The contributions of normal and anomalous osmosis to the osmotic effects arising across charged membranes with solutions of electrolytes

The osmotic effect arising across a porous membrane separating the solution of an electrolyte from water (or a more dilute solution) is ordinarily due to both normal osmosis, as it occurs also with non-electrolytes, and to "anomalous" osmosis. It is shown that the normal osmotic component cannot be measured quantitatively by the conventional comparison with a non-electrolytic reference solute. Anomalous osmosis does not occur with electroneutral membranes. Accordingly, with membranes which can be charged and discharged reversibly (without changes in geometrical structure), such as many proteinized membranes, the osmotic effects caused by an electrolyte can be measured both when only normal osmosis arises (with the membrane in the electroneutral state) and when normal as well as anomalous osmosis occurs (with the membrane in a charged state). The difference between these two effects is the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, with solutions of a variety of electrolytes using a concentration ratio of 2:1 over a wide range of concentrations. The rates of the movement of liquid across the membrane against an inconsequentially small hydrostatic head are recorded instead of, as conventional, the physiologically less significant pressure rises after a standard time.     

NEW EXPERIMENTS ON ANOMALOUS OSMOSIS

1. It is impossible to reproduce Loeb''s observations on anomalous osmosis with membranes prepared from relatively pure brands of collodion, whereas positive effects can be obtained using collodion containing acidic impurities. 2. The inactive (purer) collodion membranes may be activated by oxidation with NaOBr solution. 3. Properly oxidized membranes give much greater anomalous osmotic effects than those described by Loeb.     

True Anomalous Osmosis in Multi-Solute Model Membrane Systems

The transport of liquid across charged porous membranes separating two electrolytic solutions of different composition consists of both a normal and an anomalous osmotic component. Anomalous osmosis does not occur with electroneutral membranes. Thus, with membranes which can be charged and discharged reversibly, normal osmosis can be measured with the membrane in the electroneutral state, and normal together with anomalous osmosis with the membrane in a charged state, the difference between these two effects being the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, in multi-solute systems with 0.2 and 0.4 osmolar solutions of a variety of electrolytes and of glucose against solutions of other solutes of the same, one-half, and twice these osmolarities. In the simpler systems the magnitude of the true anomalous osmosis can be predicted semiquantitatively by reference to appropriate single-solute systems. In isoosmolar systems with two electrolytic solutions the anomalous osmotic flow rates may reach 300 µl./cm.² hr. and more; systems with electrolytic solutions against solutions of glucose can produce twice this rate. These fluxes are of the same order of magnitude as the liquid transport rates across such living structures as the mucosa of dog gall bladder, ileum, and urinary bladder.     

THE STRUCTURE OF THE COLLODION MEMBRANE AND ITS ELECTRICAL BEHAVIOR : VI. THE PROTAMINE-COLLODION MEMBRANE,A NEW ELECTROPOSITIVE MEMBRANE

1. Strongly electropositive porous membranes were prepared by the adsorption of protamine (salmine) on porous collodion membranes. These membranes retain their electrochemical chracteristics for at least 12 months without change. 2. They are distinctly electropositive between pH 1 and 10, the range of most pronounced electropositive behavior occurring in solutions between pH 3 and pH 8. The filtration rates and ohmic resistance of these membranes do not differ significantly from similar uncoated membranes. 3. The porous protamine-collodion membranes show very pronounced positive anomalous osmosis, the observed effects with proper electrolytes being similar to those obtained with oxidized collodion membranes. They also show very conspicuous negative osmosis with strong acids. 4. Protamine-collodion membranes which correspond in their properties to the activated dried collodion membranes were prepared by the adsorption of protamine on porous collodion membranes followed by drying in air. The concentration potentials across such dried protamine-collodion membranes closely approach the thermodynamically possible maximum.     

A Physical Interpretation of the Phenomenological Coefficients of Membrane Permeability

A "translation" of the phenomenological permeability coefficients into friction and distribution coefficients amenable to physical interpretation is presented. Expressions are obtained for the solute permeability coefficient ω and the reflection coefficient σ for both non-electrolytic and electrolytic permeants. An analysis of the coefficients is given for loose membranes as well as for dense natural membranes where transport may go through capillaries or by solution in the lipoid parts of the membrane. Water diffusion and filtration and the relation between these and capillary pore radius of the membrane are discussed. For the permeation of ions through the charged membranes equations are developed for the case of zero electrical current in the membrane. The correlation of σ with ω and L_p for electrolytes resembles that for non-electrolytes. In this case ω and σ depend markedly on ion concentration and on the charge density of the membrane. The reflection coefficient may assume negative values indicating anomalous osmosis. An analysis of the phenomena of anomalous osmosis was carried out for the model of Teorell and Meyer and Sievers and the results agree with the experimental data of Loeb and of Grim and Sollner. A set of equations and reference curves are presented for the evaluation of ω and σ in the transport of polyvalent ions through charged membranes.     

Effect of Ba2+ on the K+ conductance pathways in the frog cornea

Two types of transepithelial potential difference (PD) responses have been observed in the bullfrog, Rana catesbeiana, when the K+ concentration is changed in the aqueous solution. (1) A normal response, that is, a decrease in the positivity of the aqueous solution when the K+ is increased in this solution. (2) An anomalous response, that is, an increase in PD when K+ is increased from 0 to 4 mM in the aqueous solution. In present experiments 2 mM Ba2+ results in a significant decrease in transepithelial PD and an increase in resistance (R), consistent with the well-known effect of Ba2+ on the K+ conductance in other biological membranes. In the presence of Ba2+ compared to its absence the normal PD responses were decreased when K+ was increased from 4 to 20 or to 79 mM in the aqueous solution. Barium enhanced, but not significantly, the anomalous PD response (PD increase) when K+ was increased from 0 to 4 mM. An anomalous PD response (PD decrease) was obtained with Ba2+ when K+ was changed from 4 to 0 mM while in its absence the response was normal (PD increase) or did not change. These findings support the concept that anomalous PD responses as a result of the electrogenic (Na+ + K+)-ATPase may be obtained when the resistance of the simple K+ pathway is increased.     

Distribution of osmotic flow in stomach and gallbladder

Stomach and gallbladder actively transport fluids which are nearly isotonic to plasma. Consideration of the measured areas of the appropriate transporting surfaces gives a more realistic view of the osmotic gradient required to account for the observed net flow of water. Simple osmosis may be adequate if the transporting membrane has an osmotic permeability in the range observed for synthetic lecithin-cholesterol bilayer membranes.     

INFLUENCE OF A SLIGHT MODIFICATION OF THE COLLODION MEMBRANE ON THE SIGN OF THE ELECTRIFICATION OF WATER

1. It is shown that collodion membranes which have received one treatment with a 1 per cent gelatin solution show for a long time (if not permanently) afterwards a different osmotic behavior from collodion membranes not treated with gelatin. This difference shows itself only towards solutions of those electrolytes which have a tendency to induce a negative electrification of the water particles diffusing through the membrane, namely solutions of acids, acid salts, and of salts with trivalent and tetravalent cations; while the osmotic behavior of the two types of membranes towards solutions of salts and alkalies, which induce a positive electrification of the water particles diffusing through the membrane, is the same. 2. When we separate solutions of salts with trivalent cation, e.g. LaCl₃ or AlCl₃, from pure water by a collodion membrane treated with gelatin, water diffuses rapidly into the solution; while no water diffuses into the solution when the collodion membrane has received no gelatin treatment. 3. When we separate solutions of acid from pure water by a membrane previously treated with gelatin, negative osmosis occurs; i.e., practically no water can diffuse into the solution, while the molecules of solution and some water diffuse out. When we separate solutions of acid from pure water by collodion membranes not treated with gelatin, positive osmosis will occur; i.e., water will diffuse rapidly into the solution and the more rapidly the higher the valency of the anion. 4. These differences occur only in that range of concentrations of electrolytes inside of which the forces determining the rate of diffusion of water through the membrane are predominantly electrical; i.e., in concentrations from 0 to about M/16. For higher concentrations of the same electrolytes, where the forces determining the rate of diffusion are molecular, the osmotic behavior of the two types of membranes is essentially the same. 5. The differences in the osmotic behavior of the two types of membranes are not due to differences in the permeability of the membranes for solutes since it is shown that acids diffuse with the same rate through both kinds of membranes. 6. It is shown that the differences in the osmotic behavior of the two types of collodion membranes towards solutions of acids and of salts with trivalent cation are due to the fact that in the presence of these electrolytes water diffuses in the form of negatively charged particles through the membranes previously treated with gelatin, and in the form of positively charged particles through collodion membranes not treated with gelatin. 7. A treatment of the collodion membranes with casein, egg albumin, blood albumin, or edestin affects the behavior of the membrane towards salts with trivalent or tetravalent cations and towards acids in the same way as does a treatment with gelatin; while a treatment of the membranes with peptone prepared from egg albumin, with alanine, or with starch has no such effect.     

THE KINETICS OF OSMOSIS

It is shown that by combining the osmotic pressure and rate of diffusion laws an equation can be derived for the kinetics of osmosis. The equation has been found to agree with experiments on the rate of osmosis for egg albumin and gelatin solutions with collodion membranes.     

The Electroosmotic Effects Arising from the Interaction of the Selectively Anion and Selectively Cation Permeable Parts of Mosaic Membranes

It has been previously shown, theoretically and in model system experiments, that mosaic membranes composed of anion-selective (electropositive) and cation-selective (electronegative) parts interposed between electrolytic solutions of different concentrations give rise to local electrical circuits. In this work with model systems it is shown that these currents produce electroosmosis. In systems with permselective electronegative membranes and KCl solutions, the electroosmotic water transport was 16 moles/faraday. With the permselective electronegative membrane replaced by more porous electronegative membranes, the electroosmotic effects were about twice as high. With Li salts, the water transport was considerably larger. A system with a permselective electropositive membrane of 50 cm² effective area and an electronegative membrane of 120 cm² gave internally generated currents up to 20 ma. In extrapolating from the results with macromodels to effects with true mosaics, i.e. microsystems, it is stressed that current depends on the linear distance over which membranes interact. In true mosaic membranes, the current pathways will be of the same order as the dimensions of individual membrane microelements; the sum of all local microcurrents will be correspondingly larger than the current in the macromodel, and the electroosmotic effects will be proportionately greater. Electroosmotic effects with true charge-mosaic membranes may be of the same order or larger than the liquid transport by normal and anomalous osmosis which might occur across the individual parts of the charge-mosaic.     

Controlling Anomalous Diffusion in Lipid Membranes

Diffusion in cell membranes is not just simple two-dimensional Brownian motion but typically depends on the timescale of the observation. The physical origins of this anomalous subdiffusion are unresolved, and model systems capable of quantitative and reproducible control of membrane diffusion have been recognized as a key experimental bottleneck. Here, we control anomalous diffusion using supported lipid bilayers containing lipids derivatized with polyethylene glycol (PEG) headgroups. Bilayers with specific excluded area fractions are formed by control of PEG lipid mole fraction. These bilayers exhibit a switch in diffusive behavior, becoming anomalous as bilayer continuity is disrupted. Using a combination of single-molecule fluorescence and interferometric imaging, we measure the anomalous behavior in this model over four orders of magnitude in time. Diffusion in these bilayers is well described by a power-law dependence of the mean-square displacement with observation time. Anomaleity in this system can be tailored by simply controlling the mole fraction of PEG lipid, producing bilayers with diffusion parameters similar to those observed for anomalous diffusion in biological membranes.     

NaCl reflection coefficients in proximal tubule apical and basolateral membrane vesicles. Measurement by induced osmosis and solvent drag.

Two independent methods, induced osmosis and solvent drag, were used to determine the reflection coefficients for NaCl (sigma NaCl) in brush border and basolateral membrane vesicles isolated from rabbit proximal tubule. In the induced osmosis method, vesicles loaded with sucrose were subjected to varying inward NaCl gradients in a stopped-flow apparatus. sigma NaCl was determined from the osmolality of the NaCl solution required to cause no initial osmotic water flux as measured by light scattering (null point). By this method sigma NaCl was greater than 0.92 for both apical and basolateral membranes with best estimates of 1.0. sigma NaCl was determined by the solvent drag method using the Cl-sensitive fluorescent indicator, 6-methoxy-N-[3-sulfopropyl]quinolinium (SPQ), to detect the drag of Cl into vesicles by inward osmotic water movement caused by an outward osmotic gradient. sigma NaCl was determined by comparing experimental data with theoretical curves generated using the coupled flux equations of Kedem and Katchalsky. By this method we found that sigma NaCl was greater than 0.96 for apical and greater than 0.98 for basolateral membrane vesicles, with best estimates of 1.0 for both membranes. These results demonstrate that sigma NaCl for proximal tubule apical and basolateral membranes are near unity. Taken together with previous results, these data suggest that proximal tubule water channels are long narrow pores that exclude NaCl.     

Biofouling of reverse osmosis membranes used in river water purification for drinking purposes: analysis of microbial populations

Biofouling in water treatment processes represents one of the most frequent causes of plant performance decline. Investigation of clogged membranes (reverse osmosis membranes, microfiltration membranes and ultrafiltration membranes) is generally performed on fresh membranes. In the present study, a multidisciplinary autopsy of a reverse osmosis membrane (ROM) was conducted. The membrane, which was used in sulfate-rich river water purification for drinking purposes, had become inoperative after 6 months because of biofouling and was later stored for 18 months in dry conditions before analysis. SSU rRNA gene library construction, clone sequencing, T-RFLP, light microscope, and scanning electron microscope (SEM) observations were used to identify the microorganisms present on the membrane and possibly responsible for biofouling at the time of removal. The microorganisms were mainly represented by bacteria belonging to the phylum Actinobacteria and by a single protozoan species belonging to the Lobosea group. The microbiological analysis was interpreted in the context of the treatment plant operations to hypothesize as to the possible mechanisms used by microorganisms to enter the plant and colonize the ROM surface.     

Biofouling of reverse osmosis membranes used in river water purification for drinking purposes: analysis of microbial populations

Biofouling in water treatment processes represents one of the most frequent causes of plant performance decline. Investigation of clogged membranes (reverse osmosis membranes, microfiltration membranes and ultrafiltration membranes) is generally performed on fresh membranes. In the present study, a multidisciplinary autopsy of a reverse osmosis membrane (ROM) was conducted. The membrane, which was used in sulfate-rich river water purification for drinking purposes, had become inoperative after 6 months because of biofouling and was later stored for 18 months in dry conditions before analysis. SSU rRNA gene library construction, clone sequencing, T-RFLP, light microscope, and scanning electron microscope (SEM) observations were used to identify the microorganisms present on the membrane and possibly responsible for biofouling at the time of removal. The microorganisms were mainly represented by bacteria belonging to the phylum Actinobacteria and by a single protozoan species belonging to the Lobosea group. The microbiological analysis was interpreted in the context of the treatment plant operations to hypothesize as to the possible mechanisms used by microorganisms to enter the plant and colonize the ROM surface.     

Solubilisation of the γ-Aminobutyric Acid/Benzodiazepine Receptor from Rat Cerebellum: Optimal Preservation of the Modulatory Responses by Natural Brain Lipids

We have solubilised the gamma-aminobutyric acid/benzodiazepine (GABA/BDZ) receptor from rat cerebellum using 3-[(3-cholamidopropyl)dimethylammonio] 1-propane sulphonate (CHAPS) in the presence of a natural brain lipid extract and cholesteryl hemisuccinate. The soluble material shows a homogeneous [3H]flunitrazepam ([3H]FNZ) binding population with an equilibrium dissociation constant (KD) of 4.4 +/- 0.2 nM compared to a KD of 2.3 +/- 0.2 nM in cerebellar synaptosomal membranes. The receptor complex in solution retains the characteristic facilitation of [3H]flunitrazepam binding induced by GABA, the pyrazolopyridine cartazolate, and the depressant barbiturate pentobarbital to the same extent as that observed in synaptosomal membranes. Furthermore, these responses are retained both quantitatively and qualitatively when this preparation is stored for 48 h at 4 degrees C. This is contrary to the results obtained with a CHAPS-soluble preparation including asolectin in which these responses are anomalous and extremely labile on storage.     

Electroosmosis in Membranes: Effects of Unstirred Layers and Transport Numbers: I. Theory

When a current is passed through a membrane system, differences in transport numbers between the membrane and the adjacent solutions will, in general, result in depletion and enhancement of concentrations at the membrane-solution interfaces. This will be balanced by diffusion back into the bulk solution, diffusion of solute back across the membrane itself, and osmosis resulting from these local concentration gradients. The two main results of such a phenomenon are (1) that there is a current-induced volume flow, which may be mistaken for electroosmosis, and (2) that there will generally develop transient changes in potential difference (PD) across membranes during and after the passage of current through them.     

Sugar Syrup Concentration Using Reverse Osmosis Membranes

In sugar manufacturing industries, initially dilute syrup is obtained from the cane sugar or beetroot, which should be concentrated. In many factories, sugar syrup concentration is carried out using evaporation. This process has two main problems. Firstly, it consumes a huge amount of energy due to high latent heat of water and secondly, heating may decompose the sugar molecules resulting in low‐quality and dark‐colored sugar. Low energy consuming reverse osmosis may be employed for concentrating sugar syrup without decomposing the molecules, resulting in high‐quality sugar with low cost. In this study different commercial reverse osmosis membranes (DS, DSII, PVD, FT30, BW30) and one nanofiltration membrane (NF45) were used for sugar syrup concentration. The results show that nanofiltration NF45 membrane has no effect on sugar syrup concentration. The rejections of sugar using DSII and PVD reverse osmosis membranes vary between 23 % and 33 % for different operating conditions. DS membrane rejected around 10 % of the sugar molecules in best conditions. FT30 membrane initially showed better performance (55 %). However, the rejection was decreased during time (minimum 7 %). For BW30 membrane, the rejection of sugar was better (60 %) compared to the other membranes used in this work. For two‐stage processes (i.e. the permeate of the first stage used as a feed for the second stage) the highest rejection (88 %) was obtained.     

Factors affecting the attachment of micro-organisms isolated from ultrafiltration and reverse osmosis membranes in dairy processing plants

Aims:  To identify the types of micro-organisms involved in the formation of biofilms on dairy ultrafiltration and reverse osmosis membranes and investigate factors affecting the attachment of those isolates.
Methods and Results:  Micro-organisms isolated from industrial membranes following standard cleaning were identified using the API culture identification system. Thirteen different isolates representing eight genera were isolated and their ability to attach to surfaces was compared using a microtitre plate assay. Three Klebsiella strains attached best, while mixed strains of Pseudomonas and Klebsiella attached better than individual strains. Whey enhanced the attachment of the isolates. The micro-organisms were characterized according to cell surface hydrophobicity using the microbial adhesion to hydrocarbon (MATH) test, and cell surface charge by measuring the zeta potential. These cell surface characteristics did not show a clear relationship with the attachment of our strains.
Conclusions:  A variety of different micro-organisms is associated with dairy ultrafiltration and reverse osmosis membranes after cleaning, suggesting several possible sources of contamination. The cleaning of these membranes may be inadequate. The attachment of the different isolates is highly variable and enhanced in the presence of whey.
Significance and Impact of the Study:  Knowledge of persistent microflora colonizing dairy membrane systems will help develop strategies to mitigate biofilm development in this environment, improving hygiene in membrane processing plants.