RESUMEN
We investigated the effect of pH (5.2 to 6.8) on the hydrolysis of a sodium polyphosphate in water, milk, calcium caseinate, and spreadable processed cheese, as well as the effect of pH on the cheese structure. Monitoring of the hydrolysis in water and the different milk matrices was carried out using 31P nuclear magnetic resonance technique. In general, the decrease in pH increased the hydrolysis of polyphosphates in all matrices. The presence of calcium in milk increased the rate of hydrolysis. Hydrolysis in milk was higher than in calcium caseinate, probably due to lower molecular mobility in concentrated systems with high viscosity. Increasing the pH decreased the hardness and adhesiveness of the cheeses. At low pH (5.2 and 5.6), the cheeses presented a granular structure, although, at more neutral pH (6.0 to 6.8), the structure was continuous, homogeneous, and more fluid. These results highlight the importance of precise pH control in the manufacture of processed cheeses.
Asunto(s)
Caseínas/química , Queso/análisis , Leche/química , Polifosfatos/química , Adhesividad , Animales , Dureza , Concentración de Iones de Hidrógeno , Hidrólisis , Fosfatos/química , Sodio/química , ViscosidadRESUMEN
1H, 13C and 15N NMR spectra of eight 2-amino-N'-(aryl)-benzamidines and of the parent compound were recorded, and unequivocal chemical shift assignments through the use of COSY, 1H-J resolved, HETCOR and COLOC sequences were performed. 1H and 13C chemical shifts for the nuclei of the benzamidine aromatic ring were not affected by the substituents present at N'-phenyl group, while the substituent effects in the chemical shifts of the same nuclei of N'-phenyl ring were very similar to the ones reported for the corresponding monosubstituted benzenes, indicating that there is no interaction between the two aromatic rings. 15N NMR spectra (DEPT sequence) show just two hydrogenated nitrogen atoms, which confirm that the amino form is the most stable tautomer, but the observation of a sharp signal and two broad signals (15N decoupled spectra), and the corresponding broad signal for the =C-NH(2) protons (in the 1H spectra), indicates the occurrence of tautomerism between the amino and imino forms, observable for some of the studied benzamidines. Theoretical calculations lead to the conclusion that these compounds occur mostly as the amino tautomer with Z configuration, which is stabilized by hydrogen bonding.
Asunto(s)
Benzamidinas/química , Calorimetría , Espectroscopía de Resonancia Magnética/métodos , Modelos Teóricos , Conformación MolecularRESUMEN
The carbonyl stretching vibration of 2-bromocyclohexanone (1) has been measured in a variety of solvents. It is shown that its component intensities are not only dependent on the populations of the axial and equatorial conformers, but are also dependent on the molar absorptivities (epsilon ) which are specific for each conformer in each solvent. In CCl(4), the axial and equatorial conformers have epsilon values of 417 and 818 l mol(-1) x cm(-1), respectively, while in CH(3)CN solution, the values were 664 and 293 l mol(-1) x cm(-1). These results are supported by results of theoretical calculations of frequencies, which gave an intensity of 223.8 kM mol(-1) x(1782 cm(-1)) for the axial and 174.4 kM mol(-1) x (1802 cm(-1)) for the equatorial conformer, indicating that the axial conformer presents a larger molar absorptivity than the equatorial one in the vapor phase. Moreover, the results presented here clearly demonstrate that although infrared spectroscopy at a single temperature can be an important auxiliary technique for conformational analysis, it must not be used to quantify conformational preferences of a molecule if the absorption molar coefficients for each conformer are not known or not amenable to experimental determination.
Asunto(s)
Espectrofotometría Infrarroja/métodos , Carbono/química , Ciclohexanonas/química , Modelos Químicos , Conformación Molecular , TemperaturaRESUMEN
The conformational equilibrium of 2-methoxycyclohexanone has been analyzed through infrared spectroscopy and theoretical calculations. These calculations indicate that six conformations may be present in the vapor phase, due to the rotation of the methoxy group around the O-C(2) bond, leading to axial (g(+), g(-) and anti) and equatorial (g(+), g(-) and anti) conformers. However, the infrared spectrum in CCl(4) solution shows just three carbonyl stretching bands, corresponding to the conformers of lower energies. An additional band is observed for the CH(3)CN solution, attributed to a fourth conformer stabilized by a dipole-dipole interaction between this conformer, having a high dipole moment, and the very polar solvent. An interpretation of the governing factors of 2-methoxycyclohexanone equilibria is also given.