Ferroelectricity Modulates Polaronic Coupling at Multiferroic Interfaces

Physics of the multiferroic interfaces is currently understood mostly within a phenomenological framework including screening of the polarization field and depolarizing charges. Largely unexplored still remains the band dependence of the interfacial charge modulation, as well as the associated changes of the electron-phonon interaction, coupling the charge and lattice degrees of freedom. Here, multiferroic heterostructures of the colossal-magnetoresistance manganite La1-xSrxMnO3 buried under ferroelectric BaTiO3 and PbZrxTi1-xO3 are explored using soft-X-ray angle-resolved photoemission. The experimental band dispersions from the buried La1-xSrxMnO3 identify coexisting two-dimensional hole and three-dimensional electron charge carriers. The ferroelectric polarization modulates their charge density, changing the band filling and orbital occupation in the interfacial region. Furthermore, these changes in the carrier density affect the coupling of the 2D holes and 3D electrons with the lattice which forms large Froelich polarons inherently reducing mobility of the charge carriers. We find that the fast dynamic response of electrons makes them much more efficient in screening of the electron-lattice interaction compared to the holes. Our k-resolved results on the orbital occupancy, band filling and electron-lattice interaction in multiferroic oxide heterostructures modulated by the ferroelectric polarization disclose most fundamental physics of these systems needed for further progress of beyond-CMOS ferro-functional electronics.

Insight into the stacking and the species-ordering dependences of interlayer bonding in SiC/GeC polar heterostructures

Two-dimensional (2D) polar materials experience an in-plane charge transfer between different elements due to their electron negativities. When they form vertical heterostructures, the electrostatic force triggered by such charge transfer plays an important role in the interlayer bonding beyond van der Waals (vdW) interaction. Our comprehensive first principle study on the structural stability of the 2D SiC/GeC hybrid bilayer heterostructure has found that the electrostatic interlayer interaction can induce the π-π orbital hybridization between adjacent layers under different stacking and out-of-plane species ordering, with strong hybridization in the cases of Si-C and C-Ge species orderings but weak hybridization in the case of the C-C ordering. In particular, the attractive electrostatic interlayer interaction in the cases of Si-C and C-Ge species orderings mainly controls the equilibrium interlayer distance and the vdW interaction makes the system attain a lower binding energy. On the contrary, the vdW interaction mostly controls the equilibrium interlayer distance in the case of the C-C species ordering and the repulsive electrostatic interlayer force has less effect. Interesting finding is that the band structure of the SiC/GeC hybrid bilayer is sensitive to the layer-layer stacking and the out-of-plane species ordering. An indirect band gap of 2.76 eV (or 2.48 eV) was found under the AA stacking with Si-C ordering (or under the AB stacking with C-C ordering). While a direct band gap of 2.00 eV – 2.88 eV was found under other stacking and species orderings, demonstrating its band gap tunable feature. Furthermore, there is a charge redistribution in the interfacial region leading to a built-in electric field. Such field will separate the photo-generated charge carriers in different layers and is expected to reduce the probability of carrier recombination, and eventually give rise to the electron tunneling between layers.

Standard binding free energy and membrane desorption mechanism for a phospholipase C

Peripheral membrane proteins (PMPs) bind temporarily to cellular membranes and play important roles in signalling, lipid metabolism and membrane trafficking. Obtaining accurate membrane-PMP affinities using experimental techniques is more challenging than for protein-ligand affinities in aqueous solution. At the theoretical level, calculation of standard protein-membrane binding free energy using molecular dynamics simulations remains a daunting challenge owing to the size of the biological objects at play, the slow lipid diffusion and the large variation in configurational entropy that accompanies the binding process. To overcome these challenges, we used a computational framework relying on a series of potential-of-mean-force (PMF) calculations including a set of geometrical restraints on collective variables. This methodology allowed us to determine the standard binding free energy of a PMP to a phospholipid bilayer using an all-atom force field. Bacillus thuringiensis phosphatidylinositol-specific phospholipase C (BtPI-PLC) was chosen due to its importance as a virulence factor and owing to the host of experimental affinity data available. We computed a standard binding free energy of -8.2±1.4 kcal/mol in reasonable agreement with the reported experimental values (-6.6±0.2 kcal/mol). In light of the 2.3-μs separation PMF calculation, we investigated the mechanism whereby BtPI-PLC disengages from interactions with the lipid bilayer during separation. We describe how a short amphipathic helix engages in transitory interactions to ease the passage of its hydrophobes through the interfacial region upon desorption from the bilayer.

Interfacial Characteristics and Mechanical Properties of CuSn15/HT250 Prepared via Additive Manufacturing Combined with an Inconel 718 Interlayer

Tremendous discrepancies in the positive enthalpy of mixing and the coefficient of thermal expansion emerge between the copper alloy and the gray cast iron, accounting for numerous pores and cracks in the interfacial region during the metallurgical bonding process. To enhance the interfacial bonding properties of these two refractory materials, laser-directed energy deposition was applied to fabricate the CuSn15 alloy on the HT250 substrate; meanwhile, Inconel 718 alloy, acting as the interlayer, was added to their bonding region. Firstly, the effect of the deposition process on deposition layer quality was investigated, and then the effects of Inconel 718 addition on the interfacial morphology, element distribution, phase composition, bonding strength, microhardness were studied. The results showed that a substrate (HT250) without cracks and a deposition layer (CuSn15) free from pores could be obtained via parameter optimization combined with preheating and slow cooling processes. Adding the Inconel 718 interlayer eliminated the interfacial pores and cracks, facilitated interfacial element (Cu, Fe, Ni) diffusion, and enhanced interfacial bonding strength. The interface between HT250 and CuSn15 mainly contained the FeSn2 phase, while the interfaces of the CuSn15-Inconel 718 and the Inconel 718-HT250 were mainly composed of the Ni3Sn4, Cr5Si3, FeSi2, Cr7C3. The microhardness and fracture morphology of the interfacial region in the samples with and without the interlayer were also studied. Finally, CuSn15 was also successfully deposited on the surface of the HT250 impeller with large size and complex structure, which was applied in the root blower.

The Effect of surfactant on the drag and wall correction factor of a drop in a bounded medium

In the present article, the analytical solution for creeping motion of a drop/bubble characterized by insoluble surfactant is examined at the instant it passes the center of a spherical container filled with Newtonian fluid at low Reynolds number. The presence of surfactant characterizes the interfacial region by an axisymmetric interfacial tension gradient and coefficient of surface dilatational viscosity. Under the assumption of the small capillary number, the deformation of spherical phase interface is not taken into account. The computations not only yield information on drag force and wall correction factor, but also on interfacial velocity and flow field for different values of surface tension gradient and surface dilatational viscosity. In the limiting cases, the analytical solutions describing the drag force and wall correction factor for a drop in a bounded medium reduces to expressions previously stated by other authors in literature. The results reveal the strong influence of the surface dilatational viscosity and surface tension gradient on the motion of drop/bubble. Increasing the surface tension gradient and surface dilatational viscosity, results in linear variation of drag force. When the surface tension gradient increases, the drag force for unbounded medium increases more as compared to the bounded medium hence wall correction factor decreases with increase in surface tension gradient whereas it increases with increase in surface dilatational viscosity.

Multipoint correlation functions at phase separation. Exact results from field theory

We consider near-critical two-dimensional statistical systems with boundary conditions inducing phase separation on the strip. By exploiting low-energy properties of two-dimensional field theories, we compute arbitrary n-point correlation of the order parameter field. Finite-size corrections and mixed correlations involving the stress tensor trace are also discussed. As an explicit illustration of the technique, we provide a closed-form expression for a three-point correlation function and illustrate the explicit form of the long-ranged interfacial fluctuations as well as their confinement within the interfacial region.

What Does Time-Dependent Fluorescence Shift (TDFS) in Biomembranes (and Proteins) Report on?

The organization of biomolecules and bioassemblies is highly governed by the nature and extent of their interactions with water. These interactions are of high intricacy and a broad range of methods based on various principles have been introduced to characterize them. As these methods view the hydration phenomena differently (e.g., in terms of time and length scales), a detailed insight in each particular technique is to promote the overall understanding of the stunning “hydration world.” In this prospective mini-review we therefore critically examine time-dependent fluorescence shift (TDFS)—an experimental method with a high potential for studying the hydration in the biological systems. We demonstrate that TDFS is very useful especially for phospholipid bilayers for mapping the interfacial region formed by the hydrated lipid headgroups. TDFS, when properly applied, reports on the degree of hydration and mobility of the hydrated phospholipid segments in the close vicinity of the fluorophore embedded in the bilayer. Here, the interpretation of the recorded TDFS parameters are thoroughly discussed, also in the context of the findings obtained by other experimental techniques addressing the hydration phenomena (e.g., molecular dynamics simulations, NMR spectroscopy, scattering techniques, etc.). The differences in the interpretations of TDFS outputs between phospholipid biomembranes and proteins are also addressed. Additionally, prerequisites for the successful TDFS application are presented (i.e., the proper choice of fluorescence dye for TDFS studies, and TDFS instrumentation). Finally, the effects of ions and oxidized phospholipids on the bilayer organization and headgroup packing viewed from TDFS perspective are presented as application examples.

Composite Films of HDPE with SiO2 and ZrO2 Nanoparticles: The Structure and Interfacial Effects

Herein, we investigated the influence of two types of nanoparticle fillers, i.e., amorphous SiO2 and crystalline ZrO2, on the structural properties of their nanocomposites with high-density polyethylene (HDPE). The composite films were prepared by melt-blending with a filler content that varied from 1% to 20% v/v. The composites were characterized by small- and wide-angle x-ray scattering (SAXS and WAXS), small-angle neutron scattering (SANS), Raman spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). For both fillers, the nanoaggregates were evenly distributed in the polymer matrix and their initial state in the powders determined their surface roughness and fractal character. In the case of the nano-ZrO2 filler, the lamellar thickness and crystallinity degree remain unchanged over a broad range of filler concentrations. SANS and SEM investigation showed poor interfacial adhesion and the presence of voids in the interfacial region. Temperature-programmed SANS investigations showed that at elevated temperatures, these voids become filled due to the flipping motions of polymer chains. The effect was accompanied by a partial aggregation of the filler. For nano-SiO2 filler, the lamellar thickness and the degree of crystallinity increased with increasing the filler loading. SAXS measurements show that the ordering of the lamellae is disrupted even at a filler content of only a few percent. SEM images confirmed good interfacial adhesion and integrity of the SiO2/HDPE composite. This markedly different impact of both fillers on the composite structure is discussed in terms of nanoparticle surface properties and their affinity to the HDPE matrix.

Recent Advances in the Development of Triose Phosphate Isomerase Inhibitors as Antiprotozoal Agents

Background: Parasitic diseases caused by protozoa such as Chagas disease, leishmaniasis, malaria, African trypanosomiasis, amebiasis, trichomoniasis, and giardiasis are considered serious public health problems in developing countries. Drug-resistance among parasites justifies the search for new therapeutic drugs and the identification of new targets becomes a valuable approach. In this scenario, glycolysis pathway which consists of the conversion of glucose into pyruvate plays an important role in the protozoa energy supply and it is therefore considered as a promising target. In this pathway, triose phosphate isomerase (TIM) plays an essential role in efficient energy production. Furthermore, protozoa TIM show structural differences with human enzyme counterparts suggesting the possibility of obtaining selective inhibitors. Therefore, TIM is considered a valid approach to develop new antiprotozoal agents, inhibiting the glycolysis in the parasite. Objective: In this review, we discuss the drug design strategies, structure-activity relationship, and binding modes of outstanding TIM inhibitors against Trypanosoma cruzi, Trypanosoma brucei, Plasmodium falciparum, Giardia lamblia, Leishmania mexicana, Trichomonas vaginalis, and Entamoeba histolytica. Results: TIM inhibitors showed mainly aromatic systems and symmetrical structure, where the size and type of heteroatom are important for enzyme inhibition. This inhibition is mainly based on the interaction with i) the interfacial region of TIM inducing changes on the quaternary and tertiary structure or ii) with the TIM catalytic region were the main pathways that disabled the catalytic activity of the enzyme. Conclusion: Benzothiazole, benzoxazole, benzimidazole, and sulfhydryl derivatives stand out as TIM inhibitors. In silico and in vitro studies demonstrate that the inhibitors bind mainly at the TIM dimer interface. In this review, the development of new TIM inhibitors as antiprotozoal drugs is demonstrated as an important pharmaceutical strategy that may lead to new therapies for these ancient parasitic diseases.