Electric condensation of divalent counterions by humic acid nanoparticles

2016 ◽  
Vol 13 (1) ◽  
pp. 76 ◽  
Author(s):  
Herman P. van Leeuwen ◽  
Raewyn M. Town
Keyword(s):  
Humic Acid ◽  
Charge Density ◽  
Double Layer ◽  
Ion Pairs ◽  
Ion Pairing ◽  
Counterion Condensation ◽  
Counterion Binding ◽  
Satisfactory Description ◽  
Poisson Boltzmann ◽  
Very High

Environmental context Humic acids are negatively charged soft nanoparticles that play a governing role in the speciation of many ionic and molecular compounds in the environment. The charge density in the humic acid nanoparticle can be very high and the binding of divalent cations such as Ca2+ appears to go far beyond traditional ion pairing or Poisson–Boltzmann electrostatics. A two-state approach, combining counterion condensation in the intraparticulate double layer and classical Donnan partitioning in the bulk of the particle, provides a satisfactory description of the physicochemical speciation. Abstract Experimental data for divalent counterion binding by soil humic acid nanoparticles are set against ion distributions as ensuing from continuous Poisson–Boltzmann electrostatics and a two-state condensation approach. The results demonstrate that Poisson–Boltzmann massively underestimates the extent of binding of Ca2+ by humic acid, and that electric condensation of these counterions within the soft nanoparticulate body must be involved. The measured stability of the Ca2+–humic acid associate is also much greater than that predicted for ion pairing between single Ca2+ ions and monovalent negative humic acid sites, which also points to extensive electrostatic cooperativity within the humic acid particle. At sufficiently high pH, the charge density inside the humic acid entity may indeed become so high that the bulk particle attains a very high and practically flat potential profile throughout. At this limit, all the intraparticulate Ca2+ is at approximately the same electrostatic potential and the status of individual ion pairs has become immaterial. A two-state model, combining counterion condensation in the charged intraparticulate part of the double layer at the particle–medium interface and Donnan partitioning in the uncharged bulk of the humic acid particle, seems to lead the way to adequate modelling of the divalent counterion binding for various particle sizes and different ionic strengths.

scholarly journals Electric Double Layer and Orientational Ordering of Water Dipoles in Narrow Channels within a Modified Langevin Poisson-Boltzmann Model

Entropy ◽  
2020 ◽  
Vol 22 (9) ◽  
pp. 1054
Author(s):  
Mitja Drab ◽  
Ekaterina Gongadze ◽  
Veronika Kralj-Iglič ◽  
Aleš Iglič
Keyword(s):  
Charge Density ◽  
Double Layer ◽  
Electric Double Layer ◽  
Energy Functional ◽  
Large Radius ◽  
Charged Surface ◽  
Volume Charge ◽  
Volume Charge Density ◽  
Poisson Boltzmann ◽  
Orientational Ordering

The electric double layer (EDL) is an important phenomenon that arises in systems where a charged surface comes into contact with an electrolyte solution. In this work we describe the generalization of classic Poisson-Boltzmann (PB) theory for point-like ions by taking into account orientational ordering of water molecules. The modified Langevin Poisson-Boltzmann (LPB) model of EDL is derived by minimizing the corresponding Helmholtz free energy functional, which includes also orientational entropy contribution of water dipoles. The formation of EDL is important in many artificial and biological systems bound by a cylindrical geometry. We therefore numerically solve the modified LPB equation in cylindrical coordinates, determining the spatial dependencies of electric potential, relative permittivity and average orientations of water dipoles within charged tubes of different radii. Results show that for tubes of a large radius, macroscopic (net) volume charge density of coions and counterions is zero at the geometrical axis. This is attributed to effective electrolyte charge screening in the vicinity of the inner charged surface of the tube. For tubes of small radii, the screening region extends into the whole inner space of the tube, leading to non-zero net volume charge density and non-zero orientational ordering of water dipoles near the axis.

Ion Pairing and Dielectric Decrement in Glycosaminoglycan Brushes

2020 ◽  
Author(s):  
James Sterling ◽  
Wenjuan Jiang ◽  
Wesley M. Botello-Smith ◽  
Yun L. Luo
Keyword(s):  
Molecular Dynamics ◽  
Ion Pairs ◽  
Mean Field ◽  
Salt Bridge ◽  
Ion Pairing ◽  
Donnan Potential ◽  
Mean Field Models ◽  
Ion Exclusion ◽  
Dynamics Simulations ◽  
Contact Ion Pairs

Molecular dynamics simulations of hyaluronic acid and heparin brushes are presented that show important effects of ion-pairing, water dielectric decrease, and co-ion exclusion. Results show equilibria with electroneutrality attained through screening and pairing of brush anionic charges by cations. Most surprising is the reversal of the Donnan potential that would be expected based on electrostatic Boltzmann partitioning alone. Water dielectric decrement within the brush domain is also associated with Born hydration-driven cation exclusion from the brush. We observe that the primary partition energy attracting cations to attain brush electroneutrality is the ion-pairing or salt-bridge energy associated with cation-sulfate and cation-carboxylate solvent-separated and contact ion pairs. Potassium and sodium pairing to glycosaminoglycan carboxylates and sulfates consistently show similar abundance of contact-pairing and solvent-separated pairing. In these crowded macromolecular brushes, ion-pairing, Born-hydration, and electrostatic potential energies all contribute to attain electroneutrality and should therefore contribute in mean-field models to accurately represent brush electrostatics.

scholarly journals Debye-Hückel Free Energy of an Electric Double Layer with Discrete Charges Located at a Dielectric Interface

Membranes ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 129
Author(s):  
Guilherme Volpe Bossa ◽  
Sylvio May
Keyword(s):  
Free Energy ◽  
Double Layer ◽  
Electric Double Layer ◽  
Low Dielectric Constant ◽  
Surface Charges ◽  
Dielectric Interface ◽  
Charge Densities ◽  
Low Dielectric ◽  
Poisson Boltzmann ◽  
The Continuum

Poisson–Boltzmann theory provides an established framework to calculate properties and free energies of an electric double layer, especially for simple geometries and interfaces that carry continuous charge densities. At sufficiently small length scales, however, the discreteness of the surface charges cannot be neglected. We consider a planar dielectric interface that separates a salt-containing aqueous phase from a medium of low dielectric constant and carries discrete surface charges of fixed density. Within the linear Debye-Hückel limit of Poisson–Boltzmann theory, we calculate the surface potential inside a Wigner–Seitz cell that is produced by all surface charges outside the cell using a Fourier-Bessel series and a Hankel transformation. From the surface potential, we obtain the Debye-Hückel free energy of the electric double layer, which we compare with the corresponding expression in the continuum limit. Differences arise for sufficiently small charge densities, where we show that the dominating interaction is dipolar, arising from the dipoles formed by the surface charges and associated counterions. This interaction propagates through the medium of a low dielectric constant and alters the continuum power of two dependence of the free energy on the surface charge density to a power of 2.5 law.

Photoisomerization-induced patterning of ion-pairing materials based on anionic azobenzene and its complex with a fluorescent π-electronic system

2021 ◽  
Vol 57 (35) ◽  
pp. 4287-4290
Author(s):  
Ryohei Yamakado ◽  
Issei Kitamura ◽  
Mitsuo Hara ◽  
Shusaku Nagano ◽  
Takahiro Seki ◽  
...  
Keyword(s):  
Surface Tension ◽  
Mass Transport ◽  
Trace Amount ◽  
Ion Pairs ◽  
Ion Pairing ◽  
Electronic System ◽  
Large Mass ◽  
System P ◽  
The Difference

Large mass transport driven by the difference in the photoisomerization-induced surface tension was demonstrated in ion pairs, enabling fluorescence patterning using a trace amount of photoisomerized anions in complexation with a π-electronic system.

Tracing absorption and emission characteristics of halogen-bonded ion pairs involving halogenated imidazolium species

2021 ◽  
Vol 23 (12) ◽  
pp. 7480-7494
Author(s):  
Sarah Karbalaei Khani ◽  
Bastian Geissler ◽  
Elric Engelage ◽  
Patrick Nuernberger ◽  
Christof Hättig
Keyword(s):  
Ion Pairs ◽  
Ion Pairing ◽  
Emission Characteristics ◽  
Absorption And Emission ◽  
Spectroscopic Signatures

Spectroscopic signatures of ion-pairing are identified by variation of counterion and substitution and comparison with theory.

Elektronentransfer und Ionenpaare, 15 [ 1– 3] Radikalanion und Radikal-Kontakt-Ionenpaare von Dimesityl-tetraketon / Electron Transfer and Ion Pairing, 15 [1-3] Radical Anion and Radical Ion Pairs of Dimesityl Tetraketone

1990 ◽  
Vol 45 (8) ◽  
pp. 1197-1204 ◽  
Author(s):  
H. Bock ◽  
P. Hänel ◽  
H.-F. Herrmann
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Ion Pairs ◽  
Ion Pairing ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Temperature Dependent ◽  
Contact Ion Pairs

The radical anion of dimesityltetraketone (ERed, I = -0.40 V) is easily generated in THF by potassium mirror/[2.2.2]-cryptand reduction. Its contact ion pairs with Na⊕, Cs⊕ and Ba⊕⊕ counter cations, prepared in THF solution by single electron transfer from the respective metals, are characterized by their ESR/ENDOR spectra, which exhibit temperature-dependent metal couplings of aNa⊕ = 0.061 mT (190 K), aCs⊕ = 0.021 mT (190 K), and aBa⊕⊕ = 0.145 mT (295 K).

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