Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

An Intercomparison of Regional Atmospheric Circulation and the Melt Season Loss of Arctic Snow Cover and Sea Ice Extent Across the Land-Ocean Boundary

This study is designed to compare the monthly continental snow cover and sea ice extent loss in the Arctic with regional atmospheric conditions including: mean sea level pressure, 925 hPa air temperature, and mean wind direction among others during the melt season (March-August) over the 29-year study period 1979-2007. Little research has gone into studying the concurrent variations in the annual loss of continental snow cover and sea ice extent across the land-ocean boundary, since these data are largely stored in incompatible formats. However, the analysis of these data, averaged spatially over three autonomous study regions located in Siberia, North America, and Western Russia, reveals a distinct difference in the response of snow and sea ice to the atmospheric forcing. On average, sea ice extent is lost earlier in the year, in May, than snow cover, in June, although Arctic sea ice is located farther north than continental snow in all three study regions. Once the loss of snow and ice extent begins, snow cover is completely removed sooner than sea ice extent, even though ice loss begins earlier in the melt season. Further, the analysis of the atmospheric conditions surrounding loss of snow and ice cover over the independent study regions indicates that conditions of cool temperatures with strong northeasterly winds in the later melt season months are effective at removing sea ice cover, likely through ice divergence, as are warmer temperatures via southerly winds directly forcing melt. The results of this study set the framework for further analysis of the direct influence of snow cover loss on later melt season sea ice extents and the predictability of snow and sea ice extent responses to modeled future climate conditions