Optimal inference of molecular interaction dynamics in FRET microscopy.

Intensity-based time-lapse fluorescence resonance energy transfer (FRET) microscopy has been a major tool for investigating cellular processes, converting otherwise unobservable molecular interactions into fluorescence time series. However, inferring the molecular interaction dynamics from the observables remains a challenging inverse problem, particularly when measurement noise and photobleaching are nonnegligible-a common situation in single-cell analysis. The conventional approach is to process the time-series data algebraically, but such methods inevitably accumulate the measurement noise and reduce the signal-to-noise ratio (SNR), limiting the scope of FRET microscopy. Here, we introduce an alternative probabilistic approach, B-FRET, generally applicable to standard 3-cube FRET-imaging data. Based on Bayesian filtering theory, B-FRET implements a statistically optimal way to infer molecular interactions and thus drastically improves the SNR. We validate B-FRET using simulated data and then apply it to real data, including the notoriously noisy in vivo FRET time series from individual bacterial cells to reveal signaling dynamics otherwise hidden in the noise.

Energy-saving hydrogen production by seawater electrolysis coupling tip-enhanced electric field promoted electrocatalytic sulfion oxidation.

Hydrogen production by seawater electrolysis is significantly hindered by high energy costs and undesirable detrimental chlorine chemistry in seawater. In this work, energy-saving hydrogen production is reported by chlorine-free seawater splitting coupling tip-enhanced electric field promoted electrocatalytic sulfion oxidation reaction. We present a bifunctional needle-like Co3S4 catalyst grown on nickel foam with a unique tip structure that enhances the kinetic rate by improving the current density in the tip region. The assembled hybrid seawater electrolyzer combines thermodynamically favorable sulfion oxidation and cathodic seawater reduction can enable sustainable hydrogen production at a current density of 100 mA cm-2 for up to 504 h. The hybrid seawater electrolyzer has the potential for scale-up industrial implementation of hydrogen production by seawater electrolysis, which is promising to achieve high economic efficiency and environmental remediation.

Conversion-type anode chemistry with interfacial compatibility toward Ah-level near-neutral high-voltage zinc ion batteries.

High-voltage aqueous zinc ion batteries (AZIBs) with a high-safety near-neutral electrolyte is of great significance for practical sustainable application; however, they suffer from anode and electrode/electrolyte interfacial incompatibility. Herein, a conversion-type anode chemistry with a low anodic potential, which is guided by the Gibbs free energy change of conversion reaction, was designed for high-voltage near-neutral AZIBs. A reversible conversion reaction between ZnC2O4·2H2O particles and three-dimensional Zn metal networks well-matched in CH3COOLi-based electrolyte was revealed. This mechanism can be universally validated in the battery systems with sodium or iodine ions. More importantly, a cathodic crowded micellar electrolyte with a water confinement effect was proposed in which lies the core for the stability and reversibility of the cathode under an operating platform voltage beyond 2.0 V, obtaining a capacity retention of 95% after 100 cycles. Remarkably, the scientific and technological challenges from the coin cell to Ah-scale battery, sluggish kinetics of the solid-solid electrode reaction, capacity excitation under high loading of active material, and preparation complexities associated with large-area quasi-solid electrolytes, were explored, successfully achieving an 88% capacity retention under high loading of more than 20 mg cm-2 and particularly a practical 1.1 Ah-level pouch cell. This work provides a path for designing low-cost, eco-friendly and high-voltage aqueous batteries.

Validating Operating Stability and Biocompatibility Toward Safer Zinc-Based Batteries.

Wearable and implantable electronics are standing at the frontiers of science and technology, driven by the increasing demands from modernized lifestyles. Zinc-based batteries (ZBs) are regarded as ideal energy suppliers for these biocompatible electronics, but the corresponding biocompatibility validation is still in the initial stage. Meanwhile, complicated working conditions and some extreme electrolyte environments raise strict challenges, leaving less choices for safe ZBs. Toward higher operating stability and biocompatibility, this work proposes a hydrogel electrolyte featuring the moisture maintaining ability and a robust interface, which could further provide a milder environment for Zn-MnO2 batteries and Zn-air batteries. The cytotoxicity and tissue injury of batteries are evaluated with human cell lines and battery implantations on the animal models, which demonstrate the high biocompatibility of ZBs, while preliminary wearable devices implementation further verifies their operating stability. This work may provide a pathway for developing and validating biocompatible ZBs, contributing to their future practical employment in relevant fields.

Unraveling Paradoxical Effects of Large Current Density on Zn Deposition.

Aqueous zinc-based batteries (ZBs) have been widely investigated owing to their intrinsic safety, low cost, and simple assembly. However, the actual behavior of Zn deposition under large current density is still a severe issue associated with obscure mechanism interpretation of ZBs under high loading. Here, differing from the conventional understanding that short circuit is induced by dendrite penetrating under large current density (10-100 mA cm-2), the separator permeation effect is unraveled to illustrate the paradox between smooth deposition and short lifespan. Generally, a dense plating morphology is achieved under large current density because of intensive nuclei and boosted plane growth. Nevertheless, in the scenes applying separators, the multiplied local current density derived from narrow separator channels leads to rapid Zn2+ exhaustion, converting the Zn deposition mode from nucleation control to concentration control, which eventually results in separator permeation and short circuit. This effect is validated in other aqueous metal anodes (Cu, Sn, Fe) and receives similar results. Based on the understanding, a micro-pore (150 µm) sponge foam is proposed as separators for large-current anodes to provide broader Zn2+ path and mitigate the separator permeation effect. This work provides unique perspectives on coordinating fast-charging ability and anode stability of ZBs.

Constructing Ionic Self-Concentrated Electrolyte via Introducing Montmorillonite Toward High-Performance Aqueous Zn-MnO2 Batteries.

Aqueous zinc metal batteries are regarded as one of the most promising alternatives to lithium-ion batteries for large-scale energy storage due to the abundant zinc resources, high safety, and low cost. Herein, an ionic self-concentrated electrolyte (ISCE) is proposed to enable uniform Zn deposition and reversible reaction of MnO2 cathode. Benefitting from the compatibility of ISCE with electrodes and its adsorption on the electrode surface for guidance, the Zn/Zn symmetrical batteries exhibit the long-life cycle stability with more than 5000 and 1500 h at 0.2 and 5 mA cm-2 , respectively. The Zn/MnO2 battery also exhibits a high capacity of 351 mA h g-1 at 0.1 A g-1 and can enable a stability over 2000 cycles at 1 A g-1 . This work provides a new insight into electrolyte design for stable aqueous Zn-MnO2 battery.

Reconstructing interfacial manganese deposition for durable aqueous zinc-manganese batteries.

Low-cost, high-safety, and broad-prospect aqueous zinc-manganese batteries (ZMBs) are limited by complex interfacial reactions. The solid-liquid interfacial state of the cathode dominates the Mn dissolution/deposition process of aqueous ZMBs, especially the important influence on the mass and charge transfer behavior of Zn2+ and Mn2+. We proposed a quasi-eutectic electrolyte (QEE) that would stabilize the reversible behavior of interfacial deposition and favorable interfacial reaction kinetic of manganese-based cathodes in a long cycle process by optimizing mass and charge transfer. We emphasize that the initial interfacial reaction energy barrier is not the main factor affecting cycling performance, and the good reaction kinetics induced by interfacial deposition during the cycling process is more conducive to the stable cycling of the battery, which has been confirmed by theoretical analysis, quartz crystal microbalance with dissipation monitoring, depth etching X-ray photon-electron spectroscopy, etc. As a result, the QEE electrolyte maintained a stable specific capacity of 250 mAh g-1 at 0.5 A g-1 after 350 cycles in zinc-manganese batteries. The energy density retention rate of the ZMB with QEE increased by 174% compared to that of conventional aqueous electrolyte. Furthermore, the multi-stacked soft-pack battery with a cathodic mass load of 54.4 mg maintained a stable specific capacity of 200 mAh g-1 for 100 cycles, demonstrating its commercial potential. This work proves the feasibility of adapting lean-water QEE to the stable aqueous ZMBs.

Robust, Scalable, and Cost-Effective Surface Carbonized Pulp Foam for Highly Efficient Solar Steam Generation.

Recently, a solar-driven evaporator has been applied in seawater desalination, but the low stability, high cost, and complex fabrication limit its further application. Herein, we report a novel, low-cost, scalable, and easily fabricated pulp-natural rubber (PNR) foam with a unique porous structure, which was directly used as a solar-driven evaporator after facile surface carbonization. This surface carbonized PNR (CPNR) foam without interface adhesion or modification was composed of a top photothermal layer with light absorption ability and a bottom hydrophilic foam layer with a porous and interconnected network structure. Due to the strong light absorption ability (93.2%) of the carbonized top layer, together with the low thermal conductivity (0.1 W m K-1) and good water adsorption performance (9.9 g g-1) of the bottom layer, the evaporation rate and evaporation efficiency of the pulp foam evaporator under 1 sun of illumination attained 1.62 kg m-2 h-1 and 98.09%, respectively, which were much higher than those of most cellulose-based solar-driven evaporators. Furthermore, the CPNR foam evaporator with high cost-effectiveness presented high light-thermal conversion, heat localization, and good salt rejection properties due to the unique porous structure. Additionally, the CPNR foam evaporator exhibited potential applications in the treatments of simulated sewage, metal ion concentration, and seawater desalination. Its cost-effectiveness was clearly higher than that of most reported evaporators as well. Therefore, this novel, low-cost, and stable pulp foam evaporator demonstrated here can be a very promising solution for water desalination and purification.

Hetero Nucleus Growth Stabilizing Zinc Anode for High-Biosecurity Zinc-Ion Batteries.

Biocompatible devices are widely employed in modernized lives and medical fields in the forms of wearable and implantable devices, raising higher requirements on the battery biocompatibility, high safety, low cost, and excellent electrochemical performance, which become the evaluation criteria toward developing feasible biocompatible batteries. Herein, through conducting the battery implantation tests and leakage scene simulations on New Zealand rabbits, zinc sulfate electrolyte is proved to exhibit higher biosecurity and turns out to be one of the ideal zinc salts for biocompatible zinc-ion batteries (ZIBs). Furthermore, in order to mitigate the notorious dendrite growth and hydrogen evolution in mildly acidic electrolyte as well as improve their operating stability, Sn hetero nucleus is introduced to stabilize the zinc anode, which not only facilitates the planar zinc deposition, but also contributes to higher hydrogen evolution overpotential. Finally, a long lifetime of 1500 h for the symmetrical cell, the specific capacity of 150 mAh g-1 under 0.5 A g-1 for the Zn-MnO2 battery and 212 mAh g-1 under 5 A g-1 for the Zn-NH4V4O10 battery are obtained. This work may provide unique perspectives on biocompatible ZIBs toward the biosecurity of their cell components.

Development of a linear ion trap mass spectrometer capable of analyzing megadalton MALDI ions.

Detecting megadalton matrix-assisted laser desorption/ionization (MALDI) ions in an ion trap mass spectrometer is a technical challenge. In this study, megadalton protein and polymer ions were successfully measured by MALDI linear ion trap mass spectrometer (LIT-MS) for the first time. The LIT-MS is comprised of a Thermo linear ion trap mass analyzer and a highly sensitive charge-sensing particle detector (CSPD). A newly designed radio frequency (rf) scan mode with dipolar resonance ejection techniques is proposed to extend the mass range of LIT-MS up to one million Thomson (Th). We analyze high mass ions with mass-to charge (m/z) ratios ranging from 100 kTh to 1 MTh, including thyroglobulin, alpha-2-macroglobulin, immunoglobulins (e.g., IgG and IgM), and polymer (∼ 940 kTh) ions. Besides, it is also very challenging for ion trap mass spectrometry to detect megadalton ions at low concentrations. By adopting high affinity carboxylated/oxidized detonation nanodiamonds (oxDNDs) to enrich IgM molecules and form antibody-nanodiamond conjugates, we have successfully reached âˆ¼ 5 nM (5 µg/mL) concentration which is better than that by the other techniques.

Facile Fabrication of Cellulose Nanofibrils/Chitosan Beads as the Potential pH-Sensitive Drug Carriers.

It is highly desirable to develop a safe, highly efficient, and biodegradable drug carrier with an enhanced drug transport efficiency. Cellulose nanofibrils (CNF) and chitosan (CS) composite hydrogels are promising candidate carriers with biological compatibility and non-cytotoxicity. Herein, the CNF/CS composite beads were prepared by dissolving cellulose and CS in LiBr molten salt hydrate and regenerating in ethanol. This preparation method is facile and efficient, and the obtained porous CNF/CS beads with the weight ratio of 8:2 exhibited a large specific surface area, uniform micro-nano-sized pores, strong mechanical property, and water absorption-resistance. Moreover, these beads as drug (tetracycline hydrochloride, TH) carriers showed a higher encapsulation efficiency (47.4%) at the TH concentration of 5 mg/mL in 24 h, and a higher drug loading rate (12.0%) than pure CNF and other CNF/CS beads prepared with different ratios. In addition, the TH releasing behavior of CNF/CS (8:2) beads fitted well into the zero-order, first-order, and Higuchi models under an acid condition, indicating that the drug release of these pH-sensitive beads was mainly affected by drug concentration under an acid condition. Therefore, these CNF/CS beads have great potential to be used as drug carriers for medical applications.

Issues and Opportunities Facing Aqueous Mn2+ /MnO2 -based Batteries.

Aqueous Mn2+ /MnO2 -based batteries have attracted enormous attentions in aqueous energy storage fields, owing to their high working voltage and theoretical capacity (616 mAh g-1 ) brought by the two-electron reaction (Mn2+ /Mn4+ ). However, there are currently several tricky challenges facing Mn2+ /MnO2 -based batteries: their complicated working mechanisms, existing issues, and optimization strategies. This Perspective aims to provide a mechanistic understanding and an overview of the insufficiency, optimization, and future development for Mn2+ /MnO2 -based batteries. The existing issues and deficiency in Mn2+ /MnO2 -based batteries have been systematically analyzed, and optimization strategies have also been rationally summarized and discussed with deep insights. Also, the often-overlooked optimized objects and aspects have been highlighted with unique perspectives. The proposals of testing methods and performance assessment are presented, containing different degradation mechanisms. Based on the above points, this Perspective will provide guidance and contribute to the further development of aqueous Mn2+ /MnO2 -based batteries.

Recent Progress on Phosphate Cathode Materials for Aqueous Zinc-Ion Batteries.

Rechargeable zinc-ion batteries (ZIBs) are attractive for large-scale energy storage due to their superiority in resources, safety, and environmental friendliness. However, the lack of suitable ZIBs cathode materials limits their practical applications. In consideration of the excellent electrochemical performance of phosphate materials in monovalent ion (Li+ , Na+ ) batteries, they were also employed as ZIBs cathode materials recently and performed well with high potential. But they also suffer from low capacity and poor conductivity, and the energy storage mechanism is not clear yet. This Review provides a state-of-the art overview on the developments of phosphate cathode materials in ZIBs, including NASICON-type phosphates, fluorophosphates, olivine-structured, layered-structured, and novel-structured phosphate materials mainly. This study presents the reaction mechanism and electrochemical performance of phosphate cathode materials in aqueous ZIBs, and future research directions are discussed, which are intended to provide guidance for exploring high-potential cathode materials for ZIBs.

Balanced Interfacial Ion Concentration and Migration Steric Hindrance Promoting High-Efficiency Deposition/Dissolution Battery Chemistry.

The solid-liquid transition reaction lays the foundation of electrochemical energy storage systems with high capacity, but realizing high efficiency remains a challenge. Herein, in terms of thermodynamics and dynamics, this work demonstrates the significant role of both interfacial H+ concentration and Mn2+ migration steric hindrance for the high-efficiency deposition/dissolution chemistry of zinc-manganese batteries. Specially, the introduction of formate anions can buffer the generated interfacial H+ to stabilize interfacial potential according to the Nernst equation, which stimulates high capacity. Compared with acetate and propionate anions, the formate anion also provides high adsorption density on the cathode surface to shield the electrostatic repulsion due to the small spatial hindrance. Particularly for the solvated Mn2+ , the formate-anion-induced lower energy barrier of the rate-determining step during the step-by-step desolvation process results in lower polarization and higher electrochemical reversibility. In situ tests and theoretical calculations verify that the electrolyte with formate anions achieve a good balance between ion concentration and ion-migration steric hindrance. It exhibits both the high energy density of 531.26 W h kg-1  and long cycle life of more than 300 cycles without obvious decay.

Surface-Preferred Crystal Plane for a Stable and Reversible Zinc Anode.

Aqueous zinc-ion batteries are largely restricted by the unsatisfactory performance of zinc (Zn) anodes, including their poor stability and irreversibility. In particular, the mechanism behind the electrochemical contrast caused by the surface crystal plane, which is a decisive factor of the electrochemical characteristics of the hostless Zn anode, is still relatively indistinct. Hence, new insight into a novel anode with a surface-preferred (002) crystal plane is provided. The interfacial reaction and morphology evolution are revealed by theoretical analysis and post-mortem/operando experimental techniques, indicating that Zn anodes with more exposed (002) basal planes exhibit free dendrites, no by-products, and weak hydrogen evolution, in sharp contrast to the (100) plane. These features benefit the Zn (002) anode by enabling a long cyclic life of more than 500 h and a high average coulombic efficiency of 97.71% for symmetric batteries, along with delivering long cycling stability and reversibility with life spans of over 2000 cycles for full batteries. This work provides new insights into the design of high-performance Zn anodes for large-scale energy storage and can potentially be applied to other metal anodes suffering from instability and irreversibility.