Chinese Journal of Magnetic Resonance ›› 2026, Vol. 43 ›› Issue (2): 146-163.doi: 10.11938/cjmr20253182cstr: 32225.14.cjmr20253182
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LIU Jia1, WANG Yingxiong1,*(
), ZHAO Jiancheng2,#()
Received:2025-09-23
Published:2026-06-05
Online:2025-12-10
Contact:
WANG Yingxiong, ZHAO Jiancheng
E-mail:wangyingxiong@tyut.edu.cn;zhaojiancheng@sxicc.ac.cn
CLC Number:
LIU Jia, WANG Yingxiong, ZHAO Jiancheng. NMR Study of Tautomeric Distribution of Monosaccharides in Imidazolyl Ionic Liquids/DMSO-d6[J]. Chinese Journal of Magnetic Resonance, 2026, 43(2): 146-163.
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Fig. 1
(a) Tautomeric structure of aldoses (R = OH is D-glucose, R = NH2·HCl is D-glucosamine hydrochloride, R = NHCOCH3 is N-acetyl-D-glucosamine); (b) Tautomeric structure of D-mannose; (c) Tautomeric structure of D-fructose
Fig. 2
Structure of ionic liquids
Fig. 3
Preparation of [BMIM]ZnCl3
Fig. 4
(a) The proportion of β-pyranose of D-glucose over time in imidazolyl ionic liquids/DMSO-d6(n(D-glucose) : n(IL) = 1 : 1, 25 ℃); (b) Partial enlarged figure
Fig. 5
(a) The proportion of β-pyranose of D-mannose over time in imidazolyl ionic liquids/DMSO-d6(n(D-mannose) : n(IL) = 1 : 1, 25 ℃); (b) The proportion of tautomer over time in [BMIM]ZnCl3/DMSO-d6(n(D-mannose) : n(IL) = 1 : 1, 25 ℃)
Fig. 6
(a) The proportion of tautomer of D-mannose over time in [BMIM]OAc/DMSO-d6(n(D-mannose) : n(IL) = 1 : 1, 25 ℃); (b) The proportion of tautomer of D-mannose over time in [BMIM]PF6/DMSO-d6(n(D-mannose) : n(IL) = 1 : 1, 25 ℃)
Fig. 7
(a) The 1H-13C HSQC spectra of D-mannose in [BMIM]OAc/DMSO-d6 after equilibrium(n(D-mannose) : n(IL) = 1 : 1, 25 ℃); (b) The partial enlarged figure of area Ⅰ
Fig. 8
(a) The proportion of β-pyranose of GlcNAc over time in imidazolyl ionic liquids/DMSO-d6(n(GlcNAc) : n(IL) = 1 : 1, 25 ℃); (b) The proportion of β-pyranose of GlcNH2·HCl over time in [HSO3-BMIM]HSO4/DMSO-d6(n(GlcNH2·HCl) : n(IL) = 1 : 1, 25 ℃)
Fig. 9
The time-progression stack of in situ 1H qNMR of GlcNH2·HCl in [BMIM]ZnCl3/DMSO-d6(n(GlcNH2·HCl) : n(IL) = 1 : 1, m(IL) = 10 mg, 25 ℃)
Fig. 10
Tautomer distributions of D-fructose at equilibrium in imidazolyl ionic liquids/DMSO-d6(n(D-fructose) : n(IL) = 1 : 1, 25 ℃)
| [1] |
DU Y P, TIAN X Y, ZHENG X P, et al. Efficient preparation of 5-hydroxymethylfurfural from cellulose via one-step combination of mechanical and chemical pre-treatment[J]. Renew Energ, 2024, 229: 120748.
doi: 10.1016/j.renene.2024.120748 |
| [2] |
RIZVI S, GADE H M. Imidazolium-based ionic liquids as cellulose solvents: Mechanism and molecular insights[J]. Biomass Bioenerg, 2025, 196: 107758.
doi: 10.1016/j.biombioe.2025.107758 |
| [3] |
WANG S, CHENG A, LIU F, et al. Catalytic conversion network for lignocellulosic biomass valorization: a panoramic view[J]. Ind Chem Mater, 2023, 1(2): 188-206.
doi: 10.1039/D2IM00054G |
| [4] |
YE J, CHEN C, ZHENG Y, et al. Efficient conversion of cellulose to lactic acid over yttrium modified siliceous Beta zeolites[J]. Appl Catal A-Gen, 2021, 619: 118133.
doi: 10.1016/j.apcata.2021.118133 |
| [5] |
ZANG H, LOU J, JIAO S, et al. Valorization of chitin derived N-acetyl-D-glucosamine into high valuable N-containing 3-acetamido-5-acetylfuran using pyridinium-based ionic liquids[J]. J Mol Liq, 2021, 330: 115667.
doi: 10.1016/j.molliq.2021.115667 |
| [6] |
ZHAO J, LIU R, ZHANG Z, et al. Tautomer distributions of N-acetyl-D-glucosamine in the condition of commonly utilized solvents and catalysts for biorefinery: NMR study[J]. J Mol Struct, 2022, 1251: 131995.
doi: 10.1016/j.molstruc.2021.131995 |
| [7] |
OSADA M, KIKUTA K, YOSHIDA K, et al. Non-catalytic synthesis of Chromogen I and III from N-acetyl-D-glucosamine in high-temperature water[J]. Green Chem, 2013, 15(10): 2960-2966.
doi: 10.1039/c3gc41161c |
| [8] |
JIA L, WANG Y, QIAO Y, et al. Efficient one-pot synthesis of deoxyfructosazine and fructosazine from D-glucosamine hydrochloride using a basic ionic liquid as a dual solvent-catalyst[J]. RSC Adv, 2014, 4(83): 44253-44260.
doi: 10.1039/C4RA06832G |
| [9] |
WU C, WANG C, ZHANG A, et al. Preparation of 3-acetamido-5-acetylfuran from N-acetylglucosamine and chitin using biobased deep eutectic solvents as catalysts[J]. React Chem Eng, 2022, 7(8): 1742-1749.
doi: 10.1039/D2RE00118G |
| [10] |
ZHAO J, PEDERSEN C M, CHANG H, et al. Switchable product selectivity in dehydration of N-acetyl-D-glucosamine promoted by choline chloride-based deep eutectic solvents[J]. iScience, 2023, 26(7): 106980.
doi: 10.1016/j.isci.2023.106980 |
| [11] |
CHEN X, CHEW S L, KERTON F M, et al. Direct conversion of chitin into a N-containing furan derivative[J]. Green Chem, 2014, 16(4): 2204-2212.
doi: 10.1039/C3GC42436G |
| [12] |
ALEXANDERSSON E, NESTOR G. Complete 1H and 13C NMR spectral assignment of D-glucofuranose[J]. Carbohyd Res, 2022, 511: 108477.
doi: 10.1016/j.carres.2021.108477 |
| [13] |
MCGILL C J, WESTMORELAND P R. Monosaccharide isomer interconversions become significant at high temperatures[J]. J Phys Chem A, 2018, 123(1): 120-131.
doi: 10.1021/acs.jpca.8b07217 |
| [14] |
AMARASEKARA A S, WILLIAMS L D, EBEDE C C. Mechanism of the dehydration of D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 ℃: an NMR study[J]. Carbohyd Res, 2008, 343(18): 3021-3024.
doi: 10.1016/j.carres.2008.09.008 |
| [15] |
JADHAV H, PEDERSEN C M, SØLLING T, et al. 3-Deoxy-glucosone is an intermediate in the formation of furfurals from D-glucose[J]. Chem Sus Chem, 2011, 4(8): 1049-1051.
doi: 10.1002/cssc.v4.8 |
| [16] |
BICKER M, KAISER D, OTT L, et al. Dehydration of D-fructose to hydroxymethylfurfural in sub- and supercritical fluids[J]. J Supercrit Fluid, 2005, 36(2): 118-126.
doi: 10.1016/j.supflu.2005.04.004 |
| [17] |
TUCKER M H, ALAMILLO R, CRISCI A J, et al. Sustainable solvent systems for use in tandem carbohydrate dehydration hydrogenation[J]. ACS Sustainable Chem Eng, 2013, 1(5): 554-560.
doi: 10.1021/sc400044d |
| [18] |
AKIEN G R, QI L, HORVÁTH I T. Molecular mapping of the acid catalysed dehydration of fructose[J]. Chem Commun, 2012, 48(47): 5850-5852.
doi: 10.1039/c2cc31689g |
| [19] | SUN S, β-directing effect of ionic liquid in mannopyranosylation: a potential access to stereoselective construction of the 1,2-cis-β-D-mannopyranosyl linkage[J]. Chin Pharm Sci, 2011, 20(6): 549-556. |
| [20] |
SWEELEY C C, BENTLEY R, MAKITA M, et al. Gas-liquid chromatography of trimethylsilyl derivatives of sugars and related substances[J]. J Am Chem Soc, 1963, 85(16): 2497-2507.
doi: 10.1021/ja00899a032 |
| [21] |
PADINHATTATH S P, SHAIBUNA M, GARDAS R L. Ionic liquids and deep eutectic solvents: A brief prologue and their applications in sustainable extraction and separation processes[J]. J Indian Chem Soc, 2025, 102(4): 101638.
doi: 10.1016/j.jics.2025.101638 |
| [22] |
ALQAHTANI N F. Functionalized imidazolium ionic liquids-modified chitosan materials: From synthesis approaches to applications[J]. React Funct Polym, 2024, 194: 105779.
doi: 10.1016/j.reactfunctpolym.2023.105779 |
| [23] | LIU C, LI Y, HOU Y. Basicity characterization of imidazolyl ionic liquids and their application for biomass dissolution[J]. Int J Chem Eng, 2018, 2018: 1-8. |
| [24] |
HUA D, DING H, LIU Y, et al. Dehydration of xylose to furfural over imidazolium-based ionic liquid with phase separation[J]. Catalysts, 2021, 11(12): 1552.
doi: 10.3390/catal11121552 |
| [25] |
ZHAO J, LI C, FAN X, et al. Design and synthesis of Brønsted-Lewis acidic tetraimidazolyl ionic liquids for efficient catalytic conversion of glucose to 5-hydroxymethylfurfural in water/1-octanol[J]. Appl Catal A-Gen, 2023, 649: 118981.
doi: 10.1016/j.apcata.2022.118981 |
| [26] |
JIA L, PEDERSEN C M, QIAO Y, et al. Glucosamine condensation catalyzed by 1-ethyl-3-methylimidazolium acetate: mechanistic insight from NMR spectroscopy[J]. Phys Chem Chem Phys, 2015, 17(35): 23173-23182.
doi: 10.1039/c5cp02169c pmid: 26278065 |
| [27] |
CHEN X, LIU Y, KERTON F M, et al. Conversion of chitin and N-acetyl-D-glucosamine into a N-containing furan derivative in ionic liquids[J]. RSC Adv, 2015, 5(26): 20073-20080.
doi: 10.1039/C5RA00382B |
| [28] |
LIU P, PEDERSEN C M, ZHANG J, et al. Ternary deep eutectic solvents catalyzed D-glucosamine self-condensation to deoxyfructosazine: NMR study[J]. Green Energy Environ, 2021, 6(2): 261-270.
doi: 10.1016/j.gee.2020.04.010 |
| [29] |
JIA L, LIU X, QIAO Y, et al. Mechanism of the self-condensation of GlcNH2: insights from in situ NMR spectroscopy and DFT study[J]. App Catal B: Environ, 2017, 202: 420-429.
doi: 10.1016/j.apcatb.2016.09.058 |
| [30] | ZHANG J Y, NIE W B, TU Z, et al. Three-dimensional structures of 3/4/5-O-feruloylquinic acids by NMR spectroscopy and quantum chemistry calculation[J]. Chinese J Magn Reson, 2025, 42(1): 47-55. |
|
张佳钰, 聂文博, 涂朝, 等. 核磁共振实验结合量子化学计算研究3/4/5-O-阿魏酰奎宁酸三维结构[J]. 波谱学杂志, 2025, 42(1): 47-55.
doi: 10.11938/cjmr20243115 |
|
| [31] | LI Y J, ZHAO W, TAO L, et al. NMR data analysis of acarbose[J]. Chinese J Magn Reson, 2025, 42(2): 184-194. |
|
李玉江, 赵伟, 陶乐, 等. 阿卡波糖的核磁共振数据解析[J]. 波谱学杂志, 2025, 42(2): 184-194.
doi: 10.11938/cjmr20243125 |
|
| [32] |
BARCLAY T, GINIC-MARKOVIC M, JOHNSTON M R, et al. Observation of the keto tautomer of D-fructose in D2O using 1H NMR spectroscopy[J]. Carbohyd Res, 2012, 347(1): 136-141.
doi: 10.1016/j.carres.2011.11.003 |
| [33] |
WU M, ZHOU W, PEDERSEN C M, et al. Isomeric distribution of monosaccharides in deep eutectic solvents: NMR study[J]. J Mol Liq, 2018, 255: 244-249.
doi: 10.1016/j.molliq.2018.01.166 |
| [34] |
SHI K, PEDERSEN C M, GUO Z, et al. NMR studies of the tautomer distributions of D‑fructose in lower alcohols/DMSO‑d6[J]. J Mol Liq, 2018, 271: 926-932.
doi: 10.1016/j.molliq.2018.09.067 |
| [35] | FAN M M, WANG H, ZHANG P B, et al. Synthesis, characterization and catalysis performance of ionic liquid 1-butyl-3- methylimidazolium chlorozincate[J]. Chinese J Inorg Chem, 2012, 28(7): 1333-1337. |
| 范明明, 王辉, 张萍波, 等. 1-丁基-3-甲基咪唑氯化锌离子液体的合成、表征及催化性能[J]. 无机化学学报, 2012, 28(7): 1333-1337. | |
| [36] | DOU M Y, ZHAO Q, HOU X L, et al. Structural elucidation and quantitative analysis of hydrogenation products of anthracene by NMR spectroscopy[J]. Chinese J Magn Reson, 2021, 38(2): 239-248. |
|
窦梦雨, 赵奇, 侯相林, 等. 蒽加氢产物的结构指认和定量核磁共振分析[J]. 波谱学杂志, 2021, 38(2): 239-248.
doi: 10.11938/cjmr20202849 |
|
| [37] |
MORALES G, PANIAGUA M, MELERO J A, et al. Efficient production of 5-ethoxymethylfurfural from fructose by sulfonic mesostructured silica using DMSO as co-solvent[J]. Catal Today, 2017, 279: 305-316.
doi: 10.1016/j.cattod.2016.02.016 |
| [38] |
WANG H, DENG T, WANG Y, et al. Efficient catalytic system for the conversion of fructose into 5-ethoxymethylfurfural[J]. Bioresource Technol, 2013, 136: 394-400.
doi: 10.1016/j.biortech.2013.02.110 pmid: 23567707 |
| [39] |
ZHAO Q, MA H, PEDERSEN C M, et al. Pure shift NMR: application of 1D PSYCHE and 1D TOCSY-PSYCHE techniques for directly analyzing the mixtures from biomass-derived platform compound hydrogenation/hydrogenolysis[J]. ACS Sustainable Chem Eng, 2021, 9(6): 2456-2464.
doi: 10.1021/acssuschemeng.0c06882 |
| [40] |
ZHU Y, ZAJICEK J, SERIANNI A S. Acyclic forms of [1-13C]aldohexoses in aqueous solution: quantitation by 13C NMR and deuterium isotope effects on tautomeric equilibria[J]. J Org Chem, 2001, 66(19): 6244-6251.
doi: 10.1021/jo010541m |
| [41] |
MACKIE W, PERLIN A S. Pyranose-furanose and anomeric equilibria: influence of solvent and of partial methylation[J]. Can J Chem, 1966, 44(17): 2039-2049.
doi: 10.1139/v66-304 |
| [42] |
COLE E R, CRAIG D C, FITZPATRICK L J, et al. Structure and solution equilibria of D-glucose and D-mannose sulfite adducts[J]. Carbohyd Res, 2001, 335(1): 1-10.
pmid: 11553349 |
| [43] |
LIU F C, SU C R, WU T Y, et al. Efficient 1H-NMR quantitation and investigation of N-acetyl-D-glucosamine (GlcNAc) and N,N'-diacetylchitobiose (GlcNAc)2 from chitin[J]. Int J Mol Sci, 2011, 12(9): 5828-5843.
doi: 10.3390/ijms12095828 |
| [44] |
JIA L, ZHANG Z, QIAO Y, et al. Product distribution control for glucosamine condensation: nuclear magnetic resonance (NMR) investigation substantiated by density functional calculations[J]. Ind Eng Chem Res, 2017, 56(11): 2925-2934.
doi: 10.1021/acs.iecr.6b05057 |
| [45] | SCHNEIDER B, LICHTENTHALER F W, STEINLEB G, et al. Studies on ketoses, 1 Distribution of furanoid and pyranoid tautomers of D-fructose in water, dimethyl sulfoxide, and pyridine via 1H NMR intensities of anomeric hydroxy groups in [d6]DMSO[J]. Liebigs Ann Chem, 1985: 2443-2453. |
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