Tuning the Properties of Azadipyrromethene-Based Near-Infrared Dyes Using Intramolecular BO Chelation and Peripheral Substitutions.

Tetraphenylazadipyrromethenes (ADPs) are attractive near-infrared (NIR) dyes because of their simple synthesis and exceptional optical and electronic properties. The typical BF2 and less explored intramolecular BO coordination planarize the molecule, making them promising π-conjugated materials for organic electronic applications. However, their use has been mostly limited to vacuum-deposited devices. To improve the properties, we synthesized and characterized a series of ADP complexes and used density functional theory calculations to further explain the properties. Hexyloxy solubilizing groups increase the complexes' solubility in organic solvents and enable film formation from solution. Phenylethynyls at the pyrrolic positions extend π conjugation, red-shift absorption and emission peaks, and increase the ionization potential (IP) and electron affinity. When the properties of complexes with hexyloxy and phenyethynyl substitutions are compared, the BO complex is more planar and has a smaller IP than the corresponding BF2 complex because of increased electron density on the proximal phenyls. The BO complex has an unusual combination of properties: a solution λmax of 781 nm, emission at 805 nm, a small Stokes shift, and a quantum yield of 6%. It forms transparent films with a low optical gap of 1.22 eV. This new complex is a promising candidate for transparent solar cells and NIR photodetectors.

Large Non-planar Conjugated Molecule with Strong Intermolecular Interactions Achieved with Homoleptic Zn(II) Complex of Di(5-quinolylethynyl)-tetraphenylazadipyrromethene.

Zinc(II) complexes of tetraphenylazadipyrromethenes are potential non-planar n-type conjugated materials. To tune the properties, we installed 5-quinolylethynyl groups at the pyrrolic positions. Compared to the complex with 1-napthylethynyl, we found evidence for stronger intermolecular interactions in the new complex, including much higher overlap integrals in crystals. X-ray analysis revealed unconventional C-H···N hydrogen bonding between two quinolyls of neighboring molecules, pointing to a new strategy for the development of non-planar molecular semiconductors with stronger intermolecular interactions.

Development of a Regional Taste Test that uses Edible Circles for Stimulus Delivery.

INTRODUCTION: Measurements of chemosensory function within specific regions of the tongue can yield important information about the sensitivity of lingual areas to chemosensory stimuli, and may identify possible nerve damage. A novel regional chemosensory test that uses thin edible circles was developed for human testing. METHODS: Edible circles placed at six different regions of the tongue were used to examine regional sensitivity to quinine for bitter taste, NaCl for salt taste, sucralose for sweet taste, and capsaicin for pungency. The six regions included the anterior tip of the tongue, the left and right lateral margins of the tongue (anterior and posterior), and the circumvallate region. Testing was completed with the mouth open, and the mouth closed. RESULTS: Intensity ratings at all sites were higher in the closed mouth condition for the three taste stimuli. Quinine intensity was highest at the circumvallate region with the mouth closed. NaCl and sucralose intensity were highest at the anterior tip and circumvallate regions. Capsaicin intensity was most highly perceived at the anterior tip of the tongue, but open and closed mouth intensity ratings showed no significant differences. CONCLUSIONS: Regional differences in chemosensory perception were observed on the tongue, and these differences were dependent on the chemosensory stimulus, tongue region, and tasting mode. IMPLICATIONS: Edible circles show minimal diffusion with saliva, can be used to examine both taste and irritation, and may be used to identify regional papillae counts on the tongue. Finally, edible circles should be invaluable for examining damage to the oral cavity.

Lamellar, micro-phase separated blends of methyl cellulose and dendritic polyethylene glycol, POSS-PEG.

Blends of methyl cellulose (MC) and liquid pegylated polyoctahedralsilsesquioxane (POSS-PEG) were prepared from non-gelled, aqueous solutions at room temperature (RT), which was below their gel temperatures (Tm). Lamellar, fibrillated films (pure MC) and increasingly micro-porous morphologies with increasing POSS-PEG content were formed, which had RT moduli between 1 and 5GPa. Evidence of distinct micro-phase separated MC and POSS-PEG domains was indicated by the persistence of the MC and POSS-PEG (at 77K) crystal structures in the X-ray diffraction data, and scanning transmission electron images. Mixing of MC and POSS-PEG in the interface region was indicated by suppression of crystallinity in the POSS-PEG, and increases/decreases in the glass transition temperatures (Tg) of POSS-PEG/MC in the blends compared with the pure components. These interface interactions may serve as cross-link sites between the micro-phase separated domains that permit incorporation of high amounts of POSS-PEG in the blends, prevent macro-phase separation and result in rubbery material properties (at high POSS-PEG content). Above Tg/Tm of POSS-PEG, the moduli of the blends increase with MC content as expected. However, below Tg/Tm of POSS-PEG, the moduli are greater for blends with high POSS-PEG content, suggesting that it behaves like semi-crystalline polyethylene oxide reinforced with silica (SiO1.5).