Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) ¹H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g⁻¹ of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.     

Nonlinear dynamics of a flexible rotor on tilting pad journal bearings experiencing rub–impact

Nonlinear Dynamics - Rub–impact phenomenon occurring in hydrodynamic journal bearings is one of the main malfunctions in rotating machines and causes undesirable dynamic behavior. In order to...     

Single quantum dot (QD) imaging of fluid flow near surfaces

We introduce the use of quantum dot (QD) nanoparticles for near-surface velocimetry and provide preliminary data to demonstrate its feasibility. Evanescent wave illumination is used to image the motion of water-soluble (CdSe)ZnS QDs with a core size of 6 nm within a region of order 100 nm of a surface . Results are presented for the two in-plane components of the velocity field.     

Computational explorations to gain insight into the structural features of TNF-α receptor I inhibitors

TNF-α is a crucial cytokine in the process of inflammatory diseases. The adverse effect of TNF-α is mostly mediated by interaction of TNF-α with TNF-α receptor type I (TNFR1); therefore, discovery of molecules which can bind to TNFR1 preventing TNF-α-receptor complex formation would be of great interest. In the current study, using GRID/GOLPE program, a 3D-QSAR study was conducted on a series of synthetic TNFR1 binders, which resulted in a 3D-QSAR model with appropriate power of predictivity in internal (r²?=?0.94 and q²_LOO?=?0.74) and external (r²?=?0.66 and SDEP?=?0.42) validations. The structural features of TNFR1 inhibitors essential for exerting activity were explored by analyzing the contour maps of the 3D-QSAR model showing that steric interactions and hydrogen bonds are responsible for exerting TNFR1 inhibitory activity. To propose potential chemical entities for TNFR1 inhibition, PubChem database was searched and the selected compounds were virtually tested for anti-TNFR1 activity using the generated model, resulting in two potential anti-TNFR1 compounds. Finally, the possible interactions of the compounds with TNFR1 were investigated using docking studies. The findings in the current work can pave the way for designing more potent anti-TNFR1 inhibitors.     

Improved parameterization of the quantum harmonic oscillator model based on localized wannier functions to describe Van der Waals interactions in density functional theory

Recently, the quantum harmonic oscillator model has been combined with maximally localized Wannier functions to account for long‐range dispersion interactions in density functional theory calculations (Silvestrelli, J. Chem. Phys. 2013, 139, 054106). Here, we present a new, improved set of values for the three parameters involved in this scheme. To test the new parameter set we have computed the potential energy curves for various systems, including an isolated Ar2 dimer, two N2 dimers interacting within different configurations, and a water molecule physisorbed on pristine graphene. While the original set of parameters generally overestimates the interaction energies and underestimates the equilibrium distances, the new parameterization substantially improves the agreement with experimental and theoretical reference values. © 2016 Wiley Periodicals, Inc.     

Multi-photon molecular tagging velocimetry with femtosecond excitation (FemtoMTV)

We present results for first molecular tagging velocimetry (MTV) measurements in water under resonant femtosecond excitation/emission process of a phosphorescent supramolecule. Both two-photon and three-photon absorption processes are examined, and the feasibility of measurements is demonstrated by single component velocimetry in a simple jet flow. The new capabilities enabled by FemtoMTV include elimination of the need for short wavelength UV excitation source and UV optical access in flow facilities, and potential for high rep-rate flow imaging.     

Flow Around a Crack in a Porous Matrix and Related Problems

The equations governing plane steady-state flow in heterogeneous porous body containing cracks are presented first. Then, a general transformation lemma is presented which allows extending a particular solution obtained for a given flow problem to another configuration with different geometry, behaviour and boundary conditions. An existing potential solution in terms of discharges along the cracks, established by Liolios and Exadaktylos (J Solids Struct 43:3960–3982, 2006) for non-intersecting cracks in isotropic matrix, is extended to intersecting cracks in anisotropic matrix. The basic problem of a single straight crack in an infinite body submitted to a pressure gradient at infinity is then investigated and a closed-form solution is presented for the case of void cracks (infinite conductivity), as well as a semi-analytical solution for the case of cracks with Poiseuille type conductivity. These solutions, derived first for an isotropic matrix, are then extended to anisotropic matrices using the general transformation lemma. Finally, using the solution obtained for a single crack, a closed-form estimation of the effective permeability of micro-cracked porous materials with weak crack density is derived from a self-consistent upscaling scheme.     

Micro–macro approach for the rock salt behaviour

Rock salt is considered as a pure aggregate of halite (mineral NaCl) crystals and its behaviour is investigated by a micro–macro approach. The behaviour of the polycrystalline aggregate is deduced from the properties of the constituent halite crystals. A model for the elastoplastic behaviour of halite crystal has been deduced from experimental data available in the literature. The basic equations of the micro–macro model for the polycrystalline medium and the calculation method are then presented and the elastoplastic behaviour of rock salt is investigated by this method. The hardening effects obtained for the polycrystal are found to be very different from those obtained for FCC metal polycrystals. The differences are explained as a consequence of differences of families of glide systems in these crystals. Finally, the internal stresses in the polycrystal are studied in order to elucidate the origin of cracking and damage of the rock salt.     

Application of 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo)phenol in construction of ion‐selective PVC membrane electrode for determination of copper (II) in mineral water sample

The potentiometric characteristics of a new Cu²⁺‐selective electrode based on 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo) phenol as an efficient ionophore has been evaluated. The effects of influential parameters on the potentiometric responses such as the amount of plasticizer, the amount of ionophore, pH of the sample solution, and the effect of coexisting ions on the electrode signal were subsequently investigated . The selectivity of the electrode was assessed by calculating the selectivity coefficients using the matched potential method. The optimum ratio of the amount of materials required for the preparation of the electrode was found to be 1.7: 32.1: 64.2: 2.0 corresponding to carboxylated PVC, dimethyl sebacate as solvent mediators, potassium tetrakis (p‐chlorophenyl) borate as the anion localizing agent, and ionophore, respectively. The electrode had a fast response (7s) as well as a satisfactory Nernstian slope (29.26±0.91 mV/decade) to Cu²⁺ over a wide concentration range of 2.0×10^?6‐ 5.0×10^?2 M with a low detection limit of 5.9×10^?7 M. The developed sensor was successfully used for the potentiometric titration of Cu²⁺ ion with EDTA and subsequently, efficient determination of this metal ion in a mineral water sample was performed.