Diffusion structure-property correlations

Diffusion and Surface Exchange Coefficients Structure-Property Correlations... 

Figures 2.20 and 2.21 show the significant difference between diffusion in liquids and in rubbery and glassy polymers. A great deal of work has been performed over the last two decades to achieve a quantitative link between the structure of polymers and their permeation properties. No such quantitative structure-property relationship is at hand or even in sight. What has been achieved is a set of semiempirical rules that allow the permeation properties of related families of polymers to be correlated based on small changes in their chemical structures. The correlating tool most generally used is the polymer s fractional free volume v/ (cm3/cm3), usually defined as...

Third, a serious need exists for a data base containing transport properties of complex fluids, analogous to thermodynamic data for nonideal molecular systems. Most measurements of viscosities, pressure drops, etc. have little value beyond the specific conditions of the experiment because of inadequate characterization at the microscopic level. In fact, for many polydisperse or multicomponent systems sufficient characterization is not presently possible. Hence, the effort probably should begin with model materials, akin to the measurement of viscometric functions [27] and diffusion coefficients [28] for polymers of precisely tailored molecular structure. Then correlations between the transport and thermodynamic properties and key microstructural parameters, e.g., size, shape, concentration, and characteristics of interactions, could be developed through enlightened dimensional analysis or asymptotic solutions. These data would facilitate systematic... 

For a number of years the existence of a porous or polar pathway through the stratum comeum, in parallel with the lipoidal pathway, has been hypothesized. Although there has been some criticism of this concept, it is our belief that the root of the lack of a common consensus among scientists in the field can be attributed largely to the limited number of systematic studies in the literature that directly address the issue of the diffusion of polar and ionic permeants across skin. Based upon recent studies that have focused upon this aspect of transdermal diffusion, the existence of a porous permeation pathway through HEM is clear (Hatanaka et al., 1993, 1994 Peck et al., 1993, 1994, 1995). At this point, we have made no attempt to correlate the findings from our studies with specific structural properties of the HEM. In some cases, authors have implicated shunt routes such as hair follicles and sweat ducts to account for permeation data not consistent with the concept of lipoidal membrane permeation (Cornwell and Barry, 1993 Scheuplein and Blank, 1971). Under ionto-phoretic conditions, such shunt routes have been shown to contribute to current conduction (Cullander and Guy, 1991 Scott et al., 1993). When efforts have been made to estimate the effective Rp of skin samples under iontophoretic conditions (Ruddy and Hadzija, 1992), osmotic conditions (Hatanaka et al.,... 

Perhaps one of the greatest successes of the molecular dynamics (MD) method is its ability both to predict macroscopically observable properties of systems, such as thermodynamic quantities, structural properties, and time correlation functions, and to allow modeling of the microscopic motions of individual atoms. From modeling, one can infer detailed mechanisms of structural transformations, diffusion processes, and even chemical reactions (using, for example, the method of ab initio molecular dynamics).Such information is extremely difficult, if not impossible, to obtain experimentally, especially when detailed behavior of a local defect is sought. The variety of different experimental conditions that can be mimicked in an MD simulation, such as... 

We will deal with the permeability in greatest detail, because it is the quantity of most direct interest in applications. In developing a more fundamental theoretical understanding of transport, however, it will be crucial to consider the diffusivity and the solubility separately. Many of the shortcomings of simple structure-property relationships for the permeability and selectivity may possibly be overcome by a more fundamental understanding, which may therefore also be useful in future refinements and practical applications of correlative schemes. 

Several detailed analyses of the diffusion process in both rubbery polymers and in hindered glasses are offered in Chapter 2 (28). Approximate molecular interpretations have been offered for the parameters in these models (25). Nevertheless, more work is needed to verify any molecular scale connection between such parameters and the structures and motions of the polymer backbone. Spectroscopy and molecular modeling of the differences in segmental motions in a systematically varied family of polymers, e.g, the polyesters, or polyamides, can offer insight in some cases. Unfortunately, the exact segmental motions involved in the diffusive process are only partially understood, so one must be cautious about drawing conclusions based on such studies unless they are supported by actual complementary transport data. Hopefully the structure-property results presented in this book will further stimulate thinking to improve the connection between spectroscopically sensed motions, and diffusion to complement the correlations based on specific free volume in Chapters 5 S 7 (50,51). ... 

Basic requirements on feasible systems and approaches for computational modeling of fuel cell materials are (i) the computational approach must be consistent with fundamental physical principles, that is, it must obey the laws of thermodynamics, statistical mechanics, electrodynamics, classical mechanics, and quantum mechanics (ii) the structural model must provide a sufficiently detailed representation of the real system it must include the appropriate set of species and represent the composition of interest, specified in terms of mass or volume fractions of components (iii) asymptotic limits, corresponding to uniform and pure phases of system components, as well as basic thermodynamic and kinetic properties must be reproduced, for example, density, viscosity, dielectric properties, self-diffusion coefficients, and correlation functions (iv) the simulation must be able to treat systems of sufficient size and simulation time in order to provide meaningful results for properties of interest and (v) the main results of a simulation must be consistent with experimental findings on structure and transport properties. 

One of the key parameters for correlating molecular structure and chemical properties with bioavailability has been transcorneal flux or, alternatively, the corneal permeability coefficient. The epithelium has been modeled as a lipid barrier (possibly with a limited number of aqueous pores that, for this physical model, serve as the equivalent of the extracellular space in a more physiological description) and the stroma as an aqueous barrier (Fig. 11). The endothelium is very thin and porous compared with the epithelium [189] and often has been ignored in the analysis, although mathematically it can be included as part of the lipid barrier. Diffusion through bilayer membranes of various structures has been modeled for some time [202] and adapted to ophthalmic applications more recently [203,204]. For a series of molecules of similar size, it was shown that the permeability increases with octa-nol/water distribution (or partition) coefficient until a plateau is reached. Modeling of this type of data has led to the earlier statement that drugs need to be both... 

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