A transferable model for adsorption in MOFs with unsaturated metal sites

The number of newly discovered Metal-Organic Frameworks is growing exponentially. Molecular simulation is becoming increasingly important to screen large databases of structures and identify potential candidates for challenging gas separations, but such efforts rely on the availability of accurate molecular models that can predict adsorption in a wide range of different MOFs. MOFs with co-ordinatively unsaturated sites (CUS) pose particular problems because standard force fields are unable to describe their specific interactions with certain adsorbates. In this paper, we demonstrate that our previous approach to describe adsorption in open metal sites, based on a combination of classical Monte Carlo simulations and quantum-mechanical Density Functional Theory calculations, is transferable to several Cu-containing MOFs. By fitting the parameters of our model to match adsorption energies of ethylene on HKUST-1 and transferring them to the Cu-paddlewheel units of other MOFs, we have obtained predictions in good agreement with experimental adsorption measurements. Where agreement is not as satisfactory, we show that this can be explained by limited accessibility or diffusion through the pore network. For one particular MOF, UMCM-150, we show that separate parameters need to be used for the Cu-trimer unit, for which the interaction energies with ethylene are much lower than in the Cu-paddlewheel. Overall, our approach demonstrates that the specific CUS interactions in MOFs can be parameterised separately from other interaction types, such as van der Waals, thus opening the way for the development of an accurate and fully transferable force field for this class of materials

Augmented serum levels of the IGF-I/IGF-binding protein-3 ratio in pre-menopausal patients with type I breast cysts

Objective: Gross cystic disease (GCD) is the most common benign breast pathology. Although breast cysts are not considered pre-malignant lesions, an increased risk of breast cancer has been reported for patients with type I cysts (Na+/K+ < 3). Furthermore, an augmented IGF-I/IGF-binding protein-3 (IGFBP-3) ratio has been described in breast cancer patients. The objective was to evaluate serum IGF-I and binding protein concentrations of type I and type II cyst patients as compared with healthy women. Methods: Twenty-four patients with type I cysts, 17 with type II cysts and 25 healthy women were evaluated. Serum IGF-I, IGFBP-3 and IGFBP-1 concentrations were measured by IRMA. Results: IGF-I concentrations were significantly higher in sera from patients with type I cysts than in patients with type II cysts. A highly significant decrease of IGFBP-3, the major IGFBP, was found in patients with type I cysts with respect to healthy women, whereas no significant difference was evident between the different cyst types. The IGF-I/IGFBP-3 ratio, an estimate of biologically active IGF-I, was very significantly higher in patients with type I cysts than in both type II patients and healthy women. IGFBP-1 levels were significantly lower in patients with type I than in controls and type II cysts. The IGF-I/IGFBP-1 ratio was significantly higher in patients with type I cysts than in type II bearers and healthy women. Estrogen levels correlated with IGF-I in patients and controls. Conclusions: The enhanced levels of IGF-I/IGFBP-3 found in patients with type I cysts could eventually be associated with the increased risk of breast cancer described for this group.Facultad de Ciencias Exacta

Augmented serum levels of the IGF-I/IGF-binding protein-3 ratio in pre-menopausal patients with type I breast cysts

Objective: Gross cystic disease (GCD) is the most common benign breast pathology. Although breast cysts are not considered pre-malignant lesions, an increased risk of breast cancer has been reported for patients with type I cysts (Na+/K+ < 3). Furthermore, an augmented IGF-I/IGF-binding protein-3 (IGFBP-3) ratio has been described in breast cancer patients. The objective was to evaluate serum IGF-I and binding protein concentrations of type I and type II cyst patients as compared with healthy women. Methods: Twenty-four patients with type I cysts, 17 with type II cysts and 25 healthy women were evaluated. Serum IGF-I, IGFBP-3 and IGFBP-1 concentrations were measured by IRMA. Results: IGF-I concentrations were significantly higher in sera from patients with type I cysts than in patients with type II cysts. A highly significant decrease of IGFBP-3, the major IGFBP, was found in patients with type I cysts with respect to healthy women, whereas no significant difference was evident between the different cyst types. The IGF-I/IGFBP-3 ratio, an estimate of biologically active IGF-I, was very significantly higher in patients with type I cysts than in both type II patients and healthy women. IGFBP-1 levels were significantly lower in patients with type I than in controls and type II cysts. The IGF-I/IGFBP-1 ratio was significantly higher in patients with type I cysts than in type II bearers and healthy women. Estrogen levels correlated with IGF-I in patients and controls. Conclusions: The enhanced levels of IGF-I/IGFBP-3 found in patients with type I cysts could eventually be associated with the increased risk of breast cancer described for this group.Facultad de Ciencias Exacta

Causal structure of acoustic spacetimes

The so-called ``analogue models of general relativity'' provide a number of specific physical systems, well outside the traditional realm of general relativity, that nevertheless are well-described by the differential geometry of curved spacetime. Specifically, the propagation of acoustic disturbances in moving fluids are described by ``effective metrics'' that carry with them notions of ``causal structure'' as determined by an exchange of sound signals. These acoustic causal structures serve as specific examples of what can be done in the presence of a Lorentzian metric without having recourse to the Einstein equations of general relativity. (After all, the underlying fluid mechanics is governed by the equations of traditional hydrodynamics, not by the Einstein equations.) In this article we take a careful look at what can be said about the causal structure of acoustic spacetimes, focusing on those containing sonic points or horizons, both with a view to seeing what is different from standard general relativity, and to seeing what the similarities might be.Comment: 51 pages, 39 figures (23 colour figures, colour used to convey physics information.) V2: Two references added, some additional discussion of maximal analytic extension, plus minor cosmetic change

Rotational dynamics in the plastic-crystal phase of ethanol: Relevance for understanding the dynamics during the structural glass transition

12 págs.; 14 figs.; 1 tab.; 1 apéndiceThe reorientational dynamics within the rotationally disordered cubic plastic phase of solid ethanol is investigated by means of the concurrent use of computer molecular dynamics and quasielastic neutron scattering. Motions involving widely different time scales are shown to take place above the calorimetric >glass transition> which is centered at Tg≈97 K. These correspond to well-defined reorientations belonging to the cubic point group. The dynamics of this solid exhibits features remarkably close to those of the supercooled liquid that can exist at the same temperature. Such similitude of dynamic behavior serves to provide some clues for the understanding of the nature of molecular motions at temperatures close to the canonical liquid→glass transition. ©2000 The American Physical Society.This work was supported in part by Grant No. DGICYTPB95- 0072-C03 (Spain). Work at ANL was supported by the U.S. Department of Energy, BES–Materials Sciences, under Contract No. W-31-109-ENG-38.Peer Reviewe

Long-term evolution and coupling of the boundary layers in the Stratus Deck Regions of the eastern Pacific (STRATUS)

A surface mooring was deployed in the eastern tropical Pacific west of northern Chile from the R/V Melville as part of the Eastern Pacific Investigation of Climate (EPIC). EPIC is a CLIVAR study with the goal of investigating links between sea surface temperature variability in the eastern tropical Pacific and climate over the American continents. Important to that goal is an understanding of the role of clouds in the eastern Pacific in modulating atmosphere-ocean coupling. The mooring was deployed near 20°S 85°W, at a location near the western edge of the stratocumulus cloud deck found west of Peru and Chile. This deployment started a three-year occupation of that site by a WHOI surface mooring in order to collect accurate time series of surface forcing and upper ocean variability. The surface mooring was deployed by the Upper Ocean Processes Group of the Woods Hole Oceanographic Institution (WHOI). In collaboration with investigators from the University of Concepcion, Concepcion, Chile, an XBT section was made on the way out to the mooring from Arica, Chile, and an XBT and CTD section was made on the way into Arica. The buoy was equipped with meteorological instrumentation, including two Improved METeorological (IMET) systems. The mooring also carried Vector Measuring Current Meters, single-temperature recorders, and conductivity and temperature recorders located in the upper meters of the mooring line. In addition to the instrumentation noted above, a variety of other instruments, including an acoustic current meter, an acoustic doppler current profiler, a bio-optical instrument package, and an acoustic rain guage, were deployed. This report describes, in a general manner, the work that took place and the data collected during the Cook 2 cruise aboard the R/V Melville. The surface mooring deployed during this cruise will be recovered and re-deployed after approximately 12 months and again after 24 months, with a final recovery planned for 36 months after the first setting. Details of the mooring design and preliminary data from the XBT and CTD sections are included.Funding was provided by the National Oceanic and Atmospheric Administration under grant number NA96GP0429

Copper(II) defect-cubane water oxidation electrocatalysts: from molecular tetramers to oxidic nanostructures

We report on the synthesis and spectroscopic evidence for a sequence of structural transformations of a new defect-cubane type copper complex, [Cu4(pyalk)4(OAc)4](ClO4)(HNEt3), which acts as a pre-catalyst for water oxidation. In situ and post-catalytic studies showed that the tetrameric complex undergoes a structural transformation into dimeric and monomeric species, induced by water molecules and carbonate anions, respectively. Further, the observed electrocatalytic water oxidation activity has been confirmed to arise from in situ-generated Cu(II) oxidic nanostructures at the electrode interface

Chemical constituents of the volatile oil from leaves of Annona coriacea and in vitro antiprotozoal activity

The essential oil of the leaves from Annona coriacea Mart., Annonaceae, was extracted by hydrodistillation in a Clevenger apparatus and analyzed by GC/MS and GC/FID. The oil yield was 0.05% m/m. Sixty compounds were identified, in a complex mixture of sesquiterpenes (76.7%), monoterpenes (20.0%) and other constituents (3.3%). Bicyclogermacrene was its major compound (39.8%) followed by other sesquiterpenes. Most of the monoterpenes were in low concentration (<1%). Only &#946;-pinene and pseudolimonene presented the highest level of 1.6%. The volatile oil presented anti-leishmanial and trypanocidal activity against promastigotes of four species of Leishmania and trypomastigotes of Trypanosoma cruzi, showing to be more active against Leishmania (L.) chagasi (IC50 39.93 µ g/mL) (95% CI 28.00-56.95 µ g/mL)

Chemical constituents of the volatile oil from leaves of Annona coriacea and in vitro antiprotozoal activity

The essential oil of the leaves from Annona coriacea Mart., Annonaceae, was extracted by hydrodistillation in a Clevenger apparatus and analyzed by GC/MS and GC/FID. The oil yield was 0.05% m/m. Sixty compounds were identified, in a complex mixture of sesquiterpenes (76.7%), monoterpenes (20.0%) and other constituents (3.3%). Bicyclogermacrene was its major compound (39.8%) followed by other sesquiterpenes. Most of the monoterpenes were in low concentration (<1%). Only &#946;-pinene and pseudolimonene presented the highest level of 1.6%. The volatile oil presented anti-leishmanial and trypanocidal activity against promastigotes of four species of Leishmania and trypomastigotes of Trypanosoma cruzi, showing to be more active against Leishmania (L.) chagasi (IC50 39.93 µ g/mL) (95% CI 28.00-56.95 µ g/mL).21