Understanding solvent effects in the selective conversion of fructose to 5-hydroxymethyl-furfural: a molecular dynamics investigation

Selective conversion of fructose to 5-hydroxymethyl-furfural (HMF) involves the participation of high-boiling solvents like dimethyl sulfoxide (DMSO). In order to replace DMSO with low-boiling solvents, it is imperative that we understand the effect of DMSO solvation in protecting (i) HMF from rehydration and humins formation reactions and (ii) fructose from side reactions, other than its dehydration to HMF. In the present work, molecular dynamics simulations of HMF and fructose in water and in water-DMSO mixtures are carried out using the OPLS-AA force field. Radial pair distribution functions, coordination numbers and the hydrogen-bond network between the HMF/fructose molecule and the solvent molecules are analysed. The local 3-dimensional picture of the arrangement of solvent molecules around the solute, which cannot be accessed from pair distribution functions, is also computed. We show preferential coordination of DMSO around HMF and explain how this could provide a shielding effect to the HMF molecule, thus protecting it from further rehydration to levulinic acid and formic acid and from humins formation. In the case of fructose, the presence of DMSO also reduces the number of water molecules in the immediate vicinity of fructose. Though fewer water molecules coordinate around fructose, they are bound strongly to it. Analysis of the local 3-dimensional arrangement of DMSO molecules suggests that it protects the fructose molecule from side reactions that would lead to condensation or reversion products. However, the presence of DMSO molecules does not hamper the water molecules coming into contact with the oxygen atom of the hydroxyl groups of fructose, which is required for a proton transfer from water to fructose, to initiate the dehydration reaction to HMF.     

Experimental determination of three-dimensional finite-time Lyapunov exponents in multi-component flows

We present an experimental approach for estimating finite-time Lyapunov exponent fields (FTLEs) in three-dimensional multi-component or multi-phase flows. From time-resolved sequences of particle images, we directly compute the flow map and coherent structures, while avoiding and outperforming the computationally costly numerical integration. Performing this operation independently on each flow component enables the determination of three-dimensional Lagrangian coherent structures (LCSs) without any bias from the other components. The locations of concurrent LCSs for different flow elements (e.g., passive tracers, inertial particles, bubbles, or active particles) can provide new insight into the interpenetrating FTLE structure in complex flows.     

A study of barium ultra-thin films on the SrTiO3(1 0 0) surface by soft X-ray photoelectron spectroscopy

The growth and the electronic properties of Ba ultra-thin films (coverage ≤ 2 ML) on the SrTiO₃(1 0 0) surface was studied using synchrotron radiation facilities. The investigation was carried out mainly by soft X-ray photoelectron spectroscopy measurements at low core levels and the valence band region. The results show that the Ba overlayer develops in a layer-by-layer mode. The first two layers do not create any states in the band gap, thus leaving intact the insulating character of the substrate. This is due to the oxidation of Ba through transfer of O²⁻ anions from the substrate into the Ba overlayer. It is observed that the valency of the Ti atoms at the interface does not change. This is attributed to an outwards diffusion of O²⁻ anions from deeper layers promoted by substrate annealing. Within the coverage examined, no evidence for Ba metallization is found, contrary to what happens on metallic substrates. Comparing the results of this work with previous ones on similar metal–SrTiO₃(1 0 0) adsorption systems, it is concluded that a single factor such as charge transfer or thermodynamic stability is not always sufficient to determine the oxidation process of the adsorbate layer. Kinetics on surfaces as well as substrate doping and defects can also play a decisive role.     

Spatial orientation of different frequencies within the echolocation beam of a Tursiops truncatus and Pseudorca crassidens

A two-dimensional array of 16 hydrophones was created to map the spatial distribution of different frequencies within the echolocation beam of a Tursiops truncatus and a Pseudorca crassidens. It was previously shown that both the Tursiops and Pseudorca only paid attention to frequencies between 29 and 42 kHz while echolocating. Both individuals tightly focused the 30?kHz frequency and the spatial location of the focus was consistently pointed toward the target. At 50?kHz the beam was less focused and less precisely pointed at the target. At 100?kHz the focus was often completely lost and was not pointed at the target. This indicates that these individuals actively focused the beam toward the target only in the frequency range they paid attention to. Frequencies outside this range were left unfocused and undirected. This focusing was probably achieved through sensorimotor control of the melon morphology and nasal air sacs. This indicates that both morphologically different species can control the spatial distribution of different frequency ranges within the echolocation beam to create consistent ensonation of desired targets.     

Multilevel coarse graining and nano-pattern discovery in many particle stochastic systems

In this work we propose a hierarchy of Markov chain Monte Carlo methods for sampling equilibrium properties of stochastic lattice systems with competing short and long range interactions. Each Monte Carlo step is composed by two or more sub-steps efficiently coupling coarse and finer state spaces. The method can be designed to sample the exact or controlled-error approximations of the target distribution, providing information on levels of different resolutions, as well as at the microscopic level. In both strategies the method achieves significant reduction of the computational cost compared to conventional Markov chain Monte Carlo methods. Applications in phase transition and pattern formation problems confirm the efficiency of the proposed methods.     

Vortex rings in radially confined domains

The dynamics of vortex rings generated within confined domains are relevant to important hydrodynamic processes such as flow past heart valves or severe arterial constrictions. However, despite their importance, these flows have not received much attention to date. This study examines the development and evolution of radially confined vortex rings. Time-resolved digital particle image velocimetry was used to investigate two levels of radial confinement and a range of vortex ring strengths. We found that for severely confined vortex rings, the formation time and peak circulation values were unaffected for L/D ₀?<?4 cases and slightly affected for larger L/D ₀ cases. After pinch-off, circulation decay was observed with an approximately constant normalized circulation decay rate. We found that with increasing circulation strength, the nondimensional time delay between the pinch-off and the onset of circulation decay reduced due to an increased vortex ring diameter within the confinement domain and a reduction in the necessary time for the surface induced and core vorticity regions to interact. This study uncovers the dynamics of radially confined vortex rings and show that the nondimensional rate of circulation decay is dependent on the vortex ring confinement ratio (ratio of the vortex ring orifice diameter to the diameter of the outer cylinder), and the time delay between the vortex pinch-off and the onset of circulation is dependent on the vortex ring circulation strength.     

High order phase fitted multistep integrators for the Schrödinger equation with improved frequency tolerance

In this work we introduce a new family of 14-steps linear multistep methods for the integration of the Schrödinger equation. The new methods are phase fitted but they are designed in order to improve the frequency tolerance. This is achieved by eliminating the first derivatives of the phase lag function at the fitted frequency forcing the phase lag function to be ‘flat’ enough in the neighbor of the fitted frequency. The efficiency of the new family of methods is proved via error analysis and numerical applications.     

A new methodology for the development of numerical methods for the numerical solution of the Schr?dinger equation

In the present paper we introduce a new methodology for the construction of numerical methods for the approximate solution of the one-dimensional Schr?dinger equation. The new methodology is based on the requirement of vanishing the phase-lag and its derivatives. The efficiency of the new methodology is proved via error analysis and numerical applications.     

A mechanism for mitigation of blade–vortex interaction using leading edge blowing flow control

The interaction of a vortical unsteady flow with structures is often encountered in engineering applications. Such flow structure interactions (FSI) can be responsible for generating significant loads and can have many detrimental structural and acoustic side effects, such as structural fatigue, radiated noise and even catastrophic results. Amongst the different types of FSI, the parallel blade–vortex interaction (BVI) is the most common, often encountered in helicopters and propulsors. In this work, we report on the implementation of leading edge blowing (LEB) active flow control for successfully minimizing the parallel BVI. Our results show reduction of the airfoil vibrations up to 38% based on the root-mean-square of the vibration velocity amplitude. This technique is based on displacing an incident vortex using a jet issued from the leading edge of a sharp airfoil effectively increasing the stand-off distance of the vortex from the body. The effectiveness of the method was experimentally analyzed using time-resolved digital particle image velocimetry (TRDPIV) recorded at an 800 Hz rate, which is sufficient to resolve the spatio-temporal dynamics of the flow field and it was combined with simultaneous accelerometer measurements of the airfoil, which was free to oscillate in a direction perpendicular to the freestream. Analysis of the flow field spectra and a Proper Orthogonal Decomposition (POD) of the TRDPIV data of the temporally resolved planar flow fields indicate that the LEB effectively modified the flow field surrounding the airfoil and increased the convecting vortices stand-off distance for over half of the airfoil chord length. It is shown that LEB also causes a redistribution of the flow field spectral energy over a larger range of frequencies.