Interaction of a poly(acrylic acid) oligomer with dimyristoylphosphatidylcholine bilayers

We studied the influence of 5 kDa poly(acrylic acid) (PAA) on the phase state, thermal properties, and lateral diffusion in bilayered systems of dimyristoylphosphatidylcholine (DMPC) using 31P NMR spectroscopy, differential scanning calorimetry (DSC), 1H NMR with a pulsed field gradient, and 1H nuclear Overhauser enhancement spectroscopy (NOESY). The presence of PAA does not change the lamellar structure of the system. 1H MAS NOESY cross-peaks observed for the interaction between lipid headgroups and polyion protons demonstrated only surface PAA-biomembrane interaction. Small concentrations of PAA (up to ∼4 mol %) lead to the appearance of a new lateral phase with a higher main transition temperature, a lower cooperativity, and a lower enthalpy of transition. Higher concentrations lead to the disappearance of measurable thermal effects. The lateral diffusion coefficient of DMPC and the apparent activation energy of diffusion gradually decreased at PAA concentrations up to around 4 mol %. The observed effects were explained by the formation of at least two types of PAA-DMPC lateral complexes as has been described earlier (Fujiwara, M.; Grubbs, R. H.; Baldeschwieler, J. D. J. Colloid Interface Sci., 1997, 185, 210). The first one is characterized by a stoichiometry of around 28 lipids per polymer, which corresponds to the adsorption of the entire PAA molecule onto the membrane. Lipid molecules of the complex are exchanged with the "pure" lipid bilayer, with the lifetime of the complex being less than 0.1 s. The second type of DMPC-PAA complex is characterized by a stoichiometry of 6 to 7 lipids per polymer and contains PAA molecules that are only partially adsorbed onto the membrane. A decrease in the DMPC diffusion coefficient and activation energy for diffusion in the presence of PAA was explained by the formation of a new cooperative unit for diffusion, which contains the PAA molecule and several molecules of lipids. © 2011 American Chemical Society

Miocene waterfowl and other birds from central Otago, New Zealand

Copyright © The Natural History Museum 2007Abundant fossil bird bones from the lower Bannockburn Formation, Manuherikia Group, an Early-Middle Miocene lacustrine deposit, 16–19 Ma, from Otago in New Zealand, reveal the “St Bathans Fauna” (new name), a first Tertiary avifauna of land and freshwater birds from New Zealand. At least 23 species of birds are represented by bones, and probable moa, Aves: Dinornithiformes, by eggshell. Anatids dominate the fauna with four genera and five species described as new: a sixth and largest anatid species is represented by just one bone. This is the most diverse Early-Middle Miocene duck fauna known worldwide. Among ducks, two species of dendrochenines are most numerous in the fauna, but a tadornine is common as well. A diving petrel (Pelecanoididae: Pelecanoides) is described, so extending the geological range of this genus worldwide from the Pliocene to the Middle Miocene, at least. The remaining 16 taxa are left undescribed but include: a large species of gull (Laridae); two small waders (Charadriiformes, genus indet.), the size of Charadrius bicinctus and Calidris ruficollis, respectively; a gruiform represented by one specimen similar to Aptornis; abundant rail (Rallidae) bones, including a common flightless rail and a rarer slightly larger taxon, about the size of Gallirallus philippensis; an ?eagle (Accipitridae); a pigeon (Columbidae); three parrots (Psittacidae); an owlet nightjar (Aegothelidae: Aegotheles sp.); a swiftlet (Apodidae: Collocalia sp.); and three passerine taxa, of which the largest is a member of the Cracticidae. The absence of some waterbirds, such as anserines (including swans), grebes (Podicipedidae) and shags (Phalacrocoracidae), among the abundant bones, indicates their probable absence from New Zealand in the Early-Middle Miocene.T. H. Worthy, A. J. D. Tennyson, C. Jones, J. A. McNamara and B. J. Dougla

Unfrozen water content moderates temperature dependence of sub-zero microbial respiration

Abrupt increases in the temperature sensitivity of soil respiration below 0 °C have been interpreted as a change in the dominance of other co-dependent environmental controls, such as the availability of liquid-state water. Yet the relationship between unfrozen water content and soil respiration at sub-zero temperatures has received little attention because of difficulties in measuring unfrozen water contents. Using a recently-developed semi-solid <sup>2</sup>H NMR technique the unfrozen water content present in seasonally frozen boreal forest soils was quantified and related to biotic CO<sub>2</sub> efflux in laboratory microcosms maintained at temperatures between −0.5 and −8 °C. In both soils the unfrozen water content had an exponential relationship with temperature and was increased by addition of KCl solutions of defined osmotic potential. Approximately 13% unfrozen water was required to release the dependence of soil respiration on unfrozen water content. Depending on the osmotic potential of soil solution, this threshold unfrozen water content was associated with temperatures down to −6 °C; yet if temperature were the predictor of CO<sub>2</sub> efflux, then the abrupt increase in the temperature sensitivity of CO<sub>2</sub> efflux was associated with −2 °C, except in soils amended with −1500 kPa KCl which did not show any abrupt changes in temperature sensitivity. The KCl-amendments also had the effect of decreasing Q<sub>10</sub> values and activation energies (Ea) by factors of 100 and three, respectively, to values comparable with those for soil respiration in unfrozen soil. The disparity between the threshold temperatures and the reductions in Q<sub>10</sub> values and activation energies after KCl amendment indicates the significance of unfrozen water availability as an environmental control of equal importance to temperature acting on sub-zero soil respiration. However, this significance was diminished when soils were supplied with abundant labile C (sucrose) and the influences of other environmental controls, allied to the solubility and diffusion of respiratory substrates and gases, are considered to increase

Nitrous oxide production in boreal soils with variable organic matter content at low temperature - snow manipulation experiment.

Agricultural soils are the most important sources for the greenhouse gas nitrous oxide (N<sub>2</sub>O), which is produced and emitted from soils also at low temperatures. The processes behind emissions at low temperatures are still poorly known. Snow is a good insulator and it keeps soil temperature rather constant. To simulate the effects of a reduction in snow depth on N<sub>2</sub>O emission in warming climate, snow pack was removed from experimental plots on three different agricultural soils (sand, mull, peat). Removal of snow lowered soil temperature and increased the extent and duration of soil frost in sand and mull soils. This led to enhanced N<sub>2</sub>O emissions during freezing and thawing events. The cumulative emissions during the first year when snow was removed over the whole winter were 0.25, 0.66 and 3.0 g N<sub>2</sub>O-N m<sup>−2</sup> yr<sup>−1</sup> in control plots of sand, mull and peat soils, respectively. In the treatment plots, without snow cover, the respective cumulative emissions were 0.37, 1.3 and 3.3 g N<sub>2</sub>O-N m<sup>−2</sup> yr<sup>−1</sup>. Shorter snow manipulation during the second year did not increase the annual emissions. Only 20% of the N<sub>2</sub>O emission occurred during the growing season. Thus, these results highlight the importance of the winter season for this exchange and that the year-round measurements of annual N<sub>2</sub>O emissions from boreal soils are integral for estimating their N<sub>2</sub>O source strength. N<sub>2</sub>O accumulated in the frozen soil during winter and the soil N<sub>2</sub>O concentration correlated with the depth of frost but not with the winter N<sub>2</sub>O emission rates per se. Also laboratory incubations of soil samples showed high production rates of N<sub>2</sub>O at temperatures below 0°C, especially in the sand and peat soils