All commercially available chemicals were used without further purification. The solvents used in this study were processed by standard procedures. 1H-NMR experiments were carried out on a JEOL ECX-400 MHz instrument. DOSY experiment was carried out on a Bruker Avance 600 MHz instrument using a 5 mm TXI H-C/N-D Z-GRD probe. 2D sequence for diffusion measurements were conducted using stimulated echo with 1 spoil gradient. Mass spectra were obtained using a Thermo Scientific Exactive Orbitrap instrument. UV-vis measurements were performed using Agilent Cary Series UV-Vis-NIR. EPR experiments were carried out using JEOL JES-FA200 ESR Spectrometer and Bruker E580. Elemental analyses were recorded on a Thermo FlashEA 1112 elemental analyzer. The details of X-ray crystallographic measurements are summarized in Supplementary Data 5 and 6 .
Flashea 1112 elemental
Manufactured by Thermo Fisher Scientific
The FlashEA 1112 elemental analyzer is a compact and automated instrument used for the rapid and precise determination of carbon, hydrogen, nitrogen, and sulfur content in a wide range of organic and inorganic solid samples. The instrument utilizes combustion and chromatographic techniques to perform these elemental analyses.
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2 protocols using flashea 1112 elemental
1
Characterization of Chemical Compounds
2
Isotope Analysis of α-Cellulose
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For δ 13 C, dry α-cellulose was weighed (0.30-0.40 mg) into tin foil capsules and combusted using a Flash EA-1112 elemental analyser interfaced with a Finnigan MAT Delta C isotope ratio mass spectrometer (Thermo Fisher Scientific Inc.). For δ 18 O, 0.30-0.40 mg of dry α-cellulose was weighed into silver foil capsules and combusted using a Carlo Erba 1108 elemental analyser (Carlo Erba Instruments Ltd., Milan, Italy) interfaced with a Finnigan Deltaplus XP isotope ratio mass spectrometer (Thermo Fisher Scientific Inc.). Isotope ratios were expressed as per mil deviations using the δ notation relative to Vienna Pee Dee Belemnite (VPDB) standard (for carbon) and
Vienna Standard Mean Ocean Water (VSMOW) standard (for oxygen):
where n X stands for the isotopic composition, in parts per mil (‰) of the heavier isotope, and R sample and R standard represent the 13 C/ 12 C or 18 O/ 16 O ratios of the sample and the VPDB or VSMOW international standards, respectively (Farquhar, Oleary & Berry 1982) . The accuracy of the analyses (SD of working standards) was 0.06‰ (δ 13 C) and 0.25‰ (δ 18 O).
To account for changes in the δ 13 C of atmospheric CO 2 (δ 13 c a ), we calculated carbon isotope discrimination in cellulose (Δ 13 C) from δ 13 c a and plant δ 13 C (δ 13 c p ), as described by Farquhar & Richards (1984) :
Δ 13 C = (δ 13 c a -δ 13 c p )/(1+δ 13 c p /1000) (3)
Vienna Standard Mean Ocean Water (VSMOW) standard (for oxygen):
where n X stands for the isotopic composition, in parts per mil (‰) of the heavier isotope, and R sample and R standard represent the 13 C/ 12 C or 18 O/ 16 O ratios of the sample and the VPDB or VSMOW international standards, respectively (Farquhar, Oleary & Berry 1982) . The accuracy of the analyses (SD of working standards) was 0.06‰ (δ 13 C) and 0.25‰ (δ 18 O).
To account for changes in the δ 13 C of atmospheric CO 2 (δ 13 c a ), we calculated carbon isotope discrimination in cellulose (Δ 13 C) from δ 13 c a and plant δ 13 C (δ 13 c p ), as described by Farquhar & Richards (1984) :
Δ 13 C = (δ 13 c a -δ 13 c p )/(1+δ 13 c p /1000) (3)
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