CN107011213A - 一种多通道发光的荧光探针及其制备方法和应用 - Google Patents
一种多通道发光的荧光探针及其制备方法和应用 Download PDFInfo
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- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
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Abstract
本发明属于荧光染料技术领域,具体为一种含薁基团的α‑腈基苯乙烯衍生物的多通道发光的荧光探针及其制备方法和应用。本发明提供含薁‑腈基苯乙烯的衍生物,其结构式如通式为:。该化合物具有多种发光性质,经过酸或光照作用后荧光均有明显的增强,具有上转换、近红外和可见三种发光状态,可作为一类优良的多通道检测荧光探针,用于水体、土壤及生物体内的荧光标记或荧光检测。
Description
技术领域
本发明属于荧光染料技术领域,具体涉及一种含薁基团的α-腈基苯乙烯衍生物的多通道发光的荧光探针,以及该类化合物的制备方法,和该类化合物的应用。
背景技术
由于荧光分析有高的灵敏度和选择性,近年来在医学检验、药物分析、环境检测等方面有广泛的应用(Thomas, J. A., Chem. Soc. Rev., 2015, 44, 4494)。传统的荧光分子探针有特定的激发和发射波长,单一荧光探针不能根据样品实际需要的激发和发射进行波长的变化,极大的限制了在实际中的应用。而多通道发光的荧光探针可以在根据样品性质灵活的选择不同的激发波长,同时采集不同的发射区间,在实际样品分析中有很大的优势。
薁是一种非常好的pH响应性化合物,在中性环境中,薁的发光是违反kasha规则的,它几乎没有S1-S0的发光,只有S2-S0的发光(Murai, M., et al. Chem. Sci. 2014,5,3753.)。当被质子化后,薁的荧光发射有明显的增强,同时出现明显的红移现象,当原位加入碱中和体系中的酸之后,荧光发射又恢复到中性的状态,酸和碱像开关一样调控着含薁化合物的发光情况,这个过程可以反复多次,且荧光强度没有明显的衰减。但是目前基于薁结构的荧光探针方面研究仍然较少。
α-腈基二苯乙烯结构中,双键是重要的光敏基团,可以由光照调控其顺反异构的变化,这一性质可以用于分子开关、光敏调控等体系(Zhu, L., et al. J. Am. Chem. Soc. 2013,135, 5175-5182.)。但目前对α-腈基二苯乙烯的研究主要集中在“聚集诱导发光”方面,还没有多通道可控发光的报道。
上转换发光即反-斯托克斯发光,是由波长长频率低的光激发出波长短频率高的光。具有上转换发光性质的材料可以将红外光转变为可见光。近年来,这类材料在激光技术、光纤通讯技术、光信息存储等领域都有较多的应用。但是目前针对此领域的研究主要集中在稀土化合物,此类化合物发光效率低,毒性较大,不适合应用于生物体系。本发明所报导的是一类具有上转换发光性质的有机小分子,其结构简单,发光性质良好,适用于生物成像及其他检测领域,有良好的应用前景。
综合以上研究背景,开发一种能针对不同外界刺激产生不同荧光信号的多通道发光的新型荧光探针,具有重要的意义,这类荧光探针将在分析检测、细胞标记、智能材料方面有重要作用。
发明内容
本发明的目的在于提供一种能针对不同外界刺激产生不同荧光信号的多通道发光的荧光探针及其制备方法和应用。
本发明首先设计、合成一种含薁-腈基苯乙烯的衍生物;然后将其直接溶于有机溶剂中,通过调整激发波长和溶液pH,能够出现可见、近红外和上转换三种发光模式,可以作为一种多通道发光检测的荧光探针;在体系与酸作用后,出现新的近红外荧光发射谱带,在体系与碱作用后,紫外吸收有明显的变化,根据这些性质,这类化合物可以作为一种良好的pH探针。
本发明采用如下技术方案,利用薁作为对酸响应的活性位点,α-腈基苯乙烯作为对光照刺激响应的基团,联合两者不同的性质,实现了多通道可控荧光发射和灵敏的pH响应。
相对于现有的荧光探针,本发明所提供的3-薁基-2-苯基丙烯腈衍生物具有合成简单、功能多样的优点。解决了现有技术中探针发光单一、成本较高、合成路线复杂的技术问题。
本发明提供的多通道发光的荧光探针,为3-薁基-2-苯基丙烯腈衍生物,其结构式如通式I所示,
通式I
其中,R为羟基、1-8个碳原子的烷氧基、硝基或氨基。
进一步的,R为羟基、4-6个碳原子的烷氧基、硝基或氨基。
进一步的,R为羟基、4个碳原子的烷氧基、硝基或氨基。
上述化合物具有多种发光性质,经过酸或光照作用后荧光均有明显的增强,具有上转换、近红外和可见三种发光状态,可作为一类优良的多通道检测荧光探针,用于水体、土壤及生物体内的荧光标记或荧光检测。
本发明还提供上述荧光探针的制备方法,其合成路线如下所示:
。
具体步骤如下:
(a)制备3-(6-薁基)-2-(4-取代苯基)丙烯腈:在氮气保护下,将1,8-二氮杂二环十一碳-7-烯加入到6-薁甲醛(即化合物2)和4-取代苯乙腈(即化合物3)的吡啶溶液中,在回流条件下反应8-12小时,得到缩合产物3-(6-薁基)-2-(4-取代苯基)丙烯腈(式I所示化合物);
(b)制备3-(6-薁基)-2-(4-正丁氧基苯基)丙烯腈:在氮气保护下,将3-(6-薁基)-2-(4-羟基苯基)丙烯腈溶于干燥的丙酮中,加入碳酸钾和溴代正丁烷,在25-80 ℃下反应4-20小时,得到3-(6-薁基)-2-(4-正丁氧基苯基)丙烯腈;
(c)制备3-(6-薁基)-2-(4-氨基苯基)丙烯腈:在氮气保护下,将3-(6-薁基)-2-(4-硝基苯基)丙烯腈溶于乙醇中,加入氯化亚锡,在25-80 ℃下反应0.5-10小时,得到3-(6-薁基)-2-(4-氨基苯基)丙烯腈。
进一步:
在步骤(a)中,在一个反应容器中,加入6-薁甲醛和4-取代苯乙腈,氮气保护下,加入1,8-二氮杂二环十一碳-7-烯,注入干燥的吡啶,6-薁甲醛和吡啶的摩尔体积比为0.8~1.2mmol:10~30 mL,6-薁甲醛、4-取代苯乙腈、1,8-二氮杂二环十一碳-7-烯的摩尔比为0.8~1.2 mmol:0.8~2 mmol:0.8~2 mmol,在80-100℃下搅拌反应2-12小时,真空浓缩,柱层析分离,得3-(6-薁基)-2-(4-取代苯基)丙烯腈。
在步骤(b)中,碳酸钾与溴代烷和3-(6-薁基)-2-(4-取代苯基)丙烯腈(化合物I-1)的摩尔质量比为1-4mmol:1-50mmol:1-2mmol。
在步骤(c)中,氯化亚锡与3-(6-薁基)-2-(4-硝基苯基) (化合物I-3)的摩尔质量比为1-20mmol:1-2mmol。
上述通式I的化合物,包含了化合物I-1、 I-2,、I-3、I-4四个结构;其中,化合物I-1和化合物I-3直接由步骤(a)得到,化合物I-2和化合物I-4分别通过由化合物I-1和I-3再进行一步反应得到。化合物I-2和I-4在后面进行了具体发光性质的实验。
本发明所述的荧光探针可用于上转换发光,即通式I化合物在溶液中以633nm波长激发,在490nm处出现上转换发光。
本发明所述含氰基的薁-苯乙烯的化合物可以用于检测氢离子,该化合物可与氢离子反应生成具有通式II结构的化合物,导致荧光改变,从而检测氢离子:
通式II
通式II中,R与通式I表示的化合物中的R相同。
所述通式I结构的化合物用于检测氢离子的工序如下:
(1)将通式I结构的化合物与氢离子反应;
(2)测定由上述工序中的反应引起的体系荧光变化。
本发明所述的化合物可用于水体、土壤或生物体系中的检测。
附图说明
图1. 本发明提供的多通道荧光探针应用的原理示意图。
图2. 0.5 μmol/L化合物I-2的上转换发光图谱,用633nm的激光激发,可以在490nm处产生上转换荧光发光,溶液体系为三氯甲烷,横坐标为波长,纵坐标为吸光度。
图3. 0.5 μmol/L化合物I-2在以254nm的紫外光照10min后,以365 nm的紫外光激发,在480nm处的荧光发射有明显增强,溶液体系为三氯甲烷,横坐标为波长,纵坐标为吸光度。
图4. 0.5 μmol/L化合物I-2在加入0.5 mol/L的三氟乙酸后,用520nm波长的光激发,在630nm处有很强的荧光发射,溶液体系为三氯甲烷,横坐标为波长,纵坐标为荧光强度值。
图5. 0.5 μmol/L化合物I-4在加入0.05 mol/L的三氟乙酸后,用365 nm的紫外光激发,发射波长从485nm蓝移至440nm,同时荧光强度增强。溶液体系为三氯甲烷,横坐标为波长,纵坐标为荧光强度值。
具体实施方式
下面通过实施例对本发明作进一步的阐述,其目的仅在于更好地理解本发明的内容。因此,所举之例并不限制本发明的保护范围。
下列实施例中所说的室温是:25-28 ℃;所用原料及试剂均未市售品。
实施例1
(1)化合物I-1的合成
在50mL的圆底烧瓶中加入6-醛基薁(1 mmol)和5mL吡啶,随后加入乙酰基-4-羟基苯乙腈(1.2 mmol)、1,8-二氮杂二环十一碳-7-烯(1.2 mmol),在氮气保护下100 ℃反应12小时。反应结束后加入适量二氯甲烷稀释,倒入稀盐酸中,用二氯甲烷萃取三次(15mL×3),合并有机层,用饱和食盐水洗,无水硫酸钠干燥。真空浓缩后经柱层析分离纯化,以石油醚:乙酸乙酯=5:1(v/v)为洗脱剂,得绿色粉末状固体2,产率70%。1H NMR (400 MHz, CDCl3) δ(ppm):8.38 (d, J = 10.6 Hz, 2H), 7.97 (t, J = 3.8 Hz, 1H), 7.66 – 7.64 (m,1H), 7.64 – 7.61 (m, 2H), 7.58 (d, J = 10.5 Hz, 2H), 7.43 (d, J = 3.7 Hz,2H), 6.96 – 6.91 (m, 2H). HRMS m/z: [M+H]+ calcd. for C19H13NO, 272.1070;found, 272.1359.;
(2)化合物I-2的合成
在50mL的圆底烧瓶中加入20mL丙酮、化合物2、碳酸钾和1-溴正丁烷,在氮气保护下回流8小时,过滤,滤液真空浓缩后经柱层析分离纯化,以石油醚:乙酸乙酯=10:1(v/v)为洗脱剂,得绿色粉末状固体I-2,产率95%。1H NMR (400 MHz, CDCl3) δ (ppm):8.38 (d, J =10.6 Hz, 2H), 7.96 (t, J = 3.7 Hz, 1H), 7.68 – 7.63 (m, 3H), 7.58 (d, J =10.5 Hz, 2H), 7.43 (d, J = 3.7 Hz, 2H), 7.00 – 6.95 (m, 2H), 4.03 (t, J = 6.5Hz, 2H), 1.81 (ddd, J = 14.4, 11.1, 6.5 Hz, 2H), 1.55 – 1.48 (m, 2H), 1.02 –0.97 (m, 4H). HRMS m/z: [M+H]+ calcd. for C23H21NO, 328.1696; found, 328.1059.;
(3)化合物I-3的合成
在50mL的圆底烧瓶中加入10mL吡啶、6-醛基薁(1 mmol)和4-硝基苯乙腈(1 mmol),搅拌下滴入1,8-二氮杂二环十一碳-7-烯,在氮气保护下回流8小时,过滤,滤饼经柱层析分离纯化,以石油醚:乙酸乙酯=5:1(v/v)为洗脱剂,得棕色粉末状固体I-3,产率80%。1H NMR(400 MHz, CDCl3) δ (ppm):8.42 (d, J = 10.6 Hz, 2H), 8.37 – 8.32 (m, 2H), 8.04(t, J = 3.7 Hz, 1H), 7.93 – 7.88 (m, 3H), 7.63 (d, J = 10.4 Hz, 2H), 7.49 (d,J = 3.7 Hz, 2H). HRMS m/z: [M+H]+ calcd. for C19H12N2O2, 301.0972; found,301.0719.;
(4)化合物I-4的合成
在50mL的圆底烧瓶中加入20mL无水乙醇、化合物I-3和氯化亚锡,在氮气保护下回流4小时,反应完毕后倒入饱和碳酸氢钠中,剧烈搅拌30min,过滤,滤液用二氯甲烷萃取三次(3×20mL),合并有机相,经干燥后,真空浓缩后经柱层析分离纯化,以石油醚:乙酸乙酯=5:1(v/v)为洗脱剂,得墨绿色粉末状固体I-4,产率75%。1H NMR (400 MHz, CDCl3) δ (ppm):8.37 (d, J = 10.6 Hz, 2H), 7.94 (t, J = 3.7 Hz, 1H), 7.61 – 7.52 (m, 5H),7.41 (d, J = 3.7 Hz, 2H), 6.77 – 6.71 (m, 2H), 3.95 (s, 2H). HRMS m/z: [M+H]+calcd. for C19H14N2, 271.1230; found, 271.0725.。
实施例2
(1)化合物I-2的性质测试
将上述所得化合物I-2溶解于三氯甲烷中,配置成0.5 μmol/L的溶液。将2mL溶液加入到1 cm×1 cm×4 cm的带塞比色皿中,测试其上转换发光光谱,λex = 633 nm,结果如图2所示,化合物I-2在490nm处有很强的上转换发光。测试上述溶的下转换发光光谱,λex = 365nm,,结果如图3所示,化合物I-2在480nm处有很强的荧光发射。在化合物I-2的三氯甲烷溶液中加入一定量的三氟乙酸均匀混合1分钟后,测试化合物I-2的荧光发射光谱,λex = 520nm,结果如图4所示,由于三氟乙酸的加入,溶液在630nm处出现了很强的荧光发射;
(2)化合物I-4的性质测试
将上述所得化合物I-4溶解于三氯甲烷中,配置成0.5 μmol/L的溶液。将2mL溶液加入到1 cm×1 cm×4 cm的带塞比色皿中,然后用微量注射器分别加入一定体积的三氟乙酸后均匀混合1分钟后,测试化合物I-3的荧光发射光谱,λex = 365 nm,结果如图5所示,由于三氟乙酸的加入,溶液的荧光发射从485nm蓝移至440nm,同时荧光强度增强。
Claims (10)
1.一种多通道发光的荧光探针,其特征在于,结构式如通式I所示,
通式I
通式I中,R为羟基、1-8个碳原子的烷氧基、硝基、氨基。
2.如权利要求1所述的荧光探针,其特征在于,结构式中R为羟基、4-6个碳原子的烷氧基、硝基、氨基。
3.如权利要求1所述的荧光探针,其特征在于,结构式中R为羟基、4个碳原子的烷氧基、硝基、氨基。
4.权利要求1所述的荧光探针的制备方法,其特征在于,具体步骤为:
(a)制备3-(6-薁基)-2-(4-取代苯基)丙烯腈:在氮气保护下,将1,8-二氮杂二环十一碳-7-烯加入到6-薁甲醛和4-取代苯乙腈的吡啶溶液中,在回流条件下反应8-12小时,得到缩合产物3-(6-薁基)-2-(4-取代苯基)丙烯腈;
(b)制备3-(6-薁基)-2-(4-正丁氧基苯基)丙烯腈:在氮气保护下,将3-(6-薁基)-2-(4-羟基苯基)丙烯腈溶于干燥的丙酮中,加入碳酸钾和溴代正丁烷,在25-80 ℃下反应4-20小时,得到3-(6-薁基)-2-(4-正丁氧基苯基)丙烯腈;
(c)制备3-(6-薁基)-2-(4-氨基苯基)丙烯腈:在氮气保护下,将3-(6-薁基)-2-(4-硝基苯基)丙烯腈溶于乙醇中,加入氯化亚锡,在25-80 ℃下反应0.5-10小时,得到3-(6-薁基)-2-(4-氨基苯基)丙烯腈。
5. 如权利要求4所述的荧光探针的制备方法,其特征在于,在步骤(a)中,在反应容器中加入6-薁甲醛和4-取代苯乙腈,氮气保护下,加入1,8-二氮杂二环十一碳-7-烯,注入干燥的吡啶,6-薁甲醛和吡啶的摩尔体积比为0.8~1.2 mmol:10~30 mL,6-薁甲醛、4-取代苯乙腈、1,8-二氮杂二环十一碳-7-烯的摩尔比为0.8~1.2 mmol:0.8~2 mmol:0.8~2 mmol,在80-100℃下搅拌反应2-12小时,真空浓缩,柱层析分离,得3-(6-薁基)-2-(4-取代苯基)丙烯腈。
6.如权利要求4所述的荧光探针的制备方法,其特征在于,在步骤(b)中,碳酸钾与溴代烷和3-(6-薁基)-2-(4-取代苯基)丙烯腈的摩尔质量比为1-4mmol:1-50mmol:1-2mmol。
7. 如权利要求4所述的荧光探针的制备方法,其特征在于,在步骤(c)中,氯化亚锡与3-(6-薁基)-2-(4-硝基苯基) 的摩尔质量比为1-20mmol:1-2mmol。
8.权利要求1-3中任一项所述的荧光探针在上转换发光中的应用,其特征在于,通式I化合物在溶液中以633nm波长激发,在490nm处出现上转换发光。
9.权利要求1-3中任一项所述的荧光探针在检测pH值中的应用,其特征在于:通式I化合物与H+反应后生成具有通式II结构的化合物,检测溶液中的H+;
通式II
通式II中,R与通式I的化合物中的R相同。
10.根据权利要求9所述的应用,其特征在于,所述通式I的化合物用于H+检测,包括以下工序:
(1)使具有通式I结构的化合物与H+反应;
(2)测定由上述工序中的反应引起的体系荧光变化。
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