Formation Of Hydrogen Bond Network Research Articles

Elucidating the dynamics behavior of PFASs at the water and hydrophobic low-melting mixture solvents interphase

In this work, we studied the interphase dynamics of hydrophobic low-melting mixture solvents (LoMMSs) for the advanced remediation of per- and polyfluoroalkyl substances (PFASs) in wastewater systems by using classical molecular dynamics (MD) simulations. We showed the interaction between widely prevalent PFAS-specifically perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and an innovative LoMMS composed of cineole (CIN) and linoleic acid (LNA) at equimolar ratios. Our investigations reveal that the interphase diffusion of PFASs through the LoMMS is a multi-stage process involving diffusion, interface sorption, and subsequent migration into the bulk aqueous phase. The simulations underscore a robust affinity between the PFASs molecules and the LoMMS, with the displacement of PFASs from the water interface marked by the formation of complex hydrogen-bonded networks. This intricate interplay results in a significant reorganization of water molecules, leading to potential clustering at the interface and compression of the fluid phase. These findings not only substantiate the efficacy of LoMMSs in PFASs extraction but also highlight the need to account for competitive interactions at the water interface, which could impede the absorption kinetics. By providing a detailed molecular-level narrative of the interphase capture phenomena, this study paves the way for designing efficient, low-toxicity LoMMS-based systems for the targeted removal of PFASs from contaminated water sources.

Local number fluctuations in ordered and disordered phases of water across temperatures: Higher-order moments and degrees of tetrahedrality.

The isothermal compressibility (i.e., related to the asymptotic number variance) of equilibrium liquid water as a function of temperature is minimal under near-ambient conditions. This anomalous non-monotonic temperature dependence is due to a balance between thermal fluctuations and the formation of tetrahedral hydrogen-bond networks. Since tetrahedrality is a many-body property, it will also influence the higher-order moments of density fluctuations, including the skewness and kurtosis. To gain a more complete picture, we examine these higher-order moments that encapsulate many-body correlations using a recently developed, advanced platform for local density fluctuations. We study an extensive set of simulated phases of water across a range of temperatures (80-1600K) with various degrees of tetrahedrality, including ice phases, equilibrium liquid water, supercritical water, and disordered nonequilibrium quenches. We find clear signatures of tetrahedrality in the higher-order moments, including the skewness and excess kurtosis, which scale for all cases with the degree of tetrahedrality. More importantly, this scaling behavior leads to non-monotonic temperature dependencies in the higher-order moments for both equilibrium and non-equilibrium phases. Specifically, under near-ambient conditions, the higher-order moments vanish most rapidly for large length scales, and the distribution quickly converges to a Gaussian in our metric. However, under non-ambient conditions, higher-order moments vanish more slowly and hence become more relevant, especially for improving information-theoretic approximations of hydrophobic solubility. The temperature non-monotonicity that we observe in the full distribution across length scales could shed light on water's nested anomalies, i.e., reveal new links between structural, dynamic, and thermodynamic anomalies.

Exploring structures of small anionic nickel-ethanol clusters with infrared spectroscopy.

Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O-H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]- and [Ni3(EtOH)]- clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]- cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules.

An amino acid ionic liquid-based biphasic solvent with low viscosity, small rich-phase volume, and high CO2 loading rate for efficient CO2 capture

In order to achieve efficient CO2 capture, a novel biphasic solvent based on diethylenetriamine serine ionic liquid/polyethylene glycol dimethyl ether/water ([DETA][SER]/NHD/H2O) was developed. This study achieved low viscosity by weakening the hydrogen bonding and van der Waals interactions within the pure ionic liquid (IL) by adding NHD and H2O to [DETA][SER]. Additionally, due to the low polarity and fewer hydrogen bonds formed by NHD, it is separated. The formation of a tight hydrogen bond network in the rich-phase after the reaction enables the enrichment of the product. Based on this, the optimal mass ratio of [DETA][SER]/NHD/H2O is determined to be 20 wt%/40 wt%/40 wt%. The viscosity of this solvent is 7.82 mPa·s, with a total absorption load of 1.26 mol·mol−1 IL, where the rich-phase load accounts for 99 % of the total load and occupies only 37 % of the volume. The mechanism of CO2 capture was investigated using 13C NMR, revealing the formation of zwitterions from the reaction of the primary amines on [DETA]+ and [SER]− with CO2. Subsequently, proton transfer and hydrolysis of the carbamate esters were observed. Notably, NHD was found to promote phase separation without participating in chemical reactions. These findings demonstrate the potential of this biphasic solvent system as a high-capacity solution for CO2 capture.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis.

Searching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite-type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S-vacancies modified RuS2-x exhibits outperformed HOR activity with a current density of 0.676 mA cm-2 and mass activity of 1.43 mA μg-1, which are 15-fold and 40-fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S-H bond during the HOR process, identifying the S atom of RuS2-x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface-enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2-x, together with the promoted connectivity of hydrogen-bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Reversible phase separation of CO2 responsive microemulsion: Judgment on whether and how regulated by ratio of ion to responsive surfactant concentration

CO2 responsive microemulsion is a promising solvent with diverse applications in various fields including oil exploitation, material synthesis, and metal recovery. The implementation of reversible phase separation becomes important in enabling the reuses of CO2 responsive microemulsion and facilitating the separation of products in these applications. Earlier reports have established that changes in ion concentration within CO2 responsive microemulsion result in reversible phase separation. Ion in CO2 responsive microemulsion is derived from protonation of CO2 responsive substance which is commonly used as surfactant. An increase in ion concentration leads to a decrease in surfactant concentration. In microemulsion, adsorption of surfactants and ions at the oil–water interface is correlated with interface performance, which influence the ability to achieve efficient phase separation. Interfacial tension (IFT) is an important parameter for interface performance. In this work, ratio of ion to CO2 responsive surfactant concentration was defined as ∮. The relationship between IFT and ∮ was investigated through a combination of experiments and molecular dynamic simulation to explore mechanism of reversible phase separation. The results of present study indicated that ∮ was found to play a vital role in either inhibiting or promoting the formation of hydrogen bond network by hydrophilic groups in surfactants. The changes of hydrogen bond network resulted in increase or decrease in IFT, leading to reversible phase separation. This relationship between IFT and ∮ was used as a theoretical guidance to optimize N2/CO2 bubbling time to achieve reversible phase separation. The optimization improved the efficiency of CO2 responsive microemulsion in extracting active components from Rehmannia glutinosa Libosch. leaves, and enhanced sustainability of the microemulsion. The findings of this study could be used to advance the scientific understanding of reversible phase separation, offering theoretical guidance for green and efficient utilization of CO2 responsive microemulsion in extraction of natural products. Ultimately these results could encourage the broader applications of CO2 responsive microemulsion across diverse fields.

On the Na+ transport and electrochemical stability window in NaTFSI:NMA deep eutectic solvent

Deep eutectic solvents (DES), such as the ▪:▪ (sodium bistrifluoromethane sulfonyl imide - N-methyl acetamide) system, have been considered as promising electrolytes for sodium-ion (▪) batteries. However, our current atomistic understanding of those systems is still in a state of evolution and remains incomplete. In this context, we combined classical force field molecular dynamics (MD) simulations and periodic density functional theory (DFT) calculations to enhance our atomistic understanding on the ▪ transport mechanisms, DES structure organization, hydrogen-bond network formation, and electrochemical stability windows (ESWs). Firstly, we obtained a substantial improvement in the description of the DES transport and structural properties using self-consistent MD/DFT calculations to assign effective charges on all atoms, while the remaining OPLS parameters were kept constant. From our analyses, an increasing in the ▪ mole fraction leads to different chemical environments, reflecting an electrolyte with larger aggregates, low conductivity, and high viscosity. The liquid structure seems to remain unchanged as a function of temperature. However, higher temperatures reduce the lifetime of ionic pairs and increase the mobility of ▪ ions. The disruption of the hydrogen-bonds formed between the ▪ species increases with the ▪ concentration. In addition, our periodic DFT calculations reveals the substitution of atomic sites from ▪ to ▪ during the reduction process. Furthermore, the ESW results provided evidence supporting the safeguarding of the solvent from degradation at higher salt concentrations.

Silk nanofibrous scaffolds assembled by natural polysaccharide konjac glucomannan

AbstractNatural silk fibroin nanofibers (SNF) have recently attracted great attention in the field of biomaterials due to their excellent biocompatibility, outstanding mechanical properties, and biomimetic nanostructures. However, the poor structural stability of SNF assembly in aqueous conditions remains a major obstacle to their biomedical application. In this work, SNF scaffolds with extracellular matrix‐mimicking architecture and tunable properties were developed by using a small amount of konjac glucomannan (KGM) as a physical adhesive. Fourier transform infrared spectroscopy (FTIR) results revealed that KGM facilitated the formation of hydrogen bond networks between SNF as well as nanofibers/polysaccharide molecules, thereby reinforcing the interconnectivity between SNF. The water stability test showed that SNF scaffolds exhibited good structural stability in water when the mass ratio of KGM/SNF reached 2.5/100. Raising KGM content significantly enhanced the compression strength, modulus, and swelling ratio of the porous scaffold. Whereas, the nanofibrous morphology and porosity of the scaffolds were significantly sacrificed as KGM content exceeded 10% as evidenced by scanning electron microscopy (SEM) results. In vitro, cytocompatibility results also demonstrated the excellent biocompatibility of the biomimetic nanofibrous scaffolds, and the high porosity significantly enhanced cell viability. These results suggest that KGM‐reinforced SNF scaffolds may serve as promising candidates for biomaterial applications.

Unravelling hydrogen bond network in methanol-propanol mixtures via molecular dynamics simulation and experimental techniques

ABSTRACT Hydrogen-bonded networks in 1-propanol-methanol binary mixture are studied using molecular dynamics simulation along with experimental techniques (FTIR, dielectric spectroscopy and refractive index measurements) for the entire concentration range. The structure of hydrogen-bonded networks is studied through radial distribution function, hydrogen bond statistics and graph theoretical analysis from molecular dynamics. It is observed that the probability of hydrogen bonding is maximum in methanol molecules followed by hydrogen bonding between methanol and 1-propanol molecules and minimum among 1-propanol molecules, as the concentration changes. The graph theory results show the formation of linear chain hydrogen bond networks, with no caged structures, which is validated from the experimental results. Further, the deconvolution of the FTIR OH peak suggests the presence of linear multimers in all concentrations of the binary system. Average degree of the hydrogen-bonded networks from graph theory indicates a complex networks among pure alcohols and dimers between methanol and 1-propanol in their binary mixtures at all concentrations. The negative values of excess permittivity indicate that the components of the mixture interact in a manner such that the net dipole polarisation decreases.

Elucidating the water-anatase TiO2(101) interface structure using infrared signatures and molecular dynamics.

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO2, a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti5c) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O2c) atoms. As the coverage increases, water adsorption on O2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti5c and O2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. The results reported here provide critical details of the structure of the water-anatase (101) interface that were previously hypothesized but unconfirmed experimentally.

Hydrogen bonding network formation in epoxidized natural rubber

Hydrogen bonding network formation in epoxidized natural rubber

Hierarchically porous MOFs self-supporting copolymers for ultrafast transport and precise recognition of flavonoids: A triple interfacial crosslinking strategy based on microreactors

The main obstacles of recognition of flavoniods are low concentration and complexity of extract wastewater solutions. The structural and stability limitation of the sorbents is the significant reason for the difficulty in increasing the adsorption amount in the separation system. Hereon, a novel hierarchical-pore boronic acid-functionalized-MOFs based on macroporous organo/hydro copolymers (CPs@H-UiO-66-NH2@BA) were firstly fabricated through the triple sacrificial cross-linking strategy, which allowed the formation of multiple hydrogen bond networks (i.e. main crosslinked networks and weak crosslinked networks) at oil–water interface. Noticeably, the MOFs with polymer chain entanglement effects as a physical sacrificial cross-linking network, significantly enhancing the mechanical properties. The maximum equilibrium binding capacity of CPs@H-UiO-66-NH2@BA was 40.93 µmol g−1 for NRG at 308 K. Furthermore, it also showed superior regeneration capacity capability (only 7.81% loss) after six cycles. Meanwhile, they had a stronger selectivity towards NRG. It can effectively purify the low purity of the actual sample ground to 92.68%. It is anticipated that in-situ the introduction of nanoboronic-functionalized MOFs construction into copolymers would hold great promise in the selective capture of target flavonoids in actual samples.

Electrochemical capacitor in aqueous electrolyte with long lifespan improved by hydrogen bond donor addition

In the electrochemical capacitors (ECs) operating with aqueous electrolytes, corrosion of the current collector is one of critical issues that affects the cycling life, efficiency, and capacitance of the devices. So far, there are no stable metal current collectors in the water-based electrolyte because of its corrosive nature, even if the pH is close to neutral. Here, urea (CH4N2O) is used as an anticorrosive, green additive to 1 M lithium sulfate electrolyte for low-cost electrochemical capacitors based on carbon BP2000 electrodes. In this work, the corrosion study of stainless steel in the presence of such amide demonstrates an effective corrosion-inhibiting character owing to the urea interaction with water in the hydrogen-bonded network. Chemical stability of current collectors owing to a significant 10-fold decrease of the corrosion current and shift of the corrosion potential into negative side has been achieved when 2 M urea, i.e., hydrogen-bond donor (HBD) is added to electrolyte. Furthermore, the addition of this organic compound improves the capacitive performance of the system and prevents the fading of the device with no influence on the electrolyte conductivity. During the floating test of EC at 1.6 V operating in 1 M Li2SO4 with 2 M urea, the capacitance and resistance values keep the end-of-life criteria for over 350 h. Moreover, the galvanostatic investigation of such EC (at 1 A/g) displays performance of more than 60000 cycles. Furthermore, operando experiments proved that carbon-based electrodes behave differently in lithium sulfate with urea and without additive owing to the formation of strong hydrogen bond network. The molecular structure of electrolyte has been estimated by DFT calculations. Overall, by using lithium sulfate and urea as an electrolytic system, the EC current collector has not only superior corrosion resistance against the aqueous electrolyte but also a high anti-ageing character at 1.6 V, which is favorable to improve the EC electrochemical performance. The use of urea as a stable, cheap electrolyte additive provides an innovative technique to enhance the performance of low-cost aqueous based supercapacitors.

Quantitative investigation of the effects of DNA modifications and protein mutations on MeCP2-MBD-DNA interactions

DNA methylation as an important epigenetic marker, has gained attention for the significance of three oxidative modifications (hydroxymethyl-C (hmC), formyl-C (fC), and carboxyl-C (caC)). Mutations occurring in the methyl-CpG-binding domain (MBD) of MeCP2 result in Rett. However, uncertainties persist regarding DNA modification and MBD mutation-induced interaction changes. Here, molecular dynamics simulations were used to investigate the underlying mechanisms behind changes due to different modifications of DNA and MBD mutations. Alanine scanning combined with the interaction entropy method was employed to accurately evaluate the binding free energy. The results show that MBD has the strongest binding ability for mCDNA, followed by caC, hmC, and fCDNA, with the weakest binding ability observed for CDNA. Further analysis revealed that mC modification induces DNA bending, causing residues R91 and R162 closer to the DNA. This proximity enhances van der Waals and electrostatic interactions. Conversely, the caC/hmC and fC modifications lead to two loop regions (near K112 and K130) closer to DNA, respectively. Furthermore, DNA modifications promote the formation of stable hydrogen bond networks, however mutations in the MBD significantly reduce the binding free energy. This study provides detailed insight into the effects of DNA modifications and MBD mutations on binding ability. It emphasizes the necessity for research and development of targeted Rett compounds that induce conformational compatibility between MBD and DNA, enhancing the stability and strength of their interactions.

Exploring the Heterogeneous Dynamical Environment at the Interface of Aβ42 Peptide in Aqueous Ionic Liquid Solution.

In this study, we have investigated the heterogeneous dynamical environment around an ensemble of full-length amyloid-β (Aβ42) peptide monomers in binary aqueous solution containing the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] as a co-solvent. Atomistic molecular dynamics (MD) simulations have been employed with the aim of understanding the effect of the IL on the distribution of water molecules and IL components around distinct segments of the peptide. As compared to pure aqueous medium, locally heterogeneous restricted water motions at the interface have been spotted in the presence of the IL. Our calculations revealed faster diffusion of water molecules hydrating hydrophilic segments (N-term and turn) as opposed to that around hydrophobic segments (hp1, hp2, and C-term). The extent of non-uniform restriction on the center-of-mass motions as well as the reorientation of water molecules and IL ions have been similarly affected in the binary IL-water solution. The effects of IL on the formation of hydrogen bond networks have been evident from the longer hydrogen bond relaxation time scales of peptide-water, with only a small fraction of peptide-anion hydrogen bonds contributing to the structural relaxation. Due to the size and shape factors, the increasingly sluggish dynamics of the IL components in the solvation shell can be attributed to a longer time scale for the onset of maximum dynamic heterogeneity. Interestingly, the water molecules around the polar segments of the peptide take longer to attain dynamic heterogeneity, which intensifies in the presence of IL. These calculations clearly suggest that electrostatic interaction plays a crucial role in water-mediated peptide-IL interaction, thereby shielding the surface from hydrophobic collapse and preventing possible further growth of the monomers into fibrils at higher peptide concentrations.

Interlayered Interface of a Thin Film Composite Janus Membrane for Sieving Volatile Substances in Membrane Distillation

Hypersaline wastewater treatment using membrane distillation (MD) has gained significant attention due to its ability to completely reject nonvolatile substances. However, a critical limitation of current MD membranes is their inability to intercept volatile substances owing to their large membrane pores. Additionally, the strong interaction between volatile substances and MD membranes underwater tends to cause membrane wetting. To overcome these challenges, we developed a dual-layer thin film composite (TFC) Janus membrane through electrospinning and sequential interfacial polymerization of a polyamide (PA) layer and cross-linking a polyvinyl alcohol/polyacrylic acid (PP) layer. The resulting Janus membrane exhibited high flux (>27 L m-2 h-1), salt rejection of ∼100%, phenol rejection of ∼90%, and excellent resistance to wetting and fouling. The interlayered interface between the PA and PP layer allowed the sieve of volatile substances by limiting their dissolution-diffusion, with the increasing hydrogen bond network formation preventing their transport. In contrast, small water molecules with powerful dynamics were permeable through the TFC membrane. Both experimental and molecular dynamics simulation results elucidated the sieving mechanism. Our findings demonstrate that this type of TFC Janus membrane can serve as a novel strategy to design next-generation MD membranes against volatile and non-volatile contaminants, which can have significant implications in the treatment of complex hypersaline wastewater.

Super Proton Conductivity Through Control of Hydrogen-Bonding Networks in Flexible Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) have received much attention as a solid-state electrolyte in proton exchange membrane fuel cells. The introduction of proton carriers and functional groups into MOFs can improve the proton conductivity attributed to the formation of hydrogen-bonding networks, while the underlying synergistic mechanism is still unclear. Here, a series of flexible MOFs (MIL-88B, [Fe3 O(OH)(H2 O)2 (O2 C-C6 H4 -CO2 )3 ] with imidazole) is designed to modify the hydrogen-bonding networks and investigate the resulting proton-conducting characteristics by controlling the breathing behaviors. The breathing behavior is tuned by varying the amount of adsorbed imidazole into pore (small breathing (SB) and large breathing (LB)) and introducing functional groups onto ligands (-NH2 , -SO3 H), resulting in four kinds of imidazole-loaded MOFs-Im@MIL-88B-SB, Im@MIL-88B-LB, Im@MIL-88B-NH2 , and Im@MIL-88B-SO3 H. Im@MIL-88B-LB without functional groups exhibits the highest proton conductivity of 8.93×10-2 Scm-1 at 60°C and 95% relative humidity among imidazole-loaded proton conductors despite the mild condition, indicating that functional groups may not be always required to enhance proton conductivity. The elaborately controlled pore size and host-guest interaction in flexible MOFs through imidazole-dependent structural transformation are translated into the high proton concentration without the limitation of proton mobility, contributing to the formation of effective hydrogen-bonding networks in imidazole conducting media.

The Evolution of Hydrogen Bond Network in Nafion via Molecular Dynamics Simulation

The hydrogen bond network (HBN) is of primary importance to the proton transport in Nafion. However, the evolution of the HBN in Nafion with water content and the underlying thermodynamics have not been revealed. In this study, the free energy of hydrogen bond formation is calculated based on an information-theoretic approach, indicating the formation of HBN in Nafion is a thermodynamically favorable process as the water content increases. In addition, the evolution of HBN in Nafion with water content including the topology and basic building blocks has been visualized and quantified by a ring statistics approach based on graph theory. Finally, the rearrangement dynamics and heterogeneity of HBN are also disclosed. This study provides a fundamental and comprehensive understanding of HBN in Nafion including the formation thermodynamics, topology, and rearrangement dynamics, which is useful for the design of high-performance proton exchange membranes.

Spectroscopic snapshot for neutral water nonamer (H2O)9: Adding a H2O onto a hydrogen bond-unbroken edge of (H2O)8.

Structural characterization of neutral water clusters is crucial to understanding the structures and properties of water, but it has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report the size-specific infrared spectra of confinement-free neutral water nonamer (H2O)9 based on threshold photoionization, using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals in the 3200-3350cm-1 region are observed, providing unique spectral signatures for the formation of an unprecedented (H2O)9 structure evolved by adding a ninth water molecule onto a hydrogen bond-unbroken edge of the (H2O)8 octamer with D2d symmetry. This nonamer structure coexists with the five previously identified structures that can be viewed as derived by inserting a ninth water molecule into a hydrogen bond-broken edge of the D2d/S4 octamer. These findings provide key microscopic information for systematic understanding of the formation and growth mechanism of dynamical hydrogen-bonding networks that are responsible for the structure and properties of condensed-phase water.

Construction of dense H-bond acceptors in the channels of covalent organic frameworks for proton conduction

Two-dimensional (2D) COFs with a high density of oxygen atoms along the pore walls as a host loaded with H3PO4facilitated the formation of hydrogen-bond networks along the pores, further facilitating proton transport.