Observation of non-equilibrium fluctuation in the shear-stress-driven hemoglobin aggregates.

Non-equilibrium fluctuations caused by the rearrangement of hemoglobin molecules into an aggregate state under shear stress have been investigated experimentally. The flow response under the shear stress (σ) corroborates the presence of contrasting aggregate and rejuvenation states governed by entropy production and consumption events. From the time-dependent shear rate fluctuation studies of aggregate states, the probability distribution function (PDF) of the rate of work done is observed to be spread from negative to positive values with a net positive mean. The PDFs follow the steady-state fluctuation theorem, even at a smaller timescale than that desired by the theorem. The behavior of the effective temperature (Teff) that emerges from a non-equilibrium fluctuation and interconnects with the structural restrictions of the aggregate state of our driven system is observed to be within the boundary of the thermodynamic uncertainty. The increase in Teff with the applied σ illustrates a phenomenal nonlinear power flux-dependent aggregating behavior in a classic bio-molecular-driven system.

Entropy-driven nonequilibrium phonon-stimulated electron-phonon coupling in tin dioxide nanorods.

Nonequilibrium (NEQ) phonon fluctuation in a nanosystem has been studied through the statistical assessment of the entropy-production and -consumption events in ultrasmall tin dioxide (SnO_{2}) nanorods. Size- and shape-dependent alteration in free energy leading to modulation of the probability distribution function of the phonon dynamics has been observed from the x-ray diffraction and Raman scattering characterizations. The Gallavotti-Cohen nonequilibrium fluctuation theorem has been utilized to qualitatively describe the aforementioned behaviors under the influence of a global flux. The observation of entropy consumption and thermodynamically favorable entropy-production events indicates the presence of NEQ fluctuations in the phonon modes. The effective energy scale of fluctuation in driven phonon modes, dissipating energy faster than relaxation time, is quantified on the order of nanojoules. From optical absorption and photoluminescence studies, the observation of the electron-phonon coupled state confirms the interaction of the NEQ phonons with electrons. The strength of the coupling has been estimated from the temperature-independent Barry center shift and found to be enhanced to 5.35. Valence band x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy analyses reconcile NEQ phonon mediated alteration of the valence band density of states, activation of silent phonon modes, and superior excitonic transitions, suitable for the new generation of ultrafast quantum device applications.