16 research outputs found
Structure, Photophysics and the Order-Disorder Transition to the Beta Phase in Poly(9,9-(di -n,n-octyl)fluorene)
X-ray diffraction, UV-vis absorption and photoluminescence (PL) spectroscopy
have been used to study the well-known order-disorder transition (ODT) to the
beta phase in poly(9,9-(di n,n-octyl)fluorene)) (PF8) thin film samples through
combination of time-dependent and temperature-dependent measurements. The ODT
is well described by a simple Avrami picture of one-dimensional nucleation and
growth but crystallization, on cooling, proceeds only after molecular-level
conformational relaxation to the so called beta phase. Rapid thermal quenching
is employed for PF8 studies of pure alpha phase samples while extended
low-temperature annealing is used for improved beta phase formation. Low
temperature PL studies reveal sharp Franck-Condon type emission bands and, in
the beta phase, two distinguishable vibronic sub-bands with energies of
approximately 199 and 158 meV at 25 K. This improved molecular level structural
order leads to a more complete analysis of the higher-order vibronic bands. A
net Huang-Rhys coupling parameter of just under 0.7 is typically observed but
the relative contributions by the two distinguishable vibronic sub-bands
exhibit an anomalous temperature dependence. The PL studies also identify
strongly correlated behavior between the relative beta phase 0-0 PL peak
position and peak width. This relationship is modeled under the assumption that
emission represents excitons in thermodynamic equilibrium from states at the
bottom of a quasi-one-dimensional exciton band. The crystalline phase, as
observed in annealed thin-film samples, has scattering peaks which are
incompatible with a simple hexagonal packing of the PF8 chains.Comment: Submitted to PRB, 12 files; 1 tex, 1 bbl, 10 eps figure
Cage Hydrocarbons as Linkers in Dimeric Drug Design: Case Studies with Trimethoprim and Tedizolid
The looming threat of a “post-antibiotic era” has been caused by a rapid rise in antibacterial resistance and subsequent depletion of effective antibiotic agents in the clinic. An efficient strategy to address this shortfall lies in the reengineering of pre-existing and commercially available antibiotic drugs. This is exemplified by dimerization, a design concept in which two pharmacophores are covalently linked to form a new chemical entity. The cage hydrocarbons cubane (1), bicyclo[2.2.2]octane (BCO) (2), adamantane (3), and bicyclo[1.1.1]pentane (BCP) (4) present themselves as an attractive family of linkers in this regard. In this report, all four hydrocarbon cages were employed as linkers in a series of dimers based on the commercially available antibiotics trimethoprim and tedizolid. A detailed synthetic roadmap for the protection and deprotection of each pharmacophore is outlined. Several members of the trimethoprim series showed activity on par with that of their trimethoprim progenitor, although this was not the case for the tedizolid series. The design strategy outlined herein highlights the utility of the group as a platform for the rapid and modular construction of future novel antibiotics.Biljana Vujcic, Jessica Wyllie, Tania, Jed Burns, Keith F. White, Simon Cromwell, David W. Lupton, Jason L. Dutton, Tatiana P. Soares da Costa, Sevan D. Housto