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At least 37 records · Page 2

Liquid Phase Exfoliation of Chemically Prelithiated Bilayered Vanadium Oxide in Aqueous Media for Li-Ion Batteries

Bilayered vanadium oxides are attractive for energy storage due to their high initial specific capacities, which could be stabilized by integrating the bilayers with conductive nanoflakes often produced in a form of aqueous dispersions. Therefore, exfoliation of the bilayered vanadium oxides in water with high yield is desirable. Here, this work introduces the first aqueous exfoliation of chemically prelithiated bilayered vanadium oxide (i.e., δ-Li x V 2 O 5 ·nH 2 O or LVO) followed by vacuum filtration to produce a free-standing film, exhibiting a lamellar stacking of the bilayered vanadium oxide nanoflakes as evidenced by scanning electron microscopy. Due to the hydrated nature of bilayered vanadium oxides, the relationship between interlayer water content and the vacuum drying temperature (105 °C vs 200 °C) was studied using X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. It was found that vacuum drying the LVO nanoflakes at 200 °C enabled more efficient removal of crystallographic water than drying at 105 °C, and did not induce a phase transformation. Scanning transmission electron microscopy confirmed the layered structure of the samples, which was more well-ordered in the 200 °C case and had no clear boundaries between flakes at the atomic scale. Furthermore, electrochemical testing in nonaqueous Li-ion cells revealed that vacuum drying at 200 °C led to improvements in ion storage capacity and electrochemical stability. Improvements in electrochemical charge storage properties of the electrodes obtained via LVO exfoliation and free-standing film assembly in water dried at 200 °C reveal that conventional battery electrode drying protocols need to be revised as new electrochemically active materials are synthesized, such as hydrated layered oxides with expanded interlayer regions. The remaining capacity fading can be attributed to the structural LVO degradation, dissolution of vanadium oxide in electrolyte, and parasitic effects of the remaining interlayer water molecules. Our results establish an environmentally friendly and safe approach to obtain two-dimensional (2D) bilayered vanadium oxide nanoflakes and create a pathway to constructing novel 2D heterostructures for improved performance in energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spontaneous Polarization Suppression of Exciton–Exciton Annihilation in Rhombohedral-Stacked Bilayer Molybdenum Disulfide

Rapid exciton–exciton annihilation (EEA) in two-dimensional semiconductors limits access to high-density excitonic regimes essential for efficient optoelectronic operation under strong excitation. Here, we show that EEA is strongly suppressed in rhombohedral (3R)-stacked MoS 2 bilayers relative to nonpolar 2H bilayers, and that this suppression is quantitatively consistent with repulsive dipole–dipole interactions between layer-polarized excitons induced by spontaneous polarization. Using ultrafast pump–probe spectroscopy, we measure an EEA rate of γ EEA = (5.03 ± 0.99) × 10 –3 cm 2 s –1 in 3R bilayers, which is approximately 18.2-fold smaller than that in monolayers and 2.9-fold smaller than that in nonpolar 2H bilayers. Despite the higher exciton diffusivity recently reported for 3R relative to 2H bilayers, the reduced EEA rate in 3R indicates a rate-limited regime governed by the close-encounter annihilation probability rather than diffusion. A rate-limited annihilation model incorporating a dipole–dipole repulsive potential captures the observed ratio γ EEA,3R /γ EEA,2H ≈ 0.35 for an exciton–exciton encounter distance of ∼1.3 nm, consistent with the bilayer exciton Bohr radius. These results indicate that spontaneous polarization in 3R-stacked bilayers can suppress nonlinear excitonic losses and provide a route toward high-density excitonics.

dipolar excitons↗

Permeation of protons, potassium ions, and small polar molecules through phospholipid bilayers as a function of membrane thickness

Two mechanisms have been proposed to account for solute permeation of lipid bilayers. Partitioning into the hydrophobic phase of the bilayer, followed by diffusion, is accepted by many for the permeation of water and other small neutral solutes, but transient pores have also been proposed to account for both water and ionic solute permeation. These two mechanisms make distinctively different predictions about the permeability coefficient as a function of bilayer thickness. Whereas the solubility-diffusion mechanism predicts only a modest variation related to bilayer thickness, the pore model predicts an exponential relationship. To test these models, we measured the permeability of phospholipid bilayers to protons, potassium ions, water, urea, and glycerol. Bilayers were prepared as liposomes, and thickness was varied systematically by using unsaturated lipids with chain lengths ranging from 14 to 24 carbon atoms. The permeability coefficient of water and neutral polar solutes displayed a modest dependence on bilayer thickness, with an approximately linear fivefold decrease as the carbon number varied from 14 to 24 atoms. In contrast, the permeability to protons and potassium ions decreased sharply by two orders of magnitude between 14 and 18 carbon atoms, and leveled off, when the chain length was further extended to 24 carbon atoms. The results for water and the neutral permeating solutes are best explained by the solubility-diffusion mechanism. The results for protons and potassium ions in shorter-chain lipids are consistent with the transient pore model, but better fit the theoretical line predicted by the solubility-diffusion model at longer chain lengths.

NASA Program Exobiology↗

Bilayer Anion-Exchange Membrane with Low Borohydride Crossover and Improved Fuel Efficiency for Direct Borohdyride Fuel Cell

The development of membranes with low fuel crossover and high fuel efficiency is a key issue in direct borohydride fuel cells (DBFCs). In previous work, we produced a poly(vinyl alcohol) (PVA)-anion-exchange resin (AER) membrane with a low fuel crossover and a low fuel efficiency by introducing Co ions. In this work, a bilayer membrane was designed to improve the fuel efficiency and cell performance. The bilayer membrane was prepared by casting a PVA-AER wet gel onto the partially desiccated Co-PVA-AER gel. The bilayer membrane showed a borohydride permeability of 1.34 × 10 –6 cm 2 ·s –1 , which was even lower than that of the Co-PVA-AER membrane (1.98 ×10 –6 cm 2 ·s –1 ) and the PVA-AER membrane (2.80 × 10 –6 cm 2 ·s –1 ). The DBFC using the bilayer membrane exhibited a higher fuel efficiency (37.4%) and output power (1.73 Wh) than the DBFCs using the Co-PVA-AER membrane (33.3%, 1.27 Wh) and the PVA-AER membrane (34.3%, 1.2 Wh). Furthermore, the DBFC using the bilayer membrane achieved a peak power density of 327 mW·cm –2 , which was 2.14 times of that of the DBFC using the PVA-AER membrane (153 mW·cm –2 ). Finally, the drastic improvement benefited from the bilayer design, which introduced an interphase to suppress fuel crossover and avoided unnecessary borohydride hydrolysis.

36 MATERIALS SCIENCE↗

Cations Control Lipid Bilayer Memcapacitance Associated with Long-Term Potentiation

Phospholipid bilayers can be described as capacitors whose capacitance per unit area (specific capacitance, C m ) is determined by their thickness and dielectric constant–independent of applied voltage. It is also widely assumed that the C m of membranes can be treated as a “biological constant”. Recently, using droplet interface bilayers (DIBs), it was shown that zwitterionic phosphatidylcholine (PC) lipid bilayers can act as voltage-dependent, nonlinear memory capacitors, or memcapacitors. When exposed to an electrical “training” stimulation protocol, capacitive energy storage in lipid membranes was enhanced in the form of long-term potentiation (LTP), which enables biological learning and long-term memory. LTP was the result of membrane restructuring and the progressive asymmetric distribution of ions across the lipid bilayer during training, which is analogous, for example, to exponential capacitive energy harvesting from self-powered nanogenerators. Here, we describe how LTP could be produced from a membrane that is continuously pumped into a nonequilibrium steady state, altering its dielectric properties. During this time, the membrane undergoes static and dynamic changes that are fed back to the system’s potential energy, ultimately resulting in a membrane whose modified molecular structure supports long-term memory storage and LTP. Here, we also show that LTP is very sensitive to different salts (KCl, NaCl, LiCl, and TmCl 3 ), with LiCl and TmCl 3 having the most profound effect in depressing LTP, relative to KCl. This effect is related to how the different cations interact with the bilayer zwitterionic PC lipid headgroups primarily through electric-field-induced changes to the statistically averaged orientations of water dipoles at the bilayer headgroup interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Halogenation-Dependent Effects of the Chlorosulfolipids of Ochromonas danica on Lipid Bilayers

The chlorosulfolipids are amphiphilic natural products with stereochemically complex patterns of chlorination and sulfation. Despite their role in toxic shellfish poisoning, potential pharmacological activities, and unknown biological roles, they remain understudied due to the difficulties in purifying them from natural sources. The structure of these molecules, with a charged sulfate group in the middle of the hydrophobic chain, appears incompatible with the conventional lipid bilayer structure. Questions about chlorosulfolipids remain unanswered partly due to the unavailability of structural analogues with which to conduct structure–function studies. Here, we approach this problem by combining enantioselective total synthesis and membrane biophysics. Using a combination of Langmuir pressure–area isotherms of lipid monolayers, fluorescence imaging of vesicles, mass spectrometry imaging, natural product isolation, small-angle X-ray scattering, and cryogenic electron microscopy, we show that danicalipin A (1) likely inserts into lipid bilayers in the headgroup region and alters their structure and phase behavior. Specifically, danicalipin A (1) thins the bilayer and fluidizes it, allowing even saturated lipid to form fluid bilayers. Lipid monolayers show similar fluidizing upon insertion of danicalipin A (1). Furthermore, we show that the halogenation of the molecule is critical for its membrane activity, likely due to sterically controlled conformational changes. Synthetic unchlorinated and monochlorinated analogues do not thin and fluidize lipid bilayers to the same extent as the natural product. Overall, this study sheds light on how amphiphilic small molecules interact with lipid bilayers and the importance of stereochemistry and halogenation for this interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiscale analysis of large twist ferroelectricity and swirling dislocations in bilayer hexagonal boron nitride

With its atomically thin structure and intrinsic ferroelectric properties, heterodeformed bilayer hexagonal boron nitride (hBN) has gained prominence in next-generation non-volatile memory applications. However, studies to date have focused almost exclusively on small-twist bilayer hBN, leaving the question of whether ferroelectricity can persist under small heterostrain and large heterodeformation entirely unexplored. In this work, we establish the crystallographic origin of ferroelectricity in bilayer hBN configurations heterodeformed relative to high-symmetry configurations such as AA-stacking and 21.786789° twisted configurations (Σ7), using Smith normal form bicrystallography. We then demonstrate out-of-plane ferroelectricity in bilayer hBN across configurations vicinal to both the AA and Σ7 stackings. Atomistic simulations reveal that AA-vicinal systems support ferroelectricity under both small twist and small strain, with polarization switching in the latter governed by the deformation of swirling dislocations rather than the straight interface dislocations seen in the former. For Σ7-vicinal systems, where existing interatomic potentials underperform particularly under extreme out-of-plane compression, we develop a density-functional-theory-informed continuum framework—the bicrystallography-informed frame-invariant multiscale (BFIM) model, which captures out-of-plane ferroelectricity in heterodeformed configurations vicinal to Σ7 stacking. Interface dislocations in these large heterodeformed bilayer configurations exhibit markedly smaller Burgers vectors compared to interface dislocations in small-twist and small-strain bilayer hBN. The BFIM model reproduces experimental results and provides a powerful, computationally efficient framework for predicting ferroelectricity in large-unit-cell heterostructures where atomistic simulations are prohibitively expensive.

Ahmed, Md Tusher [Univ. of Illinois at Urbana-Cham↗

Microwave Meissner screening properties of proximity-coupled topological-insulator / superconductor bilayers

The proximity-coupled topological-insulator / superconductor (TI/SC) bilayer system is a representative system to realize topological superconductivity. In order to better understand this unique state and enable future applications of the TI/SC bilayer, a comprehensive characterization and understanding of the microscopic properties of the bilayer are required. In this work, a microwave Meissner screening study, which exploits a high-precision microwave resonator technique, is conducted on the SmB 6 /YB 6 thin-film bilayers as an example TI/SC system. The study reveals spatially dependent electrodynamic screening response of the TI/SC system that is not accessible to other techniques, from which the corresponding microscopic properties of a TI/SC bilayer can be obtained. The TI thickness dependence of the effective penetration depth suggests the existence of a bulk insulating region in the TI layer. The spatially dependent electrodynamic screening model analysis provides an estimate for the characteristic lengths of the TI/SC bilayer: normal penetration depth, normal coherence length, and the thickness of the surface states.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Exploring interlayer coupling in the twisted bilayer PtTe 2

We have investigated interlayer interactions in the bilayer PtTe 2 system, which influence the electronic energy bands near the Fermi level. Our diffusion Monte Carlo (DMC) calculations for the high-symmetry bilayer stackings (AA, AB, AC) manifest distinct interlayer binding characteristics among the stacking modes by revealing significantly different interlayer separations depending on the stacking, which is critical to understanding the interlayer coupling of the twisted bilayers consisting of various local stacking arrangements. Furthermore, a comparison between the interlayer separations obtained from DMC and density functional theory (DFT) shows that meta-generalized gradient approximation (GGA)-based van der Waals–DFT results agree with DMC for different layer stackings, including twisted bilayers, but only the ground-state AA stacking matches well with GGA-based DFT predictions. This underscores the importance of accurate exchange-correlation potentials even for capturing the stacking-dependent interlayer binding properties. We further show that the variability in DFT-predicted interlayer separations is responsible for the large discrepancy of band structures in the 21 . 79 ∘ twisted bilayer PtTe 2 , affecting its classification as metallic or insulating. These results demonstrate the importance of obtaining a correct description of stacking-dependent interlayer coupling in modeling delicate bilayer systems at finite twists. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Antiferromagnetic-configuration–dependent high harmonic generation in bilayer CrI 3

Abstract Bilayer CrI 3 accommodates both interlayer antiferromagnetic (AFM) and intralayer ferromagnetic couplings. Different alignments of intralayer ferromagnetic orders would lead to almost degenerate AFM configurations, which are insensitive to conventional techniques such as VSM and magneto-optical Kerr effect. Here, we demonstrate high harmonic generation (HHG) as a feasible means to detect the AFM configurations in bilayer CrI 3 with AB and stacking orders. When the intralayer magnetic moments are aligned along the z -axis, the AB stacked bilayer CrI 3 cancels the 3 n -order harmonics under the circularly polarized laser field. However, the stacked bilayer contains both even and odd harmonic. The 3 n -order harmonics are recovered as the intralayer magnetic moments of AB bilayer are in-plane aligned. For an in-plane linearly polarized laser field, the stacking bilayer with the magnetic moments along the x -axis contains both the even and odd harmonics in each component. However, when the magnetic moments are along the y -axis, the perpendicular component of HHG cancels out for the linearly polarized laser field along the x -axis. More interestingly, when the linearly polarized laser field is along the y -axis, the parallel component includes only the odd harmonics while the perpendicular component contains only the even harmonics. Our study provides HHG as a potential tool to detect AFM configurations.

Physics↗

Mechanism of unassisted ion transport across membrane bilayers

To establish how charged species move from water to the nonpolar membrane interior and to determine the energetic and structural effects accompanying this process, we performed molecular dynamics simulations of the transport of Na+ and Cl- across a lipid bilayer located between two water lamellae. The total length of molecular dynamics trajectories generated for each ion was 10 ns. Our simulations demonstrate that permeation of ions into the membrane is accompanied by the formation of deep, asymmetric thinning defects in the bilayer, whereby polar lipid head groups and water penetrate the nonpolar membrane interior. Once the ion crosses the midplane of the bilayer the deformation "switches sides"; the initial defect slowly relaxes, and a defect forms in the outgoing side of the bilayer. As a result, the ion remains well solvated during the process; the total number of oxygen atoms from water and lipid head groups in the first solvation shell remains constant. A similar membrane deformation is formed when the ion is instantaneously inserted into the interior of the bilayer. The formation of defects considerably lowers the free energy barrier to transfer of the ion across the bilayer and, consequently, increases the permeabilities of the membrane to ions, compared to the rigid, planar structure, by approximately 14 orders of magnitude. Our results have implications for drug delivery using liposomes and peptide insertion into membranes.

NASA Discipline Exobiology↗

Method of fabricating lipid bilayer membranes on solid supports

The present invention provides a method of producing a planar lipid bilayer on a solid support. With this method, a solution of lipid vesicles is first deposited on the solid support. Next, the lipid vesicles are destabilized by adding an amphipathic peptide solution to the lipid vesicle solution. This destabilization leads to production of a planar lipid bilayer on the solid support. The present invention also provides a supported planar lipid bilayer, where the planar lipid bilayer is made of naturally occurring lipids and the solid support is made of unmodified gold or titanium oxide. Preferably, the supported planar lipid bilayer is continuous. The planar lipid bilayer may be made of any naturally occurring lipid or mixture of lipids, including, but not limited to phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinsitol, cardiolipin, cholesterol, and sphingomyelin.

Cho, Nam-Joon↗

Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments

Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.

Biocatalysis↗

Stretching and Bending Moduli of Bilayer Films Inferred from Wrinkle Patterns

Wrinkling patterns were used to investigate the mechanical properties of thin poly­(styrene) (PS)/poly­(methyl methacrylate) (PMMA) and PS/gold (Au) bilayer films. Films were floated on water with a water drop on the surface to induce wrinkling. The thicknesses and thickness ratios of the films were varied over a broad range. The PS/PMMA bilayer was chosen to provide a contrast in wetting properties, with equilibrium contact angles of θPMMA = 68° and θPS = 88° with water. The PS/Au bilayer was chosen to provide a large contrast in Young’s moduli, E Au = 72 GPa and E PS = 3.4 GPa. The stretching (Y) and bending (B) moduli of the bilayer films were obtained from measurements of the length and number of wrinkles in the wrinkle patterns. The experimentally derived values of Y and B were in reasonable agreement with the values computed from the bulk Young’s moduli and the thicknesses of the two components in the bilayer. The values of Y and B did not depend on which face of the film was exposed to the water droplet or bath when the capillary stresses were considered. Thus, finite size effects from the film thicknesses were unimportant over the range of thicknesses studied, and no relative displacement of the films was found, with the films remaining well-bonded even with deformation associated with wrinkling.

Chang, Jooyoung↗

Engineering correlated insulators in bilayer graphene with a remote Coulomb superlattice

Electron superlattices allow the engineering of correlated and topological quantum phenomena. The recent emergence of moiré superlattices in two-dimensional heterostructures has led to exciting discoveries related to quantum phenomena. However, the requirement for the moiré pattern poses stringent limitations, and its potential cannot be switched on and off. Here, in this study, we demonstrate remote engineering and on/off switching of correlated states in bilayer graphene. Employing a remote Coulomb superlattice realized by localized electrons in twisted bilayer WS 2 , we impose a Coulomb superlattice in the bilayer graphene with period and strength determined by the twisted bilayer WS 2 . When the remote superlattice is turned off, the two-dimensional electron gas in the bilayer graphene is described by a Fermi liquid. When it is turned on, correlated insulating states at both integer and fractional filling factors emerge. This approach enables in situ control of correlated quantum phenomena in two-dimensional materials hosting a two-dimensional electron gas.

36 MATERIALS SCIENCE↗

Study of the magnetic interface and its effect in Fe/NiFe bilayers of alternating order

We present a comprehensive study on the magnetization reversal in the Fe/NiFe bilayer system by alternating the order of the magnetic layers. All the samples show growth-induced uniaxial magnetic anisotropy due to the oblique angle deposition technique. Strong interfacial exchange coupling between the Fe and NiFe layers leads to single-phase hysteresis loops in the bilayer system. The strength of coupling being dependent on the interface changes upon alternating the order of magnetic layers. The magnetic parameters such as coercivity H C , and anisotropy field H K become almost doubled when a NiFe layer is grown over the Fe layers. This enhancement in the magnetic parameters is primarily dependent on the increase of the thickness and magnetic moment of the Fe–NiFe interfacial layer as revealed from the polarized neutron reflectivity (PNR) data of the bilayer samples. The difference in the thickness and magnetization of the Fe–NiFe interfacial layer indicates the modification of the microstructure by alternating the order of the magnetic layers of the bilayers. The interfacial magnetic moment increased by almost 18% when the NiFe layer was grown over the Fe layer. In spite of the different values of anisotropy fields and modified interfacial exchange coupling, the Gilbert damping constant values of the ferromagnetic bilayers remain similar to the single NiFe layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creating a three-dimensional intrinsic electric dipole on rotated CrI 3 bilayers

Here two-dimensional (2D) materials are being explored as a novel multiferroic platform. One of the most studied magnetoelectric multiferroic 2D materials are antiferromagnetically coupled (AFM) CrI 3 bilayers. Neglecting magnetism, those bilayers possess a crystalline point of inversion, which is only removed by the antiparallel spin configuration among its two constituent monolayers. The resulting intrinsic electric dipole on those bilayers has a magnitude no larger than 0.04 pC/m, it points out of plane, and it reverts direction when the Ising-like-chromium spins are flipped (toward opposite layers versus away from opposite layers). The combined presence of antiferromagnetism and a weak intrinsic electric dipole makes this material a two-dimensional magnetoelectric multiferroic. Here, we remove the crystalline center of inversion of the bilayer by a relative 60° rotation of its constituent monolayers. This process enhances the out-of-plane intrinsic electric dipole tenfold with respect to its magnitude in the nonrotated AFM bilayer and also creates an even stronger and switchable in-plane intrinsic electric dipole. The ability to create a three-dimensional electric dipole is important because it enhances the magnetoelectric coupling on this experimentally accessible 2D material, which is explicitly calculated here as well.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phonon-Assisted Intervalley Scattering Determines Ultrafast Exciton Dynamics in MoSe 2 Bilayers

While valleys (energy extrema) are present in all band structures of solids, their preeminent role in determining exciton resonances and dynamics in atomically thin transition metal dichalcogenides (TMDC) is unique. Using two-dimensional coherent electronic spectroscopy, we find that exciton decoherence occurs on a much faster timescale in MoSe 2 bilayers than that in the monolayers. We further identify two population relaxation channels in the bilayer, a coherent and an incoherent one. Our microscopic model reveals that phonon-emission processes facilitate scattering events from the K valley to other lower-energy Γ and Λ valleys in the bilayer. Our combined experimental and theoretical studies unequivocally establish different microscopic mechanisms that determine exciton quantum dynamics in TMDC monolayers and bilayers. Understanding exciton quantum dynamics provides critical guidance to the manipulation of spin-valley degrees of freedom in TMDC bilayers.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗