Hydration Layer Research Articles

Iron Impurity Impairs the CO2 Capture Performance of MgO: Insights from Microscopy and Machine Learning Molecular Dynamics.

Magnesium oxide (MgO) is a promising sorbent for direct air capture (DAC) of carbon dioxide. Iron (Fe) is a common impurity in naturally occurring MgO and minerals used to produce MgO, yet a molecular-scale understanding of Fe-doping effects on carbonation is lacking. Here, we observed reduced carbonation performance in Fe-doped MgO experimentally. The energetics of adsorbing a (bi)carbonate ion on pristine and Fe-doped MgO(001) surfaces were further investigated using ab initio and machine learning potential molecular dynamics coupled with metadynamics simulations. Both pristine and Fe-doped surfaces exhibited a basic (OH-) hydration layer, where the (bi)carbonate ion adsorption is thermodynamically favorable. However, the dissolution of surface Fe had smaller energy barriers and was more favorable than Mg. Leached Fe likely neutralized the near-surface basicity, yielding reduced reactivity on Fe-doped MgO. Our observations offer critical insights for material selection and emphasize the importance of evaluating the geologic origin of earth materials used for DAC.

Hydration behavior of L-proline in the presence of mono, bis, tris-(2-hydroxyethyl) ammonium acetate protic ionic liquids: Thermophysical properties

The hydration behavior of amino acids, essential for biological macromolecules, is influenced by ammonium biomaterials. The protic ionic liquids (PILs) are gaining attention in the food and pharmaceutical industries due to their nontoxicity and adjustable properties. Thus, study of the amino acids, such as L-proline, in the presence of PILs is crucial for understanding their hydration behavior. In this work, the effect of PILs, including mono, bis, tris (2-hydroxyethyl)ammonium acetate protic ionic liquids that might be naturally produced in human body, on L-proline hydration behavior was studied using COSMO calculations and thermophysical measurements. Measurements were the density, speed of sound, viscosity, and refractive index data of the solutions (L-proline + PILs + water) at various PIL concentrations at temperatures (298.15 to 318.15) K and under atmospheric pressure. The study indicates L-proline has weaker interactions with water compared to PILs ([2-HEA][Ac], [bis-2-HEA][Ac], and [tris-2-HEA][Ac]) due to its compact structure and lower negative dielectric energy. PILs interact more strongly with water through hydrogen bonding. Increasing temperature affects L-proline’s hydration layer, releasing more water molecules compared to PIL solutions. This effect is more pronounced with [tris-2-HEA][Ac], likely due to its larger size and complex structure. While L-proline promotes an ordered water structure, PILs can disrupt this by rearranging water molecules and forming their own hydrogen bonds.

Effect of cement slurry filtrate on methane hydrate stability during deepwater cementing operations

Whether the hydrate layer is stabilized during deepwater cementing operations has a direct impact on the safety of the cementing process and the quality of the cementing. When the cement slurry enters the annular space and waits for solidification, it will be extruded to produce filtrate under the action of formation temperature and pressure. Moreover, the inorganic ions and organic matter contained in the filtrate may penetrate into the formation. However, whether these processes have an effect on the stability of the hydrate layer is not clear at present.In this paper, we initially developed a methane hydrate generation system, termed the water-quartz sand-methane system. This system efficiently produces methane hydrate within a short time and ensures a uniform distribution of the gas-solid phase, which is highly suitable for further research into methane hydrate stability. Subsequently, the primary constituents of the cement slurry filtrate and the principal functional groups of the cement additive were identified. Furthermore, enhancements were made to the existing formula for quantifying methane gas alteration. Additionally, a hydrate testing experimental system was employed to circulate a solution comprising the primary constituents of the cement slurry filtrate over the methane hydrate surface. Ultimately, utilizing the amount of change in the volume of methane gas in the cyclic process as a criterion to evaluate the impact of various components of the cement slurry filtrate on methane hydrate stability, an investigation into the effect of the cement slurry filtrate on methane hydrate stability was conducted. It was confirmed that Ca2+, Na+, Cl- ions within the cement slurry filtrate, along with the pH value, minimally influence methane hydrate stability. Conversely, the cement additive exhibits a discernible disruptive effect on methane hydrate stability, with the retarder demonstrating the most pronounced impact when mass fractions are equated.This study suggests that the adverse effects of amide and carboxyl groups on hydrate stability must be considered in the selection of additives for deepwater cementing slurries. The findings offer guidance for the research and development of additives for deepwater cementing slurries and establish a theoretical foundation for studying cementing slurry systems in hydrate formations.

Impact of pH-Dependent Dynamics of Human Serum Proteins on Dialysis Membranes: Cryptographic Structure Assessment, Synchrotron Imaging of Membrane-Protein Adsorption, and Molecular Docking Studies

Proteins are fundamental to biochemical processes and critical in hemodialysis. This study investigates the impact of pH on human serum albumin (HSA), fibrinogen (FB), and transferrin (TRF) interactions with polyarylethersulfone (PAES) hemodialysis membranes. A multi-method approach was utilized, including protein crystallography for structural insights, hydration layer analysis to explore solvation and interaction potentials, molecular docking using AutoDock 4.0 for binding affinity simulations, and in-situ X-ray synchrotron SR-μCT imaging to observe protein deposition dynamics.Molecular docking revealed that PAES demonstrated superior binding energies and interaction patterns with FB and TRF compared to cellulose triacetate (CTA), facilitated by specific hydrogen bonding within a water shell. CTA displayed weaker, hydration-sensitive interactions varying with pH. Imaging studies indicated that FB showed higher adsorption at pH 6 than at pH 7.2, predominantly in the middle membrane regions. Similarly, HSA and TRF exhibited increased adsorption at pH 6, suggesting a stronger affinity under acidic conditions. Mixed protein solutions also indicated higher adsorption at pH 6, emphasizing an increased risk of membrane fouling.These findings highlight the crucial role of pH in modulating protein-membrane interactions and enhancing the efficacy of hemodialysis. A deeper understanding of hydration environments and their effects on protein binding affinities provides valuable insights for optimizing membrane design and performance. Clinically, this research suggests that fine-tuning pH during hemodialysis could mitigate protein fouling on membranes, thereby improving procedural efficiency and potentially leading to better patient outcomes through enhanced dialysis effectiveness.

Evaluation and modeling of velocity dispersion and frequency-dependent attenuation in gas hydrate-bearing sediments

Wave velocity and attenuation of gas hydrate-bearing samples are often extrapolated from ultrasonic to lower seismic/sonic frequencies, but the impact of measurement frequency on these properties is rarely studied. This study evaluates velocity dispersion and frequency-dependent attenuation in gas hydrate-bearing sediments (GHBS) by comparing vertical seismic profile (VSP) and sonic logging data from the Nankai Trough and Mallik field. We also employ rock physics modeling to simulate the velocity dispersion and frequency-dependent attenuation at both sites. The results show strong velocity dispersion and frequency-dependent attenuation in the Nankai Trough, attributed to thin, low-saturation hydrate intervals. In contrast, the Mallik field exhibits weak dispersion and frequency dependence, likely due to thick, highly saturated hydrate layers. A compilation of global hydrate reservoir attenuations indicates frequency dependence, with a peak in the sonic logging range, likely due to pore-scale hydrate effects. These findings emphasize the necessity of considering the effect of measurement frequency when performing time-to-depth conversion for seismic data based on the sonic velocity at higher frequencies, particularly for thin and lowly saturated hydrate layers, thereby improving the accuracy of hydrate reservoir characterization.

A Core-Brush Nanoplatform with Enhanced Lubrication and Anti-Inflammatory Properties for Osteoarthritis Treatment.

Osteoarthritis (OA) is recognized as a highly friction-related joint disease primarily associated with increased joint friction and inflammation due to pro-inflammatory M1-type macrophage infiltration in the articular cavity. Therefore, strategies to simultaneously increase lubrication and relieve inflammation to remodel the damaged articular microenvironment are of great significance for enhancing its treatment. Herein, a multifunctional core-brush nanoplatform composed of a ROS-scavenging polydopamine-coated SiO2 core and lubrication-enhancing zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) brush and loaded with the anti-inflammatory drug curcumin by a reactive oxygen species (ROS)-liable conjugation (named as SiO2@PP-Cur) is rationally designed. Benefiting from the grafted zwitterionic PMPC brush, a tenacious hydration layer with enhanced lubricity for reducing joint abrasions is developed. More importantly, based on the mono-iodoacetic acid-induced arthritis (MIA) rat model, intra-articular injection of SiO2@PP-Cur nanoplatform can effectively alleviate articular inflammation via promoting macrophage polarization from the pro-inflammatory M1 to anti-inflammatory M2 state by activating the nuclear factor erythroid 2-related factor 2 (Nrf2) signaling pathway and attenuating the degradation of cartilage matrix, resulting in the remodeling of the damaged microenvironment into a pro-regenerative microenvironment. As a result, SiO2@PP-Cur can considerably inhibit OA progression. Therefore, the work may provide a novel strategy for the development of an advanced core-brush nanoplatform for enhanced OA therapy.

Ferroelectric ultrafiltration membrane with improved antifouling performance

Although membrane technologies for water purification have been widely applied over decades, membrane fouling remains an inherent challenge in the membrane filtration process. Improving the hydrophilicity or surface charge of the membrane is an effective approach to mitigate membrane fouling. Here, a ferroelectric composite ultrafiltration membrane was fabricated by incorporating dopamine modified BaTiO3 nanoparticles into poly(vinylidene fluoride) (PVDF) membranes and then charged by corona poling (p-BTO/PVDF). The water permeability of p-BTO/PVDF membrane (195.0 ± 10.5 L m-2 h−1 bar−1) was increased by 2.2 times compared to the pristine PVDF membrane. The enhanced hydrophilicity and surface potential based on ferroelectric charges promoted the formation of the hydration layer on the membrane surface and increased the electrostatic repulsion against the pollutants, thus decreasing the filtration resistance and enhancing the antifouling performance of the membrane. The water recovery efficiency of the ferroelectric membrane reached 98.2 %. Furthermore, the ferroelectric membrane showed excellent antifouling stability. This work proposes an effective and environmentally friendly strategy for using ferroelectric polarization to regulate membrane anti-fouling.

A molecular view of peptoid-induced acceleration of calcite growth

The extensive deposits of calcium carbonate (CaCO3) generated by marine organisms constitute the largest and oldest carbon dioxide (CO2) reservoir. These organisms utilize macromolecules like peptides and proteins to facilitate the nucleation and growth of carbonate minerals, serving as an effective method for CO2 sequestration. However, the precise mechanisms behind this process remain elusive. In this study, we report the use of sequence-defined peptoids, a class of peptidomimetics, to achieve the accelerated calcite step growth kinetics with the molecular level mechanistic understanding. By designing peptoids with hydrophilic and hydrophobic blocks, we systematically investigated the acceleration in step growth rate of calcite crystals using in situ atomic force microscopy (AFM), varying peptoid sequences and concentrations, CaCO3 supersaturations, and the ratio of Ca2+/ HCO3-. Mechanistic studies using NMR, three-dimensional fast force mapping (3D FFM), and isothermal titration calorimetry (ITC) were conducted to reveal the interactions of peptoids with Ca2+ and HCO3- ions in solution, as well as the effect of peptoids on solvation and energetics of calcite crystal surface. Our results indicate the multiple roles of peptoid in facilitating HCO3- deprotonation, Ca2+ desolvation, and the disruption of interfacial hydration layers of the calcite surface, which collectively contribute to a peptoid-induced acceleration of calcite growth. These findings provide guidelines for future design of sequence-specific biomimetic polymers as crystallization promoters, offering potential applications in environmental remediation (such as CO2 sequestration), biomedical engineering, and energy storage where fast crystallization is preferred.

Response of Foldable Protein Conformations to Non-Physiological Perturbations: Interplay of Thermal Factors and Confinement.

Technological advances frequently interface biomolecules with nanomaterials at non-physiological conditions, necessitating response characterization of key processes. Similar encounters are expected in cellular contexts. We report in silico investigations of the response of diverse protein conformational states to lowering of temperature and imposition of spatial constraints. Conformational states are represented by folded form of the Albumin binding domain (ABD) protein, its compact denatured form, and structurally disordered nascent folding elements. Data from extensive simulations are evaluated to elicit structural, thermodynamic and dynamic responses of the states and their associated environment. Analyses reveal alterations to folding propensity with reduced thermal energy and confinement, with signatures of trend reversal in highly disordered states. Across temperatures, confinement has restrictive effects on volume and energetic fluctuations, leading to narrowing of differences in isothermal compressibility (κ) and heat capacities (Cp). While excess (over ideal gas) entropy of the hydration layer marks dependence on the conformational state at bulk, confinement triggers erasure of differences. These observations are largely consistent with timescales of protein-water hydrogen bonding dynamics. The results implicate multi-factorial associations within a simple bio-nano complex. We expect the current study to motivate investigations of more biologically relevant interfaces towards mechanistic understanding and potential applications.

Unraveling the adsorption dynamics of asphaltene molecules on silica surfaces

Understanding the adsorption behavior of heavy oil components on reservoir solids is crucial for improving oil recovery, yet the molecular mechanism remains unclear. This study used molecular dynamics simulations to explore the adsorption kinetics and thermodynamics of asphaltene molecules on silica surfaces. The adsorption process was divided into three stages: free, adsorption, and equilibrium. In the adsorption stage, asphaltenes must pass through two dense hydration layers and adhere to the silica surface in a flat configuration. Carboxyl groups increase asphaltene hydrophilicity, raising interaction energy with water molecules and hindering adsorption. In addition, two distinct hydration layers of water molecules on the silica surface. The first hydration layer, with a peak density of 2000 kg m−3, was located around 0.6 nm from the surface, driven by hydrogen bonding between Si-OH groups and water molecules. The second layer, found at 1.44–1.80 nm, had a lower density of 1200 kg m−3, formed through hydrogen bonding between water molecules. This study aims to enhance the understanding of the physicochemical mechanisms governing oil droplet adsorption on silica surfaces, potentially informing the design of improved oil recovery strategies.

Zwitterionic Polymers for Biomedical Applications: Antimicrobial and Antifouling Strategies toward Implantable Medical Devices and Drug Delivery.

Poly(ethylene glycol) (PEG) is extensively utilized in biomedical applications due to its biocompatibility; however, its thermal instability and susceptibility to oxidative degradation significantly constrain its long-term effectiveness. Zwitterionic polymers, characterized by their distinctive structure, enhanced stability, and superior biocompatibility, offer a more advantageous alternative. These polymers exhibit super hydrophilicity, resist nonspecific protein adsorption, and maintain stability in biological environments due to their charge-neutral ionic nature. Zwitterionic polymers enhance anticancer drug delivery by precisely targeting tumor cells and facilitating an efficient drug release. Their inherent antifouling properties and prolonged circulation within the bloodstream render them highly suitable for redox-sensitive drug carriers, thereby augmenting the antitumor efficacy. Moreover, zwitterionic polymers markedly mitigate biofouling in implants, biosensors, and wound dressings, thereby improving both their functionality and their therapeutic outcomes. These advantages arise from the formation of robust hydration layers, which significantly enhance the hemocompatibility and inhibit the adhesion of proteins, platelets, and bacteria. Zwitterionic polymers, including sulfobetaine (SB), phosphorylcholine (PC), and carboxybetaine (CB), are increasingly employed in blood-contacting devices and as effective coating materials for implantable devices. This mini-review paper aims to explore the recent diverse biomedical applications of zwitterionic polymers and highlight their advantageous properties compared with unmodified polymers. We will cover their use in drug delivery systems, tumor targeting nanocarriers, antibiofouling and antibacterial activities in implantable devices, tissue engineering, and diagnostic devices, demonstrating how their unique properties can translate into different applications. Through this exploration, this Perspective will display the potential of zwitterionic polymers as innovative polymer materials in the field of biomedical engineering and beyond.

2D Titanium Carbide MXene and Single-Molecule Fluorescence: Distance-Dependent Nonradiative Energy Transfer and Leaflet-Resolved Dye Sensing in Lipid Bilayers.

Despite their growing popularity, many fundamental properties and applications of MXene materials remain underexplored. Here, the nonradiative energy transfer properties of 2D titanium carbide MXene are investigatedand their application in single-molecule biosensing is explored for the first time. DNA origami positioners are used for single dye placement immobilized by a specific chemistry based on glycine-MXene interactions, allowing precise control of their orientation on the surface. Each DNA origami structure carries a single dye molecule at predetermined heights. Single-molecule fluorescence confocal microscopy reveals that energy transfer of an organic emitter (ATTO 542) on transparent thin films made of spincast Ti3C2Tx flakes follows a cubic distance dependence, where 50% of energy transfer efficiency is reached at 2.7nm (d0). MXenes are applied as short-distance spectroscopic nanorulers, determining z distances of dye-labeled supported lipid bilayers fused on MXene's hydrophilic surface. Hydration layer (2.1nm) and lipid bilayer thickness (4.5nm) values that agree with the literature are obtained. These results highlight titanium carbide MXenes as promising substrates for single-molecule biosensing of ultrathin assemblies, owing to their sensitivity near the interface, a distance regime that is typically inaccessible to other energy transfer tools.

Zwitterionic Nanochannels in Covalent Organic Framework Membranes for Improved Flux and Antifouling Property.

Zwitterionic membranes demonstrate excellent antifouling property in water purification. The covalent organic frameworks (COFs), due to the ordered channels and abundant organic functional groups, have distinct superiority in constructing zwitterionic surfaces.Here, the zwitterionic COF membrane is prepared with precise framework structures and uniform charge distribution. The negatively charged 4,4'-diaminobiphenyl-2,2'-sisulphonic acid sodium (SA) and positively charged ethidium bromide (EB) fragments are used to react with 1,3,5-triformylphloroglucinol (TP) at the gas-liquid interface to prepare zwitterionic COF membrane. The complementary charged fragments in the inter-layer and inner-layer facilitate the formation of continuous and tight hydration layer on the membrane surface and pore walls to resist the adsorption of pollutants. The zwitterionic COF membrane effectively resists both negatively charged bovine serum albumin and positively charged lysozyme pollutants with flux recovery ratio (FRR) of 97% and 85%, respectively. Furthermore, the regular nano-channels and balanced interactions between water and surface/pore walls of the zwitterionic membrane result in outstanding permeability of up to 146 L m-2 h-1 bar-1 and excellent dye/salt separation selectivity. The water permeation and antifouling mechanism of membranes are elucidated by experimental and molecular dynamics calculation. Zwitterionic COF membranes can find promising applications in preparing high-performance antifouling membranes.

Phase behavior and synergistic gelation of scallop (Patinopecten yessoensis) male gonad hydrolysates and gellan gum driven by pH.

Previous studies have investigated complexation and coacervation of scallop Patinopecten yessoensis male gonad hydrolysates (SMGHs) and polysaccharides influenced by pH and blending ratio. It has been found that SMGHs/polysaccharide composite shows better gel properties under strongly acidic conditions. Thus, the complexation and coacervation of SMGHs and gellan gum (GG) were investigated via turbidimetric titration at different pH values (1-12) and biopolymer blending ratios (9.5:0.5-6:4). Both pHc and pHφ1 exhibited ratio-independent behavior with constant values at approximately pH 5.8 and pH 3.8, respectively, dividing SMGHs/GG blends into three phases named mixed polymers, soluble complexes and insoluble coacervates, respectively. Overall, SMGHs and GG exhibited synergistic gelation under neutral and acidic conditions, with the initial storage modulus (G') increasing by approximately 42.5-, 573.7- and 3421-fold and 97.7-, 550.3- and 0.5-fold, respectively, at pH 7, 5 and 3, compared with SMGHs and GG. As pH decreased from 7 to 3, the initial G' and viscosity η values of SMGHs/GG gels increased by 20.1- and 2.3-fold, respectively, exhibiting the greatest increase in gel strength. Moreover, the free water in the SMGHs/GG system significantly shifted toward lower relaxation times attributed to the immobilization of the outer hydration layers. SMGHs/GG gels in the insoluble phase exhibited denser networks and rougher surfaces, supporting the enhanced rheological properties and water retention capacity of the gel. This work provides a basic foundation for the development of pH-driven SMGHs/GG gelation by examining complexation and coacervation processes. © 2024 Society of Chemical Industry.

Dynamic permittivity of confined water under a static background field.

Molecular and collective reorientations in interfacial water are by-and-large decelerated near surfaces subjected to outgoing electric fields (pointing from surface to liquid, i.e., when the surface carries positive charge). In incoming fields at negatively charged surfaces, these rates show a nonmonotonic dependence on field strength where fastest reorientations are observed when the field alignment barely offsets the polarizing effects due to interfacial hydrogen bonding. This extremum coincides with a peak of local static permittivity. We use molecular dynamics simulations to explore the impact of background static field on high frequency AC permittivity in hydration water under an electric field mimicking the conditions inside a capacitor where one of the confinement walls is subject to an outgoing field and the other one to an incoming field. At strong static fields, the absorption peak undergoes a monotonic blue shift upon increasing field strength in both hydration layers. At intermediate fields, however, the hydration region at the wall under an incoming field (the negative capacitor plate) features a red shift coinciding with maximal static-permittivity and reorientation-rate. The shift is mostly determined by the variation of the inverse static dielectric constant as proposed for mono-exponentially decaying polarization correlations. Conversely, hydration water at the opposite (positively charged) surface features a monotonic blue shift consistent with conventional saturation. The sensitivity of absorption peaks on the field suggests that surface charge densities could be deduced from sub-THz dielectric spectroscopy experiments in porous materials when interfaces accommodate a major fraction of water contained in the system.

Insights into the Hydration Layer of Reduced Graphene Oxides: A Computational Stud.

Reduced graphene oxide (rGO) has emerged as a versatile material with diverse applications, particularly in aqueous environments. Understanding its interactions with water molecules is crucial for various fields, ranging from energy storage to sensing. In this study, we investigate the behavior of graphene and rGO in water, focusing on elucidating their wetting properties and the influence of oxygen-containing functional groups. Through extensive molecular dynamics simulations, we analyze the orientation and electrostatic dipole of water molecules near the rGO interface, revealing a direct correlation between rGO hydrophilicity and oxidation level. Specifically, we observe stronger hydrogen bonding networks near higher coverage rGO monolayers, indicating enhanced hydrophilicity. Furthermore, by studying water confined between rGO layers, we find uniform water transport with lateral self-diffusion coefficients comparable to bulk water, highlighting the potential of rGO membranes in various applications. Our findings provide insights into the atomic-scale interactions governing rGO-water interfaces, paving the way for the rational design of graphene-based materials for application in aqueous environments.

PH‐sensitive size/surface charge‐adaptive quaternary ammonium salt copolymer micelles for antibiofilm activity against Staphylococcus aureus

AbstractThe low penetration of antibacterial materials within biofilms results in a 1000‐fold decrease in bactericidal efficiency, complicating the complete removal of biofilms and potentially leading to persistent and recurrent bacterial infections that significantly impact human health. In this study, we present a multifunctional pH‐responsive antibacterial material based on random copolymers poly(dimethylaminoethyl methacrylate decyl ammonium bromide‐co‐polyethylene glycol methacrylate) copolymer (PQACs10‐co‐PEGMA10). The PQACs10‐co‐PEGMA10 copolymers could self‐assemble into micelles in selective solvent water. With the stealth function of polyethylene glycol (PEG), the PQACs10‐co‐PEGMA10 micelles can rapidly penetrate biofilms in a physiological environment and exhibit excellent antibacterial activity by exposing the quaternary ammonium salt (QACs) in an acidic microenvironment to eliminate biofilm. Furthermore, PQACs10‐co‐PEGMA10 micelles were applied as coatings using a dropwise method. The PEG chain formed hydration layer and the QACs chain for sterilization can hinders bacterial adhesion and proliferation, thereby preventing biofilm formation. The results show that the minimal inhibit concentration values and minimum biofilm eradication concentrations of the PQACs10‐co‐PEGMA10 micelles against Gram‐positive Staphylococcus aureus were 64 and 128 μg/mL, respectively. The antifouling and antibacterial rates of micelle coating against S. aureus were more than 99.99%. Taken together, the pH‐responsive PQACs10‐co‐PEGMA10 micelles demonstrate a good ability to clear and prevent biofilms, holding promise for complete biofilm removal and a reduction in biofilm‐related infections.

Complementary and competitive dynamics of CO2 and N2 in CH4 – Flue gas replacement within natural gas hydrates

To mitigate global warming, the paramount imperative lies in curbing the emission of CO2. The guest replacement method is a prominent carbon-neutral technological advancement that involves injecting CO2 into natural gas hydrate layers to accomplish the dual objectives of energy production and carbon storage. In this study, the guest dynamics in the CH4 – flue gas replacement process were examined, and the impacts of the N2 concentration of the injected gas were systematically analyzed. A powder X-ray diffraction analysis of the cage-specific guest distributions after CH4 − CO2 (20 %) + N2 (80 %) replacement revealed that CH4 production increased in both the large and small cages compared to the CH4 – CO2 replacement. This enhancement was attributed to the N2 molecules participating in both cages. However, this simultaneously led to a decrease in CO2 storage potential, indicating a ‘complementary’ relationship for CH4 production and a ‘competitive’ one for CO2 storage with respect to CO2 and N2. In situ Raman spectroscopy revealed that the introduction of N2 resulted in a deceleration of CO2 storage kinetics. Guest composition measurements after replacement showed an upward trend in CH4 production and a simultaneous decline in CO2 storage as the N2 composition increased. Notably, an intriguing correlation was established between the CO2/N2 ratios for the injected gas and the replaced hydrates, exhibiting a strong alignment with a simple first-order equation. The findings not only contribute to a deeper understanding of the CH4 − CO2 + N2 replacement technique but provide practical insights for its application in real-world scenarios.

Anisotropic Redox on Pristine Graphene

AbstractChemically modified graphene is an attractive electrode material for electrocatalysis, energy devices, and sensors, whereas pristine graphene is electrochemically passive. The remarkable anisotropic electrochemical nature of graphene is uncovered by π–π interaction, making pristine graphene more active than bare Au. The π–π stacking during redox reaction “dopes” the graphene, disrupting the passivating hydration layer, making it a facile electrochemical electrode. The structure during π–π stacking‐mediated redox of methylene blue (MB) is quantitatively measured by the differential reflectivity of a polarized laser on a ≈100 micron spot. The local redox reaction current varies over fourfold due to the orientation of the ≈10 micron size grains. The mosaic‐grain anisotropy on each spot shows local uniaxial orientation. The redox signal at the optimum orientation is over 2.5‐fold greater than that for bare Au on the same electrode. The redox signal is over fivefold greater at the edges of graphene compared bare Au. Remarkably, the π–π interaction increases chemical stability significantly, leading to negligible photo‐degradation at the approximate absorption wavelength of MB. The exclusive redox activity due to π–π interaction on pristine graphene adds to the toolbox of making exotic opto‐electrochemical electrode materials for electrocatalysis, sensing, and electronics.

Biomimetic joints inspired soft and hard combined 2D diamond solvent-free nanofluids with multi-layer structure for superior lubrication

The articulating joints consist of a three-layer lubricating structure, which combines soft and hard materials, including cartilage, polymer brushes, and a hydration layer. This structure leverages the synergistic effects of fluid and boundary lubrication to maintain ultra-low friction under different pressures on the same frictional surface. In this study, a biomimetic multilayer lubricating structure inspired by joint tissues is constructed using single-crystalline diamond nanosheets (SCND) as the hard phase material. Through a facile chemical reduction method and employing polydopamine (PDA) as a "bridge", a soft phase material is deposited onto the SCND surface to produce diamond composite silver nanocomposites (SCND@PDA@Ag). Subsequently, two solvent-free SCND@PDA@Ag nanofluids are prepared by grafting organic canopy substances onto the SCND@PDA@Ag surface via ionic bonds or covalent bonds, referred to as SCND@PDA@Ag-ionic bonding nanofluid and SCND@PDA@Ag-covalent bonding nanofluid, respectively. The findings reveal that the SCND@PDA@Ag-covalent bonding solvent-free nanofluid exhibits superior lubricating performance for steel/SiC contacts. The friction coefficient and wear rate for steel/SiC are significantly reduced by 93.2 % and 63.1 %, respectively, compared to dry friction, it's noteworthy that these results outperform those achieved by individual components of the lubricant. During the friction process, SCND and silver particles on the surface of SCND@PDA@Ag-covalent bonding solvent-free nanofluid work together to enhance lubrication synergistically. Furthermore, silver particles on the surface of SCND are released and fill into the worn surface, providing a repairing effect. This study highlights that the design of soft-hard multilayer structures offers a novel approach for researching nanocomposite materials in the field of tribology.