Hydrodeoxygenation of HMF over Pt/C in a continuous flow reactor

The three‐phase hydrodeoxygenation reaction of 5‐hydroxymethylfurfural (HMF) with H₂ was studied over a 10 wt % Pt/C catalyst using both batch and flow reactors, with ethanol, 1‐propanol, and toluene solvents. The reaction is shown to be sequential, with HMF reacting first to furfuryl ethers and other partially hydrogenated products. These intermediate products then form dimethyl furan (DMF), which in turn reacts further to undesired products. Furfuryl ethers were found to react to DMF much faster than HMF, explaining the higher reactivity of HMF when alcohol solvents were used. With the optimal residence time, it was possible to achieve yields approaching 70% in the flow reactor with the Pt/C catalyst. Much higher selectivities and yields were obtained in the flow reactor than in the batch reactor because side products are formed sequentially, rather than in parallel, demonstrating the importance of choosing the correct type of reactor in catalyst screening. © 2014 American Institute of Chemical Engineers AIChE J, 61: 590–597, 2015     

Synthesis and Biopharmaceutical Evaluation of Imatinib Analogues Featuring Unusual Structural Motifs

A convenient synthesis of imatinib, a potent inhibitor of ABL1 kinase and widely prescribed drug for the treatment of a variety of leukemias, was devised and applied to the construction of a series of novel imatinib analogues featuring a number of non‐aromatic structural motifs in place of the parent molecule's phenyl moiety. These analogues were subsequently evaluated for their biopharmaceutical properties (e.g., ABL1 kinase inhibitory activity, cytotoxicity). The bicyclo[1.1.1]pentane‐ and cubane‐containing analogues were found to possess higher themodynamic solubility, whereas cubane‐ and cyclohexyl‐containing analogues exhibited the highest inhibitory activity against ABL1 kinase and the most potent cytotoxicity values against cancer cell lines K562 and SUP‐B15. Molecular modeling was employed to rationalize the weak activity of the compounds against ABL1 kinase, and it is likely that the observed cytotoxicity of these agents arises through off‐target effects.     

Optimal Influence Strategies in Social Networks

This paper suggests a modeling framework to investigate the optimal strategy followed by a monopolistic firm aiming to manipulate the process of opinion formation in a social network. The monopolist and a set of consumers communicate to form their beliefs about the underlying product quality. Since the firm’s associated optimization problem can be analytically solved only under specific assumptions, we rely on the sequential quadratic programming computational approach to characterize the equilibrium. When consumers’ initial beliefs are uniform, the firm’s optimal influence strategy always involves targeting the most influential consumer. For the case of non-uniform initial beliefs, the monopolist might target the less influential consumer if the latter’s initial opinion is low enough. The probability of investing more in the consumer with the lower influence increases with the distance between consumers’ initial beliefs and with the degree of trust attributed on consumers by the firm. The firm’s profit is minimized when consumers’ influences become equal, implying that the firm benefits from the presence of consumers with divergent strategic locations in the network. In the absence of a binding constraint on total investment, the monopolist’s incentives to manipulate the network decrease with consumers’ initial beliefs and might either increase or decrease with the trust put in consumers’ opinion by the firm. Finally, the firm’s strategic motivation to communicate persistently high beliefs during the opinion formation process is positively associated with the market size, with the available budget and with the direct influence of the most influential consumer on the other but negatively associated with consumers’ initial valuation of the good.     

Methane steam reforming at microscales: Operation strategies for variable power output at millisecond contact times

The potential of methane steam reforming at microscale is theoretically explored. To this end, a multifunctional catalytic plate microreactor, comprising of a propane combustion channel and a methane steam reforming channel, separated by a solid wall, is simulated with a pseudo 2‐D (two‐dimensional) reactor model. Newly developed lumped kinetic rate expressions for both processes, obtained from a posteriori reduction of detailed microkinetic models, are used. It is shown that the steam reforming at millisecond contact times is feasible at microscale, and in agreement with a recent experimental report. Furthermore, the attainable operating regions delimited from the materials stability limit, the breakthrough limit, and the maximum power output limit are mapped out. A simple operation strategy is presented for obtaining variable power output along the breakthrough line (a nearly iso‐flow rate ratio line), while ensuring good overlap of reaction zones, and provide guidelines for reactor sizing. Finally, it is shown that the choice of the wall material depends on the targeted operating regime. Low‐conductivity materials increase the methane conversion and power output at the expense of higher wall temperatures and steeper temperature gradients along the wall. For operation close to the breakthrough limit, intermediate conductivity materials, such as stainless steel, offer a good compromise between methane conversion and wall temperature. Even without recuperative heat exchange, the thermal efficiency of the multifunctional device and the reformer approaches ～65% and ～85%, respectively. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Multiscale modeling reveals poisoning mechanisms of MgO-supported Au clusters in CO oxidation

Catalyst deactivation mechanisms on MgO-supported Au(6) clusters are studied for the CO oxidation reaction via first-principle kinetic Monte Carlo simulations and shown to depend on support vacancies. In defect-poor MgO or in the presence of a Mg vacancy, O(2) does not bind to the clusters and the catalyst is poisoned by CO. On Au clusters interacting with O vacancies of the support, O(2) can be chemisorbed and transient activity is observed. In this case, an unexpected catalyst "breathing" mechanism (restructuring) leads to carbonate formation and catalyst deactivation, rationalizing several experimental observations. Our study underscores the importance of the cluster's charge state and dynamics on catalytic activity.     

An overview of spatial microscopic and accelerated kinetic Monte Carlo methods

The microscopic spatial kinetic Monte Carlo (KMC) method has been employed extensively in materials modeling. In this review paper, we focus on different traditional and multiscale KMC algorithms, challenges associated with their implementation, and methods developed to overcome these challenges. In the first part of the paper, we compare the implementation and computational cost of the null-event and rejection-free microscopic KMC algorithms. A firmer and more general foundation of the null-event KMC algorithm is presented. Statistical equivalence between the null-event and rejection-free KMC algorithms is also demonstrated. Implementation and efficiency of various search and update algorithms, which are at the heart of all spatial KMC simulations, are outlined and compared via numerical examples. In the second half of the paper, we review various spatial and temporal multiscale KMC methods, namely, the coarse-grained Monte Carlo (CGMC), the stochastic singular perturbation approximation, and the τ-leap methods, introduced recently to overcome the disparity of length and time scales and the one-at-a time execution of events. The concepts of the CGMC and the τ-leap methods, stochastic closures, multigrid methods, error associated with coarse-graining, a posteriori error estimates for generating spatially adaptive coarse-grained lattices, and computational speed-up upon coarse-graining are illustrated through simple examples from crystal growth, defect dynamics, adsorption–desorption, surface diffusion, and phase transitions.     

Intensification of steam reforming of natural gas: Choosing combustible fuel and reforming catalyst

The steam reforming of methane in a parallel plate microreactor, consisting of alternating channels carrying out catalytic combustion and reforming on opposite sides of a wall, is modeled with fundamental kinetics and a pseudo-2D reactor model. It is shown that at high fuel conversions, the choice of hydrocarbon combustible fuel is immaterial when suitable compositions are used so that the energy input is kept the same. On the other hand, direct comparison of Rh and Ni indicates that the choice of reforming catalyst is critical. Speed up of heat transfer via miniaturization is insufficient for process intensification; catalyst-intensification is also needed to avoid hot spots and enable compact devices for portable and distributed power generation.