BSA-stabilized manganese phosphate nanoflower with enhanced nanozyme activity for highly sensitive and rapid detection of glutathione.

The development of an efficient protein-inorganic nanohybrid with superior nanozyme activity for highly sensitive detection of glutathione (GSH) is essential for early diagnosis of human diseases. Herein, a rapid and highly sensitive colorimetric assay using self-assembled bovine serum albumin-hydrated manganese phosphate nanoflowers (MnPNF) as a biomimic oxidase is developed for GSH detection in human serum. The BSA can complex with Mn2+ to serve the nucleation center to produce MnPNF in the presence of phosphate-buffered saline (PBS). The morphology and surface characterization results show that the MnPNF is assembled with hierarchical nanoplates to form 500 nm nanoflowers. The oxidase-like activity of MnPNF is based on the redox reaction with 3,3',5,5'-tetramethylbenzidine. However, the addition of GSH can reduce MnPNF to Mn2+, and subsequently supresses the oxidase-like activity and a yellow color at 450 nm is observed in the presence of H2SO4. The MnPNF-based nanozyme exhibits excellent sensing ability toward GSH detection, and a good linear relationship between the change in absorbance at 450 nm and the added amounts of GSH at 50 nM-10 µM with low limits of detection of 20 and 26.6 nM in the PBS and diluted human serum, respectively, is observed. Moreover, the sensing probe shows a superior selectivity over the other 16 interferences, which drive the determination of GSH feasible in real human serum. Since the MnPNF can be simply prepared at room temperature and no functionalization is required, this assay can be used to design the highly efficient biomimic oxidase for effective sensing of GSH and other disease-related biomolecules in biological fluid samples.

Application of sulfur-doped graphene quantum dots@gold-carbon nanosphere for electrical pulse-induced impedimetric detection of glioma cells.

Glioma is the predominant brain tumor with high death rate. The successful development of biosensor to achieve an efficient detection of glioma cells at low concentration remains a great challenge for the personalized glioma therapy. Herein, an ultrasensitive pulse induced electrochemically impedimetric biosensor for glioma cells detection has been successfully fabricated. The 4-11 nm sulfur-doped graphene quantum dots (S-GQDs) are homogeneously deposited onto gold nanoparticles decorated carbon nanospheres (Au-CNS) by Au-thiol linkage to form S-GQDs@Au-CNS nanocomposite which acts as dual functional probe for enhancing the electrochemical activity as well as conjugating the angiopep-2 (Ang-2) for glioma cell detection. Moreover, the application of an externally electrical pulse at +0.6 V expend the surface of glioma cells to accelerate the attachment of glioma cells onto the Ang-2-conjugated S-GQDs@Au-CNS nanocomposite, resulting in the enhanced sensitivity toward glioma cell detection. An ultrasensitive impedimetric detection of glioma cells with a wide linear range of 100-100,000 cells mL-1 and a limit of detection of 40 cells mL-1 is observed. Moreover, the superior selectivity with long-term stability of the developed biosensor in human serum matrix corroborates the feasibility of using S-GQDs@Au-CNS based nanomaterials as the promising sensing probe for practical application to facilitate the ultrasensitive and highly selective detection of cancer cells.