Mechanochemical
treatment offers great potential for environmentally
sustainable processing of chitin within the context of biomass valorization.
Using powder X-ray diffraction, we show that crystallinity can be
reduced by 50% in 2 h in a controlled way using a ball mill. We correlate
this crystallinity reduction with a decrease in interchain hydrogen
bonding using infrared spectroscopy as a structural probe. Furthermore,
our quantitative interpretation of the spectra reveal a decrease in
glycosidic linkage content and retention of N-acetyl
groups. The addition of a natural clay, kaolinite, in the ball mill
leads to a significant increase in the solubility of the milled materials
(up to 75.8% water-soluble products in 6 h, cf. 35.0% without kaolinite).
The products of this process were characterized as oligomers of N-acetyl-d-glucosamine (chitin oligomers) with
degrees of polymerization (DP) between 1 and 5 using a new quantitative
matrix-assisted laser desorption-ionization (MALDI-ToF) mass spectrometric
method. These data were complemented by a colorimetric assay of reducing
ends and size-exclusion chromatography (SEC). N-Acetyl-d-glucosamine (the monomer) and N,N′-diacetylchitobiose
(the dimer) were obtained in yields of 5.1 and 3.9 wt %, respectively,
within 6 h, which is comparable with yields of glucose and cellobiose
from cellulose ball milling.