Comparison of Gold Nanoparticles Prepared Using Monobasic Sodium Citrate or Sodium Borohydride for Neomycin Determination in Saliva after Solid-Phase Extraction (SPE) on a Molecularly Imprinted Polymer (MIP)

AbstractTwo distinct spherical gold nanoparticles (AuNPs) were compared for the spectrophotometric determination of neomycin in saliva. The AuNPs were produced using AuCl3 and monobasic sodium citrate (in water bath at 100 °C) under magnetic stirring (AuNPs-citrate) and using HAuCl4 and NaBH4, at room-temperature under mechanical agitation in a commercial reactor (AuNPs-H). Both AuNPs were spherical with diameters of 7.7 nm (AuNPs-H) and 26.1 nm (AuNPs-citrate) and the maximum wavelength of the localized surface plasmon resonance (LSPR) bands were at 511 nm (AuNPs-H) and 529 nm (AuNPs-citrate). Equivalent spectral extinctions were found despite the fact the large difference in concentrations of AuNPs in dispersions: 4.2 × 10−9 mol L−1 for the AuNPs-H and 8.7 × 10−11 mol L−1 for the AuNPs-citrate. Both AuNPs interacted with aminoglycosides (AMG), affecting intensity of the LSPR band as the concentration of AMG increased. The response of the AuNPs-H was more sensitive toward AMG covering the following ranges: 0.6–600 µg L−1 (gentamicin), 7.3–550 µg L−1 (neomycin) and 14–520 µg L−1 (kanamycin). AuNPs-H optical response was more robust in function of the pH with AuNPs-citrate response only observed in acid solution, favoring electrostatic interaction with AMG. Catalytic activity of AuNPs-H, in reducing the 4-phenolate ion, presented a higher rate constant (4.3 × 10−3 s−1) and was used as analytical probe to determine neomycin in saliva after solid phase extraction with a commercially available AMG imprinted polymer enabling quantification to 0.36 μg of the analyte.Keywords: Aminoglycosidesgold nanoparticleslocalized surface plasmon resonance (LSPR)saliva analysisspectrophotometry Disclosure statementNo potential conflict of interest was reported by the author(s).Additional informationFundingCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES-Brazil) – Finance Code 001 is acknowledged. Aucelio thanks scholarships from Brazilian agencies FAPERJ (E-26/200.810/2021, E-26/010.000980/2019) and CNPq (306108/2021-6) also for scientific grant from FAPERJ (E-210.104/2020), E-26/010.101131/2018 and (SEI-260003/011317/2021). Pedrozo-Peñafiel acknowledges FAPERJ (E-26/202.408/2021) and Letichevsky acknowledges FAPERJ (E-26/010.000982/2019). Analytical facilities from the Chemistry Department at PUC-Rio (CALPH PUC-Rio) and from multiuser MackGraphe Multiuser Laboratory (Mackenzie Presbyterian University) were used.