Influence of solvent polarization and non-uniform ion size on electrostatic properties between charged surfaces in an electrolyte solution

Sin, Jun-Sik

doi:10.1063/1.5002607

Cited by 13 publications

(12 citation statements)

References 42 publications

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“…As such, this phenomenon is inherently local, leading to important conceptual and practical consequences. First, this behavior can't be described within the framework of the standard DLVO theory, and specific extension (as in other extended-DLVO theories [3][4][5] ) must be implemented if one wants to take this specific behavior into account. Second, this behavior can be exquisitely sensitive to kinetic processes such as NP surface ligand exchange, that could thus dynamically alter the propensity for NP aggregation over time 35 .…”

Section: Discussionmentioning

confidence: 99%

“…The DLVO theory is generally adequate for large particles or in the long-range regime, but at smaller ("nano") length scales, the continuum assumptions required by the DLVO theory break down. As a consequence, several discrepancies arise between the DLVO predictions and experimental results, due to deficiencies in the appropriate description of solvent polarization 2 , finite size of ions 3 , and hydration forces 4,5 . These discrepancies, generally defined as non-DLVO forces, can lead to unreliable predictions when the interparticle distance is less than 2 nm 1 .…”

Section: Introductionmentioning

confidence: 99%

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Ion-mediated charge-charge interactions drive aggregation of surface-functionalized gold nanoparticles

Petretto

Ong

Olgiati

et al. 2021

Preprint

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Monolayer-protected metal nanoparticles (NPs) are not only promising materials with a wide range of potential industrial and biological applications, but they are also a powerful tool to investigate the behavior of matter at nanoscopic scales, including the stability of dispersions and colloidal systems. This stability is dependent on a delicate balance between electrostatic and steric interactions that occur in the solution, and it is described in quantitative terms by the classic Derjaguin-Landau-Vewey-Overbeek (DLVO) theory, that posits that aggregation between NPs is driven by hydrophobic interactions and opposed by electrostatic interactions. To investigate the limits of this theory at the nanoscale, where the continuum assumptions required by the DLVO theory break down, here we investigate NP dimerization by computing the Potential of Mean Force (PMF) of this process using fully atomistic MD simulations. Serendipitously, we find that electrostatic interactions can lead to the formation of metastable NP dimers. These dimers are stabilized by complexes formed by negatively charged ligands belonging to distinct NPs that are bridged by positively charged ions present in solution. We validate our findings by collecting tomographic EM images of NPs in solution and by quantifying their radial distribution function, that shows a marked peak at interparticle distance comparable with that of MD simulations. Taken together, our results suggest that not only hydrophobic interactions, but also electrostatic interactions, contribute to attraction between nano-sized charged objects at very short length scales.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ion-mediated charge-charge interactions drive aggregation of surface-functionalized gold nanoparticles

Petretto

Ong

Olgiati

et al. 2021

Preprint

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“…Based on these approaches, we studied several interesting phenomena related to multicomponent electrolytes (Sin et al 2016a), binary polar solvent mixtures (Sin et al 2016b), soft charged surfaces (Sin et al 2017) and electrostatic interaction between charged surfaces (Sin 2017).…”

Section: Introductionmentioning

confidence: 99%

“…It is worthwhile to mention that the solvent polarization effect has been extensively used to better represent biological interactions (Luque et al 1995), quantify electric double layer -mediated disjoining pressure between nanoscopically separated charged surfaces (Misra et al 2013;Sin 2017), study nitroethane deprotonation (Major et al 2005).…”

Section: Introductionmentioning

confidence: 99%

Influence of solvent polarization and non-uniform ionic size on electrokinetic transport in a nanochannel

Sin¹,

Kim²,

Kim³

et al. 2018

Microfluid Nanofluid

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In this paper, we study the electroosmotic transport in a nanofluidic channel by using a mean-field theory accounting for non-uniform size effect and solvent polarization effect. We witness that in the presence of the given zeta potential, an enhancement of ion size invariably lowers the electroosmotic velocity, thereby increasing the magnitude of electrostatic potential, irrespective of considering solvent polarization. It is also proved that solvent polarization allows both the magnitude of electrostatic potential and the electroosmotic velocities to decrease. In addition, we find that increasing zeta potential augments not only ion size effect but also solvent polarization effect. Furthermore, we demonstrate that decreasing bulk ion number density causes an increase in electroosmotic velocity at the centerline. We compare the properties of aqueous electrolytes with those of the electrolytes where solvent is ethylalcohol. Finally, we study how solvent polarization and ionic size affect streaming potential and electroviscous effect. It is emphasized that the present study can provide a good way to control the nanofluidic transport for a plethora of biological and industrial applications.

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“…To derive the above formular we follow the corresponding one of 29 . Here we introduce the following dimensionless variables for more convenient determination of physical quantities:…”

mentioning

confidence: 99%

Steric effect of water molecule clusters on electrostatic interaction and electroosmotic transport in aqueous electrolytes: a mean-field approach

Sin,

Jang,

Kim

et al. 2022

Preprint

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We theoretically study the size effect of water molecule clusters not only on electrostatic interaction between two charged surfaces in an aqueous electrolyte but also on electroosmotic transport in a nanofluidic channel. Applying a free energy based mean-field approach accounting for different sizes of ions and water molecule clusters, we derive a set of coupled equations to compute electrostatic and electroosmotic properties between charged surfaces. We verify that the smaller the size of a water cluster, the stronger the electroosmotic transport in nanofluidic channels. In addition, we find that an increase in size of a water cluster yields a decrease in electrostatic interaction strength between similar or oppositely charged planar surfaces.

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Influence of solvent polarization and non-uniform ion size on electrostatic properties between charged surfaces in an electrolyte solution

Cited by 13 publications

References 42 publications

Ion-mediated charge-charge interactions drive aggregation of surface-functionalized gold nanoparticles

Ion-mediated charge-charge interactions drive aggregation of surface-functionalized gold nanoparticles

Influence of solvent polarization and non-uniform ionic size on electrokinetic transport in a nanochannel

Steric effect of water molecule clusters on electrostatic interaction and electroosmotic transport in aqueous electrolytes: a mean-field approach

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