Membrane diffusion transverse

Certain microbes synthesize small organic molecules, ionophores, that function as shuttles for the movement of ions across membranes. These ionophores contain hy-drophihc centers that bind specific ions and are surrounded by peripheral hydrophobic regions this arrangement allows the molecules to dissolve effectively in the membrane and diffuse transversely therein. Others, Hke the well-smdied polypeptide gramicidin, form channels. 

Lateral diffusion is in the plane of the membrane, and transverse (flip-flop) diffusion is perpendicular to the membrane (through the membrane). Lateral diffusion (in two dimensions) is fast, and transverse diffusion is slow (or nonexistent) except for gases (C02, NH3) and hydrophobic, uncharged, small molecules (such as cholesterol)... 

Although phospholipids diffuse laterally in the plane of the bilayer and rotate more or less freely about an axis perpendicular to this plane, movements from one side of the bilayer to the other are a different matter. Diffusion across the membrane, a transverse, or flip-flop, motion, requires getting the polar head-group of the phospholipid through the... 

NBD probes are often used to assay flip-flop. Flip-flop refers to the reversible transversal diffusion of lipids from one leaflet to the other leaflet of a lipid bilayer membrane. In intact membranes, this transversal diffusion is very slow (fi/2 on the order of hours to days). However, it can be accelerated by biological or synthetic flippases, which are a special class of membrane transporters related to ion carriers. Alternatively, micellar pores are synthetic ion channels and pores with flippase activity and can thus be identified with flip-flop assay (Figure 2 interfacial location of the transporter, as second distinctive characteristic of micellar pores, can be identified by fluorescence depth quenching experiments with DOXYL probes). 

The membranes of cells are generally asymmetric, in that the lipids and proteins that inhabit the membrane are not evenly distributed across both the leaflets of the bilayer. To maintain this necessary membrane asymmetry, transverse diffusion of phospholipids (flip-flop. Figure 6a) in cellular membranes is accelerated by translocase enzymes like the flippases. These enzymes overcome the energy barrier for the passage of polar headgroups through the apolar center of the membrane and maintain asymmetry by the consumption of adenosine triphosphate (ATP). ... 

A cell membrane is illustrated in Fig. 6.1. It is built from a bilayer of lipids, usually phospholipids, associated with which are membrane proteins and polysaccharides. The antiparallel orientation of lipid layers in the bilayer is maintained due to the extremely slow flip-flop rate, i.e. the rate of diffusion transverse to the bilayer. The lipid bilayer is the structural foundation and the proteins and polysaccharides provide chemical functionality. The protein to lipid ratio shows a large variation depending on the cell, but proteins make up at least half of most cell membranes. A prominent exception is mammalian nerve cells which contain only 18 % protein (here also the lipids are sphingomyelins rather than phospholipids). Here, the primary requirement is that the cell membrane should be effective as an electrical... 

Lipids also undergo rapid lateral motion in membranes. A typical phospholipid can diffuse laterally in a membrane at a linear rate of several microns per second. At that rate, a phospholipid could travel from one end of a bacterial ceil to the other in less than a second or traverse a typical animal ceil in a few minutes. On the other hand, transverse movement of lipids (or proteins) from one face of the bilayer to the other is much slower (and much less likely). For example, it can take as long as several days for half the phospholipids in a bilayer vesicle to flip from one side of the bilayer to the other. 

W. R. Lieb and W. D. Stem, Non-stochesian nature of the transverse diffusion within hmnan red cell membranes. J. Membr. Biol. 1986, 92, 111-110. 

As described earlier, the inside-outside asymmetry of membrane proteins is stable, and mobifity of proteins across (rather than in) the membrane is rare therefore, transverse mobility of specific carrier proteins is not likely to account for facilitated diffusion processes except in a few unusual cases. 

To move through the membrane (change sides or transverse diffusion), a molecule must be able to pass through the hydrophobic portion of the lipid bilayer. For ions and proteins, this means that they must lose their interactions with water (desolvation). Because this is extremely difficult, ions and proteins do not move through membranes by themselves. Small molecules such as C02, NH3 (but not NH ). and water can diffuse through membranes however, most other small molecules pass through the lipid bilayer very slowly, if at all. This permeability barrier means that cells must develop mechanisms to move molecules from one side of the membrane to the other. 

Lieb WR, Stein WD (1986) Non-stokesian nature of transverse diffusion within human red blood cells. J Membrane Biol 92 111-119. 

In PEMFC systems, water is transported in both transversal and lateral direction in the cells. A polymer electrolyte membrane (PEM) separates the anode and the cathode compartments, however water is inherently transported between these two electrodes by absorption, desorption and diffusion of water in the membrane.5,6 In operational fuel cells, water is also transported by an electro-osmotic effect and thus transversal water content distribution in the membrane is determined as a result of coupled water transport processes including diffusion, electro-osmosis, pressure-driven convection and interfacial mass transfer. To establish water management method in PEMFCs, it is strongly needed to obtain fundamental understandings on water transport in the cells. 

Fig. 17 General scheme of an IWAO design, where the input and output ARROW waveguides and the active membrane and the optical fibers are indicated. Notice that the analyte diffusion direction is transverse to the light transmission direction. L membrane length and optical path length, d membrane thickness...

The overall mass-transfer rates on both sides of the membrane can only be calculated when we know the convective velocity through the membrane layer. For this, Equation 14.2 should be solved. Its solution for constant parameters and for first-order and zero-order reaction have been given by Nagy [68]. The differential equation 14.26 with the boundary conditions (14.28a) to (14.28c) can only be solved numerically. The boundary condition (14.28c) can cause strong nonlinearity because of the space coordinate and/or concentration-dependent diffusion coefficient [40, 57, 58] and transverse convective velocity [11]. In the case of an enzyme membrane reactor, the radial convective velocity can often be neglected. Qin and Cabral [58] and Nagy and Hadik [57] discussed the concentration distribution in the lumen at different mass-transport parameters and at different Dm(c) functions in the case of nL = 0, that is, without transverse convective velocity (not discussed here in detail). 

Integral proteins are usually free to move in the plane of the bilayer by lateral and rotational movement, but are not able to flip from one side of the membrane to the other (transverse movement). Immunofluorescence microscopy may be used to follow the movement of two proteins from different cells following fusion of the cells to form a hybrid heterokaryon. Immediately after fusion the two integral proteins are found segregated at either end of the heterokaryon but with time diffuse to all areas of the cell surface. The distribution of integral proteins within the membrane can be studied by electron microscopy using the freeze-fracture technique in which membranes are fractured along the interface between the inner and outer leaflets. 

In the fourth subtechnique, flow FFF (F/FFF), an external field, as such, is not used. Its place is taken by a slow transverse flow of the carrier liquid. In the usual case carrier permeates into the channel through the top wall (a layer of porous frit), moves slowly across the thin channel space, and seeps out of a membrane-frit bilayer constituting the bottom (accumulation) wall. This slow transverse flow is superimposed on the much faster down-channel flow. We emphasized in Section 7.4 that flow provides a transport mechanism much like that of an external field hence the substitution of transverse flow for a transverse (perpendicular) field is feasible. However this transverse flow—crossflow as we call it—is not by itself selective (see Section 7.4) different particle types are all transported toward the accumulation wall at the same rate. Nonetheless the thickness of the steady-state layer of particles formed at the accumulation wall is variable, determined by a combination of the crossflow transport which forms the layer and by diffusion which breaks it down. Since diffusion coefficients vary from species to species, exponential distributions of different thicknesses are formed, leading to normal FFF separation. 

In addition to the Navier-Stokes equations, the convective diffusion or mass balance equations need to be considered. Filtration is included in the simulation by preventing convection or diffusion of the retained species. The porosity of the membrane is assumed to decrease exponentially with time as a result of fouling. Wai and Fumeaux [1990] modeled the filtration of a 0.2 pm membrane with a central transverse filtrate outlet across the membrane support. They performed transient calculations to predict the flux reduction as a function of time due to fouling. Different membrane or membrane reactor designs can be evaluated by CFD with an ever decreasing amount of computational time. 

Figure 12.31. Lipid Movement in Membranes. Lateral diffusion of lipids is much more rapid than transverse diffusion (flip-flop).

Membranes are structurally and functionally asymmetric, as exemplified by the restriction of sugar residues to the external surface of mammalian plasma membranes. Membranes are dynamic structures in which proteins and lipids diffuse rapidly in the plane of the membrane (lateral diffusion), unless restricted by special interactions. In contrast, the rotation of lipids from one face of a membrane to the other (transverse diffusion, or flip-flop) is usually very slow. Proteins do not rotate across bilayers hence, membrane asymmetry can be preserved. The degree of fluidity of a... 

Flip-flop. The transverse diffusion of phospholipids in a bilayer membrane was investigated by using a paramagnetic analog of phosphatidyl choline, called spin-labeled phosphatidyl choline. 

In membranes, the motional anisotropies in the lateral plane of the membrane are sufficiently different from diffusion in the transverse plane that the two are separately measured and reported [4b, 20d,e]. Membrane ffip-ffop and transmembrane diffusion of molecules and ions across the bilayer were considered in a previous section. The lateral motion of surfactants and additives inserted into the lipid bilayer can be characterized by the two-dimensional diffusion coefficient (/)/). Lateral diffusion of molecules in the bilayer membrane is often an obligatory step in membrane electron-transfer reactions, e.g., when both reactants are adsorbed at the interface, that can be rate-limiting [41]. Values of D/ have been determined for surfactant monomers and probe molecules dissolved in the membrane bilayer typical values are given in Table 2. In general, lateral diffusion coefficients of molecules in vesicle... 

Based upon a detailed analysis of reaction transients, a mechanism was proposed for chlorophyll a-photosensitized transmembrane oxidation-reduction of aqueous phase donors and acceptors that included electron transfer between juxtaposed Chi a+ r-cations and Chi a molecules as the transmembrane charge-transfer step [112]. The maximum apparent first-order rate constant for this step was 10 s , which seems large for thermal electron transfer between chlorophyll molecules located at the opposite membrane interfaces, even considering that nuclear activation barriers may be relatively small for this reaction. Transverse flip-flop diffusion of Chi b across the membrane is 10 -fold slower than transmembrane redox under these conditions, so this alternative mechanism is almost certainly unimportant. Kinetic mapping studies have shown that some of the Chi a becomes localized within the membrane at sites that are inaccessible to aqueous phase electron acceptors, presumably within the membrane interior [114]. This suggests the possibility of a transverse hopping mechanism involving electron transfer over relatively short distances from buried Chi a to interfacial Chi a+, followed by electron transfer from Chi a at the opposite interface to the buried Chi a" ". 

The importance of the ionomer in the electrode for the performance of the PEMFC has been well known since the pioneering work of Raistrick et al. [37]. In the PEMFC, the electroosmotic drag of water due to the proton transport from the anode to the cathode leads to the membrane drying out from the anode side (back diffusion of water from cathode to anode compensates partly for the water loss from the anode side of the membrane). Therefore, the loss of conductivity of the ionomer at the anode is also an additional important issue related to the membrane topic, since the ionomer in the electrode needs to connect ionically and chemically to the membrane. In an investigation of the transverse water profile in Nafion in PEMFCs with a... 

Since the cell walls offer more resistance to diffusion than do the lumens, it is evident that transverse diffusion is essentially determined by the diffusion coefficient of the moisture through the cell walls and by the thickness of cell wall traversed per unit distanee, i.e. the basic density of the wood. The presenee of pits and the condition of their pit membranes do not influence diffusion very mueh if no diffusion occurred through the pits the transverse diffusion eoefficient would be reduced by only 10% and if the pit membranes were removed entirely the diffusion coefficient would inerease only three-fold (Stamm, 1967b). 

Fig. 3 One-dimensional loading profiles of benzene across a NaX zeolitic, single crystal membrane. The loading is the spatial average over planes perpendicular to the main diffusion direction (three-dimensional simulations are conducted periodic boundary conditions are employed in the transverse direction and Robin at the membrane interfaces exposed to the high- and low-pressure sides). The inset shows a schematic of the membrane. (View this art in color at www. dekker.com.)...

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