Influence of kappa-carrageenan gel structures on the diffusion of probe molecules determined by transmission electron microscopy and NMR diffusometry.
The influence of the microstructures of different kappa-carrageenan gels on the self-diffusion behavior of poly(ethylene glycol) (PEG) has been determined by nuclear magnetic resonance (NMR) diffusometry and transmission electron microscopy (TEM). It was found that the diffusion behavior was determined mainly by the void size, which in turn was defined by the state of aggregation of the kappa-carrageenan. The kappa-carrageenan concentration was held constant at 1 w/w%, and the aggregation was controlled by the amount of potassium and/or sodium chloride and, for samples containing potassium, also by the cooling rate. Gels containing potassium formed microstructures where kappa-carrageenan strands are rather evenly distributed over the image size, while sodium gels formed dense biopolymer clusters interspersed with large openings. In a gel with small void sizes, relatively slow diffusion was found for all PEG sizes investigated. Extended studies of the self-diffusion behavior of the 634 g mol(-)(1) PEG showed that there is a strong time dependence in the measured PEG diffusion. An asymptotic lower time limit of the diffusion coefficient was found in all gels when the diffusion observation time was increased. According to the ratio, D/D(0), where D(0) is the diffusion coefficient in D(2)O and D is the diffusion coefficient in the gels, the gels could be divided into three classes: small, medium, and large voids. For quenched kappa-carrageenan solutions with salt concentrations of 20 mM K(+), 100 mM K(+), or 20 mM K(+)/200 mM Na(+) as well as slowly cooled solutions with only 20 mM K(+), D/D(0) ratios between 0.18 and 0.29 were obtained. By quenching a kappa-carrageenan solution with 100 mM K(+), the D/D(0) was 0.5, while D/D(0) ratios between 0.9 and 1 were obtained in a quenched solution with 250 mM Na(+) and slowly cooled samples with 20 mM K(+)/200 mM Na(+) or 250 mM Na(+).
Walther
Bernhard
B
SIK, The Swedish Institute for Food and Biotechnology, PO Box 5401, SE-402 29 Göteborg, Sweden.
Lorén
Niklas
N
Nydén
Magnus
M
Hermansson
Anne-Marie
AM
D002351:Carrageenan / Q000737:chemistry*; D004058:Diffusion; D005782:Gels / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008832:Microchemistry; D046529:Microscopy, Electron, Transmission; D008970:Molecular Weight; D049329:Nanostructures / Q000737:chemistry; D043942:Nanotubes / Q000737:chemistry; D010316:Particle Size; D011092:Polyethylene Glycols / Q000737:chemistry*; D011188:Potassium / Q000737:chemistry; D013997:Time Factors
D005782:Gels; D011092:Polyethylene Glycols; D002351:Carrageenan; D011188:Potassium