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.

Chloroacetamid Spray Drift and Leaf Tatters in Hackberry

During the last decade, leaf tatters has been reported in white oak and hackberry across several Midwestern states. Herbicide spray drift studies have shown that chloroacetamides can induce leaf tatters. The objectives of this research were to: 1) identify vulnerable bud developmental stages in hackberry and 2) determine if different commercial chloroacetamides affect severity of leaf tatters. In 2008, a preliminary spray drift experiment was conducted on mature trees from a former hackberry provenance test stand. Acetochlor (Harness), S-metolachlor (Dual II Magnum), and dimethenamid (Outlook) were applied at concentrations approximating 27%, 54%, 81%, or 108% of the recommended field rate. Three developmental stages before bud burst were present on the selected trees. Leaf tatters did not develop on the selected hackberry trees. However, symptoms were observed on neighboring, non-target hackberry trees, which had been in the leaf unfolding and expanding stages at the time of spraying. In 2009, three year old hackberry seedlings were treated with 1%, 10%, and 100% of the recommended field rate of acetochlor (Harness), S-metolachlor (Dual II Magnum), and dimethenamid (Outlook). Folded buds and two unfolding leaf developmental stages were present on seedlings. Another spray study was conducted on 32 mature hackberry trees from the provenance stand. A solution of 5608 mg a.i./L dimethenamid (Outlook) was applied to trees in the unfolding and/or expanding leaf stage. Treated trees represented four provenances. Image analysis was used to calculate seedling and mature tree leaf areas and estimate the seedling percentage of leaf tissue loss. Foliar damage was not significantly different between seedlings treated with water, 1%, or 10% of the field rate. Foliar damage was significantly different between seedlings treated with 1% or 100% of the field rate, and between seedlings treated with 10% or 100% of the field rate. Foliar damage in seedlings was not significantly different between the developmental stages. Additionally, symptoms of leaf tatters were observed on the treated mature hackberry. Future studies should focus on chloroacetamide concentrations above 10% of the recommended field rate.

Perturbative analysis of the triply differential cross section and circular dichroism in photo-double-ionization of He

We extend application of our lowest-order perturbative approach (in electron-electron correlation) for analysis of photo-double-ionization (PDI) of He [A.Y. Istomin et al., J. Phys. B 35, L543 (2002)] to excess energies up to 450 eV and to analysis of circular dichroism. We find that account of electron correlation in the final state to first order provides predictions for the triply differential cross section and circular dichroism that are in reasonable agreement with absolute data for excess energies up to 80 eV. For an excess energy of 450 eV, account of electron correlation in both initial and final states is necessary and the predicted triply differential cross sections are in agreement with absolute data only for large mutual ejection angles. We find that at excess energies of a few tens of eV, the PDI is dominated by the "virtual" knock-out mechanism, while the "direct" (on-shell) knock-out process gives only small contributions for large mutual ejection angles. As a result, we conclude that the circular dichroism effect at these energies originates from the nonzero electron Coulomb phase shifts.