CN108530415A - 一种近红外双光子转换型so2荧光探针的合成及其应用 - Google Patents
一种近红外双光子转换型so2荧光探针的合成及其应用 Download PDFInfo
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- C07D311/78—Ring systems having three or more relevant rings
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G—PHYSICS
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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Abstract
本发明提供了一种近红外双光子转换型SO2荧光探针:。所述荧光探针的阴离子基团优选为高氯酸根离子。本发明的检测二氧化硫的比率型荧光探针识别速度极快,同时,消除了背景、环境的干扰,抗多种离子、氨基酸、活性氧的干扰,特异性好。对检测环境及生物体系中的二氧化硫具有潜在的应用价值。
Description
技术领域
本发明涉及一种检测二氧化硫的荧光探针,属于有机小分子荧光探针领域。
背景技术
二氧化硫是大气中主要污染物之一,是衡量大气是否遭到污染的重要标志。二氧化硫一般通过呼吸道进入人体,由于其易溶于水,很多被阻塞在上呼吸道,进而形成其衍生物如亚硫酸、硫酸盐等,更加刺激了呼吸道,从而引发一系列的呼吸道疾病,但进入血液的二氧化硫仍可通过血液循环抵达肺部产生刺激作用。进入血液的二氧化硫能破坏酶的活力,从而明显地影响碳水化合物及蛋白质的代谢,而且对肝脏有一定的损害。动物试验证明,二氧化硫慢性中毒后,机体的免疫受到明显抑制。研究发现,暴露于高剂量的硫酸氢盐中,不仅是导致呼吸疾病,也与肺癌,心血管疾病的原凶,同时与许多神经系统疾病,如中风、偏头痛、阿尔兹海默症也有密不可分的关系。亚硫酸氢盐和亚硫酸盐可作为食品添加剂,但是过量摄入将导致不良反应如低血压、腹泻、荨麻疹等。再者,SO2被认为是“第四种气体信号分子”,其在生物体的浓度与其功能密切相关。综上所述,实现二氧化硫及其衍生物的检测对环境保护、食品安全和SO2在生物体内的功能具有重要的意义。
近些年来,荧光传感技术已经越来越广泛地应用于阴离子、重金属、生物小分子以及一些有害气体的检测。与传统的分析检测方法相比,如分光光度法、色谱分析法和电化学分析法等,荧光光谱技术具有其独特的优点,如灵敏度高,选择性好,响应速度快,操作简便,最重要的一点是,荧光光谱技术可用于生物体内细胞成像及目标物的实时检测。目前,针对检测二氧化硫的分子荧光探针已有文献报道,但这些常见的荧光探针多有背景干扰、响应时间较长、散射干扰等缺陷,这样很容易受环境及浓度的影响,导致测量数据误差大,有可能影响在复杂环境中对二氧化硫检测的应用。
发明内容
针对现有检测二氧化硫的分子荧光探针易受环境及浓度的影响等问题,本发明提供一种近红外检测二氧化硫的双光子转换型荧光探针;本发明还提供了上述荧光探针的制备方法和在检测溶液、细胞和生物体中二氧化硫/亚硫酸(氢)盐中的用途。
为实现上述目的,本发明采用如下技术方案。
一种近红外双光子转换型检测SO2的荧光探针,简称为NIR-SO2-TP,其结构式为如式(I)所示:
式(I)。
所述荧光探针的阴离子基团优选为高氯酸根离子。
一种上述荧光探针的合成方法,包括以下步骤:
(1)4-二乙胺基水杨醛与环己酮在浓硫酸中加热反应,分离、纯化得化合物1:
;
(2)4-二乙胺基水杨醛与乙酰乙酸乙酯以吡啶为催化剂在乙醇中加热回流反应,分离、纯化得化合物2:
;
(3)化合物2和维尔斯迈尔试剂(三氯氧磷,N,N-二甲基甲酰胺)在N,N-二甲基甲酰胺中加热反应,分离、干燥得化合物3:
;
(4)在三氟乙酸催化下化合物1和化合物3在乙醇中加热反应,分离、干燥得荧光探针NIR-SO2-TP:
。
步骤(1)中4-二乙胺基水杨醛与环己酮的摩尔比为1:1.2。
步骤(2)中4-二乙胺基水杨醛与乙酰乙酸乙酯的摩尔比为1:1。
步骤(3)中化合物2和维尔斯迈尔试剂(三氯氧磷,N,N-二甲基甲酰胺)的摩尔比为1:2;所述三氯氧磷和N,N-二甲基甲酰胺的体积比为1:1(v/v)。
步骤(4)中化合物1与化合物3的摩尔比为1:1。
步骤(1)中,所述反应温度为80-100℃,反应时间为3-5h。
步骤(2)中,所述反应温度为80-100℃,反应时间为8-10h。
步骤(3)中,所述反应温度为80-100℃,反应时间为4-6h。
步骤(4)中,所述反应温度为80-100℃,反应时间为6-10h。
步骤(1)中,所述分离纯化步骤为将反应体系滴加适量高氯酸后加入200 mL水中,置于-5℃环境中,有大量固体析出,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥;所得粗产物以乙醇重结晶可得到提纯品。
步骤(2)中所述分离纯化步骤为将反应体系冷却至室温,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,所得粗产物以乙醇重结晶可得到提纯品。
步骤(3)中所述分离纯化步骤为将反应体系冷却至室温,加NaOH调节pH值至6倒入水中,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,然后粗产物均进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=100:1(v/v)。
步骤(4)中所述分离纯化步骤为将反应体系减压蒸馏去除溶剂,所得粗产物进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=20:1(v/v)。
上述荧光探针在测定溶液、细胞或生物体中检测SO2或SO2衍生物中的应用。所述SO2衍生物为HSO3 -或SO3 2-。
本荧光探针的检测机理如下:
本发明的二氧化硫荧光探针以香豆素为荧光团,且含有碳碳双键。本身在835 nm处具有近红外的发射,在二氧化硫衍生物(亚硫酸氢盐或亚硫酸盐)存在下,二氧化硫衍生物通过亲核加成进攻探针的不饱和C=C键,发生迈克尔加成反应,释放香豆素的荧光,在530nm处所发射的荧光,并且识别后的探针具有双光子性能。通过检测探针在835 nm处和530nm处所发射的荧光强弱,测定二氧化硫衍生物的存在与否或者浓度多少:
。
本发明具有以下优点:
本发明的检测二氧化硫的比率型荧光探针识别速度极快,同时,消除了背景、环境的干扰,抗多种离子、氨基酸、活性氧的干扰,特异性好。对检测环境及生物体系中的二氧化硫具有潜在的应用价值。
附图说明
图1为探针的1H NMR谱;
图2为探针的13C NMR谱;
图3为探针检测不同浓度的亚硫酸氢钠的荧光强度;
图4为探针在亚硫酸氢钠的PBS缓冲液中的动力学;
图5为探针的离子选择性;
图6为探针对外源亚硫酸氢钠的细胞成像;
图7为探针对斑马鱼荧光成像。
具体实施方式
下面结合实施例和附图对本发明做进一步说明,但本发明不受下述实施例的限制。
实施例1 荧光探针的合成
(1)化合物1的合成
;
在100 mL的圆底烧瓶中,加入4-二乙胺基水杨醛(1.93g,10 mmol)与环己酮(1.20g,12mmol)混合,向其中加入10 mL浓硫酸90℃加热回流搅拌5 h,冷却至室温,将反应体系置于-5 ℃环境中滴加适量高氯酸并加200 mL水,有大量固体析出,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,得到化合物1。粗产物利用乙醇重结晶可得到纯品。产率:87%;
(2)化合物2的合成
;
在100 mL的圆底烧瓶中,向其中加入乙醇30 mL,加入4-二乙胺基水杨醛(1.93g,10mmol),乙酰乙酸乙酯(1.30 g,10 mmol),以及少量哌啶(150 μL),加热到85℃回流8 h后,冷却至室温,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,得淡黄色固体,即为化合物2。所得粗产物以乙醇重结晶可得到提纯品。产率:95%;
(3)化合物3的合成
;
在100 mL的圆底烧瓶中氮气保护下向2.8 mL三氯氧磷中滴加2.8 mL N,N-二甲基甲酰胺,室温下搅拌半小时,然后向其中加入化合物2(2.59 g,10 mmol),在80℃加热反应4 h,冷却至室温后加NaOH调节pH值至6后,加入200 mL水中,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,,然后粗产物均进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=100:1;
(4)荧光探针的合成
;
在100 mL的圆底烧瓶中,向其中加入乙醇,加入化合物1(2.56 g,10 mmol)和化合物3(3.05 g,10 mmol)后滴加催化量的三氟乙酸,加热到85℃回流8 h后减压蒸馏去除溶剂,所得粗产物进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=20:1。化合物3的1H NMR谱和13CNMR谱如图1和图2所示。产率:60%。1H NMR (400 MHz, DMSO) δ 8.48 (s, 2H), 8.35 (d,J= 11.9 Hz, 1H), 7.95 (d, J = 11.1 Hz, 1H), 7.88 (d, J = 9.3 Hz, 1H), 7.68(d, J = 8.6 Hz, 1H), 7.47 (d,J = 9.0 Hz, 1H), 7.23 (s, 1H), 6.82 (d, J = 8.3Hz, 1H), 6.61 (s, 1H), 5.33 (s, 1H), 3.76 (d, J = 7.0 Hz, 4H), 3.50 (d, J=7.0 Hz, 4H), 2.87 (s, 2H), 2.80 (s, 2H), 2.68 (s, 1H), 2.34 (s, 1H), 2.00 (d,J = 7.8 Hz, 1H), 1.91 (s, 2H), 1.27 (t, J = 7.0 Hz, 6H), 1.16 (t, J = 6.9 Hz,6H). 13C NMR (101 MHz, DMSO) δ 161.19, 156.30, 156.04 , 152.51, 147.71,143.63, 136.97, 132.27, 131.52, 131.35, 129.91, 124.64, 123.07, 119.65,118.74, 113.42, 111.07, 110.61, 108.74, 96.02, 95.58, 46.07, 44.88, 27.57,26.18, 20.88, 12.76。
实施例2 荧光探针检测不同浓度的亚硫酸氢钠的荧光强度
配制浓度为1 mM的实施例1所得荧光探针的二甲基亚砜母液待用。
配制探针终浓度为10 μM,含20 %乙腈溶液的PBS溶液(pH 7.4),分别与不同浓度的亚硫酸氢钠(1μM、2μM、3μM、4μM、5μM、6μM、7μM、8μM、9μM、10μM、15μM、20μM、25μM、30μM、35μM、40μM、45μM、50μM)充分作用,进行荧光检测(λex=440 nm,λem=530 nm;λex=645 nm,λem=835nm)。得各体系中荧光强度,建立荧光强度与亚硫酸氢钠浓度标准曲线,结果如图3所示。由图3可知,随着亚硫酸氢钠浓度的增加,530 nm处的荧光强度逐渐增加,835 nm处的荧光强度逐渐降低;当亚硫酸氢钠浓度达到50 μM时,反应体系荧光强度达到饱和状态。
实施例3 荧光探针识别二氧化硫的动力学测试
配制浓度为1 mM的实施例1所得荧光探针化合物4的二甲基亚砜测试母液溶液待用。
配制探针终浓度为10 μM,含20%乙腈溶液的PBS溶液(pH 7.4),与亚硫酸氢钠(50μM)充分作用,每隔3s进行荧光检测(λex=440 nm,λem=530 nm;λex=645 nm,λem=835 nm)。得各体系中荧光强度,建立荧光强度与时间的标准曲线,如图4所示。由图4可知,随着时间的增加,530 nm处的荧光强度逐渐增加,835 nm处的荧光强度逐渐降低,反应在12 s内达到平衡,说明该探针能够快速识别二氧化硫。
实施例4 荧光探针的选择性
配制浓度为1 mM的实施例1所得荧光探针的二甲基亚砜母液待用。配制浓度为100 mM的各种不同离子,氨基酸和活性氧/活性氮,不同活性硫溶液作为备用。
在5mL的容量瓶里加入20μL探针母液、400 μL乙腈和10当量的各离子溶液或10当量的各氨基酸溶液,用PBS缓冲液(pH 7.4)定容,各干扰物质的浓度均为100 μM,摇匀后进行荧光检测(λex=440 nm,λem=530 nm;λex=645 nm,λem=835 nm),建立荧光强度与各离子的柱状图,结果如图5所示,其中,1-25号加入的物质分别是:荧光探针,氯化钙,氯化钴,硫酸铜,硫酸铁,硫酸亚铁,碘化钾,氯化镁,亚硫酸钠,硝酸钾,氟化钠,亚硝酸钠,硫酸镍,氯化亚锡,硫酸锌,硫酸银,过氧化叔丁醇,过氧化叔丁基,过氧化氢,次氯酸钠,同型半胱氨酸,半胱氨酸,谷胱甘肽,硫氢化钠,亚硫酸氢钠。由图5可以发现,其他离子(或氨基酸)对探针的荧光几乎没有影响,特异性好、抗干扰性能好,能够选择性的识别二氧化硫。
实施例5 荧光探针的细胞荧光成像
将适当密度的HeLa细胞接种到两个灭菌的35 mm成像培养皿中,在CO2培养箱(温度为37℃,5% CO2)中培养,待细胞贴壁后,向培养皿中加入实施例1所得荧光探针,使其终浓度均为5 μM;继续培养0.5 h,弃掉培养基,用pH为7.4的PBS缓冲液冲洗细胞3次,其中一个加入适量亚硫酸氢钠水溶液,使终浓度为25 μM,另一个加入等量pH为7.4的PBS缓冲液,孵育0.5 h后,随后进行成像实验(λex=440 nm,λem=530 nm;λex=645 nm,λem=835 nm),如图6所示,其中横坐标a1-e1为探针孵育细胞成像,a2-e2为探针与SO2衍生物孵育的细胞成像;而纵坐标a1、a2为明场成像获得的图像,b1、b2为绿通道成像获得的图像,c1、c2为红通道成像获得的图像,d1,d2为三图像叠加后的图像,e1、e2为双光子绿通道成像获得的图像。由图6可知,只加入探针时,细胞具有红色荧光,加入亚硫酸氢钠后,细胞红色荧光消失,而产生强烈的绿色荧光信号。
实施例6 荧光探针对斑马鱼荧光成像
将脱卵3天的斑马鱼分为两组,分别放入35 mm培养皿中。其中一组加入50 μM亚硫酸氢钠孵育10 min后,加入10 μM实施例1所得的探针;另一组加入10 μM实施例1所得的探针,分别在28 ℃下培养30 min,共聚焦显微镜下成像(激发波长488nm,检测波段为500-550 nm;激发波长633 nm,检测波段为700-800 nm),如图7所示,其中横坐标a1-e1为探针孵育斑马鱼成像,a2-e2为探针与SO2衍生物孵育的斑马鱼成像;而纵坐标a1、a2为明场成像获得的图像,b1、b2为绿通道成像获得的图像,c1、c2为红通道成像获得的图像,d1,d2为三图像叠加后的图像,e1、e2为双光子绿通道成像获得的图像。由图7可知,只加入探针时,斑马鱼具有红色荧光,加入亚硫酸氢钠后,细胞红色荧光消失,而产生强烈的绿色荧光信号。
Claims (10)
1.一种近红外双光子转换型检测SO2的荧光探针,其结构式为如式(I)所示:
式(I)。
2.根据权利要求1所述的荧光探针,其特征在于,阴离子基团为高氯酸根离子。
3.一种如权利要求1所述的荧光探针的合成方法,其特征在于,包括以下步骤:
(1)4-二乙胺基水杨醛与环己酮在浓硫酸中加热反应,分离、纯化得化合物1:
;
(2)4-二乙胺基水杨醛与乙酰乙酸乙酯以吡啶为催化剂在乙醇中加热回流反应,分离、纯化得化合物2:
;
(3)化合物2和维尔斯迈尔试剂(三氯氧磷,N,N-二甲基甲酰胺)在N,N-二甲基甲酰胺中加热反应,分离、干燥得化合物3:
;
(4)在三氟乙酸催化下化合物1和化合物3在乙醇中加热反应,分离、干燥得荧光探针:
。
4.根据权利要求3所述的合成方法,其特征在于,步骤(1)中4-二乙胺基水杨醛与环己酮的摩尔比为1:1.2;
步骤(2)中4-二乙胺基水杨醛与乙酰乙酸乙酯的摩尔比为1:1;
步骤(3)中化合物2和维尔斯迈尔试剂的摩尔比为1:2;所述三氯氧磷和N,N-二甲基甲酰胺的体积比为1:1;
步骤(4)中化合物1与化合物3的摩尔比为1:1。
5.根据权利要求3所述的合成方法,其特征在于,步骤(1)中,所述反应温度为80-100℃,反应时间为3-5h;
步骤(2)中,所述反应温度为80-100℃,反应时间为8-10h;
步骤(3)中,所述反应温度为80-100℃,反应时间为4-6h;
步骤(4)中,所述反应温度为80-100℃,反应时间为6-10h。
6.根据权利要求3所述的合成方法,其特征在于,步骤(1)中,所述分离纯化步骤为将反应体系滴加适量高氯酸后加入200 mL水中,置于-5℃环境中,有大量固体析出,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥;所得粗产物以乙醇重结晶得到提纯品。
7.根据权利要求3所述的合成方法,其特征在于,步骤(2)中,所述分离纯化步骤为将反应体系冷却至室温,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,所得粗产物以乙醇重结晶可得到提纯品。
8.根据权利要求3所述的合成方法,其特征在于,步骤(3)中,所述分离纯化步骤为将反应体系冷却至室温,加NaOH调节pH值至6倒入水中,减压过滤,滤饼用乙醇洗涤2-3次,真空干燥,然后粗产物均进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=100:1(v/v)。
9.根据权利要求3所述的合成方法,其特征在于,步骤(4)中,所述分离纯化步骤为将反应体系减压蒸馏去除溶剂,所得粗产物进行柱层析纯化,层析淋洗液为二氯甲烷:甲醇=20:1(v/v)。
10.一种如权利要求1或2所述的荧光探针在测定溶液、细胞或生物体中检测SO2或SO2衍生物中的应用。
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