Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation
Regioselective C6 and C2,C3 carboxylated cellulose nanofibrils (CNFs) have been robustly generated from dissolving pulp, a readily available source of unmodified cellulose, via stoichiometrically optimized 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO)-mediated and sequential sodium periodate-sodium c...
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MDPI AG
2024-03-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/14/5/479 |
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| author | Mengzhe Guo James D. Ede Christie M. Sayes Jo Anne Shatkin Nicole Stark You-Lo Hsieh |
| author_facet | Mengzhe Guo James D. Ede Christie M. Sayes Jo Anne Shatkin Nicole Stark You-Lo Hsieh |
| author_sort | Mengzhe Guo |
| collection | DOAJ |
| description | Regioselective C6 and C2,C3 carboxylated cellulose nanofibrils (CNFs) have been robustly generated from dissolving pulp, a readily available source of unmodified cellulose, via stoichiometrically optimized 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO)-mediated and sequential sodium periodate-sodium chlorite (PC) oxidation coupled with high-speed blending. Both regioselectively optimized carboxylated CNF series possess the widest ranges of comparable charges (0.72–1.48 mmol/g for T-CNFs vs. 0.72–1.10 mmol/g for PC-CNFs), but similar ranges of thickness (1.3–2.4 nm for T-CNF, 1.8–2.7 nm PC-CNF), widths (4.6–6.6 nm T-CNF, 5.5–5.9 nm PC-CNF), and lengths (254–481 nm T-CNF, 247–442 nm PC-CNF). TEMPO-mediated oxidation is milder and one-pot, thus more time and process efficient, whereas the sequential periodate–chlorite oxidation produces C2,C3 dialdehyde intermediates that are amenable to further chemical functionalization or post-reactions. These two well-characterized regioselectively carboxylated CNF series represent coherent cellulose nanomaterial models from a single woody source and have served as references for their safety study toward the development of a safer-by-design substance evaluation tool. |
| first_indexed | 2024-04-25T00:23:17Z |
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| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-04-25T00:23:17Z |
| publishDate | 2024-03-01 |
| publisher | MDPI AG |
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| series | Nanomaterials |
| spelling | doaj.art-63246c42e86e49e0a12cb6e6390f52b92024-03-12T16:51:44ZengMDPI AGNanomaterials2079-49912024-03-0114547910.3390/nano14050479Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite OxidationMengzhe Guo0James D. Ede1Christie M. Sayes2Jo Anne Shatkin3Nicole Stark4You-Lo Hsieh5Chemical Engineering, University of California at Davis, Davis, CA 95616, USAVireo Advisors, LLC, P.O. Box 51368, Boston, MA 02130, USAEnvironmental Science, Baylor University, Waco, TX 76798, USAVireo Advisors, LLC, P.O. Box 51368, Boston, MA 02130, USAUSDA Forest Service, Forest Products Laboratory, Madison, WI 53726, USABiological and Agricultural Engineering, Chemical Engineering, University of California at Davis, Davis, CA 95616, USARegioselective C6 and C2,C3 carboxylated cellulose nanofibrils (CNFs) have been robustly generated from dissolving pulp, a readily available source of unmodified cellulose, via stoichiometrically optimized 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO)-mediated and sequential sodium periodate-sodium chlorite (PC) oxidation coupled with high-speed blending. Both regioselectively optimized carboxylated CNF series possess the widest ranges of comparable charges (0.72–1.48 mmol/g for T-CNFs vs. 0.72–1.10 mmol/g for PC-CNFs), but similar ranges of thickness (1.3–2.4 nm for T-CNF, 1.8–2.7 nm PC-CNF), widths (4.6–6.6 nm T-CNF, 5.5–5.9 nm PC-CNF), and lengths (254–481 nm T-CNF, 247–442 nm PC-CNF). TEMPO-mediated oxidation is milder and one-pot, thus more time and process efficient, whereas the sequential periodate–chlorite oxidation produces C2,C3 dialdehyde intermediates that are amenable to further chemical functionalization or post-reactions. These two well-characterized regioselectively carboxylated CNF series represent coherent cellulose nanomaterial models from a single woody source and have served as references for their safety study toward the development of a safer-by-design substance evaluation tool.https://www.mdpi.com/2079-4991/14/5/479cellulose nanofibrilTEMPOperiodate–chlorite oxidationC2,C3 regioselectivedissolving pulp |
| spellingShingle | Mengzhe Guo James D. Ede Christie M. Sayes Jo Anne Shatkin Nicole Stark You-Lo Hsieh Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation Nanomaterials cellulose nanofibril TEMPO periodate–chlorite oxidation C2,C3 regioselective dissolving pulp |
| title | Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation |
| title_full | Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation |
| title_fullStr | Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation |
| title_full_unstemmed | Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation |
| title_short | Regioselectively Carboxylated Cellulose Nanofibril Models from Dissolving Pulp: C6 via TEMPO Oxidation and C2,C3 via Periodate–Chlorite Oxidation |
| title_sort | regioselectively carboxylated cellulose nanofibril models from dissolving pulp c6 via tempo oxidation and c2 c3 via periodate chlorite oxidation |
| topic | cellulose nanofibril TEMPO periodate–chlorite oxidation C2,C3 regioselective dissolving pulp |
| url | https://www.mdpi.com/2079-4991/14/5/479 |
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