Skip to main content
SpringerLink
Log in

Proton (1H) NMR Spectroscopy

  • Chapter
Methods in Lignin Chemistry

Part of the book series: Springer Series in Wood Science ((SSWOO))

Abstract

1H NMR spectroscopy can be used for the characterization and classification of lignins and determination of lignin structure. Ludwig (1971) reviewed the literature dealing with the 1H NMR spectroscopy of lignins through 1968, and a comprehensive 1H NMR study of lignins and lignin model compounds was published in 1964 by Ludwig et al. (1964a,b). In this latter instance, the lignins were analyzed as acetate derivatives using deuteriochloroform as solvent. The methodology developed by Ludwig et al. (1964) has been applied in numerous studies (e.g., Šutý and Golis 1972, Košiková et al. 1973, Faix and Schweers 1974, Simionescu et al. 1981). During the 1970s and 1980s, important developments relating to the techniques used to record NMR spectra have taken place. For example, modern high-frequency instruments of the Fourier transform-type provide comparatively well-resolved 1H NMR spectra. With such instruments, high signal/noise ratios and very accurate NMR data are obtained. Owing to these improvements, it is possible to enlarge regions of the spectra for closer examination and to determine trace amounts (~0.1%) of certain types of lignin units (e.g., benzaldehyde units).

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 149.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 199.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Adler E, Brunow G, Lundquist K (1987) Investigation of the acid-catalyzed alkylation of lignins by means of NMR spectroscopic methods. Holzforschung 41: 199–207

    Article  CAS  Google Scholar 

  • Bardet M, Robert DR, Lundquist K (1985) On the reactions and degradation of the lignin during steam hydrolysis of aspen wood. Sven Papperstidn 88: R61–67

    CAS  Google Scholar 

  • Becker H, Nimz H (1974) Untersuchungen des Lignins der Mistel (Viscum album L.) in Abhängigkeit von der jeweiligen Wirtspflanze. Z Pflanzenphysiol 72: 52–63

    CAS  Google Scholar 

  • Bland DE, Menshun M (1970) The composition and reactive groups of the lignin of Eucalyptus regnans. Appita 23: 427–433

    CAS  Google Scholar 

  • Bland DE, Sternhell S (1965) Estimation of aromatic protons in methanol lignins of Pinus radiata and Eucalyptus regnans from proton magnetic resonance spectra. Aust J Chem 18: 401–410

    Article  CAS  Google Scholar 

  • Brunow G, Lundquist K (1980) Comparison of a synthetic dehydrogenation polymer of coniferyl alcohol with milled wood lignin from spruce, using 1H NMR spectroscopy. Pap Puu 62: 669–671

    CAS  Google Scholar 

  • Brunow G, Sipilä J, Mäkelä T (1989) On the mechanism of formation of non-cyclic benzyl ethers during lignin biosynthesis. Holzforschung 43: 55–59

    Article  CAS  Google Scholar 

  • Ede RM, Brunow G, Simola LK, Lemmetyinen J (1990) Two-dimensional 1H-1H chemical shift correlation and J-resolved NMR studies on isolated and synthetic lignins. Holzforschung 44: 95–101

    Article  CAS  Google Scholar 

  • Faix O, Schweers W (1974) Vergleichende Untersuchungen an Polymermodellen des Lignins (DHP’s) verschiedener Zusammensetzungen. Holzforschung 28: 179–185

    Article  CAS  Google Scholar 

  • Gagnaire D, Robert D (1977) A polymer model of lignin (DHP) 13C selectively labelled at the benzylic positions: synthesis and NMR study. Makromol Chem 178: 1477–1495

    Article  CAS  Google Scholar 

  • Gellerstedt G, Gierer J (1971) The reactions of lignin during acidic sulphite pulping. Sven Papperstidn 74: 117–127

    CAS  Google Scholar 

  • Gellerstedt G, Gierer J, Pettersson E-L, Szabo-Lin I (1976) Über die Reaktionen des Lignins während der Neutralsulfitkochung, VI Reaktionen von Zwischenprodukten des Stilbentyps. Liebigs Ann Chem 1976: 2021–2036

    Google Scholar 

  • Glasser WG, Gratzl JS, Collins JJ, Forss K, McCarthy JL (1973) Lignin. XVI. Synthesis, nuclear magnetic resonance and mass spectroscopy of several monomeric and dimeric lignin-like sulfonates. Macromolecules 6: 114–128

    Article  CAS  Google Scholar 

  • Hagström-Näsi C, Sjöström E (1987) Oxidative pretreatment of pine wood prior to alkaline pulping. Part II. Characterization of lignin by spectroscopic methods. Holzforschung 41: 39–45

    Article  Google Scholar 

  • Hauteville M, Lundquist K, von Unge S (1986) NMR studies of lignins. 7. 1H NMR spectroscopic investigation of the distribution of erythro and threo forms of β-O-4 structures in lignins. Acta Chem Scand B40: 31–35

    Article  Google Scholar 

  • Hawkes GE, Smith CZ, Utley JHP, Chum HL (1986) Key structural features of acetone- soluble phenol-pulping lignins by 1H and 13C NMR spectroscopy. Holzforschung Suppl 40: 115–123

    CAS  Google Scholar 

  • Hemmingson JA (1983) The structure of lignin from Pinus radiata exploded wood. J Wood Chem Technol 3: 289–312

    Article  CAS  Google Scholar 

  • Johansson B, Miksche GE (1972) Über die Benzyl-arylätherbindung im Lignin II. Versuche an Modellen. Acta Chem Scand 26: 289–308

    Article  CAS  Google Scholar 

  • Kirk TK, Chang H-m (1975) Decomposition of lignin by white-rot fungi II. Characterization of heavily degraded lignins from decayed spruce. Holzforschung 29: 56–64

    Article  CAS  Google Scholar 

  • Kosikovä B, Polcin J, Joniak D (1973) NMR Studies of lignin-carbohydrate complexes. Holzforschung 27: 59–64

    Article  Google Scholar 

  • Lapierre C, Lallemand JY, Monties B (1982) Evidence of poplar lignin heterogeneity by combination of 13C and 1H NMR spectroscopy. Holzforschung 36: 275–282

    Article  CAS  Google Scholar 

  • Liptaj T, Remko M, Polcin J (1980) Analysis of ’H-NMR spectra of cinnamaldehyde type model substances of lignin. Collect Czech Chem Commun 45: 330–334

    CAS  Google Scholar 

  • Ludwig CH (1971) Magnetic resonance spectra. In: Sarkanen KV, Ludwig CH (eds) Lignins-occurrence, formation, structure and reactions. Wiley, New York, 299–344

    Google Scholar 

  • Ludwig CH, Nist BJ, McCarthy JL (1964a) Lignin. XII. The high resolution nuclear magnetic resonance spectroscopy of protons in compounds related to lignin. J Am Chem Soc 86: 1186–1196

    Article  CAS  Google Scholar 

  • Ludwig CH, Nist BJ, McCarthy JL (1964b) Lignin. XIII. The high resolution nuclear magnetic resonance spectroscopy of protons in acetylated lignins. J Am Chem Soc 86: 1196–1202

    Article  CAS  Google Scholar 

  • Lundquist K (1979a) NMR studies of lignins. 2. Interpretation of the 1H NMR spectrum of acetylated birch lignin. Acta Chem Scand B33: 27–30

    Article  Google Scholar 

  • Lundquist K (1979b) NMR studies of lignins. 3. 1H NMR spectroscopic data for lignin model compounds. Acta Chem Scand B33: 418–420

    Article  Google Scholar 

  • Lundquist K (1980) NMR studies of lignins. 4. Investigation of spruce lignin by NMR spectroscopy. Acta Chem Scand B34: 21–26

    Article  Google Scholar 

  • Lundquist K (1981a) NMR studies of lignins. 5. Investigation of non-derivatized spruce and birch lignin by 1H NMR spectroscopy. Acta Chem Scand B35: 497–501

    Article  Google Scholar 

  • Lundquist K (1981b) Analysis of lignins by spectral methods. Proc. The Ekman Days Int Symp on Wood and Pulping Chem Stockholm 1: 81–85

    CAS  Google Scholar 

  • Lundquist K (1987) On the occurrence of β-1 structures in lignins. J Wood Chem Technol 7: 179–185

    Article  CAS  Google Scholar 

  • Lundquist K, Olsson T (1977) NMR studies of lignins. 1. Signals due to protons in formyl groups. Acta Chem Scand B31: 788–792

    Article  CAS  Google Scholar 

  • Lundquist K, Paterson A, Ramsey L (1983) NMR studies of lignins. 6. Interpretation of the 1H NMR spectrum of acetylated spruce lignin in a deuterioacetone solution. Acta Chem Scand B37: 734–736

    Article  Google Scholar 

  • Lundquist K, Simonson R, Tingsvik K (1979) On the occurrence of carbohydrates in milled wood lignin preparations. Sven Papperstidn 82: 272–275

    CAS  Google Scholar 

  • Lundquist K, Simonson R, Tingsvik K (1980) Studies on lignin carbohydrate linkages in milled wood lignin preparations. Sven Papperstidn 83: 452–454

    CAS  Google Scholar 

  • Lundquist K, Simonson R, Tingsvik K (1981) Investigation of lignins from soda and soda anthraquinone cooking of spruce wood. Pap Puu 63: 709–712, 734

    Google Scholar 

  • Lundquist K, Stern K (1989) Analysis of lignins by ’H NMR spectroscopy. Nord Pulp Pap Res J 4: 210–213

    Article  CAS  Google Scholar 

  • Lundquist K, Stomberg R, von Unge S (1987) Stereochemical assignment of the threo and erythro forms of 2-(2,6-dimethoxyphenoxy)-l-(3,4-dimethoxyphenyl)-l,3-propanediol from X-ray analyses of the synthetic intermediates (Z)-2-(2,6-dimethoxyphenoxy)-3-(3,4-dimethoxyphenyl)-2-propenoic acid and threo-2-(2,6-dimethoxyphenoxy)-3-(3,4-dimethoxyphenyl)-3-hydroxypropanoic acid. Acta Chem Scand B41: 499–510

    Article  Google Scholar 

  • Lundquist K, von Unge S (1986) NMR studies of lignins. 8. Examination of pyridine-ds solutions of acetylated lignins from birch and spruce by 1H NMR spectroscopy. Acta Chem Scand B40 791–797

    Article  Google Scholar 

  • Mânsson P (1983) Quantitative determination of phenolic and total hydroxyl groups in lignin. Holzforschung 37: 143–146

    Article  Google Scholar 

  • Marchessault RH, Coulombe S, Morikawa H, Robert D (1982) Characterization of aspen exploded wood lignin. Can J Chem 60: 2372–2382

    Article  CAS  Google Scholar 

  • Môrck R, Kringstad KP (1985) l3C-NMR spectra of kraft lignins. II. Kraft lignin acetates. Holzforschung 39: 109–119

    Google Scholar 

  • Nakatsubo F, Higuchi T (1975) Synthesis of 1,2-diarylpropane-l,3-diols and determination of their configurations. Holzforschung 29: 193–198

    Article  CAS  Google Scholar 

  • Ralph J, Ede RM, Robinson NP, Main L (1987) Reactions of β-aryl lignin model quinone methides with anthrahydroquinone and antranol. J Wood Chem Technol 7: 133–160

    Article  CAS  Google Scholar 

  • Ralph J, Young RA (1983) Stereochemical aspects of lignin model β-aryl ether quinone methide reactions. J Wood Chem Technol 3: 161–182

    Article  CAS  Google Scholar 

  • Sarkanen KV, Wallis AFA (1973) Oxidative dimerizations of (E)- and (Z)-isoeugenol (2- methoxy-4-propenylphenol) and (E)- and (Z)-2,6-dimethoxy-4-propenylphenol. JCS Perkin I 1973: 1869–1878

    Article  Google Scholar 

  • Simionescu CI, Dragovova R, Kusmanova D (1981) NMR-Spektroskopische Untersuchungen von Dioxanligninfraktionen. Cellul Chem Technol 15: 455–464

    CAS  Google Scholar 

  • Suty L, Golis E (1972) Chemical structure of beech lignin and its changes during water hydrolysis. Cellul Chem Technol 6: 485–491

    CAS  Google Scholar 

  • Tollier M-T, Monties B, Lapierre C, Hervé du Penhoat C, Rolando C (1986) Inhomogeneity of angiosperm lignin: Comparison of the monomeric composition of lignin fractions isolated from different wood species. Holzforschung Suppl 40: 75–79

    CAS  Google Scholar 

  • Wallis AFA (1973) Oxidation of (E) and (Z)-2,6-dimethoxy-4-propenylphenol with ferric chloride - a facile route to the 2-aryl ethers of l-arylpropane-l,2-diols. Aust J Chem 26: 585–594

    Article  CAS  Google Scholar 

Download references

Authors
  1. K. Lundquist
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. LignoTech USA Inc., 100 Highway 51 South, 54474, Rothschild, WI, USA

    Stephen Y. Lin

  2. 600 Black Walnut Court, 28792, Hendersonville, NC, USA

    Carlton W. Dence

Rights and permissions

Reprints and permissions

Copyright information

© 1992 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Lundquist, K. (1992). Proton (1H) NMR Spectroscopy. In: Lin, S.Y., Dence, C.W. (eds) Methods in Lignin Chemistry. Springer Series in Wood Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-74065-7_17

Download citation

  • DOI: https://doi.org/10.1007/978-3-642-74065-7_17

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-74067-1

  • Online ISBN: 978-3-642-74065-7

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation