scholarly journals THE REVERSAL OF THE SIGN OF THE CHARGE OF MEMBRANES BY HYDROGEN IONS

1920 ◽  
Vol 2 (5) ◽  
pp. 577-594 ◽  
Author(s):  
Jacques Loeb

1. It had been shown in previous papers that when a collodion membrane has been treated with a protein the membrane assumes a positive charge when the hydrogen ion concentration of the solution with which it is in contact exceeds a certain limit. It is pointed out in this paper that by treating the collodion membrane with a protein (e.g. oxyhemoglobin) a thin film of protein adheres to the membrane and that the positive charge of the membrane must therefore be localized in this protein film. 2. It is further shown in this paper that the hydrogen ion concentration, at which the reversal in the sign of the charge of a collodion membrane treated with a protein occurs, varies in the same sense as the isoelectric point of the protein, with which the membrane has been treated, and is always slightly higher than that of the isoelectric point of the protein used. 3. The critical hydrogen ion concentration required for the reversal seems to be, therefore, that concentration where enough of the protein lining of the membrane is converted into a protein-acid salt (e.g. gelatin nitrate) capable of ionizing into a positive protein ion (e.g. gelatin) and the anion of the acid used (e.g. NO3).

Author(s):  
O. M. Yonge

1. In the Lamellibranchs, as typified by Pecten maximus, Mya arenaria and Ensis siliqua, the entire, gut has an acid reaction, the stomach being the most acid region and the pH rising along the mid-gut and rectum.2. The origin of the acidity of the gut lies in the style. This has a low pH (5·4 in Pecten and Mytilus, 4·6 in Ensis and 4·45 in Mya), and, after it has been artificially extracted from Mya or induced to disappear, by keeping the animals under abnormal conditions, in Mytilus, Tapes and Pecten, the pH of the stomach invariably rises (by as much as 0·825 in Mya and 0·72 in Tapes), although the pH in the mantle cavity has fallen.3. The style, which dissolves rapidly in alkaline or weakly acid media, is not dissolved in fluids below a certain pH—4·4 for Ensis, 4·2 for Mya, 3·6 for Pecten and Mytilus.4. The style is never absent, even though animals are starved, so long as they are kept under otherwise healthy conditions. The disappearance of the style under abnormal conditions is probably due to a lowering of the vital activities, which include the secretion of the style substance, and the consequent dissolution of the style by the less acid contents of the stomach.5. The style is only maintained as a result of a balance between the rate of its secretion and the rate of its dissolution.6. There is a well-marked correlation between the tolerance of the presence of hydrogen ions possessed by the cilia from the various regions of the gut and the degree of acidity of the fluid with which they are normally surrounded.7. The pH of the gut in five Gastropods has been investigated. The fore-gut and stomach have invariably the lowest pH.8. This acidity may be caused by the salivary glands (Patella and Buccinum), the digestive gland (Doris and Aplysia), or the style (Crepidula).9. The mid-gut and rectum have a high pH, except in Doris, where there is little secretion of mucus, the gut being free and muscular.10. The style of Orepidula has similar properties to those of the Lamellibranchs. It has a pH of 5·8, and is not dissolved in fluid of pH 3·6 or lower.11. The cilia from the gut of Buccinum and Doris can function in a pH of 5·0, but there is little difference in the toleration of the various cilia to the presence of hydrogen ions.


1918 ◽  
Vol 1 (2) ◽  
pp. 237-254 ◽  
Author(s):  
Jacques Loeb

1. It is shown by volumetric analysis that on the alkaline side from its isoelectric point gelatin combines with cations only, but not with anions; that on the more acid side from its isoelectric point it combines only with anions but not with cations; and that at the isoelectric point, pH = 4.7, it combines with neither anion nor cation. This confirms our statement made in a previous paper that gelatin can exist only as an anion on the alkaline side from its isoelectric point and only as a cation on the more acid side of its isoelectric point, and practically as neither anion nor cation at the isoelectric point. 2. Since at the isoelectric point gelatin (and probably amphoteric colloids generally) must give off any ion with which it was combined, the simplest method of obtaining amphoteric colloids approximately free from ionogenic impurities would seem to consist in bringing them to the hydrogen ion concentration characteristic of their isoelectric point (i.e., at which they migrate neither to the cathode nor anode of an electric field). 3. It is shown by volumetric analysis that when gelatin is in combination with a monovalent ion (Ag, Br, CNS), the curve representing the amount of ion-gelatin formed is approximately parallel to the curve for swelling, osmotic pressure, and viscosity. This fact proves that the influence of ions upon these properties is determined by the chemical or stoichiometrical and not by the "colloidal" condition of gelatin. 4. The sharp drop of these curves at the isoelectric point finds its explanation in an equal drop of the water solubility of pure gelatin, which is proved by the formation of a precipitate. It is not yet possible to state whether this drop of the solubility is merely due to lack of ionization of the gelatin or also to the formation of an insoluble tautomeric or polymeric compound of gelatin at the isoelectric point. 5. On account of this sudden drop slight changes in the hydrogen ion concentration have a considerably greater chemical and physical effect in the region of the isoelectric point than at some distance from this point. This fact may be of biological significance since a number of amphoteric colloids in the body seem to have their isoelectric point inside the range of the normal variation of the hydrogen ion concentration of blood, lymph, or cell sap. 6. Our experiments show that while a slight change in the hydrogen ion concentration increases the water solubility of gelatin near the isoelectric point, no increase in the solubility can be produced by treating gelatin at the isoelectric point with any other kind of monovalent or polyvalent ion; a fact apparently not in harmony with the adsorption theory of colloids, but in harmony with a chemical conception of proteins.


1919 ◽  
Vol 2 (2) ◽  
pp. 145-160 ◽  
Author(s):  
Edwin J. Cohn ◽  
Joseph Gross ◽  
Omer C. Johnson

The state in which a protein substance exists depends upon the nature of its combination with acids or bases and is changed by change in the protein compound. The nature of the compound of a protein that exists at any hydrogen ion concentration can be ascertained if the isoelectric point of the protein is known. Accordingly information regarding the isoelectric points of vegetable proteins is of importance for operations in which it may be desirable to change the state of protein substances, as in the dehydration of vegetables. The Protein in Potato Juice.—The hydrogen ion concentration of the filtered juice of the potato is in the neighborhood of 10–7N. Such juice contains the globulin tuberin to the extent of from 1 to 2 per cent. The character of the compound of tuberin that exists in nature was suggested by its anodic migration in an electric field. The addition of acid to potato juice dissociated this compound and liberated tuberin at its isoelectric point. The isoelectric point of tuberin coincided with a slightly lower hydrogen ion concentration than 10–4N. At that reaction it existed most nearly uncombined. The flow of current during cataphoresis was greatest in the neighborhood of the isoelectric point. This evidence supplements that of the direction of the migration of tuberin, since it also suggests the existence of the greatest number of uncombined ions near this point. At acidities greater than the isoelectric point tuberin combined with acid. The compound that was formed contained nearly three times as much acid as was needed to dissociate the tuberin compound that existed in nature. At such acidities tuberin migrated to the cathode. Though never completely precipitated tuberin was least soluble in the juice of the potato in the neighborhood of its isoelectric point. Both the compounds of tuberin with acids and with bases were more soluble in the juice than was uncombined tuberin. The nature of the slight precipitate that separated when potato juice was made slightly alkaline was not determined. The Protein in Carrot Juice.—The isoelectric point of the protein in carrot juice coincided with that of tuberin. Remarkably similar also were the properties of carrot juice and the juice of the potato. Existing in nature at nearly the same reaction they combined with acids and bases to nearly the same extent and showed minima in solubility at the same hydrogen ion concentrations. The greatest difference in behavior concerned the alkaline precipitate which, in the carrot, was nearly as great as the acid precipitate. The Protein in Tomato Juice.—The protein of the tomato existed in a precipitated form near its isoelectric point. Accordingly it was not present to any extent in filtered tomato juice. If, however, the considerable acidity at which the tomato exists was neutralized the protein dissolved and was filterable. It then migrated to the anode in an electric field. The addition of sufficient acid to make the hydrogen ion concentration slightly greater than 10–5N again precipitated the protein at its isoelectric point. At greater acidities migration was cathodic.


1922 ◽  
Vol 4 (5) ◽  
pp. 617-619 ◽  
Author(s):  
Jacques Loeb

1. It had been noticed in the previous experiments on the influence of the hydrogen ion concentration on the P.D. between protein solutions inside a collodion bag and aqueous solutions free from protein that the agreement between the observed values and the values calculated on the basis of Donnan's theory was not satisfactory near the isoelectric point of the protein solution. It was suspected that this was due to the uncertainty in the measurements of the pH of the outside aqueous solution near the isoelectric point. This turned out to be correct, since it is shown in this paper that the discrepancy disappears when both the inside and outside solutions contain a buffer salt. 2. This removes the last discrepancy between the observed P.D. and the P. D. calculated on the basis of Donnan's theory of P.D. between membrane equilibria, so that we can state that the P.D. between protein solutions inside collodion bags and outside aqueous solutions free from protein can be calculated from differences in the hydrogen ion concentration on the opposite sides of the membrane, in agreement with Donnan's formula.


1938 ◽  
Vol s2-80 (320) ◽  
pp. 593-599
Author(s):  
G. J. van OORDT

The structure of the spermatheca of Loligo vulgaris is described; it lies on the inner wall of the buccal membrane and within it large quantities of inactive spermatozoa are stored. This inactivity of the spermatozoa within the spermatheea is attributed to the effect of the secretion of the goblet-cells, situated as unicellular glands on the inner wall of the spermatheca. Inactive spermatozoa from the spermatheca become very active in sea-water, but are immobilized again after a few moments' contact with the pulp of the spermatheca contents. The hydrogen-ion concentration of the spermatheca contents is approximately 6.06; and, since spermatozoa become inactive in sea-water, the hydrogen-ion concentration of which is increased to this level, it seems probable that the inactivity of the spermatozoa within the spermatheca is due to the presence of hydrogen-ions. The spermatheca is functionally comparable to the mammalian epididymis.


2020 ◽  
pp. 2182-2198
Author(s):  
Julian Seifter

The normal pH of human extracellular fluid is maintained within the range of 7.35 to 7.45. The four main types of acid–base disorders can be defined by the relationship between the three variables, pH, Pco2, and HCO3 –. Respiratory disturbances begin with an increase or decrease in pulmonary carbon dioxide clearance which—through a shift in the equilibrium between CO2, H2O, and HCO3 –—favours a decreased hydrogen ion concentration (respiratory alkalosis) or an increased hydrogen ion concentration (respiratory acidosis) respectively. Metabolic acidosis may result when hydrogen ions are added with a nonbicarbonate anion, A−, in the form of HA, in which case bicarbonate is consumed, or when bicarbonate is removed as the sodium or potassium salt, increasing hydrogen ion concentration. Metabolic alkalosis is caused by removal of hydrogen ions or addition of bicarbonate. Laboratory tests usually performed in pursuit of diagnosis, aside from arterial blood gas analysis, include a basic metabolic profile with electrolytes (sodium, potassium, chloride, bicarbonate), blood urea nitrogen, and creatinine. Calculation of the serum anion gap, which is determined by subtracting the sum of chloride and bicarbonate from the serum sodium concentration, is useful. The normal value is 10 to 12 mEq/litre. An elevated value is diagnostic of metabolic acidosis, helpful in the differential diagnosis of the specific metabolic acidosis, and useful in determining the presence of a mixed metabolic disturbance. Acid–base disorders can be associated with (1) transport processes across epithelial cells lining transcellular spaces in the kidney, gastrointestinal tract, and skin; (2) transport of acid anions from intracellular to extracellular spaces—anion gap acidosis; and (3) intake.


1922 ◽  
Vol 4 (4) ◽  
pp. 463-486 ◽  
Author(s):  
Jacques Loeb

1. It has been shown in previous publications that when solutions of different concentrations of salts are separated by collodion-gelatin membranes from water, electrical forces participate in addition to osmotic forces in the transport of water from the side of the water to that of the solution. When the hydrogen ion concentration of the salt solution and of the water on the other side of the membrane is the same and if both are on the acid side of the isoelectric point of gelatin (e.g. pH 3.0), the electrical transport of water increases with the valency of the cation and inversely with the valency of the anion of the salt in solution. Moreover, the electrical transport of water increases at first with increasing concentration of the solution until a maximum is reached at a concentration of about M/32, when upon further increase of the concentration of the salt solution the transport diminishes until a concentration of about M/4 is reached, when a second rise begins, which is exclusively or preeminently the expression of osmotic forces and therefore needs no further discussion. 2. It is shown that the increase in the height of the transport curves with increase in the valency of the cation and inversely with the increase in the valency of the anion is due to the influence of the salt on the P.D. (E) across the membrane, the positive charge of the solution increasing in the same way with the valency of the ions mentioned. This effect on the P.D. increases with increasing concentration of the solution and is partly, if not essentially, the result of diffusion potentials. 3. The drop in the transport curves is, however, due to the influence of the salts on the P.D. (ϵ) between the liquid inside the pores of the gelatin membrane and the gelatin walls of the pores. According to the Donnan equilibrium the liquid inside the pores must be negatively charged at pH 3.0 and this charge is diminished the higher the concentration of the salt. Since the electrical transport is in proportion to the product of E x ϵ and since the augmenting action of the salt on E begins at lower concentrations than the depressing action on ϵ, it follows that the electrical transport of water must at first rise with increasing concentration of the salt and then drop. 4. If the Donnan equilibrium is the sole cause for the P.D. (ϵ) between solid gelatin and watery solution the transport of water through collodion-gelatin membranes from water to salt solution should be determined purely by osmotic forces when water, gelatin, and salt solution have the hydrogen ion concentration of the isoelectric point of gelatin (pH = 4.7). It is shown that this is practically the case when solutions of LiCl, NaCl, KCl, MgCl2, CaCl2, BaCl2, Na2SO4, MgSO4 are separated by collodion-gelatin membranes from water; that, however, when the salt has a trivalent (or tetravalent?) cation or a tetravalent anion a P.D. between solid isoelectric gelatin and water is produced in which the wall assumes the sign of charge of the polyvalent ion. 5. It is suggested that the salts with trivalent cation, e.g. Ce(NO3)3, form loose compounds with isoelectric gelatin which dissociate electrolytically into positively charged complex gelatin-Ce ions and negatively charged NO3 ions, and that the salts of Na4Fe(CN)6 form loose compounds with isoelectric gelatin which dissociate electrolytically into negatively charged complex gelatin-Fe(CN)6 ions and positively charged Na ions. The Donnan equilibrium resulting from this ionization would in that case be the cause of the charge of the membrane.


Author(s):  
Christopher O. Oriakhi

Water is a weak acid. At 25°C, pure water ionizes to form a hydrogen ion and a hydroxide ion: H2O ⇋ H+ + OH− Hydration of the proton (hydrogen ion) to form hydroxonium ion is ignored here for simplicity. This equilibrium lies mainly to the left; that is, the ionization happens only to a slight extent. We know that 1 L of pure water contains 55.6 mol. Of this, only 10−7 mol actually ionizes into equal amounts of [H+] and [OH−], i.e., [H+] = [OH−] = 10−7M Because these concentrations are equal, pure water is neither acidic nor basic. A solution is acidic if it contains more hydrogen ions than hydroxide ions. Similarly, a solution is basic if it contains more hydroxide ions than hydrogen ions. Acidity is defined as the concentration of hydrated protons (hydrogen ions); basicity is the concentration of hydroxide ions. Pure water ionizes at 25°C to produce 10−7 M of [H+] and 10−7 M of [OH−]. The product Kw = [H+]×[OH−] = 10−7 M×10−7 M= 10−14 M is known as the ionic product of water. Note that this is simply the equilibrium expression for the dissociation of water. This equation holds for any dilute aqueous solution of acid, base, and salt. The pH of a solution is defined as the negative logarithm of the molar concentration of hydrogen ions. The lower the pH, the greater the acidity of the solution. Mathematically: pH=−log10[ H+] or −log10[H3O+] This can also be written as: pH = log10 1/[H+] or log10 1/[H3O+] Taking the antilogarithm of both sides and rearranging gives: [H+] = 10−pH This equation can be used to calculate the hydrogen ion concentration when the pH of the solution is known.


1920 ◽  
Vol 2 (6) ◽  
pp. 659-671 ◽  
Author(s):  
Jacques Loeb

1. Trivalent cations cause a collodion membrane covered with a protein film to be charged positively while they do not produce such an effect on collodion membranes not possessing a protein film. The same had been found for the reversal of the sign of charge of the membrane by acid. 2. This reversal in the sign of charge of the membrane by trivalent cations occurs on the alkaline side of the isoelectric point of the protein used; while the reversal by acid occurs on the acid side of the isoelectric point. 3. The reversal seems to be due to or to be accompanied in both cases by a chemical change in the protein. The chemical change which occurs when the hydrogen ions reverse the sign of charge of the protein film consists in the formation of a protein-acid salt whereby the H ion becomes part of a complex protein cation; while the chemical change which occurs when trivalent cations reverse the sign of charge of the protein film consists in the formation of an insoluble and therefore sparingly or non-ionizable metal proteinate.


1922 ◽  
Vol 4 (5) ◽  
pp. 597-615 ◽  
Author(s):  
David I. Hitchcock

1. It has been shown by titration experiments that the globulin edestin behaves like an amphoteric electrolyte, reacting stoichiometrically with acids and bases. 2. The potential difference developed between a solution of edestin chloride or acetate separated by a collodion membrane from an acid solution free from protein was found to be influenced by salt concentration and hydrogen ion concentration in the way predicted by Donnan's theory of membrane equilibrium. 3. The osmotic pressure of such edestin-acid salt solutions was found to be influenced by salt concentration and by hydrogen ion concentration in the same way as is the potential difference. 4. The colloidal behavior of edestin is thus completely analogous to that observed by Loeb with gelatin, casein, and egg albumin, and may be explained by Loeb's theory of colloidal behavior, which is based on the idea that proteins react stoichiometrically as amphoteric electrolytes and on Donnan's theory of membrane equilibrium.


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