Role of Surface Chemistry in Nanoscale Electrokinetic Transport

Abstract

This dissertation work presents the efforts to study the electrofluidics phenomena, with a focus on surface charge properties in nanoscale systems with the potential applications in imaging, energy conversion, ultrafiltration, DNA analysis/sequencing, DNA and protein transport, drug delivery, biological/chemical agent detection and micro/nano chip sensors. Since the ion or molecular or particle transport and also liquid confinement in nano-structures are strongly dominated by the surface charge properties, in regards of the fundamental understanding of electrofluidics at nanoscale, we have used surface charge chemistry properties based on 2-pK charging mechanism. Using this mechanism, we theoretically and analytically showed the surface charge properties of silica nanoparticles as a function of their size, pH level and salt ionic strength of aqueous solution. For a fixed particle size, the magnitude of the surface charge typically increases with an increase in pH or background salt concentration. Furthermore, we investigated the surface charge properties of a charged dielectric nanoparticle and flat wall in electrostatic interactions. According to the theoretical results strong interactions cause a non-uniform surface charge density on the nanoparticle and the plate as a result of the enhancement of proton concentration in the gap between the particle and the plate. This effect increases with decreased separation distance (Kh). We moreover investigated the ion confinement inside the nanospaces and using a continuum model, we showed the proton enhancement in extended nanochannels. The proton enrichment at the center of the nanochannel is significant when the bulk pH is medium high and the salt concentration is relatively low. The results gathered are informative for the development of biomimetic nanofluidic apparatuses and the interpretation of relevant experimental data. Later, we have developed an analytical model for electroosmotic ion transport inside pH-regulated nanoslits and compared the results with the numerical study. We showed the influences of background salt concentration, pH level and the length of nanoslit on EOF velocity. The predictions show that the EOF velocity increases first and then decrease with background salt concentration increasing and the EOF velocity increases with pH level of aqueous solution