| 1. |
- Aspelin, Vidar, et al.
(författare)
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Counterintuitive Electrostatics upon Metal Ion Coordination to a Receptor with Two Homotopic Binding Sites
- 2022
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 144:7, s. 2921-2932
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Tidskriftsartikel (refereegranskat)abstract
- The consecutive binding of two potassium ions to a bis(18-crown-6) analogue of Tröger’s base (BCETB) in water was studied by isothermal titration calorimetry using four different salts, KCl, KI, KSCN, and K2SO4. A counterintuitive result was observed: the enthalpy change associated with the binding of the second ion is more negative than that of the first (ΔH°bind,2 < ΔH°bind,1). This remarkable finding is supported by continuum electrostatic theory as well as by atomic scale replica exchange molecular dynamics simulations, where the latter robustly reproduces experimental trends for all simulated salts, KCl, KI, and KSCN, using multiple force fields. While an enthalpic K+–K+attraction in water poses a small, but fundamentally important, contribution to the overall interaction, the probability of the collapsed conformation (COL) of BCETB, where both crown ether moieties (CEs) of BCETB are bent in toward the cavity, was found to increase successively upon binding of the first and second potassium ions. The promotion of the COL conformation reveals favorable intrinsic interactions between the potassium coordinated CEs, which further contribute to the observation that ΔH°bind,2 < ΔH°bind,1. While the observed trend is independent of the counterion, the origin of the significantly larger magnitude of the difference ΔH°bind,2 - ΔH°bind,1 observed experimentally for KSCN was studied in light of the weaker hydration of the thiocyanate anion, resulting in an enrichment of thiocyanate ions close to BCETB compared to the other studied counterions.
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| 2. |
- Cautela, Jacopo, et al.
(författare)
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Supracolloidal Atomium
- 2020
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-086X .- 1936-0851. ; 14:11, s. 15748-15756
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Tidskriftsartikel (refereegranskat)abstract
- Nature suggests that complex materials result from a hierarchical organization of matter at different length scales. At the nano- and micrometer scale, macromolecules and supramolecular aggregates spontaneously assemble into supracolloidal structures whose complexity is given by the coexistence of various colloidal entities and the specific interactions between them. Here, we demonstrate how such control can be implemented by engineering specially customized bile salt derivative-based supramolecular tubules that exhibit a highly specific interaction with polymeric microgel spheres at their extremities thanks to their scroll-like structure. This design allows for hierarchical supracolloidal self-assembly of microgels and supramolecular scrolls into a regular framework of “nodes” and “linkers”. The supramolecular assembly into scrolls can be triggered by pH and temperature, thereby providing the whole supracolloidal system with interesting stimuli-responsive properties. A colloidal smart assembly is embodied with features of center-linker frameworks as those found in molecular metal–organic frameworks and in structures engineered at human scale, masterfully represented by the Atomium in Bruxelles.
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| 3. |
- Makasewicz, Katarzyna, et al.
(författare)
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Cooperativity of alpha-Synuclein Binding to Lipid Membranes
- 2021
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Ingår i: ACS Chemical Neuroscience. - : American Chemical Society (ACS). - 1948-7193. ; 12:12, s. 2099-2109
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Tidskriftsartikel (refereegranskat)abstract
- Cooperative binding is a key feature of metabolic pathways, signaling, and transport processes. It provides tight regulation over a narrow concentration interval of a ligand, thus enabling switching to be triggered by small concentration variations. The data presented in this work reveal strong positive cooperativity of alpha-synuclein binding to phospholipid membranes. Fluorescence cross-correlation spectroscopy, confocal microscopy, and cryo-TEM results show that in excess of vesicles alpha-synuclein does not distribute randomly but binds only to a fraction of all available vesicles. Furthermore, alpha-synuclein binding to a supported lipid bilayer observed with total internal reflection fluorescence microscopy displays a much steeper dependence of bound protein on total protein concentration than expected for independent binding. The same phenomenon was observed in the case of alpha-synuclein binding to unilamellar vesicles of sizes in the nm and mu m range as well as to flat supported lipid bilayers, ruling out that nonuniform binding of the protein is governed by differences in membrane curvature. Positive cooperativity of alpha-synuclein binding to lipid membranes means that the affinity of the protein to a membrane is higher where there is already protein bound compared to a bare membrane. The phenomenon described in this work may have implications for alpha-synuclein function in synaptic transmission and other membrane remodeling events.
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| 4. |
- Stenberg, Samuel, et al.
(författare)
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Grand canonical simulations of ions between charged conducting surfaces using exact 3D Ewald summations
- 2020
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Ingår i: Physical chemistry chemical physics : PCCP. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 22:24, s. 13659-13665
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Tidskriftsartikel (refereegranskat)abstract
- We present a useful methodology to simulate ionic fluids confined by two charged and perfectly conducting surfaces. Electrostatic interactions are treated using a modified 3D Ewald sum, which accounts for all image charges across the conductors, as well as the 2D periodicity, parallel to the surfaces. The energy expression is exact, and the method is trivial to implement in existing Ewald codes. We furthermore invoke a grand canonical scheme that utilizes a bias potential, that regulates the surface charge density. The applied bias potential also enables us to calculate individual chemical potentials of the ions. Finally, we argue that our approach leads to a pedagogically appealing description of the Donnan potential, and what it measures in these systems.
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| 5. |
- Stenqvist, Björn, et al.
(författare)
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Generalized Moment Correction for Long-Ranged Electrostatics
- 2020
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Ingår i: Journal of Chemical Theory and Computation. - : American Chemical Society (ACS). - 1549-9618 .- 1549-9626. ; 16:6, s. 3737-3745
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Tidskriftsartikel (refereegranskat)abstract
- Describing long-ranged electrostatics using short-ranged pair potentials is appealing because the computational complexity scales linearly with the number of particles. The foundation of the approach presented here is to mimic the long-ranged medium response by cancelling electric multipoles within a small cutoff sphere. We propose a rigorous and formally exact new method that cancels up to infinitely many multipole moments and is free of operational damping parameters often required in existing theories. Using molecular dynamics simulations of water with and without added salt, we discuss radial distribution functions, Kirkwood-Buff integrals, dielectrics, diffusion coefficients, and angular correlations in relation to existing electrostatic models. We find that the proposed method is an efficient and accurate alternative for handling long-ranged electrostatics as compared to Ewald summation schemes. The methodology and proposed parameterization are applicable also for dipole-dipole interactions.
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| 6. |
- Stenqvist, Björn, et al.
(författare)
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Membrane permeability based on mesh analysis
- 2023
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 633, s. 526-535
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Tidskriftsartikel (refereegranskat)abstract
- The main function of a membrane is to control the exchange of matter between the surrounding regions. As such, accurate modeling of membranes is important to properly describe their properties. In many cases in both biological systems and technical applications, the membranes are composite structures where transport properties may vary between the different sub-regions of the membrane. In this work we develop a method based on Mesh analysis that is asymptotically exact and can describe diffusion in composite membrane structures. We do this by first reformulating a generalized Fick's law to include the effects from activity coefficient, diffusion coefficient, and solubility using a single condensed param-eter. We then use the derived theory and Mesh analysis to, in essence, retrieve a finite element method approach. The calculated examples are based on a membrane structure that reassembles that of the brick and mortar structure of stratum corneum, the upper layer of our skin. Resulting concentration profiles from this procedure are then compared to experimental results for the distribution of different probes within intact stratum corneum, showing good agreement. Based on the derived approach we further investigate the impact from a gradient in the fluidity of the stratum corneum mortar lipids across the membrane, and find that it is substantial. We also show that anisotropic organisation of the lipid mortar can have large impact on the effective permeability compared to isotropic mortar lipids. Finally, we examine the effects of corneocyte swelling, and their lateral arrangement in the membrane on the overall membrane permeability.
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| 7. |
- Stenqvist, Björn, et al.
(författare)
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Modeling the assembly of oppositely charged multi-indented lock- and key-colloids
- 2022
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 18:26, s. 4983-4990
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Tidskriftsartikel (refereegranskat)abstract
- The interactions between oppositely charged multi-indented lock- and spherical key-particles are investigated by means of Monte Carlo simulations at low volume fractions. The specificity of the interactions is initially investigated in an excess of either lock- or key-particles, and we find ordered clusters with highly directional bonds. This suggests electrostatics alone to be capable of inducing the assembly of specifically bound clusters. Considering different numbers of indentations and number ratios corresponding to perfect lattices (cubic/hexagonal/diamond), we however only find gel-like structures with no tendency to form dense ordered aggregates or lattices. We conjecture that the high entropic cost that comes with specific binding of several keys to a single lock impedes the spontaneous formation of defined lattices at low volume fractions and “lock” the assembly into disordered gel-like structures.
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| 8. |
- Stenqvist, Björn, et al.
(författare)
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Tortuosity in the Brick and Mortar Model Based on Chemical Conduction
- 2020
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Ingår i: Chemical Engineering Science. - : Elsevier BV. - 0009-2509. ; 223
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Tidskriftsartikel (refereegranskat)abstract
- Diffusion is a reoccurring phenomena in many fields and is affected by the geometry in which it takes place. Here we investigate the effects of geometry on diffusion in a Brick and Mortar model system. The tortuous effects are evaluated based on generalized Fick's law, i.e. diffusion driven by differences in chemical potential. The presented formalism gives a general (semi-) exact analytic expression for the tortuosity using impermeable bricks, which is successfully validated against standard techniques and finite element method results. The approach allows for anisotropic properties of the mortar, which we show can be significant and is not captured with known analytic techniques. Based on the introduced concept of chemical conductivity we also find generalized Fick's law consistent with Ohm's and Fourier's law in terms of their constituent parts, which further makes the main results for Brick and Mortar structures directly applicable to diffusion of either charge, heat, or mass.
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