On the mass dependence of diffusion within biological membranes and polymers

Summary A simple probability argument suggests that the diffusion coefficient for biological membranes (and polymers) should vary exponentially with the reciprocal of the molecular weight of the diffusant. A test of this relationship shows that it fits the experimental data at least as well as the empirical relation previously proposed. Since the present treatment has some theoretical justification, it would seem to be preferred.     

The diffusion of ions across biological membranes

Summary The derivation of a diffusion equation is given for the transport of ions across biological membranes. It is suggested that the diffusion proceeds by the jumps of ions from one site to another and the number of such sites in the membrane is restricted.     

Oxygen diffusion in biological and artificial membranes determined by the fluorochrome pyrene

Quenching of pyrene fluorescence by oxygen was used to determine oxygen diffusion coefficients in phospholipid dispersions and erythrocyte plasma membranes. The fluorescence intensity and lifetime of pyrene in both artificial and natural membranes decreases about 80% in the presence of 1 atm O2, while the fluorescence excitation and emission spectra and the absorption spectrum are unaltered. Assuming the oxygen partition coefficient between membrane and aqueous phase to be 4.4, the diffusion coefficients for oxygen at 37 degrees C are 1.51 X 10(-5) cm2/s in dimyristoyl lecithin vesicles, 9.32 X 10(-6) cm2/s in dipalmitoyl lecithin vesicles, and 7.27 X 10(-6) cm2/s in erythrocyte plasma membranes. The heats of activation for oxygen diffusion are low (less than 3 kcal/degree-mol). A dramatic increase in the diffusion constant occurs at the phase transition of dimyristoyl and dipalmitoyl lecithin, which may result from an increase in either the oxygen diffusion coefficient, partition coefficient, or both. The significance of the change in oxygen diffusion below and above the phase transition for biological membranes is discussed.     

Lipid microdomains--plant membranes get organized

The plant plasma membrane is now known to be a more sophisticated structure than was previously thought. Sebastien Mongrand et al. and Georg Borner et al. have isolated specific plasma membrane microdomains ('lipid rafts') that are enriched in sterols and sphingolipids. These rafts contain distinct sets of proteins and might help to explain how plasma membrane proteins are positioned in certain parts of the cell to function in development and signalling.     

Lateral diffusion in biological membranes. A normal-mode analysis of diffusion on a spherical surface.

A new approach is described for the analysis of lateral diffusion in biological membranes. It is shown that a suitably defined first moment of the concentration distribution on a spherical surface decays as a single exponential with a relaxation rate proportional to the diffusion coefficient and inversely proportional to the square of the radius of the sphere. The approach is illustrated with an example of fluorescence redistribution after photobleaching of membrane proteins in a spectrin-deficient spherocytic mouse erythrocyte membrane.     

On the principles of functional ordering in biological membranes

Integrating the available data on lipid-protein interactions and ordering in lipid mixtures allows to emanate a refined model for the dynamic organization of biomembranes. An important difference to the fluid mosaic model is that a high degree of spatiotemporal order should prevail also in liquid crystalline, "fluid" membranes and membrane domains. The interactions responsible for ordering the membrane lipids and proteins are hydrophobicity, coulombic forces, van der Waals dispersion, hydrogen bonding, hydration forces and steric elastic strain. Specific lipid-lipid and lipid-protein interactions result in a precisely controlled yet highly dynamic architecture of the membrane components, as well as in its selective modulation by the cell and its environment. Different modes of organization of the compositionally and functionally differentiated domains would correspond to different functional states of the membrane. Major regulators of membrane architecture are proposed to be membrane potential controlled by ion channels, intracellular Ca2+, pH, changes in lipid composition due to the action of phospholipase, cell-cell coupling, as well as coupling of the membrane with the cytoskeleton and the extracellular matrix. Membrane architecture is additionally modulated due to the membrane association of ions, lipo- and amphiphilic hormones, metabolites, drugs, lipid-binding peptide hormones and amphitropic proteins. Intermolecular associations in the membrane and in the membrane-cytoskeleton interface are further selectively controlled by specific phosphorylation and dephosphorylation cascades involving both proteins and lipids, and regulated by the extracellular matrix and the binding of growth factors and hormones to their specific receptor tyrosine kinases. A class of proteins coined architectins is proposed, as a notable example the pp60src kinase. The functional role of architectins would be in causing specific changes in the cytoskeleton-membrane interface, leading to specific configurational changes both in the membrane and cytoskeleton architecture and corresponding to (a) distinct metabolic/differentiation states of the cell, and (b) the formation and maintenance of proper three dimensional membrane structures such as neurites and pseudopods.     

Lateral diffusion in nuclear membranes

Chemical modification of rat liver nuclei with citraconic anhydride selectively removed outer nuclear membrane. This conclusion was based on (a) transmission electron microscopy, (b) lipid analysis, (c) lamin B as an inner membrane-associated marker, and (d) the demonstration of phospholipid lateral mobility on outer membrane-depleted nuclei as a criteria for inner membrane integrity. Addition of urea or N-ethylmaleimide resulted in the additional disruption of inner membrane. Fluorescence photobleaching was used to determine the long range (greater than 4 microns) lateral transport of lectin receptors and a phospholipid analog in both membranes. The diffusion coefficient for wheat germ agglutinin on whole nuclei was 3.9 X 10(-10) cm2/s whereas the diffusion coefficient for wheat germ agglutinin in outer membrane-depleted nuclei was less than or equal to 10(-12) cm2/s. Phospholipid mobilities were the same in whole and outer membrane-depleted nuclei (3.8 X 10(-9) cm2/s). The protein diffusion differences observed between whole and outer membrane-depleted nuclei may be interpreted in the context of two functionally different membrane systems that compose the double bilayer of the nucleus.     

Restricted diffusion in photosynthetic membranes

The structural organization of membrane proteins and their linkage by diffusion are topics of much debate. Functional studies in photosynthetic membranes, where rapid equilibration of electron transport between redox centers appears restricted to isolated domains, shed new light on the subject.     

Domains in biological membranes

Our current view on biological membranes has gradually evolved from the influential fluid mosaic model of the early 1970s to a distinctively more complex picture. Biological membranes are now assumed to encompass multiple membrane domains and a plethora of protein-lipid and protein-protein interactions that compartmentalize and temporarily order what has originally been envisioned to be mostly random. In this minireview, we will first highlight some structural principles that govern membrane domain formation and permit a classification of membrane domains. We will then focus on the still controversial issue of lipid-based membrane domains, or lipid rafts, and discuss recent advances in detecting these enigmatic structures in living cells. Finally we will evaluate biochemical approaches to characterize lipid rafts and discuss their contribution to the emerging topic of lipid raft diversity     

Femtosecond charge separation in organized assemblies: free-radical reactions with pyridine nucleotides in micelles

Femtosecond laser UV pulse-induced charge separation and electron transfer across a polar interface have been investigated in anionic aqueous micells (sodium lauryl sulfate) containing an aromatic hydrocarbon (phenothiazine). The early events of the photoejection of the electron from the micellized chromophore and subsequent reaction of electron with the aqueous perimicellar phase have been studied by ultrafast infrared and visible absorption spectroscopy. The charge separation (chromophore +...e-) inside the micelle occurs in less than 10(-13) s (100 fs). The subsequent thermalization and localization of the photoelectron in the aqueous phase are reached in 250 fs. This results in the appearance of an infrared band assigned to a nonrelaxed solvated electron (presolvated state). This transient species relaxes toward the fully solvated state of the electron in 270 fs. In anionic aqueous micelles containing pyridine dinucleotides at high concentration (0.025-0.103 M), a single electron transfer can be initiated by femtosecond photoionization of phenothiazine. The one-electron reduction of the oxidized pyridine dinucleotide leads to the formation of a free pyridinyl radical. The bimolecular rate constant of this electron transfer depends on both the pH of the micellar system and the concentration of oxidized acceptor. The free-radical reaction is analyzed in terms of the time dependence of a diffusion-controlled process. In the first 2 ps following the femtosecond photoionization of PTH inside the micelle, an early formation of a free pyridinyl radical is observed. This suggests that an ultrafast free-radical reaction with an oxidized form of pyridine nucleotide can be triggered by a single electron transfer in less than 5 X 10(11) s-1.     

On the decay of lateral phase separations in biological membranes

A theory for the decay of a lateral phase separation in a biological membrane has been developed based upon the edge decay of a population of circular molecular domains of uniform size. The theory has been applied to the case of vesicle fusion at a presynaptic membrane. It is shown that the efficiency of fusion decays exponentially in time with a rate constant $\text{solπ}\text{2τ}\text{N}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ which decreases as the rate at which bonds are broken within each domain (τ^?1) decreases and as the number of molecules within each domain (N) increases. Moreover, it has been speculated that this mechanism may offer in part an explanation for the slow, exponential decay during post-tetanic potentiation where it is known that the efficiency of neurotransmitter release at the presynaptic membrane is rate-controlling and decays exponentially.     

Density and diffusion limited aggregation in membranes

Aggregation of membrane molecules is a crucial phenomenon in developing organisms, a classic example being the aggregation of post-synaptic receptors during synaptogenesis. Our understanding of the molecular events involved is improving, but most models of the aggregation or concentration process do not address binding events on the molecular level. An exception is the study of diffusion limited aggregation, in which the aggregation process is simulated on a molecular level. In this analysis, however, important physical parameters such as molecular size, diffusion constant and initial density are not addressed. Thus no predictions about the rate at which such aggregates will form is possible. In the present work the model of diffusion limited aggregation is extended to incorporate these parameters and make the corresponding predictions.     

Nonlinear diffusion in biological systems

Diffusion problem with variabale diffusion coefficient in a spherical biological system is investigated. Also included in this study is the biological reaction of the Michaelis-Menten type. The problem formulated consists of a highly nonlinear differential equation which, however, can be efficiently solved by the orthogonal collocation method on a digital computer. The effects of the dimensionless governing parameters on the transient and steady state concentration responses are parametrically examined for the diffusion system with and without biological reaction.