scholarly journals Measuring anion binding at biomembrane interfaces

Author(s):  
Xin Wu ◽  
Patrick Wang ◽  
William Lewis ◽  
Yun-Bao Jiang ◽  
Philip Alan Gale

Understanding non-covalent molecular recognition events at biomembrane interfaces is important in biological, medicinal, and materials chemistry research.1 Despite the crucial regulatory roles of anion binding/transport processes at biomembranes, no information is available regarding how strongly anions can bind to naturally occurring or synthetic receptors in lipid bilayer environments compared to their well-established behaviour in solutions.2 To bridge this knowledge gap, we synthesised a flat macrocycle that possesses a record aqueous SO42– affinity among neutral receptors and exploited its unique fluorescence response at interfaces. We show that the determinants of anion binding are extraordinarily different in organic solvents and in lipid bilayers. The high charge density of dihydrogen phosphate and chloride ions prevails in DMSO, however in lipids they fail to bind the macrocycle. Perchlorate and iodide hardly bind in DMSO but show significant affinities for the macrocycle in lipids. Our results demonstrate a surprisingly great advantage of large, charge-diffuse anions to bind to a lipid-embedded synthetic receptor mainly attributed to their higher polarisabilities and deeper penetration into the bilayer, beyond the common knowledge of dehydration energy-governed selectivity. The elucidation of these principles enhances our understanding of biological anion recognition functions in membranes and guides the design of ionophores and molecular machines operating at biomembrane interfaces.

2021 ◽  
Author(s):  
Xin Wu ◽  
Patrick Wang ◽  
William Lewis ◽  
Yun-Bao Jiang ◽  
Philip Alan Gale

Understanding non-covalent molecular recognition events at biomembrane interfaces is important in biological, medicinal, and materials chemistry research.1 Despite the crucial regulatory roles of anion binding/transport processes at biomembranes, no information is available regarding how strongly anions can bind to naturally occurring or synthetic receptors in lipid bilayer environments compared to their well-established behaviour in solutions.2 To bridge this knowledge gap, we synthesised a flat macrocycle that possesses a record aqueous SO42– affinity among neutral receptors and exploited its unique fluorescence response at interfaces. We show that the determinants of anion binding are extraordinarily different in organic solvents and in lipid bilayers. The high charge density of dihydrogen phosphate and chloride ions prevails in DMSO, however in lipids they fail to bind the macrocycle. Perchlorate and iodide hardly bind in DMSO but show significant affinities for the macrocycle in lipids. Our results demonstrate a surprisingly great advantage of large, charge-diffuse anions to bind to a lipid-embedded synthetic receptor mainly attributed to their higher polarisabilities and deeper penetration into the bilayer, beyond the common knowledge of dehydration energy-governed selectivity. The elucidation of these principles enhances our understanding of biological anion recognition functions in membranes and guides the design of ionophores and molecular machines operating at biomembrane interfaces.


2021 ◽  
Author(s):  
Xin Wu ◽  
Patrick Wang ◽  
William Lewis ◽  
Yun-Bao Jiang ◽  
Philip Alan Gale

Understanding non-covalent molecular recognition events at biomembrane interfaces is important in biological, medicinal, and materials chemistry research.1 Despite the crucial regulatory roles of anion binding/transport processes at biomembranes, no information is available regarding how strongly anions can bind to naturally occurring or synthetic receptors in lipid bilayer environments compared to their well-established behaviour in solutions.2 To bridge this knowledge gap, we synthesised a flat macrocycle that possesses a record aqueous SO42– affinity among neutral receptors and exploited its unique fluorescence response at interfaces. We show that the determinants of anion binding are extraordinarily different in organic solvents and in lipid bilayers. The high charge density of dihydrogen phosphate and chloride ions prevails in DMSO, however in lipids they fail to bind the macrocycle. Perchlorate and iodide hardly bind in DMSO but show significant affinities for the macrocycle in lipids. Our results demonstrate a surprisingly great advantage of large, charge-diffuse anions to bind to a lipid-embedded synthetic receptor mainly attributed to their higher polarisabilities and deeper penetration into the bilayer, beyond the common knowledge of dehydration energy-governed selectivity. The elucidation of these principles enhances our understanding of biological anion recognition functions in membranes and guides the design of ionophores and molecular machines operating at biomembrane interfaces.


eLife ◽  
2021 ◽  
Vol 10 ◽  
Author(s):  
Benjamin C McIlwain ◽  
Roja Gundepudi ◽  
B Ben Koff ◽  
Randy B Stockbridge

Fluc family fluoride channels protect microbes against ambient environmental fluoride by undermining the cytoplasmic accumulation of this toxic halide. These proteins are structurally idiosyncratic, and thus the permeation pathway and mechanism have no analogy in other known ion channels. Although fluoride binding sites were identified in previous structural studies, it was not evident how these ions access aqueous solution, and the molecular determinants of anion recognition and selectivity have not been elucidated. Using x-ray crystallography, planar bilayer electrophysiology and liposome-based assays, we identify additional binding sites along the permeation pathway. We use this information to develop an oriented system for planar lipid bilayer electrophysiology and observe anion block at one of these sites, revealing insights into the mechanism of anion recognition. We propose a permeation mechanism involving alternating occupancy of anion binding sites that are fully assembled only as the substrate approaches.


Heterocycles ◽  
2019 ◽  
Vol 98 (4) ◽  
pp. 551
Author(s):  
Quan Gan ◽  
Guoping Li ◽  
Jiulong Li ◽  
Chaocao Lu ◽  
Bu Htan ◽  
...  

2000 ◽  
Vol 6 (4) ◽  
pp. 415-428
Author(s):  
O. Wowra ◽  
M.J. Setzer

Abstract Besides the formation of Friedel salt the transport and binding of chlorides in concrete is mainly defined by the electrochemical double layer at the interface between cement matrix and pore solution. Due to the alkaline pore solution the surface of hardened cement paste is negatively charged which may change to positive values by the potential regulating calcium ions. Inverting of the surface charge leads to an attraction of anions and therefore, to an adsorption of chloride ions in the diffuse part of the electrochemical double layer. Influence from outside like sulphates and carbon dioxide may lead to a decomposition of Friedel salt. Apart from these effect temperature, pH-value and certain environmental conditions affects the electrochemical double layer as well. The chloride equilibrium is mainly controlled by adsorbed ions in the electrochemical double layer. The model presented here is relevant for the assessment of ion transport processes in mineral building materials. Continuing investigations may lead to optimize transport models and a better evaluation of the critical chloride threshold value in reinforced concrete.


Molecules ◽  
2019 ◽  
Vol 24 (9) ◽  
pp. 1807 ◽  
Author(s):  
Alena Khadieva ◽  
Vladimir Gorbachuk ◽  
Dmitriy Shurpik ◽  
Ivan Stoikov

A multicyclophane with a core based on tris(2-aminoethyl)amine (TREN) linked by amide spacers to three fragments of pillar[5]arene was synthesized. The choice of the tris-amide core allowed the multicyclophane to bind to anion guests. The presence of three terminal pillar[5]arene units provides the possibility of effectively binding the colorimetric probe N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine (PhTz). It was established that the multicyclophane complexed PhTz in chloroform with a 1:1 stoichiometry (lgKa = 5.2 ± 0.1), absorbing at 650 nm. The proposed structure of the complex was confirmed by 1H-NMR spectroscopy: the amide group linking the pillar[5]arene to the TREN core forms a hydrogen bond with the PhTz imino-group while the pillararenes surround PhTz. It was established that the PhTz:tris-pillar[5]arene complex could be used as a colorimetric probe for fluoride, acetate, and dihydrogen phosphate anions due to the anion binding with proton donating amide groups which displaced the PhTz probe. Dye displacement resulted in a color change from blue to pink, lowering the absorption band at 650 nm and increasing that at 533 nm.


2019 ◽  
Vol 90 (2) ◽  
pp. 024106 ◽  
Author(s):  
Evan P. Jahrman ◽  
William M. Holden ◽  
Alexander S. Ditter ◽  
Devon R. Mortensen ◽  
Gerald T. Seidler ◽  
...  

Author(s):  
Michael D. Morris ◽  
Kenneth A. Christensen ◽  
Nancy L. Bradley

Recent technological advances including high spectral resolution liquid-crystal tunable filters and high-transmission well-corrected imaging spectrographs have made Raman microscopy a practical technique for study of real-world chemical systems. With modem multivariate signal processing techniques, such as image reconstruction and principal components analysis (PCA) detailed information can be obtained from sets of relatively noisy images or spectra. In this talk we discuss techniques and results in two areas of materials chemistry: crystallization and freeze-drying mechanisms of alkali phosphates and strengthening mechanisms of glasses employed in dental restoration.We employ Raman microspectroscopy to elucidate the structure of aqueous phosphates in solutions ranging in concentration from dilute to supersaturated. PCA of the concentration-dependent spectra of dihydrogen phosphate solutions unambiguously demonstrates the presence of at least three species, monomer, dimer and trimer or short polymer (Figure 1). PCA resolves long-standing disputes over the number and relative concentration of dihydrogen phosphate species PCA can to identify the spectrally unresolved solution species near the surface of a growing dihydrogen phosphate crystal.


2011 ◽  
Vol 138 (2) ◽  
pp. 249-270 ◽  
Author(s):  
Radda Rusinova ◽  
Karl F. Herold ◽  
R. Lea Sanford ◽  
Denise V. Greathouse ◽  
Hugh C. Hemmings ◽  
...  

The thiazolidinediones (TZDs) are used in the treatment of diabetes mellitus type 2. Their canonical effects are mediated by activation of the peroxisome proliferator–activated receptor γ (PPARγ) transcription factor. In addition to effects mediated by gene activation, the TZDs cause acute, transcription-independent changes in various membrane transport processes, including glucose transport, and they alter the function of a diverse group of membrane proteins, including ion channels. The basis for these off-target effects is unknown, but the TZDs are hydrophobic/amphiphilic and adsorb to the bilayer–water interface, which will alter bilayer properties, meaning that the TZDs may alter membrane protein function by bilayer-mediated mechanisms. We therefore explored whether the TZDs alter lipid bilayer properties sufficiently to be sensed by bilayer-spanning proteins, using gramicidin A (gA) channels as probes. The TZDs altered bilayer elastic properties with potencies that did not correlate with their affinity for PPARγ. At concentrations where they altered gA channel function, they also altered the function of voltage-dependent sodium channels, producing a prepulse-dependent current inhibition and hyperpolarizing shift in the steady-state inactivation curve. The shifts in the inactivation curve produced by the TZDs and other amphiphiles can be superimposed by plotting them as a function of the changes in gA channel lifetimes. The TZDs’ partition coefficients into lipid bilayers were measured using isothermal titration calorimetry. The most potent bilayer modifier, troglitazone, alters bilayer properties at clinically relevant free concentrations; the least potent bilayer modifiers, pioglitazone and rosiglitazone, do not. Unlike other TZDs tested, ciglitazone behaves like a hydrophobic anion and alters the gA monomer–dimer equilibrium by more than one mechanism. Our results provide a possible mechanism for some off-target effects of an important group of drugs, and underscore the importance of exploring bilayer effects of candidate drugs early in drug development.


2006 ◽  
Vol 985 ◽  
Author(s):  
Ivan Escobar ◽  
Claudia Lamas ◽  
Lars Werme ◽  
Virginia Oversby

AbstractCopper of the quality oxygen free and high conductivity, doped with phosphorus (Cu OFP) has been chosen as the material for the fabrication of high level nuclear waste containers in Sweden. This material will be the corrosion barrier for spent fuel in the environment of a deep geological repository. It is planned that the service life of this container will be 100,000 years. During this time water with high concentration of chloride ions might come in contact with the copper surface. If pH conditions are appropriate, this might cause pitting corrosion. This work reports a study of the susceptibility of Cu OFP to corrosion when chloride ions are present, both deionized water (DW) and in standard synthetic underground water (SUW). The techniques used were electrochemical methods such as corrosion potential evolution and Tafel curves. In addition, this system was studied with Electrochemical Impedance Spectroscopy (EIS). We also used characterization techniques such as Scanning Electronic Microscopy (SEM), Energy Disperse Spectroscopy (EDS) . The main conclusions are that copper is more susceptible to corrosion at high chloride ion concentration. Additionally, when the chloride concentration is low, it is possible to form copper chloride crystals, but at the highest concentration, copper chloride complexes are formed, leaving the copper surface without deposits. When the chloride concentration is low (<0.1 M) the corrosion process is mainly controlled by diffusion, while at higher concentrations (0.1M to 1M) corrosion is controlled by transport processes. At low concentration of sulfide ( <3*10-5M), copper corrosion in the presence of chloride is controlled by diffusional processes.


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