After preparation and NMR analysis of the full DoE array of samples (Figure ), it is clear that it is possible to prepare samples where 6-acetylation is restricted to fibril surfaces or to additionally induce a bulk topochemical conversion -yielding CTAdomains while still retaining unmodified crystalline cellulose, likely within the fibrillar bundle cores. This was further supported by wide-angle X-ray scattering (WAXS) analysis of the representative samples (Figure ). The diffractograms for the representative samples illustrate a progression to lower degrees of crystallinity, for harsher reaction conditions, by the reduction of signal intensity of the typical cellulose I diffraction peaks . As the main (200) cellulose I diffraction peak (22.5 o ) corresponds to a diffraction plane across the diameter of the elementary fibrils, along the 'hydrophobic plane', the peak width for the upper portion of the peak gives an indication of the intact elementary fibril diameters, based on the use of the Scherrer relationship . The fibril diameters are observed to decrease (from 5.3 to 4.5 nm) as the CTA composition increases. However, the decrease is not as significant as one might expect, based on a maximum bulk DS value of 0.74, for the more highly acetylated sample, possibly indicating that there are some elementary fibrillar aggregates (due to hornification) which prevents access to all fibrils. After these results, it was clear that a representative set of samples was available for biodegradation studies, to test the effect of a controlled surface modification. In addition, acetylation of cellulose nanofibril (CNF)-based nano-paper samples was also performed, and representative samples of the macro-and nano-paper samples were made on a large enough scale for soil biodegradation studies. Quantitation of the DS for all paper samples was performed using quantitative 1 H NMR and diffusion-edited 1 H NMR (see the SI for details).