Raman Spectroscopy as a Tool for Measuring Mutual-Diffusion Coefficients in Hydrogels

Raman spectroscopy has been exploited to characterize the diffusion properties of solutes in hydrogels. Raman active vibrations were used as intrinsic probes of the solute concentration along gel cylinders. The resulting one-dimensional solute distribution, characterized as a function of both time and space, could be analyzed with a model based on Fick's diffusion law, and the mutual-diffusion coefficient (Dm) was then determined. To illustrate the potential of this approach, we measured the Dm of two polyethylene glycols (PEG) in Ca–alginate gels. In this case, the intensity of the CH stretching band was used to obtain the concentration profiles of PEGs, whereas the OH stretching band of water was used as an internal intensity standard. In addition to providing a straightforward approach to measuring diffusion coefficients, the Raman profile analysis provides information relative to the accessibility of gels to large molecules. As an example, it was found that the PEG penetration in Ca–alginate gels was restricted, a phenomenon that was dependent on PEG size. The Raman technique presented here effectively characterizes transport properties of solutes in gels, and such characterization is required for developing several technical applications of gels, such as their use as materials for controlled release of drugs.

[1]  B. Amsden,et al.  Solute Diffusion within Hydrogels. Mechanisms and Models , 1998 .

[2]  P. Wahl,et al.  Diffusion of proteins in the chromatographic gel AcA-34 , 1991 .

[3]  Wim E. Hennink,et al.  Controlled release of proteins from dextran hydrogels , 1996 .

[4]  J. Williams,et al.  Partition and permeation of dextran in polyacrylamide gel. , 1998, Biophysical journal.

[5]  A. Donald,et al.  Diffusion of bovine serum albumin in amylopectin gels measured using Fourier transform infrared microspectroscopy , 1994 .

[6]  F. Yuan,et al.  Available Space and Extracellular Transport of Macromolecules: Effects of Pore Size and Connectedness , 2001, Annals of Biomedical Engineering.

[7]  V V Tuchin,et al.  [Water exchange in human crystalline lens studied by combined dispersion confocal microspectroscopy]. , 1998, Biofizika.

[8]  F. R. Pérez,et al.  Mass Diffusion Transport Studies of Lithium Sulfate in Aqueous Solutions Using Raman Spectroscopy , 1995 .

[9]  K. Arndt,et al.  Investigation of swelling and diffusion in polymers by 1H NMR imaging: LCP networks and hydrogels , 2000 .

[10]  V. Klepko,et al.  Self-diffusion of water in gelatin gels: 1. Macroscopic measurements by tracer technique , 1993 .

[11]  P. Wahl,et al.  Study of the translational diffusion of macromolecules in beads of gel chromatography by the FRAP method. , 1988, Biophysical chemistry.

[12]  John Crank,et al.  The Mathematics Of Diffusion , 1956 .

[13]  G. Stephanopoulos,et al.  Diffusion coefficients of glucose and ethanol in cell‐free and cell‐occupied calcium alginate membranes , 1986, Biotechnology and bioengineering.

[14]  Ivar Storrø,et al.  Alginate as immobilization material: III. Diffusional properties , 1992, Biotechnology and bioengineering.

[15]  B. Amsden Solute diffusion in hydrogels. , 1998 .

[16]  I. Tokimitsu,et al.  Relationship between covalently bound ceramides and transepidermal water loss (TEWL) , 2000, Archives of Dermatological Research.

[17]  Jung-heon Lee,et al.  Curdlan gels as protein drug delivery vehicles , 2000, Biotechnology Letters.

[18]  G. Skjåk-Bræk,et al.  Inhomogeneous polysaccharide ionic gels , 1989 .

[19]  I. Sutherland,et al.  Structure-function relationships in microbial exopolysaccharides. , 1994, Biotechnology advances.

[20]  Hideo Tanaka,et al.  Diffusion characteristics of substrates in Ca‐alginate gel beads , 1984, Biotechnology and bioengineering.

[21]  P. Lundberg,et al.  Diffusion of solutes in agarose and alginate gels: 1H and 23Na PFGSE and 23Na TQF NMR studies , 1997, Magnetic resonance in medicine.

[22]  K. Draget,et al.  Alginate based new materials. , 1997, International journal of biological macromolecules.

[23]  H. Damme,et al.  Microscale and Macroscale Diffusion of Water in Colloidal Gels. A Pulsed Field Gradient and NMR Imaging Investigation , 1999 .

[24]  Wayne R. Gombotz,et al.  Protein release from alginate matrices. , 1998, Advanced drug delivery reviews.

[25]  H. Svendsen,et al.  The effective diffusion coefficient and the distribution constant for small molecules in calcium‐alginate gel beads , 1995, Biotechnology and bioengineering.

[26]  J. Anderson,et al.  Partitioning and diffusion of proteins and linear polymers in polyacrylamide gels. , 1996, Biophysical journal.

[27]  A. Donald,et al.  Diffusion of mixed micelles of bile salt-lecithin in amylopectin gels: a Fourier transform infrared microspectroscopy approach. , 1996, Biophysical chemistry.

[28]  C. Sammon,et al.  Materials analysis using confocal Raman microscopy , 1999 .

[29]  X. Zhu,et al.  Physical models of diffusion for polymer solutions, gels and solids , 1999 .

[30]  Alan H. Muhr,et al.  Diffusion in gels , 1982 .

[31]  D. Sellen Laser light scattering study of polyacrylamide gels , 1987 .

[32]  G. Junter,et al.  Diffusion in immobilized-cell agar layers: influence of microbial burden and cell morphology on the diffusion coefficients ofl-malic acid and glucose , 2004, Applied Microbiology and Biotechnology.

[33]  M. Dewhirst,et al.  Available volume fraction of macromolecules in the extravascular space of a fibrosarcoma: implications for drug delivery. , 1999, Cancer research.

[34]  J. C. Selser,et al.  Asymptotic behavior and long-range interactions in aqueous solutions of poly(ethylene oxide) , 1991 .

[35]  E. V. Meerwall,et al.  Interpreting pulsed‐gradient spin–echo diffusion experiments with permeable membranes , 1981 .