Multi-CeIII-Inserted Phospho(III)tungstate Containing Three Building Units with Prominent Peroxidase-Mimicking Activity for Detecting l-Cysteine.
Multi-CeIII-Inserted Phospho(III)tungstate Containing Three Building Units with Prominent Peroxidase-Mimicking Activity for Detecting l-Cysteine.
复制标题
DOI：
10.1021/acs.inorgchem.3c01218
复制
发表时间：
2023-06
影响因子：
4.6
通讯作者：
Baoxing Zeng;Yanzhou Li;Guoping Liu;Qingqing Cui;Feng Tang;D. Shi;Lijuan Chen;Junwei Zhao
中科院分区：
文献类型：
--
作者：
Baoxing Zeng;Yanzhou Li;Guoping Liu;Qingqing Cui;Feng Tang;D. Shi;Lijuan Chen;Junwei Zhao
在HINA存在的情况下，将HPO32-异质离子模板引入Ce3+/WO42-体系中，通过精心设计的一步组装策略，分离出了具有吸引力的异烟酸修饰的八元- ceiii -插入磷酸（III）钨酸盐[H2N(CH3)2]6Na8[Ce8(H2O)30W8Na2O20(INA)4][HPIIIW4O17]2[HPIIIW9O33]4·30H2O (1-Ce) （HINA =异烟酸）。1-Ce的多氧阴离子由两个相同的[Ce4(H2O)15W4NaO10(INA)2][HPIIIW4O17][HPIIIW9O33]2}7-亚基组成，由Ce-O-W键连接。聚氧阴离子表现出三种聚氧钨酸盐构建单元[W4NaO20(INA)2]17-、[HPIIIW4O17]6-和[HPIIIW9O33]8-，其中[W4NaO20(INA)2]17-和[HPIIIW4O17]6-构建单元可以看作是由附加Ce3+离子配位驱动的种子，诱导[HPIIIW9O33]8-片段聚集。此外，1-Ce具有较高的过氧化物酶样活性，在H2O2存在下可氧化3,3',5,5'-四甲基联苯胺，周转率为6.20 × 10-3 s-1。由于l-半胱氨酸（l-Cys）能将oxTMB降至TMB，因此基于1- ce基H2O2比色生物传感平台建立l-Cys的检测，线性范围为5-100 μM，检出限为4.28 μM。本工作不仅拓展了稀土多氧钨酸盐配位化学和材料化学的科学研究，而且为液体活检临床诊断提供了实际应用的可能性。
An attractive isonicotinic acid-ornamented octa-CeIII-inserted phospho(III)tungstate [H2N(CH3)2]6Na8[Ce8(H2O)30W8Na2O20(INA)4][HPIIIW4O17]2[HPIIIW9O33]4·30H2O (1-Ce) (HINA = isonicotinic acid) has been isolated through the deliberately designed one-step assembly strategy, in which the HPO32- heteroanion template was introduced into the Ce3+/WO42- system in the presence of HINA. The polyoxoanion of 1-Ce consists of two identical [Ce4(H2O)15W4NaO10(INA)2][HPIIIW4O17][HPIIIW9O33]2}7- subunits linked by Ce-O-W bonds. The polyoxoanion exhibits three kinds of polyoxotungstate building blocks [W4NaO20(INA)2]17-, [HPIIIW4O17]6-, and [HPIIIW9O33]8-, in which [W4NaO20(INA)2]17- and [HPIIIW4O17]6- building units can be considered as seeds driven by the coordination of additional Ce3+ ions to induce aggregation of [HPIIIW9O33]8- fragments. Furthermore, 1-Ce possesses high peroxidase-like activity and can oxidize 3,3',5,5'-tetramethylbenzidine in the presence of H2O2 with a turnover rate of 6.20 × 10-3 s-1. Because l-cysteine (l-Cys) can reduce oxTMB to TMB, the detection of l-Cys was established based on the 1-Ce-based H2O2 colorimetric biosensing platform with the linear range of 5-100 μM and the limit of detection of 4.28 μM. This work not only can expand the scientific research studies on coordination chemistry and materials chemistry of rare-earth-inserted polyoxotungstates but also can provide practical application possibility in clinical diagnosis using liquid biopsy.