Frequency spectrum of enthalpy fluctuations associated with macromolecular transitions.

A multifrequency calorimeter has been designed to measure the amplitude and time regime of the enthalpic fluctuations associated with structural or conformational transitions in biological macromolecular systems. The heat capacity function at constant pressure is directly proportional to the magnitude of the enthalpic fluctuations in a system. Biological macromolecules undergo thermally induced transitions of different kinds. Within the transition region, these systems exhibit relatively large enthalpy fluctuations that give rise to the characteristic peaks observed by conventional differential scanning calorimetry. The multifrequency calorimeter developed in this laboratory has been designed to measure the frequency spectrum of the enthalpy fluctuations, thus allowing us to estimate thermodynamic parameters as well as relaxation times. This information is obtained from the attenuation in the amplitude or phase-angle shift of the response of the system to a periodic temperature oscillation. This instrument has been used to study the gel-liquid crystalline transition of phosphatidylcholine bilayers. The frequency-temperature response surface for large dimyristoyl phosphatidylcholine vesicles has been measured in the frequency range 0.04-1 Hz. The data are consistent with two enthalpic relaxation processes with time constants on the order of 3.8 s and 80 ms at the midpoint of the main gel-liquid crystalline transition.