Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface: Expression and Asymptotic Scaling Laws

Jérôme F.L. Duval, Raewyn M. Town, Herman P. Van Leeuwen

Research output: Contribution to journalArticleAcademicpeer-review

4 Citations (Scopus)

Abstract

The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it is only recently that a definition was elaborated for the lability of metal complexes with nanoparticles (NPs) in aqueous dispersions. The definition includes the thickness of the nonequilibrium reaction layer operational at the (bio)interface and the extent of geometrical exclusion of NPs therefrom. In this work, an explicit expression is derived for the lability of nanoparticulate metal complexes (M-NP) toward a macroscopic reactive (bio)interface. Interpretation accounts for the M-NP chemodynamic properties that depend on the NP size, electrostatics, metal diffusion and dehydration rates, and density of metal binding sites for various NP types, for example, soft/core-shell and hard NPs having volume and surface site distribution, respectively. Computational examples under practical conditions illustrate how these factors jointly determine the remarkable nonmonotonous dependence of the M-NP lability parameter on the NP size. The analysis is supported by the formulation of asymptotic scaling laws clarifying how local M-NP dissociation dynamics affect the lability parameter for M-NP complexes at the scale of the macroscopic (bio)interface.
Original languageEnglish
Pages (from-to)6052-6065
JournalJournal of Physical Chemistry C
Volume122
Issue number11
DOIs
Publication statusPublished - 22 Mar 2018

Fingerprint

Scaling laws
Coordination Complexes
Metal complexes
scaling laws
Metals
Nanoparticles
nanoparticles
metals
Binding sites
exclusion
Dehydration
Dispersions
organisms
dehydration
Metal ions
Electrostatics
metal ions
Binding Sites
Ligands
dissociation

Cite this

@article{16a001438ae1447ab0519e60b49c53b1,
title = "Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface: Expression and Asymptotic Scaling Laws",
abstract = "The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it is only recently that a definition was elaborated for the lability of metal complexes with nanoparticles (NPs) in aqueous dispersions. The definition includes the thickness of the nonequilibrium reaction layer operational at the (bio)interface and the extent of geometrical exclusion of NPs therefrom. In this work, an explicit expression is derived for the lability of nanoparticulate metal complexes (M-NP) toward a macroscopic reactive (bio)interface. Interpretation accounts for the M-NP chemodynamic properties that depend on the NP size, electrostatics, metal diffusion and dehydration rates, and density of metal binding sites for various NP types, for example, soft/core-shell and hard NPs having volume and surface site distribution, respectively. Computational examples under practical conditions illustrate how these factors jointly determine the remarkable nonmonotonous dependence of the M-NP lability parameter on the NP size. The analysis is supported by the formulation of asymptotic scaling laws clarifying how local M-NP dissociation dynamics affect the lability parameter for M-NP complexes at the scale of the macroscopic (bio)interface.",
author = "Duval, {J{\'e}r{\^o}me F.L.} and Town, {Raewyn M.} and {Van Leeuwen}, {Herman P.}",
year = "2018",
month = "3",
day = "22",
doi = "10.1021/acs.jpcc.7b11982",
language = "English",
volume = "122",
pages = "6052--6065",
journal = "The Journal of Physical Chemistry Part C: Nanomaterials and Interfaces",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "11",

}

Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface : Expression and Asymptotic Scaling Laws. / Duval, Jérôme F.L.; Town, Raewyn M.; Van Leeuwen, Herman P.

In: Journal of Physical Chemistry C, Vol. 122, No. 11, 22.03.2018, p. 6052-6065.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface

T2 - Expression and Asymptotic Scaling Laws

AU - Duval, Jérôme F.L.

AU - Town, Raewyn M.

AU - Van Leeuwen, Herman P.

PY - 2018/3/22

Y1 - 2018/3/22

N2 - The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it is only recently that a definition was elaborated for the lability of metal complexes with nanoparticles (NPs) in aqueous dispersions. The definition includes the thickness of the nonequilibrium reaction layer operational at the (bio)interface and the extent of geometrical exclusion of NPs therefrom. In this work, an explicit expression is derived for the lability of nanoparticulate metal complexes (M-NP) toward a macroscopic reactive (bio)interface. Interpretation accounts for the M-NP chemodynamic properties that depend on the NP size, electrostatics, metal diffusion and dehydration rates, and density of metal binding sites for various NP types, for example, soft/core-shell and hard NPs having volume and surface site distribution, respectively. Computational examples under practical conditions illustrate how these factors jointly determine the remarkable nonmonotonous dependence of the M-NP lability parameter on the NP size. The analysis is supported by the formulation of asymptotic scaling laws clarifying how local M-NP dissociation dynamics affect the lability parameter for M-NP complexes at the scale of the macroscopic (bio)interface.

AB - The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it is only recently that a definition was elaborated for the lability of metal complexes with nanoparticles (NPs) in aqueous dispersions. The definition includes the thickness of the nonequilibrium reaction layer operational at the (bio)interface and the extent of geometrical exclusion of NPs therefrom. In this work, an explicit expression is derived for the lability of nanoparticulate metal complexes (M-NP) toward a macroscopic reactive (bio)interface. Interpretation accounts for the M-NP chemodynamic properties that depend on the NP size, electrostatics, metal diffusion and dehydration rates, and density of metal binding sites for various NP types, for example, soft/core-shell and hard NPs having volume and surface site distribution, respectively. Computational examples under practical conditions illustrate how these factors jointly determine the remarkable nonmonotonous dependence of the M-NP lability parameter on the NP size. The analysis is supported by the formulation of asymptotic scaling laws clarifying how local M-NP dissociation dynamics affect the lability parameter for M-NP complexes at the scale of the macroscopic (bio)interface.

U2 - 10.1021/acs.jpcc.7b11982

DO - 10.1021/acs.jpcc.7b11982

M3 - Article

VL - 122

SP - 6052

EP - 6065

JO - The Journal of Physical Chemistry Part C: Nanomaterials and Interfaces

JF - The Journal of Physical Chemistry Part C: Nanomaterials and Interfaces

SN - 1932-7447

IS - 11

ER -