Host-guest interactions between xanthones and water: the role of O-H center dot center dot center dot O, C-H center dot center dot center dot O, and pi center dot center dot center dot pi contacts in the channel- and cage-type frameworks

In this article were studied two xanthone derivatives known as 1,5-dihydroxy-8-methoxyxanthone (I) and 1,3,7-trihydroxy-8-methoxyxanthone (II), which show one water molecule into their crystal structures. In xanthone I, there are water wires contributing to build up channel-like cavities along the c axis, whereas in xanthone II the water is surrounded by three xanthone molecules forming a cage-type structure. The geometries of I and II were optimized using the density functional theory method with B3LYP functional, and the results were compared with crystal structure. Both theoretical and experimental investigations reveal a concordance between structural parameters, with the xanthone core presenting an almost flat conformation and substituents adopting the more stable orientations. In the two compounds, the hydroxyl group linked at position 1 is involved in a resonance-assisted hydrogen bond with the carbonyl group. Besides, the supramolecular arrangement of the host/guest systems are stabilized mainly by classical intermolecular hydrogen bonds (O-H center dot center dot center dot O) involving xanthone-to-water and xanthone-to-xanthone. In addition, C-H center dot center dot center dot O weak hydrogen bonds, as well as pi-pi interactions play an important role to stabilize the crystal self-assembly of xanthones I and II. The results reported here underline the role of inclusion of water molecules and their different arrangement into the crystal structure of two xanthone host/guest systems.

Abundance of phytoplankton, heterotrophic nanoflagellates and bacteria through the water column at time series station L4 in the Western English Channel. 2007-2011

The marine laboratories in Plymouth have sampled at two principle sites in the Western English Channel for over a century in open-shelf (station E1; 50° 02'N, 4° 22'W) and coastal (station L4; 50° 15'N, 4° 13'W) waters. These stations are seasonally stratified from late-April until September, and the variable biological response is regulated by subtle variations in temperature, light, nutrients and meteorology. Station L4 is characterized by summer nutrient depletion, although intense summer precipitation, increasing riverine input to the system, results in pulses of increased nitrate concentration and surface freshening. The winter nutrient concentrations at E1 are consistent with an open-shelf site. Both stations have a spring and autumn phytoplankton bloom; at station E1, the autumn bloom tends to dominate in terms of chlorophyll concentration. The last two decades have seen a warming of around 0.6°C per decade, and this is superimposed on several periods of warming and cooling over the past century. In general, over the Western English Channel domain, the end of the 20th century was around 0.5°C warmer than the first half of the century. The warming magnitude and trend is consistent with other stations across the north-west European Shelf and occurred during a period of reduced wind stress and increased levels of insolation (+20%); these are both correlated with the larger scale climatic forcing of the North Atlantic Oscillation.