Temperature-resolved nanoscale hydration of a layered manganese oxide.

Water films captured in the interlayer region of birnessite (MnO2) nanosheets can play important roles in biogeochemical cycling, catalysis, energy storage, and even atmospheric water harvesting. Understanding the temperature-dependent loadings and properties of these interlayer films is crucial to comprehend birnessite reactivity when exposed to moist air and temperature gradients. Using vibrational spectroscopy we show that birnessite intercalates one water (1W) monolayer at up to ∼40 °C, but that loadings decrease by half at up to 85 °C. Our results also show that the vibrational properties of intercalated water are unaffected by temperature, implying that the hydrogen bonding network of water remains intact. Using molecular simulations, we found that the lowered water storage capacity at high temperatures cannot be explained by variations in hydrogen bond numbers or in the solvation environments of interlayer K+ ions initially present in the interlayer region. It can instead be explained by the compounded effects of larger evolved heat, as inferred from immersion energies, and by the larger temperature-driven mobility of water over that of K+ ions, which are electrostatically bound to birnessite basal oxygens. By shedding new light on the temperature-driven intercalation of water in a nanolayered mineral, this study can guide future efforts to understand the (geo)chemical reactivity of related materials in natural and technological settings.

MgO nanocube hydroxylation by nanometric water films.

Hydrophilic nanosized minerals exposed to air moisture host thin water films that are key drivers of reactions of interest in nature and technology. Water films can trigger irreversible mineralogical transformations, and control chemical fluxes across networks of aggregated nanomaterials. Using X-ray diffraction, vibrational spectroscopy, electron microscopy, and (micro)gravimetry, we tracked water film-driven transformations of periclase (MgO) nanocubes to brucite (Mg(OH)2) nanosheets. We show that three monolayer-thick water films first triggered the nucleation-limited growth of brucite, and that water film loadings continuously increased as newly-formed brucite nanosheets captured air moisture. Small (8 nm-wide) nanocubes were completely converted to brucite under this regime while growth on larger (32 nm-wide) nanocubes transitioned to a diffusion-limited regime when (∼0.9 nm-thick) brucite nanocoatings began hampering the flux of reactive species. We also show that intra- and inter-particle microporosity hosted a hydration network that sustained GPa-level crystallization pressures, compressing interlayer brucite spacing during growth. This was prevalent in aggregated 8 nm wide nanocubes, which formed a maze-like network of slit-shaped pores. By resolving the impact of nanocube size and microporosity on reaction yields and crystallization pressures, this work provides new insight into the study of mineralogical transformations induced by nanometric water films. Our findings can be applied to structurally related minerals important to nature and technology, as well as to advance ideas on crystal growth under nanoconfinement.

Polyoxoniobates as molecular building blocks in thin films.

Niobium oxide thin films have been prepared by spin-coating aqueous solutions of tetramethylammonium salts of the isostructural polyoxometalate clusters [Nb10O28]6-, [TiNb9O28]7- and [Ti2Nb8O28]8- onto silicon wafers, and annealing them. The [Nb10O28]6- cluster yields films of Nb2O5 in the orthorhombic and monoclinic crystal phases when annealed at 800 °C and 1000 °C, respectively, whereas the [TiNb9O28]7- and [Ti2Nb8O28]8- clusters yield the monoclinic crystal phases of Ti2Nb12O29 and TiNb2O7 (titanium-niobium oxides) in different ratios. We also demonstrate a protocol for depositing successive layers of metal oxide films. Finally, we explore factors affecting the roughness of the films.

Detection of Surgical Wrap Defects in the Operating Room Setting.

Surgical site infection is a challenging complication that places a significant burden on the patient and the health care system. Emphasis is being placed on the prevention and treatment of surgical site infections. We evaluated the accuracy of identifying surgical wrap defects based on defect size, location, and operating room staff experience. Forty sterilization wraps were divided into 4 separate groups based on the size of the puncture defects created. Defects measuring 1.2 mm, 3.7 mm, and 6.8 mm were compared with a control group of surgical wraps with no defects. Defects were randomly placed on an inner or outer line with circumference of 7 cm or 14 cm, respectively. Twenty operating room staff of varying levels of experience evaluated each wrap for defects. The detection rates for the 1.2-mm, 3.7-mm, and 6.8-mm wraps and the wraps with no defects were 3%, 73%, 80%, and 99%, respectively. A significant difference was seen between the detection rates for the small defects vs all other size defects. No significant difference was seen in detection rate based on the location of defects. The detection rate was higher among staff members with greater than 1 year of experience vs those with less than 1 year of experience. Sterilization wrap defects of all sizes went undetected at very high rates. Small defects of 1.2 mm, which have been shown to allow bacterial contamination, were missed 97% of the time. Operating room staff with more experience detected more defects than those with less than 1 year of experience. Wrap defects may be a source of bacterial contamination that may frequently go unnoticed. [Orthopedics. 2021;44(6):735-e738.].

Polyoxometalates as Effective Nano-inhibitors of Amyloid Aggregation of Pro-inflammatory S100A9 Protein Involved in Neurodegenerative Diseases.

Pro-inflammatory and amyloidogenic S100A9 protein is central to the amyloid-neuroinflammatory cascade in neurodegenerative diseases. Polyoxometalates (POMs) constitute a diverse group of nanomaterials, which showed potency in amyloid inhibition. Here, we have demonstrated that two selected nanosized niobium POMs, Nb10 and TiNb9, can act as potent inhibitors of S100A9 amyloid assembly. Kinetics analysis based on ThT fluorescence experiments showed that addition of either Nb10 or TiNb9 reduces the S100A9 amyloid formation rate and amyloid quantity. Atomic force microscopy imaging demonstrated the complete absence of long S100A9 amyloid fibrils at increasing concentrations of either POM and the presence of only round-shaped and slightly elongated aggregates. Molecular dynamics simulation revealed that both Nb10 and TiNb9 bind to native S100A9 homo-dimer by forming ionic interactions with the positively charged Lys residue-rich patches on the protein surface. The acrylamide quenching of intrinsic fluorescence showed that POM binding does not perturb the Trp 88 environment. The far and near UV circular dichroism revealed no large-scale perturbation of S100A9 secondary and tertiary structures upon POM binding. These indicate that POM binding involves only local conformational changes in the binding sites. By using intrinsic and 8-anilino-1-naphthalene sulfonate fluorescence titration experiments, we found that POMs bind to S100A9 with a Kd of ca. 2.5 µM. We suggest that the region, including Lys 50 to Lys 54 and characterized by high amyloid propensity, could be the key sequences involved in S1009 amyloid self-assembly. The inhibition and complete hindering of S100A9 amyloid pathways may be used in the therapeutic applications targeting the amyloid-neuroinflammatory cascade in neurodegenerative diseases.

Nanoscale Hydration in Layered Manganese Oxides.

Birnessite is a layered MnO2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (MnIV, MnIII, and MnII), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium-water and direct water-birnessite interactions, and involves negligible water-water interactions. Using our composite adsorption-condensation-intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.

Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores.

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ∼5.0 Å from the clay basal-plane), observed in the MD simulations.

Structure and Mobility of Lactose in Lactose/Sodium Montmorillonite Nanocomposites.

This study aims at investigating the molecular level organization and molecular mobility in montmorillonite nanocomposites with the uncharged organic low-molecular-weight compound lactose commonly used in pharmaceutical drug delivery, food technology, and flavoring. Nanocomposites were prepared under slow and fast drying conditions, attained by drying at ambient conditions and by spray-drying, respectively. A detailed structural investigation was performed with modulated differential scanning calorimetry, powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, scanning electron microscopy, microcalorimetry, and molecular dynamics simulations. The lactose was intercalated in the sodium montmorillonite interlayer space regardless of the clay content, drying rate, or humidity exposure. Although, the spray-drying resulted in higher proportion of intercalated lactose compared with the drying under ambient conditions, nonintercalated lactose was present at 20 wt % lactose content and above. This indicates limitations in maximum loading capacity of nonionic organic substances into the montmorillonite interlayer space. Furthermore, a fraction of the intercalated lactose in the co-spray-dried nanocomposites diffused out from the clay interlayer space upon humidity exposure. Also, the lactose in the nanocomposites demonstrated higher molecular mobility than that of neat amorphous lactose. This study provides a foundation for understanding functional properties of lactose/Na-MMT nanocomposites, such as loading capacity and physical stability.

Partitioning into Colloidal Structures of Fasted State Intestinal Fluid Studied by Molecular Dynamics Simulations.

We performed molecular dynamics (MD) simulations to obtain insights into the structure and molecular interactions of colloidal structures present in fasted state intestinal fluid. Drug partitioning and interaction were studied with a mixed system of the bile salt taurocholate (TCH) and 1,2-dilinoleoyl-sn-glycero-3-phosphocholine (DLiPC). Spontaneous aggregation of TCH and DLiPC from unconstrained MD simulations at the united-atom level using the Berger/Gromos54A7 force fields demonstrated that intermolecular hydrogen bonding between TCH molecules was an important factor in determining the overall TCH and DLiPC configuration. In bilayered systems, these intermolecular hydrogen bonds resulted in embedded transmembrane TCH clusters. Free energy simulations using the umbrella sampling technique revealed that the stability of these transmembrane TCH clusters was superior when they consisted of 3 or 4 TCH per bilayer leaflet. All-atom simulations using the Slipids/GAFF force fields showed that the TCH embedded in the bilayer decreased the energy barrier to penetrate the bilayer (ΔGpen) for water, ethanol, and carbamazepine, but not for the more lipophilic felodipine and danazol. This suggests that diffusion of hydrophilic to moderately lipophilic molecules through the bilayer is facilitated by the embedded TCH molecules. However, the effect of embedded TCH on the overall lipid/water partitioning was significant for danazol, indicating that the incorporation of TCH plays a crucial role for the partitioning of lipophilic solutes into e.g. lipidic vesicles existing in fasted state intestinal fluids. To conclude, the MD simulations revealed important intermolecular interactions in lipidic bilayers, both between the bile components themselves and with the drug molecules.

Porosity investigation of compacted bentonite using XRD profile modeling.

Many countries intend to use compacted bentonite as a barrier in their deep geological repositories for nuclear waste. In order to describe and predict hydraulic conductivity or radionuclide transport through the bentonite barrier, fundamental understanding of the microstructure of compacted bentonite is needed. This study examined the interlayer swelling and overall microstructure of Wyoming Bentonite MX-80 and the corresponding homo-ionic Na(+) and Ca(2+) forms, using XRD with samples saturated under confined swelling conditions and free swelling conditions. For the samples saturated under confined conditions, the interparticle, or so-called free or external porosity was estimated by comparing the experimental interlayer distances obtained from one-dimensional XRD profile fitting against the maximum interlayer distances possible for the corresponding water content. The results showed that interlayer porosity dominated total porosity, irrespective of water content, and that the interparticle porosity was lower than previously reported in the literature. At compactions relevant for the saturated bentonite barrier (1.4-1.8 g/cm(3)), the interparticle porosity was estimated to ≤3%.