CN108822138B - 一种金属配合物荧光探针在检测气体中硫化氢的应用 - Google Patents
一种金属配合物荧光探针在检测气体中硫化氢的应用 Download PDFInfo
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Abstract
本发明公开了一种金属配合物荧光探针的制备方法,丹磺酰氯衍生物具有大的斯托克位移和相对高的量子产率,合成路线简单,具有良好的光稳定性;且含有一个多齿配体,与铜离子配位后,生成稳定的丹磺酰氯铜金属配合物探针。铜配合物探针对硫化氢有很好的敏感性分析,且对硫化氢有良好的选择性。
Description
技术领域
本发明涉及分析化学技术领域,尤其涉及一种金属配合物荧光探针的制备方法。
背景技术
改革开放以来,伴随着经济的快速发展,工业水平的突飞猛进,人类生活水平显著提高的同时也带来了一系列的环境问题,其中大气污染问题尤为严峻包含硫氧化物、氮氧化物、碳氢化合物、一氧化碳等气体的污染。例如,硫化氢H2S--一种有毒的污染气体,无色,恶臭味,剧毒,易燃。主要来源于硫磺、硫酸、染料和化妆品的制造过程,以及微生物的分解过程。微量的硫化氢就能刺激呼吸道引起头晕、头痛、咽喉不适、咳嗽等症状,若长时间暴露在H2S气体中会导致嗅觉神经麻痹,严重损害中枢神经、呼吸***、危害人类健康。另一方面,H2S作为一种非常重要的生物体内活性硫物质,是继NO、CO之后发现的第三个内源性气体信号分子,在心肌保护、神经调制、血管舒张、抗炎、中枢神经、呼吸道、胃肠道以及内分泌***等生理学过程扮演重要的角色,并且与Huntington’s、帕金森病、阿兹海默病甚至癌症密切相关。因此,发展高选择性、高灵敏性检测硫离子的方法对环境污染的监测和人类的健康都具重大的研究意义。
硫化氢的分析最早局限于化学分析法和电化学分析法,检测方法灵敏度低。20世纪60年代以来,随着光谱和色谱技术的广泛应用,推动了硫化氢分析的发展,如电感耦合等离子体原子发射光谱,高效液相和气相色谱法。随着技术的开发和应用,硫化氢分析技术有了更新的进展,包括现代光谱分析、现代色谱分析、波谱-色谱联用、生物传感和免疫分析等,这些方法大部分可达到对硫化氢痕量分析的要求,并具有很高的精度和灵敏度。但是它们都不同程度存在着操作复杂、费时费力、成本高等缺点,而且所用监测仪器体积庞大、价格昂贵,不能满足现场快速检测硫化氢的目的。
近年来,荧光分析技术吸引了越来越多研究者的青睐,因为荧光分析法最大优点在于响应时间短、灵敏度高、检测范围宽、以及较为简单的操作技术。Nagano课题组基于荧光的方法合成制备了一种检测硫化氢的大环铜离子配合物荧光探针,识别仅需几秒即可完成,实现了对硫化氢的关开检测。然而,目前大多检测硫化氢的荧光探针都是基于荧光猝灭turn-off的过程,这种检测方式容易受到很多环境条件的影响。然而基于荧光增强型turn-on的检测方式报道较少。丹磺酰氯衍生物具有大的斯托克位移和相对高的量子产率,合成路线简单,具有良好的光稳定性,并有较好的水溶性。基于丹磺酰氯优越的光谱性能,我们设计制备了一种turn-on荧光增强型的丹磺酰氯金属配合物荧光探针,实现了对用于硫化氢的分析检测。
发明内容
基于背景技术存在的技术问题,本发明提出一种金属配合物荧光探针的制备方法,设计合成了一类水溶性荧光功能化丹磺酰氯金属配合物的新方法,通过优选金属配合物来选择反应位点与荧光基团的试剂合成相结合来制备目标产物,提高合成效率和优化配合物的反应性能问题。以及通过荧光开关机制,解决反应过程荧光信号输出与硫化氢浓度关系的问题。
一种金属配合物荧光探针的制备方法,方法步骤如下:
S1:将丹磺酰氯和三乙胺加入到含有二氯甲烷的圆底烧瓶中,然后再加入氯乙胺盐酸盐,在氮气的保护下,室温反应搅拌0.5-1.5h,用旋转蒸发仪除去二氯甲烷溶剂,得到黄色油状物;
S2:然后将所得物质用硅胶柱进行分离纯化,得到产物Ds-1;
S3:称取Ds-1产物放置到DMF中溶解,再加入呋喃-2-基甲基-吡啶-2-基甲基-胺和无水碳酸钾,室温搅拌22-26h后,向反应混合液加入冰水,有大量沉淀生成,过滤得到沉淀物固体,然后将所得物质用硅胶柱进行分离纯化,得到黄色油状产物Ds-2:
S4:将固体产物Ds-2溶解于乙醇溶液中,得到浓度为100mM的溶液。然后与相同体积和相同浓度的氯化铜水溶液混合搅拌5-15min,得到50mM的丹磺酰氯的铜离子配合物Ds-Cu工作溶液,放置冰箱备用。
优选的,所述S1中丹磺酰氯、三乙胺、二氯甲烷、氯乙胺盐酸盐的质量体积添加比为:(0.1-0.2)g:(80-160)μL:(8-12)mL:(0.0043-0.0086)g。
优选的,所述S2中硅胶柱的展开剂为石油醚:乙酸乙酯=4:1,Rf=0.42。
优选的,所述S3中Ds-1、DMF、呋喃-2-基甲基-吡啶-2-基甲基-胺、无水碳酸钾、冰水的质量体积添加比为:(0.06-0.07)g:(2-4)mL:(0.03-0.04)g:(0.02-0.03)g:(12-18)mL。
优选的,所述S3中硅胶柱的展开剂为石油醚:乙酸乙酯=4:1-1:1。
本发明提出的一种丹磺酰氯铜金属配合物探针应用于检测硫化氢。
作用原理:
此类探针利用重金属离子电子效应或电子转移机制,猝灭荧光团,特别是有机荧光配体与Cu(Ⅱ)形成稳定的金属配合物,产生的原因主要依赖顺磁性Cu(Ⅱ)中心空的d轨道能够接受发色团中的激发态电子,阻断了配体荧光产生的过程。因此,一旦移除配合物中的铜离子释放出自由配体,配体的荧光就会恢复。根据软硬酸碱理论,S2-与Cu2+之间具有很强的亲和性,形成的硫化铜沉淀非常稳定,其Ksp=1.27×10-36。在溶液中加入H2S后,Cu(II)可脱离配合物,释放自由荧光配体,恢复荧光。因此,通过荧光开关机制,为金属配合物荧光探针在硫化氢检测领域的运用提供理论基础。
本发明中的有益效果:
本发明提出一种金属配合物荧光探针的制备方法,丹磺酰氯衍生物具有大的斯托克位移和相对高的量子产率,合成路线简单,具有良好的光稳定性;且含有一个多齿配体,与铜离子配位后,生成稳定的丹磺酰氯铜金属配合物探针。铜配合物探针对硫化氢有很好的敏感性分析,且对硫化氢有良好的选择性。
附图说明
附图用来提供对本发明的进一步理解,并且构成说明书的一部分,与本发明的实施例一起用于解释本发明,并不构成对本发明的限制。在附图中:
图1为丹磺酰氯铜金属配合物合成路线;
图2为丹磺酰氯铜金属配合物荧光探针的结构及其荧光光谱;
图3为探针对硫化氢小分子检测时的荧光关开过程图;
图4为硫化氢浓度与探针荧光恢复强度之间的线性关系图;
图5为探针对其他六种小分子气体选择性检测的荧光光谱图。
具体实施方式
下面结合具体实施例对本发明作进一步解说。
实施例1
一种金属配合物荧光探针的制备方法,方法步骤如下:
S1:将0.1g丹磺酰氯和80μL三乙胺加入到含有8mL的二氯甲烷的圆底烧瓶中,然后再加入0.0043g氯乙胺盐酸盐,在氮气的保护下,室温反应搅拌0.5h,用旋转蒸发仪除去二氯甲烷溶剂,得到黄色油状物;
S2:然后将所得物质用硅胶柱在石油醚:乙酸乙酯=4:1,Rf=0.42条件下进行分离纯化,得到产物Ds-1;
S3:称取0.06gDs-1产物放置到2mL的DMF中溶解,再加入0.03g呋喃-2-基甲基-吡啶-2-基甲基-胺和0.02g无水碳酸钾,室温搅拌22h后,向反应混合液加入12mL的冰水,有大量沉淀生成,过滤得到沉淀物固体,然后将所得物质用硅胶柱石油醚/:乙酸乙酯=4:1条件下进行分离纯化,得到黄色油状产物Ds-2:
S4:将固体产物Ds-2溶解于乙醇溶液中,得到浓度为100mM的溶液。然后与相同体积和相同浓度的氯化铜水溶液混合搅拌5min,得到50mM的丹磺酰氯的铜离子配合物Ds-Cu工作溶液,放置冰箱备用。
实施例2
S1:将0.1500g丹磺酰氯和117μL三乙胺加入到含有10mL的二氯甲烷的圆底烧瓶中,然后再加入0.0065g氯乙胺盐酸盐,在氮气的保护下,室温反应搅拌1h,用旋转蒸发仪除去二氯甲烷溶剂,得到黄色油状物;
S2:然后将所得物质用硅胶柱在石油醚:乙酸乙酯=4:1,Rf=0.42条件下进行分离纯化,得到产物Ds-1;
S3:称取0.0625gDs-1产物放置到3mL的DMF中溶解,再加入0.0376g呋喃-2-基甲基-吡啶-2-基甲基-胺和0.0276g无水碳酸钾,室温搅拌24h后,向反应混合液加入15mL的冰水,有大量沉淀生成,过滤得到沉淀物固体,然后将所得物质用硅胶柱石油醚:乙酸乙酯=3:1条件下进行分离纯化,得到黄色油状产物Ds-2:
S4:将固体产物Ds-2溶解于乙醇溶液中,得到浓度为100mM的溶液。然后与相同体积和相同浓度的氯化铜水溶液混合搅拌10min,得到50mM的丹磺酰氯的铜离子配合物Ds-Cu工作溶液,放置冰箱备用。
实施例3
S1:将0.2g丹磺酰氯和160μL三乙胺加入到含有12mL的二氯甲烷的圆底烧瓶中,然后再加入0.0086g氯乙胺盐酸盐,在氮气的保护下,室温反应搅拌1.5h,用旋转蒸发仪除去二氯甲烷溶剂,得到黄色油状物;
S2:然后将所得物质用硅胶柱在石油醚:乙酸乙酯=4:1,Rf=0.42条件下进行分离纯化,得到产物Ds-1;
S3:称取0.07gDs-1产物放置到4mL的DMF中溶解,再加入0.04g呋喃-2-基甲基-吡啶-2-基甲基-胺和0.04g无水碳酸钾,室温搅拌26h后,向反应混合液加入18mL的冰水,有大量沉淀生成,过滤得到沉淀物固体,然后将所得物质用硅胶柱石油醚:乙酸乙酯=1:1条件下进行分离纯化,得到黄色油状产物Ds-2:
S4:将固体产物Ds-2溶解于乙醇溶液中,得到浓度为100mM的溶液。然后与相同体积和相同浓度的氯化铜水溶液混合搅拌15min,得到50mM的丹磺酰氯的铜离子配合物Ds-Cu工作溶液,放置冰箱备用。
实施例4丹磺酰氯铜金属配合物探针对硫化氢的敏感性分析
实施例2制得的铜配合物探针的荧光光谱如图2所示,然后记录了1μM的配合物探针溶液在不同浓度的H2S存在下的荧光光谱的变化,H2S浓度范围从0-1.0μM,如图3所示,随着H2S浓度的增加,探针在538nm处的荧光强度逐渐增强,构成一个“关-开”模式的检测硫离子的荧光探针。
图4是配合物探针Ds-Cu的荧光强度与H2S浓度之间的线性关系,图中纵坐标表示加入硫离子前后探针荧光强度的比值(F/F0),其中F0代表的未加入硫化氢探针Ds-Cu的荧光强度,F代表的加入硫化氢后探针Ds-Cu的荧光强度。从图可以明显看出F/F0比值强度随着H2S浓度的增加而升高,在硫离子浓度0到1μM的浓度范围内,强度比值F/F0与硫离子存在一个很好的线性关系,所得线性相关系数R2=0.998,线性方程为F/F0=0.929+14.143[H2S],以此线性关系为依据,可实现对H2S的定量分析,根据检测限的定义,计算得出检测溶液中H2S的检测限为0.014μM。
实施例5丹磺酰氯铜金属配合物探针对硫化氢的选择性分析
为了研究探讨配合物探针体系对硫化氢的选择性,我们选择了一些常见的稳定的气体如NH3,NO2,N2,SO2,CO2和CO作为选择性气体。分别将这些气体注射到含有探针的溶液中,观察探针荧光光谱的变化,如图5所示,只有H2S气体使得探针荧光强度明显增强,其他气体对探针基本没有干扰,这些结果充分说明探针可用于对气体H2S的选择性很好。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
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