Synthesis of 1.4 nm α-cyclodextrin-protected gold nanoparticles for luminescence sensing of mercury(II) with picomolar detection limit

Man Chin Paau, Chung Keung Lo, Xiupei Yang, Martin M F CHOI

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46 Citations (Scopus)

Abstract

The synthesis of gold nanoparticles (core size less than 2.0 nm) capped by thiolate α-cyclodextrin (α-CD-SH) has been studied and characterized by infrared spectroscopy, UV-visible absorption spectroscopy, high-resolution transmission electron microscopy, and photoluminescence spectroscopy. Hydrogen tetrachloroaurate(III) trihydrate (HAuCl4•3H2O) is reduced by NaBH4 in the presence of α-CD-SH to produce thiolate α-cyclodextrin-stabilized gold nanoparticles (α-CD-S-AuNPs). The particle size of the as-synthesized α-CD-S-AuNPs is highly dependent on the initial molar ratio of α-CD-SH to AuCl4- (α-CD-SH/Au) precursors. When the α-CD-SH/Au is kept greater than or equal to 1, α-CD-S-AuNPs (core size < 2.0 nm) are acquired, and their size increases with increasing α-CD-SH/Au. It is postulated that the increase in particle size is attributed to the interhydrogen bond between the α-CD-SH molecules at higher concentrations with a concomitant decrease in the availability of free α-CD-SH to stabilize the AuNP surface. By contrast, when the α-CD-SH/Au is controlled at <1, larger α-CD-S-AuNPs (core size >2.5 nm) with typical surface plasmon bands are obtained, and the particle size increases with the decrease in α-CD-SH/Au. The average chemical compositions of such AuNPs in the empirical formula Aux(α-CD-S)y are further determined by thermogravimetric analysis, mass spectrometry, and atomic absorption spectroscopy. These α-CD-S-AuNPs (core size < 2.0 nm) display remarkably strong blue emissions at 478 nm when excited at 400 nm. The 1.4 nm-sized α-CD-S-AuNP shows photoluminescence enhancement in the presence of tetraalkylammonium ions but is strongly quenched by Hg(II). The α-CD-S-AuNP possesses ultrahigh sensitivity and good selectivity for the determination of Hg(II) with the limit of detection at 49 pM (9.7 ppt).

Original languageEnglish
Pages (from-to)15995-16003
Number of pages9
JournalJournal of Physical Chemistry C
Volume114
Issue number38
DOIs
Publication statusPublished - 30 Sep 2010

Scopus Subject Areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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