Dehydration of raffinose pentahydrate: structures of raffinose 5-, 4.433-, 4.289- and 4.127-hydrate at 93†K.

Raffinose [or O-α-D-galactopyranosyl-(1→6)-α-D-glucopyranosyl-(1→2)-ß-D-fructofuranoside] pentahydrate, C18H32O16·5H2O, (I), and three lower hydrates, namely the 4.433-, (II), 4.289-, (III), and 4.127-hydrated, (IV), forms, obtained in the course of the dehydration of (I), have been studied. The unit cells in the space group P212121 are of similar dimensions for all the crystals. The conformation of the raffinose molecules remains almost the same across the four crystal structures. The raffinose molecules are linked into a three-dimensional hydrogen-bonded network involving all the -OH groups, the ring and glycosidic O atoms, and the water molecules. Six water sites were identified in the structures of (II), (III) and (IV), of which W1, W4 and W6 (W = water) are partially occupied with their populations coupled. W1, W4 and one of the -OH groups of the galactose ring form an infinite hydrogen-bonding chain around a 21 axis parallel to the a axis (denoted chain A), and W6 and the same -OH group form a similar chain (chain A') disordered with chain A. The occupancy ratio of chain A to chain A' for N-hydrates (N is a hydration number between 4 and 5) is (N - 4):(5 - N). The transformation of chain A to chain A' as part of the dehydration process has little effect on the rest of the structure. Thus, the dehydration proceeds without significant impact on the crystal structure.

Equations for spectrophotometric determination of relative concentrations of myoglobin derivatives in aqueous tuna meat extracts.

The percentage of metmyoglobin (%metMb) in aqueous meat extracts of bigeye and bluefin tuna and beef samples were estimated using previously reported equations derived from the absorption spectra of horse Mb. The results demonstrate that in an aqueous extract, the difference in %metMb estimated by the different equations was negligible for beef samples. Conversely, in an aqueous tuna extract, different %metMb values were obtained with the different equations. The discrepancy in the tuna sample results might be due to differences in absorption spectra for horse and tuna Mb. Therefore, a new set of equations derived from the absorption spectra of bigeye tuna Mb, reported by Matsuura and Hashimoto (1955), was established. The accuracy of the proposed equations was compared with the cyanmetmyoglobin (cyanmetMb) method. The results show that the total Mb concentrations estimated by our proposed equations were in good agreement with the results obtained by the conventional cyanmetMb method (R(2)=0.984). Therefore, the new set of proposed equations is valid for the spectrophotometric determination of the relative proportions of Mb derivatives and total Mb concentration in aqueous tuna meat extracts.

Ice nucleation and supercooling behavior of polymer aqueous solutions.

We determined the homogeneous nucleation temperature depression, DeltaT(f,hom), the equilibrium melting point depression, DeltaT(m), and the value lambda, which can be obtained from the linear relationship DeltaT(f,hom)=lambdaDeltaT(m), for aqueous solutions of PEG (200-20,000 g mol(-1)), PVP (10,000, 35,000, 40,000 g mol(-1)), and dextran (10,000 g mol(-1)) in the concentration range 0-40 wt% using the emulsion method. The molecular weight dependence of T(f,hom), T(m), and lambda in PEG aqueous solutions was found to change in the vicinity of Mw 600-1540 at all concentrations. In addition, it was confirmed that for all of the polymers studied, there was a good linear relationship between lambda and the logarithmic value of the self-diffusion coefficient D(0) of the solute molecule. These results indicate that the parameters that describe non-equilibrium freezing, such as T(f,hom) and lambda, are dependent on solution properties such as viscosity and self-diffusion of solute molecules.