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At least 127 records · Page 7

Dynamic in situ imaging of methane hydrate formation in coal media

Fast 3D X-ray imaging has proved to provide crucial insights into multi-phase dynamic processes in various geomaterials. In particular, many in situ imaging experiments have been made to study gas-hydrate formation in porous sandy samples. Such imaging is challenging for the methane gas-hydrate formation in coal samples because of the coal micro-porosity structure and lower X-ray contrast. Here we present results of the first dynamic in situ micro-computed tomography experiment of methane-hydrate formation in coal samples. Synchrotron phase-contrast tomography techniques allowed to achieve necessary contrast levels to separate all the materials of interest (gas, water, coal, and gas hydrate) in reconstructed images with high spatial and temporal resolution. The imaging results are compared to the ones from a similar tomographic experiment with sand samples. Methane-hydrate formation is accompanied by the water movements caused by cryogenic water suction that happens in sequences of short fast movements with longer equilibrium states in between. Only one type of the hydrate formation was observed in coal (growth as shells on grain boundaries) as opposed to three types in sand (shells, growth into gas pockets, and inside water volumes). In particular, this leads to a slower hydrateformation speed in coal. For the coal sample, we also observed water extraction from grains, and interpreted it as competitive sorption of methane. Lastly, we visualized the dynamic behavior of this water extraction via microchannels inside the coal grains, and performed nano-tomography imaging of these channels for a better understanding of this phenomenon.

58 GEOSCIENCES↗

Hydrated Anions: From Clusters to Bulk Solution with Quasi-Chemical Theory

The interactions of hydrated ions with molecular and macromolecular solution and interface partners are strong on a chemical energy scale. Here we recount the foremost ab initio theory for the evaluation of the hydration free energies of ions, namely, quasi-chemical theory (QCT). We focus on anions, particularly halides but also the hydroxide anion, because they have been outstanding challenges for all theories. For example, this work supports understanding the high selectivity for F – over Cl – in fluoride-selective ion channels despite the identical charge and the size similarity of these ions. QCT is built by the identification of inner-shell clusters, separate treatment of those clusters, and then the integration of those results into the broader-scale solution environment. Recent work has focused on a close comparison with mass-spectrometric measurements of ion-hydration equilibria. We delineate how ab initio molecular dynamics (AIMD) calculations on ion-hydration clusters, elementary statistical thermodynamics, and electronic structure calculations on cluster structures sampled from the AIMD calculations obtain just the free energies extracted from the cluster experiments. That theory–experiment comparison has not been attempted before the work discussed here, but the agreement is excellent with moderate computational effort. This agreement reinforces both theory and experiment and provides a numerically accurate inner-shell contribution to QCT. The inner-shell complexes involving heavier halides display strikingly asymmetric hydration clusters. Asymmetric hydration structures can be problematic for the evaluation of the QCT outer-shell contribution with the polarizable continuum model (PCM). Nevertheless, QCT provides a favorable setting for the exploitation of PCM when the inner-shell material shields the ion from the outer solution environment. For the more asymmetrically hydrated, and thus less effectively shielded, heavier halide ions clustered with waters, the PCM is less satisfactory. We therefore investigate an inverse procedure in which the inner-shell structures are sampled from readily available AIMD calculations on the bulk solutions. This inverse procedure is a remarkable improvement; our final results are in close agreement with a standard tabulation of hydration free energies, and the final composite results are independent of the coordination number on the chemical energy scale of relevance, as they should be. Finally, a comparison of anion hydration structure in clusters and bulk solutions from AIMD simulations emphasize some differences: the asymmetries of bulk solution inner-shell structures are moderated compared with clusters but are still present, and inner hydration shells fill to slightly higher average coordination numbers in bulk solution than in clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

Uranyl fluoride (UO 2 F 2 ) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2 F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction on vibrational frequencies, electronic structure, and geometry of anhydrous UO 2 F 2 . A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2 F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Many-Body Effects Determine the Local Hydration Structure of Cs+ in Solution

A systematic analysis of the hydration structure of Cs+ ions in solution is derived from simulations carried out using a series of molecular models built upon a hierarchy of approximate representations of many-body effects in ion-water interactions. It is found that a pairwise-additive model, commonly used in biomolecular simulations, provides poor agreement with experimental X-ray spectra, indicating an incorrect description of the underlying hydration structure. Although the agreement with experiment improves in simulations with a polarizable model, the predicted hydration structure is found to lack the correct sequence of water shells. Progressive inclusion of explicit many- body effects in the representation of Cs+-water interactions as well as account for nuclear quantum effects is shown to be necessary for quantitatively reproducing the experimental spectra. Besides emphasizing the importance of many-body effects, these results suggests that molecular models rigorously derived from many-body expansions hold promise for realistic simulations of aqueous solutions. Work by J.L.F. and G.K.S. was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

Zhuang, Debbie↗

Sequence Modulates Polypeptoid Hydration Water Structure and Dynamics

We use molecular dynamics simulations to investigate the effect of polypeptoid sequence on the structure and dynamics of its hydration waters. Polypeptoids provide an excellent platform to study small-molecule hydration in disordered polymers, as they can be precisely synthesized with a variety of sidechain chemistries. We examine water behavior near a set of peptoid oligomers in which the number and placement of nonpolar versus polar sidechains are systematically varied. To do this, we leverage a new computational workflow enabling accurate sampling of polypeptoid conformations. We find that the hydration waters are less dense, are more tetrahedral, and have slower dynamics compared to bulk water. The magnitude of these shifts increases with the number of nonpolar groups. Here, we also find that shifts in the water structure and dynamics are strongly correlated, suggesting that experimental insight into the dynamics of hydration water obtained by Overhauser dynamic nuclear polarization (ODNP) also contains information about water structural properties. We then demonstrate the ability of ODNP to probe site-specific dynamics of hydration water near these model peptoid systems.

36 MATERIALS SCIENCE↗

Influence of Dissolved Iron in Solution on MgO Hydroxylation and Carbonation

MgO (periclase) is a promising material for direct air capture of CO 2 using a mineral looping process, but it is unknown how impurities in the environment will affect the CO 2 uptake and hence process economics. Here, we investigated the effects of dissolved iron on the extents of MgO hydroxylation and subsequent carbonation reactions to determine if this has a beneficial or detrimental effect. On single-crystal MgO, dissolved iron prevented hydration of MgO to Mg(OH) 2 (brucite) and instead formed a shell of lepidocrocite (γ-FeOOH). This did not passivate the MgO as dissolution below the shell was observed. During hydroxylation of MgO powders in the presence of dissolved iron, formation of brucite containing Fe(II) was observed. In addition, formation of nanoscale iron oxides containing Fe(III) was observed using magnetometry and Mössbauer spectroscopy. Subsequent carbonation experiments showed increased carbonation of MgO hydroxylated in the presence of iron. Our results indicate that the presence of dissolved solute impurities during hydroxylation may be beneficial for carbonation of hydroxylated MgO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prediction of Redox Potentials for the Late Actinides Cm to Lr Using Electronic Structure Methods

Our previously developed computational method for calculating the aqueous redox potentials of the early actinides has been extended to the later elements in the actinide series: Cm, Bk, Cf, Es, Fm, Md, No, and Lr in multiple oxidation states. These calculations were performed using density functional theory with small-core pseudopotentials and their associated basis sets. Solvation effects were considered via a supermolecule-continuum approach, with 30 water molecules representing two solvation shells. Both the COSMO and SMD implicit solvation models were utilized. The structural parameters and hydration numbers for Cm(III), Bk(III), Bk(IV), and Cf(III) are in reasonable agreement with the available experimental data. For redox processes involving atomic cations in solution, the B3LYP/COSMO approach predicted redox potentials to within ±0.2 V of experiment for most redox couples, consistent with our prior work. Inclusion of spin-orbit corrections in specific redox pairs, especially those with the later actinides in high oxidation states, yields improved results relative to calculations including only scalar-relativistic corrections. The An +m /An(0) redox potentials were calculated using a Born-Haber cycle incorporating sublimation, ionization, and hydration energies. Due to a lack of experimental data, three sets of ionization energies were used for the Born-Haber cycle. The calculated An(III/0) potentials showed better agreement with experimental data when using the COSMO solvation model and the test set comprising the NIST recommended ionization energies. Furthermore, the Md(II/0) potential was better described with the SMD model, whereas No(II/0) was not well described by all methods. Finally, the computational approach was able to predict redox potentials that for most cases agreed with the current available experimental or estimated data.

Actinides↗

Relationships between Water’s Structure and Solute Affinity at Polypeptoid Brush Surfaces

Excellent antifouling surfaces are generally thought to create a tightly bound layer of water that resists solute adsorption, and highly hydrophilic surfaces such as those with zwitterionic functionalities are of significant current interest as antifoulant strategies. Furthermore, despite significant proofs-of-concept, we still lack a fundamental understanding of how the nanoscopic structure of this hydration layer translates to reduced fouling, how surface chemistry can be tuned to achieve antifouling through hydration water, and why, in particular, zwitterionic surfaces seem so promising. Here, we use molecular dynamics simulations and free energy calculations to investigate the molecular relationships among surface chemistry, hydration water structure, and surface–solute affinity across a variety of surface-decorated chemistries. Specifically, we consider polypeptoid-decorated surfaces that display well-known experimental antifouling capabilities and that can be synthesized sequence specifically, with precise backbone positioning of, e.g., charged groups. Through simulations, we calculate the affinities of a range of small solutes to polypeptoid brush surfaces of varied side-chain chemistries. We then demonstrate that measures of the structure of surface hydration water in response to a particular surface chemistry signal solute–surface affinity; specifically, we find that zwitterionic chemistries produce solute–surface repulsion through highly coordinated hydration water while suppressing tetrahedral structuring around the solute, in contrast to uncharged surfaces that show solute–surface affinity. Based on the relationship of this structural perturbation to the affinity of small-molecule solutes, we propose a molecular mechanism by which zwitterionic surface chemistries enhance solute repulsion, with broader implications for the design of antifouling surfaces.

36 MATERIALS SCIENCE↗

A hydrated crystalline calcium carbonate phase: Calcium carbonate hemihydrate

As one of the most abundant materials in the world, calcium carbonate, CaCO 3 , is the main constituent of the skeletons and shells of various marine organisms. It is used in the cement industry and plays a crucial role in the global carbon cycle and formation of sedimentary rocks. For more than a century, only three polymorphs of pure CaCO 3 —calcite, aragonite, and vaterite—were known to exist at ambient conditions, as well as two hydrated crystal phases, monohydrocalcite (CaCO 3 ·1H 2 O) and ikaite (CaCO 3 ·6H 2 O). While investigating the role of magnesium ions in crystallization pathways of amorphous calcium carbonate, we unexpectedly discovered an unknown crystalline phase, hemihydrate CaCO 3 ·½H 2 O, with monoclinic structure. This discovery may have important implications in biomineralization, geology, and industrial processes based on hydration of CaCO 3 .

Science & Technology - Other Topics↗

A missing layer in COVID-19 studies: Transmission of enveloped viruses in mucus-rich droplets

Here we evaluate the influence of mucus layers on the evaporation time and transport of enveloped viruses, including SARS-CoV-2. Enveloped viruses must remain moist to be fully infective. Yet, the Wells model based on water droplets divides respiratory droplets into either quickly evaporated aerosolized particles termed droplet nuclei (<10 s) or liquid droplets that fall to the nearest surface, leaving no physical mechanism for airborne transmission of fully infective enveloped viruses over large distances (greater than a few meters). Yet, the role of mucus layers on evaporation times has not been considered even though the formation of mucus shells around liquid cores of respiratory droplets has been shown experimentally. Here we show that mucus shells increase the drying time by orders of magnitude so that enveloped virions may remain well hydrated and, thus, fully infective at substantial distances. Further, this provides a mechanism by which infective enveloped virus particles can transmit as aerosols within buildings and between buildings over extended distances. This analysis is important because public health agencies typically follow the Wells model to establish health policies including social/physical distancing guidelines.

60 APPLIED LIFE SCIENCES↗

Water structure around a left-handed Z-DNA fragment analyzed by cryo neutron crystallography

Even in high-quality X-ray crystal structures of oligonucleotides determined at a resolution of 1 Å or higher, the orientations of first-shell water molecules remain unclear. We used cryo neutron crystallography to gain insight into the H-bonding patterns of water molecules around the left-handed Z-DNA duplex [d(CGCGCG)] 2 . The neutron density visualized at 1.5 Å resolution for the first time allows us to pinpoint the orientations of most of the water molecules directly contacting the DNA and of many second-shell waters. In particular, H-bond acceptor and donor patterns for water participating in prominent hydration motifs inside the minor groove, on the convex surface or bridging nucleobase and phosphate oxygen atoms are finally revealed. Several water molecules display entirely unexpected orientations. For example, a water molecule located at H-bonding distance from O6 keto oxygen atoms of two adjacent guanines directs both its deuterium atoms away from the keto groups. Exocyclic amino groups of guanine (N2) and cytosine (N4) unexpectedly stabilize waters H-bonded to O2 keto oxygens from adjacent cytosines and O6 keto oxygens from adjacent guanines, respectively. Our structure offers the most detailed view to date of DNA solvation in the solid-state undistorted by metal ions or polyamines.

59 BASIC BIOLOGICAL SCIENCES↗

Importance of nuclear quantum effects on the hydration of chloride ion

Path-integral ab initio molecular dynamics (PI-AIMD) calculations have been employed to probe the nature of chloride ion solvation in aqueous solution. Nuclear quantum effects (NQEs) are shown to weaken hydrogen bonding between the chloride anion and the solvation shell of water molecules. As a consequence, the disruptive effect of the anion on the solvent water structure is significantly reduced compared to what is found in the absence of NQEs. Additionally, the chloride hydration structure obtained from PI-AIMD agrees well with information extracted from neutron scattering data. In particular, the observed satellite peak in the hydrogen-chloride-hydrogen triple angular distribution serves as a clear signature of NQEs. The present results suggest that NQEs are likely to play a crucial role in determining the structure of saline solutions.

36 MATERIALS SCIENCE↗

Primary biomolecular adsorption energetics of core–shell nanocomplexes: Implications for biological interactions

Molecular organization at the nano-bio interface governing the colloidal stability, reactivity, immune recognition, and drug delivery performance of nanoparticles remains difficult to predict. Quantifying the primary hydration energetics of biomolecule-coated nanomaterials can determine those interactions and provide a basis for engineered nanocarriers with tailored behavior in biological systems. Here, we measured the thermodynamics of water adsorption on patchy dry magnetite (Fe 3 O 4 ) nanoparticles coated with three model biomolecules, bovine serum albumin, potato starch, and lauric acid and compared these properties to the hydration energetics of the corresponding free dry biomolecules. The results demonstrate how the surface functionalization alters the hydrophilicity, the accessible hydrophilic surface, and the interaction potential of the nanocomplex surface with biological media. The protein coating increases the interaction potential of the surface of the nanocomplex. The weaker interaction potential of the polysaccharide coating and the relatively large hydrophilic surface area allow dynamic and reversible binding, while the fatty acid rearranges into a partial bilayer with very strong hydrophilicity. The findings establish the hydration enthalpy as a quantitative basis to determine and interpret nanoparticle interactions with proteins, membranes, and biological fluids, and provide a thermodynamic foundation for designing nanocarriers with predictable biological reactivity.

59 BASIC BIOLOGICAL SCIENCES↗

The evolution of the M1 local structure during preparation of VMoNbTeO catalysts for ethane oxidative dehydrogenation to ethylene

The so-called M1 phase (the common formula (TeO) x (Mo, V, Nb) 5 O 14 ) is a very promising catalyst for ethane oxidative dehydrogenation (ODE). It shows 90% selectivity to ethylene at 78% ethane conversion (400 °C, contact time – 5.5 s). The active crystal structure is formed under certain synthetic conditions in VMoNbTe mixed oxides. This paper is devoted to the analysis of how the local and average structure of the M1 phase is developed during the synthesis and what happens at particular synthetic steps. The analysis of the local structure was performed using the EXAFS and pair distribution function (PDF) methods. The EXAFS analysis of the initial VMoTe water solution and VMoNbTe slurry showed that Anderson-type heteropoly anions are formed in the solution and are preserved after fast spray-drying of the slurry. Nb cations do not enter the structure of the polyanions, but form an extended hydrated oxide matrix, where distorted NbO 6 and NbO 7 polyhedrons are connected to each other. The hydrated oxide matrix with captured polyanions provides the compositional homogeneity of the precursor. The distances in the second coordination shell are redistributed after thermal treatment at 310 °C. After being heated at T > 350°, the local structure of the M1 phase is organized and pentagonal domains are formed. These domains consist of a NbO 7 pentagonal bipyramid and five MeO 6 adjacent octahedra (Me = Mo, V). In the first stages, the building blocks are stacked along the [001] direction. The crystallization process results in the connection of the pentagonal domains to the extended polygonal grid. The formation of the regular grid with TeO x containing channels is accompanied by the increase in ethane conversion and ethylene selectivity of the catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the influence of interfacial solvation on electrochemical CO 2 reduction using plasmon‐enhanced vibrational sum frequency generation spectroscopy

Although interfacial solvation plays an important role in determining carbon dioxide reduction (CO 2 R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO 2 R remains limited. This article summarizes the development and recent applications of plasmon-enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO 2 R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation-mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO 2 R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fe-containing nanocomposites based on a biocompatible copolymer 1-vinyl-1,2,4-triazole with N-vinylpyrrolidone

New polymer nanocomposites containing iron oxide nanoparticles stabilized with a biocompatible copolymer of 1-vinyl-1,2,4-triazole with N-vinylpyrrolidone were produced. The synthesis was conducted using the method of chemical reduction of iron ions with hydrazine hydrate in an aqueous medium in the presence of a polymer matrix. The ESR spectroscopy data showed that the core—shell type nanoparticles were obtained. The core generally consistsed of zero-valence iron coated with an oxide shell. According to the data of transmission electron microscopy, the obtained polymer nanocomposites consisted of nanoparticles of mainly spherical shape with a diameter from 1 to 14 nm. Aggregates formed from individual stabilized nanoparticles of up to 75 nm in size (in most cases) were also observed. These aggregated particles were found to self-organize and form branched chains. Nanocomposites were characterized by a different particle-size distribution, which was determined by the initial ratio of the copolymer and the precursor of iron nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

K/T spherules from Haiti and Wyoming: Origin, diagenesis, and similarity to some microtektites

Spherules with relict glass cores in the K/T boundary bed of Haiti allow for a comparison of these bodies with hollow goyazite shells in the K/T boundary claystone of Wyoming and with younger microtektites of the Ivory Coast strewn field. Samples of the Haitian beds from undisturbed sections at Beloc, as determined by Jehanno et al., contain both hollow shells and relict glass cores rimmed by palagonite that has been partially converted to smectite. These palagonite rims developed from hydration zones formed when hot, splash-form droplets of andesitic impact glass were deposited into water. Mutual collisions between these droplets in the ejecta curtain may have formed point-source stresses on their surfaces. Initiation of hydration would be facilitated at these surface stress points and propagated radially into the glass. The inner surface of these merged hemispherical fronts appears mammillary, which is reflected as scalloping in Haitian relict glass cores.

Bohor, B. F.↗