Ammonium Molecules Research Articles

Electroformed Giant Vesicles from a Binary Mixture of Phospholipids and Quaternary Ammonium Salts

In this article, positively charged GVs were electroformed in a binary system of quaternary ammonium salts and egg phosphatidylcholine (EggPC) under an alternative current (AC) electric field. The diameter and charge density of the GVs is controlled by doping suitable cationic quaternary ammonium molecules into the EggPC bilayer. By developing positively charged GVs, there will be expanded the applications for phospholipids vesicles, especially the investigation of charge-induced interactions between cationic lipid membranes and macromolecules, such as colloidal particles or proteins.

Repairable mesoporous silica film with replenishing corrosion inhibitor as corrosion protection layer of aluminum alloy

Cetyltrimethylammonium bromide (CTAB) encapsulating mesoporous silica (MS) film shows strong corrosion protection property for aluminum alloy in NaCl solution. The corrosion protection capability of the MS film is reversible upon calcination or long term service and the replenishing with corrosion inhibitors. Replenishing the MS film with a quaternary ammonium bromide is molecular size selective. The corrosion protection capability of the replenished MS film is enhanced by increasing the carbon chain length of the ammonium molecule. The replenishing technique ensures the MS film as a repairable anti-corrosion film and extends its service life. The strong corrosion protection property of the MS film is attributed to its lowly porous structure and hydrophobic nature.

Improvement of the adsorption of quaternary ammonium on polypropylene affinity membrane through the control of its surface properties

Polypropylene fiber meshes were plasma-treated in order to attach new chemical functions corresponding to acidic or basic groups without altering the roughness of such thin material. An almost complete wettability of these plasma-treated materials is obtained. Because of the plasma-grafting of acid or amino moieties, such surface treatment allows increasing the adsorption rate of quaternary ammonium molecule like Aliquat 336. This increase was explained by specific interactions of ammonium head of the Aliquat 336 and hydrophilic group of plasma-treated PP, followed by the adsorption of a further layer of Aliquat 336 through hydrophobic interactions of its hydrocarbon chain. These interactions between the carrier and the polymeric surface were characterized leading to physisorption mechanism. Such new material could be applied to the extraction process since no evidence of aging was given.

Effect of Functional Group on the Monolayer Structures of Biodegradable Quaternary Ammonium Surfactants

The monolayer structures and conformational ordering of cationic surfactants including the biodegradable quaternary ammonium molecules have been systematically characterized by π-A isotherm, surface potential, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and sum frequency generation (SFG) vibrational spectroscopy. It was found that the monolayer of the typical dialkyl dimethylammonium on the water surface was less densely packed along with many conformational gauche defects. The packing density and ordering of these monolayers were improved as halide ions were added to the subphase. A similar condensation effect was also observed when amide or ester groups are present in the alkyl tails of the surfactant. These results are discussed on the basis of the repulsive electrostatic interactions between the terminal ammonium moieties, the hydrogen bonding between the functional groups in the alkyl chains, as well as the flexibility of the alkyl chains in these surfactants. The present study is crucial to understanding the relationship between the interfacial structures and the functionalities of the biodegradable quaternary ammonium surfactants.

Affinities of bispyridinium non-oxime compounds to [3H]epibatidine binding sites of Torpedo californica nicotinic acetylcholine receptors depend on linker length

The toxicity of organophosphorus nerve agents or pesticides arises from accumulation of acetylcholine and overstimulation of both muscarinic and nicotinic acetylcholine receptors (mAChRs and nAChRs) due to inhibition of acetylcholinesterase (AChE). Standard treatment by administration of atropine and oximes, e.g., obidoxime or pralidoxime, focuses on antagonism of mAChRs and reactivation of AChE, whereas nicotinic malfunction is not directly treated. An alternative approach would be to use nAChR active substances to counteract the effects of accumulated acetylcholine. Promising in vitro and in vivo results were obtained with the bispyridinium compounds SAD-128 (1,1′-oxydimethylene bis(4-tert-butylpyridinium) dichloride) and MB327 (1,1′-(propane-1,3-diyl)bis(4-tert-butylpyridinium) di(iodide)), which were partly attributed to their interaction with nAChRs. In this study, a homologous series of unsubstituted and 4-tert-butyl-substituted bispyridinium compounds with different alkane linker lengths was investigated in competition binding experiments using [3H]epibatidine as a reporter ligand. Additionally, the effect of the well-characterised MB327 on the [3H]epibatidine equilibrium dissociation (KD) constant in different buffers was determined. This study demonstrated that divalent cations increased the affinity of [3H]epibatidine. Since quaternary ammonium molecules are known to inhibit AChE, the obtained affinity constants of the tested bispyridinium compounds were compared with the inhibition of human AChE. In competition experiments, bispyridinium derivatives of longer linker length displaced [3H]epibatidine and inhibited AChE strongly. Bispyridinium compounds with short linkers, at most, have an allosteric interaction with the [3H]epibatidine binding sites and barely inhibited AChE. In dependence on alkane linker length, the bispyridinium compounds seemed to interact at different binding sites. However, the exact binding sites of the bispyridinium compounds responsible for the positive pharmacological effects have still not been identified, making predictive drug design difficult.

Electric conduction of PbBr-based layered perovskite organic–inorganic superlattice having carbazole chromophore-linked ammonium molecule as an organic layer

We have successfully prepared thin films of PbBr-based layered perovskite having hole-transporting carbazole chromophore-linked ammonium molecules as an organic layer by a simple spin-coating from the N,N-dimethylformamide solution in which the stoichiometric amount of lead bromide and carbazole-linked ammonium bromides was dissolved. Their X-ray diffraction profiles exhibited that their layer structure formed (00n)-orientation, where c-axis is perpendicular to the substrate plane. Their layer structure depended on the alkyl chain length of ammonium molecules. When methylene length of C5H10 was employed in the carbazole-linked ammonium molecules, highest orderliness of the layer structure was attained; higher-order X-ray diffraction peaks were observed in the layered perovskite films. In the layered pervskite film, in-plane conduction, namely conduction in the direction of the stacking of carbazole chromophore, was measured. For comparison, conductivity of poly(N-vinylcarbazole) (PVCBz) thin film was also measured. The conductivity of the layered perovskite thin film (1.8×10−10Scm−1 at 303K) was about three order of magnitude larger than that of the PVCBz thin film (5.3×10−14Scm−1 at 303K). Despite the much higher conductivity of the layered peroskite thin film, the activation energy of the conductivity of the layered perovskite thin film (1.44eV) was about 2.4 times larger than that of the PVCBz thin film (0.61eV). This phenomenon is probably due to difference in film morphology through considering the results of AFM observation.

Wood Protective Fungicidal Treatment: Quaternary Ammonium Molecules Grafting on Cellulose Assisted by Afterglows at Atmospheric Pressure

AbstractWood or cellulosic materials protection against fungi is possible by binding covalent molecules as quaternary ammonium compounds (QAC) on the hydroxyl reactive groups present in cellulose. This work firstly consists in the synthesis of a specific quaternary ammonium molecule containing a long aliphatic chain and an epoxide reactive group: Glycidyldimethyldodecylammonium chloride (GDDAC). Fungicidal properties of this molecule have been proven. Secondly, afterglows issued from atmospheric pressure Dielectric Barrier Discharges (DBDs), can assist QAC grafting on cellulose. The efficiency of the reaction is improved by adding a few percentage of oxygen in nitrogen DBD. Antifungal efficiency of GDDAC grafting on wood sawdust is finally shown demonstrating the great interest of such process. magnified image

Facile Synthesis of Supramolecular Ionic Polymers That Combine Unique Rheological, Ionic Conductivity, and Self‐Healing Properties

A new family of supramolecular ionic polymers is synthesized by a simple method using (di-/tri-)carboxylic acids and (di-/tri-)alkyl amines. These polymers are formed by carboxylate and ammonium molecules that are weakly bonded together by a combination of ionic and hydrogen bonds, becoming solid at room temperature. The supramolecular ionic polymers show a sharp rheological transition from a viscoelastic gel to a viscous liquid between 30 and 80 °C. This sharp viscosity decrease is responsible for an unprecedented jump in ionic conductivity of four orders of magnitude in that temperature range. As a potential application, this chemistry can be used to develop polymeric materials with self-healing properties, since it combines properties from supramolecular polymers and ionomers into the same material.

Effects of Cross Linking on the Chromatographic Nitrogen Isotope Separation

The effects of cross linking with porous cation exchange resin were studied for nitrogen isotope separation. The displacement chromatography was conducted by the resin with cross linking rang from 20% to 40%. A sharp adsorbed ammonium band was maintained for each operation. Enriched 15N isotopes with 0.93% were obtained by 20% cross linking resin and two meters chromatographic operation which started from the natural abundance of ammonium molecule. The effect of cross linking percentage on the height equivalent to a theoretical plate (HETP) was evaluated in the present work and the HETP value is proportional to the cross linking percentage. HETP value of 0.036 cm was obtained at the present system by using 20% cross linking resin.

IODINE CATALYSIS GOES GREEN

WITH JUST A PINCH of salt, a team of researchers in Japan have come up with an environmentally friendly catalyst to build 2,3-dihydrobenzofuran motifs via asymmetric oxidative cyclization of ketophenols. The team, led by Muhammet Uyanik and Kazuaki Ishihara of Nagoya University, employs iodine as a way to sidestep the toxic heavy metals normally required to build these pharmaceutically useful motifs ( Science 2010, 328, 1376). The enantioselective reaction also uses reagents that are greener than those used in previous iodine-based catalytic strategies. To create the catalyst, the team uses hydrogen peroxide or tert -butyl hydroperoxide to convert iodide into hypoiodite (IO – ) or iodite (IO 2 – ), with water as a waste product. These two anionic catalysts can’t perform asymmetric reactions without help, which comes in the form of a chiral ammonium cation, Ishihara notes. Using a variety of aromatically substituted ammonium molecules, the team was able to do the cycloetherification with enantiomeric exces...

Electron-Wavepacket Reaction Dynamics in Proton Transfer of Formamide

We apply the semiclassical Ehrenfest theory, which provides electron wavepacket dynamics coupled to nuclear motion, to a study of water-assisted proton relay in formamide compared with a forced proton transfer in gas phase, both of which are associated with the tautomerization. We start with the enol (imidic acid) form HO-CH=NH and track its proton transfer process to the keto (amide) form O=CH-NH(2). Identifying the fact that this is indeed a "proton transfer process" rather than hydrogen-atom migration in terms of radical character on the proton, we show a collective quantum flux of electrons, which flows backward against the proton motion. This backward flux compensates the electrons tightly covering the proton, as represented in the Mulliken charge. The enol form formamide is one of the simplest species in the group O=CR(1)-NHR(2), which is a unit of polypeptide. In the gas phase, the nitrogen atom may have a pyramidal structure as in the ammonium molecule; therefore, the C-N bond may allow low barrier rotation along it. This rotation is strongly prohibited by the formation of the double bond C horizontal lineN induced by the proton transfer. Not only the dynamical process of proton transfer itself but also the electronic structures left behind are greatly affected by the presence of water molecule(s) and polar solvents. In discussing the relative stability of the formamide after the proton transfer, the following resonance structures are frequently mentioned, O(-)-CH=N(+)H(2) <--> O=CH-NH(2). Here we address the dynamical manifestation of the resonance structures in terms of our dynamical electron theory.

Effect of surfactant C12TMA molecules on the self-association of R6G dye in thin films of laponite clay

The effect of the surfactant dodecyltrimethyl ammonium (C12TMA) molecules on the aggregation of rhodamine 6G (R6G) laser dye intercalated in the interlayer space of clay laponite (Lap) thin films is studied by absorption and fluorescence spectroscopies. The presence of C12TMA molecules reduces in nearly one order of magnitude the tendency of the dye molecules to self-associate. Moreover, the organophilic environment created by the surfactant molecules promotes the formation of fluorescent J-type R6G aggregates with respect to those aggregates formed in pure Lap films with a hydrophilic ambience. Consequently, the fluorescence ability of dye/clay systems is improved by the presence of surfactant molecules, mainly in those samples with moderate/high dye loadings.

Branched quaternary ammonium amphiphiles: nematic ionic liquid crystals near room temperature

Branched quaternary ammonium molecules were synthesized and characterized by calorimetric, optical and X-ray diffraction studies; two of the molecules exhibited interesting nematic liquid crystalline behavior close to room temperature.

Nanoporous Organosilicate Films Prepared in Acidic Conditions Using Tetraalkylammonium Bromide Porogens

AbstractOrganosilicate films with narrow pore size distribution tunable in the range of 1–3.4 nm were prepared by spin‐coating of silicon wafers with sols prepared in acidic conditions using tetraethyl orthosilicate, methyltrimethoxysilane, and tetraalkylammonium bromide (TAABr) porogen. The pore size was defined by the alkyl chain length of the quaternary ammonium molecule and the porogen concentration. The pore network in the films and the hydrophobicity of the pore surfaces were characterized using ellipsometric porosimetry with toluene and water adsorbates. In the absence of TAABr, the pore volume was 9 vol% and the pore size 1 nm. By using TAABr porogens, monomodal pore size distributions were obtained in the range of 1.2–3.5 nm. The pore volume was in the range from 18 vol% at 1.2 nm pore diameter up to 54 vol% at 3.5 nm diameter. The hydrophobicity of the pores was dependent on the pore diameter, with smaller pores being the least hydrophobic. The increase of hydrophobicity with pore size was explained by an increased distance between silanol groups on the curved pore surfaces. The mechanical properties and dielectric constant of these films were comparable to reference materials prepared using more sophisticated porogens reported in the literature.

Structure, stability, and infrared spectroscopy of (H2O)nNH4+ clusters: A theoretical study at zero and finite temperature

The combined effects of size and temperature on the stable structures of water clusters doped with one ammonium molecule have been investigated theoretically using an empirical potential and density-functional theory (DFT) calculations. Global optimization with Monte Carlo methods has been performed using an explicit intermolecular potential based on the Kozack-Jordan polarizable model. Putative lowest-energy structures based on this empirical potential are reported. Our results indicate a high propensity for the NH(4)(+) impurity to be fully solvated by water molecules. Clathratelike patterns are formed for clusters containing more than 11 molecules. Local reoptimizations of candidate structures carried out at the DFT level with the B3LYP hybrid functional and the 6-311++G(d,p) basis set confirm the general trends obtained with the intermolecular potential. However, some reorderings between isomers often due to zero-point energy corrections are found in small clusters, leading to stable geometries in agreement with other first-principles studies. Temperature effects have been assessed using a simple harmonic superposition approximation for selected cluster sizes and using dedicated Monte Carlo simulations for (H(2)O)(20)NH(4)(+). The clusters are found to melt near 200 K, and possibly isomerize already below 50 K. The free energy barrier for core/surface isomerization of the impurity in the 21-molecule cluster is estimated to be only a few kcal/mol at 150 K. The vibrational spectroscopic signatures of the clusters obtained from the electronic structure calculations show the usual four O-H stretching bands. As the cluster size increases, the double acceptor-single donor band near 3700 cm(-1) increasingly dominates over the three other bands. While we do not find conclusive evidence for a O-H stretching spectroscopic signature of the ammonium impurity to be in the core or at the surface in the 20-molecule cluster, a possible signature via the N-H stretching bands is suggested near 2800-2900 cm(-1). In the larger (H(2)O)(49)NH(4)(+) cluster, the impurity is slightly more stable at the surface.

Quantized detector networks, particle decays and the quantum Zeno effect

Quantized detector networks (QDN) deal with observers and their apparatus rather than with systems under observation. QDN can be used to investigate the detailed structure of particle decays and the quantum Zeno effect without assuming temporal continuity or invoking non-Hermitian Hamiltonians or complex energies. The formalism is applied to single channel decays, the ammonium molecule and neutral Kaon and B meson decays.

A Priori Phase Prediction of Zeolites: Case Study of the Structure-Directing Effects in the Synthesis of MTT-Type Zeolites

This study first uses molecular modeling to examine the structure-directing effects of small amines that are selective for the crystallization of MTT-type zeolite phases. The optimized van der Waals interactions of these small amines are compared within the one-dimensional pore zeolites with the MTT, TON, and MTW frameworks. From these results and our previous molecular modeling studies of structure-directing agents (SDA) for MTT-type zeolites, a large number of amines or quaternary ammonium molecules are successfully predicted to be selective for MTT phases. These molecules were chosen by matching the crystallographic periodicity of the pore structure with the distances between the centers of branched groups in these molecules. These molecules vary in length and in the number of branched moieties, and a few of these molecules are polymeric or oligomeric. In test cases where the distances between the branched groups are not multiples of the pore periodicity, with few exceptions these molecules usually do not produce MTT phases. Finally, we discuss the inorganic conditions necessary for crystallization of MTT phases in borosilicate preparations with some of the diamines in this investigation.

State-independent Block of BK Channels by an Intracellular Quaternary Ammonium

Intracellular blockade by quaternary ammonium (QA) molecules of many potassium channels is state dependent, where the requirement for channel opening is evidenced by a time-dependent component of block in the macroscopic record. Whether this is the case for Ca2+- and voltage-activated potassium (BK) channels, however, remains unclear. Previous work (Li, W., and R.W. Aldrich. 2004. J. Gen. Physiol. 124:43–57) tentatively proposed a state-dependent, trapping model, but left open the possibility of state-independent block. Here, we found BK channel blockade by a novel QA derivative, bbTBA, was time dependent, raising the possibility of state-dependent, open channel block. Alternatively, the observed voltage dependence of block could be sufficient to explain time-dependent block. We have used steady-state and kinetic measurements of bbTBA blockade in order to discriminate between these two possibilities. bbTBA did not significantly slow deactivation kinetics at potentials between −200 and −100 mV, suggesting that channels can close unhindered by bound bbTBA. We further find no evidence that bbTBA is trapped inside BK channels after closing. Measurements of steady state fractional block at +40 mV revealed a 1.3-fold change in apparent affinity for a 33-fold change in Po, in striking contrast to the 31-fold change predicted by state-dependent block. Finally, the appearance of a third kinetic component of bbTBA blockade at high concentrations is incompatible with state-dependent block. Our results suggest that access of intracellular bbTBA to the BK channel cavity is not strictly gated by channel opening and closing, and imply that the permeation gate for BK channels may not be intracellular.

Rietveld structure refinement of NH4-exchanged natural chabazite

In this work the results of the X-ray Rietveld structure refinement of a natural and the corresponding NH 4 -exchanged chabazite from Nova Scotia (Canada) are exposed. Experimental data were collected using a laboratory powder diffractometer equipped with copper tube and graphite crystal monochromator. The outcome of this crystal-structure study is useful for (i) understanding the structure modifications induced by the NH 4 + exchange; (ii) understanding the physical-chemical and technological properties of NH 4 -chabazite, a zeolite vastly used for industrial applications; (iii) understanding the mechanism of proton conductivity of the NH 4 -exchanged zeolites, precursors of catalytically active H + forms. The position and orientation of the NH 4 + ion were initially refined using the rigid body model and later with the aid of soft constraints. The coordination number of the ammonium ion is 9 with two equally possible and mutually exclusive configurations. One coordination environment includes 3 oxygen atoms O3, 3 oxygen atoms O4, and 3 H 2 O molecules W2a. The other environment includes 3 oxygen atoms O3, 3 oxygen atoms O4, and 3 H 2 O molecules W3. As already shown for other NH 4 -zeolites, the N-O distances are larger than the N-H 2 O distances. The local geometry of the ammonium ion points to a monodentate configuration. A bidentate configuration of the hydrogen bonds for NH 4 + is also possible if the long H2…O3 separation is considered to be at bond distance. For industrial and technological applications, knowledge of the local environment of NH 4 + in the cavities of zeolites is important. Weak hydrogen bonds with framework oxygen atoms implies that the ammonium molecule can be easily exchanged or desorbed. This property is attractive for agronomy, horticulture and soil remediation where zeolite can be added to chemical fertilizers to improve the soil9s chemical and physical properties for plant growth, to increase fertilizer efficiency and to reduce the leaching of nutrients, to reduce the dissolution rate of a soluble fertilizer via ion exchange or combination of mineral dissolution and ion exchange, and to act as remediation agents in soils.

On the Dissociation of Methyl Orange: Spectrophotometric Investigation in Aqueous Solutions from 10 to 90 ∘C and Theoretical Evidence for Intramolecular Dihydrogen Bonding

The dissociation of methyl orange was investigated by spectrophotometry in aqueous solutions from 10 to 90 ∘C and by quantum chemical calculations. Combined chemometric and thermodynamic analyses of the spectrophotometric data were used to simultaneously extract the thermodynamic stabilities and the spectrophotometric attributes of the dominant methyl orange species in solutions containing less than 20.00 mmol-kg−1 perchloric acid and submillimolal concentrations of methyl orange. The analyses revealed the presence of only one monomeric deprotonated and one monomeric protonated species. The spectra did not reveal any evidence for the presence of tautomeric equilibria between the protonated azo and ammonium species in the experimental range studied. Thermodynamic analyses of the temperature-dependent dissociation constants showed the reactions to be endothermic and enthalpy driven with increasing acidity and increasing temperature. All molar absorption coefficients in the 275–375 nm range can be adequately reproduced in the 10–90 ∘C range with a set of Gauss–Lorentz parameters and used to predict the absorption spectra for any desired condition. The dominant features of the spectrophotometric attributes of the methyl orange species could also be retrieved in Time Dependent–Density Functional Theory (TD–DFT) calculations. Topological analyses of the electron density also revealed the formation of a dihydrogen bond between the azo proton and an adjacent phenyl ring hydridic hydrogen which increases the stability of the azo molecules relative to the ammonium molecule.