Nanoscale confinement can be defined as a space confined by interfaces with at least one nanometer-scale dimension. Objects under nanoscale confinement have a large ratio of interfacial area to volume that makes interfacial properties have significant impact. This dissertation examines three cases in which liquids are confined between solids. The main focus (two papers) describes how electrostatic interactions between two interfaces affect ions confined within the liquid. Commonly, the charge distribution near an interface is described by electrical double layer model, where the characteristic decay length of the potential is the Debye length κ^(-1), which is typically 1–100 nm. In a nanoscale confinement, the electrostatic potential from both confining surfaces overlaps, and there is no bulk solution in the confined liquid. If the two surfaces have the same potential in isolation, the potential will increase throughout the liquid phase. I examine two hypotheses for ions under confinement in aqueous solution: (1) diffusion of ions will be hindered by the electrostatic potential; (2) surfactants will form surface aggregates (a form of micelles) that would not occur without the modified potential. To test the first hypothesis, I studied diffusion of fluorescein sodium salt in the nanoscale water confined between glass surfaces. The confining glass surfaces were fabricated by thermally bonding Borofloat glass wafers. Fluorescence microscopy was used to monitor the amount of fluorescein throughout the confined water, and thereby to understand the diffusion Measurements with done for a variety of different Debye lengths and water film thicknesses. I found that the time for fluorescein to reach equilibrium distribution in the nano-scale confinement could be 10× longer when there was no salt initially present compared to when salt was present. However, even a small amount of salt initially in the confined liquid led to a very weak effect of Debye length on diffusion. Thus, provided that the surface potential inside a thin film is initially screened by even a low concentration of electrolyte inside the confinement, diffusion is unhindered. A practical application of this result is delivery of dissolved species should not be preceded by infusion of pure water into pores if speedy delivery is desired. For the second hypothesis, I studied adsorption and aggregation of dodecyltrimethylammonium bromide (DTAB), a cationic surfactant, within the same type of nanoscale confinement by Borofloat glass. A fluorescent dye, Nile red, whose fluorescence depends on its solvent environment was used to indicate formation of surface aggregates by the surfactant. We found that surface aggregation of DTAB occurred at a very low surfactant concentration (<1 % of the critical micelle concentration) when the confinement was less than 30 nm, which was about one Debye length of the solution. This finding overturns a major assumption of many surface forces measurements and ideas of colloidal stability. It has been customary to assume that the state of surfactant aggregation is constant when two particles approach, whereas we find that aggregation changes with the solution is confined. The change in aggregation can lead to a change in electrical potential, which affects the surface forces and colloidal stability. Past work that used this assumption will need to be re-interpreted. The third topic was the study of the displacement of oil trapped in dead-end nanopores by water. This is a model of the process of tertiary oil recovery. Surfactants are used to assist with oil recovery, but the mechanism is not well studied. Three hypotheses were considered for the effect of surfactant on oil displacement: (1) Lowering of the oil–water interfacial tension; (2) Adsorption to the water–solid interface; and (3) Effects on transport rather than thermodynamics. Measurements of three different types of surfactants: sodium dodecyl sulfate (SDS), an anionic surfactant; Aerosol OT (AOT), an anionic surfactant; dodecyltrimethylammonium bromide (DTAB), a cationic surfactant; and no surfactant. Results show that AOT was the only surfactant that led to substantial spontaneous displacement of oil within 12 hours. The effect was attributed to AOT's ability for form reverse micelles in the oil phase that could deliver water to the hydrophilic solid walls, thereby displacing oil. No prior literature describing this mechanism has been found. / Doctor of Philosophy / Nanoscale confinement are domains contained by interfaces with at least one dimension on the nanometer scale level. This dissertation describes very thin (1–100 nm) layers of water between solids. Such thin layers of water are important in oil recovery, cellular processes, delivery of sham-poo to hair, drug delivery, etc. I studied the transport and adsorption of ions in these thin layers, particularly when the solid walls were charged. Results show that (1) Diffusion of ions could be se-verely hindered by unscreened electrostatic potential within the thin film of water. Diffusion times were increased by up to 10 times; (2) Surfactant aggregation occurred in the thin film, even when it did not occur in bulk solution at the same concentration; (3) Water could not displace oil in a thin film, even when assisted by a variety of surfactants. One particular surfactant, Aerosol OT could displace the oil, which I attribute to its ability to transport water through the oil and onto the solid.

Two-dimensional (2D) nanoscale confinement effects on poly(ε-caprolactone) (PCL) crystallization were probed through crystallization studies of PCL-b-poly(tert-butyl acrylate) (PCL-b-PtBA) copolymers, PCL with bulky tri-tert-butyl ester endgroups (PCL triesters), PCL with triacid end groups (PCL triacids), and magnetic nanoparticles stabilized by PCL triacid (PCL MNPs) at the air/water (A/W) interface. Thermodynamic analyses of surface pressure-area per monomer (Π−A)) isotherms for the Langmuir films at the A/W interface showed that PCL-b-PtBA copolymers, PCL triheads and PCL MNPs all formed homogenous monolayers below the dynamic collapse pressure of PCL, Π_C ~11 mN•m⁻¹. For compression past the collapse point, the PCL monolayers underwent a phase transition to three-dimensional (3D) crystals and the nanoscale confinements impacted the PCL crystalline morphologies. Studies of PCL-b-PtBA copolymers revealed that the morphologies of the LB-films became smaller and transitioned to dendrites with defects, stripes and finally nano-scale cylindrical features as the block length of PtBA increased. For the case of PCL triester, irregularly shaped crystals formed at the A/W interface and this was attributed to the accumulation of bulky tert-butyl ester groups around the crystal growth fronts. In contrast, regular, nearly round-shaped lamellar crystals were obtained for PCL triacids. These morphological differences between PCL triacids and PCL triesters were molar mass dependent and attributed to differences in dipole density and the submersion of carboxylic acid groups in the subphase. Nonetheless, enhanced uniformity for PCL triacid crystals was not retained once the polymers were tethered to the spherical surface of a PCL MNP. Instead, the PCL MNPs exhibited small irregularly shaped crystals. This nano-scale confinement effect on the surface morphology at the A/W interface was also molar mass dependent. For the small molar mass PCL MNPs, two layers of collapsed nanoparticles were observed. In a later chapter, studies of polyethylene glycol (PEG) surfactant adsorption onto phospholipid bilayers through quartz crystal microbalance with dissipation monitoring (QCM-D) measurements revealed a strong dependence of the adsorption and desorption kinetics on hydrophobic tail group structure. PEG surfactants with a single linear alkyl tail inserted and saturated the bilayer surface quickly and the surfactants had relatively fast desorption rates. In contrast, PEG lipids, including dioleoyl PEG lipids and cholesterol PEGs, demonstrated slower adsorption and desorption kinetics. The interactions of Pluronics and Nonoxynol surfactants with phospholipid bilayers were also studied. Pluronics showed no apparent affinity for the phospholipid bilayer, while the Nonoxynol surfactants damaged the lipid bilayers as PEG chain length decreased. / Ph. D.

Extracellular neuroelectronic interfacing has important applications in the fields of neural prosthetics, biological computation and whole-cell biosensing for drug screening and toxin detection. While the field of neuroelectronic interfacing holds great promise, the recording of high-fidelity signals from extracellular devices has long suffered from the problem of low signal-to-noise ratios and changes in signal shapes due to the presence of highly dispersive dielectric medium in the neuron-microelectrode cleft. This has made it difficult to correlate the extracellularly recorded signals with the intracellular signals recorded using conventional patch-clamp electrophysiology. For bringing about an improvement in the signalto-noise ratio of the signals recorded on the extracellular microelectrodes and to explore strategies for engineering the neuron-electrode interface there exists a need to model, simulate and characterize the cell-sensor interface to better understand the mechanism of signal transduction across the interface. Efforts to date for modeling the neuron-electrode interface have primarily focused on the use of point or area contact linear equivalent circuit models for a description of the interface with an assumption of passive linearity for the dynamics of the interfacial medium in the cell-electrode cleft. In this dissertation, results are presented from a nonlinear dynamic characterization of the neuroelectronic junction based on Volterra-Wiener modeling which showed that the process of signal transduction at the interface may have nonlinear contributions from the interfacial medium. An optimization based study of linear equivalent circuit models for representing signals recorded at the neuron-electrode interface subsequently iv proved conclusively that the process of signal transduction across the interface is indeed nonlinear. Following this a theoretical framework for the extraction of the complex nonlinear material parameters of the interfacial medium like the dielectric permittivity, conductivity and diffusivity tensors based on dynamic nonlinear Volterra-Wiener modeling was developed. Within this framework, the use of Gaussian bandlimited white noise for nonlinear impedance spectroscopy was shown to offer considerable advantages over the use of sinusoidal inputs for nonlinear harmonic analysis currently employed in impedance characterization of nonlinear electrochemical systems. Signal transduction at the neuron-microelectrode interface is mediated by the interfacial medium confined to a thin cleft with thickness on the scale of 20-110 nm giving rise to Knudsen numbers (ratio of mean free path to characteristic system length) in the range of 0.015 and 0.003 for ionic electrodiffusion. At these Knudsen numbers, the continuum assumptions made in the use of Poisson-Nernst-Planck system of equations for modeling ionic electrodiffusion are not valid. Therefore, a lattice Boltzmann method (LBM) based multiphysics solver suitable for modeling ionic electrodiffusion at the mesoscale neuron-microelectrode interface was developed. Additionally, a molecular speed dependent relaxation time was proposed for use in the lattice Boltzmann equation. Such a relaxation time holds promise for enhancing the numerical stability of lattice Boltzmann algorithms as it helped recover a physically correct description of microscopic phenomena related to particle collisions governed by their local density on the lattice. Next, using this multiphysics solver simulations were carried out for the charge relaxation dynamics of an electrolytic nanocapacitor with the intention of ultimately employing it for a simulation of the capacitive coupling between the neuron and the v planar microelectrode on a microelectrode array (MEA). Simulations of the charge relaxation dynamics for a step potential applied at t = 0 to the capacitor electrodes were carried out for varying conditions of electric double layer (EDL) overlap, solvent viscosity, electrode spacing and ratio of cation to anion diffusivity. For a large EDL overlap, an anomalous plasma-like collective behavior of oscillating ions at a frequency much lower than the plasma frequency of the electrolyte was observed and as such it appears to be purely an effect of nanoscale confinement. Results from these simulations are then discussed in the context of the dynamics of the interfacial medium in the neuron-microelectrode cleft. In conclusion, a synergistic approach to engineering the neuron-microelectrode interface is outlined through a use of the nonlinear dynamic modeling, simulation and characterization tools developed as part of this dissertation research.