Anisotropic Thermal Conductivity of Inkjet-Printed 2D Crystal Films: Role of the Microstructure and Interfaces.

Two-dimensional (2D) materials are uniquely suited for highly anisotropic thermal transport, which is important in thermoelectrics, thermal barrier coatings, and heat spreaders. Solution-processed 2D materials are attractive for simple, low-cost, and large-scale fabrication of devices on, virtually, any substrate. However, to date, there are only few reports with contrasting results on the thermal conductivity of graphene films, while thermal transport has been hardly measured for other types of solution-processed 2D material films. In this work, inkjet-printed graphene, h-BN and MoS2 films are demonstrated with thermal conductivities of ∼10 Wm-1K-1 and ∼0.3 Wm-1K-1 along and across the basal plane, respectively, giving rise to an anisotropy of ∼30, hardly dependent on the material type and annealing treatment. First-principles calculations indicate that portion of the phonon spectrum is cut-off by the quality of the thermal contact for transport along the plane, yet the ultra-low conductivity across the plane is associated with high-transmissivity interfaces. These findings can drive the design of highly anisotropic 2D material films for heat management applications.

Room temperature second sound in cumulene.

Second sound is known as the thermal transport regime occurring in a wave-like fashion, usually identified in a limited number of materials only at cryogenic temperatures. Here we show that second sound in a µm-long carbon chain (cumulene) might occur even at room temperature. To this aim, we calibrate a many-body force field on the first principles calculated phonon dispersion relations of cumulene and, through molecular dynamics, we mimic laser-induced transient thermal grating experiments. We provide evidence that by tuning temperature as well as the space modulation of its initial profile we can reversibly drive the system from a wave-like to a diffusive-like thermal transport. By following three different theoretical methodologies (molecular dynamics, the Maxwell-Cattaneo-Vernotte equation, and heat transport microscopic theory) we estimate for cumulene a second sound velocity in the range of 2.4-3.2 km s-1.

Hydrodynamic Heat Transport Regime in Bismuth: A Theoretical Viewpoint.

Bismuth is one of the rare materials in which second sound has been experimentally observed. Our exact calculations of thermal transport with the Boltzmann equation predict the occurrence of this Poiseuille phonon flow between ≈1.5 and ≈3.5 K, in a sample size of 3.86 and 9.06 mm, consistent with the experimental observations. Hydrodynamic heat flow characteristics are given for any temperature: heat wave propagation length, drift velocity, and Knudsen number. We discuss a gedanken experiment allowing us to assess the presence of a hydrodynamic regime in any bulk material.

Structural Properties of Green Tea Catechins.

Green tea catechins are polyphenols which are believed to provide health benefits; they are marketed as health supplements and are studied for their potential effects on a variety of medical conditions. However, their mechanisms of action and interaction with the environment at the molecular level are still not well-understood. Here, by means of atomistic simulations, we explore the structural properties of four green tea catechins, in the gas phase and water solution: specifically, (-)-epigallocatechin-3-gallate, which is the most abundant, (-)-epicatechin-3-gallate, (-)-epigallocatechin-3-O-(3-O-methyl)-gallate, and (-)-epigallocatechin. We characterize the free energy conformational landscapes of these catechins at ambient conditions, as a function of the torsional degrees of freedom of the pholyphenolic rings, determining the stable conformers and their connections. We show that these free energy landscapes are only subtly influenced by the interactions with the solvent and by the structural details of the polyphenolic rings. However, the number and position of the hydroxyl groups (or their sustituents) and the presence/absence of the galloyl moiety have significant impact on the selected catechin solvation shells and hydrogen bond capabilities, which are ultimately linked to their ability to interact with and affect the biological environment.

Phonon hydrodynamics in two-dimensional materials.

The conduction of heat in two dimensions displays a wealth of fascinating phenomena of key relevance to the scientific understanding and technological applications of graphene and related materials. Here, we use density-functional perturbation theory and an exact, variational solution of the Boltzmann transport equation to study fully from first-principles phonon transport and heat conductivity in graphene, boron nitride, molybdenum disulphide and the functionalized derivatives graphane and fluorographene. In all these materials, and at variance with typical three-dimensional solids, normal processes keep dominating over Umklapp scattering well-above cryogenic conditions, extending to room temperature and more. As a result, novel regimes emerge, with Poiseuille and Ziman hydrodynamics, hitherto typically confined to ultra-low temperatures, characterizing transport at ordinary conditions. Most remarkably, several of these two-dimensional materials admit wave-like heat diffusion, with second sound present at room temperature and above in graphene, boron nitride and graphane.

Thermal conductivity of graphene and graphite: collective excitations and mean free paths.

We characterize the thermal conductivity of graphite, monolayer graphene, graphane, fluorographane, and bilayer graphene, solving exactly the Boltzmann transport equation for phonons, with phonon-phonon collision rates obtained from density functional perturbation theory. For graphite, the results are found to be in excellent agreement with experiments; notably, the thermal conductivity is 1 order of magnitude larger than what found by solving the Boltzmann equation in the single mode approximation, commonly used to describe heat transport. For graphene, we point out that a meaningful value of intrinsic thermal conductivity at room temperature can be obtained only for sample sizes of the order of 1 mm, something not considered previously. This unusual requirement is because collective phonon excitations, and not single phonons, are the main heat carriers in these materials; these excitations are characterized by mean free paths of the order of hundreds of micrometers. As a result, even Fourier's law becomes questionable in typical sample sizes, because its statistical nature makes it applicable only in the thermodynamic limit to systems larger than a few mean free paths. Finally, we discuss the effects of isotopic disorder, strain, and chemical functionalization on thermal performance. Only chemical functionalization is found to play an important role, decreasing the conductivity by a factor of 2 in hydrogenated graphene, and by 1 order of magnitude in fluorogenated graphene.

A computational exploration of the interactions of the green tea polyphenol (-)-Epigallocatechin 3-Gallate with cardiac muscle troponin C.

Thanks to its polyphenols and phytochemicals, green tea is believed to have a number of health benefits, including protecting from heart disease, but its mechanism of action at the molecular level is still not understood. Here we explore, by means of atomistic simulations, how the most abundant of the green tea polyphenols, (-)-Epigallocatechin 3-Gallate (EGCg), interacts with the structural C terminal domain of cardiac muscle troponin C (cCTnC), a calcium binding protein that plays an important role in heart contractions. We find that EGCg favourably binds to the hydrophobic cleft of cCTnC consistently with solution NMR experiments. It also binds to cCTnC in the presence of the anchoring region of troponin I (cTnI(34-71)) at the interface between the E and H helices. This appears to affect the strength of the interaction between cCTnC and cTnI(34-71) and also counter-acts the effects of the Gly159Asp mutation, related to dilated cardiomyopathy. Our simulations support the picture that EGCg interacting with the C terminal domain of troponin C may help in regulating the calcium signalling either through competitive binding with the anchoring domain of cTnI or by affecting the interaction between cCTnC and cTnI(34-71).

Constant pressure molecular dynamics simulations for ellipsoidal, cylindrical and cuboidal nano-objects based on inertia tensor information.

We present an extension to a constant-pressure molecular dynamics method for ellipsoidal finite systems that allows one to deal with nano-objects of cylindrical and cuboidal shapes. The method is based on the inclusion of a pressure x volume term in the system Lagrangian, where the volume is defined as a function of the eigenvalues of the inertia tensor. We illustrate how such a method works for selected systems, including CdSe nanocrystals and nanorods, carbon nanotubes and NaCl nanocrystals over a range of pressures. We also assess its performance in comparison with the use of an auxiliary pressure transmitting medium.