HYDRODYNAMIC RELAXATION TIMES OF DNA FROM DECAY OF FLOW DICHROISM MEASUREMENTS

The relaxation of the flow dichorism signal of native DNA molecules after rapid (∼0.004 sec) stoppage of the flow has been studied in the narrow‐channel flow dichroism apparatus previously described. The flow dichroism signal decays with a spectrum of relaxation times. The slowest relaxation time accounts for about 0.40 of the total signal for shear gradients in the range of 100–300 sec−1 and for about 0.25 of the total signal for shear gradients in the range of 5,000– 20,000 sec−1. This longest relaxation time in dilute aqueous salt solution at 25°C for T4‐DNA molecules is measured as 0.45 sec; in the molecular weight range from 125 × 106 to 12 × 106, the relaxation time varies as. M1.6±0.1. The relaxation time is proportional to η/T for large (sixfold) changes in solvent viscosity and for temperature changes between 25 and 0°C, showing that the molecular relaxation is hydrodynamically limited. An accurate analysis of the data at short times to determine the shorter relaxation times was not possible. A theoretical prediction based on the Zimm‐Rouse theory of polymer dynamics for the longest relaxation time is in good agreement with the observed value, but the theory predicts that 87%, of the total signal should decay with this relaxation time, whereas experimentally only a smaller fraction of the total signal does so. This discrepancy occurs because the theory is applicable to low hydrodynamic shear stress flows and the experiments were made at higher shear stresses. Copyright © 1969 John Wiley & Sons, Inc.