Gold nanorods (AuNRs), as versatile sensing materials, have wide analytical applications due to their unique optical properties. Cetyltrimethylammonium bromide (CTAB), a conventional reagent in AuNR synthesis, also often acts as a stabilizer of AuNRs in applications. However, CTAB-stabilized AuNRs undergo severe spontaneous aggregation and etching under extreme pH conditions, greatly limiting their optical sensing applications. Herein, we accidentally discovered that octadecyl trimethylammonium bromide (CTAB), a rarely used surfactant for AuNRs, has a substantially higher stabilizing ability than CTAB in preventing spontaneous aggregation and etching of AuNRs, which enables CTAB-stabilized AuNRs as a superior sensing platform, demonstrating a 100-fold higher sensitivity than CTAB-stabilized AuNRs for detection of model analytes. The excellent stability of CTAB-stabilized AuNRs can be attributed to the higher surfactant coverage density on the gold surface, evidenced by the red-shifted longitudinal band (5 nm), which is tuned by the metal surface refraction index. The experimental results show that CTAB-stabilized AuNRs can keep monodispersed and unchanged optical properties at very acidic and alkaline conditions with a low concentration of surfactant (0.05 mM). Moreover, the CTAB-stabilized AuNRs can prevent spontaneous etching in the acidic sensing system and maintain their unchanged plasmon band, therefore decreasing the intensity of the noise signal. Benefiting from these findings, we established a reliable and ultrasensitive CTAB-stabilized AuNR sensing platform and achieved the ultrasensitive detection of the model biomarker p-aminophenol (pAP), with a visual detection limit of 8 nM. This sensitivity represents at least a 100-fold improvement over the existing method using CTAB-stabilized AuNRs. Moreover, CTAB-stabilized AuNRs were successfully applied to detect pAP in urine samples with satisfactory recovery rates of 99.84-114.91%, further validating its reliability in practical applications. In summary, CTAB-stabilized AuNRs provide a powerful tool for trace-level visual detection in chemo- and biosensing.

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http://dx.doi.org/10.1021/acs.langmuir.5c00150DOI Listing

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