title: Regioselectively substituted 6-O- and 2,3-di-O-acetyl-6-O-triphenylmethylcellulose: its chain dynamics and hydrophobic association in polar solvents.
abstract: Two kinds of regioselectively substituted cellulose derivatives, i.e., 6-O-triphenylmethylcellulose (6TC) and 2,3-di-O-acetyl-6-O-triphenylmethylcellulose (2,3Ac6TC), were prepared via cellulose. In these samples, C-6 position hydroxyls in the anhydroglucose units (AGU) along the cellulose chain were selectively substituted by the hydrophobic triphenylmethyl groups, but C-2 and -3 position hydroxyls remained in 6TC or were substituted completely by O-acetyls in 2,3Ac6TC. Their chain dynamics in polar solvents, dimethyl sulfoxide (DMSO) and N,N-dimethylacetamide (DMAc), in dilute solution were investigated by dynamic light scattering in the viewpoint of cluster formation. The results were compared with those of cellulose diacetates (CDA) in DMAc where three hydroxyls in the AGU were statistically substituted up to 2.44 by O-acetyls but hydroxyls at C-6 positions remained predominantly. It was found that 6TC and 2,3Ac6TC formed a dynamic structure about 10 times larger than single chains and that the structure would be a temporary and local association due to concentration fluctuations (dynamic structures) which were originated from the hydrophobic interactions between intermolecular triphenylmethyl groups. The dynamics and structures were in clear contrast to those of CDA where a solvent-mediated hydrogen bonding between intermolecular C-6 position hydroxyls was essential to cluster formation. The present structures were so weak as to dissipate easily under low shear field.
authors.affiliation: Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
authors.forename: Y
authors.initials: Y
authors.lastname: Tsunashima
authors.forename: K
authors.initials: K
authors.lastname: Hattori
authors.forename: H
authors.initials: H
authors.lastname: Kawanishi
authors.forename: F
authors.initials: F
authors.lastname: Horii
mesh_terms: D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy; D008747:Methylcellulose / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D012997:Solvents; D013816:Thermodynamics; D014783:Viscosity
chemical_list: D046911:Macromolecular Substances; D012997:Solvents; D008747:Methylcellulose