Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices

A modified polysulfone containing benzylamine groups was synthesized as a reactive membrane material. Polysulfone was activated at the ortho-sulfone site by direct lithiation with n-butyllithium, and the resulting lithiated polysulfone was then reacted with benzonitrile; this yielded a polymer with pendant benzimine groups. The structure was confirmed by NMR and IR spectroscopy and by the transformation of imine to ketone by acid hydrolysis. The polymeric benzimine was also reduced to benzylamine with sodium cyanoborohydride in an acidic medium. The structure and degree of substitution of both benzylamine derivatives were determined by NMR and IR spectroscopy. The modified polysulfone containing benzylamine groups initiated the polymerization of N-carboxyanhydride of gamma-benzyl-L-glutamate [Glu(OBzl)-NCA]. The side-chain oligopeptide of Glu(OBzl)-NCA attached to polysulfone was converted into molecular recognition sites.NRC publication: Ye

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane ( CH 3 I ) is investigated by ionization above the iodine 4 d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules

Coulomb-explosion imaging of concurrent photodissociation dynamics

The dynamics following laser-induced molecular photodissociation of gas-phase CH2BrI at 271.6 nm were investigated by time-resolved Coulomb-explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH2BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH2Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb-explosion imaging as a real-time probe of chemical dynamics