Hydrogen bonded supramolecular elastomers : correlating hydrogen bonding strength with morphology and rheology

A series of six low molecular weight elastomers with hydrogen bonding end-groups have been designed, synthesised and studied. The poly(urethane) based elastomers all contained essentially the same hard block content (ca. 11%) and differ only in the nature of their end-groups. Solution state 1H NMR spectroscopic analysis of model compounds featuring the end-groups demonstrate that they all exhibit very low binding constants, in the range 1.4 to 45.0 M-1 in CDCl3, yet the corresponding elastomers each possess a markedly different nanoscale morphology and rheology in the bulk. We are able to correlate small variations of the binding constant of the end-groups with dramatic changes in the bulk properties of the elastomers. These results provide an important insight into the way in which weak non-covalent interactions can be utilized to afford a range of self-assembled polyurethane based materials that feature different morphologies.

Hydrology and climatology at Laguna La Gaiba, lowland Bolivia: complex responses to climatic forcings over the last 25,000 years

Diatom, geochemical and isotopic data provide a record of environmental change in Laguna La Gaiba, lowland Bolivia (17°450S, 57°350W), over the last ca. 25 000 years. High-resolution diatom analysis around the Last Glacial–Interglacial Transition provides new insights into this period of change. The full and late glacial lake was generally quite shallow, but with evidence of periodic flooding. At about 13 100 cal a BP, just before the start of the Younger Dryas chronozone, the diatoms indicate shallower water conditions, but there is a marked change at about 12 200 cal a BP indicating the onset of a period of high variability, with rising water levels punctuated by periodic drying. From ca. 11 800 to 10 000 cal a BP, stable, deeper water conditions persisted. There is evidence for drying in the early to middle Holocene, but not as pronounced as that reported from elsewhere in the southern hemisphere tropics of South America. This was followed by the onset of wetter conditions in the late Holocene consistent with insolation forcing. Conditions very similar to present were established about 2100 cal a BP. A complex response to both insolation forcing and millennial-scale events originating in the North Atlantic is noted.

The role of plasma membrane STIM1 and Ca(2+)entry in platelet aggregation. STIM1 binds to novel proteins in human platelets.

Ca(2+) elevation is essential to platelet activation. STIM1 senses Ca(2+) in the endoplasmic reticulum and activates Orai channels allowing store-operated Ca(2+) entry (SOCE). STIM1 has also been reported to be present in the plasma membrane (PM) with its N-terminal region exposed to the outside medium but its role is not fully understood. We have examined the effects of the antibody GOK/STIM1, which recognises the N-terminal region of STIM1, on SOCE, agonist-stimulated Ca(2+) entry, surface exposure, in vitro thrombus formation and aggregation in human platelets. We also determined novel binding partners of STIM1 using proteomics. The dialysed GOK/STIM1 antibody failed to reduced thapsigargin- and agonist-mediated Ca(2+) entry in Fura2-labelled cells. Using flow cytometry we detect a portion of STIM1 to be surface-exposed. The dialysed GOK/STIM1 antibody reduced thrombus formation by whole blood on collagen-coated capillaries under flow and platelet aggregation induced by collagen. In immunoprecipitation experiments followed by proteomic analysis, STIM1 was found to extract a number of proteins including myosin, DOCK10, thrombospondin-1 and actin. These studies suggest that PM STIM1 may facilitate platelet activation by collagen through novel interactions at the plasma membrane while the essential Ca(2+)-sensing role of STIM1 is served by the protein in the ER.