Abstract
Novel cellobiose and cellulose (DP n =ca. 30) derivatives, N-(1-pyrenebutyloyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (6), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (7), N-(1-pyrenebutyloyl)-β-cellulosylamine (13), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-β-cellulosylamine (14) carrying a pyrene group as a single fluorescent probe at the reducing end, were prepared in order to investigate their self-assembly systems in solutions. The relative intensity of the excimer emission at ca. 480 nm due to dimerized pyrenes (intensity I E) to the monomer emission at ca. 380 nm due to isolated pyrene (intensity I M), i.e., I E/I M, was monitored in various solutions. In water/dimethyl sulfoxide (DMSO) mixed solvent (0–98%, v/v), the ratio I E/I M remained low (0.04) for compound 6 over the range of water concentrations, indicating that pyrenes at C-1 position of compound 6 were diffused. On the other hand, the ratio I E/I M increased (0.04–4.96) for compound 7 with the increase in water concentration, indicating that pyrenes at C-1 position were associated. In aqueous NaOH solutions (4.4–17.5%, w/w), compound 14 showed a large increase in the ratio I E/I M (0.84–8.14) with the increase in NaOH concentration, compared to compound 13 (0.06–0.41). It was found that the association of hydrophobic groups at the reducing-end of cellulose could be controlled by the hydrophilic–hydrophobic balance of compounds and the solvent polarity.
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Acknowledgements
This investigation was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture of Japan (Nos. 11760122, 13760132, and 15780124).
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Enomoto, Y., Kamitakahara, H., Takano, T. et al. Synthesis of diblock copolymers with cellulose derivatives. 3. Cellulose derivatives carrying a single pyrene group at the reducing-end and fluorescent studies of their self-assembly systems in aqueous NaOH solutions. Cellulose 13, 437–448 (2006). https://doi.org/10.1007/s10570-005-9005-4
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DOI: https://doi.org/10.1007/s10570-005-9005-4