Electrochemical sensor for the discrimination of bilirubin in real human blood based on Au nanoparticles/ tetrathiafulvalene –carboxylate functionalized reduced graphene oxide 0D-2D heterojunction

• Published in: Analytica chimica acta Vol. 1072; pp. 46 - 53
• Main Authors: Zheng, Zhixiang, Feng, Qingliang, Zhu, Meijie, Shang, Jing, Li, Meng, Li, Chun, Kou, Liangzhi, Zheng, Jianbang, Wang, Chunming
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 23.09.2019; Elsevier BV
• Subjects: 0D-2d heterojunction; AuNPs; Bilirubin; Bilirubin - blood; Biocompatibility; Biomolecules; Blood; Body fluids; Carboxylic Acids - chemistry; Catalysis; Chemical bonds; Chemical sensors; Clinical medicine; Discrimination; Electrochemical Techniques; Electrochemistry; Electrodes; Electron conductivity; Electron transfer; Gold; Gold - chemistry; Graphene; Graphite - chemistry; Heterocyclic Compounds - chemistry; Heterojunctions; Humans; Jaundice; Liver diseases; Metal Nanoparticles - chemistry; Nanoparticles; Nanostructure; Neonates; Reduced graphene oxide; Self-assembly; Sensors; Septicemia; Silver - chemistry; Tetrathiafulvalene-carboxylate; Urine; Tetrathiafulvalene-carboxylate; 0D-2d heterojunction; Reduced graphene oxide; Bilirubin; AuNPs
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2019.04.040

In clinical practice, the excess concentration of bilirubin can trigger diseases such as neonatal jaundice, hepatic failure, septicemia, and so on. The concentration of bilirubin is one of important clinical indexes to evaluate patients with hepatic function disease in clinical practice. Therefore, it is very necessary to develop a rapid detection technique detecting the bilirubin in body fluids. Here, a new electrochemical sensor based on Au nanoparticles/tetrathiafulvalene-carboxylate functionalized reduced grapheneoxide 0D-2D heterojunction(AuNPs/TTF-COOH/RGO) was fabricated for the discrimination of bilirubin in real human blood. The TTF-COOH could effectively repair electron conductivity of RGO nanosheets, decrease interface resistance, and also enhance the dispersity of TTF-COOH/RGO nanosheets in water. What's more, the S atoms of TTF-COOH can bonding the gold nano-particles (AuNPs) to fabricate a 0D-2D heterojunction with excellent biocompatibility and enhanced specific surface area. After bilirubin oxidases were self-assembled on the surface of AuNPs, a specific recognition interface was formed as a sensor for the detection of bilirubin. The heterojunction showed enhanced interface electron transfer rate, excellent biocompatibility, and also prominent electrocatalytic activity for the high efficiency catalysis of bilirubin. The sensor shows a linear response for bilirubin from 2.66 to 83  μmol L−1 and a low detection limit of 0.74 μmol L−1 at 3σ. This work provides one novel approach to detection of bilirubin by functional RGO nanosheets, and broadens the application area of RGO nanosheets in selective catalysis and detection of biomolecule in biological specimens, such as blood, urine. In this work, the reduced graphene oxide (RGO) was functionalized with tetrathiafulvalene-carboxylate (TTF-Ce the interface resistance, and also enhance the dispersity of TTF-COOH/RGO nanosheets in water. What's more, the S atoms of TTF-COOH can adsorb OOH) to fabricate a 0D-2D heterojunction for sensitive detection of bilirubin. The selected TTF-COOH molecules could repair electron conductivity of RGO nanosheets, decreasgold nano-particles (AuNPs) to fabricate a 0D-2D heterojunction with excellent biocompatibility of enhanced specific surface area. And then, the bilirubin oxidases were self-assembled on the surface of AuNPs, and constructed a specific recognition interface as a sensor for detection. The heterojunction showed an enhanced interface electron transfer rate, excellent biocompatibility, and also prominent electrocatalytic activity for the high efficiency catalysis of bilirubin. The detector showed a linear range from 2.66 μmol L−1 to 83 μmol L−1 and a low detection limit of 0.74 μmol L−1 at 3σ, which fully covers the content of bilirubin in normal man body (1.71–21 μmol L−1). Specially, this detection process could finish in 1 min with the volume of blood at microliter level. This work provides a novel approach for the detection of bilirubin by functional RGO nanosheets, and broadens the application of RGO nanosheets in selective catalysis and detection of molecules in real human blood. [Display omitted] •Au NPs/TTF-COOH/RGO showed excellent biocompatibility, prominent electrocatalytic activity for bilirubin.•The fabricated sensor shows a large linear range for detection of bilirubin.•This detection process could finish in one minute with the volume of blood at microliter level.