Bauhinoxepins A and B: New Antimycobacterial Dibenzo[b,f]oxepins from Bauhinia saccocalyx

Two new antimycobacterial dibenzo[b,f]oxepins, bauhinoxepins A (=3,3,5‐trimethylbenzo[b]pyrano[g][1]benzoxepin‐6,11‐diol; 1 ) and B (=6‐methoxy‐7‐methyl‐2‐(3‐methylbut‐2‐enyl)dibenzo[b,f]oxepine‐1,8‐diol; 2 ), were isolated from the roots of Bauhinia saccocalyx, and their structures were elucidated by analysis of spectroscopic data. Bauhinoxepins A and B exhibited antimycobacterial activities with respective minimum‐inhibitory concentrations (MIC) of 6.25 and 12.5 μg/ml. They were inactive (at 20 μg/ml) against the malarial parasite, and also inactive (at 20 μg/ml) towards the Vero, KB, and BC cell lines.     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Theoretical study of methane adsorption and C─H bond activation over Fe-embedded graphene: Effect of external electric field

The effect of an external electric field (EF) on the methane adsorption and its activation on iron-embedded graphene (Fe-GPs) are investigated by using the M06-L density functional method. The EF is applied in the perpendicular direction to the graphene in the range of −0.015 to +0.015 a.u. with the interval of 0.005 a.u. The effects of EF on the adsorption, transition state and product complexes of the methane activation reaction are revealed. The binding energies of methane on Fe site in Fe-GPs are increased from −12.9 to −15.3, −18.1 and −21.5 kcal/mol for the negative EF of −0.005, −0.010 and −0.015, respectively. By applying positive EF, the activation barriers for methane activation are reduced in range of 3–8 kcal/mol (around 12–31%) and the reaction energies are more exothermic. The positive EF kinetically favors the reaction compared to the system without EF. The adsorption and activation of methane on Fe-GPs can be easily tuned by adjusting the external electric field for various applications. © 2019 Wiley Periodicals, Inc.     

An Integrated Inventory-Routing System for Multi-item Joint Replenishment with Limited Vehicle Capacity

In this paper, we develop a mathematical programming approach for coordinating inventory and transportation decisions in an inbound commodity collection system. In particular, we consider a system that consists of a set of geographically dispersed suppliers that manufacture one or more non-identical items, and a central warehouse that stocks these items. The warehouse faces a constant and deterministic demand for the items from outside retailers. The items are collected by a fleet of vehicles that are dispatched from the central warehouse. The vehicles are capacitated, and must also satisfy a frequency constraint. Adopting a policy in which each vehicle always collects the same set of items, we formulate the inventory-routing problem of minimizing the long-run average inventory and transportation costs as a set partitioning problem. We employ a column generation approach to determine a lower bound on the total costs, and develop a branch-and-price algorithm that finds the optimal assignment of items to vehicles. We also propose greedy constructive heuristics, and develop a very large-scale neighborhood (VLSN) search algorithm to find near-optimal solutions for the problem. Computational tests are performed on a set of randomly generated problem instances.The work of this author was supported by a scholarship of the Faculty of Engineering of Ubonratchathani University, Ubonratchathani, Thailand., The work of this author was supported in part by the National Science Foundation under Grant No. DMI-0085682.     

A quantum chemical study of the haptotropic rearrangements of Cr(CO)(3) on naphthalene and phenanthrene systems

First-principles gradient-corrected density functional theory electronic structure calculations of the haptotropic rearrangement of a Cr(CO)(3) unit on naphthalene and phenanthrene derivatives are reported. Coupled-cluster calibration studies of Cr(CO)(3) complexes with benzene and naphthalene derivatives confirm the accuracy of the applied Becke exchange and Perdew correlation functionals. Characteristic points on the energy hypersurface (reactants, products, intermediates, and transition states) were located for various substituents on the aromatic skeleton. It is argued that a -OH/-O(-) substituent may provide a means to steer the haptotropic shift depending on the pH value, i.e., to construct a molecular switch. In addition, the mechanism of the [3 + 2 + 1] benzannulation of chromium pentacarbonyl naphthylcarbene complexes with alkynes was investigated, and the preference of the angular benzannulation leading to phenanthrene complexes of Cr(CO)(3) over the linear benzannulation leading to corresponding anthracene complexes is explained.