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.

Harbor Porpoise (Phocoena phocoena) Abundance in Alaska: Bristol Bay to Southeast Alaska, 1991-1993

Between 1991 and 1993, Alaska harbor porpoise (Phocoena phocoena) abundance was investigated during aerial surveys throughout much of the coastal and offshore waters from Bristol Bay in the eastern Bering Sea to Dixon Entrance in Southeast Alaska. Line-transect methodology was used, and only those observations made during optimal conditions were analyzed. Survey data indicated densities of 4.48 groups/100 km2, or approximately 3,531 harbor porpoises (95% C.I. 2,206-5,651) in Bristol Bay and 0.54 groups/100 km2, or 136 harbor porpoises (95% C.I. 11-1,645) for Cook Inlet. Efforts off Kodiak Island resulted in densities of 1.85 groups/100 km2, or an abundance estimate of 740 (95% C.I. 259-2,115). Surveys off the south side of the Alaska Peninsula found densities of 2.03 groups/100 km2 and an abundance estimate of 551 (95% C.I. 423-719). Surveys of offshore waters from Prince William Sound to Dixon Entrance yielded densities of 4.02 groups/100 km’ and an abundance estimate of 3,982 (95% C.I. 2,567-6,177). Combining all years and areas yielded an uncorrected density estimate of 3.82 porpoises per 100 km2, resulting in an abundance estimate of 8,940 porpoises (CV = 13.8%) with a 95% confidence interval of 6,746-11,848. Using correction factors from other studies to adjust for animals missed by observers, the total number of Alaska harbor porpoises is probably three times this number.