Understanding Nanopore Window Distortions in the Reversible Molecular Valve Zeolite RHO

Molecular valves are becoming popular for potential biomedical applications. However, little is known concerning their performance in energy and environmental areas. Zeolite RHO shows unique pore deformations upon changes in hydration, cation siting, cation type, or temperature-pressure conditions. By varying the level of distortion of double eight-rings, it is possible to control the adsorption properties, which confer a molecular valve behavior to this material. We have employed interatomic potentials-based simulations to obtain a detailed atomistic view of the structural distortion mechanisms of zeolite RHO, in contrast with the averaged and space group restricted information provided by diffraction studies. We have modeled four aluminosilicate structures, containing Li$^+$, Na$^+$, K$^+$, Ca$^{2+}$, and Sr$^{2+}$ cations. The distortions of the three different zeolite rings are coupled, and the six- and eight-membered rings are largely flexible. A large dependence on the polarizing power of the extra-framework cations and with the loading of water has been found for the minimum aperture of the eight-membered rings that control the nanovalve effect. The calculated energy barriers for moving the cations across the eight-membered rings are very high, which explains the experimentally observed slow kinetics of the phase transition as well as the appearance of metastable phases

Dynamical mechanism of anticipating synchronization in excitable systems

We analyze the phenomenon of anticipating synchronization of two excitable systems with unidirectional delayed coupling which are subject to the same external forcing. We demonstrate for different paradigms of excitable system that, due to the coupling, the excitability threshold for the slave system is always lower than that for the master. As a consequence the two systems respond to a common external forcing with different response times. This allows to explain in a simple way the mechanism behind the phenomenon of anticipating synchronization.Comment: 4 pages including 7 figures. Submitted for publicatio

16α,17α-Ep­oxy-5α-hydr­oxy-6β-nitrooxy-20-oxopregnan-3β-yl acetate

The title steroid, C23H33NO8, is a pregnane derivative obtained regio-, stereo- and chemoselectively from the ring opening of the corresponding 5α,6α;16α,17α-diepoxide with bis­muth(III) nitrate. There are two symmetry-independent mol­ecules in the asymmetric unit that show no significant differences concerning bond lengths and angles. All rings are trans-fused. The conformations of the six-membered rings are close to chair forms, while the five-membered ring adopts an envelope conformation. The mol­ecules are held together by an extensive O—H⋯O hydrogen-bonding network of chains runnning along the a axis

6β-Acetamido-5α-hydroxy­cholestan-3β-yl acetate

The title steroid, C31H53NO4, was prepared from the corresponding 5α,6α-epoxy­cholestane. The conformation of the six-membered rings is close to a chair form, while the five-membered ring adopts a twist conformation. The hydroxyl and acetamide groups are in axial positions. The nucleophilic species bound to the steroid nucleus at position 6 by the β-face, whereas the hydroxyl group at position 5 has α-orientation. All rings are trans-fused. The crystal packing shows that the mol­ecules related by twofold symmetry exist as O—H⋯O hydrogen-bonded dimers

Efficient methane production from lipid-rich wastewater in high-rate anaerobic treatment

In this work, high rate anaerobic mineralization of a synthetic dairy effluent containing 50% COD as oleic acid was accomplished in two reactors operated in parallel. The anaerobic reactors were able to accommodate organic loading rates up to 21 kg COD m-3 day-1, HRT of 9 hours, attaining 99% of soluble COD removal efficiency and methane yield higher than 70%. Long chain fatty acids (LCFA) accumulated inside the reactor only during the last two phases of operation and palmitic acid was the main LCFA quantified, representing 40–100% of the total LCFA detected. High specific methanogenic activity was determined at the end of the operation, in the presence of acetate (1346±87 mg COD-CH4 gVS-1 day-1) and H2/CO2 (3582±309 mg COD-CH4 gVS-1 day-1). The specific activity of the anaerobic consortia present in the reactors during the operation was also determined, and a maximum value of 1170±170 mg COD-CH4 gVS-1 day-1 was obtained. The high performance accomplished in the reactors was a consequence of the discontinuous acclimation strategy applied, that produced an anaerobic microbial community specialized in the efficient mineralization of LCFA.Fundação para a Ciência e Tecnologia (FCT) projecto FAT-METHANE (POCTI/CTA/46328/2002), bolsa de doutoramento SFRH/BD/24256/200