The self-assembly and solid-state structures of host-guest inclusion compounds with lamellar architectures based on a common building block, a resilient hydrogen-bonded sheet consisting of guanidinium ions and sulfonate moieties of organodisulfonate "pillars", are described. The pillars connect adjacent sheets to generate galleries with molecular-scale cavities occupied by guest molecules. The size, shape, and physicochemical character of the inclusion cavities can be systematically adjusted by interchanging framework components while maintaining the lamellar architecture, enabling prediction and control of crystal lattice metrics with a precision that is unusual for "crystal engineering". The reliability of the lamellar architecture is a direct consequence of conformational flexibility exhibited by these hosts that, unlike rigid systems, enables them to achieve optimal packing with guest molecules. The adaptability of these hosts is further reflected by an architectural isomerism that is driven by guest templating during assembly of the inclusion compounds. Host frameworks constructed with various pillars display metric interdependences among specific structural features that reveal a common mechanism by which these soft frameworks adapt to different guests. This unique feature facilitates structure prediction and provides guidance for the design of inclusion compounds based on these hosts.
1. A broadened concept of biodiversity, encompassing spatio‐temporal heterogeneity, functional processes and species diversity, could provide a unifying theme for river ecology. 2. The theoretical foundations of stream ecology often do not reflect fully the crucial roles of spatial complexity and fluvial dynamics in natural river ecosystems, which has hindered conceptual advances and the effectiveness of efforts at conservation and restoration. 3. Inclusion of surface waters (lotic and lentic), subsurface waters (hyporheic and phreatic), riparian systems (in both constrained and floodplain reaches), and the ecotones between them (e.g. springs) as interacting components contributing to total biodiversity, is crucial for developing a holistic framework of rivers as ecosystems. 4. Measures of species diversity, including alpha, beta and gamma diversity, are a result of disturbance history, resource partitioning, habitat fragmentation and successional phenomena across the riverine landscape. A hierarchical approach to diversity in natural and altered river‐floodplain ecosystems will enhance understanding of ecological phenomena operating at different scales along multidimensional environmental gradients. 5. Re‐establishing functional diversity (e.g. hydrologic and successional processes) across the active corridor could serve as the focus of river conservation initiatives. Once functional processes have been reconstituted, habitat heterogeneity will increase, followed by corresponding increases in species diversity of aquatic and riparian biota.
The hexadentate N6-donor podand tris[3-(2-pyridyl)pyrazolyl]hydroborate (TpPy) contains 2-pyridyl fragments attached to the pyrazolyl C3-positions such that each arm is a bidentate chelate. Three series of lanthanide(III) complexes were prepared: [M(TpPy)(MeOH)2F][PF6] (series A), [M(TpPy)(NO3)2] (series B), and [M(TpPy)2][BPh4] (series C). Crystallographic studies showed that series A and B have a 1:1 metal:TpPy ratio, with the metal ion lying within the podand cavity and the remaining coordination sites occupied by solvent molecules and/or counterions to give 9-coordination (A, with one fluoride and two methanol ligands) or 10-coordination (B, with two bidentate nitrate ligands). The C complexes were prepared in the absence of any coordinating anions and have a 1:2 metal:TpPy ratio with an unusual icosahedral geometry arising from coordination of the 12 nitrogen donors from two interleaved podands. Conductivity studies on the B complexes show that in water the nitrates dissociate to give [M(TpPy)(H2O) q ](NO3)2; the relaxivity of [Gd(TpPy)(NO3)2] in water is 4.4 s-1 mM-1, a value comparable to those of clinically useful MRI contrast enhancement agents. Comparison of emission lifetimes of [M(TpPy)(NO3)2] (M = Eu, Tb) in H2O/D2O and CH3OH/CD3OD give values for q, the number of coordinated solvent molecules, of 3.6 (water) and 2.6 (methanol). The C complex [Tb(TpPy)2][BPh4] also has q = 2.6 in methanol, suggesting that partial ligand dissociation allows access of solvent molecules to the metal coordination sphere.
The pattern of temporal change in recruitment of steelhead trout (Oncorhynchus mykiss) entering the ocean between 1963 and 1990 was geographically coherent in all regions of British Columbia. A major increase in recruitment was evident for smolts entering the ocean after 1977. Subsequently, an out‐of‐phase response occurred after 1990, indicating that the effect of a possible 1990 regime shift had both temporal and geographical structure. Steelhead entering northern regions had increasing recruitment, while steelhead entering southern BC coastal regions had sharply decreasing recruitment. The evidence clearly indicates that the overall recruitment response since 1977 was primarily shaped by changes in marine (not freshwater) survival. Similar sudden changes in adult recruitment also appear to be occurring for other species of Pacific salmon in BC and Oregon, such as coho (O. kisutch), which appear to occur suddenly and show considerable persistence. A possible explanation for the change is that ocean productivity declined in coastal regions of southern BC after 1990, reducing the marine growth of juvenile salmon. The Bakun upwelling index shows a pattern of geographical coherence along the west coast of North America that could in principle explain the observed pattern of changes in recruitment. However, no evidence for a temporal shift in this index occurring around 1977 and 1990 is apparent. The reason for the sudden and persistent decline in ocean survival is therefore uncertain.
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