Enhanced Osteogenesis in 2D and 3D Culture Systems Using RGD Peptide and α-TCP Phase Transition within Alginate-Based Hydrogel.

Cell-laden hydrogels have been extensively investigated in various tissue engineering fields by their potential capacity to deposit numerous types of cells in a specific area. They are largely used in soft-tissue engineering applications because of their low mechanical strength. In addition, sodium alginate is well-known for its encapsulation, loading capacity and for being easily controllable; however, it lacks cell-binding ligands and hence the ability to adhere cells. In this study, it is aimed to enhance osteogenesis in cells encapsulated in alginate and improve its mechanical properties by introducing a synthetic peptide and calcium phosphate phase transition. To increase cell-hydrogel interactions and increasing cell viability, an RGD peptide is added to a photocrosslinkable methacrylate-modified alginate, and alpha-tricalcium phosphate (α-TCP) is added to the hydrogel to increase its mechanical strength via phase transition. Cell proliferation, growth, and differentiation are assessed in both 2D and 3D cell cultures. The addition of α-TCP significantly improved the mechanical properties of the hydrogel. Moreover, the RGD peptide and α-TCP showed a synergistic effect with significantly improved cell adhesion and osteogenesis in both 2D and 3D cell cultures. Therefore, the functional hydrogel developed in this study can potentially be used for bone tissue regeneration.

Reversible Solubility Switching of a Polymer Triggered by Visible-Light Responsive Azobenzene Photochromism with Negligible Thermal Relaxation.

This study reports the reversible solubility switching of a polymer triggered by non-phototoxic visible light. A photochromic polymerizable azobenzene monomer with four methoxy groups at the ortho-position (mAzoA) was synthesized, exhibiting reversible photoisomerization between trans- and cis-states using green (546 nm) and blue light (436 nm). Free radical copolymerization of hydrophilic dimethylacrylamide (DMAAm) with mAzoA produced a light-responsive random copolymer (P(mAzoA-r-DMAAm)) that shows a reversible photochromic reaction to visible light. Optimizing mAzoA content resulted in P(mAzoA10.7-r-DMAAm)3.0 kDa exhibiting LCST-type phase separation in PBS (pH 7.4) with trans- and cis-states at 39.2 °C and 32.9 °C, respectively. The bistable temperature range of 6.3 °C covers 37 °C, suitable for mammalian cell culture. Reversible solubility changes were demonstrated under alternating green and blue light at 37 °C. 1H NMR indicated significant retardation of thermal relaxation from cis- to trans-states, preventing undesired thermal mechanical degradation. Madin Darby Canine Kidney (MDCK) cells adhered to the P(mAzoA-r-DMAAm) hydrogel, confirming its non-cytotoxicity and potential for biocompatible interfaces. This principle is useful for developing hydrogels that can reversibly stimulate cells mechanically or chemically in response to visible light.

Spontaneous piezoeletric effect as evidence of ferroelastoelectricity in guanidine zinc sulfate crystal.

The crystal of [C(NH2)3]2Zn(SO4)2 guanidine zinc sulfate was grown and its structure, dilatometric, dielectric, elastic and piezoelectric properties were studied in a broad temperature range, covering the phase transition point. The crystal undergoes a continuous phase transition at 178 K from the room temperature tetragonal phase with a space group I 4 ¯ 2 d to the tetragonal low temperature phase with a space group I 4 ¯ . The structural X-ray studies allowed proposing molecular mechanism associated with the rearrangement in the configuration of N-H⋯O hydrogen bonds and reorientation of guanidine cations in the structure, leading to a change in the symmetry of the low temperature phase. Results of thermal expansion and dielectric studies are typical of a structural nonferroelectric continuous transition. Also measurement of piezoelectric and elastic properties revealed small anomalies at 178 K. Below the transition temperature, a new piezoelectric component, that is a ferroelastoelectric macroscopic order parameter, was found.

Conformational Transition of Semiflexible Ring Polyelectrolyte in Tetravalent Salt Solutions: A Simple Numerical Modeling without the Effect of Twisting.

In this work, the conformational behaviors of ring polyelectrolyte in tetravalent salt solutions are discussed in detail through molecular dynamics simulation. For simplification, here we have neglected the effect of the twisting interaction, although it has been well known that both bending and twisting interactions play a deterministic in the steric conformation of a semiflexible ring polymer. The salt concentration CS and the bending energy b take a decisive role in the conformation of the ring polyelectrolyte (PE). Throughout our calculations, the b varies from b = 0 (freely joint chain) to b = 120. The salt concentration CS changes in the range of 3.56 × 10-4 M ≤ CS ≤ 2.49 × 10-1 M. Upon the addition of salt, ring PE contracts at first, subsequently re-expands. More abundant conformations are observed for a semiflexible ring PE. For b = 10, the conformation of semiflexible ring PE shifts from the loop to two-racquet-head spindle, then it condenses into toroid, finally arranges into coil with the increase of CS. As b increases further, four phase transitions are observed. The latter two phase transitions are different. The semiflexible ring PE experiences transformation from toroid to two racquet head spindle, finally to loop in the latter two phase transitions. Its conformation is determined by the competition among the bending energy, cation-bridge, and entropy. Combined, our findings indicate that the conformations of semiflexible ring PE can be controlled by changing the salt concentration and chain stiffness.

Selective Segregation of Thermo-Responsive Microgels via Microfluidic Technology.

Separation of equally sized particles distinguished solely by material properties remains still a very challenging task. Here a simple separation of differently charged, thermo-responsive polymeric particles (for example microgels) but equal in size, via the combination of pressure-driven microfluidic flow and precise temperature control is proposed. The separation principle relies on forcing thermo-responsive microgels to undergo the volume phase transition during heating and therefore changing its size and correspondingly the change in drift along a pressure driven shear flow. Different thermo-responsive particle types such as different grades of ionizable groups inside the polymer matrix have different temperature regions of volume phase transition temperature (VPTT). This enables selective control of collapsed versus swollen microgels, and accordingly, this physical principle provides a simple method for fractioning a binary mixture with at least one thermo-responsive particle, which is achieved by elution times in the sense of particle chromatography. The concepts are visualized in experimental studies, with an intend to improve the purification strategy of the broad distribution of charged microgels into fractioning to more narrow distribution microgels distinguished solely by slight differences in net charge.

Leveraging Entropy and Crystal Structure Engineering in Prussian Blue Analogue Cathodes for Advancing Sodium-Ion Batteries.

The synergistic engineering of chemical complexity and crystal structures has been applied to Prussian blue analogue (PBA) cathodes in this work. More precisely, the high-entropy concept has been successfully introduced into two structure types of identical composition, namely, cubic and monoclinic. Through the utilization of a variety of complementary characterization techniques, a comprehensive investigation into the electrochemical behavior of the cubic and monoclinic PBAs has been conducted, providing nuanced insights. The implementation of the high-entropy concept exhibits crucial selectivity toward the intrinsic crystal structure. Specifically, while the overall cycling stability of both cathode systems is significantly improved, the synergistic interplay of crystal structure engineering and entropy proves particularly significant. After optimization, the cubic PBA demonstrates structural advantages, showcasing good reversibility, minimal capacity loss, high thermal stability, and unparalleled endurance even under harsh conditions (high specific current and temperature).

Kinetic Exploration of Nanoscale Polymorphs through Interface Energy Adjustment.

Traditionally, the study of crystal polymorphism has relied on thermodynamics and measurements averaged over time and the crystal's constituents. This work introduces a kinetic approach to phase identification─millisecond cinematographic electron microscopic imaging of the dynamics of phase transitions of crystals of a few nm in diameter. We demonstrate a remarkable impact of the interface energy on the relative stability of the nanocrystal's polymorphs, enabling in situ manipulation of phase transitions through size increase or decrease. Starting with the B1 NaI polymorph at 298 K, we identified the previously unknown B2 polymorph of a 1 s lifetime upon sublimation of the crystal. From the CsCl liquid phase, we produced the B1 phase, previously described only at 749 K.

Real-Space Imaging of Intrinsic Symmetry-Breaking Spin Textures in a Kagome Lattice.

The electronic orders in kagome materials have emerged as a fertile platform for studying exotic quantum states, and their intertwining with the unique kagome lattice geometry remains elusive. While various unconventional charge orders with broken symmetry is observed, the influence of kagome symmetry on magnetic order has so far not been directly observed. Here, using a high-resolution magnetic force microscopy, it is, for the first time, observed a new lattice form of noncollinear spin textures in the kagome ferromagnet in zero magnetic field. Under the influence of the sixfold rotational symmetry of the kagome lattice, the spin textures are hexagonal in shape and can further form a honeycomb lattice structure. Subsequent thermal cycling measurements reveal that these spin textures transform into a non-uniform in-plane ferromagnetic ground state at low temperatures and can fully rebuild at elevated temperatures, showing a strong second-order phase transition feature. Moreover, some out-of-plane magnetic moments persist at low temperatures, supporting the Kane-Mele scenario in explaining the emergence of the Dirac gap. The observations establish that the electronic properties, including both charge and spin orders, are strongly coupled with the kagome lattices.

Structure-dependent destructive adsorption of organophosphate flame retardants on lipid membranes.

The widespread use of organophosphate flame retardants (OPFRs), a serious type of pervasive environmental contaminants, has led to a global concern regarding their diverse toxicities to living beings. Using a combination of experimental and theoretical approaches, we systematically studied the adsorption, accumulation, and influence of a series of OPFRs on the lipid membranes of bacteria and cells. Our results revealed that OPFRs can aggregate in lipid membranes, leading to the destruction of membrane integrity. During this process, the molecular structure of the OPFRs is a dominant factor that significantly influences the strength of their interaction with the lipid membrane, resulting in varying degrees of biotoxicity. Triphenyl phosphate (TPHP), owing to its large molecular size and strong hydrophobicity, causes severe membrane disruption through the formation of nanoclusters. The corresponding severe toxicity originates from the phase transitions of the lipid membranes. In contrast, smaller OPFRs such as triethyl phosphate (TEP) and tris(2-chloroethyl) phosphate (TCEP) have weaker hydrophobicity and induce minimal membrane disturbance and ineffective damage. In vivo, gavage of TPHP induced more severe barrier damage and inflammatory infiltration in mice than TEP or TCEP, confirming the higher toxicity of TPHP. Overall, our study elucidates the structure-dependent adsorption of OPFRs onto lipid membranes, highlighting their destructive interactions with membranes as the origin of OPFR toxicity.

Impurity Level-Induced Broadband Photoelectric Response in Wide-Bandgap Semiconductor SrSnO3.

Broadband spectrum detectors exhibit great promise in fields such as multispectral imaging and optical communications. Despite significant progress, challenges like materials instability in such devices, complex manufacturing process, and high cost still hinder their further application. Here, we present a method that achieves broadband spectral detection by impurity-level in SrSnO3. We report over 500 mA/W photoresponsivity at 275 nm (ultraviolet C solar-bind) and 367 nm (ultraviolet A) and ∼60 mA/W photoresponsivity at 532 and 700 nm (visible) with a voltage bias of -5 V. Further transport and photoluminescence results reveal a new phase transition at 88 K, which would significantly affect the impurity level of the La-doped SrSnO3 film, indicating that the broadband response attributes to the impurity levels and mutual interactions. Additionally, the photodetector demonstrates excellent robustness and stability under repeated tests and prolonged exposure in air. These findings show the potential of SrSnO3 as a material for photodetectors and propose a method to achieve broadband spectrum detection, creating new possibility for the development of single-phase, low-cost, simple structure, and high-efficiency photodetectors.

Facile Coordination Transitions in AgCrX2 (X = S, Se): Unprecedented Electrostrain, Negative Piezoelectricity and Thermal Expansion.

The coefficients of piezoelectricity and thermal expansion are generally positive due to the bond anharmonicity. For converse piezoelectricity, the electrostrain obtained in prevalent ceramics is only around 1%. Here we propose that the coordination transition of metal cations may make a paradigm shift. Through first-principles calculations, we predict a series of low-energy phases with distinct coordinations for Ag ions in superionic conductor AgCrX2 (X = S, Se), including ferroelectric and nonpolar phases with distinct interlayer distances. The mobile feature of Ag ions, which can be attributed to its complex coordination chemistry, can facilitate transformation between various coordination phases. Such facile transitions with ultralow barriers can be driven by applying either pressure, an electric field, or a change in temperature, giving rise to various exotic effects, including electrostrain, negative piezoelectricity, and negative thermal expansion. All with unprecedented giant constants, those mechanisms stem from the coordination transitions, distinct from the weak linear effects in previous reports.

In Situ Electrochemical Recovery: Sediment Transformation under Chromium Poisoning in Reversible Solid Oxide Cells with La0.6Sr0.4Co0.2Fe0.8O3-σ-Based Oxygen Electrodes.

Reversible solid oxide cells (RSOCs) are an all-solid-state electrochemical device, which can convert H2 into electricity in the fuel cell (SOFC) mode and electrolyze H2O into fuel gas in the electrolytic cell (SOEC) mode, exhibiting good application prospect in the development of carbon neutrality. However, the degradation of the air electrode caused by Cr-containing steel interconnects is a major obstacle that limits the broader application of RSOCs. Herein, the Cr poisoning effect on La0.6Sr0.4Co0.2Fe0.8O3-σ (LSCF)-based oxygen electrodes under the electrolysis mode was systematically investigated. The phase transition of the sediment during the chromium poisoning process was captured and monitored. When tested under the presence of Fe-Cr interconnects at 800 °C for 40 h, SrCrO4 on the surface of LSCF was clearly identified through XRD and Raman analysis as the main deposition, and with the prolonged operating time, LaCrO3 slowly emerged. Due to the much higher electrical conductivity of LaCrO3 compared to SrCrO4, the negative effect induced by Cr poisoning was offset along with test progressing due to the deposition transition phenomenon. Inspired by the interesting discoveries, transition from SrCrO4 to LaCrO3 can be artificially facilitated by switching the operating mode to the SOEC mode, which can partially recover the dramatic degradation caused by the Cr poisoning effect under the SOFC mode. The feasibility of the in situ electrochemical recovery method was also verified by the experimental results. The peak power density of the cells decreased from 0.829 to 0.505 W/cm2 when operating under the SOFC mode with an Fe-Cr metal connector, and after in situ electrochemical recovery in the SOEC mode, the peak power density recovered to 0.630 W/cm2. This study provides a new strategy for achieving high performance and stability of RSOCs.

Engineering Multiphase Phase Transitions for Exceptional Electrocaloric Performance and Ultraweak Electrostrictive Response in Ferroelectrics.

In the pursuit of eco-friendly alternatives for refrigeration technology, electrocaloric materials have emerged as promising candidates for efficient solid-state refrigeration due to their high efficiency and integrability. However, current advancements in electrocaloric effects (ECEs) are often constrained by high temperatures and elevated electric fields (E-field), limiting practical applicability. Informed by phase-field simulation, this study introduces a (1-x)Pb(Yb1/2Nb1/2)O3-xPb(Mg1/3Nb2/3)O3 system, strategically engineered to incorporate highly ordered YN and disordered MN mixtures. The synergistic interplay between E-field/temperature-induced polarization reorientation and cation shift initiates multiple ferroelectric-antiferroelectric-paraelectric phase transitions. Our results demonstrate that under a moderate E-field of 50 kV cm-1, the x = 0.22 composition achieves remarkable performance with a giant temperature change (ΔT) of 3.48 K, a robust ECE strength (ΔT/ΔE) of 0.095 K cm kV-1, and a wide temperature span (Tspan) of 38 °C. Notably, the disrupted lattice structure contributes to ultralow electrostrains below 0.008%, with an average electrostrictive coefficient Q33 of 0.007 m4 C-2. The significantly weakened electrostrictive activity favors enhancing the performance stability of subsequent devices. This work introduces an innovative strategy for developing robust electrocaloric materials, offering substantial ΔT and low electrostrains, presenting promising advancements in ECE applications with an extended lifetime.

Highly Diffusive Nonluminescent Carriers in Hybrid Phase Lead Triiodide Perovskite Nanowires.

Crystal structural rearrangements unavoidably introduce defects into materials, where even these small changes in local lattice structure could arouse a prominent impact on the overall nature of crystals. Contrary to the traditional notion that defects obstruct carrier transport, herein, we report a promoted transport mechanism of nonluminescent carriers in single-crystalline CH3NH3PbI3 nanowires (1345.2 cm2 V-1 s-1, about a 14-fold improvement), enabled by the phase transition induced defects (PTIDs). Carriers captured by PTIDs evade both the radiative and non-radiative recombinations during the incomplete tetragonal-to-orthorhombic phase transition at low temperatures, forming a specific nonluminescent state that exhibits an efficient long-distance transport and thereby realize a prominent enhancement of photocurrent responsivity for photodetector applications. The findings provide broader insights into the carrier transport mechanism in perovskite semiconductors and have significant implications for their rational design for photoelectronic applications at varied operating temperatures.

Incognizant 1T/1H Charge-Density-Wave Phases in Monolayer NbTe2.

While experimental realization of multiple charge-density waves (CDWs) has been ascribed to monolayer 1T-NbTe2, their atomic structures are still largely unclear, preventing a deep understanding of their novel electronic structures. Here, comparing first-principles-calculated orbital textures with reported STM measurements, we successfully identify multiple CDWs in monolayer NbTe2. Surprisingly, we reveal that both 1T/1H phases could exist in monolayer NbTe2, which was incognizant before. Particularly, we find that the experimentally observed 4 × 1 and 4 × 4 CDWs could be attributed to 1H stacking, while the observed 19×19 phase could possess 1T stacking. The existence of 1T/1H phases results in competition between CDW, spin-density wave (SDW), and ferromagnetism in 1H stacking under an external field and results in CDW-induced quantum phase transitions from a Kramers-Weyl fermion to a topological insulator in 1T stacking. Our study suggests NbTe2 as an exotic platform to investigate the interplay between CDW, SDW, and topological phases, which are largely unexplored in current experiments.

Near-Zero Temperature Coefficient of Resonance Frequency in Rare-Earth Titanates via the Phase Transition Strategy.

This study presents an approach to achieve a near-zero temperature coefficient of resonance frequency (τf) in rare-earth titanate microwave dielectric ceramics (MWDCs) by inducing a phase transition. By Zr4+ substitution at the B site, a series of Sm2Ti1-xZrxO5 (0.02 ≤ x ≤ 0.55) ceramics are synthesized using the solid-state method to intentionally alter the radius ratio of the A/B sites, realizing in a controlled phase transition from orthorhombic (Pnma) to biphasic coexistence and ultimately to cubic (Fd3̅m) structure. The phase composition is rigorously identified through X-ray diffraction (XRD) Rietveld refinement, high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), and Raman spectroscopy. A comprehensive analysis is conducted to elucidate the relationships between factors such as ionic polarizability, packing fraction, bond valence, complex chemical bonding, and far-infrared reflectivity spectra with microwave dielectric properties. The results demonstrate that these ceramics exhibit a broad range of permittivity (14.30-23.18), high-quality factors (14,828-22,300 GHz), opposite temperature coefficient of resonance frequency (-16.0 to + 22.4 ppm/°C), and nice thermal conductivity (1.81-2.76 W·m-1·K-1), particularly at x = 0.30 with a near-zero τf value of +1.6 ppm/°C. The findings not only provide insights into designing MWDCs with a near-zero τf but also offer a promising route for developing advanced microwave materials with improved performance and reliability.

Topological Anderson phases in heat transport.

Topological Anderson phases (TAPs) offer intriguing transitions from ordered to disordered systems in photonics and acoustics. However, achieving these transitions often involves cumbersome structural modifications to introduce disorders in parameters, leading to limitations in flexible tuning of topological properties and real-space control of TAPs. Here, we exploit disordered convective perturbations in a fixed heat transport system. Continuously tunable disorder-topology interactions are enabled in thermal dissipation through irregular convective lattices. In the presence of a weak convective disorder, the trivial diffusive system undergos TAP transition, characterized by the emergence of topologically protected corner modes. Further increasing the strength of convective perturbations, a second phase transition occurs converting from TAP to Anderson phase. Our work elucidates the pivotal role of disorders in topological heat transport and provides a novel recipe for manipulating thermal behaviors in diverse topological platforms.

Polarized Raman mapping and phase-transition by CW excitation for fast purely optical characterization of VO2 thin films.

Vanadium dioxide has attracted much interest due to the drastic change of the electrical and optical properties it exhibits during the transition from the semiconductor state to the metallic state, which takes place at a critical temperature of about 68 °C. Much study has been especially devoted to developing advanced fabrication methodologies to improve the performance of VO2 thin films for phase-change applications in optical devices. Films structural and morphological characterisation is normally performed with expensive and time consuming equipment, as x-ray diffractometers, electron microscopes and atomic force microscopes. Here we propose a purely optical approach which combines Polarized Raman Mapping and Phase-Transition by Continuous Wave Optical Excitation (PTCWE) to acquire through two simple measurements structural, morphological and thermal behaviour information on polycrystalline VO2 thin films. The combination of the two techniques allows to reconstruct a complete picture of the properties of the films in a fast and effective manner, and also to unveil an interesting stepped appearance of the hysteresis cycles probably induced by the progressive stabilization of rutile metallic domains embedded in the semiconducting monoclinic matrix.

Temperature-Induced Phase Transition in 2D Alkylammonium Lead Halide Perovskites: A Molecular Dynamics Study.

Molecular dynamics simulations are utilized to unravel the temperature-driven phase transition in double-layered butylammonium (BA) methylammonium (MA) lead halide perovskite (BA)2(MA)Pb2I7, which holds great promise for a wide range of optoelectronics and sensor applications. The simulations successfully capture the structural transition from low to high symmetry phases with rising temperatures, consistent with experimental observations. The phase transition is initiated at two critical interfaces: the first is between the inorganic and organic layers, where the melting of N-H bonds in BA leads to a significant reduction in hydrogen bonding between BA and iodides, and the second is at the interface between the top and bottom organic layers, where the melting of the tail bonds in BA triggers the phase transition. Following this, BA cations exhibit a patterned and synchronized motion reminiscent of a conical pendulum, displaying a mix of ordered and disordered behaviors prior to evolving into a completely molten and disordered state. While the melting of BA cations is the primary driver of the phase transition, the rotational dynamics of MA cations also plays a critical role in determining the phase transition temperature, influenced by the BA-MA interaction. Such an interaction alters the polarization patterns of MA cations across the phase transition. In particular, an antiparallel polarization pattern is observed in the low-temperature phase. Additionally, displacive elements of the phase transition are identified in the simulations, characterized by the shear and distortion of the inorganic octahedra. Notably, at lower temperatures, the octahedral distortion follows a bimodal distribution, reflecting significant variations in distortion among octahedra. This variation is attributed to an anisotropic hydrogen bonding network between iodides and BA cations. Our study reveals the phenomena and mechanisms extending beyond the order-disorder transition mechanism, suggesting potential phase engineering through strategic tuning of organic and inorganic components.

Crystal structures, phase transition, and Hirshfeld surface analyses of the bromide and chloride congeners of aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) halide.

During the course of exploring crystallization conditions in generating metal-organic frameworks (MOFs) for use in the crystalline sponge method, two discrete metal-organic complexes, namely, aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) bromide, [Zn(C18H12N6)(H2O)]Br2, and aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) chloride, [Zn(C18H12N6)(H2O)]Cl2, were encountered. Structures in the orthorhombic space group Pnma (No. 62) for the bromide congener at 299 K and the chloride congener at 100 K were obtained. A phase transition for the bromide congener occurred upon cooling from 299 to 100 K, yielding a crystal polymorph with four domains that exhibits monoclinic P21/m space-group symmetry (No. 11), which arises from conformational changes. The main intramolecular contacts that contribute to the crystal packing in all observed structures are H...H, Halide...H/H...Halide, C...H/H...C, and N...H/H...N. Intramolecular hydrogen bonding between the Zn-bound water and non-Zn-bound pyridyl N atoms is a prominent feature within the three-dimensional networks. Aromatic π-stacking between the non-Zn-bound pyridine rings and contacts involving the halide ligands further stabilize the crystal packing.