Magnetic Titanium Dioxide Nanocomposites as a Recyclable SERRS Substrate for the Ultrasensitive Detection of...

A highly sensitive, selective and recyclable histidine detection method based on magnetic Fe₃O₄@mTiO₂ (M-TiO₂) nanocomposites with SERRS was developed. Mesoporous M-TiO₂ nanoparticles were functionalized with 4-aminothiophenol and then coupled with histidine through an azo coupling reaction in 5 min, producing the corresponding azo compound. The strong and specific SERRS response of the azo product allowed for ultrasensitive and selective detection for histidine with an M-TiO₂ device loaded with Ag NPs due to the molecular resonance effect and plasmonic effect of Ag NPs under a 532 nm excitation laser. The sensitivity was further enhanced with the magnetic enrichment of M-TiO₂. The limit of detection (LOD) was as low as 8.00 × 10^-12 mol/L. The M-TiO₂ demonstrated applicability towards histidine determination in human urine without any sample pretreatment. Additionally, the M-TiO₂ device can be recycled for 3 cycles with the photodegradation of the azo product under UV irradiation due to TiO₂-assisted and plasmon-enhanced photocatalysis. In summary, a multifunctional and recyclable M-TiO₂ device was synthesized based on azo coupling and SERRS spectroscopy for ultra-sensitive and specific histidine sensing. In addition, the proposed system demonstrated the potential for the multiplex determination of toxic compounds in the fields of food safety, industrial production and environmental protection, which benefit from the fingerprint property and universality of SERRS.