Oxidase-like nanozymes

  • 文章类型: Journal Article
    由于含硫化合物(SCCs)在生物体和疾病诊断中的重要作用,因此开发准确鉴定和分析含硫化合物(SCCs)的方法具有重要意义。在这里,制备了硒掺杂改善的铁基碳材料(Fe-Se/NC)的类氧化酶活性,并将其用于构建四通道比色传感器阵列,用于检测和鉴定SCC(包括生物硫醇和含硫金属盐)。Fe-Se/NC可以实现3,3'的显色氧化,5,5'-四甲基联苯胺(TMB)通过激活O2而不依赖于H2O2,可以被不同的SCC抑制到不同的程度,以产生不同的比色响应变化,如传感器阵列上的“指纹”。主成分分析(PCA)和层次聚类分析(HCA)表明,可以很好地区分9种SCC。传感器阵列还用于检测SCC,线性范围为1-50μM,检测限为0.07-0.2μM。此外,比色传感器阵列受到真实样本中不同级别SCC的启发,用于区分癌细胞和食物样本,证明了其在疾病诊断和食品监测领域的潜在应用。环境含义:在这项工作中,成功构建了用于准确识别和检测SCC的四通道比色传感器阵列.受真实样品中不同SCC水平启发的比色传感器阵列也用于区分癌细胞和食物样品。因此,这种基于Fe-Se/NC的传感器阵列有望应用于环境监测和环境相关疾病诊断领域。
    Developing methods for the accurate identification and analysis of sulfur-containing compounds (SCCs) is of great significance because of their essential roles in living organisms and the diagnosis of diseases. Herein, Se-doping improved oxidase-like activity of iron-based carbon material (Fe-Se/NC) was prepared and applied to construct a four-channel colorimetric sensor array for the detection and identification of SCCs (including biothiols and sulfur-containing metal salts). Fe-Se/NC can realize the chromogenic oxidation of 3,3\',5,5\'-tetramethylbenzidine (TMB) by activating O2 without relying on H2O2, which can be inhibited by different SCCs to diverse degrees to produce different colorimetric response changes as \"fingerprints\" on the sensor array. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) revealed that nine kinds of SCCs could be well discriminated. The sensor array was also applied for the detection of SCCs with a linear range of 1-50 μM and a limit of detection of 0.07-0.2 μM. Moreover, colorimetric sensor array inspired by the different levels of SCCs in real samples were used to discriminate cancer cells and food samples, demonstrating its potential application in the field of disease diagnosis and food monitoring. ENVIRONMENTAL IMPLICATIONS: In this work, a four-channel colorimetric sensor array for accurate SCCs identification and detection was successfully constructed. The colorimetric sensor array inspired by the different levels of SCCs in real samples were also used to discriminate cancer cells and food samples. Therefore, this Fe-Se/NC based sensor array is expected to be applied in the field of environmental monitoring and environment related disease diagnosis.
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  • 文章类型: Journal Article
    传统的类氧化酶(OXD)纳米酶主要依靠O2介导的超氧阴离子(O2·-)过程进行催化氧化和有机磷(Ops)检测。而在实际检测过程中,O2的浓度是不恒定的,可以很容易地随着外部环境的变化,扭曲检测结果。在这里,设计了具有核壳纳米结构的高氧化性Au@MnO2-X纳米酶,可触发从内部Au核到外部超薄MnO2-X层的大量电子转移。根据实验和理论计算,Au@MnO2-X的核壳纳米结构和超薄MnO2-X导致较大的表面缺陷,高氧空位和MnIII比率。因此,特殊结构的Au@MnO2-X纳米酶具有高度氧化性,并且催化氧化可以仅通过电子转移而不是O2介导的O2·-过程来完成。基于此,使用均相电化学(HEC)建立了一种不依赖氧的超灵敏纳米酶传感器,在0.039ngmL-1的LOD下检测到其Ops。结合3,3'的紫外可见光谱,5,5'-四甲基联苯胺(TMB),五个运算的线性判别分析,即,Ethion,氧化乐果,Diazinon,甲基毒死蜱和双歧杆菌取得了优越的辨别后果。因此,基于强氧化纳米酶的HEC为开发高性能电化学传感器提供了新的途径,并展示了对实际样品中农药残留测定的潜在适用性。
    Traditional oxidase-like (OXD) nanozymes rely primarily on O2-mediated superoxide anion (O2·-) process for catalytic oxidation and organophosphorus (Ops) detection. While during the actual detection process, the concentration of O2 is inconstant that can be easily changed with the external environment, distorting detection results. Herein, highly-oxidizing Au@MnO2-X nanozymes with core-shell nanostructure are designed which trigger substantial electron transfer from inner Au core to outer ultrathin MnO2-X layer. According to experimental and theoretical calculations, the core-shell nanostructure and ultrathin MnO2-X of Au@MnO2-X result in the large surface defects, high oxygen vacancies and MnIII ratios. The specially structured Au@MnO2-X nanozymes are therefore highly-oxidizing and the catalytic oxidation can be completed merely through electrons transferring instead of the O2-mediated O2·- process. Based on this, an oxygen independent and ultrasensitive nanozyme-based sensor is established using homogeneous electrochemistry (HEC), its Ops is detected at a LOD of 0.039 ng mL-1. Combined with the UV-vis spectrum of 3,3\',5,5\'-tetramethylbenzidine (TMB), the linear discriminant analysis of five Ops i.e., Ethion, Omethoate, Diazinon, Chlorpyrifos methyl and Dipterex has achieved superior discrimination results. Therefore, HEC based on strong oxidizing nanozymes provide a new avenue for the development of high-performance electrochemical sensors and demonstrate potential applicability to pesticide residue determination in real samples.
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