Hydration of guanidinium depends on its local environment

Hydration of gaseous guanidinium (Gdm⁺) with up to 100 water molecules attached was investigated using infrared photodissociation spectroscopy in the hydrogen stretch region between 2900 and 3800 cm^–1. Comparisons to IR spectra of low-energy computed structures indicate that at small cluster size, water interacts strongly with Gdm⁺ with three inner shell water molecules each accepting two hydrogen bonds from adjacent NH₂ groups in Gdm⁺. Comparisons to results for tetramethylammonium (TMA⁺) and Na⁺ enable structural information for larger clusters to be obtained. The similarity in the bonded OH region for Gdm(H₂O)₂₀ ⁺ vs. Gdm(H₂O)₁₀₀ ⁺ and the similarity in the bonded OH regions between Gdm⁺ and TMA⁺ but not Na⁺ for clusters with <50 water molecules indicate that Gdm⁺ does not significantly affect the hydrogen-bonding network of water molecules at large size. These results indicate that the hydration around Gdm⁺ changes for clusters with more than about eight water molecules to one in which inner shell water molecules only accept a single H-bond from Gdm⁺. More effective H-bonding drives this change in inner-shell water molecule binding to other water molecules. These results show that hydration of Gdm⁺ depends on its local environment, and that Gdm⁺ will interact with water even more strongly in an environment where water is partially excluded, such as the surface of a protein. This enhanced hydration in a limited solvation environment may provide new insights into the effectiveness of Gdm⁺ as a protein denaturant.     

Inherent Ethyl Acetate Selectivity in a Trianglimine Molecular Solid

Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle ( TAMC ) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, “templated” cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation.     

Approaches to achieve surface sensitivity in the in situ XAS of electrocatalysts

In situ and operando techniques providing information regarding adsorbate bonding and atomic arrangements on the electrode surface along with pure electrochemical measurements are needed to more fully understand the detailed mechanism of electrocatalytic reactions on high surface areas/nanoparticle electrocatalysts. X-ray adsorption spectroscopy (XAS) is a powerful tool to interrogate the electronic structure and local coordination environment of such electrocatalysts under working conditions, but it should be acknowledged that standard XAS methods are not intrinsically surface sensitive. This review will present recent in situ XAS studies on single-atom, metal, and metal oxide electrocatalysts, highlighting the approaches taken to achieve surface sensitivity by careful designing of the sample under investigation.     

Configurational Lability at Tetrahedral Phosphorus: syn/anti-Isomerization of a P-Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus

Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH₂CHPh][OTf] (Mes*=2,4,6-(t-Bu)₃C₆H₂) occurred under mild conditions at 60 °C in CD₂Cl₂, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu₄][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C₆Cl₄O₂)₃) followed by chromatography on silica removed [NBu₄][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH₂CHPh][Δ-TRISPHAT]?x[NBu₄][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P.     

Strain-field analysis acquired through correlation of X-ray radiographs of a fiber-reinforced composite laminate

The strain fields can be determined on the surface of fiber-reinforced composites by correlation analysis of X-ray radiographs of the specimen. One radiograph is taken of the specimen in an unloaded state and another radiograph of the same specimen is taken in a deformed state. Each radiograph is then imaged by a video camera and digitized using a Matrox digitization board. The displacement map is obtained from the two radiographs by dividing one image into subsets of 20 pixels by 20 pixels and using a correlation algorithm to identify the corresponding subsets in the second image. The correlation is completed between patterns of the grey-level intensities for each subset. The appropriate discrete derivatives can then be evaluated by first difference taken to form the in-plane strains. The X-ray radiographs correlation analysis strain-field method outlined above was applied to a uniaxially loaded [90, 0] _s Gl-Ep coupon. Simultaneously, an extensometer measured the average longitudinal strain over a 2.54-cm (1-in.) gage length. The error between the two methods was less than three percent of the applied strain of 1.3 percent. The same specimen was impacted and re-examined. A radical shift in the strain field was observed when the specimen was reloaded. Further investigation showed the method reliable down to 0.5-percent strain. Paper was presented at the 1986 SEM Spring Conference on Experimental Mechanics held in New Orleans, LA on June 8–13.     

Hydraulic fracturing of a saturated porous medium-II: Special cases

This investigation deals with the problem of steady state hydraulic fracture in an infinite isotropic fluid-saturated elastic porous medium induced by a uniform pressure applied to the crack surfaces. A quasi-static approach is employed in the study. A boundary value problem is formulated and then analyzed by means of the Fourier transform associated with the Wiener-Hopf technique. Stress intensity factor and potential energy release rate are found by asymptotic analysis and the superposition principle as functions of the speed of crack propagation. The material breakdown process at the crack tip is discussed based on Dugdale's model. Finally, a brief discussion of the effect of pressure drop on the hydraulic fracture process and the decrease in crack speed during crack extension is included.     

Horizontal bubble flow

An experimental investigation of cocurrent bubble flow in 0.0254 m and 0.0508 m diameter horizontal pipelines has been performed. Gas and liquid mass velocities ranged from 0.00955 to 0.675 and 2720 to 6040 kg/m² sec, respectively, and gas-phase holdups or void fractions ranged from 0.13 to 7.59%.High speed motion pictures revealed that the gas, introduced into the liquid with a concentric nozzle, emerged in the form of a rough jet which was ultimately sheared into 1 times; 10^minus;3 to 3 times; 10^minus;3m diameter bubbles. Approximately 4 meters downstream from the nozzle, a well developed bubble flow was observed where bubble number density and axial velocity were constant with respect to axial position in the pipeline. Bubble velocities ranged from 0.001 to 0.57 m/sec greater than the average liquid velocities. Bubble radial and circumferential spatial distributions were found to be a strong function of the degree of turbulence in the liquid phase. Because of these turbulent flow conditions, bubble shapes were much different than those of equivalent diameter bubbles rising in stagnant liquids. A sphere-ellipsoid of revolution model was developed for characterization of bubble shape and computation of gas-liquid interfacial area and two-phase pressure drop.     

High Entropy Alloys as Filler Metals for Joining

In the search for applications for alloys developed under the philosophy of the High Entropy Alloy (HEA)-type materials, the focus may be placed on applications where current alloys also use multiple components, albeit at lower levels than those found in HEAs. One such area, where alloys with complex compositions are already found, is in filler metals used for joining. In soldering (<450 °C) and brazing (>450 °C), filler metal alloys are taken above their liquidus temperature and used to form a metallic bond between two components, which remain both unmelted and largely unchanged throughout the process. These joining methods are widely used in applications from electronics to aerospace and energy, and filler metals are highly diverse, to allow compatibility with a broad range of base materials (including the capability to join ceramics to metals) and a large range of processing temperatures. Here, we review recent developments in filler metals relevant to High Entropy materials, and argue that such alloys merit further exploration to help overcome a number of current challenges that need to be solved for filler metal-based joining methods.