Hydrogen-bonded Network Structure Research Articles

Why the Gas Uptake Behavior of Dry Salt Water Is Vastly Different above 279 K? A Dynamics-Controlled Process That Can Be Intensified by the Cooling Stimulation Method

The effect of temperature on CO2 uptake behavior of dry salt water was investigated by kinetics measurements and molecular dynamics simulations. The gas uptake capacity was found to be dramatically decreased at 279 K by the direct cooling adsorption procedure. By means of simulations, it was realized that the orientation of water and the hydrogen bond network structure near the silica surface are sensitive to temperature. With the temperature decreased, the water layer becomes local-structured by forming more hydrogen bonds, facilitating the capture of CO2 by forming the hydrate precursor easily. The change of the structure is irreversible once the CO2 uptake process occurred; hence, the gas uptake can carry on continuously even if the temperature rises. A cooling stimulation procedure was found to efficiently trigger the gas uptake process at temperatures higher than 279 K. By using this method, gas adsorption can be induced because the energy barrier of nucleation is reduced. This technology can save a ...

Fracture of the Intermolecular Hydrogen Bond Network Structure of Glycerol Modified by Carbon Nanotubes

An intermolecular hydrogen bond network structure is usually formed in the liquid state and affects physicochemical properties, such as melting point, boiling point, and viscosity. The intermolecul...

Chloridobis(ethane-1,2-diamine-κ2 N,N′)(3-methylpyridine-κN)cobalt(III) dichloride monohydrate

In the title hydrated salt, [CoCl(C6H7N)(C2H8N2)2]Cl2·H2O, the CoIII ion exhibits a distorted octahedral coordination envirnoment defined by four N atoms of two ethane-1,2-diamine ligands, another N atom of the pyridine ligand and a Cl− ligand. The pyridine N atom and the Cl− ligand are in cis positions relative to each other. The crystal packing is dominated by intermolecular N—H...Cl, O—H...Cl and O—H...H hydrogen-bonding interactions involving the amino groups of the complex cation, the lattice water molecule and the non-coordinating Cl− anions. Weak C—H...Cl interactions consolidate the three-dimensional hydrogen-bonded network structure.

Selective and low potential electrocatalytic oxidation of NADH using a 2,2-diphenyl-1-picrylhydrazyl immobilized graphene oxide-modified glassy carbon electrode

DPPH (2,2-diphenyl-1-picrylhydrazil), a free radical-containing organic compound, is used widely to evaluate the antioxidant properties of plant constituents. Here, we report an efficient electroactive DPPH molecular system with excellent electrocatalytic sensor properties, which is clearly distinct from the traditional free radical-based quenching mechanism. This unusual molecular status was achieved by the electrochemical immobilization of graphene oxide (GO)-stabilized DPPH on a glassy carbon electrode (GCE). Potential cycling of the DPPH adsorbed-GCE/GO between − 1 and 1 V (Ag/AgCl) in a pH 7 solution revealed a stable and well-defined pair of redox peaks with a standard electrode potential, E0′ = 0 ± 0.01 V (Ag/AgCl). Several electrochemical characterization studies as well as surface analysis of the GCE/GO@DPPH-modified electrode by transmission electron microscopy, Raman, and infrared spectroscopy collectively identified the imine/amine groups as the redox centers of the electroactive DPPH on GO. The use of different carbon-supports showed that only oxygen-functionalized GO and MWCNTs could provide major electroactivity for DPPH. This highlights the importance of a strong hydrogen-bonded network structure assisted by the concomitant π-π interactions between the organic moiety and oxygen function groups of carbon for the high electroactivity and stability of the GCE/GO@DPPH-NH/NH2-modified electrode. The developed electrode exhibited remarkable performance towards the electrocatalytic oxidation of NADH at 0 V (Ag/AgCl). The amperometric i-t sensing of NADH showed high sensitivity (488 nA μM−1 cm−2) and an extended linear range (50 to 450 μM) with complete freedom from several common biochemical/chemical interferents, such as ascorbic acid, hydrazine, glucose, cysteine, citric acid, nitrate, and uric acid.

Interplay between translational diffusion and large-amplitude angular jumps of water molecules.

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

Hydrogen-bonded structures from adamantane-based catechols

Adamantane-based bis- and tris-catechols were synthesized to examine the effect of hydrogen bonds on the arrangement and packing of the components in the crystalline state. Single-crystal X-ray crystallographic analysis revealed that hydrogen bonds formed by the hydroxyl groups of catechol groups play essential roles in the production of various types of unique structures. 1,3-Bis(3,4-dihydroxyphenyl)adamantane (1) provided hydrogen-bonded network structures composed of helical chains in crystal from chloroform/methanol, and layer structures in crystal from ethyl acetate/hexane. The complexation of 1 with 1,3,5-trinitrobenzene or 1,2,4,5-tetracyanobenzene resulted in the formation of co-crystals, respectively. One-dimensional hydrogen-bonded structures were constructed from the adamantane-based molecules, which participated in charge-transfer interactions with guests. 1,3,5-Tris(3,4-dihydroxyphenyl)adamantane also afforded crystal, and the components were assembled into infinite polymers.

Structural Origin of Shear Viscosity of Liquid Water.

The relation between the microscopic structure and shear viscosity of liquid water was analyzed by calculating the cross-correlation between the shear stress and the two-body density using the molecular dynamics simulation. The slow viscoelastic relaxation that dominates the steady-state shear viscosity was ascribed to the destruction of the hydrogen-bonding network structure along the compression axis of the shear distortion, which resembles the structural change under isotropic hydrostatic compression. It means that the shear viscosity of liquid water reflects the anisotropic destruction-formation dynamics of the hydrogen-bonding network.

Competition between hydrogen bonds and van der Waals forces in intermolecular structure formation of protonated branched-chain alcohol clusters.

To investigate the influence of bulky alkyl groups on hydrogen-bonded (H-bonded) network structures of alcohols, infrared (IR) spectra of protonated clusters of 2-propanol (2-PrOH) and tert-butyl alcohol (t-BuOH) were observed in the OH and CH stretch regions. In addition, by varying the tag species, the temperature dependence profile of the isomer population of H+(t-BuOH)n was revealed. An extensive search for stable isomers was performed using dispersion-corrected density functional theory methods, and temperature-dependent IR spectral simulations were done on the basis of the harmonic superposition approximation. The computational results qualitatively agreed with the observed size and temperature dependence of the H-bonded network structures of these protonated bulky alcohol clusters. However, the difficulty in the quantitative evaluation of dispersion was also demonstrated. It was shown that H+(2-PrOH)n (n = 4-7) have essentially the same network structures as the protonated normal alcohol clusters studied so far. On the other hand, H+(t-BuOH)n (n = 4-8) showed a clear preference for the smaller-membered ring structures, that is very different from the preference of the protonated normal alcohol clusters. The origin of the different structure preferences was discussed in terms of the steric effect and dispersion.

Hydrogen bond network structures of protonated short-chain alcohol clusters.

Because of the hydrogen bond coordination properties of alcohols, their possible hydrogen bond network structures are categorized into only a few types. Therefore, gas phase clusters of alcohols can be a very simple model system to examine the properties of hydrogen bond networks, such as structural development with cluster size and temperature dependence. In this perspective, we focus on the structural study of protonated short-chain alcohol clusters, whose excess protons (charge) enable size-selective spectroscopy in combination with mass spectrometric techniques. Size-selective infrared spectroscopy and a theoretical multi-scale isomer search were applied to protonated clusters of methanol, which is a prototype of short-chain alcohols, and their hydrogen bond network development is elucidated in detail. Complete isomer population switching with increasing temperature was predicted by the quantum harmonic superposition approximation and this isomer switching was evidenced by the remarkable temperature (internal vibrational energy) dependence of the observed infrared spectra. The characteristics of the temperature dependence of protonated methanol were compared with those of water and neutral methanol. In addition, possible hydrogen bond networks of methanolated ions were discussed on the basis of the results for protonated methanol. Stepwise changes in the internal energy of clusters with inert gas tagging are demonstrated. Convergence of the hydrogen bond network to the bulk-like network in large clusters is also discussed. The hydrogen bond structures of the protonated clusters of longer normal alkyl chain alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) are determined by comparison of their infrared spectra with those of the protonated methanol clusters. It is demonstrated that the normal alkyl chain interferes only slightly with the most stable hydrogen bond structure, although a few exceptional cases were also found. These exception cases serve as good model systems for further theoretical and computational studies.

Temperature and Size Dependence of Characteristic Hydrogen-Bonded Network Structures with Ion Core Switching in Protonated (Methanol)6-10-(Water)1 Mixed Clusters: A Revisit.

Hydrogen-bonded network structures and preferential ion core in the protonated methanol-water mixed clusters, H+(methanol)n-(water)1 (n = 6-10), were explored by a combination of infrared spectroscopy and theoretical calculations. Infrared spectra of the OH stretch region of the clusters were measured at the two different temperature ranges by using Ar-tagging. Stable isomer structures of the clusters were searched by the multiscale modeling approach and temperature dependent infrared spectra were simulated based on the statistical populations of the isomers. The combined experimental and theoretical studies revealed that the characteristic multiring structures begin to form at n = 7 under the low temperature condition and they are preferential at the wide temperature range in n ≥ 8. It was also demonstrated that the preferential ion core type changes from methanol (MeOH2+) to water (H3O+) with increasing cluster size. In n ≤ 8, the observed infrared spectral features partly depend on the monitoring vibrational predissociation channel, and weak correlations between the hydrogen-bonded network structure and preferential dissociation channels were suggested. However, the ion core type does not necessarily correlate to the preferential dissociation channel. This implies that large rearrangement of the hydrogen-bonded network structure occurs prior to the dissociation.

Analysis of shear viscosity and viscoelastic relaxation of liquid methanol based on molecular dynamics simulation and mode-coupling theory.

The role of the prepeak structure of liquid methanol in determining its shear viscosity was studied by means of molecular dynamics (MD) simulation and mode-coupling theory (MCT). The autocorrelation function of the shear stress and the intermediate scattering functions at both the prepeak and the main peak were calculated from the MD trajectories. Their comparison based on MCT suggests that the viscoelastic relaxation in the ps regime is affected by the slow structural dynamics at the prepeak. On the other hand, the MCT for molecular liquids based on the interaction-site model (site-site MCT) fails to describe the coupling between the prepeak dynamics and shear stress. The direct evaluation of the coupling between the two-body density and the shear stress reveals that the viscoelastic relaxation is actually affected by the prepeak dynamics, although the coupling is not captured by the site-site MCT. The site-site MCT works well for a model methanol without partial charges, suggesting that the failure of the site-site MCT originates from the existence of a hydrogen-bonding network structure.

Synergistic toughening of polymer nanocomposites by hydrogen-bond assisted three-dimensional network of functionalized graphene oxide and carbon nanotubes

We report a facile method to enhance mechanical properties of polymer nanocomposites using three-dimensional (3D) network structures of functionalized graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) in a polymer matrix. The GO and MWCNTs were functionalized using Fisher indole and diazonium-salt reactions to produce pyridine (Py) moiety on the GO and MWCNTs. The functionalized GO (Py-RGO) and MWCNT (Py-MWCNT) nanocomposites exhibited hydrogen-bond assisted 3D network structures in a polyimide (PI) matrix. By incorporating 1 wt% of carbon materials (0.9 wt% Py-RGO and 0.1 wt% Py-MWCNTs) in a PI, the tensile strength and modulus of the ternary nanocomposites reached 581 MPa and 31 GPa, respectively, which was an enhancement of 221% and 312% compared with pristine PI. The fracture energy of the PI/Py-RGO/Py-MWCNT nanocomposites improved 200% and approached 29.7 MJ m−3. The formation of the 3D network structure of the functionalized carbon nanomaterials is considered to significantly affect load transfer of nanofillers in the polymer matrix, and produce high performance polymer nanocomposites.

Adsorption Studies of Molecules on the Halloysite Surfaces: A Computational and Experimental Investigation

We report the results of joint computational and experimental investigations on the adsorption capability of halloysite toward a set of common molecules (water, alcohols, halides, and carboxylic acids). The halloysite system has been modelized by means of a cluster approach choosing a portion of a spiral nanotube; it has a slight curvature, with a convex aluminic layer. The adsorption geometries are described in terms of hydrogen bond network structures; calculated interaction energies invariably indicate that the inner aluminic surface is the place for preferential adsorption of polar molecules. The presence of substitutional defects on the outer or inner surface of the halloysite model causes sometimes slight variations in the adsorption properties. The calculated adsorption energy values confirm that the carboxylic group interacts with the substrate much more strongly than the alcoholic group, which in turn interacts stronger than the halides, a trend that is in agreement with the results obtained by m...

The role of hydrogen bonds in anomalies of dielectric properties of Diglycine Nitrate and Triglycine Tellurate

ABSTRACTDielectric spectroscopy measurements have been carried out at 10−1−107 Hz in the temperature range between 0 and 100°C on single crystals from the Triglycine Sulphate family - Triglycine Tellurate and Diglycine Nitrate, which contain 2.6÷2.9 Å hydrogen bonds. Temperature and frequency dependencies of complex dielectric permittivity, conductivity, electric modulus and calculated parameters of relaxation time spectra demonstrate anomalous behaviour at temperatures close to those of anomalies of physical properties of water. The results are interpreted from the point of view that the structure and dynamic properties of hydrogen bond network in water and in studied crystals are similar.

Long-Range Interactions Restrict Water Transport in Pyrophyllite Interlayers.

Water diffusion within smectite clay interlayers is reduced by confinement and hence is highly determined by the interlayer spacings that are adopted during swelling. However, a molecular understanding of the short- and long-range forces governing interlayer water structure and dynamics is lacking. Using molecular dynamics simulations of water intercalated between pyrophyllite (smectite prototype) layers we provide a detailed picture of the variation of interlayered water mobility accompanying smectite expansion. Subtle changes in hydrogen bond network structure cause significant changes in water mobility that is greater for stable hydration states and reduced for intermediate separations. By studying pyrophyllite with and without external water we reveal that long-range electrostatic forces apply a restraining effect upon interlayer water mobility. Our findings are relevant for broad range of confining nanostructures with walls thin enough to permit long-range interactions that could affect the mobility of confined solvent molecules and solute species.

Vibrational Spectroscopy and Dynamics of Water.

We present an overview of recent static and time-resolved vibrational spectroscopic studies of liquid water from ambient conditions to the supercooled state, as well as of crystalline and amorphous ice forms. The structure and dynamics of the complex hydrogen-bond network formed by water molecules in the bulk and interphases are discussed, as well as the dissipation mechanism of vibrational energy throughout this network. A broad range of water investigations are addressed, from conventional infrared and Raman spectroscopy to femtosecond pump-probe, photon-echo, optical Kerr effect, sum-frequency generation, and two-dimensional infrared spectroscopic studies. Additionally, we discuss novel approaches, such as two-dimensional sum-frequency generation, three-dimensional infrared, and two-dimensional Raman terahertz spectroscopy. By comparison of the complementary aspects probed by various linear and nonlinear spectroscopic techniques, a coherent picture of water dynamics and energetics emerges. Furthermore, we outline future perspectives of vibrational spectroscopy for water researches.

A facile approach for preparation of underwater superoleophobicity cellulose/chitosan composite aerogel for oil/water separation

We fabricate cellulose/chitosan (CE/CS) aerogel with stable superhydrophilic (θ ≈ 0°) and underwater superoleophobic (θoil > 150°) through a simple way. During the process of preparation of CE/CS aerogel, chitosan will self-assemble into number micron diameter particles on the surface of aerogel. Furthermore, the hydrogen bonding network structure of cellulose was destroyed and more hydrophilic groups (–OH) were exposed. Rough surface and hydrophilicity make CE/CS aerogel have a property of underwater superoleophobicity. CE/CS aerogel shows underwater superoleophobicity to different oils, and it still have stable superoleophobicity in corrosive solution. The important thing is that CE/CS aerogel can separate free oil/water mixture and surfactant-stabilized emulsions under gravity effectively. The sample is green, low cost, and environmental friendly, which is a promising candidate to be used in oil/water separation.

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

Construction and Conversion of a Self-assembled Hydrogen-bonding Network Structure Composed of S-Bridged Trinuclear Nickel(II) Units with Chiral Multidentate Ligands

Treatment of dicyandiamide, D-penicillamine (D-H2pen), and NiII produced a NiII3 trinuclear complex, [Ni3(D-bgpen)2(D-pen)] (1), as a kinetic product, which was converted to a NiII2 dinuclear complex, [Ni2(D-bgpen)2] (2), as a thermodynamic product by soaking the crystals of 1 in heated water. In both 1 and 2, self-assembled hydrogen-bonding 3D network structures are constructed through double hydrogen bonds between the biguanide moiety as a hydrogen-bonding donor and the carboxylate group as an acceptor.

(Acetato-κO){2-[(2-aminoethyl-κN)disulfanyl]ethanaminium}dichloridozinc(II)

In the title compound, [Zn(C4H13N2S2)(CH3COO)Cl2], the ZnIIion is in a tetrahedral coordination geometry, coordinated by one acetate, two chloride and one 2-[(2-aminoethyl)disulfanyl]ethanaminium ligand, with a Zn—O distance of 1.977 (3) Å, a Zn—N distance of 2.015 (3) Å and Zn—Cl distances of 2.2673 (18) and 2.2688 (15) Å. In the crystal, molecules are self-assembled by N—H...Cl hydrogen bonds, leading to a one-dimensional chain structure. The chains interact with each other through N—H...O, N—H...S, C—H...Cl and C—H...S hydrogen bonding, completing a three-dimensional hydrogen-bonding network structure.