CN113461958B - 两种三齿羧酸配体的In基金属有机骨架材料合制备方法及应用 - Google Patents
两种三齿羧酸配体的In基金属有机骨架材料合制备方法及应用 Download PDFInfo
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Abstract
两种三齿羧酸配体的In基金属有机骨架材料合制备方法及应用,属于晶态多孔材料制备的技术领域。这两种MOF材料分别由有机配体1,3,5‑三(4‑羧基苯基乙炔基)苯(BTETA)和2,4,6‑三甲基‑1,3,5‑三(4‑羧基苯基乙炔基)苯(TTETA)与硝酸铟在溶剂热条件下合成。两种MOF材料互为同构,都具有较高的孔隙率以及笼状结构,各个笼之间通过孔道连接,有助于被检测物分子与MOF骨架之间的相互作用。这两种MOF材料均对三种硝基呋喃类污染物(NZF、NFT、FZD)存在较好的荧光淬灭作用,对于此类污染物的检测具有应用前景。
Description
技术领域
本发明属于晶态材料的技术领域,技术涉及两种新型金属有机配位聚合物材料(Metal organic frameworks,MOF)的制备方法及其应用,特征是两种In的金属有机骨架材料制备方法及其在荧光检测抗生素领域的研究。
背景技术
抗生素类药物的滥用是造成环境污染的重要因素之一。环境中残留的抗生素易随食物链被人体富集,使得耐药性菌类大量繁殖导致人体菌群失调。长期以来会导致腹泻、营养不良,甚至耐药细菌感染,为后续治疗带来困难。硝基呋喃类药物是一类光谱抗生素,主要包括呋喃唑酮(FZD)、呋喃妥因(NFT)和呋喃西林(NZF)三种。其主要用于畜牧业以及水产养殖业,治疗大肠杆菌或沙门氏菌所引起的一系列疾病。其对于人体具有致癌性、致畸性,严重危害人类健康。目前,对于抗生素类药物的检测主要依赖于高效液相色谱(HPLC)、气相色谱-质谱(GC-MS)联用、毛细管电泳(CE)、生物检测等技术。然而,这些方法面临着检测成本较高、样品预处理较为复杂、耗时较长、操作难度大等不足之处。因此,对于开发操作简便、高效灵敏、选择性高的抗生素类检测方法对于环境保护以及人体健康具有重要意义。基于传感器-分析物相互作用引起荧光变化的检测方法具有简单、高效、便捷等优点。该方法面临的主要的问题在于荧光材料的选择。金属-有机骨架材料(Metal-OrganicFrameworks,MOFs)是一种由金属离子或金属簇与有机配体通过配位键相连的晶态多孔材料。其具有比表面积大、孔隙率高、孔道可调等优势,在传感/检测领域具有潜在应用价值。荧光MOFs(LMOFs)是一类具有荧光性能的MOF,其多孔性有利于被分析物的预富集作用进而提升荧光检测的灵敏度,因此荧光MOFs在荧光检测方面具有应用前景。本发明采用两种具有较强荧光性能的三齿羧酸配体1,3,5-三(4-羧基苯基乙炔基)苯(BTETA)、2,4,6-三甲基-1,3,5-三(4-羧基苯基乙炔基)苯(TTETA)与硝酸铟在水热条件下自组装形成了两种同构的微孔笼状MOF材料。这两种MOF具有较强的共轭体系结构,其中TTETA-In在362nm激发波长激发下,可在发射出450nm波长的荧光;BTETA-In在294nm激发波长激发下,可发射出373nm波长的荧光,为荧光检测奠定了基础。此外,两种MOF具有较高的孔隙率以及笼状结构,有利于被检测物的预富集作用。该材料的荧光可较好地被呋喃唑酮(FZD)、呋喃妥因(NFT)和呋喃西林(NZF)三种硝基呋喃类抗生素淬灭,从而实现高效检测。
发明内容
本发明的目的在于提供了两种In-MOF材料的制备方法,两种MOF均可用于呋喃唑酮(FZD)、呋喃妥因(NFT)和呋喃西林(NZF)三种硝基呋喃类抗生素的检测。
两种三齿羧酸配体的In基金属有机骨架材料,其中一种三齿羧酸配体的In基金属有机骨架材料的分子式为[In5(TTETA)11/3(OH)4(H2O)],TTETA为2,4,6-三甲基-1,3,5-三(4-羧基苯基乙炔基)苯;另一种三齿羧酸配体的In基金属有机骨架材料的分子式[In5(BTETA)11/3(OH)4(H2O)],BTETA为1,3,5-三(4-羧基苯基乙炔基)苯。三齿有机配体TTETA较BTETA区别在于中心苯环的2,4,6位分别以甲基取代了氢原子。
分子式为[In5(TTETA)11/3(OH)4(H2O)]的材料,从晶体结构角度分析,TTETA-In属于六方晶系,空间群为R3c,晶胞参数为 α=90°,β=90°,γ=120°。其化学式为In5C132O27H77(TTETA-In)
分子式为[In5(BTETA)11/3(OH)4(H2O)]的材料即BTETA-In,属于六方晶系,空间群为R3c,晶胞参数为 α=90°,β=90°,γ=120°。其化学式为In5C121O27 H55(BTETA-In)。
上述两种In-MOF配位模式相同,互为同构;两种In-MOF中,金属簇为由“In-O”相连的链状次级构筑单元(SBU)结构,每两个铟离子由一个桥联氧相连;每个铟离子分别与四个来自不同配体羧酸的氧原子,以及两个连接相邻铟离子的桥连氧(OH/H2O)进行配位,构成六配位模式。
本发明上述两种In-MOF的合成方法,其特征在于,其中TTETA-In合成方法如下:
(1)将有机配体TTETA和In(NO3)3溶解于N,N-二甲基甲酰胺(DMF)、硝酸和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热,获得块状单晶,先后用DMF和丙酮洗涤;
上述TTETA-In技术方案的TTETA和In(NO3)3的摩尔比为2:1~6:1;混合溶剂中DMF、水和浓硝酸的体积比例为250:10:1;溶剂热反应温度为110℃~130℃,反应时间为8h~14h。
上述得到的TTETA-In材料经过DMF洗涤以及丙酮溶剂交换并真空脱出溶剂分子以后得到用于选择性荧光检测三种硝基呋喃类抗生素(FZD、NZF、NFT)的材料。
BTETA-In合成方法如下:
(1)将有机配体BTETA与In(NO3)3溶解于N,N-二甲基甲酰胺(DMF)和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热反应,获得块状单晶,先后用DMF和丙酮洗涤。
上述BTETA-In技术方案的BTETA和In(NO3)3的摩尔比为1:1~1:1.5;混合溶剂中DMF与水的体积比为20:1;溶剂热反应温度为110℃~130℃,反应时间为8h~14h。
上述得到的BTETA-In材料经过DMF洗涤以及甲醇或二氯甲烷溶剂交换并真空脱出溶剂分子以后得到用于选择性荧光检测三种硝基呋喃类抗生素(FZD、NZF、NFT)的材料。
本发明基于两种具有较强共轭体系的三齿羧酸配体1,3,5-三(4-羧基苯基乙炔基)苯(BTETA)和2,4,6-三甲基-1,3,5-三(4-羧基苯基乙炔基)苯(TTETA),分别与金属铟源制备了两种新型铟基微孔同构MOF材料,热重分析实验表明这两种配位聚合物的配位框架具有较好热稳定性。荧光淬灭实验证明,在几类常见抗生素里,两种In-MOF对三种硝基呋喃类抗生素NZF、NFT和FZD具有较高的淬灭效率。
附图说明
图1为本发明中两种金属-有机骨架的次级构筑单元图。
图2为两种金属-有机骨架的三维结构示意图。
图3为两种金属-有机骨架的热分析图。
图4为两种金属-有机骨架新鲜合成样品及水处理后样品的粉末衍射图。
图5为两种金属-有机骨架材料对不同抗生素的淬灭百分比柱状图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实例1:(BTETA-In)
第一步:称取15.3mgBTETA有机配体,12mg硝酸铟,溶解于2mLN,N-二甲基甲酰胺(DMF)、0.1mL去离子水之后装入5mL玻璃小瓶中,然后将玻璃小瓶以塑料瓶盖密封并超声20分钟。最后将玻璃小瓶转移至120℃烘箱下反应14h,得到BTETA-In晶体样品。
第二步:选择一颗大小合适,结晶度高的单晶样品,在298K条件下利用单晶衍射仪收集衍射数据,然后利用结构解析软件Olex2精修得到晶体结构,具体笼状结构特征见说明书附图。
第三步:为了去除材料孔道内的溶剂分子,上述得到的晶态样品经过DMF溶剂洗涤之后浸泡于丙酮溶剂中,溶剂交换持续8-10次。将交换完的晶态样品转移至新鲜的丙酮溶剂中,用磁子搅拌的方式搅拌8h来减小材料的粒径,以提高制备材料在水中悬浊液的分散性。
第四步:在进行荧光滴定实验之前,将第三步中材料粉末的丙酮悬浊液在5000rpm转速下离心10min,倒掉上清液,在60℃下脱气1h得到材料粉末干样。取5mg该粉末分散于40ml去离子水中,以此悬浊液进行荧光滴定实验。
实例2:(TTETA-In)
第一步:称取5.5mgTTETA有机配体,3mg硝酸铟,溶解于2.5mLN,N-二甲基甲酰胺(DMF)、0.1mL去离子水之中后装入5mL玻璃小瓶中,加入10μL浓硝酸后以塑料瓶盖密封并超声20分钟。最后将玻璃小瓶转移至120℃烘箱下反应6h,得到TTETA-In晶体样品。
第二步:选择一颗大小合适,结晶度高的单晶样品,在298K条件下利用单晶衍射仪收集衍射数据,然后利用结构解析软件Olex2精修得到晶体结构,具体笼状结构特征见说明书附图。
第三步:为了去除材料孔道内的溶剂分子,上述得到的晶态样品经过DMF溶剂洗涤之后浸泡于丙酮溶剂中,溶剂交换持续8-10次。将交换完的晶态样品转移至新鲜的丙酮溶剂中,用磁子搅拌的方式搅拌8h来减小材料的粒径,以提高制备材料在水中悬浊液的分散性。
第四步:在进行荧光滴定实验之前,将第三步中材料粉末的丙酮悬浊液在5000rpm转速下离心10min,倒掉上清液,在60℃下脱气1h得到材料粉末干样。取5mg该粉末分散于40ml去离子水中,以此悬浊液进行荧光滴定实验。
其中有机配体BTETA/TTETA合成步骤参考以下文献:(Yao,Q.;Bermejo Gómez,A.;Su,J,et al.Chemistry of Materials 2015,27(15),5332-5339;Yang,J.;Wang,X.;Wang,R,et al.Crystal Growth&Design 2014,14(12),6521-6527.)
TTETA-In晶体数据如下:
BTETA-In晶体数据如下:
图1两种金属-有机骨架的次级构筑单元图表明:该配合物骨架由较稳定的链状SBU(In-O-In)构成。
图3中两种活化后金属-有机骨架的热分析图证明TTETA-In和BTETA-In具有较高的热稳定性,在400℃之前,未见MOF骨架结构的明显坍塌。(100℃之前的质量损失推测为孔道中丙酮分子的移除。)
图4中两种金属-有机骨架材料粉末衍射图表明:两种MOF结构相同,且在水处理后仍保持较好结晶度,结构未坍塌。
图5中两种金属-有机骨架材料对不同抗生素(呋喃西林(NZF)、呋喃妥因(NFT)、呋喃唑酮(FZD)、二甲胺四环素(MIN)、磺胺二甲嘧啶(SMZ)、磺胺甲恶唑(STZ)、磺胺嘧啶(SDZ)、四环素(TCY)、土霉素(OXY)和甲砜霉素(TAP))的淬灭百分比柱状图表明:三种硝基呋喃类抗生素药物(NZF、NFT、FZD)对这两种MOF具有较高的淬灭效率。其中两种MOF在水中的浓度为0.125mg/mL,加入的各种抗生素的浓度为100ppm。
上述结果表明两种MOF材料均具有一定稳定性,框架内存在笼状结构以及孔道,有利于与客体分子充分接触,从而提升荧光淬灭效率。其中,两种材料均对三种硝基呋喃类污染物(NZF、NFT、FZD)具有较高的淬灭效率,为选择性检测这三种抗生素奠定了基础。以上内容为本发明的较佳实例而已,但本发明不应局限于该实例所公开内容。所以凡不脱离本发明所公开的精神下完成的等效或修改,都落入本发明保护的范围。
Claims (7)
3.按照权利要求1或2所述的一种三齿羧酸配体的In基金属有机骨架材料,其特征在于,两种In-MOF中,金属簇为由“In-O”相连的链状次级构筑单元结构,每两个铟离子由一个桥联氧相连;每个铟离子分别与四个来自不同配体羧酸的氧原子,以及两个连接相邻铟离子的桥连氧进行配位,构成六配位模式。
4.权利要求1所述的一种三齿羧酸配体的In基金属有机骨架材料的制备方法,其特征在于,合成方法如下:
(1)将有机配体TTETA和In(NO3)3溶解于N,N-二甲基甲酰胺(DMF)、硝酸和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热,获得块状单晶,先后用DMF和丙酮洗涤;
TTETA和In(NO3)3的摩尔比为2:1~6:1;混合溶剂中DMF、水和浓硝酸的体积比例为250:10:1,溶剂热反应温度为110℃~130℃,反应时间为8h~14h。
5.权利要求1所述的一种三齿羧酸配体的In基金属有机骨架材料的应用,得到的In基金属有机骨架材料经过DMF洗涤以及丙酮溶剂交换并真空脱出溶剂分子以后用于选择性荧光检测硝基呋喃类抗生素FZD、NZF、NFT。
6.权利要求2所述的一种三齿羧酸配体的In基金属有机骨架材料的制备方法,其特征在于,合成方法如下:
(1)将有机配体BTETA与In(NO3)3溶解于N,N-二甲基甲酰胺(DMF)和水的混合溶液中;
(2)将步骤(1)中的混合溶液超声波震荡、搅拌后,进行溶剂热反应,获得块状单晶,先后用DMF和丙酮洗涤;
BTETA和In(NO3)3的摩尔比为1:1~1:1.5;混合溶剂中DMF与水的体积比为20:1;溶剂热反应温度为110℃~130℃,反应时间为8h~14h。
7.权利要求2所述的一种三齿羧酸配体的In基金属有机骨架材料的应用,得到的In基金属有机骨架材料经过DMF洗涤以及甲醇或二氯甲烷溶剂交换并真空脱出溶剂分子以后用于选择性荧光检测硝基呋喃类抗生素FZD、NZF、NFT。
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