Silver nanoparticle colloids with γ-cyclodextrin: enhanced stability and Gibbs–Marangoni flow

Although cyclodextrins (CD) are effective stabilizers for metal nanoparticle colloids, differences between α-, β- and γ-CD in stabilizing such colloids have not been previously reported. In this study, silver nanoparticles (AgNP) were synthesized using NaBH₄ as reducing agent and cyclodextrins as stabilizers. Long-term stability of AgNP colloids in equilibrium conditions showed no marked differences between CD types. Transmission electron microscopy and quantitative image analysis revealed only marginal differences in particle sizes for CD-AgNP, although statistically significant. CD-AgNP colloids showed dispersed particles with average diameters of 7.3 ± 2.2, 6.3 ± 2.9 and 4.9 ± 1.9 nm for α-, β- and γ-CD, respectively, and with similar ζ-potentials about −25 to −30 mV. AgNP without CD showed bigger and aggregated particles of 15.0 ± 2.0 nm with lower ζ-potentials of about −40 mV. When subjected to centrifugal forces, i.e. non-equilibrium conditions, γ-CD was markedly more efficient than α- and β-CD in stabilizing the colloids. Drying patterns of colloid droplets showed a typical self-pinned coffee ring for all but the colloid stabilized by γ-CD, which showed a pattern resulting from a dominant Gibbs–Marangoni flow inside the drying droplet. Calculations using the Derjaguin, Landau, Verwey and Overbeek (DLVO) theory supported the stabilizing effect of CD in equilibrium conditions; it however did not provide clues for the superior stabilization by γ-CD in conditions of hydrodynamic stress.