Structural Transition Research Articles

Large out-of-plane piezoelectric response and ultra-low polarization transition barriers in two-dimensional MoGe2N4/MoSi2N4 heterostructures

With the help of the first principle calculations, two-dimensional (2D) MoGe2N4/MoSi2N4 van der Waals (vdW) heterojunction was confirmed as a type II bandgap arrangement with distinct piezoelectric properties dependent on the stacking orders and interlayer interactions. This structural change is facilitated by slip interactions between the layers and is characterized by a process with a low energy barrier, allowing for efficient and responsive phase transition of structures. Notably, this heterojunction exhibits a particularly large out-of-plane piezoelectric coefficient, d33, within a finite thickness. Concurrently, the piezoelectric coefficient can be enhanced by adjusting the vertical strain to a specific value, and the out-of-plane piezoelectric coefficient d33 can be as high as 73.28 pm/V, which is larger than the values of the available 2D materials or their heterojunctions. In addition, we simulated a piezoelectric actuator on a two-dimensional scale, where the deformation of the upper surface of the piezoelectric brake was linearly modulated by adjusting the driving voltage, Thus, our research paves the way for the conceptualization and creation of cutting-edge nanoelectronic devices, electromechanical systems, and multifunctional atomic-scale appliances.

Improvement of the production of pequi almond (Caryocar brasiliense Camb.) protein hydrolysates through ultrasound-assisted enzymolysis: Impact on hydrolysis kinetics, structure and functional properties of hydrolysates

This study investigated the kinetics of ultrasound (US)-assisted hydrolysis of pequi almond protein (PAP) and the conformational and multifunctional characteristics of the hydrolysates. The US-assisted enzymolysis of PAP using Alcalase® was conducted in a US bath (20kHz, 38W/L) for 180min at 60 °C and pH 7.5. The results showed an increase in the rate of proteolysis by 11.3%, leading to a higher final degree of hydrolysis (25.2%) and a greater concentration of TCA-soluble proteins after 45min and 180min (29% and 8%, respectively). Both conventional and US-assisted hydrolysis led to the breakdown of the protein structure, forming low molecular weight peptides (<15kDa). However, US-assisted hydrolysis demonstrated greater fragmentation of the PAP surface, enhancing enzymatic efficacy. Intrinsic fluorescence and UV spectroscopy indicated increased exposure of hydrophobic groups throughout hydrolysis, and FTIR spectroscopy revealed changes in the amide bands, suggesting structural transitions in the protein. Finally, the hydrolysates obtained from the USassisted reaction showed higher solubility (≤27% at pH 6.0), foaming capacity (≤82% at pH 6.0), and antioxidant activity (≤40%). Therefore, these results indicate the potential of the US to improve the performance of Alcalase® in the hydrolysis of PAP, producing compounds of industrial interest.

Intermediate-spin state of Co ions in magnetic and thermoelectric properties of double perovskite Ba2CoNbO6

Double perovskite Ba2CoNbO6, obtained by pyrolysis of nitrate-organic mixtures, was studied by XRD, XRF, DFT, AC/DC-magnetization, specific-heat, thermoelectric, and ESR methods. The sample has cubic symmetry space group Pm3m with a = b = c = 4.0074(11) Å. Deficiency in oxygen ions shows the presence of Co ions in both 3+ and 2+ valency. According to AC-magnetization and specific-heat data, Ba2CoNbO6 demonstrates spin-glass ordering at TSG = 30 K at external field value of 0.1 kOe. This temperature of spin glass transition drops with field power increase down to complete suppression at 10 kOe. The effective magnetic moment determined using the Curie-Weiss approximation is 4.29 μB, which is consistent with the theoretical estimation for Co ions in the intermediate-spin state. The peak at T = 90 K, observed in the temperature dependence of the specific heat and accompanied by a peak in the ESR linewidth, is possibly due to the structural transition at this temperature. The Seebeck coefficient of the compound is S = 4–6.5 μV/K and the band gap obtained within the small-polaron-jump conductivity model is ΔE = 0.284 eV in the temperature range of 350-550 K connected with DFT calculation. An intensity ESR line, related to Co2+ ions, was observed in ESR spectra.

Pseudo-proper two-dimensional electron gas formation

Abstract In spite of the interest in the two-dimensional electron gases (2DEGs) experimentally found at surfaces and interfaces, important uncertainties remain about the observed insulator–metal transitions (IMTs). Here we show how an explicit pseudo-proper coupling of carrier sources with a relevant soft mode significantly affects the transition. The analysis presented here for 2DEGs at polar interfaces is based on group theory, Landau-Ginzburg theory, and illustrated with first-principles calculations for the prototypical case of the LaAlO3⁄SrTiO3 interface, for which such a structural transition has recently been observed. This direct coupling implies that the appearance of the soft mode is always accompanied by carriers. For sufficiently strong coupling an avalanchelike first-order IMT is predicted.&amp;#xD;

Structural phase transition in NH₄F under extreme pressure conditions.

Ammonium fluoride (NH₄F) exhibits a variety of crystalline phases depending on temperature and pressure. By employing Raman spectroscopy and synchrotron X-ray diffraction beyond megabar pressures (up to 140 GPa), we have here observed a novel dense solid phase of NH₄F, characterised by the tetragonal P4/nmm structure also observed in other ammonium halides under less extreme pressure conditions, typically a few GPa. Using detailed ab-initio calculations and reevaluating earlier theoretical models pertaining to other ammonium halides, we examine the microscopic mechanisms underlying the transition from the low-pressure cubic phase (P-43m) to the newly identified high-pressure tetragonal phase (P4/nmm). Notably, NH₄F exhibits distinctive properties compared to its counterparts, resulting in a significantly broader pressure range over which this transition unfolds, facilitating the identification of its various stages. Our analysis points to a synergistic interplay driving the transition to the P4/nmm phase, which we name phase VIII. At intermediate pressures (around 40 GPa), a displacive transition of fluorine ions initiates a tetragonal distortion of the cubic phase. Subsequently, at higher pressures (around 115 GPa), every second ammonium ion undergoes a rotational shift, adopting an anti-tetrahedral arrangement. This coupled effect orchestrates the transition process, leading to the formation of the tetragonal phase.

Transient Phase-Mediated Li+ Transportation in the Lithium Lanthanum Titanate Solid-State Electrolyte.

The lithium lanthanum titanium oxide (LLTO) perovskite is one type of superior lithium (Li)-ion conductor that is of great interest as a solid-state electrolyte for all-solid-state lithium batteries. Structural defects and impurity phases formed during the synthesis of LLTO largely affect its Li-ion conductivity, yet the underlying Li+ diffusion mechanism at the atomic scale is still under scrutiny. Herein, we use aberration-corrected transmission electron microscopy to perform a thorough structural characterization of the LLTO ceramic pellet. We reveal a prevalent transient phase transition of (La, Ti)2O3 existing at the antiphase boundaries between single-crystalline LLTO domains. This transient phase exhibits a specific crystal orientation with the LLTO phase and shows a gradual structural transition to a tetragonal LLTO structure, which enables detailed crystallographic analysis to correlate their formation to the sintering process of LLTO powders into ceramic pellets. We also find that Li diffusion is retarded by this phase and correlated with the excess amount of La, which is corroborated by the theoretical evaluation of the atomistic mechanisms of Li diffusion across this phase.

Exploring the role of transition metal ions doping on the optical, magnetic and energy storage properties of Bi0.96Eu0.04FeO3 nanoparticles

Bismuth ferrite has been quite extensively studied because of its unique multiferroic properties. The introduction of dopants strategically at the ‘A’ and ‘B’ sites has been known to improve the multiferroic properties of bismuth ferrite. This study focuses on the detailed investigation of the structural, morphological, optical, magnetic, and electrochemical properties of sol-gel synthesized bismuth ferrite as well as Bi0.96Eu0.04Fe0.95M0.05O3(M=Mn, Cu, Co, Zn) nanoparticles. The crystal structure and morphological analysis are done using XRD, Rietveld refinement, and FESEM. The XRD analysis and Rietveld Refinement have confirmed a structural transition to the orthorhombic phase upon simultaneous co-doping of ‘Eu’ and ‘M’(M= Mn, Cu, Co, Zn) ions at the ‘A’ and ‘B’ sites respectively. The evidence of different ratios of mixed valence states of ‘Fe’ and oxygen vacancies in the co-doped nanoparticles dictates the enhanced magnetic properties. There is a significant decrease in the band-gap of co-doped nanoparticles obtained from Tauc’s plot, with the lowest achieved band-gap of 1.8 eV in the case of ‘Eu’ and ‘Mn’ doped nanoparticles. Room-temperature M-H loops have recorded an increase in the value of maximum magnetization from 0.1 emu/g in case of pristine bismuth ferrite to 0.79 emu/g for ‘Eu’ and ‘Co’ doped bismuth ferrite nanoparticles. The unsaturated loops, however, have confirmed the presence of anti-ferromagnetic component along with the ferromagnetic part. The electrochemical studies have shown superior specific capacitance in co-doped bismuth ferrite, with the maximum specific capacitance of 273 F/g for ‘Eu’ and ‘Zn’ doped bismuth ferrite. It has also shown remarkable capacitive retention of 84.8 % after 5000 cycles at 10 A/g.

Oxidation-induced graded bandgap narrowing in Two-dimensional tin sulfide for high-sensitivity broadband photodetection

Two-dimensional (2D) layered group-IV monochalcogenides with large surface-to-volume ratio and high surface activity make that their structural and optoelectronic properties are sensitive to air oxidation. Here, we report the utilization of oxidation-induced gradient doping to modulate electronic structures and optoelectronic properties of 2D group-IV monochalcogenides by using SnS nanoplates grown by physical vapor deposition as a model system. By a precise control of oxidation time and temperature, the structural transition from SnS to SnSOx could be driven by the layer-by-layer oxygen doping and intercalation. The resulting SnSOx with a graded narrowing bandgap exhibits the enhanced optical absorption and photocurrent, leading to the fabricated SnSOx photodetector with remarkable photoresponsivity and fast response speed (<64 μs) at a broadband spectrum range of 520–1550 nm. The peak responsivity (7294 A/W) and detectivity (9.54 × 109 Jones) of SnSOx device are at least two orders of magnitude larger than those of SnS photodetector. Moreover, its photodetection performance can be competed with state-of-the-art of 2D materials-based photodetectors. This work suggests that the air oxidation could be utilized as an efficient strategy to engineer the electronic and optical properties of SnS and other 2D group-IV monochalcogenides for the development of high-performance broadband photodetectors.

Spontaneous Dimerization and Distinct Packing Modes of Transmembrane Domains in Receptor Tyrosine Kinases.

The insulin receptor (IR) and the insulin-like growth factor-1 receptor (IGF1R) are homodimeric transmembrane glycoproteins that transduce signals across the membrane on binding of extracellular peptide ligands. The structures of IR/IGF1R fragments in apo and liganded states have revealed that the extracellular subunits of these receptors adopt Λ-shaped configurations to which are connected the intracellular tyrosine kinase (TK) domains. The binding of peptide ligands induces structural transitions in the extracellular subunits leading to potential dimerization of transmembrane domains (TMDs) and autophosphorylation in TKs. However, the activation mechanisms of IR/IGF1R, especially the role of TMDs in coordinating signal-inducing structural transitions, remain poorly understood, in part due to the lack of structures of full-length receptors in apo or liganded states. While atomistic simulations of IR/IGF1R TMDs showed that these domains can dimerize in single component membranes, spontaneous unbiased dimerization in a plasma membrane having a physiologically representative lipid composition has not been observed. We address this limitation by employing coarse-grained (CG) molecular dynamics simulations to probe the dimerization propensity of IR/IGF1R TMDs. We observed that TMDs in both receptors spontaneously dimerized independent of their initial orientations in their dissociated states, signifying their natural propensity for dimerization. In the dimeric state, IR TMDs predominantly adopted X-shaped configurations with asymmetric helical packing and significant tilt relative to the membrane normal, while IGF1R TMDs adopted symmetric V-shaped or parallel configurations with either no tilt or a small tilt relative to the membrane normal. Our results suggest that IR/IGF1R TMDs spontaneously dimerize and adopt distinct dimerized configurations.

Density Functional Theory Study of Lanthanide Monoxides under High Pressure: Pressure-Induced B1–B2 Transition

Using density functional theory, we study the influence of hydrostatic pressure on the crystal structure of lanthanide monoxides, focusing on the monoxides formed by the fifteen elements of the lanthanide series, from La to Lu. Calculations are performed using two methods for the ambient pressure B1 (NaCl type) structure, the general gradient approximation (GGA) and the local density approximation (LDA). Through a systematic comparison with existent experimental data, we find that the first method agrees better with the experiments. In addition, considering other cubic structures previously reported for lanthanide monoxides, as B2 (CsCl type) and B3 (ZnS type), we explore the possibility of the occurrence of pressure-induced phase transitions. Based on the better accuracy of GGA to describe the B1 phase at ambient conditions, we exclusively use GGA for the high pressure study. We find, for the fifteen studied compounds, that, at ambient pressure, the B1 structure is the one with the lowest enthalpy, being therefore the most thermodynamically stable structure. We also determine that, at elevated pressures, all the studied compounds undergo a structural phase transition to the B2 phase. We finally establish the relationship between pressure and volume of the unit cell, along with the associated isothermal equation of state, determining the bulk modulus.

Pressure-induced structural transition and superconductivity in hard compound IrB4

The recent discovery of MoB2 with a superconducting transition temperature (Tc) of up to 32 K at 100 GPa provides new insights into the metallization and subsequently high-Tc superconductivity of diborides, highlighting the potential of transition metals in these compounds. We herein re-evaluated the structure, mechanical, and superconducting properties of IrB4 under pressure up to 300 GPa using first-principles. Our calculations reveal that a new P21/c phase exhibiting a hardness of 15.75 GPa surpasses the stability of the C2/m structure identified through the particle swarm optimization at ambient pressure. Upon compressing, the P21/c phase transforms into an MgB2-type structure with a space group of P63/mmc at 62.5 GPa and then into the orthorhombic Cmca phase above 109 GPa. Unlike semiconductor behavior of the atmospheric pressure phase, the two high-pressure structures are metallic and superconducting, with Tc values of 29.90 for P63/mmc at 62.5 GPa and 13.45 K for Cmca at 125 GPa. Analysis of the electronic structure and electron–phonon coupling (EPC) reveals that the high Tc, similar to MgB2-type MoB2, stems from the Van Hove Singularities (VHS) near the Fermi level donated by transition metal Ir. The effect further enhances the EPC based on the boron contribution. More interestingly, pressure has little impacts on the position of the VHS. These findings provide a new platform for designing advanced high-Tc superconductors.

Inverse and conventional dual magnetocaloric effects in Ni substituted Y-type Sr2Zn2-xNixFe12O22 hexaferrites

The effects of Ni substitution on magnetic and magnetocaloric effect (MCE) are investigated in polycrystalline Y-type hexaferrites of Sr2Zn2-xNixFe12O22 (x = 0.0, 0.8, and 2.0). With the increasing of temperature, the M-T curves indicate successive magnetic structure transitions exist in Sr2Zn2-xNixFe12O22 (x = 0.0, 0.8, and 2.0), which play significant roles in MCE behaviors. As the Ni2+ doping ratio increases, the shape of −ΔSM−T curves near room temperature evolves gradually from a table-like to a peak-like form. Particularly, a significant contrast between CMCE and IMCE is observed below 100 K, whose behavior can be inherently exploited for heat sink in magnetic refrigeration applications. Among the samples in this series, Sr2Zn1.2Ni0.8Fe12O22 plays the best CMCE and IMCE performances, with the maximum magnetic entropy change (−ΔSMmax) values of 0.78 J/kg K at 354 K and −0.56 J/kg K at 16 K for ΔH=50kOe , respectively. Our work demonstrates that Sr2Zn2-xNixFe12O22 hexaferrites have great potential to be tailored for magnetic refrigeration with special needs such as different operating temperature zones, Ericsson cycle or heat sink at refrigeration.

Emergence of Topological Phase and Non-Trivial Surface States in Rare-Earth Semimetal GdSb with Pressure

Abstract We studied the evolution of band topology with external pressure in rare-earth GdSb using first-principles calculations. This material crystallizes in a rocksalt-type structure and shows the structural phase transition to CsCl-type structure at 26.1 GPa. The phonon dispersions are analyzed to ascertain the dynamical stability of this material. We used the hybrid density functional theory with the inclusion of spin-orbit coupling to investigate the structural, electronic, and topological phase transitions. At ambient pressure, GdSb shows a topologically trivial state which agrees with the existing experimental reports. The first topological phase transition is observed at 6 GPa of hydrostatic pressure (at the high symmetry X-point) verified with the help of single band inversions and surface states analysis along the (001) plane. The non-zero value of the first Z2 topological invariant and the presence of the Dirac cone also confirm the topological phase of this material. Further, an increase in pressure to 12 GPa, two band inversions, at Γ- as well as X-points, are observed which corresponds to the trivial nature of GdSb. The same is verified with (0;000) values of Z2 topological invariants and a pair of Dirac cones in surface states. It is noted that the crystal symmetries are preserved throughout the study and topological phase transition values are much lower than structural phase transition pressure i.e., 26.1 GPa.

Sodium Ion‐Induced Structural Transition on the Surface of a DNA‐Interacting Protein

Sodium Ion‐Induced Structural Transition on the Surface of a DNA‐Interacting Protein

Meron-Mediated Phase Transitions in Quasi-Two-Dimensional Chiral Magnets with Easy-Plane Anisotropy: Successive Transformation of the Hexagonal Skyrmion Lattice into the Square Lattice and into the Tilted FM State.

I revisit the well-known structural transition between hexagonal and square skyrmion lattices and subsequent first-order phase transition into the tilted ferromagnetic state as induced by the increasing easy-plane anisotropy in quasi-two-dimensional chiral magnets. I show that the hexagonal skyrmion order first transforms into a rhombic skyrmion lattice, which, adjusts into a perfect square arrangement of skyrmions ("a square meron-antimeron crystal") within a narrow range of anisotropy values. These transitions are mediated by merons and anti-merons emerging in the boundaries between skyrmion cells; energetically unfavorable anti-merons annihilate, whereas pairs of neighboring merons merge. The tilted ferromagnetic state sets in via mutual annihilation of oppositely charged merons; as an outcome, it contains bimeron clusters (chains) with the attracting inter-soliton potential. Additionally, I demonstrate that domain-wall merons are actively involved in the dynamic response of the square skyrmion lattices. As an example, I theoretically study spin-wave modes and their excitations by AC magnetic fields. Two found resonance peaks are the result of the complex dynamics of the domain-wall merons; whereas in the high-frequency mode the merons rotate counterclockwise, as one might expect, in the low-frequency mode merons are instead created and annihilated consistently with the rotational motion of the domain boundaries.

RETRACTION: Structural Characteristics and Development Model of Fluid Diapirs Within the Structural Transition Zone, Northern South China Sea

RETRACTION: Y. Qin, C. Liu, G. Peng, L. Huang, C. Liang, H. Li, Z. Wu and L. Yang, “,” Geological Journal 59, no. (2024): 1906–1923, https://doi.org/10.1002/gj.4968. The above article, published online on 28 April 2024 in Wiley Online Library (wileyonlinelibrary.com), has been retracted by agreement between the authors; the journal Editor‐in‐Chief, Ian D. Somerville and Yunpeng Dong; and John Wiley &amp; Sons Ltd. The retraction has been agreed as some of the data included within the article was not authorized for publication. Furthermore, the authors are not confident that the fluid diapir labels shown in figure 7 are correct and admit they may be problematic. As a result the editors have decided to retract this article.

On ablation characteristics based on two-temperature model involving a multivariate lattice heat capacity by ultrashort laser-irradiated in zirconia

To explore the mechanism of material removal, this paper conducts a systematic study on picosecond laser processing of zirconia by using both theory and experiment. Comparing the multivariate lattice heat capacity of the Einstein and Debye models, two-temperature model (TTM) is developed to improve the accuracy of the temperature field. Then, to verify the effectiveness of TTM proposed, ablation experiments are performed by single-pulse picosecond laser on zirconia at different laser energy density. The results show that the measured craters profiles are well agree with the simulated melting/vaporization temperature distribution. Micro-morphology is significantly affected by phase transition induced by temperature rise. Moreover, the results confirmed that increased temperature can lead to transition in zirconia crystal structure and oxygen vacancies. Finally, the effect of coupling temperature variations on the elemental and physical phase variations are focused to investigate, which can help to optimize the processing quality due to crystalline phase transitions. This study provides guidance for optimizing picosecond laser processing of zirconia.

Spatiotemporal formation of a single liquid-like condensate and amyloid fibrils of α-synuclein by optical trapping at solution surface

Liquid-like protein condensates have recently attracted much attention due to their critical roles in biological phenomena. They typically show high fluidity and reversibility for exhibiting biological functions, while occasionally serving as sites for the formation of amyloid fibrils. To comprehend the properties of protein condensates that underlie biological function and pathogenesis, it is crucial to study them at the single-condensate level; however, this is currently challenging due to a lack of applicable methods. Here, we demonstrate that optical trapping is capable of inducing the formation of a single liquid-like condensate of α-synuclein in a spatiotemporally controlled manner. The irradiation of tightly focused near-infrared laser at an air/solution interface formed a condensate under conditions coexisting with polyethylene glycol. The fluorescent dye-labeled imaging showed that the optically induced condensate has a gradient of protein concentration from the center to the edge, suggesting that it is fabricated through optical pumping-up of the α-synuclein clusters and the expansion along the interface. Furthermore, Raman spectroscopy and thioflavin T fluorescence analysis revealed that continuous laser irradiation induces structural transition of protein molecules inside the condensate to β-sheet rich structure, ultimately leading to the condensate deformation and furthermore, the formation of amyloid fibrils. These observations indicate that optical trapping is a powerful technique for examining the microscopic mechanisms of condensate appearance and growth, and furthermore, subsequent aging leading to amyloid fibril formation.

Acoustic Shock Wave-Induced Rutile to Anatase Phase Transition of TiO2 Nanoparticles and Exploration of Their Unconventional Thermodynamic Structural Transition Path of Crystallization Behaviors.

Titanium dioxide (TiO2) is one of the most well-known and long-standing polymorphic materials in the transition metal oxide group of materials. The transition from rutile to anatase is one of the long-standing fundamental questions among materials science researchers because seeking the nucleation site at the beginning of the phase transition is highly challenging. Until now, there have been no studies on the unconventional structural phase transition of TiO2 nanoparticles by acoustic shock waves. In the present study, this work provides the first evidence on the solid-state nanostructure of the rutile-to-anatase phase transition of TiO2 by acoustic shock waves whereby these phase transition results are evaluated by Raman spectroscopy, thermal calorimetry, X-ray photoelectron spectroscopy, and microscopic techniques. We propose a novel mechanism for the occurrence of the rutile-to-anatase phase transition based on thermophysical properties and shock wave-induced melting concepts. Under shocked conditions, the R-A phase transition occurs because of the anatase phase's lower interfacial energy (γL/A) and surface energy compared to rutile. We strongly believe that the present work can provide in-depth insight into understanding the crystallization concepts of the TiO2 NPs under extreme conditions, especially with regard to the rutile-to-anatase phase transition.

Boosting the intrinsic kinetics of lithium vanadium phosphate via an electrochemically active cross-link framework

The monoclinic lithium vanadium phosphate Li3V2(PO4)3 (LVP) is considered a promising cathode for lithium-ion batteries (LIBs) due to its high working voltage (>4.0 V, vs. Li+/Li) and high theoretical specific capacity (197 mAh g−1). However, the electrochemical procedure accompanied by three-electron reactions in LVP has proven challenging due to the complexity or asymmetry of the reaction pathways, thus limiting its wide application. Herein, an electrochemically active cross-link framework of LVP, LiFe0.3Mn0.7PO4 (LFMP) and graphene are successfully synthesized by an in situ catalytic process, which enables stable cycling and high-rate capabilities up to 4.8 V (vs. Li+/Li). Graphene-like carbon can be formed in situ with VOx as the catalyst and polyvinyl alcohol as the carbon source, and LFMP also inhibits the growth of LVP particles, allowing rapid Li+ and electron transport in the cathodes. Both in situ and ex situ X-ray diffraction prove that the cross-link framework efficiently smooths the lattice mismatch and achieves highly reversible structural phase transitions. The prepared 0.9LVP·0.1LFMP is able to provide a superior rate capability of 123 mAh g−1 at 20 C. After 150 cycles, the 0.9LVP·0.1LFMP shows 97.4 % capacity retention even under a voltage of 4.8 V (vs. Li+/Li). This work develops a new strategy for the future design of high-voltage and high-power cathode materials for LIBs.