CN111393445B - 一种基于吩嗪衍生物的超分子传感器及其制备和应用 - Google Patents
一种基于吩嗪衍生物的超分子传感器及其制备和应用 Download PDFInfo
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Abstract
本发明设计合成了一种基于吩嗪衍生物的超分子传感器,是以DMF为溶剂,以2,3‑二氨基吩嗪和8‑羟基‑5‑甲酰基喹啉为底物,冰醋酸作为催化剂,于85℃~90℃下反应8‑9小时,反应结束后抽滤,再用DMF/H2O混合液重结晶得到。该超分子传感器能与挥发性有机溶剂发生作用,呈现出不同的荧光颜色,因此可用于检测识别挥发性有机溶剂。此外,传感器应用于pH(2‑13)检测时,在DMF‑H2O溶液能够选择性荧光增强识别的pH为9~13,比色识别的pH为12~13。
Description
本发明涉及一种基于吩嗪衍生物的超分子传感器及制备方法,本发明同时还涉及超分子传感器识别挥发性有机溶剂、pH的应用,属于化学合成领域、挥发性有机溶剂检测和pH检测领域。
背景技术
吩嗪及其衍生物最早的应用是染料,后来发现它们有生物活性而可以被用作杀菌剂。近年来吩嗪在医药、农药、发色体、导体和电池材料等领域的应用越来越广泛。吩嗪染料,特别是吩嗪隐色基染料的中间体,被用于工业领域已经有100多年的历史,最早用作染料的为脓毒紫(1-羟基-5-甲基吩嗪),因其能够提供红色、橙色和品红等色调,被广泛应用于染料的制备,但在其3-位、或7-位以及3,7-位上基本没有其他的取代基团,使得应用受到限制,因此,开发一种新的带有其他取代基的吩嗪是很有必要的。此外,8-羟基喹啉作为一种荧光基团,由于大的共轭体系、高额的荧光量子产率等优点,被广泛的应用于离子检测和药物合成方面,因此设计含有8-羟基喹啉的衍生物可以为超分子研究提供一个更广阔的平台。
VOCs(volatile organic compounds)挥发性有机物,是指常温下饱和蒸汽压大于70 Pa、常压下沸点在260℃以下的有机化合物,或在20℃条件下蒸汽压大于或者等于10 Pa具有相应挥发性的全部有机化合物。特别是像常见的挥发性有机化合物,如:丙酮、二氯甲烷、四氢呋喃等易挥发性的溶剂,对人体有很大的伤害。室内空气中挥发性有机化合物浓度过高时很容易引起急性中毒,轻者会出现头痛、头晕、咳嗽、恶心、呕吐或呈酩醉状;重者会出现肝中毒甚至昏迷,有的还可能有生命危险。长期居住在挥发性有机化合物污染的室内,可引起慢性中毒,损害肝脏和神经系统、引起全身无力、瞌睡、皮肤瘙痒等。经国外医学研究在证实,生活在挥发性有机化合物污染环境中的妊妇,造成胎儿畸形的几率远远高于常人,并且有可能对孩子今后的智力发育造成影响。同时,室内空气中的挥发性有机化合物是造成儿童神经系统、 血液系统、儿童后天疾患的重要原因。因此,研究开发一种荧光检测常见挥发性有机溶剂的传感器在当前社会是很有必要的。
碱性pH传感器与皮革加工、废水处理、造纸行业、金属采矿、涂布等领域密切相关。但目前报道的pH传感器大多对中性或酸性范围有明显的响应,目前对碱性pH的检测报道较少,尤其是对强碱性pH区(pH>10)的检测报道较少。因此,开发适用于碱性pH的传感器仍是十分必要的。
发明内容
本发明的目的是提供一种基于吩嗪衍生物的超分子传感器;
本发明的另一目的是提供上述超分子传感器的合成方法;
本发明还有一个目的是提供超分子传感器识别挥发性有机溶剂、pH的应用。
一、超分子传感器及其合成
本发明传基于吩嗪衍生物的超分子传感器,分子式为:C22H13N5O,,其结构式为:
传感器分子FQ-5的合成:是以DMF为溶剂,以2,3-二氨基吩嗪和8-羟基-5-甲酰基喹啉为底物,冰醋酸作为催化剂,于85~90℃下反应8~9h,反应结束后抽滤,再用DMF/H2O混合液重结晶得到目标化合物,标记为:FQ-5。其中,2,3-二氨基吩嗪与8-羟基-5-甲酰基喹啉的摩尔比为1:1.1~1:1.2;冰醋酸的用量为2,3-二氨基吩嗪摩尔量的0.005~0.015倍。
上述合成的传感器分子FQ-5氢谱、质谱和红外谱图见图1、图2和图3,表明合成成功。
二、超分子传感器FQ-5的荧光性能及对挥发性有机溶剂的荧光识别
将超分子传感器FQ-5加入到挥发性有机溶剂二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷中(CFQ-5 = 1.0×10-4 M),超分子传感器FQ-5在不同挥发性有机溶剂中表现出很好的荧光现象(如图4),并且我们在CIE图可以很明显看出FQ-5在不同溶剂中具有不同荧光颜色:FQ-5在二甲基亚砜或N,N-二甲基甲酰胺呈现黄色荧光,在二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷分别呈现绿色、草绿色、天蓝色、浅蓝色、橄榄绿色、蓝绿色、深蓝色荧光(如图5),因此超分子传感器FQ-5可以荧光识别上述挥发性有机溶剂。
通过紫外全扫描得到最佳的良溶剂为N,N-二甲基甲酰胺(DMF),发现环己烷、水为不良溶剂(如图6),又考虑到清洁能源、环境污染等原因,因此,我们选择N,N-二甲基甲酰胺作为良溶剂,水作为不良溶剂,探究了FQ-5的聚集诱导荧光增强效应,发现在含水10%的时候FQ-5表现出最佳的荧光性能(如图7)。
三、超分子传感器对pH的识别
1、pH缓冲溶液的制备
称取0.1192g的N-2-羟乙基哌嗪-N’-2-2-乙磺酸,加入100ml的蒸馏水备用。然后分别取少量的高氯酸和四丁基氢氧化铵加入蒸馏水稀释备用。将配好的N-2-羟乙基哌嗪-N’-2-2-乙磺酸溶液分别加到12支试管中,在分别各自滴加高氯酸和四丁基氢氧化铵溶液,用pH计进行测量,误差在(0.01~0.03)之间,得到pH(2~13)缓冲溶液。
2、超分子传感器荧光选择性识别pH
在超分子传感器FQ-5的DMF-H2O(9:1,V/V)溶液(CFQ-5 = 1.0×10-4 M)中,分别加入pH(2~13)缓冲溶液,结果发现,pH值为9~13的缓冲溶液的加入可以使FQ-5的DMF-H2O溶液黄色的荧光增强,pH为2~8的缓冲溶液的加入使得FQ-5的DMF-H2O溶液黄色荧光猝灭(如图8)。因此,FQ-5在DMF-H2O溶液能够选择性荧光增强识别出pH为9~13。
3、荧光量子产率的计算
从图9中可以看到pH为9~10的紫外吸收峰并没有发生变化,pH=11时483nm处的吸收峰有所降低,pH为11~13时在531nm处出现新的吸收峰。因此,我们以硫酸奎宁为荧光量子产率的基准物质,测定了pH为11~13时FQ-5和硫酸奎宁的荧光光谱和紫外光谱(如图10、11、12)。根据荧光量子产率的公式:[Y待测=Y参比×(F待测/F参比)×(A参比/A待测) ,Y参比=0.55,F为荧光积分面积,A为吸光度,计算了pH为11~13的荧光量子产率,分别达到47.1%、80.9%、77.0%。所以,FQ-5在DMF-H2O溶液中能够选择性荧光增强识别的pH为9~13,并且pH为11~13时具有高额的荧光量子产率。
4、超分子传感器比色选择性识别pH
在超分子传感器FQ-5的DMF-H2O(9:1,V/V)溶液(CFQ-5 = 1.0×10-4 M)中,分别加入pH(2~13)缓冲溶液,结果发现,pH为12~13的缓冲溶液的加入可以使FQ-5的DMF-H2O溶液颜色由黄色变为紫色,其他pH值缓冲溶液的加入对FQ-5的DMF-H2O溶液颜色无明显影响。在相应的紫外光谱中,pH为12~13缓冲溶液的加入使得FQ-5的DMF-H2O溶液的紫外光谱在531nm处出现一个新的吸收峰,其余pH缓冲溶液的加入对FQ-5的DMF-H2O溶液的紫外光谱影响不大(如图9)。因此,FQ-5在DMF-H2O溶液能够选择性比色识别的pH为12~13。
5、超分子传感器对pH的识别机理分析
通过核磁滴定和扫描电镜实验表征了超分子传感器对pH的识别机理。如图13所示,通过向含有FQ-5的DMSO-d6中逐渐滴加OH-,我们发现咪唑N上的H1逐渐向高场移动,当加入到0.2倍当量时,发现H1消失;此外,再向其中加入H+,发现喹啉羟基上的H2也向高场移动,并且随着H+的加入,H2没有消失,咪唑N上的H1并没有恢复,这是由于FQ-5中含有羟基官能团,而羟基是一个供电子基团,当向FQ-5中加入H+,容易与羟基形成分子间的氢键作用,导致FQ-5发生自身组装,使荧光猝灭;而加入OH-,它破坏了之前的组装方式,并且脱掉咪唑上的H1质子,使荧光增强。另外,我们也可以从扫描电镜(图14)中看到FQ-5本身是呈现出不规则块状形貌(图14a),当加入pH=2和pH=7的溶液时分别呈现出珊瑚状形貌(图14b)和层状形貌(图14c),这说明发生了组装;而当加入pH=13溶液时,FQ-5呈现断条形貌(图14d),说明破坏了之前的组装方式,并且也没有恢复到原有的形貌,这不仅直接证明了以上机理的正确性,也说明了对于pH的识别是由于分子间氢键作用和脱质子所导致的。
附图说明
图1为本发明传感器分子FQ-5的氢谱图;
图2为本发明传感器分子FQ-5的质谱图;
图3为本发明传感器分子FQ-5的红外谱图;
图4为本发明传感器分子FQ-5在不同溶剂中的全扫描(λex= 430nm); DMSO (二甲基亚砜); DMF (N,N-二甲基甲酰胺); Acetone (丙酮); DCM (二氯甲烷); EtOH (乙醇);MeOH (甲醇); MeCN (乙腈); EtOAC (乙酸乙酯);Hexane (环己烷);
图5为本发明传感器分子FQ-5在不同溶剂中的CIE图;DMSO (二甲基亚砜); DMF(N,N-二甲基甲酰胺); Acetone (丙酮); DCM (二氯甲烷); EtOH (乙醇); MeOH (甲醇);MeCN (乙腈); EtOAC (乙酸乙酯);Hexane (环己烷);
图6为本发明传感器分子FQ-5在不同溶剂中的紫外全扫描;
图7为本发明传感器分子FQ-5在DMF中含不同比例水的荧光全扫描;
图8为本发明传感器分子FQ-5的DMF-H2O(9:1,V/V)溶液在不同pH值下的荧光全扫描(λex= 430nm);
图9为本发明传感器分子FQ-5的DMF-H2O(9:1,V/V)溶液在不同pH值下的紫外全扫描;
图10为本发明传感器分子FQ-5和硫酸奎宁在pH=11的荧光光谱(a)和紫外光谱(b);
图11为本发明传感器分子FQ-5和硫酸奎宁在pH=12的荧光光谱(a)和紫外光谱(b);
图12为本发明传感器分子FQ-5和硫酸奎宁在pH=13的荧光光谱(a)和紫外光谱(b);
图13为本发明传感器溶液中加入H+和OH-的核磁滴定谱图,(a) FQ-5;(b) 0.1当量的OH-;(c) 0.2当量的OH-; (c) 0.1当量的H+ ; (d) 0.2当量的H+; (e) 0.3当量的H+ ;(f) 0.5当量的H+;
图14为本发明传感器溶液中加入H+和OH-的电镜照片图。
具体实施方式
下面通过具体实施例对本发明传感器分子FQ-5的制备和应用做进一步说明。
实施例一、FQ-5的制备
将2,3-二氨基吩嗪(0.42 g, 2 mmol)和8-羟基-5甲酰基喹啉(0.38 g, 2.2mmol)加入20 mLN,N-二甲基甲酰胺中,加入冰醋酸(1mL, 0.001mmol)作为催化剂,于85℃下反应8小时;反应结束后抽滤,用DMF/H2O重结晶得到化合物FQ-5,产率:22%。反应式如下:
实施例二、FQ-5对挥发性有机溶剂的荧光识别
称取0.00363g的FQ-5分别加入到二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷中(体积均为10ml),加热使其完全溶解。然后分别移取0.5ml各自的溶液到新的试管中,再分别加入4.5ml以上溶剂,使其浓度为1×10-4M。
超分子传感器FQ-5在二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷中表现出很好的荧光现象(如图4),并且我们在CIE图可以很明显看出FQ-5在不同溶剂中具有不同荧光颜色,FQ-5在二甲基亚砜或N,N-二甲基甲酰胺呈现黄色荧光,在二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷分别呈现绿色、草绿色、天蓝色、浅蓝色、橄榄绿色、蓝绿色、深蓝色荧光(如图5),因此超分子传感器FQ-5可以荧光识别上述挥发性有机溶剂。
实施例三、FQ-5对 pH的荧光识别
1、pH缓冲溶液的制备
称取0.1192g的N-2-羟乙基哌嗪-N’-2-2-乙磺酸,加入100ml的蒸馏水备用。然后分别取少量的高氯酸和四丁基氢氧化铵加入蒸馏水稀释备用。将配好的N-2-羟乙基哌嗪-N’-2-2-乙磺酸溶液分别加到12支试管中,在分别各自滴加高氯酸和四丁基氢氧化铵溶液,用pH计进行测量,误差在(0.01-0.03)之间,得到pH(2~13)缓冲溶液。
2、FQ-5对 pH的荧光识别
移取0.5ml(1.0×10-4M)的超分子传感器分子FQ-5的DMF-H2O(9:1,V/V)溶液,分别加入0.5ml的不同pH缓冲溶液(2~13),震荡均匀,发现pH为9~13的缓冲溶液的加入可以使FQ-5的DMF-H2O溶液黄色的荧光增强。pH为11~13的荧光量子产率分别达到47.1%、80.9%、77.0%。所以,FQ-5在DMF-H2O溶液中能够选择性荧光识别的pH为9~13,并且pH为11~13时具有高额的荧光量子产率。
3、FQ-5对 pH的比色识别
移取0.5ml(1.0×10-4 M)的超分子传感器分子FQ-5的DMF-H2O(9:1,V/V)溶液,分别加入0.5ml的不同pH缓冲溶液(2~13),震荡均匀,pH为12~13的缓冲溶液的加入可以使FQ-5的DMF溶液颜色由黄色变为紫色,其余的pH值缓冲溶液的加入对FQ-5的DMF-H2O溶液颜色无明显影响。因此,FQ-5在DMF-H2O溶液中能够选择性比色识别的pH为12~13。
Claims (7)
2.如权利要求1所述基于吩嗪衍生物的超分子传感器FQ-5 的合成方法,是以DMF为溶剂,以2,3-二氨基吩嗪和8-羟基-5-甲酰基喹啉为底物,冰醋酸作为催化剂,于85~90℃下反应8~9h,反应结束后抽滤,再用DMF/H2O混合液重结晶得到目标化合物FQ-5。
3.如权利要求2所述基于吩嗪衍生物的超分子传感器FQ-5 的合成方法,其特征在于:2,3-二氨基吩嗪与8-羟基-5-甲酰基喹啉的摩尔比为1:1.1~1:1.2。
4.如权利要求2所述基于吩嗪衍生物的超分子传感器FQ-5 的合成方法,其特征在于:冰醋酸的用量为2,3-二氨基吩嗪摩尔量的0.005~0.015倍。
5.如权利要求1所述基于吩嗪衍生物的超分子传感器FQ-5 在荧光识别挥发性有机溶剂中的应用,其特征在于:将超分子传感器FQ-5加入到挥发性有机溶剂二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷中,FQ-5在二甲基亚砜或N,N-二甲基甲酰胺中呈现黄色荧光,在二氯甲烷、丙酮、乙醇、甲醇、乙腈、乙酸乙酯和环己烷中分别呈现绿色、草绿色、天蓝色、浅蓝色、橄榄绿色、蓝绿色、深蓝色荧光。
6.如权利要求1所述基于吩嗪衍生物的超分子传感器FQ-5 在荧光识别pH值中的应用,其特征在于:在超分子传感器FQ-5 的DMF-H2O溶液中,分别加入pH2~13缓冲溶液,pH为9~13的缓冲溶液的加入可以使FQ-5的DMF-H2O溶液黄色的荧光增强,pH为2~8的缓冲溶液的加入使得FQ-5的DMF-H2O溶液黄色荧光猝灭;DMF-H2O溶液中,H2O的体积含量为10~20%。
7.如权利要求1所述基于吩嗪衍生物的超分子传感器FQ-5 在比色识别pH值中的应用,其特征在于:在超分子传感器FQ-5的DMF-H2O溶液中,分别加入pH2~13缓冲溶液,pH为12~13的缓冲溶液的加入可以使FQ-5的DMF-H2O溶液颜色由黄色变为紫色,其余pH值缓冲溶液的加入对FQ-5的DMF-H2O溶液颜色无明显影响;DMF-H2O溶液中,H2O的体积含量为10~20%。
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