中,分别加入15μLNaCl,Na2SO4,NaClO4,NaNO2,NaNO3,Na3PO4,NaH2PO4,NaHSO3,Na2S2O3,Na2HPO4的钠盐水溶液(浓度为0.1M),若超分子有机水凝胶BI-G的荧光猝灭,则说明滴加的是NaNO2,若超分子有机水凝胶的荧光没有猝灭,则说明滴加的不是NaNO2。
实施例4、超分子有机水凝胶BI-G裸眼测试
移取超分子有机水凝胶BI-G于一系列点滴板中,分别加入NaCl,Na2SO4,NaClO4,NaNO2,NaNO3,Na3PO4,NaH2PO4,NaHSO3,Na2S2O3,Na2HPO4的钠盐水溶液(浓度为0.1M),若超分子有机水凝胶BI-G颜色由白色转变为浅黄色,则说明滴加的是NaNO2,若超分子有机水凝胶的颜色没有发生变化,则说明滴加的不是NaNO2。
Claims (6)
2.如权利要求1所述基于苯并咪唑鎓盐的超分子有机水凝胶在荧光识别亚硝酸根离子中的应用,其特征在于:所述苯并咪唑鎓盐的制备方法,是以乙腈为溶剂,2-十一烷基-1-H-苯并咪唑-3-乙酸甲酯和碘甲烷为底物,于85~90℃下反应30~32h;反应结束后冷却至室温,抽滤除溶剂,用DMF/EtOH/H2O重结晶,即得。
3.如权利要求2所述基于苯并咪唑鎓盐的超分子有机水凝胶在荧光识别亚硝酸根离子中的应用,其特征在于:底物2-十一烷基-1H-苯并咪唑-3-乙酸甲酯与碘甲烷的摩尔比为1:1~1:3。
4.如权利要求1所述基于苯并咪唑鎓盐的超分子有机水凝胶在荧光识别亚硝酸根离子中的应用,其特征在于:苯并咪唑鎓盐以1~2mg/mL的质量体积比加热溶解于有机溶剂-水的二元混合溶剂中。
5.如权利要求1所述基于苯并咪唑鎓盐的超分子有机水凝胶在荧光识别亚硝酸根离子中的应用,其特征在于:有机溶剂-水的二元混合溶剂中,有机溶剂为乙腈、乙二醇、二甲基亚砜、N,N-二甲基甲酰胺的一种;有机溶剂与水的体积比为1:1~1:9。
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