固体蛍光測定によるシクロデキストリン混合粉砕物中のp-ジメチルアミノベンゾニトリルの分子状態

概要

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The molecular status of a freeze-dried sample or a ground mixture of p-dimethylaminobenzonitrile (DMABN) with α-, β-, or γ-cyclodextrins (CDs) was examined using solid-state fluorescence measurements. A twisted intramolecular charge transfer (TICT) emission of DMABN crystals was shown at 475nm. Emission peaks of freeze-dried samples were observed at 450, 380, and 393nm in α-CD/DMABN, β-CD/DMABN, and γ-CD/DMABN systems, respectively. It was speculated that DMABN molecules existed as a twisted form in the cavity of α-CD, and as a plane structure in that of β-CD or γ-CD. On the other hand, fluorescence emission peaks of ground mixtures of DMABN with α-, β-, or γ-CD were observed at around 450nm. When DMABN was ground together with microcrystalline cellulose, which cannot form an inclusion complex, only TICT emission was detected. These results suggest that the observed shift in the fluorescence peak could be due to inclusion phenomena. When the ground mixtures were crystallized under humid conditions, fluorescence emission peaks were observed at 450nm in α-CD and of around 400nm in β- and γ-CD systems. It is concluded that the conformation of the DMABN molecules in a crystalline CD/DMABN inclusion complex change depending on the size of the CD cavity.
2009-02-01