CN107344947A - 一种铁离子荧光探针分子及其制备方法和应用 - Google Patents
一种铁离子荧光探针分子及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 7
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011668 ascorbic acid Substances 0.000 claims description 3
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
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- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种铁离子荧光探针分子及其制备方法和应用,属于阳离子检测领域。本发明的荧光探针分子是利用点击反应,通过高度稀释法合成的,产率高达60 %。该荧光探针分子是一个环蕃分子,具有较大的空腔,是很好的荧光发光材料。实验结果表明,该荧光探针分子在CH3CN/H2O的体系中可以选择识别Fe3+,不受其他阳离子的干扰。只有Fe3+的加入使得荧光探针分子在380 nm处发生荧光淬灭;加入50 μM 后,荧光强度发生了明显淬灭。因此,该荧光探针分子可用于Fe3+的荧光快速检测,其最低检测限可以达到0.15μM。
Description
技术领域
本发明属于阳离子检测领域,涉及一种三价铁离子荧光探针分子的制备;本发明还涉及荧光探针分子高选择性荧光识别铁离子的应用及环蕃受体分子的合成方法。
背景技术
铁是人体各项生理活动不可或缺的元素,参与血液中氧的转运和质子转移等,是各种酶和血红蛋白的重要组成部分。一旦人体体内铁元素缺乏, 就导致各种各样生理机能系统紊乱,从而引起疾病;而过量的铁也存在潜在的危害, 研究表明体内铁贮存过多与多种疾病如心脏和肝脏疾病、糖尿病以及某些肿瘤有关。因此,开发高效、高选择识别Fe3+的方法受到人们的广泛关注。目前,分光光度法、原子吸收光谱法、伏安法、原子发射光谱法和荧光分析法已用来检测铁离子。然而这些方法大多需要复杂的仪器以及繁琐的样品制备过程,相比之下,荧光技术具有选择性好、灵敏度高、成本低、简便快捷等优点,提供了一个方便、快捷的检测方式。
化学传感器探针的开发与研究在生物、环境、化工等领域具有重要的意义。而荧光探针化学传感器由于具有快速检测时间和低成本的优势已经成为非常受欢迎的检测分析手段。近年来,越来越多的人报道了有关Fe3+的荧光探针分子,但由于其局限在有机溶剂中选择识别,不能得到广泛的应用。目前尚未有关于在水溶液下选择识别Fe3+的荧光探针分子的报道。
发明内容
本发明的目的是提供一种铁离子荧光探针分子;
本发明的另外一个目的是提供一种铁离子荧光探针分子的制备方法;
本发明的更重要的目的是提供荧光探针分子在水溶液中检测铁离子的方法。
一、铁离子荧光探针分子
本发明铁离子荧光探针分子,化学名称为:(32Z, 72Z) - 11H, 31H, 71H, 91H - 12,15, 18三氧杂 - 3(1, 3), 7(3, 1) - 二苯并[d]咪唑-1, 9 (5, 1) - 二三氮杂-5(1,3)- 茚-5-基氧杂环己烷六氟磷酸盐。其结构式如下:
1,3-二(三溴丙炔基苯并咪唑基)苯的合成步骤:
在氮气保护下,将苯并咪唑和无水碳酸钾加入干燥三口烧瓶,随后加入DMF使固体溶解。将体系温度升高至60 ℃,后缓慢滴加入3-溴丙炔。控制体系温度至60 ℃,反应过夜。反应结束后,用二氯甲烷与水洗涤,除去反应体系中的DMF。用无水Na2SO4干燥,得到暗黄色油状粗产品。进行柱层析,得到黄色油状液体丙炔基苯并咪唑 (a) Maračić S, Kraljević TG, Paljetak H Č, et al. Bioorganic & medicinal chemistry, 2015, 23(23):7448-7463. 在N2保护下,将丙炔基苯并咪唑和 1,3-二(溴甲基)苯加入三口烧瓶,用1,4-二氧六环使其溶解。将体系加热至105 ℃,回流,重结晶得到暗黄色固体1,3-二(三溴丙炔基苯并咪唑基)苯。m.p. 153-154℃. 1H NMR (400 MHz, DMSO-d 6) δ 10.10 (s, 1H),8.08 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.82 (s, 1H), 7.73 (t, J= 7.8 Hz, 2H), 7.61 (t, J = 7.8 Hz, 2H), 7.53 (d, J = 7.5 Hz, 2H), 7.50 –7.42 (m, 1H), 5.83 (s, 2H), 5.57 (d, J = 2.4 Hz, 3H), 3.94 (t, J = 2.4 Hz,1H).
(1)丙炔基苯并咪唑的合成路线
(2)1,3-二(三溴丙炔基苯并咪唑基)苯的合成路线
铁离子荧光探针分子的合成方法:是以甲醇为溶剂,以五水硫酸铜和抗坏血酸为催化剂,使1-叠氮基-2-(2-(2-(2-叠氮基乙氧基)乙氧基)乙氧基)乙烷与1,3-二(三溴丙炔基苯并咪唑基)苯以8:1~10:1的摩尔比,回流反应时间为3-5天,加入5当量的六氟磷酸铵,回流反应24 h,减压除去溶剂,重结晶,得到白色固体。
(3)铁离子荧光探针分子的合成路线
其中:将反应物分别缓慢滴入反应体系中,通过高度稀释法,从而减少副反应的产生。
二、铁离子荧光探针分子的荧光性能
1、荧光探针分子的激发和发射谱图研究
将荧光探针分子配制成2.5×10-5 mol/L的乙腈溶液进行荧光光谱性质的测试。狭缝宽度分别为2.5 nm,电压为700 V,分别进行荧光激发光谱和荧光发射光谱进行扫描,最大激发波长为280 nm,最大发射波长为380 nm,如图1。
2、荧光探针分子对不同含水量的荧光强度研究
将荧光探针分子在不同含水量的乙腈混合溶剂下配制成浓度为2.5×10-5 mol/L。以280 nm为激发波长,扫描荧光探针分子的发射谱图。如图2和图3,随着加入水的量逐渐增大,荧光强度呈现先增大后减小。当CH3CN:H2O (V:V=1:1)体系时,荧光强度达到最大;当CH3CN:H2O (V:V=1:39)体系时,荧光强度又变为纯乙腈溶液时的荧光强度。因此以CH3CN:H2O (V:V=1:39)混合溶剂进行后续的离子识别。
3、荧光探针分子对Fe3+的荧光识别
将荧光探针分子在CH3CN:H2O (V:V=1:39)混合溶剂下配制成浓度为2.5×10-5 mol/L。向荧光探针分子溶液中分别加入20当量的不同金属离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+)。当向荧光探针分子溶液中加入Fe3+时,荧光强度发生了淬灭;而滴入其它阳离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+)后,受体分子的荧光基本没有变化。为了更清楚地看出荧光探针分子的荧光变化趋势,我们做了荧光探针分子在380 nm波长的荧光强度变化柱状图,如图4所示。可以清楚看出,只有Fe3+的加入,荧光探针分子的荧光强度发生了淬灭,荧光探针分子对阳离子的识别能力依次为:Fe3+>> Cr3+> Cd2+> Al3+≈ Cu2+≈ Co2+≈ Hg2+≈ Mg2+ ≈ Mg2+≈ Na+≈ Ni2+ ≈ Pb2+≈ Zn2 +。这说明荧光探针分子在水溶液条件下可以高效选择识别Fe3+。
4、荧光探针分子对Fe3+识别的抗干扰性。
对离子识别的受体来讲,抗干扰性能是一个非常重要的指标,为了研究荧光探针分子对Fe3+识别的抗干扰性能,我们做了如下的抗干扰实验:将5倍当量的Fe3+加入荧光探针分子(c=2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液中,再将20倍当量的不同金属离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+)分别加入上述体系中,进行荧光测试。实验结果与只加入Fe3+的现象是相同的。选取荧光光谱中380 nm处的荧光强度数据做柱状图。如图5所示,我们可以清晰的看到,其他阳离子对Fe3+的识别没有干扰。因此,荧光探针分子可以单一选择识别Fe3+。
5、荧光探针分子对Fe3+的荧光滴定。
为了进一步探究荧光探针分子对Fe3+的作用趋势,我们进行了荧光发射光谱滴定实验。移取3 mL荧光探针分子(c=2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液于4mL离心管,分别依次加入不同当量的Fe3+ (c=2.5×10-3 mol/L)的水溶液,静置,进行荧光测试。如图6和7所示,随着Fe3+的加入,荧光光谱在380 nm的荧光强度逐渐减弱;当加入4倍当量Fe3+时,荧光强度完全淬灭,F/F0比值为0.007。
6、荧光探针分子对Fe3+的荧光最低检测限。
根据3ó/k方法计算荧光探针分子对Fe3+的荧光光谱最低检测限可以达0.15 μM(见图8)。因此,该荧光探针分子对Fe3+的检测具有较高的灵敏度。
7、荧光探针分子对Fe3+的结合常数测定。
根据Benesi-Hildebrand方程可计算出荧光探针分子对Fe3+的结合常数及结合比。以Fe3+浓度的倒数为横坐标,以 (I-I0) 的倒数为纵坐标作图(如图9)。由图可知,(I-I0)的倒数与Fe3+浓度的倒数呈现线性关系,R2为0.98。因此表明荧光探针分子与Fe3+的结合比为1: 1,结合常数为1.89×104 M-1。
8、荧光探针分子对Fe3+的荧光响应时间。
众所周知,常见的化学传感器总是存在时间过长的问题。图10为荧光探针分子检测Fe3+的响应时间。小心沿着比色皿边沿缓慢加入5当量的Fe3+时,立刻进行荧光测试;实验结果表明,荧光探针分子在380 nm处的荧光强度发生完全淬灭。随后,荧光强度保持稳定。这表明整个识别过程快速便捷。
附图说明
图1 为荧光探针分子(c=2.5×10-5 mol/L)在乙腈溶液体系中的荧光激发光谱和荧光发射光谱。
图2 为荧光探针分子(c=2.5×10-5 mol/L)在含有不同水的乙腈的荧光发射光谱(ëex=280 nm)。
图3 为荧光探针分子(c=2.5×10-5 mol/L)在含有不同水的乙腈的波长在380 nm荧光强度柱状图(ëex=280 nm),其中a~g分别为:(a) CH3CN; (b) CH3CN:H2O (V:V=4:1);(c) CH3CN:H2O (V:V=4:1); (d) CH3CN:H2O (V:V=1:1); (e) CH3CN:H2O (V:V=1:4) (f)CH3CN:H2O (V:V=1:19); (g) CH3CN:H2O (V:V=1:39)
图4 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液中,加入不同阳离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=2.5×10-3mol/L)在380 nm的荧光光谱柱状图。
图5 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液中对Fe3+( c=2.5×10-3 mol/L)识别的抗干扰图(黑:荧光探针分子加入其他各阳离子的荧光强度,条纹:加入Fe3+后再加入个阳离子的荧光强度)。
图6 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液中对Fe3+的荧光滴定图。
图7 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液中对不同浓度的Fe3+在380 nm处的荧光强度变化图。
图8 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液对Fe3+的工作曲线。
图9 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液对Fe3+的Benesi-Hildebrand曲线。
图10 荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液对Fe3+的响应时间。
具体实施方式
下面对通过具体实施例对本发明荧光探针分子的结构、合成以及铁离子的识别方法进行了详细的说明。
1、荧光探针分子的制备
取1000 mL的四口烧瓶,将(5 mg, 0.02 mmol, 0.05eq)五水硫酸铜和(7 mg, 0.04mmol, 0.1 eq)抗坏血酸加入反应瓶中,加入300 mL甲醇使其溶解得到反应液。分别称取(100 mg, 约0.2 mmol) 1,3-二(三溴丙炔基苯并咪唑基)苯和(488 mg, 2 mmol, 10 eq)1-叠氮基-2-(2-(2-(2-叠氮基乙氧基)乙氧基)乙氧基)乙烷,分别用100 mL甲醇溶解后滴加,于氮气保护下,回流反应3~5天。反应结束后,加入5当量六氟磷酸铵,继续反应24 h。减压除去溶剂,重结晶,得到白色固体114 mg,产率为60%,m.p. 153-155 ℃。
2、荧光探针分子的结构表征
荧光探针分子的1H NMR、IR、MS、HRMS如下:1H NMR (400 MHz, DMSO-d 6) δ 9.95 (s,2H), 8.31 (s, 2H), 8.05 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.73 -7.48 (m, 8H), 5.87 (s, 4H), 5.78 (s, 4H), 4.54 (s, 4H), 3.76 (s, 4H), 3.41(s, 4H), 3.29 (s, 4H). MS-ESI: [M-PF6 -]+ at m/z 805.38. HRMS calcd for: [M-PF6 -]+ at m/z 805.2901. Found 805.2921.
3、荧光探针分子的光谱性质
在荧光测试实验中,用移液枪移取3.0 mL的荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)水溶液带有编号的4 mL离心试管,分别向各离心试管移取等当量的不同金属阳离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=2.5×10-3mol/L),静置5 min,进行荧光光谱测试。
4、荧光探针分子的滴定
在荧光滴定实验中,用移液枪移取3.0 mL的荧光探针分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)水溶液于带有编号的4 mL离心试管,分别向各离心试管移取不同当量的三价铁离子(0.00 eq~10.0 eq, c=2.5×10-3 mol/L),静置5 min后,进行荧光光谱测试。
5、荧光探针分子对多种金属阳离子的荧光柱状图
在4 mL离心试管中加入3 mL的荧光受体分子(2.5×10-5 mol/L)的CH3CN:H2O (V:V=1:39)的水溶液,在分别加入5当量其它的金属离子(Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=2.5×10-3 mol/L),在加入5.0当量Fe3+,分别测定其荧光强度,绘制不同金属阳离子对于380 nm荧光强度柱状图,见图5试验证明,其它金属阳离子不干扰体系对Fe3+的检测。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
1.一种铁离子荧光探针分子,其特征在于,其结构式如下:
。
2.如权利要求1所述铁离子荧光探针分子的制备方法,其特征在于,是以甲醇为溶剂,以五水硫酸铜和抗坏血酸为催化剂,使1-叠氮基-2-(2-(2-(2-叠氮基乙氧基)乙氧基)乙氧基)乙烷与1,3-二(三溴丙炔基苯并咪唑基)苯以8:1~10:1的摩尔比反应,反应温度控制在65~70 ℃,反应时间为3-5天;然后在反应体系中再加入5当量的六氟磷酸铵,回流反应24h,减压除去溶剂,固体析出,过滤,洗涤,重结晶,得到白色固体即为所述铁离子荧光探针分子。
3.根据权利要求2所述铁离子荧光探针分子的制备方法,其特征在于:所述1,3-二(三溴丙炔基苯并咪唑基)苯的制备方法包括:在N2保护下,将丙炔基苯并咪唑和 1,3-二(溴甲基)苯加入三口烧瓶,用1,4-二氧六环使其溶解;将体系加热至105 ℃,回流,重结晶得到暗黄色固体1,3-二(三溴丙炔基苯并咪唑基)苯。
4.根据权利要求2所述铁离子荧光探针分子的制备方法,其特征在于:通过高度稀释法,将反应物分别滴入反应体系中,从而减少副反应的产生。
5.如权利要求1所述铁离子荧光探针分子的应用,其特征在于,所述铁离子荧光探针分子在体积比为1/39的CH3CN/H2O混合体系中选择识别铁离子的应用。
6.根据权利要求5所述铁离子荧光探针分子的应用,其特征在于,在体积比为1/39的CH3CN/H2O混合体系中,加入Fe3+的水溶液,铁离子荧光探针分子在380 nm处发生了荧光淬灭。
7.根据权利要求5所述铁离子荧光探针分子的应用,其特征在于,在体积比为1/39的CH3CN/H2O混合体系中,铁离子荧光探针在小于25μM 浓度下,具有良好的线性相关,对Fe3+最低检测限为0.15μM。
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