Zwitterion Intercalated Manganese Dioxide Nanosheets as High-Performance Cathode Materials for Aqueous Zinc Ion Batteries.

In this study, a novel approach is introduced to address the challenges associated with structural instability and sluggish reaction kinetics of δ-MnO2 in aqueous zinc ion batteries. By leveraging zwitterionic betaine (Bet) for intercalation, a departure from traditional cation intercalation methods, Bet-intercalated MnO2 (MnO2-Bet) is synthesized. The positively charged quaternary ammonium groups in Bet form strong electrostatic interactions with the negatively charged oxygen atoms in the δ-MnO2 layers, enhancing structural stability and preventing layer collapse. Concurrently, the negatively charged carboxylate groups in Bet facilitate the rapid diffusion of H+/Zn2+ ions through their interactions, thus improving reaction kinetics. The resulting MnO2-Bet cathode demonstrates high specific capacity, excellent rate capability, fast reaction kinetics, and extended cycle life. This dual-function intercalation strategy significantly optimizes the electrochemical performance of δ-MnO2, establishing it as a promising cathode material for advanced aqueous zinc ion batteries.

Hydrophobic Two-Dimensional Layered Superstructure of a Polyoxometalate Cluster as the Cathode Material for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries hold promise for sustainable energy storage, yet challenges in finding high-performance cathode materials persist. Polyoxovanadates (POVs) are emerging as potential candidates due to their structural diversity and robust redox activity. Despite their potential, issues like dissolution in electrolytes, structural degradation, and byproduct accumulation persist. This work introduces a POV-based hydrophobic two-dimensional (2D) layered superstructure that addresses these challenges. The hydrophobic nature minimizes POV dissolution, enhancing structural stability and inhibiting phase transitions during cycling. The 2D arrangement ensures a larger surface area and improved electronic conductivity, resulting in faster kinetics and higher specific capacity. The superstructure demonstrates improved cycle life and an increased operating voltage, marking a significant advancement in POV-based cathode materials for aqueous zinc-ion batteries.

MnO2 superstructure cathode with boosted zinc ion intercalation for aqueous zinc ion batteries.

The simultaneous intercalation of protons and Zn2+ ions in aqueous electrolytes presents a significant obstacle to the widespread adoption of aqueous zinc ion batteries (AZIBs) for large-scale use, a challenge that has yet to be overcome. To address this, we have developed a MnO2/tetramethylammonium (TMA) superstructure with an enlarged interlayer spacing, designed specifically to control H+/Zn2+ co-intercalation in AZIBs. Within this superstructure, the pre-intercalated TMA+ ions work as spacers to stabilize the layered structure of MnO2 cathodes and expand the interlayer spacing substantially by 28 % to 0.92 nm. Evidence from in operando pH measurements, in operando synchrotron X-ray diffraction, and X-ray absorption spectroscopy shows that the enlarged interlayer spacing facilitates the diffusion and intercalation of Zn2+ ions (which have a large ionic radius) into the MnO2 cathodes. This spacing also helps suppress the competing H+ intercalation and the formation of detrimental Zn4(OH)6SO4·5H2O, thereby enhancing the structural stability of MnO2. As a result, enhanced Zn2+ storage properties, including excellent capacity and long cycle stability, are achieved.

Chiral Transfer and Evolution in Cysteine Induced Cobalt Superstructures.

Chiral organic additives have unveiled the extraordinary capacity to form chiral inorganic superstructures, however, complex hierarchical structures have hindered the understanding of chiral transfer and growth mechanisms. This study introduces a simple hydrothermal synthesis method for constructing chiral cobalt superstructures with cysteine, demonstrating specific recognition of chiral molecules and outstanding electrocatalytic activity. The mild preparation conditions allow in situ tracking of chirality evolution in the chiral cobalt superstructure, offering unprecedented insights into the chiral transfer and amplification mechanism. The resulting superstructures exhibit a universal formation process applicable to other metal oxides, extending the understanding of chiral superstructure evolution. This work contributes not only to the fundamental understanding of chirality in self-assembled structures but also provides a versatile method for designing chiral inorganic nanomaterials with remarkable molecular recognition and electrocatalytic capabilities.

Probability-Distribution-Configurable True Random Number Generators Based on Spin-Orbit Torque Magnetic Tunnel Junctions.

The incorporation of randomness into stochastic computing can provide ample opportunities for applications such as simulated annealing, non-polynomial hard problem solving, and Bayesian neuron networks. In these cases, a considerable number of random numbers with an accurate and configurable probability distribution function (PDF) are indispensable. Preferably, these random numbers are provided at the hardware level to improve speed, efficiency, and parallelism. In this paper, how spin-orbit torque magnetic tunnel junctions (SOT-MTJs) with high barriers are suitable candidates for the desired true random number generators is demonstrated. Not only do these SOT-MTJs perform excellently in speed and endurance, but their randomness can also be conveniently and precisely controlled by a writing voltage, which makes them a well-performed Bernoulli bit. By utilizing these SOT-MTJ-based Bernoulli bits, any PDF, including Gaussian, uniform, exponential, Chi-square, and even arbitrarily defined distributions can be realized. These PDF-configurable true random number generators can then promise to advance the development of stochastic computing and broaden the applications of the SOT-MTJs.

Synergistic Cation-π Interactions and PEDOT-Based Protective Double-Layer for High Performance Zinc Anode.

Ensuring effective and controlled zinc ion transportation is crucial for functionality of the solid electrolyte interphase (SEI) and overall performance in zinc-based battery systems. Herein the first-ever demonstration of incorporate cation-π interactions are provided in the SEI to effectively facilitate uniform zinc ion flux. The artificial SEI design involves the immobilization of 4-amino-p-terphenyl (TPA), a strong amphiphilic cation-π interaction donor, as a monolayer onto a conductive poly(3,4-ethylenedioxythiophene) (PEDOT) matrix, which enable the establishment of a robust network of cation-π interactions. Through a carefully-designed interfacial polymerization process, a high-quality, large-area, robust is achieved, thin polymeric TPA/PEDOT (TP) film for the use of artificial SEI. Consequently, this interphase exhibits exceptional cycling stability with low overpotential and enables high reversibility of Zn plating/stripping. Symmetrical cells with TP/Zn electrodes can be cycled for more than 3200 hours at 1 mA cm-2 and 1 mAh cm-2 . And the asymmetric cells can cycle 3000 cycles stably with a high Coulomb efficiency of 99.78%. Also, under the extreme conditions of lean electrolyte and low N/P ratio, the battery with TP protective layer can still achieve ultra-stable cycle.

Electrochemical Failure Mechanism of δ-MnO2 in Zinc Ion Batteries Induced by Irreversible Layered to Spinel Phase Transition.

Phase transitions of Mn-based cathode materials associated with the charge and discharge process play a crucial role on the rate capability and cycle life of zinc ion batteries. Herein, a microscopic electrochemical failure mechanism of Zn-MnO2 batteries during the phase transitions from δ-MnO2 to λ-ZnMn2O4 is presented via systematic first-principle investigation. The initial insertion of Zn2+ intensifies the rearrangement of Mn. This is completed by the electrostatic repulsion and co-migration between guest and host ions, leading to the formation of λ-ZnMn2O4. The Mn relocation barrier for the λ-ZnMn2O4 formation path with 1.09 eV is significantly lower than the δ-MnO2 re-formation path with 2.14 eV, indicating the irreversibility of the layered-to-spinel transition. Together with the phase transition, the rearrangement of Mn elevates the Zn2+ migration barrier from 0.31 to 2.28 eV, resulting in poor rate performance. With the increase of charge-discharge cycles, irreversible and inactive λ-ZnMn2O4 products accumulate on the electrode, causing continuous capacity decay of the Zn-MnO2 battery.

Chirality-enhanced 2D conductive polymer for flexible electronics and chiral sensing applications.

Chiral two-dimensional (2D) conductive polymers, encompassing chiral, 2D, flexible, and conductive properties, constitute a novel class of material that remains largely unexplored. The infusion of chirality into 2D conductive polymers taps into the unique characteristics associated with chirality, presenting opportunities to enhance or tailor the electronic, optical, and structural properties of materials for specific technological applications. In this study, we synthesized a chiral 2D PEDOT:PMo11V nanofilm through interfacial polymerization, effectively integrating a chiral monolayer, conductive polymer, and inorganic cluster. The inclusion of inorganic cluster serves to enhance the conductivity of the resulting chiral nanofilm. Furthermore, we demonstrated the chiral nanofilm as a capable electrochemical sensor for detecting drug enantiomers. The inherent flexibility of the chiral nanofilm also lays the groundwork for the development of chiral flexible/wearable devices.

In Situ Grown Coordination-Supramolecular Layer Holding 3D Charged Channels for Highly Reversible Zn Anodes.

Dynamic reversible noncovalent interactions make supramolecular framework (SF) structures flexible and designable. A three-dimensional (3D) growth of such frameworks is beneficial to improve the structure stability while maintaining unique properties. Here, through the ionic interaction of the polyoxometalate cluster, coordination of zinc ions with cationic terpyridine, and hydrogen bonding of grafted carboxyl groups, the construction of a 3D SF at a well-crystallized state is realized. The framework can grow in situ on the Zn surface, further extending laterally into a full covering without defects. Relying on the dissolution and the postcoordination effects, the 3D SF layer is used as an artificial solid electrolyte interphase to improve the Zn-anode performance. The uniformly distributed clusters within nanosized pores create a negatively charged nanochannel, accelerating zinc ion transfer and homogenizing zinc deposition. The 3D SF/Zn symmetric cells demonstrate high stability for over 3000 h at a current density of 5 mA cm-2.

Expression and correlation analysis of silent information regulator 1 (SIRT1), sterol regulatory element-binding protein-1 (SREBP1), and pyroptosis factor in gestational diabetes mellitus.

BACKGROUND AND AIM: Globally, the prevalence of gestational diabetes mellitus (GDM) is rising each year, yet its pathophysiology is still unclear. To shed new light on the pathogenesis of gestational diabetes mellitus and perhaps uncover new therapeutic targets, this study looked at the expression levels and correlations of SIRT1, SREBP1, and pyroptosis factors like NLRP3, Caspase-1, IL-1, and IL-18 in patients with GDM. METHODS: This study involved a comparative analysis between two groups. The GDM group consisted of 50 GDM patients and the control group included 50 pregnant women with normal pregnancies. Detailed case data were collected for all participants. We utilized real-time quantitative PCR and Western Blot techniques to assess the expression levels of SIRT1 and SREBP1 in placental tissues from both groups. Additionally, we employed an enzyme-linked immunosorbent assay to measure the serum levels of SIRT1, SREBP1, and pyroptosis factors, namely NLRP3, Caspase-1, IL-1ß, and IL-18, in the patients of both groups. Subsequently, we analyzed the correlations between these factors and clinical. RESULTS: The results showed that there were significantly lower expression levels of SIRT1 in both GDM group placental tissue and serum compared to the control group (p < 0.01). In contrast, the expression of SREBP1 was significantly higher in the GDM group than in the control group (p < 0.05). Additionally, the serum levels of NLRP3, Caspase-1, IL-1ß, and IL-18 were significantly elevated in the GDM group compared to the control group (p < 0.01). The expression of SIRT1 exhibited negative correlations with the expression of FPG, OGTT-1h, FINS, HOMA-IR, SREBP1, IL-1ß, and IL-18. However, there was no significant correlation between SIRT1 expression and OGTT-2h, NLRP3, or Caspase-1. On the other hand, the expression of SREBP1 was positively correlated with the expression of IL-1ß, Caspase-1, and IL-18, but has no apparent correlation with NLRP3. CONCLUSIONS: Low SIRT1 levels and high SREBP1 levels in placental tissue and serum, coupled with elevated levels of pyroptosis factors NLRP3, Caspase-1, IL-1ß, and IL-18 in serum, may be linked to the development of gestational diabetes mellitus. Furthermore, these three factors appear to correlate with each other in the pathogenesis of GDM, offering potential directions for future research and therapeutic strategies.

Relationship between serum NLRP3 along with its effector molecules and pregnancy outcomes in women with hyperglycemia.

OBJECTIVE: The study aims to investigate the levels of serum NLRP3 along with its effector molecules (Caspase-1, IL-1ß, and IL-18) in the mid-pregnancy in pregnant women with hyperglycemia, and explore the relationship between NLRP3, along with its effector molecules (Caspase-1, IL-1ß, and IL-18) and insulin resistance, as well as pregnancy outcomes. METHODS: The levels of serum NLRP3 along with its effector molecules (Caspase-1, IL-1ß, and IL-18) in three groups of pregnant women with gestational diabetes mellitus (GDM), pregestational diabetes mellitus (PGDM) and normal glucose tolerance (NGT) were measured in mid-pregnancy, and their relationship with insulin resistance and pregnancy outcomes was analyzed. The ROC curve was also used to evaluate the predictive value of serum NLRP3 inflammasome and its effector molecules for pregnancy outcomes. RESULTS: There were no statistical differences in the general clinical data of the three groups, and the concentrations of serum NLRP3 along with its effector molecules were higher in the GDM and PGDM groups than in the NGT group, and NLRP3 along with its effector molecules were positively correlated with fasting blood glucose, fasting insulin, and insulin resistance index in both groups (r > 0, p < .05). The incidence of preterm delivery, hypertensive disorders of pregnancy, premature rupture of membranes, neonatal hypoglycemia and macrosomia was significantly higher in both groups than in the NGT group (p < .05). The value of the combined serum NLRP3 and its effector molecules in mid-pregnancy to predict adverse pregnancy outcomes was highest, and the AUCs for the combined prediction of late hypertensive disorders of pregnancy, premature rupture of membranes, preterm delivery, neonatal hypoglycemia and macrosomia were 0.84 (95% CI 0.79-0.88, p < .001), 0.81 (95% CI 0.75-0.85, p < .001), 0.76 (95% CI 0.70-0.81, p < .001), 0.76 (95% CI 0.70-0.81, p < .001) and 0.72 (95% CI 0.63-0.81, p < .001), respectively. CONCLUSIONS: Increased serum NLRP3 along with its effector molecules in pregnant women with hyperglycemia are associated with the levels of insulin resistance and the subsequent development of adverse pregnancy outcomes.

Trade-Off between Rough and Smooth Electrode Surfaces toward Stable Zn Stripping/Plating in Aqueous Electrolytes.

The effects of surface roughness on the performance of the Zn metal anode in aqueous electrolytes are investigated by experiments and computational simulations. Smooth surfaces can homogenize the nucleation and growth of Zn, which helps to form a flat Zn anode under high current density. In spite of these advantages, the whole surface of the smooth electrode serves as the reactive contact area for parasitic reactions, generating severe hydrogen evolution, corrosion, and byproduct formation, which seriously hinder the long-term cycle stability of the Zn anode. To trade off this double-sided effect, we identify a medium degree of surface roughness that could stabilize the Zn anode for 1000 h cycling at 1.0 mAh cm-2. The electrode also enabled stable cycling for 800 h at a high current density of 5.0 mAh cm-2. This naked Zn metal anode with optimized surface roughness holds great promise for direct use in aqueous zinc ion batteries.

Ionic Layer Epitaxy Growth of Organic/Inorganic Composite Protective Layers for Large-Area Li and Zn Metal Anodes.

Li and Zn metal batteries using organic and aqueous electrolytes, respectively, are desirable next-generation energy storage systems to replace the traditional Li-ion batteries. However, their cycle life and safety performance are severely constrained by a series of issues that are attributed to dendrite growth. To solve these issues, a nanothick ZnO-oleic acid (ZnO-OA) composite protective layer is developed by a facile ionic layer epitaxy method. The ZnO-OA layer provides strong lithophilic and zincophilic properties, which can effectively induce uniform ion deposition. As a result, the ZnO-OA protected Li and Zn metal anodes can cycle stably for over 600 and 1000 h under a large current density of 10 mA cm-2. Employing the ZnO-OA protected anodes, the Li||LiFePO4 cell can maintain a capacity retention of 99.5% after 600 cycles at a 1 C rate and the Zn||MnO2 cell can operate stably for 1000 cycles at 1 A g-1 current density.

Development of Ferroelectric P(VDF-TrFE) Microparticles for Ultrasound-Driven Cancer Cell Killing.

Current breast cancer treatments involve aggressive and invasive methods, leaving room for new therapeutic approaches to emerge. In this work, we explore the possibility of using piezoelectric [P(VDF-TrFE)] microparticles (MPs) as a source of inducing irreversible electroporation (IRE) of 4T1 breast cancer cells. We detail the MP formation mechanism and size control and subsequent characterizations of the as-synthesized MPs which confirms the presence of piezoelectric ß-phase. Production of the necessary piezoelectric output of the MPs is achieved by ultrasound agitation. We confirm the primary factor of the IRE effect on 4T1 breast cancer cells to be the local electric field produced from the MPs by using confocal imaging and an alamarBlue assay. The results show a 52.6% reduction in cell viability, indicating that the MP treatment can contribute to a reduction of live cancer cells. The proposed method of ultrasound-stimulated P(VDF-TrFE) MPs may offer a more benign cancer treatment approach.

Room temperature field-free switching of perpendicular magnetization through spin-orbit torque originating from low-symmetry type II Weyl semimetal.

Spin-orbit torque (SOT) is a promising strategy to deterministically switch the perpendicular magnetization, but usually requires an in-plane magnetic field for breaking the mirror symmetry, which is not suitable for most advanced industrial applications. Van der Waals (vdW) materials with low crystalline symmetry and topological band structures, e.g., Weyl semimetals (WSMs), potentially serve as an outstanding system that may simultaneously realize field-free switching and high energy efficiency. Yet, the demonstration of these superiorities at room temperature has not been realized. Here, we achieve a field-free switching of perpendicular magnetization by using a layered type II WSM, TaIrTe4, in a TaIrTe4/Ti/CoFeB system at room temperature with the critical switching current density ~2.4 × 106 A cm-2. The field-free switching is ascribed to the out-of-plane SOT allowed by the low crystal symmetry. Our work suggests that using low-symmetry materials to generate SOT is a promising route for the manipulation of perpendicular magnetization at room temperature.

Pure Amorphous and Ultrathin Phosphate Layer with Superior Ionic Conduction for Zinc Anode Protection.

Fast and uniform ion transport within the solid electrolyte interphase (SEI) is considered a crucial factor for ensuring the long-term stability of metal electrodes. In this study, we present the fabrication of ultrathin artificial interphases consisting of a zinc phosphate nanofilm with pure amorphous characteristics and a surfactant overlayer. The thickness of the interphases can be precisely controlled within the range of a few tens of nanometers. We explore the impact of artificial SEI structure, including thickness and crystallinity, on its protective capabilities. The pure amorphous phosphate layer with optimized nanoscale thickness is found to provide an abundance of short and isotropic ion migration pathways and a low diffusion energy barrier. These features facilitate rapid and homogeneous Zn2+ transportation, resulting in compact and planar zinc deposition. Meanwhile, the hydrophobic alkyl moieties of the overlayer prevent disassociation of water at the interface. As a result, this nanofilm endures ultralong cycling stability with a low overpotential and enables high Zn plating/stripping reversibility. The Zn||MnO2 full cell shows a stable cycle life for 700 cycles under practical conditions of lean electrolyte, high areal capacity cathode, and limited Zn excess. These findings provide insights into the design and optimization of SEI layers for protection of metal anodes.

Defect-Engineered VS2 Electrocatalysts for Lithium-Sulfur Batteries.

Defective two-dimensional transition metal dichalcogenides can be effective electrocatalysts for Li-S batteries, but the relationship between defect types and battery performance is unclear. In this work, we designed S vacancy-type SV-VS2 and V self-intercalated-type VI-VS2 and measured their catalytic activities in Li-S batteries. Compared with self-intercalating V atoms, S vacancies accelerated Li+ diffusion and SV-VS2 as a Li+ "reservoir" promoted the sulfur conversion kinetics significantly. In addition, the presence of sulfur vacancies promoted the lithiation behavior of SV-VS2 during discharge, leading to an enhancement of the catalytic ability of SV-VS2. However, this lithiation phenomenon weakened the catalytic activity of VI-VS2. Overall, SV-VS2 had better adsorption and catalytic activity. Li-S batteries with SV-VS2-coated separators delivered high rate performance and excellent cycling stability, with a capacity decay rate of 0.043% over 880 cycles at 1.0 C. This work provides an effective strategy for designing efficient Li-S battery electrocatalysts using defect engineering.

Oxygen Radical Anion Substituted Iron Phthalocyanine as an Effective Redox Mediator for Li-O2 Batteries.

Transition metal phthalocyanines are potential soluble redox mediators for Li-O2 batteries. In this work, effective strategies to control the redox potentials and activities of iron phthalocyanine (FePc) based redox mediators are designed by the introduction of electron-withdrawing or electron-donating groups. Substituted electron-donating groups can shift the oxidation potential of FePc to a higher energy level, consequently reducing the charging voltage of Li-O2 batteries. Especially, oxygen radical anion (-O-) modified FePc (FePc-O-) shows the most significant improvement to the oxygen reduction and evolution reactions of Li-O2 batteries. Electronic analysis indicates that -O- substitution can break the symmetry of electronic structures of FePc which further tunes the reduction of O2 and the oxidation of Li2O2. Detailed reaction mechanisms of (FePc-O-)-mediated Li-O2 batteries are proposed based on first-principles molecular dynamics simulations and thermodynamic free energy calculations.

Strain-Correlated Piezoelectricity in Quasi-Two-Dimensional Zinc Oxide Nanosheets.

Two-dimensional (2D) piezoelectric materials have recently drawn intense interest in studying the nanoscale electromechanical coupling phenomenon and device development. A critical knowledge gap exists to correlate the nanoscale piezoelectric property with the static strains often found in 2D materials. Here, we present a study of the out-of-plane piezoelectric property of nanometer-thick 2D ZnO-nanosheets (NS) in correlation to in-plane strains, using in situ via strain-correlated piezoresponse force microscopy (PFM). We show that the strain configuration (either tensile or compressive) can dramatically influence the measured piezoelectric coefficient (d33) of 2D ZnO-NS. A comparison of the out-of-plane piezoresponse is made for in-plane tensile and compressive strains approaching 0.50%, where the measured d33 varies between 2.1 and 20.3 pm V-1 resulting in an order-of-magnitude change in the piezoelectric property. These results highlight the important role of in-plane strain in the quantification and application of 2D piezoelectric materials.

A Multifunctional Organic Electrolyte Additive for Aqueous Zinc Ion Batteries Based on Polyaniline Cathode.

The practical applications of aqueous zinc ion batteries are hindered by the formation of dendrites on the anode, the narrow electrochemical window of electrolyte, and the instability of the cathode. To address all these challenges simultaneously, a multi-functional electrolyte additive of 1-phenylethylamine hydrochloride (PEA) is developed for aqueous zinc ion batteries based on polyaniline (PANI) cathode. Experiments and theoretical calculations confirm that the PEA additive can regulate the solvation sheath of Zn2+ and form a protective layer on the surface of the Zn metal anode. This broadens the electrochemical stability window of the aqueous electrolyte and enables uniform deposition of Zn. On the cathode side, the Cl- anions from PEA enter the PANI chain during charge and release fewer water molecules surrounding the oxidized PANI, thus suppressing harmful side reactions. When used in a Zn||PANI battery, this cathode/anode compatible electrolyte exhibits excellent rate performance and long cycle life, making it highly attractive for practical applications.