CN101776602A - 一种磷光化学传感器及其应用 - Google Patents
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Abstract
Description
技术领域
本发明涉及一种铱配合物,具体涉及一种基于铱配合物的磷光化学传感器及其应用。
背景技术
汞是对人体和环境最具威胁和毒害作用的金属元素之一,汞在自然界的主要存在形式有三种:元素汞、无机汞和有机汞。汞及其污染物可以通过火山喷发、采矿、固体废弃物焚化等各种各样的自然或人为的过程而广泛分布,从而污染大量的水、空气和土壤,并且通过环境中细菌的作用,汞元素和汞离子都可以被转化成甲基汞,即使是很低的浓度也可以进一步通过食物链富积于人体中。环境中的汞污染主要来源于工业使用的汞,如化学工业中用汞作催化剂,各种汞制仪表等。大气中的汞可来自汞矿开采冶炼、煤和石油燃料燃烧等。
有机汞的毒性大于金属汞和无机汞化合物,因而更容易发生中毒。有机汞和甲基汞均可通过呼吸道、消化道、皮肤侵入人体。无机汞在人体内的蓄积部位主要是肾脏,其次是肝脏和脾脏;甲基汞除蓄积在肝、肾等脏器之外,还可通过血脑屏障蓄积于脑组织内。汞中毒能损伤中枢神经系统,轻者表现为口腔炎、震颤、急躁、易怒和情绪不稳定,重者则精神紊乱、行为支配能力降低、四肢瘫痪、耳聋眼瞎,甚至成为痴呆。此外,大量使用有机汞农药,通过生物富集作用进而危害人体,也是汞中毒的主要原因之一。各种形态的汞及其化合物都具有高度的化学反应活性,它能与体内蛋白质、酶和核酸等生物分子中的巯基、羧基和磷酸基等官能团发生强烈缔合,进而扰乱细胞分裂和神经子传递等生命过程,对人的健康有极大的损害。同时它对大脑、骨骼、肾脏以及中枢神经,免疫以及内分泌等系统都有不同程度的毒害作用。
因此,Hg2+的检测在环保方面有着重要的意义。迄今对于Hg2+的检测已经发展出多种方法,如原子吸收光谱、原子发射光谱等。然而这些方法有着很多缺点,如样品需要处理、检测不够快速、检测价格昂贵等。在许多重要的应用场合,人们迫切需要快速、准确、低成本并能选择性地分析检测汞的方法,而化学传感器能较好地满足以上要求。
化学传感器是近年发展起来的一种新型微量和痕量分析技术,化学传感器指的是有着分子尺寸或比分子尺寸较大一些的、在与被分析物相互作用时能够给出实时信号的一种分子器件。它是把特定的化学物质的种类和浓度变成检测信号来表示的功能元件。主要是利用光敏感材料与被测物质中的分子、离子或生物物质相互接触时直接或间接地引起光信号的变化,使得很少的化学物质加入体系后,会有放大了许多倍的信号被检出,借此可以获得某种化学物质的浓度。根据不同的应用课题,人们可以设计出各种各样的化学传感器。化学传感器具有体积小、费用低、不需要预处理、能用于现场分析和监控以及远距离探测等优点,因此受到人们的广泛关注。
荧光化学传感器作为一类重要的检测技术,广泛应用于过渡金属及重金属离子的检测,可实现微环境的原位,实时检测。通常人们利用纯有机化合物作为过渡金属和重金属荧光检测探针,特别是含有冠醚类的大环化合物一直以来倍受关注,但这些有机化合物一般合成较复杂,并且一般纯有机化合物的荧光寿命短,斯托可位移小,容易受到来自背景的干扰,灵敏度不高。而对于重金属配合物,例如铱、铂、钌、锇等重金属配合物具有较长的磷光寿命,有较大的stokes位移,磷光发射不易受到来自背景荧光的干扰,他们独特的光物理性质越来越引起人们的注意。同时,配体对这些配合物的光物理和电化学等性质起着决定性的影响。
发明内容
本发明的目的在于根据现有技术中存在的不足,以含有二硫代氨基甲酸衍生物结构单元的铱配合物作为磷光化学传感器,该传感器具有磷光响应速度快,易于荧光背景区分,幅度大等特点。
本发明另一目的在于提供上述磷光化学传感器在检测金属离子中的应用。
本发明上述目的通过以下技术方案予以实现;
一种基于铱配合物的磷光化学传感器,包括主配体和辅助配体,其中,主配体是2-苯基吡啶,辅助配体是二硫代氨基甲酸衍生物,该磷光化学传感器以铱配合物作为识别分子并通过光信号变化有效表达探测结果,其结构通式如式I所示:
其中,辅助配体中的R1优选氢原子、甲基、乙基、甲氧基、乙氧基、苯基、萘基或联苯基;R2优选氢原子、甲基、乙基、甲氧基、乙氧基、苯基、萘基或联苯基。
本发明磷光化学传感器可用于检测金属离子,对汞离子特别敏感。
本发明磷光化学传感器对金属离子特别是汞离子产生的响应方式包括磷光发射光谱的强度变化和峰值及峰形变化、紫外可见吸收光谱的变化、溶液或固体薄膜的颜色变化。当遇到金属离子时,该化学传感器的磷光强度出现减弱,磷光发射光谱出现蓝移。
在合适的激发光源照射下,磷光化学传感器在溶液中或其固体薄膜可以发出强的磷光。当金属离子特别是汞离子存在时,会导致传感器的磷光强度减弱或淬灭,该原理是由于铱配合物上的硫原子与金属离子发生相互作用,使铱配合物单元上的电子离域程度发生变化,从而影响铱配合物从激发态向基态的磷光跃迁。同时由于该铱配合物中的铱原子与辅助配体形成的四元环上有两个硫原子,其与汞离子具有更强烈的作用,反映出的磷光发射强度和颜色变化更明显,因此有着更高的汞离子识别敏感度。
与现有技术相比,本发明具有如下有益效果:
(1)本发明的磷光化学传感器基于铱配合物,该铱配合物的辅助配体与金属铱形成的杂环上含有两个硫原子,与金属汞离子的作用强烈,有很高的探测灵敏度;
(2)该磷光化学传感器有很好的溶解性,适合应用于在不同的溶剂中;
(3)该磷光化学传感器具有很高的光、热稳定性,可以应用于苛刻的环境中;
(4)与有机荧光材料相比,该磷光传感器具有较大的stokes位移和较长的发射寿命,长的发射寿命有利于使用时间分辨技术使磷光信号与背景的荧光信号相区分。
附图说明
图1为铱配合物(ppy)2Ir(ddc)的合成路线;
图2为铱配合物(ppy)2Ir(ssc)的化学结构式;
图3为实施例3中,随着汞离子的含量增加,基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器在乙腈溶液中吸收光谱的变化情况;
图4为实施例4中,随着汞离子的含量增加,基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器在乙腈溶液中磷光发光光谱的变化情况;
图5为实施例5中,加入不同的金属离子后,基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器在乙腈溶液中的颜色变化情况;
图6为实施例6中,加入不同的金属离子后,基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器在乙腈溶液中的发光光谱的变化情况。
具体实施方式
以下结合实施例来进一步解释本发明,但实施例并不对本发明做任何形式的限定。
实施例1
铱配合物(ppy)2Ir(ddc)的合成方法如图1所示:
在4℃的条件下,二硫化碳(3.1mL,0.052mol)和50wt%的氢氧化钠水溶液(4mL)缓慢加入到二苄胺(9.9g,0.05mol)的乙醇溶液中。搅拌5小时后,冷却并除去易挥发物,然后用乙醇重结晶,得到二苄基二硫代氨基甲酸钠。
称取IrCl3·3H2O(0.2g,0.567mmol)和2-苯基吡啶(0.22g,1.42mmol)加入到双颈瓶中,在双排管上抽真空-充氮气-抽真空,循环三次,最后用氮气保护反应体系。用注射器注入15mL的2-乙氧基乙醇和水混合物(3∶1,v/v)后,将反应混合物加热至100℃,搅拌反应约20小时。反应停止后将反应混合物降至室温,过滤得到沉淀。所得沉淀分别用水、乙醇洗,得到黄色固体铱二氯桥化合物(ppy)2Ir(μ-Cl)2Ir(ppy)2。
将铱二氯桥化合物、辅助配体二苄基二硫代氨基甲酸钠(0.50g,1.7mmol)和24mL的2-乙氧基乙醇加入到双颈瓶中,在双排管上抽真空-充氮气-抽真空,循环三次,最后用氮气保护反应体系。将反应混合物加热至110℃,搅拌反应约20小时。反应停止后将反应混合物降至室温,过滤得到沉淀,晾干后柱层析(二氯甲烷/石油醚)分离得到铱配合物(ppy)2Ir(ddc)。产率:71%;ESI-MS:774(m/z);Anal.Calcd.for C37H30N3S2Ir:C,57.49;H,3.91;N,5.44.Found:C,57.35;H,3.88;N,5.40。
实施例2铱配合物(ppy)2Ir(ssc)的制备
称取IrCl3·3H2O(0.2g,0.567mmol)和2-苯基吡啶(0.22g,1.42mmol)加入到双颈瓶中,在双排管上抽真空-充氮气-抽真空,循环三次,最后用氮气保护反应体系。用注射器注入15ml的2-乙氧基乙醇和水混合物(3∶1,v/v)后,将反应混合物加热至100℃,搅拌反应约20小时。反应停止后将反应混合物降至室温,过滤得到沉淀。所得沉淀分别用水、乙醇洗,得到黄色固体铱二氯桥化合物(ppy)2Ir(μ-Cl)2Ir(ppy)2。
将铱二氯桥化合物、辅助配体二乙基二硫代氨基甲酸钠盐(0.29g,1.7mmol)和24mL2-乙氧基乙醇加入到双颈瓶中,在双排管上抽真空-充氮气-抽真空,循环三次,最后用氮气保护反应体系。将反应混合物加热至110℃,搅拌反应约20小时。反应停止后将反应混合物降至室温,过滤得到沉淀,晾干后柱层析(二氯甲烷/石油醚)分离得到铱配合物(ppy)2Ir(ssc),其化学结构式如图2所示。1HNMR(CDCl3,500MHz)δ(ppm):9.57(d,2H),7.81,(d,2H),7.66(t 2H),7.50(d,2H),7.21-7.14(m,2H),6.76(t,2H),6.60(t,2H),6.28(d,2H),3.80-3.73(m,2H),3.53-3.46(m,2H),1.25-1.20(t,6H).Anal.Calcd.for C27H26N3S2Ir:C,49.98;H,4.04;N,6.48.Found:C,50.07;H,4.04;N,6.48。
实施例3
基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器对汞离子响应的紫外可见吸收光谱测试如图3所示,随Hg2+(0~4.0×10-5mol/L)的加入,(ppy)2Irssc乙睛溶液(2.0×10-5mol/L)的紫外-可见吸光谱发生明显的变化。290nm处的吸收峰逐渐变弱,而250nm处的吸收峰变得更强。
实施例4
基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器对汞离子响应的磷光发射光谱测试如图4所示,在乙腈溶液中,(ppy)2Ir(ssc)的发射为黄绿色,其最大发射峰在506nm。随着Hg2+的逐渐加入,506nm的发射峰的强度逐渐降低,并在470nm处出现新的发射峰。
实施例5
基于铱配合物(ppy)2Ir(ssc)的磷光化学传感器对不同金属离子的选择性测试。该铱配合物(ppy)2Ir(ssc)在乙腈溶液(5.0x10-4mol/L)中对10种金属离子(Hg2+、Na+、K+、Mg2+、Ni2+、Fe3+、Cu2+、Co2+、Cr3+、Mn2+)的选择性测试如图5所示。左边第一个是未加入任何离子的配合物溶液,呈黄色;当加入相对于配合物三倍量的Hg2+离子(1.5x10-3mol/L)后溶液颜色出现明显的变化,由黄色变为了无色。当加入三倍量的Na+、K+、Mg2+、Ni2+、Cr3+、Mn2+等金属离子(1.5x10-3mol/L)时,溶液颜色不发生变化;加入3倍量的Fe3+、Cu2+离子时,由于离子本身具有颜色,因此溶液颜色微弱变化,显示为两色的叠加。Co2+离子的乙腈溶液为蓝色,所以加入后黄色和蓝色叠加表现为绿色。
实施例6
加入不同金属离子(1.5×10-3mol/L)后,铱配合物(ppy)2Ir(ssc)在乙腈溶液(5.0×10-4mol/L)中发射光谱的变化如图6所示。可以看到未加入金属离子的溶液的发射峰在507nm处;加入Na+、K+、Mg2+、Cu2+、Co2+、Cr3+、Mn2+等离子后,峰强变化很小、峰的位置不发生变化;加入Ni2+、Fe3+、Cr3+离子后,虽然峰强有一定的减小,不过峰的位置并没改变。相比而言,加入Hg2+后,配合物溶液的光谱发生了很大的变化,原本在507nm处的波峰减弱明显,峰值蓝移到499nm处,在468nm处又形成了新的峰,并成为最大峰。该比较实验说明Hg2+的加入对配合物(ppy)2Ir(ssc)的溶液光物理性质作用明显,并且配合物对Hg2+离子有很好的选择件。
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CN102190685A (zh) * | 2011-03-18 | 2011-09-21 | 南京邮电大学 | 含铱配合物磷光材料及制备和用于汞离子和乙腈的检测方法 |
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CN105906669A (zh) * | 2016-05-11 | 2016-08-31 | 东北师范大学 | 一种磷光金属铱配合物及其制备方法和应用 |
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CN102190685A (zh) * | 2011-03-18 | 2011-09-21 | 南京邮电大学 | 含铱配合物磷光材料及制备和用于汞离子和乙腈的检测方法 |
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