The dispersion state or degree of agglomeration of graphene is known to have a significant influence on the percolation threshold and electrical conductivity of graphene-based polymer nanocomposites. In addition, an imperfectly conducting interface and tunneling-assisted interfacial conductivity can also affect the overall conductivity. In this paper, a continuum theory is developed that considers all these factors. We first present a two-scale composite model consisting of graphene-rich regions serving as the agglomerates and a graphene-poor region as the matrix. We then introduce the effective-medium theory to determine the percolation threshold and electrical conductivity of the agglomerate and the composite. To account for the effect of imperfect interfaces, a thin layer of interphase with low conductivity is introduced to build a thinly coated graphene, while to account for the contribution of electron hopping from one graphene to another, Cauchy's statistical function which can reflect the increased tunneling activity near the percolation threshold is introduced. It is shown that the percolation threshold of the nanocomposite is controlled by two dispersion parameters, a and b, and the aspect ratio of agglomerates, αR. It is also shown that the overall conductivity of the nanocomposite mainly depends on the intrinsic conductivity of graphene and polymer matrix, the intrinsic interfacial resistivity, and the tunneling-assisted hopping process. We highlight the conceived theory by demonstrating that a set of recently measured data on the percolation threshold and electrical conductivity of graphene/polystyrene nanocomposites can be well captured by it.
When subject to applied electric pulses, a lipid membrane exhibits complex responses including electrodeformation and electroporation. In this work, the electrodeformation of giant unilamellar vesicles under strong dc electric fields was investigated. Specifically, the degree of deformation was quantified as a function of the applied field strength and the electrical conductivity ratio of the fluids inside and outside of the vesicles. The vesicles were made from L-α-phosphatidylcholine with diameters ranging from 14 to 30 μm. Experiments were performed with field strengths ranging from 0.9 to 2.0 kV/cm, and intra-to-extra-vesicular conductivity ratios varying between 1.92 and 53.0. With these parametric configurations, the vesicles exhibited prolate elongations along the direction of the electric field. The degree of deformation was, in general, significant. In some cases, the aspect ratio of a deformed vesicle exceeded 10, representing a strong-deformation regime previously not explored. The aspect ratio scaled quadratically with the field strength, and increased asymptotically to a maximum value at high conductivity ratios. Appreciable area and volumetric changes were observed both during and after pulsation, indicating the concurrence of electroporation. A theoretical model is developed to predict these large deformations in the strongly permeabilized limit, and the results are compared with the experimental data. Both agreements and discrepancies are found, and the model limitations and possible extensions are discussed.
Electroporation is an electro-physical, non-viral approach to perform DNA, RNA, and protein transfections of cells. Upon application of an electric field, the cell membrane is compromised, allowing the delivery of exogenous materials into cells. Cell viability and electro-transfection efficiency (eTE) are dependent on various experimental factors, including pulse waveform, vector concentration, cell type/density, and electroporation buffer properties. In this work, the effects of buffer composition on cell viability and eTE were systematically explored for plasmid DNA encoding green fluorescent protein following electroporation of 3T3 fibroblasts. A HEPES-based buffer was used in conjunction with various salts and sugars to modulate conductivity and osmolality, respectively. Pulse applications were chosen to maintain constant applied electrical energy (J) or total charge flux (C/m 2). The energy of the pulse application primarily dictated cell viability, with Mg 2+-based buffers expanding the reversible electroporation range. The enhancement of viability with Mg 2+-based buffers led to the hypothesis that this enhancement is due to ATPase activation via re-establishing ionic homeostasis. We show preliminary evidence for this mechanism by demonstrating that the enhanced viability is eliminated by introducing lidocaine, an ATPase inhibitor. However, Mg 2+ also hinders eTE compared to K +-based buffers. Collectively, the results demonstrate that the rational selection of pulsing conditions and buffer compositions are critical for the design of electroporation protocols to maximize viability and eTE.
Over 50 years ago, Anderson and Blount proposed that ferroelectric-like structural phase transitions may occur in metals, despite the expected screening of the Coulomb interactions that often drive polar transitions. Recently, theoretical treatments have suggested that such transitions require the itinerant electrons be decoupled from the soft transverse optical phonons responsible for polar order. However, this decoupled electron mechanism (DEM) has yet to be experimentally observed. Here we utilize ultrafast spectroscopy to uncover evidence of the DEM in LiOsO 3, the first known band metal to undergo a thermally driven polar phase transition ( T c ≈ 140 K). We demonstrate that intra-band photo-carriers relax by selectively coupling to only a subset of the phonon spectrum, leaving as much as 60% of the lattice heat capacity decoupled. This decoupled heat capacity is shown to be consistent with a previously undetected and partially displacive TO polar mode, indicating the DEM in LiOsO 3 .
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