Interaction and Dynamics in a Fully Biodegradable Glucose-Containing Naturally Abundant Deep Eutectic Solvent: Temperature-Dependent Time-Resolved Fluorescence Measurements.

Abstract

A new room-temperature deep eutectic solvent (DES) composed of glucose, urea, and water has been prepared and its relaxation dynamics explored via temperature-dependent time-resolved fluorescence measurements employing hydrophilic and hydrophobic solute probes. Differential scanning calorimetry measurements indicate a glass transition temperature (Tg) of ∼236 K. Measured viscosity coefficients (η) vary from ∼600 to ∼100 cP in the temperature range 318 ≤ T/K ≤ 343 and exhibit Arrhenius-type temperature dependence with an activation energy of ∼65 kJ mol-1. Interestingly, this DES forms a stable liquid at ∼300 K but is too viscous to be accurately measured by us below 318 K. Temperature-dependent dynamic fluorescence anisotropy measurements using hydrophobic and hydrophilic solutes of similar sizes reveal bi-exponential kinetics and Arrhenius-type temperature dependence for solute rotation times (⟨τr⟩) but with significantly decreased activation energies, ∼31 kJ mol-1 (hydrophobic) and ∼21 kJ mol-1 (hydrophilic). Deviation from hydrodynamics is further reflected in the strong fractional viscosity dependence of ⟨τr⟩: ⟨τr⟩ ∝ (η/T)p with p ≈ 0.3-0.5, indicating pronounced temporal heterogeneity in the relaxation dynamics. Dynamic fluorescence Stokes shift measurements (temporal resolution ∼85 ps) produce dynamic shifts of ∼500-700 cm-1, bi-exponential solvation energy relaxation with time constants in the range ∼0.2 ns and ∼4 ns, and estimated missing amplitudes of ∼65-75%. Impact of the density difference between a nonpolar solvent and this DES on the estimated missing amplitudes is explored via measuring the temperature-dependent densities and refractive indices of this DES. Lifetime measurements suggest considerable temperature dependence for the hydrophobic solute but no such dependence for the hydrophilic one. Excitation energy dependence of fluorescence emission of various solutes with widely different lifetimes indicates mild spatial heterogeneity for this DES.