Proton Counterflow Research Articles

Nickel (II) Preconcentration and Speciation Analysis During Transport from Aqueous Solutions Using a Hollow-fiber Permeation Liquid Membrane (HFPLM) Device.

Nickel (II) preconcentration and speciation analysis using a hollow fiber supported liquid membrane (HFSLM) device was studied. A counterflow of protons coupled to complexation with formate provided the driving force of the process, while Kelex 100 was employed as carrier. The influence of variables related to module configuration (acceptor pH and carrier concentration) and to the sample properties (donor pH) on the preconcentration factor, E, was simultaneously studied and optimized using a 3 factor Doehlert matrix response surface methodology. The effect of metal concentration was studied as well. Preconcentration factors as high as 4240 were observed depending on the values of the different variables. The effects of the presence of inorganic anions (NO2−, SO42−, Cl−, NO3−, CO32−, CN−) and dissolved organic matter (DOM) in the form of humic acids were additionally considered in order to carry out a speciation analysis study. Nickel preconcentration was observed to be independent of both effects, except when cyanide was present in the donor phase. A characterization of the transport regime was performed through the analysis of the dependence of E on the temperature. E increases with the increase in temperature according to the equation E(K) = −8617.3 + 30.5T with an activation energy of 56.7 kJ mol−1 suggesting a kinetic-controlled regime. Sample depletion ranged from 12 to 1.2% depending on the volume of the donor phase (100 to 1000 mL, respectively).

Applicability of a liquid membrane in enrichment and determination of nickel traces from natural waters

In this work, a bulk liquid membrane method has been applied for Ni enrichment and separation from natural waters. The carrier-mediated transport was accomplished by pyridine-2-acetaldehyde benzoylhydrazone dissolved in toluene as a complexing agent. The preconcentration was achieved through pH control of source and receiving solutions via a counterflow of protons. The main variables were optimized by using a modified simplex technique. High transport efficiencies (101.2 +/- 1.8-99.7 +/- 4.2%) were provided by the carrier for nickel ions in a receiving phase of 0.31 mol L(-1) nitric acid after 9-13 h depending on sample salinity. The precision of the method was 2.05% (without a saline matrix) and 4.04% (with 40 g L(-1) NaCl) at the 95% confidence level and the detection limit of the blank was 0.015 mug L(-1) Ni for detection by atomic absorption spectroscopy. The applicability of the method was tested on certified reference and real water samples with successful results, even for saline samples. The relative errors were -0.60% for certified reference materials and ranged from -0.39 to 2.90% and from 0.3 to 11.05% for real samples, obtained by comparison of inductively coupled plasma mass spectrometry and adsorptive cathodic stripping voltammetry measurements, respectively.

Selective transport of copper(II) ions across a liquid membrane mediated by Piroxicam

Piroxicam was found to be a highly selective carrier for uphill transport of Cu2+ ions through a chloroform liquid membrane. The transport occurs via a counterflow of protons from the receiving phase to the source phase. The effects of several parameters on the transport of Cu2+ ions, such as the carrier concentration, pH of the source phase, composition of the receiving phase, and duration are described. A high transport efficiency (98+/-2%) was provided by the carrier for Cu2+ ions in a receiving phase of 0.01 mol l(-1) sulfuric acid after 4 h. Different metal ion transport experiments showed that Cu2+ ions were selectively transported over other ions, such as Co2+, Ni2+, Cd2+, Pb2+, Zn2+, UO2(2+) and ZrO2(2+) . In the presence of fluoride ions (used as a suitable masking agent in the source phase), the interfering effects of UO2(2+) and ZrO2(2+) ions were eliminated. The applicability of the method was tested on a real sample, and the results obtained show that it is potentially useful for solvent extraction of copper.

Coherent Curvature Radiation and Proton Counterflow in the Pulsar Magnetosphere

In the proton counterflow model of a pulsar magnetosphere that we have recently proposed, nonrelativistic protons are supplied from the magnetosphere to flow toward the pulsar surface and screen an electric field above the polar cap region. In this Letter, we show that the proton counterflow is also suitable for the bunching of pair plasma. The two-stream instability is easily excited and can produce bunches of pairs with a relevant length scale to emit coherent curvature radiation.

Electric field screening by a proton counterflow in the pulsar polar cap

We propose a new mechanism to screen the electric field in the pulsar polar cap. Previous studies have shown that if an electron beam from the stellar surface is accelerated to energies high enough to create electron-positron pairs, the required electric field parallel to the magnetic field lines is too strong to be screened out by the produced pairs. We argue here that if non-relativistic protons are supplied from the magnetosphere to flow towards the stellar surface, they can provide an anode to screen out such a strong electric field. Injected electron-positron pairs yield an asymmetry of the electrostatic potential around the screening point. The required pair creation rate in this model is consistent with the conventional models.

Characterization of Schizosaccharomyces pombe malate permease by expression in Saccharomyces cerevisiae.

In Saccharomyces cerevisiae, L-malic acid transport is not carrier mediated and is limited to slow, simple diffusion of the undissociated acid. Expression in S. cerevisiae of the MAE1 gene, encoding Schizosaccharomyces pombe malate permease, markedly increased L-malic acid uptake in this yeast. In this strain, at pH 3.5 (encountered in industrial processes), L-malic acid uptake involves Mae1p-mediated transport of the monoanionic form of the acid (apparent kinetic parameters: Vmax = 8.7 nmol/mg/min; Km = 1.6 mM) and some simple diffusion of the undissociated L-malic acid (Kd = 0.057 min(-1)). As total L-malic acid transport involved only low levels of diffusion, the Mae1p permease was further characterized in the recombinant strain. L-Malic acid transport was reversible and accumulative and depended on both the transmembrane gradient of the monoanionic acid form and the DeltapH component of the proton motive force. Dicarboxylic acids with stearic occupation closely related to L-malic acid, such as maleic, oxaloacetic, malonic, succinic and fumaric acids, inhibited L-malic acid uptake, suggesting that these compounds use the same carrier. We found that increasing external pH directly inhibited malate uptake, resulting in a lower initial rate of uptake and a lower level of substrate accumulation. In S. pombe, proton movements, as shown by internal acidification, accompanied malate uptake, consistent with the proton/dicarboxylate mechanism previously proposed. Surprisingly, no proton fluxes were observed during Mae1p-mediated L-malic acid import in S. cerevisiae, and intracellular pH remained constant. This suggests that, in S. cerevisiae, either there is a proton counterflow or the Mae1p permease functions differently from a proton/dicarboxylate symport.

Definitive assignment of proton selectivity and attoampere unitary current to the M2 ion channel protein of influenza A virus.

The viral ion channel protein M2 supports the transit of influenza virus and its glycoproteins through acidic compartments of the cell. M2 conducts endosomal protons into the virion to initiate uncoating and, by equilibrating the pH at trans-Golgi membranes, preserves the native conformation of acid-sensitive viral hemagglutinin. The exceptionally low conductance of the M2 channel thwarted resolution of single channels by electrophysiological techniques. Assays of liposome-reconstituted M2 yielded the average unitary channel current of the M2 tetramer--1.2 aA (1.2 x 10(-18) A) at neutral pH and 2.7 to 4.1 aA at pH 5.7--which activates the channel. Extrapolation to physiological temperature predicts 4.8 and 40 aA, respectively, and a unitary conductance of 0.03 versus 0.4 fS. This minute activity, below previous estimates, appears sufficient for virus reproduction, but low enough to avert abortive cytotoxicity. The unitary permeability of M2 was within the range reported for other proton channels. To address the ion selectivity of M2, we exploited the coupling of ionic influx and efflux in sealed liposomes. Metal ion fluxes were monitored by proton counterflow, employing a pH probe 1,000 times more sensitive than available Na+ or K+ probes. Even low-pH-activated M2 did not conduct Na+ and K+. The proton selectivity of M2 was estimated to be at least 3 x 10(6) (over sodium or potassium ions), in agreement with electrophysiological studies. The stringent proton selectivity of M2 suggests that the cytopathology of influenza virus does not involve direct perturbation of cellular sodium or potassium gradients.

Magnesium and calcium ions transport by synthetic analogues of teichoic acids with 1,2‐ and 1,3‐linked phosphodiester units

Abstract2‐Ethylhexylpoly(trimethylene 1,3‐phosphate) (3), poly(1,2‐glycerol phosphate) (1) and poly‐(1‐acetoxy‐2,3‐glycerol phosphate) (2) were synthesized and used as synthetic analogues of teichoic acids. Their properties as a carrier of magnesium and calcium ions were examined in the competitive exchange diffusion process with the countertransport of hydrogen or sodium ions. It turned out that polymers with 1,2‐glycerol phosphate units (1,2) exhibit lower ability to transport preferentially magnesium ions than poly(1,3‐alkylene phosphate)s (3). In all cases the efficiency of polyphosphates in preferential transport of magnesium ions is higher when transport is coupled with proton counterflow.

Functional characterization of the uncoupler-insensitive Na + pump of the halotolerant bacterium, Ba 1

Respiration initiates Na + efflux from Na +-preloaded cells of the halotolerant bacterium, Ba 1. This efflux can take place against the concentration and electrochemical gradients. Since it is not inhibited by carbonylcyanide- p-trifluoromethoxyphenyl-hydrazone or N'N'-dicyclohexylcarbodiimide, it seems unlikely that either Δ p (electrochemical potential difference of H + across the membrane) generated by the primary proton pump or ATP play a role in the transduction of the energy supplied by electron transport. The electrogenic extrusion of Na + causes passive counterflow of protons and/or simultaneous flux of permeant anions. In the absence of permeant anions the charge compensation attained by influx of protons is not complete. The membrane potential which persists in this case is inside negative and insensitive to uncoupler. The influx of protons builds up a ΔpH of reversed sign (more acid inside), which is insensitive to uncoupler. The simultaneous efflux of Na + and permeant anions diminishes the intracellular salt content and, as a corollary, causes volume contraction. Thus, the respiration-linked, uncoupler-insensitive Na + pump may play a role in the regulation of the intracellular salt content.

Membrane transport systems. II. Transport of alkali metal ions against their concentration gradients

An artificial membrane system based on a series of macrocyclic polyether carriers (crown ethers) is described. Under the influence of a proton gradient the carriers move alkali metal ions from basic to acidic solution through a chloroform membrane phase. Transport occurs against the concentration gradient of the transported ion as a result of a coupled counterflow of protons. Different transport behaviors are observed depending upon the metal ion concentration. At high metal ion concentration the amount transported is a linear function of time; at lower metal ion concentration the amount transported is a complex function of time which may be described as the result of a pair of consecutive first order processes. Effects of metal ion, carrier, and proton concentration on transport rate are considered. The rate increases with increasing metal ion or carrier concentration but is essentially independent of the pH of either aqueous phase. Increased lipophilicity of the carrier also results in a rate increase. Carriers derived from 18-crown-6 transport potassium selectively and all ions more rapidly than 15-crown-5 derivatives which are, however, selective for sodium. The overall efficiency of the system is discussed in terms of competing "leak" reactions, either of cations from the basic phase or of anions from the acidic phase.