CN110684525B - 一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途 - Google Patents
一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途 Download PDFInfo
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 57
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 54
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- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims description 18
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- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 6
- OSTCHNZICIUMFJ-UHFFFAOYSA-N N#CS.O=C(NC(N1)=O)NC1=O Chemical compound N#CS.O=C(NC(N1)=O)NC1=O OSTCHNZICIUMFJ-UHFFFAOYSA-N 0.000 claims description 6
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
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- WLTIKGGMMPYVJJ-UHFFFAOYSA-N [Pt+2].N(=C=S)C=1C(=NC=CC1)C1=NC=CC=C1C1=NC=CC=C1.[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical group [Pt+2].N(=C=S)C=1C(=NC=CC1)C1=NC=CC=C1C1=NC=CC=C1.[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WLTIKGGMMPYVJJ-UHFFFAOYSA-N 0.000 claims description 5
- IQBIMHWYNOTFRL-UHFFFAOYSA-L 2,3-dipyridin-2-ylpyridine platinum(2+) dichloride Chemical compound [Cl-].[Cl-].[Pt+2].N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 IQBIMHWYNOTFRL-UHFFFAOYSA-L 0.000 claims description 3
- RWXBCACDXSTLCL-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine;platinum Chemical compound [Pt].N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 RWXBCACDXSTLCL-UHFFFAOYSA-N 0.000 claims description 3
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- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 abstract description 4
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- UPCLHGSYIYSFAH-UHFFFAOYSA-N [Pt+2].[N+](=O)([O-])[O-].N#[C-].N1=C(C=CC=C1)C1=NC=CC=C1C1=NC=CC=C1 Chemical compound [Pt+2].[N+](=O)([O-])[O-].N#[C-].N1=C(C=CC=C1)C1=NC=CC=C1C1=NC=CC=C1 UPCLHGSYIYSFAH-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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Abstract
本发明公开了一种基于聚集诱导发光效应的比色‑荧光探针及其制备方法和用途,所述比色‑荧光探针为硝酸化异硫氰根•(三联吡啶)合铂(Ⅱ),将采用常规方法制备的硫氰酸化异硫氰根•(三联吡啶)合铂(Ⅱ)在过饱和的硝酸钠或硝酸钾溶液中进行银离子置换,得到硝酸化异硫氰根•(三联吡啶)合铂(Ⅱ)探针分子。该比色‑荧光探针具有良好的水溶性,溶液呈淡黄色且无荧光;加入高氯酸根或氯酸根能使其发生聚集行为,导致溶液颜色变为紫红色并发出明亮的红色荧光。利用该比色‑荧光探针的聚集诱导发光特性来快速、准确、直观地检测高氯酸根或氯酸根,可实现双模式验证,选择性好,可靠性高,灵敏度好,检测快速。同时该探针安全、稳定和高效。
Description
技术领域
本发明属于化学传感技术领域,涉及一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途。
背景技术
高氯酸盐和氯酸盐是制造烟火的重要原料,也是最常用的非制式爆炸物原料之一。此外,高氯酸盐和氯酸盐易溶于水,是一种具有高度扩散性的持久性无机污染物,危害人体甲状腺功能。因此,高氯酸根或氯酸根的探测对公共安全、环境保护、人体健康具有极其重要的意义。
目前,检测无机盐或阴离子的技术有离子迁移谱技术、便携式拉曼光谱技术、电化学方法等。然而这些技术存在设备昂贵,操作复杂且携带不便的缺点。光学法,如比色或荧光的方法具有检测价廉、快速、灵敏、可视化、不依赖仪器、抗干扰性强等优点,是极具应用前景的现场检测方法。然而,目前开发的用于检测高氯酸盐和氯酸盐的光学探针较少,常用有机染料不仅合成和提纯繁琐,而且其检测机制主要基于主客相互作用,如氢键、静电作用、范德华力、配位作用和π-π相互作用等,极易受到溶液中水分子的干扰,极大地限制其实际应用。
近年来,基于聚集诱导发光的检测机制受到广泛关注,这一类发光团在分散态时荧光强度很弱或者不发光,在聚集态时发出很强的荧光。按物质种类分,目前开发的聚集诱导发光的探针可以被分为有机分子探针和过渡金属配合物探针。相比纯有机分子,过渡金属配合物具有制备简单,稳定性好,光学特性丰富,磷光寿命长和化学结构易于调控等特点,越来越广泛应用于阴离子探测领域。目前,基于过渡金属配合物的聚集诱导发光策略实现水溶液中高氯酸根或氯酸根检测的报道还很少,且存在检测限差,选择性和抗干扰性差的缺点。
发明内容
本发明的目的是,克服现有检测高氯酸根或氯酸根存在的不足,提供一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途,所述比色-荧光探针为硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ),采用常规方法制备硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),然后再将硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)在硝酸钠溶液中进行银离子置换,得到硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。该比色-荧光探针具有良好的水溶性,溶液呈淡黄色且无荧光;加入高氯酸根或氯酸根能使其发生聚集行为,导致溶液颜色变为紫红色并发出明亮的红色荧光。利用该探针的聚集诱导发光特性来快速、准确、直观地检测高氯酸根或氯酸根,可实现双模式验证,选择性好,可靠性高,灵敏度好,检测快速。同时该探针安全、稳定和高效。
本发明所述的一种基于聚集诱导发光效应的比色-荧光探针,该荧光探针的化学名称为硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ),其结构式(1)为:
所述基于聚集诱导发光效应的比色-荧光探针的制备方法,按下列步骤进行:
a、称取氯亚铂酸钾1g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度80℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度40-50℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入0.1-5g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用唱过的重结晶法将产物提纯;
d、取20-80g硝酸钾或硝酸钠加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钾或硝酸钠固体析出,得到过饱和硝酸钾或硝酸钠溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钠或硝酸钾溶液中,搅拌30-60min,得到黄色固体,过滤后在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
所述基于聚集诱导发光效应的比色-荧光探针在检测高氯酸根或氯酸根中的用途。
本发明的优点和有益效果是:
本发明所述的一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途,通过阴离子诱导探针分子聚集实现对高氯酸根和氯酸根的双模式识别;具有良好的水溶性,其水溶液态呈现淡黄色且不发荧光,该荧光探针能特异性检测高氯酸根和氯酸根,高氯酸根和氯酸根能使探针分子聚集,使溶液颜色变为紫红色并发出明亮的红色荧光。对高氯酸根和氯酸根响应速度快,检测灵敏度高,选择性好、抗干扰性好、而且其颜色和荧光双模检测方式有利于提高复杂环境下检测的可靠性。
本发明所述的一种基于聚集诱导发光效应的比色-荧光探针及其制备方法和用途,该比色-荧光探针为异硫氰根·(三联吡啶)合铂(Ⅱ),在液态时为淡黄色溶液,紫外灯下不发出荧光,高氯酸根或氯酸根能够诱导其发生聚集,伴随着颜色从黄色到紫红色,荧光从没有荧光到发出红色荧光,这是由于聚集态的铂盐分子间产生金属-金属和π-π相互作用的结果。本发明的比色-荧光探针对高氯酸根或氯酸根响应速度快;检测灵敏度高,检测限为0.022mM;选择性好;抗干扰性好;而且其颜色-荧光双模检测方式大大提高复杂环境下检测的可靠性。
附图说明
图1为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对高氯酸根或氯酸根检测的选择性,a为日光灯下显色的图片,b为365nm紫外灯下显色的图片;
图2为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对高氯酸根检测的抗干扰性,以575nm处的紫外-可见吸收峰强度表示;
图3为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对高氯酸根检测的抗干扰性,以677nm处的发射峰强度表示,以519nm光激发;
图4为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对氯酸根检测的抗干扰性,以575nm处的紫外-可见吸收峰强度表示;
图5为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对氯酸根检测的抗干扰性,以677nm处的发射峰强度表示,以519nm光激发;
图6为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测高氯酸根的紫外吸收光谱随其含量的变化情况;
图7为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测高氯酸根的荧光强度随其含量的变化情况;
图8为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测氯酸根的紫外吸收光谱随其含量的变化情况;
图9为本发明的比色-荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测氯酸根的荧光强度随其含量的变化情况。
具体实施方式
下面通过具体实施例对本发明做进一步的说明,但发明不限制于这些实施例。
实施例1
a、称取氯亚铂酸钾1g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度80℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度40℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入0.1g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用常规的重结晶法将产物提纯;其中重结晶采用将产物溶于5mL N,N-二甲基甲酰胺中,再缓慢加入乙醚,直至沉淀完全;
d、取20g硝酸钾加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钾固体析出,得到过饱和硝酸钾溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钾溶液中,搅拌30min,得到黄色固体,过滤,在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
实施例2
a、称取氯亚铂酸钾1g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度80℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度50℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入1g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用重结晶法将产物提纯,其中重结晶采用将产物溶于5mL N,N-二甲基甲酰胺中,再缓慢加入乙醚,直至沉淀完全;
d、取70g硝酸钾加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钾固体析出,得到过饱和硝酸钾溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钾溶液中,搅拌60min,得到黄色固体,过滤后在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
实施例3
a、称取氯亚铂酸钾1g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度80℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度45℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入3g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用重结晶法将产物提纯,其中重结晶采用将产物溶于5mL N,N-二甲基甲酰胺中,再缓慢加入乙醚,直至沉淀完全;
d、取46g硝酸钠加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钠固体析出,得到过饱和硝酸钠溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钠溶液中,搅拌40min,得到黄色固体,过滤后在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
实施例4
a、称取氯亚铂酸钾14g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度804℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度50℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入5g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用重结晶法将产物提纯,重结晶采用将产物溶于5mL N,N-二甲基甲酰胺中,再缓慢加入乙醚,直至沉淀完全;
d、取80g硝酸钠加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钠固体析出,得到过饱和硝酸钠溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钠溶液中,搅拌60min,得到黄色固体,过滤后在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
实施例5
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)具有良好的水溶性:
室温下,分别将0.0017g、0.0034g、0.0082g、0.0164g、0.0266g和0.0365g的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)加入烧杯中,再用容量瓶将其定容到50ml,得到检测试剂的浓度分别为0.06mM、0.13mM、0.29mM、0.58mM、0.94mM和1.29mM,这些试剂均为淡黄色溶液,并且在365nm紫外灯下不发出荧光,测试各个不同浓度探针溶液的紫外吸收光谱,并对它们在425nm处紫外吸收值做线性拟合,结果表明:在该处的线性拟合度很高,相关性高达0.9992,溶液浓度在0.06-1.29mM范围内符合朗伯比尔定律,表明其溶解性良好。
实施例6
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对高氯酸根或氯酸根的检测性能,如图1所示:
取3mL 1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液于试管中,在其中滴加0.3mL 100mM的高氯酸盐溶液,1秒内试管内溶液变成紫红色的沉淀,该沉淀在365nm紫外灯下发出明亮的红色荧光,表明高氯酸根的存在;
取3mL 1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液于试管中,在其中滴加0.3mL 100mM的氯酸盐溶液,1秒内试管内溶液变成紫红色的沉淀,该沉淀在365nm紫外灯下发出明亮的红色荧光,表明氯酸根的存在。
实施例7
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测高氯酸根或氯酸根的选择性,如图1所示:
室温下,取若干份3mL 1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液于试管中,再在其中分别加入0.3mL 100mM常见阴离子如氟离子、氯离子、次氯酸根离子、溴离子、溴酸根离子、碘离子、碘酸根离子、硝酸根离子、亚硝酸根离子、硫酸根离子、磷酸根离子和碳酸根离子,其结果这些离子并不能像氯酸根和高氯酸根一样使溶液变成紫红色并发出红色的荧光,实际上,这些离子大多不能有效的诱导探针分子聚集,即使能诱导发生聚集,如碘离子,也不能使其产生特异的颜色变化,从紫外吸收光谱图上看,只有加入氯酸根和高氯酸根后,才会在575nm处的出现吸收峰,其他的离子的加入不能在575nm处产生新的吸收峰;从荧光光谱上看,只有加入氯酸根和高氯酸根后,在以519nm光激发下,荧光光谱在677nm处出现了新的发射峰,其他的离子的加入不能使探针分子在677nm处产生新的发射峰,表明探针分子对氯酸根和高氯酸根的选择性良好。
实施例8
验证实施例1-4得到的任意一种的比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测高氯酸根的抗干扰性,如图2和图3所示;和检测氯酸根的抗干扰性,如图4和图5所示:
室温下,取若干份3mL 1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液于试管中,再在其中同时加入0.3mL 100mM高氯酸根和0.3mL 100mM的其他阴离子如氟离子、氯离子、次氯酸根离子、溴离子、溴酸根离子、碘离子、碘酸根离子、硝酸根离子、亚硝酸根离子、硫酸根离子、磷酸根离子和碳酸根离子,这些离子的存在对高氯酸根的颜色和荧光响应没有明显影响,表明其对高氯酸根的抗干扰性良好;同样,室温下,取若干份3mL 1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液于试管中,再在其中同时加入0.3mL 100mM氯酸根和0.3mL 100mM的其他阴离子如氟离子、氯离子、次氯酸根离子、溴离子、溴酸根离子、碘离子、碘酸根离子、硝酸根离子、亚硝酸根离子、硫酸根离子、磷酸根离子和碳酸根离子,这些离子的存在对氯酸根的颜色和荧光响应没有明显影响,表明其对氯酸根的抗干扰性良好。
实施例9
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测高氯酸根的灵敏性,紫外滴定实验如图6所示,荧光滴定实验如图7所示:
室温下,在0.06mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液中分别加入浓度为0-0.6mM高氯酸根溶液后,在575nm处出现新的吸收峰,并随着高氯酸根的浓度增加该吸收峰不断增强,插图是不同高氯酸根浓度下在575nm处紫外吸收的变化,从中看出:当高氯酸根浓度在0.1-0.325mM时,吸收峰与高氯酸根浓度呈线性相关,基于检测限计算公式3σ/m,其中σ为11次空白样品的标准方差,m为拟合直线的斜率,算得紫外吸收的检测限为0.097mM;同样,荧光滴定实验中,室温下,在0.06mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液中分别加入浓度为0-0.6mM高氯酸根溶液后,以519nm的光激发,在677nm处出现发射峰,并随着高氯酸根的浓度增加该发射峰不断增强,插图是不同高氯酸根浓度下在677nm处发射峰强度的变化,从中看出,当高氯酸根浓度在0.1-0.325mM时,发射峰与高氯酸根浓度呈线性相关,基于检测限计算公式3σ/m,其中σ为11次空白样品的标准方差,m为拟合直线的斜率,算得荧光的检测限为0.12mM。
实施例10
验证实施例1-4得到的任意一种的比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)检测氯酸根的灵敏性,紫外滴定实验如图8所示,荧光滴定实验如图9所示:
室温下,在0.06mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液中分别加入浓度为0-0.6mM氯酸根溶液后,在575nm处出现新的吸收峰,并随着氯酸根的浓度增加该吸收峰不断增强,插图是不同氯酸根浓度下在575nm处的紫外吸收峰值变化,从中看出,当氯酸根浓度在0.1-0.325mM时,吸收峰强度与氯酸根浓度呈线性相关,基于检测限计算公式3σ/m,其中σ为11次空白样品的标准方差,m为拟合直线的斜率,算得紫外吸收的检测限为0.092mM;同样,荧光滴定实验中,室温下,在0.06mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液中分别加入浓度为0-0.6mM氯酸根溶液后,以519nm的光激发,在677nm处出现新的发射峰,并随着氯酸根的浓度增加该处的发射峰不断增强;插图是不同氯酸根浓度下在677nm处发射峰强度的变化,从中看出,当氯酸根浓度在0.1-0.325mM时,发射峰强度与氯酸根浓度呈线性相关,基于检测限计算公式3σ/m,其中σ为11次空白样品的标准方差,m为拟合直线的斜率,算得荧光的检测限为0.12mM。
实施例11
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)浓度对检测高氯酸根灵敏性的影响:
室温下,在浓度分别为0.06mM、0.13mM、0.29mM、0.58mM、0.94mM和1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液中分别加入浓度为0-0.6mM高氯酸根溶液,然后测试其紫外吸收光谱,找出在575nm处的吸收峰与高氯酸根的浓度变化的关系,基于检测限计算公式3σ/m,其中σ为11次空白样品的标准方差,m为拟合直线的斜率,算得不同探针浓度下检测高氯酸根的紫外吸收的检测限;当探针浓度为0.06mM,检测限为0.097mM;当探针浓度为0.13mM,检测限为0.029mM;当探针浓度为0.29mM,检测限为0.022mM;当探针浓度为0.58mM,检测限为0.026mM;当探针浓度为0.94mM,检测限为0.039mM;当探针浓度为1.29mM,检测限为0.040mM;由此可以看出,提高探针浓度,有利于降低检测限,这是由于探针浓度提高有效地抑制了产物的溶解,从而提高响应程度;但是探针分子浓度过高,会使灵敏度降低,这是因为初始的光学背景增加了;因此,最佳的探针分子浓度为0.29mM,对应最佳的紫外检测限。
实施例12
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对鞭炮中的高氯酸盐或氯酸盐的检测效果:
首先,掰开鞭炮外包装,用药匙取少量鞭炮的有效成分,置于滤纸上,取0.5mL1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液滴加到含有样品的滤纸上,1秒内有紫红色物质生成,并且该物质在365nm紫外灯下发出明亮的红色荧光,表明鞭炮中有高氯酸盐或氯酸盐的存在。
实施例13
验证实施例1-4得到的任意一种比色/荧光探针硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)对烟花中的高氯酸盐或氯酸盐的检测效果:
首先,掰开烟花外包装,用药匙取少量烟花的有效成分,置于滤纸上,取0.5mL1.29mM的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)溶液滴加到含有样品的滤纸上,1秒内有紫红色物质生成,并且该物质在365nm紫外灯下发出明亮的红色荧光,表明烟花中有高氯酸盐和氯酸盐的存在。
Claims (3)
2.根据权利要求1所述的该比色-荧光探针的制备方法,其特征在于:
a、称取氯亚铂酸钾1g溶解在20mL水中,加入醋酸24ml和1,5-环辛二烯1mL,加热温度80℃,反应30min,有淡黄色的晶体沉淀,将沉淀依次用50mL水、50mL乙醇和50mL乙醚进行清洗,去除未反应的原料,然后在温度60℃下干燥1小时,得到的二氯·(1,5-环辛二烯)合铂(Ⅱ);
b、将步骤a得到的二氯·(1,5-环辛二烯)合铂(Ⅱ)0.15g置于10mL水中,加入0.094g三联吡啶,温度40-50℃恒温,时间15min,固体溶解,过滤未反应的二氯·(1,5-环辛二烯)合铂(Ⅱ),滤液通过旋蒸后获得固体为氯化氯·(三联吡啶)合铂(Ⅱ),再用50mL乙醚洗涤3次,置于空气中干燥;
c、将步骤b得到的氯化氯·(三联吡啶)合铂(Ⅱ)0.1g溶解在5mL水中,加入0.1-5g的硫氰酸钾,得到橙红色沉淀硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ),过滤,在温度60℃下干燥1小时,然后利用常规的重结晶法将产物提纯;
d、取20-80g硝酸钾或硝酸钠加入50mL水中,加热水温至其完全溶解,然后冷却至室温,有硝酸钾或硝酸钠固体析出,得到过饱和硝酸钾或硝酸钠溶液;
e、将步骤c得到的提纯后的硫氰酸化异硫氰根·(三联吡啶)合铂(Ⅱ)置于步骤d的过饱和硝酸钠或硝酸钾溶液中,搅拌30-60min,得到黄色固体,过滤后在温度60℃下干燥1小时,即得到结构式(1)所示的硝酸化异硫氰根·(三联吡啶)合铂(Ⅱ)探针分子。
3.根据权利要求1所述的基于聚集诱导发光效应的比色-荧光探针在检测高氯酸根或氯酸根中的用途。
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