Ionic Environments Research Articles

Molecular dynamics simulations unveil the aggregation patterns and salting out of polyarginines at zwitterionic POPC bilayers in solutions of various ionic strengths

This study employs molecular dynamics (MD) simulations to investigate the adsorption and aggregation behavior of simple polyarginine cell-penetrating peptides (CPPs), specifically modeled as R9 peptides, at zwitterionic phosphocholine POPC membranes under varying ionic strengths of two peptide concentrations and two concentrations of NaCl and CaCl2. The results reveal an intriguing phenomenon of R9 aggregation at the membrane, which is dependent on the ionic strength, indicating a salting-out effect. As the peptide concentration and ionic strength increase, peptide aggregation also increases, with aggregate lifetimes and sizes showing a corresponding rise, accompanied by the total decrease of adsorbed peptides at the membrane surface. Notably, in high ionic strength environments, large R9 aggregates, such as octamers, are also observed occasionally. The salting-out, typically uncommon for short positively charged peptides, is attributed to the unique properties of arginine amino acid, specifically by its side chain containing amphiphilic guanidinium (Gdm+) ion which makes both intermolecular hydrophobic like-charge Gdm+ – Gdm+ and salt-bridge Gdm+ – C-terminus interactions, where the former are increased with the ionic strength, and the latter decreased due to electrostatic screening. The aggregation behavior of R9 peptides at membranes can also be linked to their CPP translocation properties, suggesting that aggregation may aid in translocation across cellular membranes.

PH monitoring in high ionic concentration environments: performance study of graphene-based sensors.

Graphene-based pH sensors, acclaimed for their exceptional sensitivity to environmental variations, have garnered significant interest in scientific research. However, the sensor performance in high ionic concentration environments is limited, due to the Debye length ion screening effect. In this study, an innovative graphene channel pH sensing device was developed and modified by cross-linked poly(methyl methacrylate) (PMMA). Furthermore, even in high ionic concentrations, the pH value can be precisely measured by this sensor. The sensor has remarkable sensitivity, and high response rate of - 70.49mV/pH within the pH range from 7 to 10. Notably, the sensors retain uniform response direction and sensitivity under different ionic concentrations environmental and maintain consistent reversibility and stability. This advancement in sensor technology paves the way for broader applications in complex ionic environments.

The (un)known issue with using rose bengal as a standard of singlet oxygen photoproduction.

Rose bengal (RB) is a widely used photosensitizer for determining quantum yields of singlet oxygen generation. While it is known to aggregate in polar environments at concentrations above 2 μM, the relationship between RB concentration and singlet oxygen photogeneration remains unclear. This study investigates the shift from monomeric to dimeric RB with increasing concentration and its impact on singlet oxygen generation in D2O-based solutions and DMPC liposomes. Absorbance maxima for RB were observed at 514 nm (dimer) and 549 nm (monomer), with ionic environments influencing aggregation rates. Singlet oxygen phosphorescence showed non-linear dependency above 2 μM, indicating the effects of aggregation. Results suggest that RB concentrations should be kept at 1 μM or lower in photochemical studies to avoid aggregation-related discrepancies in singlet oxygen yield determination. These findings highlight the importance of considering RB aggregation in photochemical research and medical applications.

Biodegradable taro stem cellulose aerogel: A simple approach for adsorbing microplastics and dyestuffs contaminants

Water pollution and agricultural waste are pressing global issues. Herein, a biomass aerogel derived from waste taro stem microcrystalline cellulose (TS-MCC) was fabricated, in which, the effects of cellulose amount, cross-linker content, pre-freezing protocols on the aerogel’s property were studied. The optimized TS-MCC2.0 aerogel exhibited a hierarchical porous structure with good mechanical property (65.04 kPa) and adsorption capacities, with the qm towards microplastics (Polystyrene, PS) and dye (Congo red, CR) being 418.6 mg/g and 951.51 mg/g at 298 K, respectively. Meanwhile, it exhibited good applicability under different pH (3–11) and ionic strength environments, as well as the retained notably simultaneous adsorption ability even under mixed contaminant systems. The mathematical models suggested that the adsorption of PS and CR both fitted pseudo-second-order kinetics, and the adsorption isotherms could be described by the Langmuir and Freundlich models, respectively. Hydrogen bonding, electrostatic attraction, and π–π interactions were inferred as the main adsorption mechanisms towards PS and CR according to Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy analysis. Moreover, the adsorption efficiencies were 92.37 % for PS and 88.34 % for CR after 5 reuse cycles. Therefore, this study provides a green aerogel sorbent for adsorbing microplastics and dyes contaminants.

A polylysine/hyaluronan-based core-shell nanoparticle triggers drug delivery by ATP/hyaluronidase dual stimuli for inducing apoptosis of breast cancer cells

The limitations of self-assembled polymeric nanoparticles for cancer therapy, including instability in the bloodstream, non-specific targeting of cancer cells, and unregulated intracellular drug delivery, were effectively addressed by the development of core-shell SNX@PLL-FPBA/mHA NPs. The core was SNX@PLL-FPBA NPs prepared from polylysine conjugated 3-fluoro-4-carboxyphenylboronic acid (PLL-FPBA) self-assembly and SNX encapsulation, while the shell was methacrylate-modified hyaluronic acid (mHA) adhering to the core by electrostatic interactions and subsequently stabilized by photo-crosslinking, without the use of any organic solvent. SNX@PLL-FPBA/mHA NPs exhibited good stability in varying ionic strengths (0–0.30 M NaCl), pH levels (6.8 and 7.4), and plasma environments mimicking the blood, ensuring their efficacy in systemic circulation. The drug delivery from the nanoparticles was highly sensitive to ATP/Hyals stimuli (82 % within 48 h), closely mimicking the intracellular environment of breast cancer cells. The nanoparticles demonstrated good hemocompatibility and non-toxicity towards human skin fibroblasts. Efficient internalization of SNX@PLL-FPBA/mHA NPs by MCF-7 and MDA-MB-231 breast cancer cells was observed by CLSM and flow cytometry. The intracellular ATP/Hyals stimuli triggered the rapid drug delivery and induced cellular apoptosis. Thus, SNX@PLL-FPBA/mHA NPs were a promising drug nanocarrier for breast cancer therapy, offering improved stability, targeted delivery, and controlled drug release to enhance treatment outcomes.

Preparation and characterization of hydrophobically-modified sodium alginate derivatives as carriers for fucoxanthin

Micelles are nano-architectured structures capable of encapsulating hydrophobic substances in aqueous solutions, thereby improving their stability, solubility, and bioavailability to control the release of bioactive compounds. In this study, the sodium alginate backbone was modified via a hydrophobic modification scheme where octyl chains were covalently attached to the alginate chains via esterification reactions. Fourier-transformed infrared spectrometry (FTIR), 1H nuclear magnetic resonance (1H NMR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA) were used to characterize the structure of the sodium alginate derivatives of varying molar mass (ALG-C8). Fluorescence spectroscopy, surface tension measurements, and dynamic light scattering (DLS) were employed to assess the self-assembly performance of ALG-C8. The three methods produced consistent results, indicating that self-assembly decreased with higher molar mass. The self-assembled ALG-C8 micelles were utilized to encapsulate fucoxanthin. The loading capacity (LC) and encapsulation efficiency (EE) were determined using UV–Vis spectrophotometry. The molar mass of ALG-C8 has a key influence on fucoxanthin loading and release behavior. The ALG-C8 molecules with the lowest molar mass produced micelles with the smallest hydration diameter, resulting in the highest LC and EE. Furthermore, the release of fucoxanthin is significantly influenced by the pH and ionic strength of the medium. ALG-C8 micellar-like aggregates exhibit resistance to low pH and high ionic strength environments, releasing encapsulated material at the target site under alkaline conditions. Therefore, synthesized ALG-C8 is a potential candidate for preparing pH-responsive self-assembled micellar-like aggregates, enabling targeted delivery and gradual release of hydrophobic functional food components.

Heteroatom Doping Promoted Ultrabright and Ultrastable Photoluminescence of Water-Soluble Au/Ag Nanoclusters for Visual and Efficient Drug Delivery to Cancer Cells.

Photoluminescence (PL) metal nanoclusters (NCs) have attracted extensive attention due to their excellent physicochemical properties, good biocompatibility, and broad application prospects. However, developing water-soluble PL metal NCs with a high quantum yield (QY) and high stability for visual drug delivery remains a great challenge. Herein, we have synthesized ultrabright l-Arg-ATT-Au/Ag NCs (Au/Ag NCs) with a PL QY as high as 73% and excellent photostability by heteroatom doping and surface rigidization in aqueous solution. The as-prepared Au/Ag NCs can maintain a high QY of over 61% in a wide pH range and various ionic environments as well as a respectable resistance to photobleaching. The results from structure characterization and steady-state and time-resolved spectroscopic analysis reveal that Ag doping into Au NCs not only effectively modifies the electronic structure and photostability but also significantly regulates the interfacial dynamics of the excited states and enhances the PL QY of Au/Ag NCs. Studies in vitro indicate Au/Ag NCs have a high loading capacity and pH-triggered release ability of doxorubicin (DOX) that can be visualized from the quenching and recovery of PL intensity and lifetime. Imaging-guided experiments in cancer cells show that DOX of Au/Ag NCs-DOX agents can be efficiently delivered and released in the nucleus with preferential accumulation in the nucleolus, facilitating deep insight into the drug action sites and pharmacological mechanisms. Moreover, the evaluation of anticancer activity in vivo reveals an outstanding suppression rate of 90.2% for mice tumors. These findings demonstrate Au/Ag NCs to be a superior platform for bioimaging and visual drug delivery in biomedical applications.

Aluminum Molecular Ring Meets Deep Eutectic Solvents: Adaptive Assembly and Optical Behavior.

Different from the previous neutral reaction solvent system, this work explores the synthesis of Al-oxo rings in ionic environments. Deep eutectic solvents (DESs) formed by quaternary ammonium salts hydrogen bond acceptor (HBA) and phenols hydrogen bond donor (HBD) further reduce the melting point of the reaction system and provide an ionic environment. Further, the quaternary ammonium salt was chosen as the HBA because it contains a halogen anion that matches the size of the central cavity of the molecular ring. Based on this thought, five Al8 ion pair cocrystals were synthesized via "DES thermal". The general formula is Q+ ⊂ {Cl@[Al8(BD)8(μ2-OH)4L12]} (AlOC-180-AlOC-185, Q+ = tetrabutylammonium, tetrapropylammonium, 1-butyl-3-methylimidazole; HBD = phenol, p-chlorophenol, p-fluorophenol; HL = benzoic acid, 1-naphthoic acid, 1-pyrenecarboxylic acid, anthracene-9-carboxylic acid). Structural studies reveal that the phenol-coordinated Al molecular ring and the quaternary ammonium ion pair form the cocrystal compounds. The halogen anions in the DES component are confined in the center of the molecular ring, and the quaternary ammonium cations are located in the organic shell. Such an adaptive cocrystal binding pattern is particularly evident in the structures coordinated with low-symmetry ligands such as naphthoic acid and pyrene acid. Finally, the optical behavior of these cocrystal compounds is understood from the analysis of crystal structure and theoretical calculation.

Confined Ionic Environments Tailoring the Reactivity of Molecules in the Micropores of BEA-Type Zeolite.

In the presence of water, hydronium ions formed within the micropores of zeolite H-BEA significantly influence the surrounding environment and the reactivity of organic substrates. The positive charge of these ions, coupled with the zeolite's negatively charged framework, results in an ionic environment that causes a strongly nonideal solvation behavior of cyclohexanol. This leads to a significantly higher excess chemical potential in the initial state and stabilizes at the same time the charged transition state in the dehydration of cyclohexanol. As a result, the free-energy barrier of the reaction is lowered, leading to a marked increase in the reaction rates. Nonetheless, there is a limit to the reaction rate enhancement by the hydronium ion concentration. Experiments conducted with low concentrations of reactants show that beyond an optimal concentration, the required spatial rearrangement between hydronium ions and cyclohexanols inhibits further increases in the reaction rate, leading to a peak in the intrinsic activity of hydronium ions. The quantification of excess chemical potential in both initial and transition states for zeolites H-BEA, along with findings from HMFI, provides a basis to generalize and predict rates for hydronium-ion-catalyzed dehydration reactions in Brønsted zeolites.

Nanohybrid layered clay composite decorated with polyaniline for intensified Cr(VI) removal through enhanced Cr(VI) reduction

Hexavalent chromium (Cr(VI)) is mainly detected as a harmful anion in aquatic ecosystems. In this study, a novel nanohybrid layered clay composite decorated with polyaniline (PANI) (PANI/LDH@MMt) was successfully synthesized by a layer-by-layer assembly strategy and utilized for Cr(VI) removal. Layered double hydroxide (LDH) and montmorillonite (MMt) in nanohybrid layered clay (LDH@MMt) can facilitate Cr(VI) elimination through reinforced Cr(VI) reduction. Some key experimental parameters were evaluated in detail for their potential impact on Cr(VI) removal. The experimental results illustrated that PANI/LDH@MMt displayed high Cr(VI) removal efficiency (>99 %) at most appropriate conditions and maintained over 95 % performance even in ionic coexistence and natural water environments. Kinetic models, isothermal models, and thermodynamic analyses were also employed to explore the Cr(VI) removal behavior on PANI/LDH@MMt. Finally, the mechanism analysis suggested that Cr(VI) could be captured by electrostatic interaction of -NH-+, -N=+, and –OH2+, and anion exchange of LDH, and reduced to Cr(III) by -NH-. Subsequently, Cr(III) could chelate with -N=, −NH−, and −OH, complex with OH-, and be immobilized by MMt through cation exchange. This study presents a new insight into the reasonable construction of highly efficient adsorbents with low cost for Cr(VI) removal.

Enhanced removal of trace thallium by photo-promoted adsorption using Prussian blue@filter papers: Performance and mechanistic insights

Developing highly efficient adsorbents for the removal of trace thallium(I) (Tl+) is crucial for addressing environmental challenges. In this study, we successfully synthesized cubic Prussian blue (PB) loading on filter papers using an intermediate layer (dopamine/polyethyleneimine) via in-situ methods. The as-prepared PB-modified FP demonstrated outstanding anti-interference properties and light-enhanced adsorption performance for Tl+ (0.5 mg/L) under ultraviolet (UV) irradiation, exhibiting twice the effectiveness compared to dark conditions, even in acidic and coexisting ionic environments. This indicated its suitability for treating complex Tl+-contaminated water. Notably, the removal efficiency for trace Tl+ was almost 100%, with a maximum experimental adsorption capacity of 86.2 mg/g after 1-h photo-promoted adsorption under 365 nm UV. Characterization results supported a proposed photo-driven redox mechanism that elucidated the interaction between Tl+ and PB-modified FP. Specifically, the accelerated Fe(III) to Fe(II) redox reaction facilitated Tl+ accommodation on the surface and/or lattice of PB, enhancing Tl+ adsorption by compensating for missed positive charges. This study provides valuable insights into utilizing PB-based materials to enhance the photo-enhanced Tl+ adsorption capacity in a cost-effective, easy-to-synthesize, and environmentally friendly manner.

Robust Oxidase-Mimetic Supramolecular Nanocatalyst for Lignin Biodegradation.

Enzymatic catalysis presents an eco-friendly, energy-efficient method for lignin degradation. However, challenges arise due to the inherent incompatibility between enzymes and native lignin. In this work, we introduce a supramolecular catalyst composed of fluorenyl-modified amino acids and Cu2+, designed based on the aromatic stacking of the fluorenyl group, which can operate in ionic liquid environments suitable for the dissolution of native lignin. Amino acids and halide anions of ionic liquids shape the copper site's coordination sphere, showcasing remarkable catechol oxidase-mimetic activity. The catalyst exhibits thermophilic property, and maintains oxidative activity up to 75 °C, which allows the catalyzed degradation of the as-dissolved native lignin with high efficiency even without assistance of the electron mediator. In contrast, at this condition, the native copper-dependent oxidase completely lost its activity. This catalyst with superior stability and activity offer promise for sustainable lignin valorization through biocatalytic routes compatible with ionic liquid pretreatment, addressing limitations in native enzymes for industrially relevant conditions.

Aptamer Clicked Poly(ferrocenylsilanes) at Au Nanoparticles as Platforms with Multiple Function[†

Aptamers are widely used in biosensing due to their specific sensitivity toward many targets. Thus, gold nanoparticle (AuNP) aptasensors are subject to intense research due to the complementary properties of aptamers as sensing elements and AuNPs as transducers. We present herein a novel method for the functional coupling of thrombin-specific aptamers to AuNPs via an anionic, redox-active poly(ferrocenylsilane) (PFS) polyelectroyte. The polymer acts as a co-reductant and stabilizer for the AuNPs, provides grafting sites for the aptamer, and can be used as a redox sensing element, making the aptamer-PFS-AuNP composite (aptamer-AuNP) a promising model system for future multifunctional sensors. The aptamer-AuNPs exhibit excellent colloidal stability in high ionic strength environments owing to the combined electrosteric stabilizing effects of the aptamer and the PFS. The synthesis of each assembly element is described, and the colloidal stability and redox responsiveness are studied. As an example to illustrate applications, we present results for thrombin sensitivity and specificity using the specific aptamer.

Production of an eco-friendly concrete by including high-volume zeolitic supplementary cementitious materials and quicklime

The production of ordinary Portland cement (OPC) is one of the main global causes of CO2 release to the atmosphere. However, its availability and unique characteristics as a binding material make it difficult to be substituted by eco-friendlier materials. However, OPC partial replacement with pozzolanic materials is one of the best solutions to this problem. Hence, in this study, various types of high-volume zeolite were employed as supplementary cementitious materials (SCM), substituting the OPC by up to 50 wt.% in the composition of the created mortars. Besides, quicklime and inorganic accelerators were included in some of the mortar mixtures to improve the hydration reaction and enhance its speed. The mechanical, durability and durability in sea water properties were investigated. Although the usage of SCM caused a decrease in the mechanical and durability properties of the specimens, the addition of 10 wt.% quicklime palliated this degradation by enhancing by 40% the 28-days compressive strength of the specimens and by significantly improving their durability (porosity, freeze–thaw resistance and carbonation resistance). Moreover, the mixtures were proved to be resistance to aggressive ionic environments, since their compressive strength even increased after 28-day immersion in seawater, due to the additional formation of hydration compounds.

Polymeric integration of structure-switching aptamers on transistors for histamine sensing.

Aptamers that undergo large conformational rearrangements at the surface of electrolyte-gated field-effect transistor (EG-FETs)-based biosensors can overcome the Debye length limitation in physiological high ionic strength environments. For the sensitive detection of small molecules, carbon nanotubes (CNTs) that approach the dimensions of analytes of interest are promising channel materials for EG-FETs. However, functionalization of CNTs with bioreceptors using frequently reported surface modification strategies (e.g., π-π stacking), requires highly pristine CNTs deposited through methods that are incompatible with low-cost fabrication methods and flexible substrates. In this work, we explore alternative non-covalent surface chemistry to functionalize CNTs with aptamers. We harnessed the adhesive properties of poly-D-lysine (PDL), to coat the surface of CNTs and then grafted histamine-specific DNA aptamers electrostatically in close proximity to the CNT semiconducting channel. The layer-by-layer assembly was monitored by complementary techniques such as X-ray photoelectron spectroscopy, optical waveguide lightmode spectroscopy, and fluorescence microscopy. Surface characterization confirmed histamine aptamer integration into PDL-coated CNTs and revealed ∼5-fold higher aptamer surface coverage when using CNT networks with high surface areas. Specific aptamers assembled on EG-CNTFETs enabled histamine detection in undiluted high ionic strength solutions in the concentration range of 10 nM to 100 μM. Sequence specificity was demonstrated via parallel measurements with control EG-CNTFETs functionalized with scrambled DNA. Histamine aptamer-modified EG-CNTFETs showed high selectivity vs. histidine, the closest structural analog and precursor to histamine. Taken together, these results implied that target-specific aptamer conformational changes on CNTs facilitate signal transduction, which was corroborated by circular dichroism spectroscopy. Our work suggests that layer-by-layer polymer chemistry enables integration of structure-switching aptamers into flexible EG-CNTFETs for small-molecule biosensing.

The critical role of aromatic residues in the binding of the SARS-CoV-2 fusion peptide to phospholipid bilayer membranes.

Based on the SARS-CoV-2 fusion peptide (FP) structure determined from the NMR experiment, we created six FP models under different environmental conditions to explore the effects of salt and cholesterol on FP-membrane binding. The all-atom molecular dynamics (MD) simulation results indicated that ionic environments notably impact the FP structure as well as the stability of the helical elements within the peptide. Our findings highlighted the unpredictable influence of ions on the secondary structures and dynamics of the FP, emphasizing the complexity and sensitivity of the peptide's conformations to ionic conditions. When exploring the peptide's interaction with a cholesterol-free phospholipid bilayer membrane, we found that the helical elements of the FP remain stable irrespective of the salt type (Na+ or Ca2+). This result emphasizes the crucial role of phospholipid bilayer membranes in supporting the secondary structures of the FP. The MD simulation results showed that Ca2+ ions facilitated deeper membrane penetration than Na+ ions, highlighting the critical role of calcium ions in the FP-membrane binding. Our study indicates the essential role of the aromatic residues (such as Phe833 and Tyr837) in the FP-membrane binding process. Finally, we investigated the FP-membrane binding patterns in the presence of cholesterol. The MD simulation results demonstrated that the coupling of Ca2+ ions and cholesterol would also benefit the FP-membrane binding. Furthermore, our findings reveal that while the type of ion and cholesterol content exert varied and unpredictable influences on FP-membrane binding patterns, aromatic residues like tyrosine (Tyr) and phenylalanine (Phe) play an essential role in FP-membrane binding. In particular, deep mutational scanning (DMS) experiments have confirmed that mutating phenylalanine in the FP significantly decreases viral mutational fitness, emphasizing the pivotal role of phenylalanine residues in membrane fusion. This knowledge can aid in developing more effective therapeutic strategies targeting the viral fusion peptide and its key amino acids, ultimately contributing to developing treatments and vaccines against the virus.

Mobility of Condensed Counterions in Ion-Exchange Membranes: Application of Screening Length Scaling Relationship in Highly Charged Environments.

Ion-exchange membranes (IEMs) are widely used in water, energy, and environmental applications, but transport models to accurately simulate ion permeation are currently lacking. This study presents a theoretical framework to predict ionic conductivity of IEMs by introducing an analytical model for condensed counterion mobility to the Donnan-Manning model. Modeling of condensed counterion mobility is enabled by the novel utilization of a scaling relationship to describe screening lengths in the densely charged IEM matrices, which overcame the obstacle of traditional electrolyte chemistry theories breaking down at very high ionic strength environments. Ionic conductivities of commercial IEMs were experimentally characterized in different electrolyte solutions containing a range of mono-, di-, and trivalent counterions. Because the current Donnan-Manning model neglects the mobility of condensed counterions, it is inadequate for modeling ion transport and significantly underestimated membrane conductivities (by up to ≈5× difference between observed and modeled values). Using the new model to account for condensed counterion mobilities substantially improved the accuracy of predicting IEM conductivities in monovalent counterions (to as small as within 7% of experimental values), without any adjustable parameters. Further adjusting the power law exponent of the screen length scaling relationship yielded reasonable precision for membrane conductivities in multivalent counterions. Analysis reveals that counterions are significantly more mobile in the condensed phase than in the uncondensed phase because electrostatic interactions accelerate condensed counterions but retard uncondensed counterions. Condensed counterions still have lower mobilities than ions in bulk solutions due to impedance from spatial effects. The transport framework presented here can model ion migration a priori with adequate accuracy. The findings provide insights into the underlying phenomena governing ion transport in IEMs to facilitate the rational development of more selective membranes.

Enhanced Intrinsic Electrochemical Capacitance in Carbon Nanotube Yarns for Increasing Electrical Power Generation

Mechanical energy harvesters, which convert mechanical energy to electrical energy, have gained significant attention as potential replacements for conventional energy devices like batteries and capacitors. Triboelectric and piezoelectric nanogenerators have been researched to improve harvesting performance and to harness them low-power electrical devices[1,2]. For practical use, considering the surrounding environments are necessary because harvesting performance is dependent on surrounding conditions such as frequency of mechanical motion, humidity, and temperature. The ocean, in particular, provides a troublesome environment for conventional mechanical energy harvesters, given its submerged conditions, the presence of various ions, and low-frequency mechanical motion, making it challenging to generate electrical energy[3].Chemo-mechanical energy harvesters, a novel type of mechanical energy harvester, have been developed to generate electrical energy within ionic environments (i.e., immersed in electrolytes). These harvesters, which consist of working electrodes, counter electrodes, and electrolytes, provide electrical energy from changes in the electrochemical accessible area induced by mechanical energy. Coiled carbon nanotube (CNT) yarn harvesters, a type of chemo-mechanical energy harvester, were reported in 2017 as a promising approach for ocean-specific harvesters.[4] Coiled CNT yarns, a key elements for generating electrical energy, is fabricated from the highly twist insertion in the CNT sheets with large intrinsic electrochemical capacitance (IEC). This densification process provides the stretching-induced large changes in IEC in coiled CNT yarn, thus generating highest frequency-normalized peak power compared to other mechanical energy harvesters. However, the inevitably decreased IEC during densification hindered optimal harvesting performance in coiled CNT yarns.To address this issue, this study proposes a novel spinning method called longitudinally aligned (LAY) yarn-spinning to enhance IEC in coiled CNT yarns. Compared to the conventional coiled CNT yarn, our coiled CNT yarn named L-coiled CNT yarn provided a large IEC (5.6 F g−1) and large IEC variations (35%) during stretching to 80%. Using this novel structure in in coiled CNT yarn, our chemo- mechanical harvester delivered 2.6 times the open circuit voltage (OCV, 270 mV), 4 times the peak power (540 W kg − 1), and twice the efficiency (2.15%) of prior Twistron reported in 2017. The experimental structure analysis and computational analysis successfully supported our results. Especially, it is discovered that the enhanced IEC enables a decrease in matching impedance, resulting in more energy-efficient circuits with harvesters. For the practical use, L-coiled CNT yarn harvesters was investigated in an ocean-like environment with a frequency ranging from 0.1 to 1 Hz, it demonstrated the high volumetric power of 1.6 to10.45 mW cm−3. We believe presented approaches including the LAY spinning process, related electrical circuit integration, and lowering matching impedance could be a guidance for future studies.Reference[1] Jianlong Wang et al., "Enhancing Output Performance of Triboelectric Nanogenerator via Charge Clamping", Adv. Energy Mater. 2021, 11, 2001669.[2] Xiaomin Huang et al., "Piezoelectric Nanogenerator for Highly Sensitive and Synchronous Multi-Stimuli Sensing" ACS Nano. 2021, 15,19789-19792.[3] Minyi Xu et al., "High Power Density Tower-like Triboelectric Nanogenerator for Harvesting Arbitrary Directional Water Wave Energy", ACS Nano. 2019, 13,1932-1939.[4] S H Kim et al., "Harvesting electrical energy from carbon nanotube yarn twist" Science. 2017, 357, 773.

Designing the major active site of Cu atom for OER via a composite electrocatalyst of Agx@HEO: Experiment and theory

Copper element with low chemical activity is hard to be used as the major active site for oxygen evolution reaction (OER). To improve its OER performance, a specialized structural and chemical environments need be designed. In this work, the composite electrocatalyst of Agn@HEO were synthesized by a simple co-precipitation plus annealing methods. With the aid of the elemental Ag0 atom, part of Cu ions in high entropy oxide (HEO) phases were gradually transferred to the elemental Cu0 atoms and mixed with Ag0 atom for CuAg alloy. This transition evidently altered the chemical environments of Cu element. Thanks to the largest molar percentage of Cu0 atom, the designed Ag1@HEO specimen exhibited the fairly low experimental OER overpotential of 249 (308) mV at the current density of 10 (100) mA cm−2 with the small Tafel slope of 55.2 mV dec-1 and stable electrocatalytic activity. Based on the density functional theory simulation, the theoretical OER overpotential of Cu active site could be adjusted along with the ridges of “volcanic” in both atomic and ionic environments, and achieved the smallest value of 213 mV as the d band center of Cu0 atom had a suitable value near the “volcanic” peak. This design strategy would be adopted to provide an effective enhancement scheme for OER on Cu active site.

Controllable Solid Electrolyte Interphase by Ionic Environment Regulation for Stable Zn-Ion Battery.

Artificial solid electrolyte interphase in organic solutions is effective and facile for long-cycling aqueous zinc ion batteries. However, the specific effects on different ionic environments have not been thoroughly investigated. Herein, pyromellitic acid (PA) are employed as organic ligand to coordinate with Zn2+ under various ionic environments. The connection between the ionic environment and reaction spontaneity is analyzed to provide insights into the reasons behind the effectiveness of the SEI layer and to characterize its protective impact on the zinc anode. Notably, the PA solution (pH4) lacking OH- contributes to the formation of a dense and ultrathin SEI with Zn-PA coordination, preventing direct contact between the anode and electrolyte. Moreover, the presence of organic functional groups facilitates a uniform flux of Zn2+. These advantages enable stable cycling of the PA4-Zn symmetric cell at a current density of 3mA cm-2 for over 3500 h. The PA4-Zn//MVO full cell demonstrates excellent electrochemical reversibility. Investigating the influence of the ionic environment on SEI generation informs the development of novel SEI strategies.