scholarly journals Organotin-mediated exchange diffusion of anions in human red cells.

1979 ◽  
Vol 73 (6) ◽  
pp. 765-788 ◽  
Author(s):  
J O Wieth ◽  
M T Tosteson

Organotin cations (R3Sn+) form electrically neutral ion pairs with monovalent anions. It is demonstrated that the tin derivatives induce exchange diffusion of chloride in red cells and resealed ghosts, without any detectable increase of membrane permeability to net movements of chloride ions. The obligatory anion exchange is believed to be due to the permeation of electroneural ion pairs, whereas the organic cation (R3Sn+) has an extremely low membrane permeability. Exchange fluxes of chloride increased with the lipophilicity of the substituting group (R3). At the same molar concentration of organotin, the relative potencies of the tin derivatives as anion carriers (with trimethyltin as a reference) were: methyl 1, ethyl 30, propyl = phenyl 1,00, and butyl 10,000. Tributyltin-mediated anion exchange was studied in detail. The organotin-induced anion transport increased through the sequence: F- less than Cl- less than Br- less than I- = SCN- less than OH-. Partitioning of tributyltin into red cell membranes was greater in iodide than in chloride media (partition coefficients 6.6 and 1.7 x 10(-3) cm, respectively). Bicarbonate, fluoride, nitrate, phosphate, and sulphate did not exchange with chloride in the presence of tributyltin. Chloride exchange fluxes increased linearly with tributylin concentrations up to 10(-5) M, and with chloride concentrations up to at least 0.9 M. The apparent turnover number for tributyltin-mediated chloride exchange increased from 15 to 1,350 s-1 between 0 and 38 degrees C. These figures are minimum turnover numbers, because it is not known what fraction of the organotin in the membrane exists as chloride ion pairs.

1975 ◽  
Vol 65 (6) ◽  
pp. 731-749 ◽  
Author(s):  
R B Gunn ◽  
J O Wieth ◽  
D C Tosteson

In order to test the range of pH values over which the titratable carried model for inorganic anion exchange is valid, chloride self-exchange across human red blood cells was examined between pH 4.75 and 5.7 at 0 decrees c. It was found that chloride self-exchange flux had a minimum near pH 5 and increased again with further increase in hydrogen ion activity. The Arrhenius activation energy for chloride exchange was greatly reduced at low pH values. The chloride flux at pH 5.1 did not show the saturation kinetics reported at higher pH values but was proportional to the value of the chloride concentration squared. In addition, the extent of inhibition of chloride self-exchange flux by phloretin was reduced at low pH. Our interpretation of these findings is that the carrier-mediated flux becomes a progressively smaller fraction of the total flux at lower pH values and that a different transport mode requiring two chloride ions to form the permeant species and having a low specificity and temperature dependence becomes significant below pH5. A possible mechanism for this transport is that chloride crosses red cell membranes as dimers of HCl at these very low pH values.


1979 ◽  
Vol 73 (6) ◽  
pp. 789-800 ◽  
Author(s):  
M T Tosteson ◽  
J O Wieth

This paper describes the effect of tributyltin (TBT) on the inorganic anion permeability of lipid bilayers. When this compound is added in micromolar concentrations to one or both sides of a phosphatidyl ethanolamine (PE) membrane formed in 0.1 M NaCl or KCl (pH 7), there is no change in the electrical conductance. Under these circumstances, the Cl self-exchange flux measured with 36Cl (MCl) increases from a value of approximately 10(-12) mol.cm-2.s-1, to approximately 10(-8) mol.cm-2.s-1. It was further found that the relation between chloride flux and [TBT] and [Cl] can be described as: MCl = B[TBT] [Cl]. When chloride was replaced by an equimolar concentration of different univalent anions in the trans compartment, the heteroexchange flux of chloride followed the sequence: I greater than Br greater than Cl greater than F greater than NO3. Under all experimental conditions tested, the chloride flux was always more than 10(3) times the maximum flux predicted from the value of the membrane conductance, and at least 100 times higher than the expected fluxes of ion pairs (TBT-Cl) diffusing across the unstirred layers. Thus, the mechanism by which tributyltin increases anion permeability in bilayers seems to be that of an obligatory exchange diffusion, with the reaction between tributyltin and the halides occurring at the membrane surface. Measurements of interfacial potentials indicate that tributyltin chloride lowers the positive intrinsic dipole potential of PE membranes by approximately 70 mV (at a TBT concentration of 30 microM) without substantial alteration of other parameters of the bilayer. The estimated adsorption coefficient of TBT-Cl was found to be 3 x 10(-4) cm.


2021 ◽  
Vol 11 (12) ◽  
pp. 5322
Author(s):  
Yang Ding ◽  
Tong-Lin Yang ◽  
Hui Liu ◽  
Zhen Han ◽  
Shuang-Xi Zhou ◽  
...  

Cement is widely used in marine concrete, and its resistance to chloride ion corrosion has been widely considered. In this paper, based on a laboratory test, the influence of different hydrostatic pressures, coarse aggregate contents and w/c ratios on the chloride resistance performance is analyzed. Based on COMSOL finite element software, a two-dimensional cementitious materials model is established, and the simulation results are compared with the experimental results. The results show that the penetration depth of chloride ions in cement increases with the increase of the w/c ratio. Under the hydrostatic pressure of 0 MPa, when the w/c ratio is 0.35, the penetration depth of chloride ions is 7.4 mm, and the simulation result is 8.0 mm. When the w/c ratio is 0.45, the penetration depth of chloride ions is 9.3 mm, and the simulation result is 9.9 mm. When the w/c ratio is 0.55, the penetration depth of chloride ions is 12.9 mm, and the simulation result is 12.1 mm. Under different hydrostatic pressures, the penetration depth of chloride ions obviously changes, and with the increase in hydrostatic pressure, the penetration depth of chloride ions deepens. Under the w/c ratio of 0.35, when the hydrostatic pressure is 0.5 MPa, the penetration depth of chloride ions is 11.3 mm, and the simulation result is 12.1 mm. When the hydrostatic pressure is 1.0 MPa, the penetration depth of chloride ions is 16.2 mm, and the simulation result is 17.5 mm.


2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Adrian Radoń ◽  
Dariusz Łukowiec ◽  
Patryk Włodarczyk

AbstractThe dielectric properties and electrical conduction mechanism of bismuth oxychloride (BiOCl) plates synthesized using chloramine-T as the chloride ion source were investigated. Thermally-activated structure rebuilding was monitored using broadband dielectric spectroscopy, which showed that the onset temperature of this process was 283 K. This rebuilding was related to the introduction of free chloride ions into [Bi2O2]2+ layers and their growth, which increased the intensity of the (101) diffraction peak. The electrical conductivity and dielectric permittivity were related to the movement of chloride ions between plates (in the low-frequency region), the interplanar motion of Cl− ions at higher frequencies, vibrations of these ions, and charge carrier hopping at frequencies above 10 kHz. The influence of the free chloride ion concentration on the electrical conductivity was also described. Structure rebuilding was associated with a lower concentration of free chloride ions, which significantly decreased the conductivity. According to the analysis, the BiOCl plate conductivity was related to the movement of Cl− ions, not electrons.


2021 ◽  
Vol 22 (14) ◽  
pp. 7394
Author(s):  
Kyoung Ho Park ◽  
Mi Hye Seong ◽  
Jin Burm Kyong ◽  
Dennis N. Kevill

A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.


Blood ◽  
1967 ◽  
Vol 30 (6) ◽  
pp. 785-791 ◽  
Author(s):  
RONALD S. WEINSTEIN ◽  
ROGER A. WILLIAMS

Abstract Electron microscopic studies on dried isolated red cell ghosts have been reported to show lesions associated with cell membranes in paroxysmal nocturnal hemoglobinuria (PNH). In this study, carbon-platinum replicas of membranes of freeze-cleaved, partially hydrated PNH red cells and isolated PNH cell ghosts failed to confirm the existence of these abnormalities. This suggests that the previously described lesions are the products of drying artifacts, although they may reflect hidden structural differences between PNH and normal red cell membranes.


1963 ◽  
Vol 47 (2) ◽  
pp. 379-392 ◽  
Author(s):  
H. Kimizuka ◽  
K. Koketsu

The changes in the membrane permeability to sodium, potassium, and chloride ions as well as the changes in the intracellular concentration of these ions were studied on frog sartorius muscles in Ca-free EDTA solution. It was found that the rate constants for potassium and chloride efflux became almost constant within 10 minutes in the absence of external calcium ions, that for potassium increasing to 1.5 to 2 times normal and that for chloride decreasing about one-half. The sodium influx in Ca-free EDTA solution, between 30 and 40 minutes, was about 4 times that in Ringer's solution. The intracellular sodium and potassium contents did not change appreciably but the intracellular chloride content had increased to about 4 times normal after 40 minutes. By applying the constant field theory to these results, it was concluded that (a) PCl did not change appreciably whereas PK decreased to a level that, in the interval between 10 and 40 minutes, was about one-half normal, (b) PNa increased until between 30 and 40 minutes it was about 8 times normal. The low value of the membrane potential between 30 and 40 minutes was explained in terms of the changes in the membrane permeability and the intracellular ion concentrations. The mechanism for membrane depolarization in this solution was briefly discussed.


1970 ◽  
Vol 117 (3) ◽  
pp. 615-621 ◽  
Author(s):  
M. C. Perry ◽  
C. N. Hales

1. The effluxes of 42K+ and 36Cl− from isolated fat-cells from the rat were studied under a variety of conditions known to affect the metabolism of the cells. 2. 42K+ efflux from isolated fat cells was increased in a Na+-free–high-K+ medium and decreased in a K+-free medium. The existence of K+ exchange diffusion across the fat-cell membrane is suggested. 3. 36Cl− efflux from isolated fat-cells was decreased when the Cl− component of the wash medium was replaced by acetate. The basal 36Cl− efflux is suggested to be partly by Cl− exchange diffusion and partly in company with a univalent cation. 4. A variety of lipolytic stimuli, adrenaline, adrenocorticotrophic hormone, N-6,O-2′-dibutyryladenosine cyclic 3′:5′-monophosphate and theophylline, increased 42K+ efflux from isolated fat-cells. The adrenaline stimulation was biphasic; an initial, rapid and transient increase in 42K+ loss from the fat-cells was followed by a slower, more prolonged, increase in 42K+ efflux. The initial phase was inhibited by phentolamine but not by propranolol. 5. Insulin increased 42K+ efflux only after preincubation with the cells.


1996 ◽  
Vol 8 (8-9) ◽  
pp. 821-825 ◽  
Author(s):  
Hanming Wang ◽  
Zemu Yu ◽  
Erkang Wang

1974 ◽  
Vol 64 (6) ◽  
pp. 706-729 ◽  
Author(s):  
W. R. Redwood ◽  
E. Rall ◽  
W. Perl

The permeability coefficients of dog red cell membrane to tritiated water and to a series of[14C]amides have been deduced from bulk diffusion measurements through a "tissue" composed of packed red cells. Red cells were packed by centrifugation inside polyethylene tubing. The red cell column was pulsed at one end with radiolabeled solute and diffusion was allowed to proceed for several hours. The distribution of radioactivity along the red cell column was measured by sequential slicing and counting, and the diffusion coefficient was determined by a simple plotting technique, assuming a one-dimensional diffusional model. In order to derive the red cell membrane permeability coefficient from the bulk diffusion coefficient, the red cells were assumed to be packed in a regular manner approximating closely spaced parallelopipeds. The local steady-state diffusional flux was idealized as a one-dimensional intracellular pathway in parallel with a one-dimensional extracellular pathway with solute exchange occurring within the series pathway and between the pathways. The diffusion coefficients in the intracellular and extracellular pathways were estimated from bulk diffusion measurements through concentrated hemoglobin solutions and plasma, respectively; while the volume of the extracellular pathway was determined using radiolabeled sucrose. The membrane permeability coefficients were in satisfactory agreement with the data of Sha'afi, R. I., C. M. Gary-Bobo, and A. K. Solomon (1971. J. Gen. Physiol. 58:238) obtained by a rapid-reaction technique. The method is simple and particularly well suited for rapidly permeating solutes.


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