CN111517947A - 一种基于功能化的双边柱[5]芳烃传感器分子及其合成和应用 - Google Patents
一种基于功能化的双边柱[5]芳烃传感器分子及其合成和应用 Download PDFInfo
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Abstract
本发明设计合成了一种基于功能化的双边柱[5]芳烃传感器分子,该传感器分子在DMSO和H2O的二元溶液中通过分子间氢键相互作用形成超分子自组装体系,该体系几乎没有荧光。当加入异烟肼、苯甲酰肼、苯肼、水合肼的DMSO‑H2O溶液时,只有异烟肼的加入可使溶液的荧光打开变成绿色,因此可用于荧光选择性识别异烟肼,而且识别过程不受其它分子的干扰并且检测速度快。基于这个结果,制作了异烟肼的荧光检测试纸可以方便快速地检测异烟肼。
Description
技术领域
本发明涉及一种基于功能化的双边柱[5]芳烃传感器分子,尤其涉及一种基于对羟基苯甲酸功能化的双边柱[5]芳烃的化学传感器分子及其合成,本发明同时还涉及该传感器分子荧光检测异烟肼的应用,属于化学合成领域和药物分子检测技术领域。
背景技术
异烟肼(IA)作为抑菌剂已单独或与其他药物(主要是利福平)联合用于结核的化学疗法。由于其生物膜穿透性好、疗效佳、毒性小、价廉、口服方便,故被列为首选抗结核药。该品易通过血脑屏障,适用于各种类型的结核病,如肺、淋巴、骨、肾、肠等结核,结核性脑膜炎、胸膜炎及腹膜炎等。但是,高浓度的这种治疗剂会导致癫痫,肝功能衰竭甚至死亡。另一方面,取决于患者的身体状况,该药物剂量的20%至70%可通过尿液排出体外,最终像其他抗生素一样进入废水中,这可能导致出现诸如细菌等危险的耐药菌株。尽管存在这些风险因素,异烟肼对结核菌素具有良好的生化抑制活性是临床用药不可缺少的。病人使用异烟肼处理后必须定期监测,以便预防副作用。因此,设计可高灵敏度检测,且具有成本效益和可靠的分析工具,用于精确测定异烟肼是临床诊断的关键。为此,设计和合成了基于柱[5]芳烃的新型超分子有机材料,可简单、快速、成本低的检测异烟肼。
伴随着科学技术的飞速发展,到目前为止,人们已经研究出多种用于检测异烟肼的分析程序,包括滴定法,可见光分光光度法,极谱法,库仑法,荧光法,化学发光法和几种色谱法。其中荧光分析法由于仪器价格较低、操作方便等、被广泛用于分子检测领域。
发明内容
本发明的目的是提供一种基于功能化的双边柱[5]芳烃传感器分子及其合成方法;
本发明的另一目的是提供一种上述传感器分子在荧光检测异烟肼的具体应用。
一、传感器分子及其合成
本发明基于功能化的双边柱[5]芳烃传感器分子,其结构如下:
本发明基于功能化的双边柱[5]芳烃传感器分子的合成方法,包括以下工艺步骤:
(1)以乙腈为溶剂,溴功能化的双边柱[5]芳烃和对羟基苯甲酸甲酯为底物,在KI和K2CO3的作用下,以氮气为保护气,于80~85℃油浴回流搅拌10~12小时,反应结束后加硅胶拌样,旋干,用柱层析法纯化,得到白色产物即为对羟基苯甲酸甲酯功能化的双边柱[5]芳烃。其中,溴功能化的双边柱[5]芳烃与对羟基苯甲酸甲酯的摩尔比为1:2~1:2.2;溴功能化的双边柱[5]芳烃与KI的摩尔比为1:4~1:4.2;溴功能化的双边柱[5]芳烃与K2CO3的摩尔比为1:4~1:4.2。
(2)将对羟基苯甲酸甲酯功能化的双边柱[5]芳烃溶于DMF中,加入NaOH溶液,于120~125℃油浴搅拌回流10~12小时,反应完冷却,加入蒸馏水,用浓盐酸调节pH至1~2,静置析出产物后减压抽滤,用乙醇和水重结晶得传感器分子ZW。其中,NaOH的浓度为1mol/L,NaOH的用量为对羟基苯甲酸甲酯功能化的双边柱[5]芳烃摩尔量的2~4倍。
图1和图2分别为传感器分子ZW的氢谱图和质谱图,表明传感器分子ZW合成成功。
二、ZW对异烟肼的识别实验
1、ZW对异烟肼的荧光响应
分别移取0.5mL含水百分之四十的ZW溶液(2×10-4mol·L-1)于一系列10mL的比色管中,用DMSO/H2O=6:4(v/v)释至5mL,分别加入异烟肼、苯甲酰肼、苯肼、水合肼的DMSO/H2O溶液(2×10-4mol·L-1)0.5 mL。此时ZW的浓度为2×10-5mol·L-1,各分子浓度为ZW浓度的10倍,观察传感器分子ZW对各分子的响应。
结果发现,当向含有ZW的溶液中分别加入上述分子时,在自然光下,基本无变化。在紫外灯下(365 nm),异烟肼的加入使溶液的荧光打开呈现出绿色荧光,传感器分子ZW在329 nm处的吸收峰发生下降,在470 nm处出现新的吸收峰 (图3)。而其余分子的加入对ZW溶液的荧光光谱无明显影响(图4)。说明该传感器分子ZW能专一选择性识别异烟肼。
2、ZW在识别异烟肼过程中的抗干扰检测
为了测定ZW在识别异烟肼过程中的抗干扰能力,我们进行了如下测试:取8支10mL的比色管分别加入0.5mL上述ZW溶液(2×10-4mol·L-1),将第1支比色管用DMSO/H2O=6:4(v/v)稀释至5mL;向第2支比色管中加入0.5mL异烟肼(IA),然后用DMSO/H2O=6:4(v/v)稀释至5mL;再取3支比色管向其中分别加入苯甲酰肼、苯肼、水合肼;向其余3支比色管中分别加入0.5mL IA,再依次加入0.5mL苯甲酰肼、苯肼、水合肼的DMSO/H2O= 6:4(v/v)溶液(4×10- 3mol·L-1),最后用DMSO/H2O=6:4(v/v)稀释至5mL。混合均匀后,测定其荧光的变化,图5荧光抗干扰图。结果发现,加入其他分子后,ZW对异烟肼的识别基本不受其它分子的干扰。
3、ZW识别异烟肼的响应时间
常见的传感器分子比色或荧光识别异烟肼的过程需要较长的反应时间,这种因素往往限制了许多传感器分子的推广使用。因此,我们探究了ZW识别异烟肼的响应时间。在紫外灯下(365 nm),当加入异烟肼后,溶液荧光瞬间打开,颜色变成绿色,可以看出,ZW对异烟肼的响应在片刻间(< 3s)即可发生。因此ZW对异烟肼具有较快的检测速度。
4、ZW对异烟肼识别实验的丁达尔效应
如图6所示,ZW稀释液无丁达尔现象。但是,随着异烟肼的加入,稀释溶液的丁达尔效应明显。
5、基于ZW的异烟肼检测试纸
将试纸剪成长方形并浸泡在含有ZW的溶液中10min,使ZW充分吸附于滤纸上,然后取出晾干,该滤纸在自然光下无色,在365nm紫外灯下并没有荧光。
向滤纸上滴加含有异烟肼的溶液,在自然光下滤纸的颜色并无变化,而在365nm紫外灯下滤纸呈现亮绿色荧光。
三、ZW对异烟肼的识别机理
针对ZW对异烟肼的识别机理,我们通过核磁滴定(1HNM)、红外、质谱和扫描电镜(SEM)进行了探究。1HNM谱图表明:12.6 ppm处ZW的-O-H信号峰随异烟肼的不断加入消失,并且4.6ppm处异烟肼的-N-H信号峰也逐渐消失(图7)。在其相应的红外光谱中,加入异烟肼后,传感器分子ZW的-O-H和-C=O以及异烟肼的-N-H峰分别由3430 cm-1,1688 cm-1和3309 cm-1轻微红移至3418 cm-1,1678 cm-1和3302 cm-1(图8),可能形成了分子间氢键。并且在ZW-IA的质谱中有ZW:IA=1:2的质谱峰([ZW+2IA+H]+:1435.6797)(图9)。SEM图表明:图10a和图10b分别为异烟肼与ZW干粉末的扫描电镜照片,可以看出异烟肼是片层状结构,ZW是块状结构,而两者组装之后是规则的棒状结构(图10c)。此外,如图6所示,ZW稀释液无丁达尔现象,但是,加入异烟肼后,稀释溶液的丁达尔效应明显。这些结果表明,ZW和异烟肼的反应产生了聚集诱导(AIE)绿色荧光。
作为比较,合成了另外三种非羧基化合物功能化的柱[5]芳烃ZQ,ZE,ZR。如图11所示,在365nm的紫外灯下,ZW中加入异烟肼观察到明显的荧光增强,荧光颜色变为亮绿色,而ZQ,ZE,ZR中加入异烟肼,溶液荧光并没有发生变化。说明化合物ZW识别异烟肼,羧基起到重要作用。
附图说明
图1为ZW的氢谱图。
图2为ZW的质谱图。
图3为ZW和ZW中加入异烟肼的荧光光谱图(λex=285nm)。
图4为ZW中加入异烟肼、苯甲酰肼、苯肼、水合肼的荧光变化光谱图(λex=285nm)。
图5为ZW对异烟肼识别的荧光抗干扰光谱图。
图6为ZW识别异烟肼的丁达尔现象照片。
图7为向ZW中逐渐加入异烟肼时的核磁变化谱图。
图8为ZW、IA和ZW-IA的红外谱图。
图9为ZW识别异烟肼后[ZW+2IA+H]+的质谱图。
图10为ZW、IA和ZW-IA的扫描电镜照片。
图11为紫外灯下(365 nm) (a) ZW, (b) ZW + IA, (c) ZQ, (d) ZQ + IA, (e)ZE,(f) ZE + IA, (g)ZR, (h) ZR + IA的照片。
具体实施方式
下面通过具体实施例对本发明异烟肼传感器分子ZW的结构、合成及异烟肼检测试纸的合成和应用作进一步说明。
实施例1、异烟肼传感器分子ZW的合成
(1)向100mL圆底烧瓶中分别加入乙腈(50mL)、溴功能化的双边柱[5]芳烃(ZE,0.523g,0.5mmol,按文献DOI:10.1039/C9SM01385G的方法合成)、对羟基苯甲酸甲酯(2.4mmol,0.4g)、KI(10mmol,1.66 g)、K2CO3(8mmol,1.0g),氮气保护80℃油浴回流搅拌10~12小时。反应结束后加硅胶拌样,旋干,用柱层析法纯化(石油醚:乙酸乙酯:二氯乙烷 =100 : 25:1),得到白色产物即为对羟基苯甲酸甲酯功能化的双边柱[5]芳烃,产率为75%。
(2)称取羟基苯甲酸甲酯功能化的双边柱[5]芳烃(1.16g,1 mmol)溶于100 mLDMF中,向该体系中加入浓度为1mol/L的NaOH水溶液4mL,120℃油浴回流搅拌10~12小时;冷却用浓盐酸调PH=1,静置析出产物后减压抽滤,用乙醇和水重结晶得传感器分子ZW,产率为91%。其合成式如下:
ZW熔点:187℃。质谱:1163.5337。
实施例2、ZW溶液检测异烟肼
分别移取0.5mL含水百分之四十的ZW溶液(2×10-4mol·L-1)于一系列10mL的比色管中,用DMSO/H2O=6:4(v/v)释至5mL,分别加入异烟肼、苯甲酰肼、苯肼、水合肼的DMSO/H2O溶液(2×10-4mol·L-1)0.5 mL。此时ZW的浓度为2×10-5mol·L-1,各分子浓度为ZW浓度的10倍,观察传感器分子ZW对各分子的响应。在紫外灯下(365 nm),加入异烟肼的ZW溶液呈现出绿色荧光,加入其他分子的ZW溶液无变化。说明该传感器分子ZW能专一选择性识别异烟肼。
实施例3、异烟肼检测试纸的合成和应用
将试纸剪成长方形并浸泡在含有ZW的溶液中10min,使ZW充分吸附于滤纸上,然后取出晾干,该滤纸在365nm紫外灯下没有荧光。分别向滤纸上滴加异烟肼、苯甲酰肼、苯肼、水合肼的溶液,若滤纸荧光增强变为绿色,说明滴加的是异烟肼;若滤纸的荧光没有发生变化,说明加入的不是异烟肼。
Claims (9)
2.如权利要求1所述基于功能化的双边柱[5]芳烃传感器分子的合成方法,包括以下工艺步骤:
(1)以乙腈为溶剂,溴功能化的双边柱[5]芳烃和对羟基苯甲酸甲酯为底物,在KI和K2CO3的作用下,以氮气为保护气,于80~85℃油浴回流搅拌10~12小时,反应结束后加硅胶拌样,旋干,用柱层析法纯化,得到白色产物即为对羟基苯甲酸甲酯功能化的双边柱[5]芳烃;
(2)将对羟基苯甲酸甲酯功能化的双边柱[5]芳烃溶于DMF中,加入NaOH溶液,于120~125℃油浴搅拌回流10~12小时,反应完冷却,加入蒸馏水,用浓盐酸调节pH至1~2,静置析出产物后减压抽滤,用乙醇和水重结晶得传感器分子ZW。
3.如权利要求2所述基于功能化的双边柱[5]芳烃传感器分子的合成方法,其特征在于:步骤(1)中,溴功能化的双边柱[5]芳烃与对羟基苯甲酸甲酯的摩尔比为1:2~1:2.2。
4.如权利要求2所述基于功能化的双边柱[5]芳烃传感器分子的合成方法,其特征在于:步骤(1)中,溴功能化的双边柱[5]芳烃与KI的摩尔比为1:4~1:4.2。
5.如权利要求2所述基于功能化的双边柱[5]芳烃传感器分子的合成方法,其特征在于:步骤(1)中,溴功能化的双边柱[5]芳烃与K2CO3的摩尔比为1:4~1:4.2。
6.如权利要求2所述基于功能化的双边柱[5]芳烃传感器分子的合成方法,其特征在于:NaOH的浓度为1mol/L,NaOH的用量为对羟基苯甲酸甲酯功能化的双边柱[5]芳烃摩尔量的2~4倍。
7.如权利要求1所述基于功能化的双边柱[5]芳烃传感器分子荧光选择性检测异烟肼的应用,其特征在于:向含有该传感器分子的DMSO/H2O溶液中分别加入异烟肼、苯甲酰肼、苯肼、水合肼的DMSO/H2O溶液,若溶液的荧光变成绿色,说明加入的是异烟肼;若溶液的荧光没有发生变化,说明加入的不是异烟肼;所述DMSO/H2O溶液中,水的体积含量为40~41%。
8.一种负载有如权利要求1所述基于功能化的双边柱[5]芳烃传感器分子的异烟肼检测试纸。
9.如权利要求8所述异烟肼检测试纸用于检测异烟肼,其特征在于:用ZW的溶液浸泡滤纸后将其晾干,再分别向晾干的滤纸上滴加异烟肼、苯甲酰肼、苯肼、水合肼的DMSO/H2O溶液,若滤纸的荧光由无色变为绿色,说明滴加的是异烟肼;若滤纸的荧光没有发生变化,说明滴加的不是异烟肼。
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