Unlocking Dynamic Solvation Chemistry and Hydrogen Evolution Mechanism in Aqueous Zinc Batteries.

Understanding the interfacial hydrogen evolution reaction (HER) is crucial to regulate the electrochemical behavior in aqueous zinc batteries. However, the mechanism of HER related to solvation chemistry remains elusive, especially the time-dependent dynamic evolution of the hydrogen bond (H-bond) under an electric field. Herein, we combine in situ spectroscopy with molecular dynamics simulation to unravel the dynamic evolution of the interfacial solvation structure. We find two critical change processes involving Zn-electroplating/stripping, including the initial electric double layer establishment to form an H2O-rich interface (abrupt change) and the subsequent dynamic evolution of an H-bond (gradual change). Moreover, the number of H-bonds increases, and their strength weakens in comparison with the bulk electrolyte under bias potential during Zn2+ desolvation, forming a diluted interface, resulting in massive hydrogen production. On the contrary, a concentrated interface (H-bond number decreases and strength enhances) is formed and produces a small amount of hydrogen during Zn2+ solvation. The insights on the above results contribute to deciphering the H-bond evolution with competition/corrosion HER during Zn-electroplating/stripping and clarifying the essence of electrochemical window widened and HER suppression by high concentration. This work presents a new strategy for aqueous electrolyte regulation by benchmarking the abrupt change of the interfacial state under an electric field as a zinc performance-enhancement criterion.

Kinetics Conditioning of (Electro) Chemically Stable Zn Anode with pH Regulation Toward Long-Life Zn-Storage Devices.

The safety, low cost, and high power density of aqueous Zn-based devices (AZDs) appeal to large-scale energy storage. Yet, the presence of hydrogen evolution reaction (HER) and chemical corrosion in the AZDs leads to local OH- concentration increasement and the formation of ZnxSOy(OH)z•nH2O (ZHS) by-products at the Zn/electrolyte interface, causing instability and irreversibility of the Zn-anodes. Here, a strategy is proposed to regulate OH- by introducing a bio-sourced/renewable polypeptide (ɛ-PL) as a pH regulator in electrolyte. The consumption of OH- species is evaluated through in vitro titration and cell in vivo in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy at a macroscopic and molecular level. The introduction of ɛ-PL is found to significantly suppress the formation of ZHS and associated side reactions, and reduce the local coordinated H2O of the Zn2+ solvation shell, widening electrochemical stable window and suppressing OH- generation during HER. As a result, the inclusion of ɛ-PL improves the cycle time of Zn/Zn symmetrical cells from 15 to 225 h and enhances the cycle time of aqueous Zn- I2 cells to 1650 h compared to those with pristine electrolytes. This work highlights the potential of kinetical OH- regulation for by-product and dendrite-free AZDs.

Surgical Removal of Fat Nodules Formed in the Tear Trough After Autologous Fat Grafting.

BACKGROUND: Autologous fat grafting is a common treatment for tear trough deformities. This procedure involves a potential complication of fat nodule formation, leading to abnormal bulging of the lower eyelid. However, limited information exists about this complication, and an effective treatment is lacking. The present study aimed to present a novel surgical approach for the removal of fat nodules caused by autologous fat grafting in the tear trough. METHODS: This retrospective study included 33 patients who underwent surgery for the removal of fat nodules formed after autologous fat grafting. The procedure was performed using a conjunctival approach, allowing exposure and removal of all fat nodules in the anterior septal space, with the method adapted according to the severity of the deformity. RESULTS: A total of 66 eyelids were treated surgically, including 30 (45.45%) with mild nodular deformity, 23 (34.85%) with moderate nodular deformity, and 13 (10.70%) with severe nodular deformity. A second surgical procedure was required on 3 eyelids (4.56%). The main complications of the surgery were conjunctival congestion (21.21%), and localized depression (18.18%), bruising (12.12%). Among the patients, 29 (87.88%) were satisfied and 4 (12.12%) were dissatisfied with the treatment results. CONCLUSION: Conjunctival approach surgery is an effective method of removing fat nodules formed after autologous fat grafting in the tear trough, with good results and high levels of patient satisfaction. This approach enables the effective management of a common complication of autologous fat grafting and may enable the wider application of autologous fat grafting in the periorbital region. LEVEL OF EVIDENCE III: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .

Visualizing and Regulating Dynamic Evolution of Interfacial Electrolyte Configuration during De-solvation Process on Lithium-Metal Anode.

Acting as a passive protective layer, solid-electrolyte interphase (SEI) plays a crucial role in maintaining the stability of the Li-metal anode. Derived from the reductive decomposition of electrolytes (e.g., anion and solvent), the SEI construction presents as an interfacial process accompanied by the dynamic de-solvation process during Li-metal plating. However, typical electrolyte engineering and related SEI modification strategies always ignore the dynamic evolution of electrolyte configuration at the Li/electrolyte interface, which essentially determines the SEI architecture. Herein, by employing advanced electrochemical in situ FT-IR and MRI technologies, we directly visualize the dynamic variations of solvation environments involving Li+-solvent/anion. Remarkably, a weakened Li+-solvent interaction and anion-lean interfacial electrolyte configuration have been synchronously revealed, which is difficult for the fabrication of anion-derived SEI layer. Moreover, as a simple electrochemical regulation strategy, pulse protocol was introduced to effectively restore the interfacial anion concentration, resulting in an enhanced LiF-rich SEI layer and improved Li-metal plating/stripping reversibility.

Active noise reduction for a differential Helmholtz photoacoustic sensor excited by an intensity-modulated light source.

A highly sensitive differential Helmholtz photoacoustic sensor with active noise reduction was reported. Coupled to one cavity of the photoacoustic cell, an intensity-modulated excitation light would reflect multiple times to produce photoacoustic signal, and meanwhile cause the solid-state photoacoustic effect forming differential mode noise with the frequency same as the photoacoustic signal, which could not be suppressed by conventional differential technology. Wavelength modulation technology is a splendid method to restrain this effect, which is not suitable for light sources with not adjustable wavelength. To suppress this kind of noise, an intensity-modulated compensation light was coupled to another cavity, whose central wavelength was at the non-absorption line of the measured gas. The compensation light was of the same frequency, phase, and power as the excitation light, by which the solid-state photoacoustic effects were produced to form destructive interference called active noise reduction. The experiment results showed that the active noise reduction significantly improved the signal-to-noise ratio and signal-to-background ratio. Compared with the differential, the differential with active noise reduction improved signal-to- noise ratio by about 1.2 times and signal-to-background ratio by about 9.4 times. When low-power near-infrared lasers were employed as the two light sources, the minimum detection limits for acetylene and methane reached 21 and 200 ppb, respectively.

Nonvolatile and Nonflammable Sulfolane-Based Electrolyte Achieving Effective and Safe Operation of the Li-O2 Battery in Open O2 Environment.

The Li-O2 battery should operate effectively/safely in an open O2 environment for practical applications, but not trapped in sealed/closed atmosphere. However, the typical use of volatile and flammable electrolyte restricts Li-O2 battery to be able to be running in open O2 environment. We report herein, for the first time, a highly electrochemical reversible Li-O2 battery operated in an open O2 environment, i.e., under the condition of keeping O2 flowing continuously based on a nonvolatile and nonflammable sulfolane (TMS) solvent. The electrochemical irreversibility of Li2O2/O2 conversion and incompatibility between Li metal anodes and electrolyte have been addressed via dissolving LiNO3 in concentrated TMS electrolyte. The tuned electrolyte not only enables a stable solid electrolyte interphase (SEI) with conformal inorganic components (including LiF, LiNxOy, and Li2O) that promotes a uniform Li electro-plating/stripping process but also results in a low charge overpotential, a stable discharge terminal plateau, and reversible O2 generation of the Li-O2 battery conducted in an open O2 environment.

Long-Life Aqueous Zn-I2 Battery Enabled by a Low-Cost Multifunctional Zeolite Membrane Separator.

Aqueous zinc iodide (Zn-I2) batteries are promising large-scale energy-storage devices. However, the uncontrollable diffuse away/shuttle of soluble I3- leads to energy loss (low Coulombic efficiency, CE), and poor reversibility (self-discharge). Herein, we employ an ordered framework window within a zeolite molecular sieve to restrain I3- crossover and prepare zeolite molecular sieve particles into compact, large-scale, and flexible membranes at the engineering level. The as-prepared membrane can confine I3- within the catholyte region and restrain its irreversible escape, which is proved via space-resolution and electrochemical in situ time-resolution Raman technologies. As a result, overcharge/self-discharge and Zn corrosion are effectively controlled by zeolite separator. After replacing the typically used glass fiber separator to a zeolite membrane, the CE of Zn-I2 battery improves from 78.9 to 98.6% at 0.2 A/g. Besides, after aging at the fully charged state for 5.0 h, self-discharge is restrained and CE is enhanced from 44.0 to 85.65%. Moreover, the Zn-I2 cell maintains 91.0% capacity over 30,000 cycles at 4.0 A/g.

Stabilizing Li-O2 Batteries with Multifunctional Fluorinated Graphene.

As a full cell system with attractive theoretical energy density, challenges faced by Li-O2 batteries (LOBs) are not only the deficient actual capacity and superoxide-derived parasitic reactions on the cathode side but also the stability of Li-metal anode. To solve simultaneously intrinsic issues, multifunctional fluorinated graphene (CFx, x = 1, F-Gr) was introduced into the ether-based electrolyte of LOBs. F-Gr can accelerate O2- transformation and O2--participated oxygen reduction reaction (ORR) process, resulting in enhanced discharge capacity and restrained O2--derived side reactions of LOBs, respectively. Moreover, F-Gr induced the F-rich and O-depleted solid electrolyte interphase (SEI) film formation, which have improved Li-metal stability. Therefore, energy storage capacity, efficiency, and cyclability of LOBs have been markedly enhanced. More importantly, the method developed in this work to disperse F-Gr into an ether-based electrolyte for improving LOBs' performances is convenient and significant from both scientific and engineering aspects.

Unveiling Atom Migration Abilities Affected Anode Performance of Sodium-Ion Batteries.

In sodium-ion batteries (SIBs), the low initial coulombic efficiency (ICE) is commonly induced by irreversible phase conversion and difficult desodiation, especially on transition metal compounds (TMCs). Yet the underlying physicochemical mechanism of poor reaction reversibility is still a controversial issue. Herein, by using in situ transmission electron microscopy and in situ X-ray diffraction, we demonstrate the irreversible conversion of NiCoP@C is caused by the rapid migration of P in carbon layer and preferential formation of isolated Na3 P during discharge. By modifying the carbon coating layer, the migration of Ni/Co/P atoms is inhibited, thus the improvement of ICE and cycle stability is realized. The inhibiting of fast atom migration which induces component separation and rapid performance degradation might be applied to a wide range of electrode materials, and guides the development of advanced SIBs.

Highly Dispersed Ru-Co Nanoparticles Interfaced With Nitrogen-Doped Carbon Polyhedron for High Efficiency Reversible Li-O2 Battery.

The lithium-oxygen (Li-O2 ) battery with high energy density of 3860 Wh kg-1 represents one of the most promising new secondary batteries for future electric vehicles and mobile electronic devices. However, slow oxygen reduction/oxygen evolution (ORR/OER) reaction efficiency and unstable cycling performance restrain the practical applications of the Li-O2 battery. Herein, Ru-modified nitrogen-doped porous carbon-encapsulated Co nanoparticles (Ru/Co@CoNx -C) are synthesized through reduction of Ru on metal-organic framework (MOFs) pyrolyzed derivatives strategies. Porous carbon polyhedra provide channels for reactive species and stable structure ensures the cyclic stability of the catalyst; abundant Co-Nx sites and high specific surface area (353 m2 g-1 ) provide more catalytically active sites and deposition sites for reaction products. Theoretical calculations further verify that Ru/Co@CoNx -C can regulate the growth of Li2 O2 to improve reversibility of Li-O2 batteries. Li-O2 batteries with Ru/Co@CoNx -C as cathode catalyst achieve small voltage gaps of 1.08 V, exhibit excellent cycle stability (205 cycles), and deliver high discharge specific capacity (17050 mAh g-1 ). Furthermore, pouch-type Li-O2 batteries that maintain stable electrochemical performance output even under conditions of bending deformation and corner cutting are successfully assembled. This study demonstrates Ru/Co@CoNx -C catalyst's great application potential in Li-O2 batteries.

Design of a high-sensitivity differential Helmholtz photoacoustic cell and its application in methane detection.

A high-sensitivity differential Helmholtz photoacoustic cell based on multiple reflection was reported, and its performance parameters and gas replacement time were optimized by finite element simulation. To realize the long absorption path of the measured gas, the collimated excitation light was reflected multiple times on the gold-plated wall of the absorption cavity, and the wavelength modulation technology was used to reduce the multiple reflection noise. Additionally, the differential could suppress external co-phase noise and double the photoacoustic signal. When a laser with a central wavelength of 1653 nm was employed as the excitation light source, the minimum detection limit of 177 ppb (signal-to-noise ratio, SNR = 1) for methane was achieved within a detection time of 1 s, and the corresponding normalized noise equivalent absorption coefficient was 4.1×10-10 cm-1WHZ-1/2.

Highly Sensitive Sphere-Tube Coupled Photoacoustic Cell Suitable for Detection of a Variety of Trace Gases: NO2 as an Example.

The concentration of trace gases in the atmospheric environment is extremely low, but it has a great impact on the living environment of organisms. Photoacoustic spectroscopy has attracted extensive attention in the field of trace gas detection because of its high sensitivity, good selectivity, and fast response. As the core of a photoacoustic detection setup, the photoacoustic cell has a significant impact on detection performance. To improve detection sensitivity, a sphere-tube coupled photoacoustic cell (STPAC) was developed, which was mainly composed of a diffuse-reflective sphere and an acoustic resonance tube. Modulated light was reflected multiple times in the sphere to increase optical path, and photoacoustic (PA) signals were further amplified by the tube. Based on STPAC, a PA gas detection setup was built with a laser diode (LD) at 450 nm as the light source. The experimental results showed that the minimum detection limit (noise equivalent concentration, NEC) of NO2 was ~0.7 parts per billion (ppb). Compared with the T-type PA cell (TPAC) in which the modulated light passed through the sphere, the signal-to-noise ratio of STPAC was increased by an order of magnitude at the same concentration of the NO2 sample.

Rapid and sensitive detection of nodularin-R in water by a label-free BLI aptasensor.

Contamination of freshwater with nodularin-R (NOD-R) represents a significant global environmental and public health concern. However, ethical problems and technical difficulties surrounding the current detection methods for NOD-R necessitate further studies to devise appropriate alternatives within a regulatory monitoring regime. In this work, we employed an aptamer as a specific recognition element and developed a biolayer interferometry (BLI) biosensor platform for NOD-R detection. The aptasensor we propose displayed a broad detection range from 40 to 600 nM NOD-R (and a linear response range from 40 to 200 nM), and achieved a detection limit as low as 167 pM. In addition, the aptamer-based biosensor was shown to possess high selectivity, as well as good reproducibility and stability. We believe that this novel aptamer-based biosensor provides a potential alternative for the sensitive and rapid detection of NOD-R.

Scaffold hopping of sampangine: discovery of potent antifungal lead compound against Aspergillus fumigatus and Cryptococcus neoformans.

Discovery of novel antifungal agents against Aspergillus fumigatus and Cryptococcus neoformans remains a significant challenge in current antifungal therapy. Herein the antifungal natural product sampangine was used as the lead compound for novel antifungal drug discovery. A series of D-ring scaffold hopping derivatives were designed and synthesized to improve antifungal activity and water solubility. Among them, the thiophene derivative S2 showed broad-spectrum antifungal activity, particularly for Aspergillus fumigatus and Cryptococcus neoformans. Moreover, compound S2 also revealed better water solubility than sampangine, which represents a promising antifungal lead compound for further structural optimization.

Experimental Investigation of Water Vapor Concentration on Fracture Properties of Asphalt Concrete.

The effect of moisture on the fracture resistance of asphalt concrete is a significant concern in pavement engineering. To investigate the effect of the water vapor concentration on the fracture properties of asphalt concrete, this study first designed a humidity conditioning program at the relative humidity (RH) levels of 2%, 50%, 80%, and 100% for the three types of asphalt concrete mixtures (AC-13C, AC-20C, and AC-25C).The finite element model was developed to simulate the water vapor diffusion and determine the duration of the conditioning period. The semi-circular bending (SCB) test was then performed at varying temperatures of 5 °C, 15 °C, and 25 °C to evaluate the fracture energy and tensile strength of the humidity-conditioned specimens. The test results showed that the increasing temperature and the RH levels resulted in a lower peak load but greater displacement of the mixtures. Both the fracture energy and tensile strength tended to diminish with the rising temperature. It was also found that moisture had a significant effect on the tensile strength and fracture energy of asphalt concrete. Specifically, as the RH level increased from 2% to 100% (i.e., the water vapor concentration rose from 0.35 g/m3 to 17.27 g/m3), the tensile strength of the three types of mixtures was reduced by 34.84% on average, which revealed that the water vapor led to the loss of adhesion and cohesion within the mixture. The genetic expression programming (GEP) model was developed to quantify the effect of water vapor concentrations and temperature on the fracture indices.

Protective effect and mechanism of Lycium ruthenicum Murray anthocyanins against retinal damage induced by blue light exposure.

Lycium ruthenicum Murray (LR) is a medicine and edible plant in Northwest China, and L. ruthenicum Murray anthocyanins (LRA) are green antioxidants with various pharmacological activities, such as antioxidant and anti-inflammatory activities. However, the protective effect and mechanism of LRA against retinal damage induced by blue light exposure are poorly understood. This study explored the protective effects and potential mechanisms of LRA on retinal damage induced by blue light exposure in vitro and in vivo. The results showed that LRA could ameliorate oxidative stress injury by activating the antioxidant stress nuclear factor-related factor 2 pathway, promoting the expression of phase II detoxification enzymes (HO-1, NQO1) and endogenous antioxidant enzymes (catalase, superoxide dismutase, glutathione peroxidase), and reducing reactive oxygen species and malondialdehyde levels. Additionally, LRA could inhibit inflammatory response by decreasing the expression of blue light exposure-induced nuclear factor-κB (NF-κB) pathway-related proteins (NF-κB and p-IκBα), as well as interleukin (IL)-6, tumor necrosis factor-α, IL-1ß pro-inflammatory factors and pro-inflammatory chemokine VEGF, and increasing the expression of anti-inflammatory factor IL-10. Furthermore, LRA could ameliorate oxidative stress-induced apoptosis by upregulating Bcl-2 and downregulating Bax and Caspase-3 protein expression. All these results indicate that LRA can be used as an antioxidant dietary supplement for the treatment or prevention of retinal diseases.

Compact gas cell for simultaneous detection of atmospheric aerosol optical properties based on photoacoustic spectroscopy and integrating sphere scattering enhancement.

Atmospheric aerosols play a pivotal role in the earth-atmospheric system. Analyzing their optical properties, specifically absorption and scattering coefficients, is essential for comprehending the impact of aerosols on climate. When different optical properties of aerosols are individually measured using multiple devices, cumulative errors in the detection results inevitably occur. To address this challenge, based on photoacoustic spectroscopy (PAS) and integrating sphere (IS) scattering enhancement, a compact gas cell (PASIS-Cell) was developed. The PASIS-Cell comprises a dual-T-type photoacoustic cell (DTPAC) and an IS. IS is coupled with DTPAC through a transparent quartz tube, thereby enhancing the scattering signal without compromising the acoustic characteristics of DTPAC. Concurrently, DTPAC can realize high-performance photoacoustic detection of absorption signal. Experimental results demonstrate that PASIS-Cell can simultaneously invert atmospheric aerosol absorption and scattering coefficients, with a minimum detection limit of less than 1 Mm-1, showcasing its potential in the analysis of aerosol optical properties.

Anomalous Inferior Zn Anode in High-Concentration Electrolyte: Leveraging Solid-Electrolyte-Interface for Stabilized Cycling of Aqueous Zn-Metal Batteries.

Aqueous Zn-metal batteries (AZMBs) are promising large-scale energy storage devices for their high safety and theoretical capacity. However, unstable Zn-electrolyte interface and severe side reactions have excluded AZMBs from long cycling required by practically reversible energy storage. Traditional high-concentration electrolyte is an effective strategy to suppress dendrites growth and resolve the poor electrochemical stability and reversibility of Zn-metal anodes, yet how scientifically universal such strategy is for hybrid electrolyte of different concentrations remains unclear. Herein, we studied the electrochemical behaviors of AZMBs comprising a ZnCl2 -based DMSO/H2 O electrolyte of two distinct concentrations (1 m vs. 7 m). The electrochemical stability/reversibility of Zn anodes in both symmetric and asymmetric cells with high-concentration electrolytes are unusually inferior to the ones with low-concentration electrolyte. It was found that more DMSO components in the solvation sheath of low-concentration electrolyte exist at the Zn-electrolyte interface than in high-concentration counterpart, enabling higher organic compositions in solid-electrolyte-interface (SEI). The rigid inorganic and flexible organic compositions of SEI decomposed from the low-concentration electrolyte is accounted for improved cycling and reversibility of Zn metal anodes and the respective batteries. This work reveals the critical role of SEI than the high concentration itself in delivering stable electrochemical cycling in AZMBs.

Protecting Li-metal in O2 atmosphere by a sacrificial polymer additive in Li-O2 batteries.

Li-O2 batteries (LOBs) with Li-metal as the anode are characterized by their high theoretical energy density of 3500 W h kg-1 and are thus considered next-generation batteries with an unlimited potential. However, upon cycling in a harsh O2 atmosphere, the poor-quality solid electrolyte interphase (SEI) film formed on the surface of the Li-metal anode cannot effectively suppress the shuttle effect from O2, superoxide species, protons, and soluble side products. These issues lead to aggravated Li-metal corrosion and hinder the practical development of LOBs. In this work, a polyacrylamide-co-polymethyl acrylate (PAMMA) copolymer was innovatively introduced in an ether-based electrolyte as a sacrificial additive. PAMMA was found to preferentially decompose and promote the formation of a dense and Li3N-rich SEI film on the Li-metal surface, which could effectively prohibit the shuttle effect from a series of detrimental species in the Li-O2 cell during the discharge/charge process. Using PAMMA, well-protected Li-metal in a harsh O2 atmosphere and significantly enhanced cycling performance of the Li-O2 cell could be achieved. Thus, the use of a sacrificial polymer additive provides a promising strategy for the effective protection of Li-metal in Li-O2 cells in a severe O2 atmosphere during practical applications.

Full-Dimensional Analysis of Electrolyte Decomposition on Cathode-Electrolyte Interface: Establishing Characterization Paradigm on LiNi0.6Co0.2Mn0.2O2 Cathode with Potential Dependence.

Cathode electrolyte interphase (CEI) layers derived from electrolyte oxidative decomposition can passivate the cathode surface and prevent its direct contact with electrolyte. The inorganics-dominated inner solid electrolyte layer (SEL) and organics-rich outer quasi-solid-electrolyte layer (qSEL) constitute the CEI layer, and both merge at the junction without a clear boundary, which assures the CEI layer with both ionic-conducting and electron-blocking properties. However, the typical "wash-then-test" pattern of characterizations aiming at the microstructure of CEI layers would dissolve the qSEL and even destroy the SEL, leading to an overanalysis of electrolyte decomposition pathway and misassignment of CEI architecture (e.g., component and morphology). In this study, we established a full-dimensional characterization paradigm (combining Fourier transform infrared, solution NMR, X-ray photoelectron spectroscopy, and mass spectrometry technologies) and reconstructed the original CEI layer model. Besides, the feasibility of this characterization paradigm has been verified in a wide operating voltage range on a typical LiNixMnyCozO2 cathode.