Surface Water Molecules Research Articles

Modulation of the Chirality and Dynamics of Self-Assembled Nanocellulose-Chiral C-Dot Film for Chiral Sensing Applications.

The detection and sensing of chirality using chiral biomaterials are growing areas of research in advanced bioelectronics. As a result, chiral-controlled biomaterials are crucial for advancing current technologies in chiral sensing applications within biosystems. A chiral carbon dot (C-dot) modulated self-assembled emissive cellulose nanocrystal (CNC) film is developed where the chirality of the CNC film can be tempered between left-handed and right-handed chirality after being doped with chiral L/D-C-dots in CNCs (C-dot-CNC film), transferring the chirality from C-dots to CNCs. The interaction between C-dots, CNCs, and carrier dynamics is investigated using a variety of steady-state and time-resolved PL spectroscopy techniques. The chiral C-dot enhanced the protonic conductivity across the CNC via the formation of hydrogen bonds with its surface functional groups and water molecules. Further, the chiral CNC-C-dots photoelectrodes demonstrate an excellent ability to distinguish between left-handed and right-handed small molecules. These findings on the underlying mechanism of spin selectivity between chiral CNC-C-dot and chiral ligand hold promise for the development of efficient chiral-sensing electronic devices.

A theoretical simulation of carbon dioxide adsorption capture on amine-functionalized graphene oxides

Amine-functionalized graphene oxides (AFGOs) are potential candidates for CO2 capture applications, as the amine functional groups could act as effective sites, promoting CO2 adsorption strength and selectivity. However, the CO2 adsorption mechanism on AFGO appears to be ambiguous, particularly with no explicit identification of the chemically bonded species. In this work, density functional theory and microkinetic simulations were carried out to investigate the physical and chemical adsorption mechanisms and behavior between AFGO and CO2. Our findings indicate that the van der Waals and hydrogen bonding (HB) interactions constitute physical binding modes between the aminated GO and CO2. The chemical adsorption pathways on AFGO materials have been revealed by the transition state search method, in which the relevant CO2 adsorption species, including carbamic acid and carbamate, and their formation conditions were theoretically identified on AFGOs. The chemisorption mechanisms have been recognized to be the nucleophilic interaction between GO-supported amines and CO2, simultaneously assisted by the cooperative effect of multiple HB interactions. More specifically, the surface hydroxyl groups and water molecules can serve as proton transfer media and offer HB interactions, thus regulating the reaction activity and chemical adsorption species. This theoretical work presents a new insight into CO2-AFGO interaction mechanisms, which is valuable for designing aminated GO adsorbents.

Structural analysis of nano-water droplets: A molecular dynamics study

Molecular dynamics simulations were performed on water droplets containing fewer than 400 molecules, exploring both, bulk and surface regions. The droplet model was evaluated using two order parameters: tetrahedrality, as defined by Errington et al., and g5, as defined by Cuthbertson et al. Comparisons were made with bulk water. Our findings revealed negative tetrahedrality for surface water molecules. Additionally, the correlation between the distance from the droplet center and g₅ indicated a decrease in the surface density of the droplet.

Mechanical release of homogenous proteins from supramolecular gels

A long-standing challenge is how to formulate proteins and vaccines to retain function during storage and transport and to remove the burdens of cold-chain management. Any solution must be practical to use, with the protein being released or applied using clinically relevant triggers. Advanced biologic therapies are distributed cold, using substantial energy, limiting equitable distribution in low-resource countries and placing responsibility on the user for correct storage and handling. Cold-chain management is the best solution at present for protein transport but requires substantial infrastructure and energy. For example, in research laboratories, a single freezer at −80 °C consumes as much energy per day as a small household1. Of biological (protein or cell) therapies and all vaccines, 75% require cold-chain management; the cost of cold-chain management in clinical trials has increased by about 20% since 2015, reflecting this complexity. Bespoke formulations and excipients are now required, with trehalose2, sucrose or polymers3 widely used, which stabilize proteins by replacing surface water molecules and thereby make denaturation thermodynamically less likely; this has enabled both freeze-dried proteins and frozen proteins. For example, the human papilloma virus vaccine requires aluminium salt adjuvants to function, but these render it unstable against freeze–thaw4, leading to a very complex and expensive supply chain. Other ideas involve ensilication5 and chemical modification of proteins6. In short, protein stabilization is a challenge with no universal solution7,8. Here we designed a stiff hydrogel that stabilizes proteins against thermal denaturation even at 50 °C, and that can, unlike present technologies, deliver pure, excipient-free protein by mechanically releasing it from a syringe. Macromolecules can be loaded at up to 10 wt% without affecting the mechanism of release. This unique stabilization and excipient-free release synergy offers a practical, scalable and versatile solution to enable the low-cost, cold-chain-free and equitable delivery of therapies worldwide.

Spontaneous Wetting Induced by Contact-Electrification at Liquid-Solid Interface.

Wettability significantly influences various surface interactions and applications at the liquid-solid interface. However, the understanding is complicated by the intricate charge exchange occurring through contact electrification (CE) during this process. The understanding of the influence of triboelectric charge on wettability remains challenging, especially due to the complexities involved in concurrently measuring contact angles and interfacial electrical signals. Here, the relationship is investigated between surface charge density and change of contact angle of dielectric films after contact with water droplets. It is observed that the charge exchange when water spared lead to a spontaneous wetting phenomenon, which is termed as the contact electrification induced wetting (CEW). Notably, these results demonstrate a linear dependence between the change of contact angle (CA) of the materials and the density of surface charge on the solid surface. Continuous CEW tests show that not only the static CA but also the dynamics of wetting are influenced by the accumulation charges at the interface. The mechanism behind CEW involves the redistribution of surface charges on a solid surface and polar water molecules within liquid. This interaction results in a decrease in interface energy, leading to a reduction in the CA. Ab initio calculations suggest that the reduction in interface energy may stem from the enhanced surface charge on the substrate, which strengthens the hydrogen bond interaction between water and the substrate. These findings have the potential to advance the understanding of CE and wetting phenomena, with applications in energy harvesting, catalysis, and droplet manipulation at liquid-solid interfaces.

Boundary slip and lubrication mechanisms of organic friction modifiers with effect of surface moisture

Surface moisture or humidity impacting the lubrication property is a ubiquitous phenomenon in tribological systems, which is demonstrated by a combination of molecular dynamics (MD) simulation and experiment for the organic friction modifier (OFM)-containing lubricant. The stearic acid and poly-α-olefin 4cSt (PAO4) were chosen as the OFM and base oil molecules, respectively. The physical adsorption indicates that on the moist surface water molecules are preferentially adsorbed on friction surface, and even make OFM adsorption film thoroughly leave surface and mix with base oil. In shear process, the adsorption of water film and desorption OFM film are further enhanced, particularly under higher shear rate. The simulated friction coefficient (that is proportional to shear rate) increases firstly and then decreases with thickening water film, in good agreement with experiments, while the slip length shows a contrary change. The wear increases with humidity due to tribochemistry revealing the continuous formation and removal of Si-O-Si network. The tribological discrepancy of OFM-containing lubricant in dry and humid conditions is attributed to the slip plane’s transformation from the interface between OFM adsorption film and lubricant bulk to the interface between adsorbed water films. This work provides a new thought to understand the boundary lubrication and failure of lubricant in humid environments, likely water is not always harmful in oil lubrication systems.

Enhancing fire resistance in wood with high-water retention silica gel: A promising flame-retardant solution

This study aims to evaluate the water retention and flame-retardant properties of silica gel prepared using anionic polyacrylamide (HPAM), gluconate-delta-lactone (GDL), and aluminum citrate (AlCit). Silica gel samples were synthesized with sodium silicate (8 wt%), sodium bicarbonate (4 wt%) and varying concentrations of HPAM (0.2-0.8 wt%) and GDL (0.1-0.3 wt%). The prepared gels were characterized using XPS, XRD, FTIR, and TGA. Optimal water retention capacity was achieved with 0.4 wt% HPAM and 0.2 wt% GDL. Compared to traditional gels, silica gel has more surface water molecules due to additional hydrophilic groups and the amorphous nature of silica. At high temperatures, silica forms a layer with the charcoal from treated wood combustion, inhibiting oxygen penetration and minimizing further combustion. After combustion at 500?C, the mass loss of wood treated with silica gel is 36-53% less than untreated wood, indicating greater weight retention and demonstrating silica gel's effectiveness in preventing continued burning.

The absorption properties of ZrO2 nanoparticles in the THz and sub-THz frequency ranges.

As terahertz (THz) and sub-THz region electromagnetic waves are becoming vital for industrial applications such as 5G wireless communication, so too are THz and sub-THz wave absorbing materials. Herein, we report the optical properties of monoclinic zirconia (m-ZrO2) nanoparticles in these frequency regions, with different crystalline sizes. The crystalline sizes of the three samples, measured by transmission electron microscopy, are 93 ± 23 nm (denoted 1), 28 ± 14 nm (denoted 2) and 2.6 ± 0.7 nm (denoted 3). X-ray diffraction and Raman spectra show that 1 and 2 have high crystallinity whereas 3 shows peak broadening due to its small crystalline size. Terahertz time-domain spectroscopy (THz-TDS) measurements of pelletised samples show that the small crystalline size sample exhibits larger absorption, e.g., the absorbance value at 300 GHz is 0.18 mm-1 (1), 0.04 mm-1 (2) and 1.11 mm-1 (3), and the related dielectric loss value (ε'') is 0.04 (1), 0.01 (2) and 0.82 (3), respectively. This is considered to be due to the proportional increase in surface water molecules for the small particle size sample due to the relative increase in surface area and under-coordinated atoms, shown by IR spectra. These results show that small crystalline size m-ZrO2 nanoparticles have potential as THz and sub-THz wave absorbing materials, which are crucial for noise reduction in THz and sub-THz wave technologies.

Self-activated superhydrophilic green ZnIn2S4 realizing solar-driven overall water splitting: close-to-unity stability for a full daytime

Engineering an efficient semiconductor to sustainably produce green hydrogen via solar-driven water splitting is one of the cutting-edge strategies for carbon-neutral energy ecosystem. Herein, a superhydrophilic green hollow ZnIn2S4 (gZIS) was fabricated to realize unassisted photocatalytic overall water splitting. The hollow hierarchical framework benefits exposure of intrinsically active facets and activates inert basal planes. The superhydrophilic nature of gZIS promotes intense surface water molecule interactions. The presence of vacancies within gZIS facilitates photon energy utilization and charge transfer. Systematic theoretical computations signify the defect-induced charge redistribution of gZIS enhancing water activation and reducing surface kinetic barriers. Ultimately, the gZIS could drive photocatalytic pure water splitting by retaining close-to-unity stability for a full daytime reaction with performance comparable to other complex sulfide-based materials. This work reports a self-activated, single-component cocatalyst-free gZIS with great exploration value, potentially providing a state-of-the-art design and innovative aperture for efficient solar-driven hydrogen production to achieve carbon-neutrality.

Polaron-assisted nonadiabatic dynamics in protonated TiO2 with surface water molecule

Polaron-assisted nonadiabatic dynamics in protonated TiO2 with surface water molecule

Enhanced Triboelectric Charge Stability by Air-Stable Radicals.

This paper demonstrates that air-stable radicals enhance the stability of triboelectric charge on surfaces. While charge on surfaces is often undesirable (e.g., static discharge), improved charge retention can benefit specific applications such as air filtration. Here, it is shown that self-assembled monolayers (SAMs) containing air-stable radicals, 2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), hold the charge longer than those without TEMPO. Charging and retention are monitored by Kelvin Probe Force Microscopy (KPFM) as a function of time. Without the radicals on the surface, charge retention increases with the water contact angle (hydrophobicity), consistent with the understanding that surface water molecules can accelerate charge dissipation. Yet, the most prolonged charge retention is observed in surfaces treated with TEMPO, which are more hydrophilic than untreated control surfaces. The charge retention decreases with reducing radical density by etching the TEMPO-silane with tetrabutylammonium fluoride (TBAF) or scavenging the radicals with ascorbic acid. These results suggest a pathway toward increasing the lifetime of triboelectric charges, which may enhance air filtration, improvetribocharging for patterning charges on surfaces, or boost triboelectric energy harvesting.

Boosting CO2 electroreduction to formate via in-situ formation of ultrathin Bi nanosheets decorated with monodispersed Pd nanoparticles

A novel electrocatalyst for CO2-to-formate conversion at low overpotentials with abundant bimetallic interfaces aroused from Pd nanoparticles anchoring in the underlying Bi nanosheet (Pd-BiNS) was developed. This unique synthesis procedure undergoes a continuous reconstruction of Pd-BiOINS to Pd-Bi2O2CO3NS to Pd-BiNS, which was confirmed by in situ Raman spectra combined with quasi-in-situ electron microscopy. The optimized Pd1-BiNS exhibits a high Faradaic efficiency of 95 % for formate at only − 0.4 V versus reversible hydrogen electrode over 30 h electrolysis, breaking the limitation that metallic Pd-site is easily poisoned by the generated CO at low overpotentials. The in situ infrared spectroscopy indicates that Pd-BiNS has much suppressed *CO binding and enhanced *OCHO adsorption to inhibit the competing hydrogen evolution reaction by repelling surface water molecules, moreover, a systematic CO2RR mechanism with HCO3− participating as pre-proton donor for formate generation is unveiled. This work provides new insight into the multisite synergistic regulation at the atomic scale.

Mechanism, Kinetics, and Potential of Mean Force of Evaporation of Water from Aqueous Sodium Chloride Solutions of Varying Concentrations.

The mechanism, kinetics, and potential of mean force of evaporation of water from aqueous NaCl solutions are investigated through both unbiased molecular dynamics simulations and also biased simulations using the umbrella sampling method. The results are obtained for aqueous solutions of three different NaCl concentrations ranging from 0.6 to 6.0 m and also for pure water. The rate of evaporation is found to decrease in the presence of ions. It is found that the process of evaporation of a surface water molecule from ionic solutions can be triggered through its collision with another water or chloride ion. Such collisions provide the additional kinetic energy that is required for evaporation. However, when the collision takes place with a Cl- ion, the evaporation of the escaping water also involves a collision with water in the vicinity of the ion at the same time along with the ion-water collision. These two collisions together provide the required kinetic energy for escape of the evaporating water molecule. Thus, the mechanism of evaporation process of ionic solutions can be more complex than that of pure water. The potential of mean force (PMF) of evaporation is found to be positive and it increases with increasing ion concentration. Also, no barrier in the PMF is found to be present for the condensation of water from vapor phase to the surfaces of the solutions. A detailed analysis of the unsuccessful evaporation attempts by surface water molecules is also made in the current study.

Interfacial water molecules contribute to antibody binding to the receptor-binding domain of SARS-CoV-2 spike protein

Antibodies that recognize the spike protein of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), especially the neutralizing antibodies, carry great hope in the treatment and final elimination of COVID-19. Driven by a synchronized global effort, thousands of antibodies against the spike protein have been identified during the past two years, with the structural information available at atomistic detail for hundreds of these antibodies. We developed an improved molecular mechanics/Poisson–Boltzmann surface area (MM/PBSA) method including explicitly treated interfacial water to calculate the binding free energy between representative antibodies and the receptor binding domain (RBD) domain of SARS-COV-2 spike proteins. We discovered that explicit treatment of water molecules located at the interface between RBD and antibody effectively improves the results for the WT and variants of concern (VOC) systems. Interfacial water molecules, together with surface and internal water molecules, behave drastically from bulk water and exert peculiar impacts on protein dynamics and energy, and thus warrant explicit treatment to complement implicit solvent models. Our results illustrate the importance of including interfacial water molecules to approach efficient and reliable prediction of binding free energy. Communicated by Ramaswamy H. Sarma

Enhancement Mechanism of Minerals on Lignite-Water Molecule Interactions.

Five coal samples were prepared by deashing Shengli lignite in distinct phases, which consisted of residual ash from spontaneous combustion. The effects of removal and introduction of inherent minerals on the water reabsorption performance of coal samples were systematically investigated in three aspects: pore structure, oxygen-containing functional groups, and lignite materials. Low-field nuclear magnetic resonance spectroscopy was employed to investigate the changes in the water molecular adsorption tendency of coal samples with the variation in the mineral content. The study elucidates that the hygroscopic performance of the coal samples is significantly reduced due to the massive removal of inherent minerals. However, the pore structure of the coal samples after HCl/HF washing becomes more developed, and the oxygen-containing functional groups on the surface are more exposed, leading to an increase in the equilibrium adsorbed moisture content (EMC) of the coal samples. The binding force between coal samples and water molecules is reduced by the removal of the inherent minerals, which weakens the interaction forces between lignite and water molecules. The oxygen-containing functional groups on the surface of lignite interact with the residual ash from spontaneous combustion to enhance the binding force between lignite and surface water molecules, thus leading to the improved tendency of lignite to adsorb water molecules. The formation of intermediate complexes between minerals and oxygen-containing functional groups, in particular, carboxyl functional groups, on the surface of lignite enhances the acting force of polar sites, which improves the interaction of lignite-water molecules.

Exploration of a Large Virtual Chemical Space: Identification of Potent Inhibitors of Lactate Dehydrogenase-A against Pancreatic Cancer.

It is imperative to explore the gigantic available chemical space to identify new scaffolds for drug lead discovery. Identifying potent hits from virtual screening of large chemical databases is challenging and computationally demanding. Rather than the traditional two-dimensional (2D)/three-dimensional (3D) approaches on smaller chemical libraries of a few hundred thousand compounds, we screened a ZINC library of 15 million compounds using multiple computational methods. Here, we present the successful application of a virtual screening methodology that identifies several chemotypes as starting hits against lactate dehydrogenase-A (LDHA). From 29 compounds identified from virtual screening, 17 (58%) showed IC50 values < 63 μM, two showed single-digit micromolar inhibition, and the most potent hit compound had IC50 down to 117 nM. We enriched the database and employed an ensemble approach by combining 2D fingerprint similarity searches, pharmacophore modeling, molecular docking, and molecular dynamics. WaterMap calculations were carried out to explore the thermodynamics of surface water molecules and gain insights into the LDHA binding pocket. The present work has led to the discovery of two new chemical classes, including compounds with a succinic acid monoamide moiety or a hydroxy pyrimidinone ring system. Selected hits block lactate production in cells and inhibit pancreatic cancer cell lines with cytotoxicity IC50 down to 12.26 μM against MIAPaCa-2 cells and 14.64 μM against PANC-1, which, under normoxic conditions, is already comparable or more potent than most currently available known LDHA inhibitors.

Study on the surface wetting mechanism of bituminous coal based on the microscopic molecular structure.

The chemical wet dust removal method is one of the hot methods for coal dust control, and the key to its success lies in whether the surface of coal dust can be well wetted or not. Nowadays, the wetting mechanism of the coal dust surface is understudied, limiting the further application of chemical wet dust removal. Thus, the exploration of the wetting mechanism based on the microscopic molecular structure characteristics of the coal surface provides a new solution to improve the wet dust removal efficiency. Herein, the bituminous coal collected from 3 groups of coal seams in the Pingdingshan mining area was used as the object of study to reveal the microscopic wetting mechanism. Proximate analysis, nuclear magnetic resonance carbon spectroscopy (13C NMR) and X-ray photoelectron spectroscopy (XPS) can well distinguish the microstructural information of the coal surface, enabling building the molecular structure models of three groups of coal. Joint contact angle experiments were conducted to explore the influencing factors between the molecular structure of coal dust and its wettability. Molecular simulation techniques, combined with indoor experiments, were used to explore the essential causes of the differences in the wetting mechanisms of bituminous coal dust. The results showed that the composition and structure of carbon and oxygen elements on the coal surface has a significant effect on the wettability of coal dust. The higher the relative content of aromatic carbon and oxygen elements, the better the wettability of the coal surface. An opposite trend occurred for the aliphatic carbon. The difference in wettability of coal surfaces mainly stems from the ability of hydrophilic functional groups on coal surfaces to form hydrogen bonds with water molecules. The aromatic hydrocarbon structure has a much greater ability to adsorb water molecules than the aliphatic hydrocarbon structure. The research results can provide scientific guidance for the design of efficient and environmentally friendly dust suppressants to realize clean coal production in mines.

Adsorption of Y(III) on the Interface of Kaolinite-H2O: A DFT Study

Ion-adsorbed rare earth minerals have rare earth ions adsorbed on the surfaces of clay minerals such as kaolinite and have high contents of medium and heavy rare earth elements. They are important resources supporting the development of high-tech industries. In this study, the CASTEP module in Materials Studio was used to study the adsorption of the rare earth ion Y(III) on the interface of (Al-OH)-H2O and (Si-O)-H2O with density functional theory. The monitoring and calculation of the chemical bond of the adsorption structure showed that Y(III) on the (Al-OH)-H2O interface has a bond with O32, O34, and water molecules in the interface. In the (Si-O)-H2O interface, Y(III) interacts with O3, O4, and O10 to form new chemical bonds. The Mulliken population and density of states analysis showed that Y(III) bonds with surface oxygen atoms and water molecules in the kaolinite-H2O interface, and finally adsorbs on the surface of kaolinite in the form of metal ion hydrate.

Intense microwave heating at strongly polarized solid acid/water interface for energy-efficient platform chemical production

A strongly polarized solid/liquid interface is constructed to create a “micro-hydrothermal” environment under microwave and promote reaction energy efficiency. Specifically, TiO2 with open crystal structure was synthesized to maximize the density of surface-active centers and the degrees of interfacial polarization. Acidic groups were grafted on the catalyst surface, which served as catalytically active sites as well as heat-generation spots under microwave irradiation. Benefited by enhanced interfacial polarization, 10 times higher energy efficiency (6.8 mmol (kJ L)−1) than commercial TiO2 can be achieved in fructose dehydration reaction. MD simulation revealed that sulfonic group polarized surface water molecules and acted as “hot-spots” to accelerate fructose dehydration to HMF. Such alignment of site-specific heating and reaction by material design has great potential to shift the energy efficiency for a wide range of chemical reactions.

Pyrolytic aerogels with tunable surface groups for efficient methane solidification storage via gas hydrates

Gas hydrate, composed of water molecule cages, is promising for safe and sustainable gas storage with minor energy consumption. However, the practical utilization of hydrate-based technologies is hindered by the sluggish formation kinetics of gas hydrate. Central to the challenge of utilizing hydrate-based gas storage is developing effective promoters and improving the understanding of the complicated interplay between a promoter’s structure and chemical composition. Herein, we reported a simple and scalable strategy to produce pyrolytic composite aerogels assembled from vermiculite nanosheets and sodium alginate as efficient promoters for the methane hydrate formation. Benefiting from the high specific surface area and finely tuned surface functional groups, the as-made aerogels significantly improve methane hydrate formation kinetics with high storage capacity and excellent cycling stability. It is found that the phase change process of water to methane hydrate conversion can be controlled by adjusting the content of carbonyl and hydroxyl groups of the as-made aerogels. Raman spectra were used to elucidate the molecular mechanisms for the enhanced methane hydrate formation due to the interaction between oxygen-containing surface functional groups and water molecules close to used aerogels. This work not only provides an effective way to fabricate aerogel-based promoters for methane hydrate formation but also sheds light on the underlying mechanism of the surface composition dependent performance for improving gas hydrate formation.