Abstract
A number of two-dimensional NMR experiments are evaluated with respect to their ability to provide unambiguous evidence for the presence or absence of non-cyclic benzyl aryl ether (α-O-4) structures in soluble lignin samples. The most suitable techniques, in terms of both sensitivity and structural information content were the homonuclear Hartmann-Hahn (HOHAHA) and heteronuclear multiple quantum coherence (HMQC) techniques. By spiking an acetylated Pinus radiata MWL sample with an oligomeric α-O-4 ether model compound, it was possible to determine a detection limit of <0.3 structures per 100 lignin C9 units for both the HOHAHA and HMQC techniques. From this, and other work, it can be shown that if α-O-4 structures are present in MWL samples, they are present at a level below the detection limit of these experiments. The implications of these results are discussed in terms of lignin biosynthesis and reactivity.
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References
E. Adler,Wood Sci. Technol.,11, 169 (1977).
G. Gellerstedt and E.L. Lindfors,Holzforschung,38, 151 (1984).
Y. Matsumoto, A. Ishizu, and J. Nakano,Mokuzai Gakkaishi,27, 750 (1981).
C. Lapierre, B. Monties and C. Rolando,J. Wood Chem. Technol.,5, 277 (1985).
C. Lapierre, B. Pollet, and B. Monties,Holzforschung,45, 61 (1991).
K. Lundquist and T. Olsson,Acta Chem. Scand.,B31, 788 (1977).
K. Lundquist,Acta Chem. Scand.,B33 418 (1979).
K. Lundquist,Acta Chem Scand. B33, 27 (1979).
G. Brunow and K. Lundquist,Pap. Puu,62, 669 (1980).
K. Lundquist,Acta Chem. Scand.,B34, 21 (1980).
K. Lundquist,Acta Chem. Scand.,B35, 497 (1981).
K. Lundquist, A. Paterson, and L. Ramsey,Acta Chem. Scand.,B37, 734 (1983).
M. Hauteville, K. Lundquist and S. Von Unge,Acta Chem. Scand.,B40, 31 (1986).
K. Lundquist,J. Wood Chem. Technol.,7, 179 (1987).
K. Lundquist and K. Stern,Nord. Pulp Pap. Res. J.,4, 210 (1989).
K. Lundquist,Nord. Pulp Pap. Res. J.,7, 4 (1992).
H. Nimz, I. Mogharab and H.-D. Lüdemann,Makromol. Chem.,175, 2563 (1974).
H.-D. Lüdemann and H. Nimz,Makromol. Chem.,175, 2393 (1974).
H.-D. Lüdemann and H. Nimz, H.Makromol. Chem.,175, 2409 (1974).
H.H. Nimz and H.-D. Lüdemann,Holzforschung,30, 33 (1976).
H.H. Nimz, D. Robert, O. Faix, and M. Nemr,Holzforschung,35, 16 (1981).
H. Nimz, M. Nemr, P. Schmidt, C. Margot, B. Schaub and M. Schlosser,J. Wood Chem. Technol.,2, 371 (1982).
H.H. Nimz, U. Tschirner, M. Stähle, R. Lehmann, and M. Schlosser,J. Wood Chem. Technol.,4, 265 (1984).
D.R. Robert and G. Brunow,Holzforschung,38, 85 (1984).
M. Bardet, M.F. Foray, and D. Robert,Makromol. Chem.,186, 1495 (1985).
L.L. Landucci,Holzforschung,39, 355 (1985).
C. Lapierre, B. Monties, E. Guittet, and J.Y. Lallemand,Holzforschung,39, 367 (1985).
J.R. Obst and L.L. Landucci,Holzforschung,40, 87 (1986).
M. Bardet, D. Gagnaire, R. Nardin, D. Robert, and M. Vincendon,Holzforschung,40, 17 (1986).
L.L. Landucci, G.C. Deka, and D.N. Roy,Holzforschung,46, 505 (1992).
J. Gravitis, R. Teeaar, B. Andersons, and E. Lippmaa,Khim. Drev., 9 (1985).
J.A. Hemmingson and R.H. Newman,J. Wood Chem. Technol.,5, 159 (1985).
G.J. Leary, R.H. Newman, and K.R. Morgan,Holzforschung,40, 267 (1986).
N.G. Lewis, J. Newman, G. Just, and J. Ripmeister,Macromolecules 20, 1752 (1987).
N.G. Lewis, R.A. Razal, K.P. Dhara, E. Yamamoto, G.H. Bokelman, and J.B. Wooten,J. Chem. Soc., Chem. Commun., 1626 (1988).
T.L. Eberhardt, M.A. Bernards, L. He, L.B. Davin, J.B. Wooten, and N.G. Lewis,J. Biol. Chem.,268, 21088 (1993).
N.G. Lewis, E. Yamamoto, J.B. Wooten, G. Just, H. Ohashi, and G.H.N. Towers,Science,237, 1344 (1987).
K. Lundquist,Acta Chem. Scand.,B35, 497 (1981).
E. Guittet, J.Y. Lallemand, C. Lapierre, and B. Monties,Tetrahedron Lett.,26, 2671 (1985).
C. Lapierre, B. Monties, E. Guittet, and J.Y. Lallemand,Holzforschung,41, 51 (1987).
R.M. Ede, G. Brunow, L.K. Simola and J. Lemmetyinen,Holzforschung,44, 95 (1990).
R.M. Ede and G. Brunow,J. Org. Chem.,57, 1477 (1992).
N. Fukagawa, G. Meshitsuka, and A. Ishizu,J. Wood Chem. Technol.,11, 373 (1991).
I. Kilpeläinen, J. Sipilä, G. Brunow, K. Lundquist, and R.M. Ede,J. Ag. Food Chem., (1994), submitted for publication.
J. Ralph, R.D. Hatfield, S. Quideau, R.F. Helm, J. Grabber, and H.G. Jung,Amer. Chem. Soc. Natl. Mtg., Denver, Abstract Cell-104 (1993).
R.M. Ede and J. Ralph,Mag. Res. Chem., (1994), submitted for publication.
N. Fukagawa, G. Meshitsuka and A. Ishizu,J. Wood Chem. Technol.,12, 425 (1992).
N. Fukagawa, G. Meshitsuka and A. Ishizu,J. Wood Chem. Technol.,12, 91 (1992).
J. Ralph, R.F. Helm, S. Quideau, and R.D. Hatfield,J. Chem. Soc., Perkin Trans. 1, 2961 (1992).
I. Kilpeläinen, Academic Dissertation, University of Helsinki (1994) Annales Academiæ Scientiarum Fennicæ, Series A.
H.-M. Chang, E.B. Cowling, W. Brown, E. Adler, and G. Miksche,Holzforschung,29, 153 (1975).
K. Freudenberg, J.M. Harkin, and H.-K. Werner,Chem. Ber.,97, 909 (1964).
Y.-Z. Lai and X.-P. Guo,Holzforschung,46, 311 (1992).
H.I. Bolker, A.-M. Fruteau de Laclos, and S.A. Mirshokraie,J. Pulp Paper Sci.,17, J194 (1991).
A. Björkman,Svensk Papperstidn.,59, 477 (1956).
A. Bax and D.G. Davis,J. Magn. Reson.,65, 355 (1985).
G. Bodenhausen and D.J. Ruben,Chem. Phys. Lett.,69, 185 (1980).
A. Bax and S. Subramanian,J. Magn. Reson,67, 565 (1986).
M.F. Summers, L.G. Marzilli, and A. Bax,J. Am. Chem. Soc.,108, 4285 (1986).
A. Bax and M.F. Summers,J. Am. Chem. Soc.,108, 2093 (1986).
A. Kumar, R.R. Ernst, and K. Wuethrich,Biochem. Biophys. Res. Commun.,95, 1 (1980).
A. Bax, and D.G. Davis,J. Magn. Reson.,63, 207 (1985).
P. Barker and R. Freeman,J. Magn. Reson.,64, 334 (1985).
S. Quideau and J. Ralph,Holzforschung,48, 124 (1994).
J. Ralph, R.D. Hatfield, S. Quideau, and R.F. Helm,Amer. Chem. Soc. Natl. Mtg., Denver, Abstract Cell-137 (1993).
L. Lerner and A. Bax,J. Magn. Reson.,69, 375 (1986).
G. Brunow, J. Sipila, and T. Makela,Holzforschung,43, 55 (1989).
D. Fengel and G. Wegener,Wood: Chemistry, Ultrastructure, Reactions, W. de Gruyter, Berlin, p. 155 (1989).
I. Kilpeläinen, J. Sipila, G. Brunow, and K. Lundquist,Amer. Chem. Soc. Natl. Mtg., Denver, Abstract Cell-79 (1993).
P. Whiting and D.A.I. Goring,Svensk Papperstidn.,84, R120 (1981).
A. Maurer and D. Fengel,Holzforschung,46, 471 (1992).
A. Maurer and D. Fengel,Holzforschung,46, 417 (1992).
G. Brunow, J. Sipila, and T. Makela,Holzforschung,43, 55 (1989).
J. Sipilä, Academic Dissertation, University of Helsinki. Annales Academiæ Scientiarum Fennicæ, Series A, (1990).
J. Sipilä and G. Brunow,Holzforschung,45, 275 (1991).
S. Quideau and J. Ralph,Holzforschung,48, 12 (1994).
D. Fengel and G. Wegener,Wood: Chemistry, Ultrastructure, Reactions, W. de Gruyter, Berlin, p. 220, (1989).
K.V. Sarkanen. In:Lignins, Occurrence, Formation, Structure and Reactions, K.V. Sarkanen and C.H. Ludwig (Eds.), Wiley-Interscience, New York (1971).
Y.Z. Lai and K.V. Sarkanen,Cellulose Chem. Technol.,9, 239 (1975).
J. Gierer,Svensk Papperstidn.,73, 571 (1970).
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Ede, R.M., Kilpeläinen, I. Homo- and hetero-nuclear 2D NMR techniques: Umambiguous structural probes for non-cyclic benzyl aryl ethers in soluble lignin samples. Res. Chem. Intermed. 21, 313–328 (1995). https://doi.org/10.1007/BF03052261
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DOI: https://doi.org/10.1007/BF03052261