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.

Few-cycle attosecond pulse chirp effects on asymmetries in ionized electron momentum distributions

The momentum distributions of electrons ionized from H atoms by chirped few-cycle attosecond pulses are investigated by numerically solving the time-dependent Schrödinger equation. The central carrier frequency of the pulse is chosen to be 25 eV, which is well above the ionization threshold. The asymmetry (or difference) in the yield of electrons ionized along and opposite to the direction of linear laser polarization is found to be very sensitive to the pulse chirp (for pulses with fixed carrier-envelope phase), both for a fixed electron energy and for the energy-integrated yield. In particular, the larger the pulse chirp, the larger the number of times the asymmetry changes sign as a function of ionized electron energy. For a fixed chirp, the ionized electron asymmetry is found to be sensitive also to the carrier-envelope phase of the few-cycle pulse.