Pulsed field gradient spin-echo NMR measurement of water diffusion coefficient in thickening and gelling agents: guar galactomannan solutions and pectin gels.

The Pulsed Field Gradient Spin-Echo (PFG-SE) method was used to study the diffusional properties of water in guar galactomannan solutions and in highly methyl-esterified (HDE) pectin solutions and gels. The diffusion coefficient of water in the non-gelling galactomannan system was the same than that of pure water and independent on polymer concentration, despite of a strong increase in viscosity. In the two-component gelling system, pectin-sucrose, the diffusion coefficient of water was lower than in the pure state, and decreasing as a function of the concentration of both constituents. A normalized diffusion coefficient, Dgel/Dsuc, was defined to discriminate the effect of the gelation process on water diffusion, and it showed a clear dependence on the extent of network formation. Unrestricted diffusion was evidenced in all cases.

1H and 23Na NMR relaxation times study of pectin solutions and gels.

1H and 23Na longitudinal and transverse relaxation times have been measured to examine the concentration dependence of the dynamic behaviour of pectin solutions and gels. T1 and T2 relaxation times were measured in HDE pectin solutions and gels prepared with different cosolutes. A lowering of T1 and T2 values was observed in relation to a better efficiency of the intermolecular forces between polymer molecules and/or the formation of more extended junction zones. The T1/T2 ratio was also exploited indicating that even bulk water experiences anisotropic motions due to the gel formation. A correspondence of NMR results with previous reported data of rheological measurements of pectin gels prepared with the same cosolutes was found.

NMR study of seed hydration: effect of pH and ionic strength on water uptake of soaked cowpeas.

A NMR method based on the analysis of the transverse magnetization decay curve of water protons, was employed to study the hydration process of Ife Brown cowpeas. In order to investigate the role of pH and Ionic Strength (IS) on the hydration process the beans were soaked in solutions at different IS and at different pH-constant IS. The kinetic constant for the hydration process and the water-holding capacity of the seeds in different conditions were measured.

NMR investigation of the dynamic behaviour of guar galactomannan water solutions.

Proton longitudinal and transverse relaxation times have been measured to examine the concentration dependence of the dynamic behaviour of guar galactomannan aqueous solutions. Two concentration regimes have been evidenced from our results, with a limiting concentration separating the two regimens at about 3% guar concentration. The T1/T2 ratio indicates that even bulk water experiences anisotropic motions over the limiting concentration. A comparison is made with T1/T2 ratios evaluated in glucose solutions which do not exhibit any deviation from isotropic behaviour of bulk water molecules. The results are discussed taking into account topological entanglement interactions between polysaccharide molecules, according to the current model for the solution behaviour of guar galactomannan.

NMR study of seed hydration: the role of the seed anatomical structures in water uptake of soaked cowpeas.

A NMR method based on the analysis of the transverse magnetization decay curve of water protons, was employed to study the hydration process of commercial cowpeas. In order to investigate the role of the different anatomical parts of the seeds, hilum and micropyle, or alternatively seed coat, were inhibited by a water resistant epoxy resin. The kinetic constant for the hydration of the different sets of beans was measured.

NMR study of seed hydration with deuterated water: dependence of proton signals on hydration level.

Proton NMR signals in seeds are shown to depend on hydration level. In fact at low water amount, as it occurs in many native seeds, protons can have a restricted mobility and are not detectable. A NMR method for measuring the dependence of proton signals on hydration is reported. The method also allows the separation of the contributions of water and non-water protons in a low-resolution NMR experiment. It is based on successive hydrations (with deuterated water) - desiccation steps and on the analysis of the transverse magnetization decay curves.

The water proton spin-lattice relaxation time measurements in liver samples from hepatectomized and sham-operated rats.

We report the proton spin-lattice relaxation times (T1) of rat liver samples taken at different times after partial hepatectomy. The T1 values obtained are compared with those of liver samples from sham-operated rats and of liver samples from rats that had not undergone any surgical treatment. The results show that surgical stress significantly influences the T1 values of sham-operated rats both in their absolute value and in their dependence on the time after the operation, while it induces only a modest early increase of the water content. Possible effects of liver regeneration on 1H-T1 are almost completely concealed by the changes due to the surgical operation. These results emphasize the importance of the choice of a suitable control for T1 measurements in biological systems.

Pyrrolnitrin analogues. V. Knorr's pyrrole condensation between N-(4-nitrophenacyl)-3,5-dimethylaniline and ethyl acetoacetate.

The reaction between N-(4-nitrophenacyl)-3,5-dimethylaniline and ethyl acetoacetate in boiling ethanol afforded 3-carbethoxy-5-(1-carbethoxyacetonyl)-4,5-dihydro-1-(3,5-dimethylphenyl)-4-hydroxy-2-methyl-4-(4-nitrophenyl)pyrrole and in low yield 3-carbethoxy-1-(3,5-dimethylphenyl)-2-methyl-4-(4-nitrophenyl)pyrrole. Chemical transformation of the former compound into 5-acetonyl-1-(3,5-dimethylphenyl)-2-methyl-4-(4-nitrophenyl)pyrrole is described. The structure of 3-carbethoxy-5-(1-carbethoxyacetonyl)-4,5-dihydro-1-(3,5-dimethylphenyl)-4-hydroxy-2-methyl-4-(4-nitrophenyl)pyrrole has been established by the aid of N.M.R. spectral data. The above reaction, when carried out in boiling ethanol in the presence of a catalytic amount of 3,5-dimethylaniline hydrobromide, led to the formation of 3-carbethoxy-1-(3,5-dimethylphenyl)-2-methyl-4-(4-nitrophenyl)pyrrole and 4,6-dimethyl-2-(4-nitrophenyl)indole, the former formed in a very good yield. Some pyrrolnitrin analogues have been prepared starting from 3-carbethoxy-1-(3,5-dimethylphenyl)-2-methyl-4-(4-nitrophenyl)pyrrole.