CN116496497B - 一种共价有机框架材料、配体和在Fe3+检测中的应用 - Google Patents
一种共价有机框架材料、配体和在Fe3+检测中的应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 20
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Abstract
一种共价有机框架材料、配体和在Fe3+检测中的应用。本发明属于荧光传感领域。本发明的共价有机框架材料COF‑ET4即使在干扰离子M(Cu2+,Al3+,Co2+,Ni2+,Ag+,Cd2+,Sr2+,Ca2+,K+,Na+,Ba2+,Zn2+,Mn2+,Pb2+,Cr3+)存在的情况下,Fe3+依然对共价有机框架材料COF‑ET4产生明显的荧光淬灭现象,使得其在Fe3+检测中展现出了优异的性能和良好的应用前景。
Description
技术领域
本发明属于荧光传感领域,具体涉及一种共价有机框架材料、配体和在Fe3+检测中的应用。
背景技术
近年来,随着经济的高速发展,环境污染问题越来越严重,其中重金属是环境污染的重要来源之一。重金属不但会在植物体内诱导其体内产生某些对酶和代谢具有毒害作用或不利影响的物质,间接引起植物伤害;还可通过空气、水、食物等渠道进入人体。进入人体的重金属不再以离子形式存在,而是与体内的有机成分结合成金属络合物或金属螯合物,从而对人体产生危害。且重金属污染具有长期性、积累性、潜伏性、不可逆性以及治理成本较高等问题,因此迫切需要开发一种切实有效的方法来检测重金属离子。
传统的检测方法包括电化学方法,电感耦合等离子体质谱,原子吸收光谱,离子色谱等,然而,昂贵的仪器和复杂的样品预处理阻碍了检测的实时性和快速性。近年来,荧光检测因其具有便携性、操作简单性、实时性以及检测限低和特异性强等优点,在重金属检测领域受到了广泛关注。寻找一种成本低廉且易于操作的荧光传感材料成为了新的研究课题。
共价有机框架材料(Covalent Organic Farmeworks, COFs)是一种新型的多孔有机纳米材料,具有高比表面积、结构可调性强及成本低廉等诸多优势。与传统的荧光材料比,共价有机框架材料具有较大的π-π共轭结构,使得其具有较强的荧光,且明确和规则的孔道使得共价有机框架材料具备良好的空间选择性,这赋予了共价有机框架材料作为荧光传感材料优异的应用前景,而不同的共价有机框架材料对不同物质的识别具有选择性,因而,本发明的目的是寻找一种对Fe3+具有高选择性的共价有机框架材料及荧光传感器。
发明内容
为了克服现有技术的不足,本发明提供了一种共价有机框架材料、配体和在Fe3+检测中的应用。
本发明的目的是通过如下技术方案来完成的:
本发明的目的之一在于提供一种共价有机框架材料,所述共价有机框架材料具有如下结构单元:
,
命名为COF-ET4。
本发明的目的之二在于提供一种制备上述共价有机框架材料的配体,所述配体具有以下结构:
。
本发明的目的之三在于提供一种荧光传感器,所述荧光传感器以上述共价有机框架材料作为荧光传感材料。
本发明的目的之四在于提供一种上述荧光传感器在选择性识别Fe3+中的应用。
本发明与现有技术相比具有的显著效果:
本发明的共价有机框架材料COF-ET4即使在干扰离子M(Cu2+, Al3+, Co2+, Ni2+,Ag+, Cd2+, Sr2+, Ca2+, K+, Na+, Ba2+, Zn2+, Mn2+, Pb2+, Cr3+)存在的情况下,Fe3+依然对共价有机框架材料COF-ET4产生明显的荧光淬灭现象,使得其在Fe3+检测中展现出了优异的性能和良好的应用前景。
附图说明
图1为本发明的共价有机框架材料COF-ET4的制备路线图;
图2为本发明实施例中中间体的核磁氢谱图;
图3为本发明实施例中中间体的核磁碳谱图;
图4为本发明实施例中中间体的质谱图;
图5为本发明实施例中配体的核磁氢谱图;
图6为本发明实施例中配体的核磁碳谱图;
图7为本发明实施例中配体的质谱图;
图8为本发明实施例中共价有机框架材料COF-ET4的质谱图;
图9为本发明实施例制得的共价有机框架材料COF-ET4的红外表征;
图10为本发明实施例制得的共价有机框架材料COF-ET4检测不同金属离子的荧光强度图;
图11为本发明实施例制得的共价有机框架材料COF-ET4在检测中对金属离子M抗干扰荧光强度对比图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器,未经特殊说明,均为本领域常规材料、试剂、方法和仪器,本领域技术人员均可通过商业渠道获得。
下述实施例中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形,意在覆盖非排它性的包括。例如,包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素,而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
本发明所述“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
下述实施例中所用5-氨基-2-溴苯甲酸(CAS:2840-02-0)、4-氰基-3-甲氧基苯基硼酸(CAS:677777-45-6)、1,4,5,8-萘四甲酸酐(CAS:81-30-1)均从上海皓鸿生物医药科技有限公司直接采购获得。元素分析使用德国ElementarUNICUBE元素分析仪得出结果。
实施例:
共价有机框架材料COF-ET4的合成路线如说明书附图1所示,具体的制备方法按以下步骤进行:
第一步、中间体的合成:
向50毫升三口瓶中依次加入4-氰基-3-甲氧基苯基硼酸(3克,18.63毫摩尔)、3.5毫升蒸馏水、3.5毫升聚乙二醇400、5-氨基-2-溴苯甲酸(4.39克,22.35毫摩尔)、二氯化钯(12毫克,0.09毫摩尔)、碳酸钾(0.82克,6.59毫摩尔),随后氮气置换三次,在25℃下搅拌8小时。反应结束后,混合物用乙醚萃取三次,每次25毫升,萃取后合并有机相。有机相用硫酸镁干燥,旋转蒸发溶剂得到粗品。用体积比为1:10的石油醚/乙酸乙酯混合溶液作为洗脱剂进行硅胶柱层析,得到白色固体1.86克,即为中间体,收率为41%。
核磁表征结果:
如图2所示,氢谱:1H NMR (400 MHz, CDCl3)δ7.80 (d, 1 H), 7.67 (d, 1 H),7.52 (d, 1 H), 7.33 (d, 1 H), 7.22 (d, 1 H), 6.97 (d, 1 H), 3.85 (s, 3 H),3.67 (s, 2 H).
如图3所示,碳谱:13C NMR (100 MHz, CDCl3):δ169.35, 157.59, 151.58,141.81, 133.40, 132.42, 129.55, 128.60, 124.33, 117.06, 116.65, 116.61,111.49, 100.78, 56.36.
如图4所示,质谱表征结果:ESI(m/z):[M+H]+calcd. for C15H12N2O3,268.08;found, 268.96.
元素分析测试结果:Calcd. for C15H12N2O3C, 67.16; H, 4.51; N, 10.44; O,17.89. Found: C, 67.21; H, 4.52; N, 10.46; O, 17.78.
根据以上分析数据可知,获得的中间体结构为:
第二步、配体的合成:
在100毫升三口瓶中加入上述中间体(0.5克,8.58毫摩尔),20毫升二氯甲烷,将反应体系降温至0℃后,在此温度下滴加2.3毫升三氟甲磺酸,得到的混合物在氮气保护下100℃反应12小时。反应结束后,向反应体系中加入30毫升蒸馏水,然后用2摩尔每升的氢氧化钠水溶液将体系的pH值调至7。过滤,滤饼用蒸馏水冲洗,干燥,即为配体。
核磁表征结果:
如图5所示,氢谱:1H NMR (400 MHz, DMSO)δ8.07 (d, 3 H), 7.91 (d, 3 H),7.57 (d, 3 H), 7.43 (d, 3 H), 7.26 (m, 3 H), 6.92 (m, 3 H), 5.53 (s, 6 H),3.83 (s, 9 H).
如图6所示,碳谱:13C NMR (100 MHz, DMSO)δ169.35, 169.32, 160.14, 151.58,140.37, 132.42, 129.55, 129.39, 128.60, 122.74, 120.47, 117.06, 116.61,111.89, 56.27.
如图7所示,质谱表征结果:ESI(m/z):[M+H]+calcd. for C45H36N6O9,804.25;found, 805.21.
元素分析测试结果:Calcd. for C45H36N6O9C, 67.16; H, 4.51; N, 10.44; O,17.89. Found: C, 67.25; H, 4.47; N, 10.43; O, 17.83.
根据以上分析数据可知,获得的配体结构为:
。
第三步、共价有机框架材料COF-ET4的制备:
将上述配体(2克,10毫摩尔)、1,4,5,8-萘四甲酸酐(0.67克,10毫摩尔)放到玛瑙研钵中研磨30分钟,随后将得到的混合物转移到氧化铝坩埚中,以5℃每分钟的加热速率进行加热,加热到345℃,在此温度下煅烧4小时,得到固体7.96克,即为COF-ET4。
元素分析测试结果:Calcd. for C372H258N30O78C, 69.85; H, 4.07; N, 6.57; O,19.51. Found: C, 69.63; H, 4.24; N, 6.68; O, 19.43.
如图8所示,质谱表征结果:TOF-MS(m/z):[M+H]+Calcd. for C372H258N30O78,6395.73;found, 6396.67.
根据以上分析数据可知,获得的共价有机框架材料COF-ET4结构为:
。
对本发明实施例得到的共价有机框架材料COF-ET4进行红外表征:
测试仪器为IRAffinity-1傅里叶变换红外光谱仪,KBr压片,测试结果如说明书附图9所示。
由说明书附图9可知,在共价有机框架材料COF-ET4中,配体上原有的N-H(3340cm-1)伸缩振动消失、1,4,5,8-萘四甲酸酐原有的C-O(1791 cm-1)伸缩振动消失,出现了新的键连C-N-C(1233 cm-1),证明了分子COF-ET4的构建成功。
对共价有机框架材料COF-ET4的荧光性能进行下述测试,测试仪器为F-7000 荧光光谱仪。
测试一:
(1)将5毫克的共价有机框架材料COF-ET4分散在200毫升无水乙醇中,超声10分钟,即为COF-ET4悬浮液。
(2)分别配置80 μM/L的Fe3+, Cu2+, Al3+, Co2+, Ni2+, Ag+, Cd2+, Sr2+, Ca2+, K+, Na+, Ba2+, Zn2+, Mn2+, Pb2+, Cr3+的水溶液,分别得到各金属离子的悬浮液。
(3)分别将上述各金属离子的悬浮液与COF-ET4悬浮液按照1:9的体积比进行混合,超声10分钟使其分散均匀,在室温下进行荧光选择性测试。
测试结果如说明书附图10所示,由图10可知,Al3+可以小幅度增强体系的荧光,Fe3 +使体系有明显的荧光淬灭现象,而加入其他金属离子后荧光强度则没有明显变化,说明共价有机框架材料COF-ET4可以作为一种良好的荧光传感器选择性检测Fe3+。
测试二:
由于在实际的检测中不会只存在固定的待检测离子,而是伴随着许多干扰离子存在,因此为了研究其他金属离子的存在是否会影响COF-ET4对于Fe3+的荧光响应,进行了抗干扰实验。
(1)将5毫克的共价有机框架材料COF-ET4分散在200毫升无水乙醇中,超声10分钟,得到COF-ET4悬浮液,即为COF-ET4体系。
(2)分别配置Cu2+, Al3+, Co2+, Ni2+, Ag+, Cd2+, Sr2+, Ca2+, K+, Na+, Ba2+, Zn2 +, Mn2+, Pb2+, Cr3+浓度为80 μM/L的水溶液,得到干扰离子M的悬浮液,然后将其与步骤(1)得到的COF-ET4悬浮液按1:9的体积比进行混合,超声十分钟使其分散均匀,得到COF-ET4+M体系。
(3)配置Fe3+浓度为20 μM/L的水溶液,得到Fe3+的悬浮液,将其与步骤(2)中的干扰离子M的悬浮液以及步骤(1)中的COF-ET4悬浮液按照1:1:9的体积比进行混合,超声十分钟使其分散均匀,得到COF-ET4+M+Fe3+体系。
(4)将上述三种体系在室温下分别进行荧光选择性测试。
实验结果如说明书附图11所示,在COF-ET4悬浮液中,干扰离子M(Cu2+, Al3+, Co2 +, Ni2+, Ag+, Cd2+, Sr2+, Ca2+, K+, Na+, Ba2+, Zn2+, Mn2+, Pb2+, Cr3+)存在的情况下,荧光强度没有明显变化,只要上述系统中存在Fe3+,淬灭作用就会显著增强,这表明,干扰离子的存在不会使COF-ET4对于Fe3+的荧光淬灭效应带来影响。
以上所述,仅为本发明较佳的具体实施方式,这些具体实施方式都是基于本发明整体构思下的不同实现方式,而且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,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (1)
1.一种荧光传感器的应用,其特征在于,它用于选择性识别Fe3+,所述荧光传感器以共价有机框架材料作为荧光传感材料,所述共价有机框架材料结构单元:
,
命名为COF-ET4,其中,用于制备共价有机框架材料的配体具有以下结构:
。
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