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

Evidence of nonuniformity in urothelium barrier function between the upper urinary tract and bladder

Purpose We compared the relative permeability of upper urinary tract and bladder urothelium to mitomycin C. Materials and Methods Ex vivo porcine bladder, ureters and kidneys were dissected out and filled with 1 mg ml–1 mitomycin C. At 60 minutes the organs were emptied and excised tissue samples were sectioned parallel to the urothelium. Sectioned tissue was homogenized and extracted mitomycin C was quantified. Transurothelial permeation across the different urothelia was calculated by normalizing the total amount of drug extracted to the surface area of the tissue sample. Average mitomycin C concentrations at different tissue depths (concentration-depth profiles) were calculated by dividing the total amount of drug recovered by the total weight of tissue. Results Mitomycin C permeation across the ureteral urothelium was significantly greater than across the bladder and renal pelvis urothelium (9.07 vs 0.94 and 3.61 μg cm–2, respectively). Concentrations of mitomycin C in the ureter and kidney were markedly higher than those achieved in the bladder at all tissue depths. Average urothelial mitomycin C concentrations were greater than 6.5-fold higher in the ureter and renal pelvis than in the bladder. Conclusions To our knowledge we report for the first time that the upper urinary tract and bladder show differing permeability to a single drug. Ex vivo porcine ureter is significantly more permeable to mitomycin C than bladder urothelium and consequently higher mitomycin C tissue concentrations can be achieved after topical application. Data in this study correlate with the theory that mammalian upper tract urothelium represents a different cell lineage than that of the bladder and it is innately more permeable to mitomycin C

Brightening of excitons in carbon nanotubes on dimensionality modification

Despite the attractive one-dimensional characteristics of carbon nanotubes, their typically low luminescence quantum yield, restricted because of their one-dimensional nature, has limited the performance of nanotube-based light-emitting devices. Here, we report the striking brightening of excitons (bound electron–hole pairs) in carbon nanotubes through an artificial modification of their effective dimensionality from one dimension to zero dimensions. Exciton dynamics in carbon nanotubes with luminescent, local zero-dimension-like states generated by oxygen doping were studied as model systems. We found that the luminescence quantum yield of the excitons confined in the zero-dimension-like states can be more than at least one order larger (~18%) than that of the intrinsic one-dimensional excitons (typically ~1%), not only because of the reduced non-radiative decay pathways but also due to an enhanced radiative recombination probability beyond that of intrinsic one-dimensional excitons. Our findings are extendable to the realization of future nanoscale photonic devices including a near-infrared single-photon emitter operable at room temperature

An <i>ex Vivo</i> Investigation into the Transurothelial Permeability and Bladder Wall Distribution of the Nonsteroidal Anti-Inflammatory Ketorolac

Transurothelial drug delivery continues to be an attractive treatment option for a range of urological conditions; however, dosing regimens remain largely empirical. Recently, intravesical delivery of the nonsteroidal anti-inflammatory ketorolac has been shown to significantly reduce ureteral stent-related pain. While this latest development provides an opportunity for advancing the management of stent-related pain, clinical translation will undoubtedly require an understanding of the rate and extent of delivery of ketorolac into the bladder wall. Using an <i>ex vivo</i> porcine model, we evaluate the urothelial permeability and bladder wall distribution of ketorolac. The subsequent application of a pharmacokinetic (PK) model enables prediction of concentrations achieved <i>in vivo</i>. Ketorolac was applied to the urothelium and a transurothelial permeability coefficient (<i>K</i>_p) calculated. Relative drug distribution into the bladder wall after 90 min was determined. Ketorolac was able to permeate the urothelium (<i>K</i>_p = 2.63 × 10^–6 cm s^–1), and after 90 min average concentrations of 400, 141 and 21 μg g^–1 were achieved in the urothelium, lamina propria and detrusor respectively. An average concentration of 87 μg g^–1 was achieved across the whole bladder wall. PK simulations (STELLA) were then carried out, using <i>ex vivo</i> values for <i>K</i>_p and muscle/saline partition coefficient (providing an estimation of vascular clearance), to predict 90 min <i>in vivo</i> ketorolac tissue concentrations. When dilution of the drug solution with urine and vascular clearance were taken into account, a reduced ketorolac concentration of 37 μg g^–1 across the whole bladder wall was predicted. These studies reveal crucial information about the urothelium’s permeability to agents such as ketorolac and the concentrations achievable in the bladder wall. It would appear that levels of ketorolac delivered to the bladder wall intravesically would be sufficient to provide an anti-inflammatory effect. The combination of such <i>ex vivo</i> data and PK modeling provides an insight into the likelihood of achieving clinically relevant concentrations of drug following intravesical administration