The role of cations in homogeneous succinoylation of mulberry wood cellulose in salt-containing solvents under mild conditions
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The role of two cations [tetraethylammonium+ (TEA+) and tetrabutylammonium+ (TBA+)] in the homogeneous succinoylation of mulberry wood (MW) cellulose in dimethyl sulfoxide (DMSO)/tetraethylammonium chloride (TEACl) and DMSO/tetrabutylammonium fluoride (TBAF) was investigated using the intrinsic viscosity and two-dimensional nuclear Overhauser effect NMR spectroscopy (2D NOESY). The intrinsic viscosity of MW cellulose solution strongly depends on the salt dosage for both TEACl and TBAF, indicating that the increase in the hydrodynamic size of cellulose chains was caused by the interactions between salts and cellulose, which promotes the solvation process of cellulose in solution. Two-dimensional NOESY spectra reveal that cations bind to cellobiose in DMSO by the interactions between α-methylene groups of TEA+ (or TBA+) and C1/C1′ groups of cellobiose, and the intensities of the respective crosspeaks increase with increasing TEACl dosage from 5 to 10 mg/ml, but no change was present with TBAF at the same concentration range. Taking cellobiose as a model compound for cellulose, it can be expected that TEA+ (or TBA+) and cellulose form polyelectrolyte-like complexes. The degree of substitution (DS) of homogeneous succinoylation of MW cellulose benefits from the interactions between TEA+ (or TBA+) and cellulose evidenced by FT-IR spectra and CP/MAS 13C NMR spectra. The DS of the succinylated cellulose declines at TBAF concentrations higher than 11 wt% probably because of the steric hindrance effects of TBA+.
KeywordsDMSO/TEACl DMSO/TBAF Mulberry wood cellulose Homogeneous succinoylation Two-dimensional NOESY Intrinsic viscosity
- 2D NOESY
Two-dimensional nuclear Overhauser effect NMR spectroscopy
Degree of substitution
This work was financially supported by the Special Fund for Forestry Scientific Research in Public Interest (201204803), Specialized Research Fund for the Doctoral Program of Higher Education (20133204120008), a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), Research Fund for the Doctoral Program of Higher Education of China (2013320412000), and the Program for Excellent Talents in Nanjing Forestry University (163030672).
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