CN103641819A - 一种用于Cr3+、Cu2+裸眼识别与检测的安替比林衍生物探针材料及其制备方法 - Google Patents
一种用于Cr3+、Cu2+裸眼识别与检测的安替比林衍生物探针材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物及其制备方法。该化合物是由基于咔唑的醛基与4-氨基安替比林中的氨基基团缩合反应得到的含有咔唑基团的席夫碱衍生物,其分子特征是席夫碱化合物结构中含有N-取代安替比林基团、-C=N基团和咔唑基团;该探针化合物具有C=N结构的席夫碱衍生物,同时分子中含有O和N等配位原子,可以与一些金属离子形成配位分子,产生特定的紫外、荧光现象。本发明化合物可以通过紫外-可见分光光度法实现对Cu2+/Cr3+离子的识别、定量检测,可以通过明显的颜色变化作为裸眼识别Cu2+/Cr3+离子的比色探针,而且在其它离子存在的情况下有很好的抗干扰性、高选择性和灵敏性。
Description
技术领域
本发明涉及金属离子检测和选择性比色识别领域,具体是一种用于Cu2+、Cr3+裸眼识别与检测的含有咔唑-安替比林席夫碱衍生物探针分子的合成及其离子识别性能的研究。
背景技术
近年来,过渡金属离子在环境和生命科学中发挥着重要的作用,因此设计合成对过渡金属离子有选择性识别功能的探针分子越来越受到关注。在众多过渡金属离子及重金属离子中,铜离子与我们的生活密切相关。铜是动植物体内必需的微量重金属元素之一,大约有二十多种作用需要有铜离子的参与,如细胞色素氧化酶、过氧化物歧化酶及酪氨酸酶等。但如果机体内铜离子含量过高,则会使细胞受损和坏死,导致脏器功能损伤和疾病的产生,同时铜离子也是污染环境的重金属离子之一。铬及其化合物被广泛应用于冶金、电镀、皮革、颜料、耐火材料、印染、涂料等工业,通过废气、废液排放最终以离子形态进入大自然。铬的毒性与其存在的价态有关,Cr6+比Cr3+毒性高100倍,并易被人体吸收且在体内蓄积,铬的污染源有含铬矿石的加工、金属表面处理、皮革鞣制、印染等排放的污水。Cr6+离子对人体有毒,而Cr3+离子是人体必需的微量元素之一,它在维持人体健康方面起关键作用。铬是正常生长发育和调节血糖的重要元素,还是葡萄糖耐量因子的组成成分,可促进胰岛素在体内充分地发挥作用。当铬缺乏时,就很容易表现出糖代谢失调,如不及时补充,就会患糖尿病,诱发冠状动脉硬化导致心血管病,严重的会导致白内障、失明、尿毒症等并发症。因此,开发能识别Cr3+及Cu2+的比色/荧光分子探针对于环境及生命科学都具有重大的意义。
一直以来,对Cu2+及Cr3+离子的检测方法主要有原子吸收法、分光光度法、高效液相分析法及电化学分析法等,但上述方法中,有的试剂选择性较差,用于某些复杂样品分析时,常需借助适当的预处理;有的仪器设备复杂,成本较高,都不是理想的识别和检测生物体内Cu2+、Cr3+离子的方法,比色及荧光分析法作为一种简单、有效而又经济的方法,具有高灵敏度和能通过裸眼识别,目前正成为生物界应用最广泛的方法之一。分子/离子探针技术因具有选择性好、灵敏度 高、简单快速且不需要借助昂贵仪器的优点而被广泛地应用于各种金属离子的检测。利用吸光度与离子浓度的关系可以对离子进行定量或定性的分析,方便、快捷,具有较高的选择性和灵敏性,非常适用于重金属离子的实时或原位检测。
发明内容
本发明的目的是针对上述存在问题提供一种对Cu2+、Cr3+具有特殊选择性,且灵敏度高、制备方法简单实用且产率较高的用于Cu2+、Cr3+检测的比色离子探针试剂及其制备方法。由于比色探针的识别性能与探针分子的空间结构及所采用的测试条件有关,所以本发明基于C=N异构化机理,以C=N中的N原子和安替比林中的O原子为识别基团、以咔唑为发色团母体,设计并合成了具有刚性结构的探针分子。
本发明采用的技术方案如下:
一种用于Cr3+、Cu2+裸眼识别与检测的含有咔唑-安替比林基席夫碱比色探针化合物,其特征在于:该化合物是由基于咔唑的醛基与4-氨基安替比林中的氨基基团缩合反应得到的含有咔唑基团的席夫碱衍生物,其分子特征是席夫碱化合物结构中含有N-取代安替比林基团、-C=N基团和咔唑基团;该探针化合物具有C=N结构的席夫碱衍生物,同时分子中含有O和N等配位原子,可以与一些金属离子形成配位分子,产生特定的紫外、荧光现象;所述的探针化合物的化学结构式如下:
其中,R是碳原子数目为n=2-8烷基取代基。
一种用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物的制备方法,其特征在于包括以下步骤:
(1)己基咔唑中间体(1)的合成
将咔唑溶于无水DMF中,室温搅拌至完全溶解后分批加入NaH,油封,继续室温搅拌20分钟后用恒压漏斗滴加含溴己烷的DMF溶液,滴毕,80℃水浴回流3小时停止反应,冷却后倒入水中,用体积比为1:1的盐酸调节pH值至中性, 静置,析出粗产品,抽滤,用乙醇重结晶即可得己基咔唑中间体;
(2)3-甲酰基-N-己基咔唑中间体(2)的合成
将上述制得的己基咔唑中间体加入无水DMF,将POCl3倒入恒压漏斗中,在冰水浴中边滴加边搅拌,滴毕,再搅拌半个小时,将烧瓶移至油浴升温至70℃反应2小时。然后,停止加热冷却至室温,继续搅拌16小时,将得到的黑红色粘稠液倒入大量碎冰中,快速搅拌,得淡黄色悬浮液,用NaOH溶液中和,乙酸乙酯萃取,无水MgSO4干燥,静置过夜,旋干有机相,真空干燥,加入中性Al2O3和少量CH2Cl2,混合旋干,经柱色谱分离即得淡黄色3-甲酰基-N-己基咔唑中间体;
(3)4-氨基安替比林缩3-甲酰基-N-己基咔唑席夫碱(3)的合成
将4-氨基安替比林和3-甲酰基-N-己基咔唑溶解在乙醇中,室温回流4h,粗产物用乙醇重结晶即得淡黄色目标产物。
步骤(1)中所述咔唑和溴己烷的摩尔比为6:7。
步骤(2)中所述己基咔唑、DMF和POCl3的摩尔比为1:40:10。
步骤(3)中所述4-氨基安替比林和3-甲酰基-N-己基咔唑的摩尔比为6:5。
该化合物(3)的乙腈溶液可以用于Cr3+和Cu2+的“裸眼”识别;在该化合物的乙腈溶剂中可以通过紫外-可见光谱法实现对Cr3+和Cu2+离子检测。
该化合物的合成路线如下所示:
其中,(1)为己基咔唑中间体;(2)为3-甲酰基-N-己基咔唑中间体;(3)为目标产物4-氨基安替比林缩3-甲酰基-N-己基咔唑席夫碱。
该化合物(3)可用于溶液中Cu2+和Cr3+离子比色识别、检测,而且对多种金 属离子有较强的抗干扰能力,可以比色识别Cu2+/Cr3+离子,并且化合物与Cu2+或Cr3+离子混合产生明显的颜色变化现象可以实现裸眼识别和比色分析。
本发明的优点:
本发明合成的席夫碱衍生物具有多功能性,可以通过紫外-可见分光光度法实现对Cu2+和Cr3+离子的识别;该化合物合成路线简单、反应条件温和、后处理简单方便且产率较高,便于应用;该化合物可用于Cu2+/Cr3+离子快速识别、定量检测,而且对Cu2+/Cr3+离子识别具有较高的选择性和较好的抗干扰能力,并且伴随明显的颜色变化,因此可在不需要仪器的情况下,很方便地用“肉眼”检测Cu2+/Cr3+。
附图说明
图1为化合物(3)乙腈溶液中加入不同金属离子的紫外吸收光谱。
图2(a)为加入Cr3+离子的化合物(3)乙腈溶液紫外-可见吸收光谱滴定图,插图是加入Cr3+离子后,溶液在288nm处的吸光度变化;(b)为加入Cu2+离子的化合物(3)乙腈溶液紫外-可见吸收光谱滴定图,插图是加入Cu2+离子后,溶液在288nm处的吸光度变化。
图3为测定化合物(3)与Cr3+/Cu2+离子的稳定常数的Benesi-Hildebrand曲线。
图4为判断Cr3+/Cu2+存在时增强常数的Stern-Volmer曲线。
图5为化合物(3)的(Amin-A)/(Amin-Amax)vs log[C]曲线。
图6为化合物(3)乙腈溶液中的金属离子选择性和抗干扰柱状图;黑色代表化合物(3)乙腈溶液中加入不同金属离子的紫外吸收;红色代表在化合物(3)乙腈溶液中加入不同金属离子和Cr3+离子的紫外吸收;蓝色代表在化合物(3)中加入不同金属离子和Cu2+离子的紫外吸收。
具体实施案例
本发明可以通过以下的实施例进一步说明,但不仅仅局限于实施例。
实施例1:化合物(3)的合成
(1)称取4g(24mmol)咔唑,加入20mL无水DMF,室温搅拌至完全溶解后分批加入1g NaH,油封,继续室温搅拌20min后用恒压漏斗滴加含4mL(28mmol)溴己烷的DMF(10mL)溶液,滴毕,80℃水浴回流3小时停止反 应,冷却后倒入水中,用体积比为1:1的盐酸调节pH值至中性,静置,析出粗产品,抽滤,乙醇重结晶,得白色针状晶体4.59g,产率约76.1%。FT-IR(KBr,cm-1):3049(=C-H),2856-2953(-CH2,-CH3),1459(-CH3),1323(-CH2-),1621-1594(structure of carbozle).1H-NMR(CDCl3,400Hz):δH8.09(d,J=7.60Hz,2H),7.38~7.48(m,4H),7.21(d,J=8.00Hz,2H),4.28(t,2H),1.86(m,2H),1.33(m,6H),0.86(t,3H)。
(2)称取2.51g(10mmol)己基咔唑置于圆底烧瓶中,冰水浴中边搅拌边加入30mL DMF,利用恒压漏斗逐滴加入15.2g(0.1mol)POCl3,滴毕,冰水浴中继续搅拌30分钟后,将烧瓶移至水浴升温70℃反应2小时,冷却至室温,继续搅拌约16小时,将得到的黑红色的粘稠液倒入大量的碎冰中,快速搅拌,得淡黄色粘稠液。逐滴加入K2CO3溶液调节pH值至中性,乙酸乙酯萃取,无水MgSO4干燥,静置过夜。第二天抽滤,旋干有机相。少量CH2Cl2溶解产物,并加入少量的中性Al2O3,经柱色谱(中性Al2O3;石油醚:乙酸乙酯=10:1)分离得淡黄色固体1.57g,产率约57%。FT-IR(KBr,cm-1):1692(-C=O),1375(-CH3),1472(-CH2),1621-1594(structure of carbozle).1H-NMR(CDCl3,400Hz):δH10.10(s,1H),8.61(s,1H),8.16(d,J=7.60Hz,1H),8.01(d,J=8.40Hz,1H),7.45~7.55(m,3H),7.32(t,1H),4.33(t,2H),1.85~1.93(m,2H),1.26~1.42(m,6H),0.86(t,3H).
(3)称取0.25g(1.2mmol)4-氨基安替比林和0.28g(1mmol)3-甲酰基-N-己基咔唑溶解在10mL乙醇中,室温回流4小时,乙醇重结晶得淡黄色固体0.45g,产率约98.77%。FT-IR(KBr,cm-1):3428(吡咯环的骨架),3057(=C-H),2954-2853(-CH2,-CH3),1662(-CH=N),1596(structure of carbozle),746(Ar-H),698(Ar-H单取代).1H-NMR(400MHz;CDCl3;Me4Si):δH9.93(s,1H),8.60(s,1H),8.15(d,J=7.60Hz,1H),8.05(s,1H),7.51~7.40(m,7H),7.32(t,1H),4.31(t,2H),3.15(s,3H),2.56(s,3H),1.92~1.84(m,2H),1.41~1.22(m,6H),0.87(t,3H).Elemental analysis:Anal.Calcd for C30H32N4O:C77.55,H6.94,N12.06,Found:C77.57,H6.95,N12.07。
实施例2:化合物(3)的紫外-可见吸收光谱测定
准确称量待测样品化合物(3)(4.7mg),溶解后转入10mL的容量瓶中,用乙腈溶剂定容,配成浓度为1.0×10-3mol/L的储备溶液。准确移取储备液进行 下一步稀释,定容配制成浓度为1.0×10-5mol/L的测试溶液。分别测定其紫外-可见光谱和荧光光谱。
取3mL浓度为1.0×10-5mol/L的待测样品于石英比色皿中(石英比色皿的厚度为1cm),然后分别加入30μL浓度为1.0×10-3mol/L的各种金属离子储备液,摇匀并放置一定的时间,测定其对探针吸收光谱及荧光光谱的影响。
在化合物(3)的乙腈溶液中各种不同的金属阳离子,测定其紫外吸收光谱的变化(如附如图1所示),在未加入金属阳离子之前,3有两个电子光谱吸收峰,分别位于286nm和293nm处的肩峰和346nm处的尖峰,而且化合物(3)的乙腈溶液为无色。当加入Cr3+后,化合物(3)溶液显黄色,346nm处的吸收明显减弱,并且发生23nm的蓝移;286nm和293nm处的肩峰的吸收明显增强,并且蓝移到274nm和287nm,蓝移后仍是一个肩峰。当加入Cu2+后,化合物(3)的乙腈溶液显淡黄色,346nm处的吸收明显减弱,并且发生23nm的蓝移,286nm和293nm处的肩峰的吸收明显增强,并且蓝移到280nm,蓝移后由原来的肩峰变为了尖峰。但是在相同的条件下,其他的金属阳离子如:Na+,K+,Ca2+,Ag+,Cd2+,Co2+,Fe2+,Fe3+,Hg2+,Mg2+,Mn2+,Ni2+,Zn2+均无明显影响。说明化合物3可以裸眼识别Cr3+/Cu2+离子,即化合物(3)为识别Cr3+/Cu2+离子的比色探针。
实施例3:化合物(3)的紫外-可见吸收光谱滴定实验及检测限的测定
Cr3+和Cu2+离子对探针化合物(3)的紫外吸收光谱滴定实验(如附图2所示),随着Cr3+离子的加入,化合物(3)的乙腈溶液逐渐由无色变为黄色,在286nm和293nm处的肩峰的吸光度逐渐增强,吸收峰逐渐蓝移,蓝移后仍是一个肩峰(274nm和287nm),而在346nm处的吸光度逐渐减弱,吸收峰逐渐蓝移,直到蓝移至322nm处;随着Cu2+离子的加入,化合物(3)的乙腈溶液逐渐由无色变为淡黄色,化合物(3)在286nm和293nm处的肩峰的吸光度逐渐增强,吸收峰逐渐蓝移,直至蓝移到280nm,蓝移后由原来的肩峰变成了尖峰,而在346nm处的吸收峰逐渐减弱并且逐渐蓝移,直到蓝移至325nm处。由此可以推断,探针化合物(3)在乙腈溶液中与Cr3+/Cu2+离子形成了稳定的配合物(3)-Cr3+和(3)-Cu2+,并且具有裸眼识别功能,可作为比色探针识别Cr3+/Cu2+离子。
实施例4:化合物(3)与Cr3+/Cu2+离子的结合常数及检测线测定
化合物(3)与Cr3+/Cu2+离子的结合常数Ka由Benesi-Hildebrand方程确定。
式中A0和A分别为加入Cr3+/Cu2+离子前后体系的吸光度。Amax为加入过量的Cr3+/Cu2+离子存在时化合物(3)的饱和吸光度。[M]为加入的金属离子(Cr3+/Cu2+)的浓度。如图3(a)所示,1/(A-A0)与1/[Cr3+]存在良好的线性关系,线性相关系数R2=0.97;如图3(b)所示,1/(A-A0)与1/[Cu2+]存在很好的线性关系,线性相关系数R2=0.997。由方程(4)计算可得探针化合物(3)与Cr3+离子的结合常数Ka为2.20×104M-1,探针化合物(3)与Cu2+离子的结合常数Ka为1.75×104M-1。
化合物(3)对Cr3+及Cu2+离子识别的灵敏性(如附图4所示),在2.0×10-6~1.0×10-5mol/L范围内,Cr3+离子浓度与吸光度呈较好的线性关系(R2=0.990)如图4(a),说明探针化合物(3)对Cr3+离子的识别具有较高的灵敏性;在1.0×10-6~1.2×10-5mol/L范围内,Cu2+离子浓度与吸光度也呈较好的线性关系(R2=0.992)如图4(b),同样也表明了探针化合物(3)对Cu2+离子的识别具有较高的灵敏性。以加入金属离子的对数值作为横坐标,(A-Amin)/(Amax-Amin)比值作为纵坐标作曲线图,并对纵坐标0.05-0.95之间的数据进行直线模拟,模拟得到的直线与X轴的交点的横坐标就是检测最低限,结果如图5所示。这样计算得到了化合物(3)与Cr3+和Cu2+离子的检测下限分别为logClim为-5.54M-1和-5.56M-1,即Clim分别为2.86×10-6M和2.75×10-6M。这表明化合物(3)对Cr3+/Cu2+离子的识别具有较低的检测下限,这也进一步验证了探针化合物(3)对Cr3+/Cu2+离子的识别具有较高的灵敏度。
实施例5:化合物(3)对Fe3+、Cr3+离子识别的选择性和抗干扰性
共存离子的影响对探针性能具有重要作用,因此我们研究了金属离子共存条件下探针化合物(3)对Cr3+/Cu2+离子识别(如附图6所示),当其他金属离子加入到探针化合物(3)的乙腈溶液中时,不会产生明显的吸收峰变化,但是再向该体系中加入Cr3+离子时,化合物(3)的乙腈溶液变为黄色,在346nm处的吸收明显减弱并伴随着明显的蓝移;286nm和293nm处肩峰的吸收明显增强,并蓝移到274nm和287nm;向该体系中加入Cu2+离子时,化合物(3)的乙腈溶液变为淡黄色,346nm处的吸收明显减弱,而且伴随着明显的蓝移,286nm和293 nm处肩峰的吸收明显增强,并且蓝移到280nm,蓝移后由原来的肩峰变为了尖峰。这些现象表明在共存离子存在的条件下,探针化合物(3)对Cr3+/Cu2+离子的识别具有较强的抗干扰能力。
Claims (7)
2.根据权利要求1所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物的制备方法,其特征在于包括以下步骤:
(1)己基咔唑中间体(1)的合成
将咔唑溶于无水DMF中,室温搅拌至完全溶解后分批加入NaH,油封,继续室温搅拌20min后用恒压漏斗滴加含溴己烷的DMF溶液,滴毕,80℃水浴回流3小时停止反应,冷却后倒入水中,用体积比为1:1的盐酸调节pH值至中性,静置,析出粗产品,抽滤,用乙醇重结晶即可得己基咔唑中间体;
(2)3-甲酰基-N-己基咔唑中间体(2)的合成
将上述制得的己基咔唑中间体加入无水DMF,将POCl3倒入恒压漏斗中,在冰水浴中边滴加边搅拌,滴毕,再搅拌半个小时,将烧瓶移至油浴升温至70℃反应2小时。然后,停止加热冷却至室温,继续搅拌16小时,将得到的黑红色粘稠液倒入大量碎冰中,快速搅拌,得淡黄色悬浮液,用NaOH溶液中和,乙酸乙酯萃取,无水MgSO4干燥,静置过夜,旋干有机相,真空干燥,加入中性Al2O3和少量CH2Cl2,混合旋干,经柱色谱分离即得淡黄色3-甲酰基-N-己基咔唑中间体;
(3)4-氨基安替比林缩3-甲酰基-N-己基咔唑席夫碱(3)的合成
将4-氨基安替比林和3-甲酰基-N-己基咔唑溶解在乙醇中,室温回流4小时,粗产物用乙醇重结晶即得淡黄色目标产物。
3.根据权利要求2所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物的制备方法,其特征在于,步骤(1)中所述咔唑和溴己烷的摩尔比为6:7。
4.根据权利要求2所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物的制备方法,其特征在于,步骤(2)中所述己基咔唑、DMF和POCl3的摩尔比为1:40:10。
5.根据权利要求2所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物的制备方法,其特征在于,步骤(3)中所述4-氨基安替比林和3-甲酰基-N-己基咔唑的摩尔比为6:5。
6.根据权利要求1所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物,其特征在于,所述化合物的乙腈溶液可以用于Cr3+和Cu2+的“裸眼”识别。
7.根据权利要求1所述的用于Cr3+、Cu2+检测与裸眼识别的含有咔唑-安替比林基席夫碱比色探针化合物,其特征在于,所述化合物的乙腈溶剂中可以通过紫外-可见光谱法实现对Cr3+和Cu2+离子检测。
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