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Title: Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates

Abstract

The crystal structures of the hydrated cationic surfactant benzethonium (Bzth) chloride, bromide, hydroxide, and citrate have been determined by X-ray diffraction analysis and compared with their structures in solution well above their critical micelle concentration. The differences in the nature of the various anions of the four Bzth-X materials lead to unique anion environments and 3-D molecular arrangements. The water molecule in the monoclinic Bzth-Cl or Bzth-Br forms is hydrogen bonded to the halides and particularly to the hydrogens of the methoxy groups of the Bzth moiety notwithstanding the weak Brønsted acidity of the methoxy hydrogens. The citrate strongly interacts with the hydrogens of the methoxy group forming an embedded anionic spherical cluster of a radius of 2.6 Å. The Bzth-OH crystallizes in a hexagonal lattice with two water molecules and reveals free water molecules forming hydrogen bonded channels through the Bzth-OH crystal along the c-axis. The distances between the cationic nitrogen and the halides are 4.04 Å and 4.20 Å, significantly longer than expected for typical van der Waals distances of 3.30 Å. The structures show weakly interacting, alternating apolar and polar layers, which run parallel to the crystallographic a-b planes or a-c planes. The Bzth-X salts were alsomore » examined in aqueous solution containing 20% (v/v) ethanol and 1.0 % (v/v) glycerol well above their critical micelle concentration by small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The [1,1,1] planes for the Bzth Cl or Br, the [0,0,2] and [1,1,0] planes for the Bzth-citrate, the [2,-1,0] planes and the [0,0,1] planes for the Bzth-OH found in the crystalline phase were also present in the solution phase, accordingly, the preservation of these phases are a strong indication of periodicity in the solution phase.« less

Authors:
 [1];  [2];  [1]
  1. The University of Salford, Joule Physics Laboratory, Faculty of Science, Engineering and Environment, Manchester M5 4 WT (United Kingdom)
  2. (Germany)
Publication Date:
OSTI Identifier:
22611574
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Advances; Journal Volume: 6; Journal Issue: 6; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANIONS; AQUEOUS SOLUTIONS; BROMIDES; CHLORIDES; CITRATES; CONCENTRATION RATIO; CRYSTALLOGRAPHY; CRYSTALS; ETHANOL; GLYCEROL; HEXAGONAL LATTICES; HYDRATES; HYDROXIDES; LAYERS; MONOCLINIC LATTICES; NITROGEN; SMALL ANGLE SCATTERING; SOLIDS; VAN DER WAALS FORCES; X-RAY DIFFRACTION

Citation Formats

Paradies, Henrich H., E-mail: hparadies@aol.com, E-mail: hparadies@jacobs-university.de, Jacobs University Bremen, Life Sciences and Chemistry Department, Campus Ring 1, D-28759 Bremen, and Reichelt, Hendrik. Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates. United States: N. p., 2016. Web. doi:10.1063/1.4954882.
Paradies, Henrich H., E-mail: hparadies@aol.com, E-mail: hparadies@jacobs-university.de, Jacobs University Bremen, Life Sciences and Chemistry Department, Campus Ring 1, D-28759 Bremen, & Reichelt, Hendrik. Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates. United States. doi:10.1063/1.4954882.
Paradies, Henrich H., E-mail: hparadies@aol.com, E-mail: hparadies@jacobs-university.de, Jacobs University Bremen, Life Sciences and Chemistry Department, Campus Ring 1, D-28759 Bremen, and Reichelt, Hendrik. 2016. "Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates". United States. doi:10.1063/1.4954882.
@article{osti_22611574,
title = {Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates},
author = {Paradies, Henrich H., E-mail: hparadies@aol.com, E-mail: hparadies@jacobs-university.de and Jacobs University Bremen, Life Sciences and Chemistry Department, Campus Ring 1, D-28759 Bremen and Reichelt, Hendrik},
abstractNote = {The crystal structures of the hydrated cationic surfactant benzethonium (Bzth) chloride, bromide, hydroxide, and citrate have been determined by X-ray diffraction analysis and compared with their structures in solution well above their critical micelle concentration. The differences in the nature of the various anions of the four Bzth-X materials lead to unique anion environments and 3-D molecular arrangements. The water molecule in the monoclinic Bzth-Cl or Bzth-Br forms is hydrogen bonded to the halides and particularly to the hydrogens of the methoxy groups of the Bzth moiety notwithstanding the weak Brønsted acidity of the methoxy hydrogens. The citrate strongly interacts with the hydrogens of the methoxy group forming an embedded anionic spherical cluster of a radius of 2.6 Å. The Bzth-OH crystallizes in a hexagonal lattice with two water molecules and reveals free water molecules forming hydrogen bonded channels through the Bzth-OH crystal along the c-axis. The distances between the cationic nitrogen and the halides are 4.04 Å and 4.20 Å, significantly longer than expected for typical van der Waals distances of 3.30 Å. The structures show weakly interacting, alternating apolar and polar layers, which run parallel to the crystallographic a-b planes or a-c planes. The Bzth-X salts were also examined in aqueous solution containing 20% (v/v) ethanol and 1.0 % (v/v) glycerol well above their critical micelle concentration by small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The [1,1,1] planes for the Bzth Cl or Br, the [0,0,2] and [1,1,0] planes for the Bzth-citrate, the [2,-1,0] planes and the [0,0,1] planes for the Bzth-OH found in the crystalline phase were also present in the solution phase, accordingly, the preservation of these phases are a strong indication of periodicity in the solution phase.},
doi = {10.1063/1.4954882},
journal = {AIP Advances},
number = 6,
volume = 6,
place = {United States},
year = 2016,
month = 6
}
  • Tetra-n-octylammonium bromide and benzethonium chloride are synthetic quaternary ammonium salts that are widely used in hospitals and industries for the disinfection and surface treatment and as the preservative agent. Recently, the activities of HERG channel inhibition by these compounds have been found to have potential risks to induce the long QT syndrome and cardiac arrhythmia, although the mechanism of action is still elusive. This study was conducted to investigate the mechanism of HERG channel inhibition by these compounds by using whole-cell patch clamp experiments in a CHO cell line stably expressing HERG channels. Tetra-n-octylammonium bromide and benzethonium chloride exhibited concentration-dependentmore » inhibitions of HERG channel currents with IC{sub 50} values of 4 nM and 17 nM, respectively, which were also voltage-dependent and use-dependent. Both compounds shifted the channel activation I–V curves in a hyperpolarized direction for 10–15 mV and accelerated channel activation and inactivation processes by 2-fold. In addition, tetra-n-octylammonium bromide shifted the inactivation I–V curve in a hyperpolarized direction for 24.4 mV and slowed the rate of channel deactivation by 2-fold, whereas benzethonium chloride did not. The results indicate that tetra-n-octylammonium bromide and benzethonium chloride are open-channel blockers that inhibit HERG channels in the voltage-dependent, use-dependent and state-dependent manners. - Highlights: ► Tetra-n-octylammonium and benzethonium are potent HERG channel inhibitors. ► Channel activation and inactivation processes are accelerated by the two compounds. ► Both compounds are the open-channel blockers to HERG channels. ► HERG channel inhibition by both compounds is use-, voltage- and state dependent. ► The in vivo risk of QT prolongation needs to be studied for the two compounds.« less
  • Absorption spectra of dilute Ni 2+ centers in melts of CsCl, RbCl, KCl, NaCl, LiCl, MgCl 2, CsBr, KBr, and LiBr were measured in the near-infrared, visible, and, in a few instances, ultraviolet regions. Substantial differences were found in these spectra which correlated with the size of the cations in the solvent salts. The coordination geometry of halides about nickel in CsCl, CsBr, RbCl, KCl, and KBr melts was identified from the spectra as distorted tetrahedral. Coordination geometry in the remaining melts was uncertain. The spectrum for MgCl 2 as solvent was very similar to that for LiCl as solvent.
  • The lithium and sodium ion pairs of the alkali-metal derivatives of 9-aryloxy-fluorenes (aryl = phenyl, p-tolyl, p-chlorophenyl, and p-bromophenyl) in 1,2-dimethoxyethane are of the solvent-separated type, and the cesium and tetra-phenylarsonium ion pairs are of the intimate type. With K/sup +/ the carbanions of 9-aryloxyfluorenes form both loose and intimate ion pairs. The dissociation constants of both the lithium and the cesium salts hardly depend at all on the substituent at the para position of the phenyl group; in the presence of Li/sup +/ they vary in the range of (5.7-6.6) x 10/sup -6/ liter/mole, and in the presence ofmore » Cs/sup +/ they vary in the range of (4.3-5.0) x 10/sup -7/ liter/mole. The rate constants were determined for the alkylation of the carbanions of 9-aryloxyfluorenes and their lithium and cesium ion pairs by butyl bromide.« less