CN108299476B - 氮杂环、羧酸锌配合物荧光探针制备方法及应用 - Google Patents
氮杂环、羧酸锌配合物荧光探针制备方法及应用 Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 39
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
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Abstract
本发明涉及发光金属配合物及荧光探针技术领域,具体涉及一种同时识别阴离子和阳离子的氮杂环、羧酸锌配合物荧光探针制备方法及应用。其化学通式为{[Zn2(btc)(atrz)(H2O)2]·2H2O}n,其中atrz为3‑氨基‑1,2,4‑三氮唑阴离子,btc为1,2,4‑苯三羧酸三价阴离子。本发明所提供的氮杂环、羧酸锌配合物为由过渡金属离子和羧酸、氮杂环共同构筑的金属荧光配合物,具有强的荧光发射行为,并能够选择性地识别特定的金属阳离子、阴离子而导致其荧光信号的猝灭。因此,该类配合物可作为金属阳离子、阴离子的探针化合物,在离子识别和检测领域中得到广泛应用。
Description
技术领域
本发明涉及发光金属配合物及荧光探针技术领域,具体涉及一种同时识别阴离子和阳离子的氮杂环、羧酸锌配合物荧光探针制备方法及应用。
背景技术
由于环境和生物体系中阴、阳离子及一些生物分子对人类的健康和发展起着相当重要的作用,因此,其检测方法一直是人们的研究热点,在目前众多的检测手段中,荧光分析方法是一种灵敏度高、选择性强、操作简单、物理参数直观多样的分析方法,近年来,在生命科学、环境科学、医药科学和核工业等方面发挥着重要作用。
作为一类重要的荧光探针材料,金属配合物一般具有良好的结晶性,较易通过X-射线单晶等技术对其结构组成及空间构型确定,有助于在结构与性质之间建立明确的关联性;而且,金属配合物一般由金属离子/金属簇与有机配体通过配位键形成,通过对所得到化合物的结构优化,可以有效地调控目标产物的结构,从而调控其性能;配合物荧光识别与传感还具有样品用量少、分析速度快、灵敏度高、选择性好、操作简单、可实时检测等特点。然而,目前报道的识别阴离子的荧光探针还比较少,特别是既能识别金属阳离子又能识别阴离子的探针配合物更少报道。
发明内容
本发明针对上述的缺少既能识别金属阳离子又能识别阴离子的探针配合物的技术问题,提出一种制备方法简单、效果显著且可以识别特定金属阳离子、阴离子的氮杂环、羧酸锌配合物荧光探针制备方法及应用。
为了达到上述目的,本发明采用的技术方案为,本发明提供一种氮杂环、羧酸锌配合物,其化学通式为{[Zn2(btc)(atrz)(H2O)2]·2H2O}n,其中atrz为3-氨基-1,2,4-三氮唑阴离子,btc为1,2,4-苯三羧酸三价阴离子。
本发明还提供了制备上述氮杂环、羧酸锌配合物的制备方法,包括以下有效步骤:
a、首先在氮气保护下将0.3mol 3-氨基1,2,4-三氮唑、0.01mol 4-二甲氨基吡啶和350mLN,N-二甲基乙酰胺混合,搅拌下升温至80℃得到黄色溶液,恒温反应半小时后降温至10℃,缓慢加入0.3mol氯化偏苯三酸酐,然后慢慢升温至40℃反应8小时,冷却后倒入大量的水中,静置,抽滤,用大量热水洗涤,干燥产品,即得到氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸;
b、然后将氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸、水合醋酸锌和氢氧化钠置于内衬有聚四氟乙烯的不锈钢反应釜中,在160℃下水热反应,反应三天后程序降到室温得到针状晶体,然后洗涤,干燥,即得到氮杂环、羧酸锌配合物。
作为优选,所述b步骤中,氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸、水合醋酸锌和氢氧化钠的摩尔比为1:2:2。
作为优选,所述b步骤中,降至室温的速度为2℃/小时~5℃/小时。
本发明所提供的氮杂环、羧酸锌配合物作为荧光探针在重铬酸根离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
本发明所提供的氮杂环、羧酸锌配合物作为荧光探针在铜离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
本发明所提供的氮杂环、羧酸锌配合物作为荧光探针在铁离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
与现有技术相比,本发明的优点和积极效果在于,
1、本发明所提供的氮杂环、羧酸锌配合物为由过渡金属离子和羧酸、氮杂环共同构筑的金属荧光配合物,具有强的荧光发射行为,并能够选择性地识别特定的金属阳离子、阴离子而导致其荧光信号的猝灭。因此,该类配合物可作为金属阳离子、阴离子的探针化合物,在离子识别和检测领域中得到广泛应用。
2、本发明所提供的氮杂环、羧酸锌配合物制备方法简单、原料易得,适合大规模推广使用。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为氮杂环、羧酸锌配合物{[Zn2(btc)(atrz)(H2O)2]·2H2O}n的晶体结构图;
图2为氮杂环、羧酸锌配合物{[Zn2(btc)(atrz)(H2O)2]·2H2O}n的阳离子识别光谱图;
图3为氮杂环、羧酸锌配合物{[Zn2(btc)(atrz)(H2O)2]·2H2O}n的阴离子识别光谱图。
具体实施方式
为了能够更清楚地理解本发明的上述目的、特征和优点,下面结合附图和实施例对本发明做进一步说明。需要说明的是,在不冲突的情况下,本申请的实施例及实施例中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是,本发明还可以采用不同于在此描述的其他方式来实施,因此,本发明并不限于下面公开说明书的具体实施例的限制。
实施例1,本实施例提供一种氮杂环、羧酸锌配合物
首先,在氮气保护下,将0.3mol 3-氨基1,2,4-三氮唑、0.01mol 4-二甲氨基吡啶和350mLN,N-二甲基乙酰胺混合,搅拌下升温至80℃得到黄色溶液,恒温反应半小时后降温至10℃,缓慢加入0.3mol氯化偏苯三酸酐。
然后慢慢升温至40℃反应8小时,冷却后倒入大量的水中,静置,抽滤,用大量热水洗涤,干燥产品后得到氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸(英文为4-((4H-1,2,4-triazol-3-yl)carbamoyl)phthalic acid)。
接着将0.25mmol氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸、0.5mmol水合醋酸锌和0.5mmol氢氧化钠置于聚四氟乙烯高压反应釜中内胆中,加入15mL蒸馏水混匀后放入不锈钢反应釜并拧紧,在烘箱中密封升温,以约5℃/min的速度持续升温至160℃,保持160℃反应3天,之后以2℃/h~5℃/h的速度缓慢降至室温。过滤、干燥后得到氮杂环、羧酸锌配合物,产率为27.3%(基于锌)。
然后将所得的化合物进行单晶表征。该化合物的X射线衍射数据是在BrukerSMART CCD面探衍射仪上,Mo-Kα射线,以ω-θ变速扫描方式,收集并进行Lp因子校正,吸收校正使用SADABS程序。用直接法解结构,然后用差值傅立叶法求出全部非氢原子坐标,并用理论加氢法得到氢原子,用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。
经测试解析可知,该化合物的化学分子为:{[Zn2(btc)(atrz)(H2O)2]·2H2O}n,其中atrz为3-氨基-1,2,4-三氮唑阴离子,btc为1,2,4-苯三羧酸三价阴离子。配合物属于三斜晶系,P-1空间群,晶胞参数为 α=106.0640(10)°,β=92.3290(10)°,γ=103.8140(10)°,晶胞体积为Z=2。晶体结构见图1。
氮杂环、羧酸锌配合物的分子式为:
{[Zn2(btc)(atrz)(H2O)2]·2H2O}n,不对称单元中包含两个晶体学独立的锌原子,一个脱质子的atrz配体(atrz=3-氨基-1,2,4-三氮唑)、一个全部脱质子的偏苯三甲酸离子、两个配位水和两个结晶水。Zn1(Ⅱ)离子分别与来自atrz-配体上的N3原子、来自两个不同的全部脱质子的偏苯三甲酸离子上的O原子(O2、O3A)和来自两个配位水上的O原子(O7,O8)配位形成畸变的三角双锥构型。Zn2(Ⅱ)离子分别与来自atrz-配体的两个N原子(N1A、N2A)、来自两个不同的偏苯三甲酸配体的两个O原子(O1、O6A)配位形成一个略变形的四面体结构。所有脱羧的atz-配体采用N1,N2,N4-桥联配位模式;全部脱质子的偏苯三甲酸离子上的三个羧基均参与配位。
应用检测:
分别称取0.0128g(0.0001mol)氮杂环、羧酸锌配合物,以DMF(N,N-二甲基甲酰胺)为溶剂,配制c=0.01mol/L的氮杂环、羧酸锌配合物悬浊液。同样的,以DMF溶液为溶剂,配制c=0.01mol/L的氯化盐溶液,其中阳离子为Pb2+、Sr2+、Al3+、Na+、Ba2+、Zn2+、Fe3+、Cu2+。分别取3mL 0.01mol/L的氮杂环、羧酸锌配合物悬浊液与等体积的不同金属离子溶液混合,将它们分别置于超声仪中超声震荡15分钟使之成为混合均匀的悬浊液。以波长为363nm的光源作为激发峰,狭缝宽度为(5,10),分别测定其荧光发射光谱,图2是在10-2mol/L的配合物中加入不同金属离子的荧光强度的柱状图(363nm激发,DMF溶剂)。
从图2中可以清楚的看到加入Mn2+、Co2+、Pb2+、Ba2+、Sr2+、Na+、K+、Ca2+、Al3+、Zn2+、Ni2 +、Cd2+,主体配合物的荧光发射强度都有一定程度的减弱但是变化不明显,但当加入Fe3+、Cu2+时,主体配合物的荧光强度明显降低,当加入Cu2+时,主体配合物的荧光强度降为6.619a.u.,荧光强度几乎有95%的被猝灭,当加入Fe3+时,荧光强度几乎完全猝灭,说明主体配合物对Cu2+、Fe3+能有效识别。从5×10-5mol/L到1×10-2mol/L范围内改变金属离子浓度,随着Cu2+浓度的增强,锌配合物的荧光强度不断降低,说明主体配合物对Cu2+不仅能够定性识别而且能够定量识别。而Fe3+浓度无论如何变化,荧光强度都是几乎完全猝灭状态。
以同样的方法配制c=0.01mol/L的钾盐溶液,其中阴离子为F-、I-、C2O4 2-、NO3-、HSO4-、SO4 2-、SCN-、P2O7 4-、HPO4 2-、PO4 3-、OH-、CO3 2-、Cr2O7 2-;
与上述条件相同,把金属阳离子改为F-、I-、C2O4 2-、NO3-、HSO4-、SO4 2-、SCN-、P2O7 4-、HPO4 2-、PO4 3-、OH-、CO3 2-、Cr2O7 2-,分别测定了3mL 0.01mol/L氮杂环、羧酸锌配合物和3mL0.01mol/L氮杂环、羧酸锌配合物加入不同阴离子离子混合液的荧光发射光谱(如图3所示)。F-、I-、Cl-、C2O4 2-、NO3-、HSO4-、SO4 2-、SCN-、P2O7 4-、HPO4 2-、PO4 3-、OH-、CO3 2-、CrO4 2-、P2O7 4-的加入对主体配合物的荧光发射强度都有一定程度的变化但是变化不明显,但当加入Cr2O7 2-时,明显使主体配合物的荧光强度降低,主体配合物的荧光强度大大降低,说明氮杂环、羧酸锌配合物对Cr2O7 2-具有较好的识别性。
另外,需要说明的是,目前,由于试验条件有限,本发明所提供的氮杂环、羧酸锌配合物荧光探针的适用对象应包括但不仅限于对Cr2O7 2-、Cu2+、Fe3+的识别。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例应用于其它领域,但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (6)
1.一种氮杂环、羧酸锌配合物的制备方法,其特征在于,其化学通式为{[Zn2(btc)(atrz)(H2O)2]·2H2O}n,其中,atrz为3-氨基-1,2,4-三氮唑阴离子,btc为1,2,4-苯三羧酸三价阴离子,所述氮杂环、羧酸锌配合物属于三斜晶系,P-1空间群,晶胞参数为α=106.0640(10)°,β=92.3290(10)°,γ=103.8140(10)°,晶胞体积为Z=2,包括以下有效步骤:
a、首先在氮气保护下将0.3mol 3-氨基1,2,4-三氮唑、0.01mol 4-二甲氨基吡啶和350mLN,N-二甲基乙酰胺混合,搅拌下升温至80℃得到黄色溶液,恒温反应半小时后降温至10℃,缓慢加入0.3mol氯化偏苯三酸酐,然后慢慢升温至40℃反应8小时,冷却后倒入大量的水中,静置,抽滤,用大量热水洗涤,干燥产品,即得到氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸;
b、然后将氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸、水合醋酸锌和氢氧化钠置于内衬有聚四氟乙烯的不锈钢反应釜中,在160℃下水热反应,反应三天后程序降到室温得到无色针状晶体,然后洗涤,干燥,即得到氮杂环、羧酸锌配合物。
2.根据权利要求1所述的氮杂环、羧酸锌配合物的制备方法,其特征在于,所述b步骤中,氮杂环有机配体4-((1,2,4-三氮唑-3-氨基甲酰基)异酞酸、水合醋酸锌和氢氧化钠的摩尔比为1:2:2。
3.根据权利要求2所述的氮杂环、羧酸锌配合物的制备方法,其特征在于,所述b步骤中,降至室温的速度为2℃/小时~5℃/小时。
4.如权利要求1或2或3所述方法制备的氮杂环、羧酸锌配合物作为荧光探针在重铬酸根离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
5.如权利要求1或2或3所述方法制备的氮杂环、羧酸锌配合物作为荧光探针在铜离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
6.如权利要求1或2或3所述方法制备的氮杂环、羧酸锌配合物作为荧光探针在铁离子的检测中应用,其中所述检测不包含疾病的诊断和治疗为目的的检测。
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