Halide Anions Tuning of Lead-Free Perovskite-Type Ferroelectric Semiconductors with Inverse High-Temperature Symmetry Breaking.

There is a noticeable gap in the literature regarding research on halogen-substitution-regulated ferroelectric semiconductors featuring multiple phase transitions. Here, a new category of 1D perovskite ferroelectrics (DFP)2SbX5 (DFP+ = 3,3-difluoropyrrolidium, X- = I-, Br-, abbreviated as I-1 and Br-2) with twophase transitions (PTs) is reported. The first low-temperature PT is a mmmFmm2 ferroelectric PT, while the high-temperature PT is a counterintuitive inverse temperature symmetry-breaking PT. By the substitution of iodine with bromine, the Curie temperature (Tc) significantly increases from 348 K of I-1 to 374 K of Br-2. Their ferroelectricity and pyroelectricity are improved (Ps value from 1.3 to 4.0 µC cm-2, pe value from 0.2 to 0.48 µC cm-2 K-1 for I-1 and Br-2), while their optical bandgaps increased from 2.1 to 2.7 eV. A critical slowing down phenomenon is observed in the dielectric measurement of I-1 while Br-2 exhibits the ferroelastic domain. Structural and computational analyses elucidate that the order-disorder movement of cations and the distortion of the chain perovskite [SbX5]2- anions skeleton lead to PT. The semiconductor properties are determined by [SbX5]2- anions. The findings contribute to the development of ferroelectric semiconductors and materials with multiple PTs and provide materials for potential applications in the optoelectronic field.

Supershear Rayleigh wave imaging for quantitative assessment of biomechanical properties of brain using air-coupled optical coherence elastography.

Recently, supershear Rayleigh waves (SRWs) have been proposed to characterize the biomechanical properties of soft tissues. The SRWs propagate along the surface of the medium, unlike surface Rayleigh waves, SRWs propagate faster than bulk shear waves. However, their behavior and application in biological tissues is still elusive. In brain tissue elastography, shear waves combined with magnetic resonance elastography or ultrasound elastography are generally used to quantify the shear modulus, but high spatial resolution elasticity assessment in 10 µm scale is still improving. Here, we develop an air-coupled ultrasonic transducer for noncontact excitation of SRWs and Rayleigh waves in brain tissue, use optical coherent elastography (OCE) to detect, and reconstruct the SRW propagation process; in combing with a derived theoretical model of SRWs on a free boundary surface, we quantify the shear modulus of brain tissue with high spatial resolution. We first complete validation experiments using a homogeneous isotropic agar phantom, and the experimental results clearly show the SRW is 1.9649 times faster than the bulk shear waves. Furthermore, the propagation velocity of SRWs in both the frontal and parietal lobe regions of the brain is all 1.87 times faster than the bulk shear wave velocity. Finally, we evaluated the anisotropy in different brain regions, and the medulla oblongata region had the highest anisotropy index. Our study shows that the OCE system using the SRW model is a new potential approach for high-resolution assessment of the biomechanical properties of brain tissue.

Enhanced Electrocaloric Effect of Lead Scandium Tantalate by Zirconium Doping.

The electrocaloric effect (ECE) is a novel technology that offers high efficiency and environmental friendliness, making it suitable for solid-state refrigeration applications. Among the extensively studied ECE materials, lead scandium tantalate (PST) stands out for its excellent performance. However, its applications are restricted by its narrow working temperature range. To overcome this limitation, we explore the enhancement of the ECE through zirconium ion doping. We synthesized PbSc0.5-0.5xTa0.5-0.5xZrxO3 samples (x = 0, 0.025, 0.05, 0.075). The introduction of zirconium ions led to an increase in the Curie temperature from 28.9 °C (x = 0) to 55.5 °C (x = 0.075). Additionally, the relaxation factor γ of the ceramics increased from 1.40 (x = 0) to 1.59 (x = 0.075). The temperature span (Tspan) exhibited a rising trend with increasing x, reaching 10.9 K at x = 0.075. The maximum temperature change (ΔTmax) was observed at x = 0.025, with a value of 1.94 K. X-ray diffraction (XRD) patterns revealed that zirconium ion doping influenced the B-site ordering degree, thereby regulating the ECE. To further validate the results, we employed direct measurements and thermodynamic calculations. Overall, the regulation of ionic ordering through zirconium doping effectively enhances the ECE performance. These findings contribute to the development of advanced materials for solid-state refrigeration technologies.

A room temperature ferroelectric material with photoluminescence: (1,3-dicyclohexylimidazole)2MnCl4.

Molecular ferroelectric materials have been widely used in capacitors and sensors due to their low cost, light weight, flexibility and good biocompatibility. Organic-inorganic hybrid complexes, on the other hand, have received a great deal of attention in the luminescence field due to their low cost and simple preparation. The combination of ferroelectricity and photoluminescence in organic-inorganic hybrid materials not only leads to tunable optical properties, but also enriches potential applications of multifunctional ferroelectrics in optoelectronic devices. Here, we report a new luminescent ferroelectric material (1,3-dicyclohexylimidazole)2MnCl4 (DHIMC). Thermogravimetric analysis (TGA) was used to measure the mass change of the material at a measurement rate of 20 K min-1 from room temperature to 900 K, and we found that this material has good thermostability, which is up to 383 K. Meanwhile, UV-vis measurements showed that it is also a fluorescent material emitting a strong green fluorescence at the wavelength of 525 nm. The ferroelectricity of the crystal was determined by two different methods: the Sawyer-Tower method and the double-wave method (DWM). Particularly, the single crystal experiences a phase transition from the ferroelectric phase to the paraelectric phase during the heating/cooling process at 318 K/313 K and the space group changes from P1̄ (centrosymmetric) to P1 (non-centrosymmetric). This work will enrich multifunctional luminescent ferroelectric materials and their application in display and sensing.

Novel acoustic radiation force optical coherence elastography based on ultrasmall ultrasound transducer for biomechanics evaluation of in vivo cornea.

We developed a novel acoustic radiation force optical coherence elastography (ARF-OCE) based on an ultrasmall ultrasound transducer for quantitative biomechanics evaluations of in vivo cornea. A custom single-sided meta-ultrasonic transducer with an outer diameter of 1.8 mm, focal spot diameter of 1.6 mm, central frequency of 930 kHz, and focal length of 0.8 mm was applied to excite the sample. The sample arm of the ARF-OCE system employed a three-dimensional printed holder that allowed for ultrasound excitation and ARF-OCE detection. The phase-resolved algorithm was combined with a Lamb wave model to depth-resolved evaluate corneal biomechanics after keratoconus and cross-linking treatments (CXL). The results showed that, compare to the healthy cornea, the Lamb wave velocity was significantly reduced in the keratoconus, increased in the cornea after CXL, and increased with cross-linked irradiation energy in the cornea. These results indicated the good clinical translation potential of the proposed novel ARF-OCE.

Lead-Free Hybrid Organic-Inorganic Ferroelectric: (3,3-Difluoropyrrolidinium)2ZnCl4·H2O.

Hybrid organic-inorganic ferroelectrics (HOIFs) have a wide range of applications in the optoelectronic field in terms of rich optoelectronic properties. Particularly, lead-free HOIFs have attracted extensive attention due to their environmental friendliness, low heavy metal toxicity, and low synthesis cost. However, there are few reports about Zn-based HOIFs due to their uncontrollable ferroelectric synthesis and other reasons. Here, we designed and synthesized a zinc-based zero-dimensional (3,3-difluoropyrrolidine)2ZnCl4·H2O (DFZC) single crystal, which undergoes a phase transition from ferroelectric to paraelectric phase (space group from Pna21 to Pnma) at 295.5 K/288.9 K during the heating/cooling process. The systematic study shows that the ferroelectric phase transition is a displacive type. The ferroelectric hysteresis loop of DFZC was obtained by the double-wave method and the Sawyer-Tower method, which has a spontaneous polarization (Ps) of ∼0.4 µC/cm2. This work reveals the strategy to design new zinc-based lead-free HOIFs for potential applications in optoelectronic fields.

Piezo-Activated Atomic-Thin Molybdenum Disulfide/MXene Nanoenzyme for Integrated and Efficient Tumor Therapy via Ultrasound-Triggered Schottky Electric Field.

Monolayer molybdenum disulfide (MoS2 ) nanoenzymes exhibit a piezoelectric polarization, which generates reactive oxygen species to inactivate tumors under ultrasonic strain. However, its therapeutic efficiency is far away from satisfactory, due to stackable MoS2 , quenching of piezo-generated charges, and monotherapy. Herein, chitosan-exfoliated monolayer MoS2 (Ch-MS) is composited with atomic-thin MXene, Ti3 C2 (TC), to self-assemble a multimodal nanoplatform, Ti3 C2 -Chitosan-MoS2 (TC@Ch-MS), for tumor inactivation. TC@Ch-MS not only inherits piezoelectricity from monolayer MoS2 , but also maintains remarkable stability. Intrinsic metallic MXene combines with MoS2 to construct an interfacial Schottky heterojunction, facilitating the separation of electron-hole pairs and endowing TC@Ch-MS increase-sensitivity magnetic resonance imaging responding. Schottky interface also leads to peroxidase mimetics with excellent catalytic performance toward H2 O2 in the tumor microenvironment under mechanical vibration. TC@Ch-MS possesses the superior photothermal conversion efficiency than pristine TC under near-infrared ray illumination, attributed to its enhanced interlaminar conductivity. Meanwhile, TC@Ch-MS realizes optimized efficiency on tumor apoptosis with immunotherapy. Therefore, TC@Ch-MS achieves an integrated diagnosis and multimodal treatment nanoplatform, whereas the toxicity to normal tissue cells is negligible. This work may shed fresh light on optimizing the piezoelectric materials in biological applications, and also give prominence to the significance of intrinsic metallicity in MXene.

Cooling Field Dependence of Exchange Bias in Mn-Doped Metal- Organic Framework [NH2(CH3)2][FeIIIFeII(HCOO)6].

Herein, an intriguing exchange bias (EB) effect manifesting itself from positive to negative with an increase in the cooling field (HFC) is reported in the single crystal of Mn-doped metal-organic framework (MOF) [NH2(CH3)2][FeIIIFeII(HCOO)6] (1) by finely tuning the exchange interactions between the magnetic ions. Note that the doping ratio of Mn relative to the total metal ions is about 15%. Negative magnetization and EB below the compensation temperature were both observed in 1, and the EB field (HE) changes its sign from positive to negative when HFC is larger than ∼10 kOe. The abnormal HFC dependence of EB can be interpreted explicitly by a combination of negative magnetization and couplings among the ions of Fe3+, Fe2+, and Mn2+ with varying the HFC. This work demonstrates a tunable EB in MOFs, in favor of designing novel magnetic devices.

Effect of positive airway pressure on cardiac troponins in patients with sleep-disordered breathing: A meta-analysis.

BACKGROUND: Cardiac troponins are highly sensitive and specific biomarkers for cardiac injury. Previous studies evaluating the effect of positive airway pressure (PAP) on cardiac troponins in patients with sleep-disordered breathing (SDB) have yielded conflicting results. The meta-analysis was performed to examine the effect of PAP on cardiac troponins in SDB patients. METHODS: PubMed, Web of Science, and EMBASE before September 2021 on original English language studies were searched. The data on cardiac troponins in both baseline and post-PAP treatment were extracted from all studies. The data on the change of cardiac troponins in both PAP and control group were extracted from randomized controlled trials. Standardized mean difference (SMD) was used to synthesize quantitative results. RESULTS: A total of 11 studies were included. PAP treatment was not associated with a significant change in cardiac troponin T between the baseline and post-PAP treatment (SMD = -0.163, 95% confidence interval [CI] = -0.652 to 0.326, z = 0.65, p = .514). The pooled estimate of SMD of cardiac troponin I between the pre- and post-PAP treatment was 0.287, and the 95% CI was -0.586 to 1.160 (z = 0.64, p = .519). The pooled SMD of change of cardiac troponin T between the PAP group and control group was -0.473 (95% CI = -1.198 to 0.252, z = 1.28, p = .201). CONCLUSIONS: This meta-analysis revealed that PAP treatment was not associated with any change of cardiac troponin in SDB patients.

Niobium carbide (MXene) reduces UHMWPE particle-induced osteolysis.

Joint replacement surgery is one of the orthopedic surgeries with high successful rates; however, wear debris generated from prostheses can ultimately lead to periprosthetic osteolysis and failure of the implant. The implant-derived particulate debris such as ultrahigh molecular weight polyethylene (UHMWPE) can initiate the local immune response and recruit monocytic cells to phagocytose particles for generating reactive oxygen species (ROS). ROS induces osteoclastogenesis and macrophages to secrete cytokines which ultimately promote the development of osteolysis. In this work, we develop the few-layered Nb2C (FNC) as an antioxidant which possesses the feature of decreasing the production of cytokines and inhibiting osteoclastogenesis by its ROS adsorption. Moreover, local injection of FNC attenuates the UHMWPE-induced osteolysis in a mouse calvarial model. In sum, our results suggest that FNC can be used for treating osteolytic bone disease caused by excessive osteoclastogenesis.

Large dielectric switch effects induced by an order-disorder transformation in cyclopropylamine perchlorate crystals.

Solid-state crystals with two distinct dielectric states can be a physical practice in binary-based technologies. A large dielectric switch effect up to 103 caused by an order-disorder structural phase transition is found in cyclopropylamine perchlorate (CPA-ClO4) crystals at temperatures around 230 K (Tc) and 220 K (T'c). Large dielectric switch effects here can be compared to that of the famous ceramic oxide dielectrics. As far as we know, this is the highest dielectric switch effect in simple organic salt crystals and organic-metal compounds so far. If the phase transition temperature can be adjusted by molecular manipulation, one of the most promising candidates for technological applications may emerge in the future.

In Vivo Evaluation of the Effects of SMILE with Different Amounts of Stromal Ablation on Corneal Biomechanics by Optical Coherence Elastography.

This work aims to depth-resolved quantitatively analyze the effect of different stromal ablation amounts on the corneal biomechanical properties during small incision lenticule extraction (SMILE) using optical coherence elastography (OCE). A 4.5-MHz ultrasonic transducer was used to excite elastic waves in the corneal tissue. The OCE system combined with the antisymmetric Lamb wave model was employed to achieve a high-resolution, high-sensitivity, and depth-resolved quantitative detection of the corneal Young's modulus. Eighteen rabbits were randomly divided into three groups; each group had six rabbits. The first and second groups underwent -3D and -6D SMILE surgeries, and the third group was the control group, respectively. Young's modulus of the corneal cap and residual stromal bed (RSB) were both increased after SMILE, which shared the stress under intraocular pressure (IOP). Furthermore, the Young's modulus of both the corneal cap and RSB after 3D SMILE group were significantly lower than that in the -6D group, which indicated that the increases in the post-operative corneal Young's modulus were positively correlated with the amount of stromal ablation. The OCE system for quantitative spatial characterization of corneal biomechanical properties can provide useful information on the extent of safe ablation for SMILE procedures.

An Organic-Inorganic Hybrid Pyrrolidinium Ferroelectric Based on Solvent Selective Effect.

Organic-inorganic hybrid ferroelectrics (OIHFs) have fueled enormous interest benefiting from their less environmental pollution, performance-tailored functionality, low product costs as well as tunability of structures. However, the lack of material synthesis approaches and diverse targeted molecular design is a stumbling block for designing novel OIHFs rationally. Here, we report a unique organic-inorganic hybrid ferroelectric (3,3-difluoropyrrolidine)2CdCl4 1 and another novel nonferroelectric crystal (3,3-difluoropyrrolidine)2Cd2Cl6 2 by changing various crystallization solvents. Significantly, 1 presents a ferroelectric phase transition behavior at ∼367 K, and the distinct symmetry breaking, i.e., mmmFm, sets up a biaxial ferroelectric with four equivalent directions of polarization, which has a Pr ∼ 0.77 µC/cm2. Systematic studies prove that ferroelectricity can be ascribed to the synergistic effects of the distortion of the inorganic anion skeleton and the ordering of organic cations. This work reveals the potential of constructing novel ferroelectrics based on the solvent selective effect and pyrrolidinium as organic cations.

NIR-Activated Multimodal Photothermal/Chemodynamic/Magnetic Resonance Imaging Nanoplatform for Anticancer Therapy by Fe(II) Ions Doped MXenes (Fe-Ti3 C2 ).

2D MXene, Ti3 C2 (TC), has displayed enormous potential in applications in photothermal therapy (PTT), attributing to its biocompatibility and outstanding photothermal conversion capability. However, some tumor ablations are difficult to be realized completely by monotherapy due to the essential defects of monotherapy and intricate tumor microenvironment (TME). In this work, the appropriate doped Fe2+ ions are anchored into the layers of 2D ultrathin TC nanosheets (TC NSs) to synthesize a novel multifunctional nanoshell of Fe(II)-Ti3 C2 (FTC) through interlayer electrostatic adsorption. FTC possesses superior photothermal conversion efficiency (PTCE) than TC NSs, attributing to the enhanced conductivity promoted by interlaminar ferrous ion-channels. Moreover, Fenton reaction based on ferrous ions endows FTC the abilities of reactive oxide species (ROS) releasing and glutathione (GSH) suppression triggered by near-infrared (NIR) laser, featuring splendid biocompatibility and curative effect in hypoxic TME. Meanwhile, magnetic resonance imaging (MRI) responding in FTC reveals the potential as an integrated diagnosis and treatment nanoplatform. FTC could provide new insights into the development of multimoded synergistic nanoplatform for biological applications, especially breaking the shackles of MXenes merely used as a photo-thermal agent (PTA), adopting it to bioimaging sensor and drug loading.

Photo-degradation organic dyes by Sb-based organic-inorganic hybrid ferroelectrics.

The organic-inorganic hybrid halide compounds have emerged as one of the most promising photoelectric material for their superior optoelectronic properties and hold great prospects for renewable energy substitutes and environmental protection as photocatalysis. Here, we report the optical properties of the Sb-based organic-inorganic hybrid ferroelectric materials: pyridine-4-aminium tetrachloroantimonate ((C5H7N2)SbCl4, sample 1), piperidin-1-aminium tetrachloroantimonate ((C5H13N2)SbCl4, sample 2) and tris(trimethylammonium) nonachlorodiantimonate (((CH3)3NH)3Sb2Cl9, sample 3), which are a kind of exploited efficient photocatalysts. Samples 2 and 3 exhibit distinct photoelectric respond, which are mainly ascribed to their minor narrow band-gap compared with sample 1. For the ferroelectrics, the intrinsic of spontaneous polarization of sample 3 at room temperature is favourable for the separation of photogenerated electrons and holes within the photorespond process. Moreover, sample 3 shows the highest efficiency of photo-decomposed Rhodamine B (90.2% within 80 min) and Methyl Orange (MO) (97.4% within 50 min), thanks to the photo-excited electrons and holes promoting the formation of oxidative radical species during the photo-redox progress. These findings prove that the development of a novel Sb-based organic-inorganic hybrid halide compounds with good stability in the degradation of organic dyes paves a way to designing new photocatalyst.

Energy Harvesting and Pd(II) Sorption Based on Organic-Inorganic Hybrid Perovskites.

Organic-inorganic hybrid perovskites are currently an active research topic in the field of energy and next-generation electronics. Their selectable organic and inorganic components provide infinite possibilities for designing functional materials with multiple applications. Herein, we present a new one-dimensional BaNiO3-like organic-inorganic hybrid perovskite (thiazolidinium)CdBr3 (1), which displays a phase transition at 263 K and a switchable second harmonic generation (SHG) response. Intriguingly, 1 shows a pyroelectric coefficient pe of ∼0.6 µC·cm-2·K-1 and a piezoelectric output voltage of ∼2.0 V for our fabricated piezoelectric generation device, indicating its great potential for pyroelectric sensors, self-powered low-voltage electronic devices, and energy harvesters. Moreover, the presence of a specific thioether donor enables 1 to appropriately adsorb Pd(II) ions, which can be monitored by the corresponding change in phase transition behavior, SHG signal, and pyroelectric response. This work provides a new insight to develop new multifunctional materials, demonstrating the feasibility of utilizing organic-inorganic hybrid perovskites to realize future self-powered low-voltage devices and energy harvesters.

High-Temperature Molecular Ferroelectric Tris(2-hydroxyethyl) Ammonium Bromide with Dielectric Relaxation.

We obtained one new molecular ferroelectric material tris(2-hydroxyethyl) ammonium bromide (TAB) that crystallizes in aqueous solution at room temperature with a space group of R3m which belongs to ten polar space groups. There is a paraelectric-to-ferroelectric phase transition at 424 K (from hexagonal R3̅m to hexagonal R3m phase). Such a high transition temperature is close to that of diisopropylamine bromide (426 K) and higher than that of many other molecular ferroelectrics, such as triethylmethylammonium tetrabromoferrate(III) (360 K); some of the organic-inorganic perovskite ferroelectrics, such as (cyclohexylammonium)2PbBr4 (363 K); and some inorganic ferroelectrics, including BaTiO3 (393 K). The saturated polarization and the coercive field of TAB measured from the ferroelectric hysteresis loop are about 0.54 µC·cm-2 and 0.62 kV/cm, respectively. Given its superior performance, including high phase transition temperature, room-temperature ferroelectricity, small coercive electric field, and adjustable ladder-shaped dielectric constant, TAB will have many potential applications.

Ferroelectricity of the Orthorhombic and Tetragonal MAPbBr3 Single Crystal.

Hybrid organic-inorganic halide perovskites (HOIPs) MAPbBr3 and their ramifications have emerged because of the photovoltaic, optical, and other fascinating performances of HOIPs in recent years. However, many intrinsic properties, such as crystal structure and ferroelectricity, are still controversial. In this work, the ferroelectricity of the orthorhombic and tetragonal MAPbBr3 single crystal was confirmed through the dielectric behavior versus bias electric field ε( E), the temperature-dependent pyroelectric current with positive/negative poling, and the positive-up-negative-down (PUND) measurements. The electric field dependence of dielectric constant curves shows a butterfly type shape in the orthorhombic and tetragonal phase. The pyroelectric current shows two maxima at 155 and 245 K, corresponding to ferroelectric-ferroelectric and ferroelectric-paraelectric phase transitions, respectively. In particular, the direction of the pyroelectric current can be reversed by a positive or negative poling electric field, which is the assertive evidence of ferroelectricity. The PUND measurements act as the most convincing proof of the ferroelectricity of the MAPbBr3 single crystal. This work reports new evidence of the ferroelectric properties of the MAPbBr3 single crystal, which provides the intrinsic property when considering their high power conversion efficiencies.

Molecular ferroelectric pyridin-2-ylmethanaminium perchlorate with phase transition induced by disorder of perchlorate.

Molecular ferroelectrics are a kind of functional materials that have large application prospects. Comparing with the traditional inorganic ferroelectrics, they have some advantages, such as easy design, environment-friendliness, nontoxicity, and flexibility. In this study, a new molecular ferroelectric pyridin-2-ylmethanaminium perchlorate was discovered, which undergoes a ferroelectric phase transition at around 264.8 K. The spontaneous polarization reaches 0.22 µC cm-2, and the coercive fields are as small as 1.1 kV cm-1 at 202 K. The single-crystal X-ray diffraction analysis reveals that the space group transforms from a polar space group of P21 at 173 K to a centrosymmetric space group of P21/c at 293 K. By analyzing the crystal structure changes below and above the phase transition temperature, it can be concluded that the phase transition is induced by the disorder of perchlorate. Its ferroelectricity was confirmed by the measurements of differential scanning calorimetry, dielectric and hysteresis loop.

Single molecule magnetic behaviour in lanthanide naphthalenesulfonate complexes.

The use of 2-naphthalenesulfonate (NAS) ligand in lanthanide chemistry afforded a family of isostructural mononuclear lanthanide complexes with the formula [Ln(NAS)2(H2O)6](NAS)·3H2O [Ln = Tb (1), Dy (2), Er (3), Yb (4)]. Crystallographic studies determined a square antiprismatic geometry (D4d) for the Ln centre and crystallization in an unprecedented chiral space group. The latter was further confirmed by the observation of Cotton effects in single crystal circular dichroism (CD) spectra. Static and dynamic magnetic measurements identified weak intermolecular dipolar interactions in 2, and such effects can be waived by dilution, which was noted by the detection of zero-field single molecule magnet (SMM) behaviour and hysteresis loop in a magnetically diluted sample (5). Compounds 2-4 exhibit SMM behaviours with energy barriers of 53, 32, and 45 K, respectively. To the best of our knowledge, these complexes are the first examples of pure 4f sulfonate-based SMMs.