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The paper deals with methods of computation of distributions of functionals of switching diffusions. The switching between two collections of diffusion coefficients occurs at the Poisson time moments which are independent of the initial diffusions. One can also consider more general diffusions when the choice is made from three or more collections of diffusion coefficients.
Highlights: • Cambinol inhibits spread of AD synaptosome derived tau seeds, from donor to recipient cells. • Cambinol inhibits nSMase2 through targeting the DK-switch in its active site. • Cambinol inhibits EV-mediated tau propagation. • Cambinol has low brain permeability and inhibition of nSMase activity in vivo. Targeting of molecular pathways involved in the cell-to-cell propagation of pathological tau species is a novel approach for development of disease-modifying therapies that could block tau pathology and attenuate cognitive decline in patients with Alzheimer's disease and other tauopathies. We discovered cambinol through a screening effort and show that it is an inhibitor of cell-to-cell tau propagation. Our in vitro data demonstrate that cambinol inhibits neutral sphingomyelinase 2 (nSMase2) enzyme activity in dose response fashion, and suppresses extracellular vesicle (EV) production while reducing tau seed propagation. Our in vivo testing with cambinol shows that it can reduce the nSMase2 activity in the brain after oral administration. Our molecular docking and simulation analysis reveals that cambinol can target the DK-switch in the nSMase2 active site.
In this work we develop control over dislocation glide dynamics in Ga x In 1-x P compositionally graded buffer layers (CGBs) through control of CuPt ordering on the group-III sublattice. The ordered structure is metastable in the bulk, so any glissile dislocation that disrupts the ordered pattern will release stored energy, and experience an increased glide force. Here we show how this connection between atomic ordering and dislocation glide force can be exploited to control the threading dislocation density (TDD) in Ga x In 1-x P CGBs. When ordered Ga x In 1-x P is graded from the GaAs lattice constant to InP, the order parameter ..eta.. decreases as x decreases, and dislocation glide switches from one set of glide planes to the other. This glide plane switch (GPS) is accompanied by the nucleation of dislocations on the new glide plane, which typically leads to increased TDD. We develop control of the GPS position within a Ga x In 1-x P CGB through manipulation of deposition temperature, surfactant concentration, and strain-grading rate. We demonstrate a two-stage Ga x In 1-x P CGB from GaAs to InP with sufficiently low TDD for high performance devices, such as the 4-junction inverted metamorphic multi-junction solar cell, achieved through careful control the GPS position. Here, experimental results are analyzed within the context of a model that considers the force balance on dislocations on the two competing glide planes as a function of the degree of ordering.
The functionally important switch-loop of the trimeric multidrug transporter AcrB separates the access and deep drug binding pockets in every protomer. This loop, comprising 11 amino acid residues, has been shown to be crucial for substrate transport, as drugs have to travel past the loop to reach the deep binding pocket and from there are transported outside the cell via the connected AcrA and TolC channels. It contains four symmetrically arranged glycine residues suggesting that flexibility is a key feature for pump activity. Upon combinatorial substitution of these glycine residues to proline, functional and structural asymmetry was observed. Proline substitutions on the PC1 proximal side completely abolished transport and reduced backbone flexibility of the switch loop, which adopted a conformation restricting the pathway towards the deep binding pocket. Here, two phenylalanine residues located adjacent to the substitution sensitive glycine residues play a role in blocking the pathway upon rigidification of the loop, since the removal of the phenyl rings from the rigid loop restores drug transport activity.
We present an approach for minimizing the critical current for the magnetization switching in magnetic tunnel junctions by optimizing the spatial distribution of the current density. We show that such a minimization is possible because critical current is determined by the condition of making one of the magnetization eigenstates grow in time. The excitation of the eigenstates is enhanced when the spatial distributions of the eigenstates and current density overlap. Critical current can be viewed as a functional of the current density spatial distribution and it can be minimized by optimizing this distribution. Such an optimization results in a major reduction of the critical current and increase of the switching efficiency, viz. the ratio between the energy barrier and critical current. The minimized critical current increases approximately linearly with the magnetic tunnel junction size, which is much slower than critical current for the case of a uniform current density. The optimized efficiency can be approximately a constant with respect to the magnetic tunnel junction size, which is much higher than the efficiency for the uniform current density. Additional optimization can be achieved by spatially modulating the material parameters, e.g., the saturation magnetization. The presented approach and obtained scaling of the critical current and efficiency offers opportunities for the magnetic tunnel junction optimization.
Single-crystal and polycrystal BaTiO{sub 3} (BTO) materials synthesized by the physical and chemical methods, respectively, have been studied based on microstructural characterizations and magnetic measurements. The results of X-ray diffraction and Raman scatting spectra show that a single crystal tetragonal to polycrystalline pseudo-cubic structure transformation occurs in BTO ferroelectrics, dependent of growth conditions and interface effects. High-resolution transmission electron microscope data indicate that the as-prepared BTO/SrTiO{sub 3} (001) and BTO/SrRuO{sub 3}/SrTiO{sub 3} (001) heterostructures are highly c-axis oriented with atomic sharp interfaces. Lattice defects (i.e., edge-type misfit dislocations and stacking faults) in the heterostructures could be identified clearly and showed tunable with the variations of interface strain. Furthermore, the effects of vacancy defects on magnetic properties of BTO are discussed, which shows a diamagnetism–ferromagnetism switching as intrinsic vacancies increase. This work opens up a possible avenue to prepare magnetic BTO ferroelectrics. - Highlights: • Structure of BTO is tunable, depending on growth conditions and interface strain. • STEM–EDX data indicate the presence of lattice defects in BTO ferroelectrics. • BTO magnetism could be controlled by defects showing dia-ferromagnetism switching. • BTO with more vacancies shows RTFM, as evidence of vacancy magnetism effects.
Highlights: • Simple polyol method for preparation of Ce{sup 3+} sensitized Tb{sup 3+} ion doped YPO{sub 4} nanophosphor. • Enhanced green color emission with incorporation of Ce{sup 3+} ion into the matrix of YPO{sub 4}:Tb{sup 3+} nanophosphor. • Highly crystalline tetragonal YPO{sub 4}:Tb{sup 3+} without any impurity phase. • Use of alternate oxidising and reducing agent for luminescence switching (ON and OFF). - Abstract: Ce{sup 3+} sensitized Tb{sup 3+} ion doped YPO{sub 4} nanophosphor is synthesized by simple polyol method using ethylene glycol as capping agent as well as reaction medium. Green emission from Tb{sup 3+} ion doped YPO{sub 4} nanophosphor has been enhanced with incorporation of Ce{sup 3+} ion into the matrix of YPO{sub 4}:Tb{sup 3+}. XRD of YPO{sub 4}:Tb{sup 3+} annealed at 900 °C reveals crystalline tetragonal structure without any impurity phase. Morphology of YPO{sub 4}:Tb{sup 3+} nanophosphor was also studied. Homogenous incorporation of rare earth, RE (RE = Tb{sup 3+}, Ce{sup 3+}) ion into the host matrix were given in EDAX spectra. TGA/DTA analysis shows phase transformation of the as-prepared sample. Also, it is found that the as-prepared sample were readily re-dispersible in water due to presence of −OH group. By using an alternate oxidising and reducing agent, behaviour of luminescence switching (ON and OFF) can be examined. Lifetime decay of Tb{sup 3+} ion doped YPO{sub 4} nanophosphor was also studied.
To unravel the relationship between trace Cu on the metal-free catalysts toward CO/CO 2 reduction reaction (CO/CO 2 RR), we investigated the effect of trace Cu loading in N-doped graphene quantum dots (NGQDs) on CO/CO 2 RR. A general trend is that increasing the Cu loading in NGQDs switches the selectivity from C 1 (CH 4 ) to C 2 products in CORR. When 2.5 μg/cm 2 Cu with the atomic size is loaded on NGQDs, the selectivity shifts from 62% Faradaic efficiency (FE) of CH 4 to 52% FE of C 2 products in CORR. Further increasing the atomic Cu loading to 3.8 μg/cm 2 promotes the FE of C 2 products to 78%. CO 2 RR requires one order of magnitude higher Cu loading than CORR to switch the selectivity from C 1 to C 2 products due to the low partial pressure of CO. Finally, this study clarifies the distinct impact of trace (ppm level) Cu on the activity/selectivity between CORR and CO 2 RR.
Combining the effects of alternating-current (AC) electric fields and sedimentation reconfigures colloidal discoids between planar and homeotropic orientational alignments, thereby controlling the material’s structural color. Here, we self-assemble micrometer-size polystyrene discoids in an isopropanol-water mixture. After sedimentation, the discoids adopt a homeotropic alignment, with the minor axis perpendicular to the substrate. Adding an AC electric field (1 kHz) of ≥0.50 V switches the discoids to planar alignment—with the minor axis parallel to the substrate—within ∼100 s. Removing the field switches them back to homeotropic alignment within ∼300 s. Kinetic modeling of the field-induced torques yields good agreement with these measurements. The peak wavelength and intensity of the crystal’s diffraction response shift significantly upon reconfiguration; scattering simulation predicts these shifts. The reconfiguration is maintained for at least 10 cycles. This method is a simple, scalable avenue to reconfigure the optical properties of colloidal crystals produced from simple dielectric spheroids.
We investigate giant magnetoelectric coupling at a Mn 3+ spin crossover in [Mn III L]BPh 4 (L = (3,5-diBr-sal) 2 323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη 2 coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, in this work, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material.
Quantum states can provide means to systematically manipulate the transport of electrons. Here, in this study, we present electron transport across quasi-bound states of two heterogeneous quantum wells (QWs), where the transport of thermally excited electrons is blocked or enabled depending on the relative positions of the two quasi-bound states, with an abrupt current onset occurring when the two QW states align. The QW switch comprises a source (Cr), QW1 (Cr 2 O 3 ), QW2 (SnO x , x < 2), a tunneling barrier (SiO 2 ), and a drain (Si), where the effective electron mass of QW1 (m* QW1 ) is selected to be larger than QW2 (m* QW2 ). The current-voltage (I-V) measurements of the fabricated devices show abrupt current onsets, with the current transition occurring within 0.25 mV, corresponding to an effective electron temperature of 0.8 K at room temperature. Since transistor power consumption is fundamentally tied to effective electron temperature, this sub-1K cold-electron QW switching holds promise for highly energy-efficient computing.
The ability to control magnetism of materials via electric field enables a myriad of technological innovations in information storage, sensing, and computing. In this paper, we use ionic-liquid-assisted ferroelectric switching to demonstrate reversible modulation of interfacial magnetism in a multiferroic heterostructure composed of ferromagnetic (FM) La 0.8 Sr 0.2 MnO 3 and ferroelectric (FE) PbZr 0.2 Ti 0.8 O 3 . It is shown that ionic liquids can be used to persistently and reversibly switch a large area of a FE film. Finally, this is a prerequisite for polarized neutron reflectometry (PNR) studies that are conducted to directly probe magnetoelectric coupling of the FE polarization to the interfacial magnetization.
Strong-field hexadentate ligands were synthesized and coordinated to cobalt metal centers to result in three new low-spin to low-spin Co(III/II) redox couples. The ligand backbone has been modified with dimethyl amine groups to result in redox potential tuning of the Co(III/II) redox couples from –200 to –430 mV versus Fc +/0 . The redox couples surprisingly undergo a reversible molecular switch rearrangement from five-coordinate Co(II) to six-coordinate Co(III) despite the ligands being hexadentate. The complexes exhibit modestly faster electron self-exchange rate constants of 2.2–4.2 M –1 s –1 compared to the high-spin to low-spin redox couple [Co(bpy) 3 ] 3 + /2 + at 0.27 M –1 s –1 , which is attributed to the change in spin state being somewhat offset by this coordination switching behavior. The complexes were utilized as redox shuttles in dye-sensitized solar cells with the near-IR AP25 + D35 dye system and exhibited improved photocurrents over the [Co(bpy) 3 ] 3 + /2 + redox shuttle (19.8 vs 18.0 mA/cm 2 ). Finally, future directions point toward pairing the low-spin to low-spin Co(II/III) tunable series to dyes with significantly more negative highest occupied molecular orbital potentials that absorb into the near-IR where outer sphere redox shuttles have failed to produce efficient dye regeneration.
Solid-electrolyte interphases (SEIs) in advanced rechargeable batteries ensure reversible electrode reactions at extreme potentials beyond the thermodynamic stability limits of electrolytes by insulating electrons while allowing working ions to transport. Such selective ion transport occurs naturally in biological cell membranes as a ubiquitous prerequisite of many life processes and a foundation of biodiversity. In addition, cell membranes can selectively open and close the ion channels in response to external stimuli (e.g., electrical, chemical, mechanical, thermal), giving rise to “gating” mechanisms that help manage intracellular reactions. We wondered whether the chemistry and structure of SEIs can mimic cell membranes, such that ion gating can be replicated. That is, can SEIs realize a reversible switching between two electrochemical behaviors, i.e., the ion intercalation chemistry of batteries and the ion adsorption of capacitors? Herein, we report such SEIs that result in thermally activated selective ion transport. The function of open/close gate switches is governed by the chemical and structural dynamics of SEIs under different thermal conditions, with precise behaviors as conducting and insulating interphases that enable battery and capacitive processes within a finite temperature window. Such an ion gating function is synergistically contributed by Arrhenius-activated ion transport and SEI dissolution/regrowth. Following the understanding of this new mechanism, we then develop an electrochemical method to heal the SEI layer in situ. As a result, the knowledge acquired in this work reveals the possibility of hitherto unknown biomimetic properties of SEIs, which will guide us to leverage such complexities to design better SEIs for future battery chemistries.
Controlling molecular conformations with atomic precision is essential for advancing molecular functional electronics, as well as our understanding of molecular dynamics. While switching between bistable molecular conformers is common in nature, creating systems with multiple, addressable states remains synthetically challenging. Here, we demonstrate a bottom-up strategy in which intermolecular interactions give rise to multilevel functionality within a simple two-molecule assembly. Using low-temperature scanning tunneling microscopy, we show that a pyrrolidine dimer on Cu(100) exhibits six distinct adsorption conformations, exceeding the four expected from two independent bistable units. This unusual complexity arises from the interplay between intermolecular van der Waals attraction and steric repulsion, which reshapes the potential energy landscape and changes a single high-energy transition into a sequential two-step pathway. Each step is driven by low-energy inelastic electron excitations, achieving a switching efficiency an order of magnitude higher than that of the monomer. Here, by tuning the bias voltage and tip–molecule distance, we achieve deterministic control over multiple stable states, establishing a general design principle for on-demand engineering of collective molecular behavior and energy-efficient multilevel molecular devices.
Protein disulfide isomerase (PDI) is an oxidoreductase essential for folding proteins in the endoplasmic reticulum. The domain structure of PDI is a–b–b'–x–a', wherein the thioredoxin-like a and a' domains mediate disulfide bond shuffling and b and b' domains are substrate binding. The b' and a' domains are connected via the x-linker, a 19-amino-acid flexible peptide. Here we identify a class of compounds, termed bepristats, that target the substrate-binding pocket of b'. Bepristats reversibly block substrate binding and inhibit platelet aggregation and thrombus formation in vivo . Ligation of the substrate-binding pocket by bepristats paradoxically enhances catalytic activity of a and a' by displacing the x-linker, which acts as an allosteric switch to augment reductase activity in the catalytic domains. This substrate-driven allosteric switch is also activated by peptides and proteins and is present in other thiol isomerases. Our results demonstrate a mechanism whereby binding of a substrate to thiol isomerases enhances catalytic activity of remote domains.
A range of artificial molecular systems have been created that can exhibit controlled linear and rotational motion. In the development of such systems, a key step is the addition of communication between molecules in a network. Here, we show that a two-dimensional array of dipolar molecular rotors can undergo simultaneous rotational switching by applying an electric field from the tip of a scanning tunnelling microscope. Several hundred rotors made from porphyrin-based double-decker complexes can be simultaneously rotated when in a hexagonal rotor network on a Cu(111) surface by applying biases above ±1 V at 80 K. The phenomenon is observed only in a hexagonal rotor network due to the degeneracy of the ground state dipole rotational energy barrier of the system. Defects are essential to increase electric torque on the rotor network and to stabilize the switched rotor domains. At low biases and low initial rotator angles, slight reorientations of individual rotors can occur resulting in the rotator arms pointing in different directions. In conclusion, analysis reveals that the rotator arm directions here are not random, but are coordinated to minimize energy via cross talk among the rotors through dipolar interactions.
The ability to manipulate domains underpins function in applications of ferroelectrics. While there have been demonstrations of controlled nanoscale manipulation of domain structures to drive emergent properties, such approaches lack an internal feedback loop required for automatic manipulation. Here, using a deep sequence-to-sequence autoencoder we automate the extraction of latent features of nanoscale ferroelectric switching from piezoresponse force spectroscopy of tensile-strained PbZr 0.2 Ti 0.8 O 3 with a hierarchical domain structure. We identify characteristic behavior in the piezoresponse and cantilever resonance hysteresis loops, which allows for the classification and quantification of nanoscale-switching mechanisms. Specifically, we identify elastic hardening events which are associated with the nucleation and growth of charged domain walls. This work demonstrates the efficacy of unsupervised neural networks in learning features of a material's physical response from nanoscale multichannel hyperspectral imagery and provides new capabilities in leveraging in operando spectroscopies that could enable the automated manipulation of nanoscale structures in materials.