吡啶二羧酸修饰的稀土嵌入碲钨酸盐的合成及电化学生物识别性质

Synthesis and Electrochemical Biosensing Properties of Pyridine Dicarboxylic Acid Decorated Rare-earth-incorporatedTellurotungstates

在乙酸钠水溶液中,采用微波加热一步自组装策略合成了一系列罕见的2,6-吡啶二羧酸修饰的稀土嵌入Keggin型碲钨酸盐(PTEA)_(7)H_(3)K[RE_(2)(B-α-TeW_(9)O_(33))_(3)W_(3)O_(5)(H_(2)O)_(3)(HDPA)]·22H_(2)O[RE=Ce^(3+)(1),Pr^(3+)(2),Nd^(3+)(3),Sm^(3+)(4);H_(2)DPA=2,6-吡啶二羧酸;PTEA=质子化的三乙醇胺].化合物1~4的聚阴离子由3个三缺位Keggin型[B-α-TeW_(9)O_(33)]^(8−)构筑块通过1个{RE_(2)W_(3)O_(5)(H_(2)O)_(3)(HDPA)}1^(3+)异金属簇连接而成.该异金属簇中,2,6-吡啶二羧酸作为四齿配体与2个稀土离子(RE1和RE2)配位形成平面三杂环结构,且RE1和RE2所在平面与W2,W2A,W16形成的平面互相垂直.此外,化合物1可与羧基化多壁碳纳米管(CMWCNT)复合形成1-CMWCNT复合材料.该复合材料可以作为电极材料构建电化学生物传感器,用于检测特定的DNA序列.

A family of rare 2,6-pyridinedicarboxylic acid decorated rare-earth(RE)-incorporated Keggin-type tellurotungstates(TTs)(PTEA)_(7)H_(3)K[RE_(2)(B-α-TeW_(9)O_(33))_(3)W_(3)O_(5)(H_(2)O)_(3)(HDPA)]·22H_(2)O[RE=Ce^(3+)(1),Pr^(3+)(2),Nd^(3+)(3),Sm^(3+)(4);H2DPA=2,6-pyridinedicarboxylic acid;PTEA=protonated triethanolamine]were synthesized by the one-step self-assembly strategy in NaAc aqueous solution via microwave heating method.The polyanion of isomorphic compounds 1-4 consists of three trivacant Keggin[B-α-TeW_(9)O_(33)]^(8−)building blocks linked by a{RE_(2)W_(3)O_(5)(H_(2)O)_(3)(HDPA)}^(13+)heterometallic cluster.In this heterometallic cluster,HDPA as quadridentate ligand coordinates with two RE ions(RE1 and RE2)to form planar tri-heterocycle structure,which is perpendicular to the planar constructed by W2,W2A and W16 centers.Additionally,compound 1 can combinate with carboxylic multi-walled carbon nanotube(CMWCNT)to produce the 1-CMWCNT composite,which was then used as electrode material to establish electrochemical biosensor for detecting sequence-specific DNA.