Determining the Gaussian Modulus and Edge Properties of 2D Materials: From Graphene to Lipid Bilayers.

The dominant deformation behavior of two-dimensional materials (bending) is primarily governed by just two parameters: bending rigidity and the Gaussian modulus. These properties also set the energy scale for various important physical and biological processes such as pore formation, cell fission and generally, any event accompanied by a topological change. Unlike the bending rigidity, the Gaussian modulus is, however, notoriously difficult to evaluate via either experiments or atomistic simulations. In this Letter, recognizing that the Gaussian modulus and edge tension play a nontrivial role in the fluctuations of a 2D material edge, we derive closed-form expressions for edge fluctuations. Combined with atomistic simulations, we use the developed approach to extract the Gaussian modulus and edge tension at finite temperatures for both graphene and various types of lipid bilayers. Our results possibly provide the first reliable estimate of this elusive property at finite temperatures and appear to suggest that earlier estimates must be revised. In particular, we show that, if previously estimated properties are employed, the graphene-free edge will exhibit unstable behavior at room temperature. Remarkably, in the case of graphene, we show that the Gaussian modulus and edge tension even change sign at finite temperatures.

Ferroelectric switching of elastin.

Ferroelectricity has long been speculated to have important biological functions, although its very existence in biology has never been firmly established. Here, we present compelling evidence that elastin, the key ECM protein found in connective tissues, is ferroelectric, and we elucidate the molecular mechanism of its switching. Nanoscale piezoresponse force microscopy and macroscopic pyroelectric measurements both show that elastin retains ferroelectricity at 473 K, with polarization on the order of 1 µC/cm(2), whereas coarse-grained molecular dynamics simulations predict similar polarization with a Curie temperature of 580 K, which is higher than most synthetic molecular ferroelectrics. The polarization of elastin is found to be intrinsic in tropoelastin at the monomer level, analogous to the unit cell level polarization in classical perovskite ferroelectrics, and it switches via thermally activated cooperative rotation of dipoles. Our study sheds light onto a long-standing question on ferroelectric switching in biology and establishes ferroelectricity as an important biophysical property of proteins. This is a critical first step toward resolving its physiological significance and pathological implications.

Rigid proteins and softening of biological membranes-with application to HIV-induced cell membrane softening.

A key step in the HIV-infection process is the fusion of the virion membrane with the target cell membrane and the concomitant transfer of the viral RNA. Experimental evidence suggests that the fusion is preceded by considerable elastic softening of the cell membranes due to the insertion of fusion peptide in the membrane. What are the mechanisms underpinning the elastic softening of the membrane upon peptide insertion? A broader question may be posed: insertion of rigid proteins in soft membranes ought to stiffen the membranes not soften them. However, experimental observations perplexingly appear to show that rigid proteins may either soften or harden membranes even though conventional wisdom only suggests stiffening. In this work, we argue that regarding proteins as merely non-specific rigid inclusions is flawed, and each protein has a unique mechanical signature dictated by its specific interfacial coupling to the surrounding membrane. Predicated on this hypothesis, we have carried out atomistic simulations to investigate peptide-membrane interactions. Together with a continuum model, we reconcile contrasting experimental data in the literature including the case of HIV-fusion peptide induced softening. We conclude that the structural rearrangements of the lipids around the inclusions cause the softening or stiffening of the biological membranes.

Anomalous piezoelectricity in two-dimensional graphene nitride nanosheets.

Piezoelectricity is a unique property of materials that permits the conversion of mechanical stimuli into electrical and vice versa. On the basis of crystal symmetry considerations, pristine carbon nitride (C3N4) in its various forms is non-piezoelectric. Here we find clear evidence via piezoresponse force microscopy and quantum mechanical calculations that both atomically thin and layered graphitic carbon nitride, or graphene nitride, nanosheets exhibit anomalous piezoelectricity. Insights from ab inito calculations indicate that the emergence of piezoelectricity in this material is due to the fact that a stable phase of graphene nitride nanosheet is riddled with regularly spaced triangular holes. These non-centrosymmetric pores, and the universal presence of flexoelectricity in all dielectrics, lead to the manifestation of the apparent and experimentally verified piezoelectric response. Quantitatively, an e11 piezoelectric coefficient of 0.758 C m(-2) is predicted for C3N4 superlattice, significantly larger than that of the commonly compared α-quartz.