Water Molecules Research Articles

Hydrogel Based UV Photodetector Based on Polarization of Free Water Molecules

AbstractConductive hydrogels retain the intrinsic softness and elasticity that are hallmark features of traditional hydrogels, and they also assimilate the electrical properties of the embedded conductive materials. Conventional epitaxial growth techniques for heterojunctions require precise lattice matching between adjacent materials, significantly limiting technological advancements in photodetector innovation. The integration of conductive hydrogels with semiconductors to fabricate photodetectors presents a feasible solution that bypasses the traditional lattice matching constraints inherent in the epitaxial growth of heterojunction semiconductor photodetectors. Herein, device integration is enhanced by developing a transparent conductive hydrogel, positioned between graphene and gallium nitride, which effectively mitigates the fluidity issues of the polar liquid complicating device encapsulation. A comprehensive analysis of the photodetection characteristics of the graphene/conductive hydrogel/gallium nitride heterostructure is conducted, thereby establishing its structural framework. Flexible transparent devices are further prepared based on PEDOT/Alg (Ca2+) and demonstrate their potential application in 360° omnidirectional photodetection. This work introduces a novel approach for the enhanced integration of hydrogel‐based spectrally selective and flexible transparent photodetectors.

Terahertz Radiation from Water Molecules Rotated by Femtosecond Laser Field

Terahertz Radiation from Water Molecules Rotated by Femtosecond Laser Field

Quantifying the influence of lipophilic carbon chain length on adhesion between emulsified asphalt and acidic aggregates

ABSTRACT Emulsified asphalt technology conserves resources and reduces costs while aligning with the principles of low-carbon and high-quality development. Acidic aggregates demonstrate excellent mechanical properties and are suitable alternatives to alkaline aggregates. This study develops molecular dynamics models and macroscopic experiments to quantify the influence of carbon chain length on the adhesion between emulsified asphalt and acidic aggregate interfaces from a molecular perspective. The results revealed that aromatics and saturates exhibit high sensitivity to variations in carbon chain length. Their adsorption on the SiO2 interface is directly proportional to the carbon chain length. The diffusion coefficient and adhesion parallelly show an initial increase followed by a decrease with the same factors. The van der Waals forces contributed to more than 67% of the adhesion. Water molecules establish hydrogen bonds with the hydroxyl groups on the SiO2 interface, thereby decreasing the adhesion between the emulsified asphalt and the SiO2 interface. The strong hydrogen bonds between free water and asphalt hinder the accumulation of asphalt at the SiO2 interface. In summary, regulating the emulsifier through the carbon chain length and chloride ions enhances the adhesion between the emulsified asphalt and acidic aggregate interface.

An Overview on the Adhesion Mechanisms of Typical Aquatic Organisms and the Applications of Biomimetic Adhesives in Aquatic Environments.

Water molecules pose a significant obstacle to conventional adhesive materials. Nevertheless, some marine organisms can secrete bioadhesives with remarkable adhesion properties. For instance, mussels resist sea waves using byssal threads, sandcastle worms secrete sandcastle glue to construct shelters, and barnacles adhere to various surfaces using their barnacle cement. This work initially elucidates the process of underwater adhesion and the microstructure of bioadhesives in these three exemplary marine organisms. The formation of bioadhesive microstructures is intimately related to the aquatic environment. Subsequently, the adhesion mechanisms employed by mussel byssal threads, sandcastle glue, and barnacle cement are demonstrated at the molecular level. The comprehension of adhesion mechanisms has promoted various biomimetic adhesive systems: DOPA-based biomimetic adhesives inspired by the chemical composition of mussel byssal proteins; polyelectrolyte hydrogels enlightened by sandcastle glue and phase transitions; and novel biomimetic adhesives derived from the multiple interactions and nanofiber-like structures within barnacle cement. Underwater biomimetic adhesion continues to encounter multifaceted challenges despite notable advancements. Hence, this work examines the current challenges confronting underwater biomimetic adhesion in the last part, which provides novel perspectives and directions for future research.

Suitable Stereoscopic Configuration of Electrolyte Additive Enabling Highly Reversible and High-Rate Zn Anodes.

Electrolyte additive engineering is a crucial method for enhancing the performance of aqueous zinc-ion batteries (AZIBs). Recently, most research predominantly focuses on the role of functional groups in regulating electrolytes, often overlooking the impact of molecule stereoscopic configuration. Herein, two isomeric sugar alcohols, mannitol and sorbitol, are employed as electrolyte additives to investigate the impact of the stereoscopic configuration of additives on the ZnSO4 electrolyte. Experimental analysis and theoretical calculations reveal that the primary factor for improving Zn anode performance is the regulation of the solvation sheath by these additives. Among the isomers, mannitol exhibits stronger binding energies with Zn2+ ions and water molecules due to its more suitable stereoscopic configuration. These enhanced bindings allow mannitol to coordinate with Zn2+, contributing to solvation structure formation and reducing the active H2O molecules in the bulk electrolyte, resulting in suppressed parasitic reactions and inhibited dendritic growth. As a result, the zinc electrodes in mannitol-modified electrolyte exhibit excellent cycling stability of 1600 h at 1 mA cm-2 and 900 h at 10 mA cm-2, respectively. Hence, this study provides novel insights into the importance of suitable stereoscopic molecule configurations in the design of electrolyte additives for highly reversible and high-rate Zn anodes.

Toward a numerically efficient description of bulk-solvated anionic states.

We investigate the vertical electron attachment energy (VAE) of 1-methyl-4-nitroimidazole, a model radiosensitizer, employing quantum mechanics/molecular mechanics (QM/MM) and QM/polarized continuum (QM/PCM) solvation models. We considered the solvent-excluded surface (QM/PCM-SES) and Van der Waals (QM/PCM-VDW) cavities within the PCM framework, the electrostatic embedding QM/MM (EE-QM/MM) model, and the self-consistent sequential QM/MM polarizable electrostatic embedding (scPEE-S-QM/MM) model. Due to slow VAE convergence concerning the number of QM solvent molecules, full QM calculations prove inefficient. Ensemble averages in these calculations do not align with VAEs computed for the representative solute-solvent configuration. QM/MM and QM/PCM calculations show agreement with each other for sufficiently large QM regions, although the QM/PCM-VDW model exhibits artifacts linked to the cavity. QM/MM models demonstrate good agreement between ensemble averages and VAEs calculated with the representative configuration. Notably, the VAE computed with the scPEE-S-QM/MM model achieves faster convergence concerning the number of QM water molecules compared to the EE-QM/MM model, attributed to enhanced efficiency from MM charge polarization in the scPEE-S-QM/MM approach. This emphasizes the importance of QM/classical models with accurate solute-solvent and solvent-solvent mutual polarization for obtaining converged VAEs at a reasonable computational cost. The full-QM approach is very inefficient, while the microsolvation model is inaccurate. Computational savings in QM/MM models result from electrostatic embedding and the representative configuration, with the scPEE-S-QM/MM approach emerging as an efficient tool for describing bulk-solvated anions within the QM/MM framework. Its potential extends to improving transient anion state descriptions in biomolecules and radiosensitizers, especially given the frequent employment of microsolvation models.

PyDFT-QMMM: A modular, extensible software framework for DFT-based QM/MM molecular dynamics.

PyDFT-QMMM is a Python-based package for performing hybrid quantum mechanics/molecular mechanics (QM/MM) simulations at the density functional level of theory. The program is designed to treat short-range and long-range interactions through user-specified combinations of electrostatic and mechanical embedding procedures within periodic simulation domains, providing necessary interfaces to external quantum chemistry and molecular dynamics software. To enable direct embedding of long-range electrostatics in periodic systems, we have derived and implemented force terms for our previously described QM/MM/PME approach [Pederson and McDaniel, J. Chem. Phys. 156, 174105 (2022)]. Communication with external software packages Psi4 and OpenMM is facilitated through Python application programming interfaces (APIs). The core library contains basic utilities for running QM/MM molecular dynamics simulations, and plug-in entry-points are provided for users to implement custom energy/force calculation and integration routines, within an extensible architecture. The user interacts with PyDFT-QMMM primarily through its Python API, allowing for complex workflow development with Python scripting, for example, interfacing with PLUMED for free energy simulations. We provide benchmarks of forces and energy conservation for the QM/MM/PME and alternative QM/MM electrostatic embedding approaches. We further demonstrate a simple example use case for water solute in a water solvent system, for which radial distribution functions are computed from 100ps QM/MM simulations; in this example, we highlight how the solvation structure is sensitive to different basis-set choices due to under- or over-polarization of the QM water molecule's electron density.

Zn, Cd and Cu Coordination Polymers for Metronidazole Sensing and for Ullmann and Chan-Lam Coupling Reactions.

Five compounds, [Zn(bpe)1/2(BPTA)H2O]·H2O (1); [Zn(bpe)(BPTA)] (2); [Cd(bpe)(BPTA)H2O] (3); [Cd(BPTA)(bpmh)]·2H2O (4); and Cu(BPTA)(bpmh)1.5(H2O)]·H2O (5) were prepared employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2, 5 BPTA) as the primary ligand and 1,2-di(pyridin-4-yl)ethane (4, 4' bpe) (1-3) and 1,2-bis(pyridin-3-ylmethylene)hydrazine (bpmh) (4-5) as the secondary ligands. Single crystal studies indicated that the compounds 1, 3 and 5 have two-dimensional layer structures and compounds 2 and 4 three-dimensional structures. The luminescence behaviour of the compounds 2 and 3 were explored for the sensing of metronidazoleboth in aqueouos solution as well as simple paper strips. The Cu compound 5 loses the coordinated water molecule at 100 °C without any structural change, which was examined towards the Lewis acidic character by carrying out the Ullmann type C-C homocoupling reaction of the aromatic halide compounds. The compounds, 4 and 5, also have the Lewis basic functionality arising out the =N-N=, aza groups. The bifunctional nature of the MOF was explored towards the Chan-Lam coupling reaction between phenyl boronic acid and aniline derivatives in the ethanol medium. In both the catalytic reactions, good yields and recyclability were observed. The present studies illustrated the rich diversity that the transition metal containing compounds exhibit in extended framework structures.

Enhancing the Amination Activity of meso-Diaminopimelate Dehydrogenase from Symbiobacterium thermophilum by Modifying the Crucial Residue His154 for Deamination

During the deamination and amination processes of meso-diaminopimelate dehydrogenase (meso-DAPDH) from Symbiobacterium thermophilum (StDAPDH), residue R71 was observed to display distinct functions. H154 has been proposed as a basic residue that facilitates water molecules to attack the D-chiral carbon of meso-DAP during deamination. Inspired by the phenomenon of R71, the effects of H154 during deamination and amination were investigated in this study with the goal of enhancing the amination activities of StDAPDH. Single site saturation mutagenesis indicated that almost all of the H154 mutants completely lost their deamination activity towards meso-DAP. However, some H154 variants showed enhanced kcat/Km values towards pyruvic acid and other bulky 2-keto acids, such as 2-oxovaleric acid, 4-methyl-2-oxopentanoic acid, 2-ketobutyric acid, and 3-methyl-2-oxobutanoic acid. When combined with the previously reported W121L/H227I mutant, triple mutants with significantly improved kcat/Km values (2.4-, 2.5-, 2.5-, and 4.0-fold) towards these 2-keto acids were obtained. Despite previous attempts, mutations at the H154 site did not yield the desired results. Moreover, this study not only recognizes the distinctive impact of H154 on both the deamination and amination reactions, but also provides guidance for further high-throughput screening in protein engineering and understanding the catalytic mechanism of StDAPDH.

Screening and Antiscreening Effects in Endohedral Nanotubes.

Recently we investigated from first-principles screening properties in systems where small molecules, characterized by a finite electronic dipole moment, are encapsulated in different nanocages. The most relevant result was the observation of an antiscreening effect in alkali-halide nanocages characterized by ionic bonds: in fact, due to the relative displacement of positive and negative ions, induced by the dipole moment of the encapsulated molecule, these cages act as dipole-field amplifiers, different from what is observed in carbon fullerene nanocages, which exhibit instead a pronounced screening effect. Here we extend the study to another class of nanostructures: the nanotubes. Using first-principles techniques based on density functional theory, we studied the properties of endohedral nanotubes obtained by encapsulation of a water molecule or a linear HF molecule. A detailed analysis of the effective dipole moment of the complexes and of the electronic charge distribution suggests that screening effects crucially depend not only on the nature of the intramolecular bonds but also on the size and the shape of the nanotubes and on the specific encapsulated molecule. As observed in endohedral nanocages, screening is maximum in covalent-bond carbon nanotubes, while it is reduced in partially ionic nanotubes, and an antiscreening effect is observed in some ionic nanotubes. However, in this case, the scenario is more complex than in corresponding ionic nanocages. In fact the specific geometric structure of alkali-halide nanotubes turns out to be crucial for determining the screening/antiscreening behavior: while nanotubes with octagonal transversal section can exhibit an antiscreening effect, which quantitatively depends on the number of layers in the longitudinal direction, instead nanotubes with dodecagonal section are always characterized by a reduction of the total dipole moment so that a screening behavior is observed. Our results show that, even in nanotube structures, in principle one can tune the dipole moment and generate electrostatic fields at the nanoscale without the aid of external potentials.

Water adsorbed in a commercial carbon: Role of nanostructure and surface chemistry

This article investigates the spatial disposition and mobility of water molecules adsorbed at room temperature in a commercial activated amorphous carbon. Previous wide-angle X-ray scattering measurements are re-examined, together with new observations, in particular by high-resolution transmission electron microscopy, high field solid-state nuclear magnetic resonance, and pulsed field gradient nuclear magnetic resonance. The dry samples are composed largely of deformed turbostratic oxidized graphitic sheets, yielding an array of slit-pores with an average spacing of more than 0.4 nm. All the adsorbed water remains close to the aromatic substrate, and the landscape of adsorption sites is extremely heterogeneous. The water molecules are mobile. Water is initially adsorbed in small confined sites. With increasing relative humidity these develop into clusters that are spatially correlated, which spread and merge, on both sides of the graphitic sheets.

Unveiling the Structural and Dynamic Characteristics of Concentrated LiNO3 Aqueous Solutions through Ultrafast Infrared Spectroscopy and Molecular Dynamics Simulations.

Highly concentrated aqueous electrolytes have attracted a significant amount of attention for their potential applications in lithium-ion batteries. Nevertheless, a comprehensive understanding of the Li+ solvation structure and its migration within electrolyte solutions remains elusive. This study employs linear vibrational spectroscopy, ultrafast infrared spectroscopy, and molecular dynamics (MD) simulations to elucidate the structural dynamics in LiNO3 solutions by using intrinsic and extrinsic vibrational probes. The N-O stretching vibrations of NO3- exhibit a distinct spectral splitting, attributed to its asymmetric interaction with the surrounding solvation structure. Analysis of the vibrational relaxation dynamics of intrinsic and extrinsic probes, in combination with MD simulations, reveals cage-like networks formed through electrostatic interactions between Li+ and NO3-. This microscopic heterogeneity is reflected in the intertwined arrangement of ions and water molecules. Furthermore, both vehicular transport and structural diffusion assisted by solvent rearrangement for Li+ were analyzed, which are closely linked with the bulk concentration.

Accelerating Density Matrix Embedding with Stochastic Density Fitting Theory: An Application to Hydrogen Bonded Clusters.

In this work, we demonstrate how using semistochastic density fitting (ss-DF) can accelerate self-consistent density matrix embedding theory (DMET) calculations by reducing the number of auxiliary orbitals in the three-indexed DF integrals. This reduction results in significant time savings when building the Hartree-Fock (HF) Coulomb and Exchange Matrices and in transforming integrals from the atomic orbital (AO) basis to the embedding orbital (EO) basis. We apply ss-DF to a range of hydrogen-bonded clusters to showcase its effectiveness. First, we examine how the amount of deterministic space impacts the quality of the calculation in a (H2O)10 cluster. Next, we test the computational efficiency of ss-DF compared to deterministic DF (d-DF) in water clusters containing 6-30 water molecules using a triple-ζ basis set. Finally, we perform numerical structural optimizations on water and hydrogen fluoride clusters, revealing that DMET can recover weak interactions using a back-transformed energy formula. This work demonstrates the potential of using stochastic resolution of identity in quantum embedding theories and highlights its capability to recover weak interactions effectively.

Interlinking the Fe doping concentration, optoelectronic properties, and photocatalytic performance of ZnO nanostructures

Doping is one of the effective strategies to modulate the optoelectronic properties and photocatalytic activity of photocatalysts. In this study, the effect of Fe doping (0–10 %) on morphology, optical and electronic properties, and photocatalytic activity of ZnO nanostructures is studied. The X-ray diffraction analysis shows that >5 % Fe doping, ZnFe2O4 is segregated as a secondary phase. The crystalline size decreases from 50.8 nm to 21.4 nm and the micro-strain increases with increasing the Fe concentration. The Fe doping-induced electronic restructuring facilitates visible light absorption through the O 2p → Fe 3d transition and the suppression of charge recombination by efficiently trapping conduction band electrons. Density functional theory (DFT) calculations are employed to unravel the underlying electronic changes induced by Fe doping in ZnO. The formation of shallow donor levels below the conduction band originates from the Fe 3d state. Photoluminescence spectra of pristine and Fe-doped ZnO nanostructures show characteristic emission peaks at approximately 384 nm and 570 nm, indicating the recombination of free excitons and oxygen interstitial defects, respectively. The results of the photocatalytic activity tests confirm that the 1 % Fe-doped ZnO nanostructures can exhibit the highest efficiency compared to the heavily doped ZnO nanostructures. The high efficiency in photocatalytic activity of 1 % Fe-doped ZnO nanostructures is ascribed to the modulated electronic structure and defect density. The adsorption affinity of methylene blue and water molecules to the surfaces of pristine and Fe-doped ZnO is simulated using the Monte-Carlo method. This study emphasizes the importance of controlling the dopant concentration to enhance the photocatalytic activity of various photocatalysts.

Stabilizing Schottky junction in conjugated polymer diodes enables long-term reliable radio-frequency energy harvesting on plastic

Due to their inherent flexibility, solution-processable conjugated polymers are increasingly being considered for the cost-effective production of thin-film semiconductor devices used in Internet of Everything (IoE) applications. With considerable improvements in charge carrier mobilities, the final challenge impeding the commercialization of conjugated polymers may be improving their environmental and electrical stabilities. Recent studies have improved the stability of computing devices (i.e., transistors) by eliminating interface traps and water molecules within conjugated polymers. However, the stability issue of Schottky diodes, which play a crucial role in configuring thin-film IoE devices used in wireless communication and energy harvesting, has been largely overlooked. This study reveals that aluminum, which is commonly used as a cathode metal in polymer Schottky diodes, creates a nonstoichiometric effect when deposited on conjugated polymers, thereby leading to the formation of charge traps over time, which reduces the rectification ratio of the Schottky diodes and induces a significant bias stress effect during operation. To address this issue, we introduce a zinc-oxide sacrificial interlayer between the conjugated polymer and cathode. This interlayer effectively eliminates the penetrated Al metal or ionized Al-induced nonstoichiometric effect without reducing the charge injection efficiency, achieving exceptional environmental and operational stability. The printed polymer Schottky diodes demonstrate consistent rectifying operation at 13.56 MHz for several months with negligible changes in electrical characteristics.

Modeling hydration of graphene oxide (GO) – Does size matter?

The biomedical applications of graphene-based materials become one of hot scientific and technological topics in the last few years. Flake graphene oxide (GO) is considered as one of the promising materials for biomedical use due to a number of specific properties, in particular in design of advanced drug delivery systems (DDS). The key factor in the formation of non-covalently bonded complexes for drug transport is the strength of non-covalent interactions of the carrier with both the drug and the environment. In the current work, we have focused on molecular modeling of solvation of zigzag-edged graphene oxide, functionalized with hydroxyl and carboxyl substituents. The hydration was determined from the magnitude of weak intermolecular interactions of GO with one or two water molecules. Our goal was to establish the dependence of the degree and type of functionalization, as well as the size of graphene flakes and the position of hydrophilic substituents on the number and strength of H-bonds. All calculations were performed using density functional theory (DFT) at the B3LYPD3BJ/6-311++G** level. The effect of water solvent was established using an explicit (discrete) model of solvent.

Dynamics of an aqueous suspension of short hyaluronic acid chains near a DPPC bilayer.

The synergy between hyaluronic acid (HA) and lipid molecules plays a crucial role in synovial fluids, cell coatings, etc. Diseased cells in cancer and arthritis show changes in HA concentration and chain size, impacting the viscoelastic and mechanical properties of the cells. Although the solution behavior of HA is known in experiments, a molecular-level understanding of the role of HA in the dynamics at the interface of HA-water and the cellular boundary is lacking. Here, we perform atomistic molecular dynamics simulation of short HA chains in an explicit water solvent in the presence of a DPPC bilayer, relevant in pathological cases. We identify a stable interface between HA-water and the bilayer where the water molecules are in contact with the bilayer and the HA chains are located away without any direct contact. Both translation and rotation of the interfacial waters in contact with the lipid bilayer and translation of the HA chains exhibit subdiffusive behavior. The diffusive behavior sets in slightly away from the bilayer, where the diffusion coefficients of water and HA decrease monotonically with increase in HA concentration. On the contrary, the dependence on HA chain size is only marginal due to enhanced chain flexibility as their size increases.

Study on preparation and properties of antifreeze compound road dust suppressant

Open-pit mine pavement dust dries and breaks easily. As such, a composite pavement dust suppressant with good wettability, moisturizing, coagulation, and antifreezing properties in winter was investigated. Monomer screening and orthogonal experiments were conducted, using evaporation rate, permeability rate, viscosity, and freezing point as evaluation indexes. Consequently, a dust suppressant solution is a mixture of glycerol (GLY), sodium dodecylbenzene sulfonate (SDBS), polyacrylamide (PAM), compound propylene glycol (PG), and potassium acetate (PA). The characteristics of the dust suppressant and its interaction mechanism with road dust were measured and analyzed. The results showed that the optimal ratio of the antifreeze-type composite dust suppressant is 3%GLY, 0.30%SDBS, 0.07% PAM, and 50%PG + 10%PA; the contact angle is 27.62°, which can effectively wet coal dust. Moreover, it easily forms hydrogen bonds with water molecules to release free -OH, which increases the oxygen-containing functional groups in the dust. The maximum viscosity is 25.4 mPa·s, and the hydrophobic groups adsorbed on the surface of the dust can condense and agglomerate the dust to form large particles, and effectively inhibit the occurrence of dust. It freezes at − 34.2 ℃, resists a temperature of − 30 ℃ without freezing, and improves dust suppression efficiency and antifreezing effect in cold areas.

Sodium alginate-based coaxial fibers synergistically integrate moisture actuation, length tracing, humidity sensing, and electric heating.

The development of wearable electronics has driven the need for smart fibers with advanced multifunctional synergy. In this paper, we present a design of a multifunctional coaxial fiber that is composed of a biopolymer-derived core and an MXene/silver nanowire (AgNW) sheath by wet spinning. The fiber synergistically integrates moisture actuation, length tracing, humidity sensing, and electric heating, making it highly promising for portable devices and protective systems. The biopolymer-derived core provides deformation for moisture-sensitive actuation, while the MXene/AgNW sheath with good conductivity enables the fiber to perform electric heating, humidity sensing, and self-sensing actuation. The coaxial fiber can be programmed to rapidly desorb water molecules to shrink to its original length by using the MXene/AgNW sheath as an electrical heater. We demonstrate proof-of-concept applications based on the multifunctional fibers for thermal physiotherapy and wound healing/monitoring. The sodium alginate@MXene-based coaxial fiber presents a promising solution for the next-generation of smart wearable electronics.

Harnessing Nuclear Magnetic Resonance Spectroscopy to Decipher Structure and Dynamics of Clathrate Hydrates in Confinement: A Perspective.

This perspective outlines recent developments in the field of NMR spectroscopy, enabling new opportunities for in situ studies on bulk and confined clathrate hydrates. These hydrates are crystalline ice-like materials, built up from hydrogen-bonded water molecules, forming cages occluding non-polar gaseous guest molecules, including CH4, CO2 and even H2 and He gas. In nature, they are found in low-temperature and high-pressure conditions. Synthetic confined versions hold immense potential for energy storage and transportation, as well as for carbon capture and storage. Using previous studies, this report highlights static and magic angle spinning NMR hardware and strategies enabling the study of clathrate hydrate formation in situ, in bulk and in nano-confinement. The information obtained from such studies includes phase identification, dynamics, gas exchange processes, mechanistic studies and the molecular-level elucidation of the interactions between water, guest molecules and confining interfaces.