Advertisement

Wood Science and Technology

, Volume 53, Issue 1, pp 7–47 | Cite as

Structure, chemical reactivity and solubility of lignin: a fresh look

  • Edward I. Evstigneyev
  • Sergey M. ShevchenkoEmail author
Original
  • 192 Downloads

Abstract

This is a review of historical and modern literature data on the structure versus properties of wood lignin in view of the concepts developed by the authors based on their own research. Changes in the structure of lignin and related changes in its chemical reactivity during alkaline wood pulping are assessed based on the comparison of the structures of lignin at three kinetically distinct stages of delignification: initial, bulk and final. Lignin gradually moves from a solid to a liquid phase during the pulping process; therefore, structures of native, dissolved and residual lignin are elucidated and compared. The emphasis is on changes in the molecular weight distribution and content of alkylarylether bonds, and functional groups, in particular phenolic hydroxyls. For comparison, splitting rates for α- and β-alkylarylether bonds in both phenolic and non-phenolic lignin model compounds are analyzed. Based on the comparative analysis of the experimental data, it is suggested that native lignin in wood consists mainly of three distinct fractions that are different in chemical reactivities of alkylarylether bonds. This phenomenon results in three kinetically distinct stages of the pulping process. Wood delignification is essentially a process of lignin functionalization followed by its dissolution. The functionalization, i.e., formation of additional functional groups in the macromolecule, continues until it reaches the level sufficient for lignin dissolution under chosen conditions, and then, delignification occurs. At the bulk stage of pulping, the rate of delignification is directly proportional to the degree of functionalization. The data characterizing the effect of redox reactions on the structure and chemical reactivity of lignin in alkali–anthraquinone pulping are analyzed in detail in view of their general importance for our understanding of the chemical reactivity of lignin. Results of polarographic studies of numerous representative lignin model compounds (> 70 samples) and lignin samples, including chemically changed lignins, are compiled, and a diagram of reduction potentials of polarographically active functional groups in lignin is drawn. From a comparison of redox properties of lignin and 32 pulping additives, criteria for selection of potential alkaline pulping catalysts are derived. Solubility belongs to basic properties of polymers, lignin included, and all methods of delignification of plant materials can be essentially reduced to solid polymer functionalization followed by its dissolution. Factors contributing to lignin solubility are analyzed, including such characteristics as molecular weight, temperature, liquid–solid ratio and ionic strength. Based on the analyzed data, a uniform scale of solubility for different lignin types is proposed, and formulae for calculating lignin solubility in alkaline media are derived.

Notes

References

  1. Agarwal UP, Atalla RH (1986) In situ Raman microprobe studies of plant cell walls: macromolecular organization and compositional variability in the secondary wall of Picea mariana. Planta 169(3):325–332Google Scholar
  2. Algar WH, Farrington A, Jessup B, Vanderhock N (1979) The mechanism of soda-quinone pulping. Appita 33(1):33–37Google Scholar
  3. Amos LW, Eckert RC (1982) Influence of methylation on the solubility and efficiency of anthraquinone in soda pulping. In: Proceedings of canadian wood chem symposium Niagara Falls, NY, pp 7–10Google Scholar
  4. Andreyev VI, Vasilieva TM, Grigoriev GP, Vlasova KI (1974) Study on interaction of dioxane lignin with aqueous solutions of sodium hydroxide by calorimetry. In: Chemistry and use of lignin, Zinatne, Riga, pp 129–133Google Scholar
  5. Asikkala J, Tamminen T, Argyropoulos DS (2012) Accurate and reproducible determination of lignin molar mass by acetobromination. J Agric Food Chem 60:8968–8973Google Scholar
  6. Atalla RH, Agarwal UP (1985) Raman microprobe evidence for lignin orientation in cell walls of native woody tissue. Science 227(4687):636–638Google Scholar
  7. Balakshin MYu, Capanema EA, Chen C-L, Gratzl JS, Gracz H (2000) The use of 2D NMR spectroscopy on structural analysis of residual and technical lignins. In: Proceedings of 6th European workshop on lignocellulosics and pulp, Bordeaux, France, pp 11–14Google Scholar
  8. Balakshin MYu, Capanema EA, Chang H (2008) Recent advances in the isolation and analysis of lignins and lignin-carbohydrate complexes. In: Hu TQ (ed) Characterization of lignocellulosic materials. Blackwell Publishing Ltd, Oxford, pp 148–170Google Scholar
  9. Bonawitz ND, Chapple C (2010) The genetics of lignin biosynthesis: connecting genotype to phenotype. In: Campbell A, Lichten M, Schupbach G (eds) Annual review of genetics. Annual reviews 44: 337–363Google Scholar
  10. Bond AM (1980) Modern polarographic methods in analytical chemistry. M Dekker, New YorkGoogle Scholar
  11. Brunow G, Miksche G (1976) Some reactions of lignin in kraft and polysulfide pulping. Appl Polym Symp 28:1155–1168Google Scholar
  12. Brunow G, Poppius KA (1981) Kinetic study on the mechanism of β-O-4 ether cleavage in soda-anthraquinone pulping. Paperi ja Puu 63(12):783–785Google Scholar
  13. Chiang VL, Kolppo K, Stokke DD (1989) Structure changes of lignin in kraft and acid sulphite delignification of western hemlock. In: Proceedings of international symposium on wood and pulping chemistry, Raleigh, NC, pp 593–597Google Scholar
  14. Chiang VL, Yu J, Eckert RC (1990) Isothermal reaction kinetics of kraft delignification of Douglas-fir. J Wood Chem Technol 10(3):293–310Google Scholar
  15. Crestini C (2014) Lignin structure: a revisitation of current paradigms through NMR analysis. In: Proceedings of 13th European workshop on lignocellulosics and pulp, Seville, Spain, pp 59–62Google Scholar
  16. Crestini C, Melone F, Sette M, Saladino R (2011) Milled wood lignin: a linear oligomer. Biomacromolecules 12(11):3928–3935Google Scholar
  17. Dimmel D, Gellerstedt G (2010) Chemistry of alkaline pulping. In: Heitner C, Dimmel DR, Schmidt JA (eds) Lignin and lignans. Advances in chemistry series. CRC Press, Boca Raton, pp 349–391Google Scholar
  18. Dimmel DR, Schuller LF (1986a) Structural/reactivity studies (I): soda reactions of lignin model compounds. J Wood Chem Technol 6(4):535–564Google Scholar
  19. Dimmel DR, Schuller LF (1986b) Structural/reactivity studies (II): reactions of lignin model compounds with pulping additives. J Wood Chem Technol 6(4):565–590Google Scholar
  20. Doherty WOS, Mousavioun P, Fellows CM (2011) Value-adding to cellulosic ethanol: lignin polymers. Ind Crops Prod 33(2):259–276Google Scholar
  21. Dudkin MS, Gromov VS (eds) (1991) Hemicelluloses. Zinatne, RigaGoogle Scholar
  22. Eckert RC, Amos LW (1980) Catalysis of alkaline pulping by fluorenone. Tappi J 63(11):89–93Google Scholar
  23. Eckert RC, Amos LW (1981) Prediction of chemical structures leading to catalysis of alkaline pulping. Tappi J 64(6):123–124Google Scholar
  24. Eckert RC, Amos LW (1982) Influence of hydrophilicity on the delignification efficiency of anthraquinone derivatives. J Wood Chem Technol 2(1):57–71Google Scholar
  25. Evstigneyev EI (2001) Structural changes in lignin during alkaline wood pulping and their effect on the rate of delignification and on properties of pulp. D.Sc. thesis, St-Petersburg Forest Technical Academy, St-Petersburg, RussiaGoogle Scholar
  26. Evstigneyev EI (2003) Basic theory of alkaline pulping. In: Pulp and paper technology. Politechnica, St-Petersburg, Russia 2(2): 7–16Google Scholar
  27. Evstigneyev EI (2009) Chemical reactivity of lignin in reactions of electrochemical reduction. In: IV national conference on progress in chemistry and chemical technology of plant biomass, Barnaul, Russia, vol 1, pp 80–83Google Scholar
  28. Evstigneyev EI (2010) Specific features of lignin dissolution in aqueous and aqueous-organic media. Russ J Appl Chem 83(3):509–513Google Scholar
  29. Evstigneyev EI (2011) Factors affecting lignin solubility. Russ J Appl Chem 84(6):1040–1045Google Scholar
  30. Evstigneyev EI (2012) On the structure of native lignin. Bull St-Petersburg Forest Technical Academy (Izvestiya SPBLTA), vol 198, pp 164–172Google Scholar
  31. Evstigneyev EI (2013) Oxidation of hydrolysis lignin with hydrogen peroxide in acid solutions. Russ J Appl Chem 86(2):258–265Google Scholar
  32. Evstigneyev EI (2014) Electrochemical reactions of lignin: a review. Khimija Rastitel nogo Syr’ja. Chem Plant Resour 3:5–42Google Scholar
  33. Evstigneyev E (2018) Selective depolymerization of lignin: assessment of the yield of monomeric products. J Wood Chem Technol 1:2–3.  https://doi.org/10.1080/02773813.2018.1500607 Google Scholar
  34. Evstigneyev EI, Rusakov AE (1990) The use of high performance liquid chromatography for studying lignin. In: Proceedings of 1st European workshop on lignocellulosics and pulp. Hamburg, Germany, pp 327–332Google Scholar
  35. Evstigneyev EI, Shalimova TV (1985a) Redox properties, catalytic activity and stabilizing effect of some quinones in soda pulping. 1. Reduction potentials and solubility. Wood Chem (Riga) 1:50–54Google Scholar
  36. Evstigneyev EI, Shalimova TV (1985b) Redox properties, catalytic activity and stabilizing effect of some quinones in soda pulping. 1. Effect on pulping. Wood Chem (Riga) 1:55–60Google Scholar
  37. Evstigneyev EI, Shalimova TV (1987) Correlation of redox properties and catalytic activity of anthraquinone derivatives in sulfate pulping. Coll Works VNIIB VNPOBumprom, pp 27–32Google Scholar
  38. Evstigneyev EI, Rusakov AE, Shalimova TV, Zakharov VI (1987a) Molecular mass distribution in lignin at various stages of soda and soda-AQ pulping. Wood Chem (Riga) 2:51–55Google Scholar
  39. Evstigneyev EI, Rusakov AE, Shalimova TV, Zakharov VI (1987b) Study on changes in molecular mass distribution in spruce Björkman lignin under the conditions of soda, soda-AQ and kraft pulping. In: Abstract of 7 conference chemistry and use of lignin. Riga, Latvia (U.S.S.R.), pp 88–89Google Scholar
  40. Evstigneyev EI, Maiyorova ED, Platonov AYu (1990) Alkaline delignification of wood and lignin functionalization. Wood Chem (Riga) 6:41–46Google Scholar
  41. Evstigneyev E, Maiyorova H, Platonov A (1991) Lignin functionalization and reactivity in alkaline pulping. In: Proceedings of 6th international symposium on wood and pulping chemistry. Melbourne, Australia, vol 2, pp 131–138Google Scholar
  42. Evstigneyev E, Maiyorova H, Platonov A (1992a) Lignin functionalization and the alkaline delignification rate. Tappi J 75(5):177–182Google Scholar
  43. Evstigneyev E, Shevchenko SM, Apushkinsky AG, Semenov SG (1992b) Electrochemistry of lignin model p-quinone methides. Ligno-cellulosics: science, technology. development and use. Ellis Horwood, New York, pp 657–670Google Scholar
  44. Evstigneyev E, Maiyorova H, Kurzin A, Platonov A (1993) About native lignin model. In: Proceedings of 7th International symposium on wood and pulping chemistry. Beijing, China, vol 3, pp 25–31Google Scholar
  45. Evstigneyev E, Kurzin A, Platonov A, Maiyorova H (1994) About residual lignin nature. In: Ext Abstract 3rd European workshop on lignocellulosics and pulp. Stockholm, pp 232–233Google Scholar
  46. Evstigneyev EI, Kurzin AV, Platonov AYu, Maiyorova ED (1996) Freudenberg lignin as a model for studying alkaline delignification of wood. Zhurn Prikl Khim 69(1):148–153Google Scholar
  47. Evstigneyev E, Maiyorova H, Platonov A (1999) Polarographically active structural fragments of lignin. I. Monomeric model compounds. J Wood Chem Technol 19(4):379–407Google Scholar
  48. Evstigneyev E, Shevchenko S, Maiyorova H, Platonov A (2004) Polarographically active structural fragments of lignin II Dimeric model compounds and lignins. J Wood Chem Technol 24(3):263–278Google Scholar
  49. Evstigneyev EI, Yuzikhin OS, Gurinov AA, Ivanov AYu, Artamonova TO, Khodorkovskiy MA, Bessonova EA, Vasilyev AV (2015) Chemical structure and physicochemical properties of oxidized hydrolysis lignin. Russ J Appl Chem 88(8):1295–1303Google Scholar
  50. Evstigneyev EI, Yuzikhin OS, Gurinov AA, Ivanov AYu, Artamonova TO, Khodorkovskiy MA, Bessonova EA, Vasilyev AV (2016) Study of structure of industrial acid hydrolysis lignin, oxidized in the H2O2–H2SO4 system. J Wood Chem Technol 36(4):259–269Google Scholar
  51. Evstigneyev E, Kalugina AV, Ivanov AYu, Vasilyev AV (2017) Contents of α-O-4 and β-O-4 bonds in native lignin and isolated lignin preparations. J Wood Chem Technol 37(4):294–306Google Scholar
  52. Evstigneyev EI, Mazur AS, Kalugina AV, Pranovich AV, Vasilyev AV (2018) Solid-state 13C CP/MAS NMR for alkyl-O-aryl bonds determination in lignin preparations. J Wood Chem Technol 38(4):137–148Google Scholar
  53. Evtuguin DV, Amado FML (2003) Application of electrospray ionization mass spectrometry to the elucidation of the primary structure of lignin. Macromol Biosci 3:339–343Google Scholar
  54. Faulon JL (1994) Stochastic generator of chemical structure. 1. Application to the structure elucidation of large molecules. J Chem Inf Comput Sci 34(5):1204–1218Google Scholar
  55. Faulon JL, Hatcher PG (1994) Is there any order in the structure of lignin? Energy&Fuels 8(2):402–407Google Scholar
  56. Favis BD, Goring DAI (1984) A model for the leaching of lignin macromolecules from pulp fibers. J Pulp Pap Sci 10(5):139–143Google Scholar
  57. Fengel D, Wegener G (1989) Wood: Chemistry, ultrastructure, reactions. Berlin-NY, Walter de Gruyter [Quoted pages refer to Russian translation: Фeнгeл Д, Beгeнep Г Дpeвecинa Xимия, yльтpacтpyктypa, peaкции Пep c aнгл M: Лecн пpoм-cть, 1988]Google Scholar
  58. Freudenberg K (1965) Lignin: its constitution and formation from p-hydroxycinnamyl alcohols. Science 148(3670):595–600Google Scholar
  59. Galkin MV, Samec JSM (2016) Lignin valorization through catalytic lignocellulose fractionation: a fundamental platform for the future biorefinery. Chemsuschem 9:1544–1558Google Scholar
  60. Gellerstedt G (1996) Chemical structure of pulp components. In: Dence CW, Reeve DW (eds) Pulp bleaching principles and practice. Tappi Press, Atlanta, pp 93–111Google Scholar
  61. Gellerstedt G, Al-Adjani WW (1998) The influence on bleachability of changes in pulping chemistry. In: Proceedings of 5th European workshop on lignocellulosics and pulp Aveiro, Portugal, pp 547–550Google Scholar
  62. Gellerstedt G, Henriksson G (2008) Lignins: major sources, structure and properties. In: Belgacem MN, Gandini A (eds) Monomers, polymers and composites from renewable resources. Elsevier, Amsterdam, pp 201–224Google Scholar
  63. Gellerstedt G, Lindfors E (1984a) Structural changes in lignin during kraft cooking. Part 4. Phenolic hydroxyl groups in wood and kraft pulps. Svensk Papperstidn 87(15):R115–R118Google Scholar
  64. Gellerstedt G, Lindfors EL (1984b) Structural changes in lignin during kraft pulping. Holzforschung 38(3):151–158Google Scholar
  65. Gierer J (1980) Chemical aspects of kraft pulping. Wood Sci Technol 14(4):241–266Google Scholar
  66. Gierer J (1982a) The chemistry of delignification. A general concept. Part I. Holzforschung 36(1):43–51Google Scholar
  67. Gierer J (1982b) The chemistry of delignification. A general concept. Part II. Holzforschung 36(2):55–64Google Scholar
  68. Gierer J, Lindenberg O (1980) Reaction of lignin during sulfate pulping. Part XIX. Isolation and identification of new dimmers from spent sulfate liquor. Acta Chem Scand 34(3):161–170Google Scholar
  69. Gierer J, Ljunggren S (1979) The reaction of lignin during sulfate pulping. 17. Kinetic treatment of the formation and competing reactions of quinone methide intermediates. Svensk Papperstidn 82(17):503–512Google Scholar
  70. Gierer J, Ljunggren S (1983) Comparative studies of the participation of different neighboring groups in the alkaline cleavage of β-aryl ether bonds in lignin. Svensk Papperstidn 86(9):R100–R106Google Scholar
  71. Gierer J, Ljunggren S, Ljungquist P, Noren I (1980) The reaction of lignin during sulfate pulping. 18. The significance of α-carbonyl groups for the cleavage of β-aryl ether structure. Svensk Papperstidn 83(3):75–82Google Scholar
  72. Guizani C, Lachenal D (2017) Controlling the molecular weight of lignosulfonates by an alkaline oxidative treatment at moderate temperatures and atmospheric pressure: a size-exclusion and reverse-phase chromatography study. Int J Mol Sci 18(12):2520–2538Google Scholar
  73. Gullichsen J (1999) Fiber line operations. In: Gullichsen J, Paulapuro H (eds) Papermaking science and technology series, Yväskylä: Finnish Paper Engineers’ Association and TAPPI, Fapet Oy, Book 6, Chapter 2Google Scholar
  74. Hansen CM, Björkman A (1998) The ultrastructure of wood from a solubility parameter point of view. Holzforschung 52(4):335–344Google Scholar
  75. Heifetz LYa, Bezugly VD (1969) Polarography of anthraquinone and its derivatives. In: Organic intermediates and dyes. Chemistry of anthraquinone. Khimiya, Moscow, Russia, vol 4, pp 164–193Google Scholar
  76. Helm RF (2000) Lignin-polysaccharide interactions in woody plants. In: Glasser WG, Northey RA, Schultz TP (eds) Lignin: historical, biological, and materials perspectives, vol 742. ACS Symp Series, Washington, pp 161–171Google Scholar
  77. Hergert HL, Pye EK (1993) Recent history of organosolv pulping. In: Proceedings of 2nd international technical conference on PapFor-93. St Petersburg, Russia, pp 79–100Google Scholar
  78. Hulanicky A, Masson MR (1987) Reactions of acids and bases in analytical chemistry. E Horwood, ChichesterGoogle Scholar
  79. Irzhak VI, Rosenberg BA, Enikolopyan NS (1979) Web polymers: synthesis, structure, properties. Nauka, MoscowGoogle Scholar
  80. Kärkäs MD, Matsuura BS, Monos TM, Magallanes G, Stephenson CRJ (2016) Transition-metal catalyzed valorization of lignin: the key to a sustainable carbon-neutral future. Org Biomol Chem 14:1853–1914Google Scholar
  81. Karmanov AP (2004) Self-organization and structure of lignin. YekaterinburgGoogle Scholar
  82. Kleinert TN (1966) Mechanisms of alkaline delignification. I. The overal reaction pattern. Tappi J 49(2):53–57Google Scholar
  83. Kondo R, Sarkanen KV (1984) Kinetics of lignin and hemicellulose dissolution during the initial stage alkaline pulping. Holzforschung 38(1):31–36Google Scholar
  84. Kondo R, Tsutsumi Y, Imamura H (1987) Kinetics of β-aryl ether cleavage of phenolic syringyl type lignin model compounds in soda and kraft systems. Holzforschung 41(2):83–88Google Scholar
  85. Kringstad KP, Mörck R (1983) 13C-NMR spectra of kraft lignins. Holzforschung 37(5):237–244Google Scholar
  86. Kurzin AV, Platonov AYu, Evstigneyev EI Mayorova ED (1997) Nucleophilicity and basicity of phenols in aminolysis of their acetates with piperidine. Zhurn Obsch Khim 67(9):1568–1571Google Scholar
  87. Laurichesse S, Averous L (2014) Chemical modification of lignins: towards biobased polymers. Progr Polymer Sci 39:1266–1290Google Scholar
  88. Lawoko M, Berggren R, Berthold F, Henriksson G, Gellerstedt G (2004) Changes in the lignin-carbohydrate complex in softwood kraft pulp during kraft and oxygen delignification: lignin-polysaccharide networks. II. Holzforschung 58:603–610Google Scholar
  89. Lawoko M, Henriksson G, Gellerstedt G (2005) Structural differences between the lignin-carbohydrate complexes in wood and chemical pulps. Biomacromolecules 6:3467–3473Google Scholar
  90. Lindberg O (1979) Studies on the chemistry of delignification in alkaline media. Chem Commun Univ Stockholm 6:1–51Google Scholar
  91. Lindenfors S (1980) Additives in alkaline pulping—What reduces what? Svensk Papperstidn 83(6):165–173Google Scholar
  92. Lindner A, Wegener G (1900) Characterization of lignins from organosolv pulping according to the Organocell process. Part 3. Molecular weight determination and investigation of fractions isolated by GPC. J Wood Chem Technol 10(3):331–350Google Scholar
  93. Lindner A, Wegener G (1988) Characterization of lignins from organosolv pulping according to the Organocell process. Part 1. Elemental analysis, nonlignin portions and functional groups. J Wood Chem Technol 8(3):323–340Google Scholar
  94. Liu C-J (2012) Deciphering the enigma of lignification: precursor transport, oxidation, and the topochemistry of lignin assembly. Mol Plant 5:304–317Google Scholar
  95. Ljunggren S (1980) The significance of aryl ether cleavage in kraft delignification of softwood. Svensk Papperstidn 83(13):363–369Google Scholar
  96. Lora J (2008) Industrial commercial lignins: sources, properties and applications. In: Belgacem MN, Gandini A (eds) Monomers, polymers and composites from renewable resources. Elsevier, Amsterdam, pp 225–241Google Scholar
  97. Luner P, Roseman G (1986) Monomolecular film properties of isolated lignins. Holzforschung 40(Suppl.):61–66Google Scholar
  98. Magalhaes Silva Moura JC, Valencise Bonine CA, de Oliveira Fernandes Viana J, Dornelas M C, Mazzafera P (2010) Abiotic and biotic stresses and changes in the lignin content and composition in plants. J Integr Plant Biol 52(4):360–376Google Scholar
  99. Maiyorova H, Platonov A, Evstigneyev E (1995) About significance of nonphenolic lignin structure in alkaline pulping with anthraquinone. In: Proceedings of 8th international symposium on wood and pulping chemistry Helsinki, Finland, vol 2, pp 291–296Google Scholar
  100. Mänsson P (1983) Quantitative determination of phenolic and total hydroxyl groups in lignins. Holzforschung 37(3):143–146Google Scholar
  101. Maunu SL (2002) NMR studies of wood and wood products. Progr Magn Reson Spectrosc 40:151–174Google Scholar
  102. Metzger JO, Bicke O, Faix O, Tuszynski W, Angermann R, Karas M, Strupat K (1992) Matrix-assisted laser desorption mass spectrometry of lignins. Angew Chem Int Ed Eng 31(6):762–764Google Scholar
  103. Mörck R, Yoshida H, Kringstad KP, Hatakeyama H (1986) Fractionation of kraft lignin by successive extaction with organic solvents. Holzforschung 40(suppl):51–60Google Scholar
  104. Mottiar Y, Vanholme R, Boerjan W, Ralph J, Mansfield SD (2016) Designer lignins: harnessing the plasticity of lignification. Curr Opin Biotechnol 37:190–200Google Scholar
  105. Niemelä K (1990) Low-molecular-weight organic compounds in birch kraft black liquor. Ann Acad Sci Fennica Series A II Chemica 229:1–142Google Scholar
  106. Nimz HH (1995) Analytical methods in wood, pulping and bleaching chemistry. In: Proceedings of 8th international symposium on wood and pulp chemistry Helsinki, Finland, vol 1, pp 1–32Google Scholar
  107. Nomura Y, Nakamura M (1978) Studies on quinone additive cooking. 1. Effect of quinone addition on alkaline cooking. Jpn Tappi 32(12):713–721Google Scholar
  108. Obst J (1983) Kinetics of alkaline cleavage of β-aryl ether bonds in lignin models: significance to delignification. Holzforschung 37(1):23–28Google Scholar
  109. Pedersen JA (1973) Electron spin resonance studies of oxidative processes of quinones and hydroquinones in alkaline solution. Formation of primary and secondary semiquinone radicals. J Chem Soc Perkin Trans Part 2(4):424–431Google Scholar
  110. Pilyugina LG, Haponen IL, Vasilieva TM, Mischenko KP (1974) Comparison of thermodynamic characteristics of separated lignins. Chemistry and use of lignin. Zinatne, Riga, pp 113–122Google Scholar
  111. Rabinovich ML (2009) Wood hydrolysis industry in the Soviet Union and Russia: What can be learned from history? In: Rautakivi A (ed) Oral presentations, Proceedings of NWBC 2009, Helsinki, Finland, 2–4 September, pp 111–120Google Scholar
  112. Rabinovich ML (2010) Wood hydrolysis industry in the Soviet Union and Russia: a mini-review. Cellulose Chem Technol 44(4–6):173–186Google Scholar
  113. Radotić K, Simić-Krstić J, Jeremić M, Trifunović MA (1994) Study of lignin formation at the molecular level by scanning tunneling microscopy. Biophys J 66(6):1763–1767Google Scholar
  114. Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis M, Davison BH, Dixon RA, Gilna P, Keller M, Langan P, Naskar AK, Saddler JN, Tschaplinski TJ, Tuskan GA, Wyman CE (2014) Lignin valorization: improving lignin processing in the biorefinery. Science 344:1246843-1–1246843-10Google Scholar
  115. Ralph J (2010) Hydroxycinnamates in lignification. Phytochem Rev 9:65–83Google Scholar
  116. Ralph J, Lundquist K, Brunow G, Lu F, Kim H, Schatz PF, Marita JM, Hatfield RD, Christensen JH, Boerjan W (2004) Lignins: natural polymer from oxidative coupling of 4-hydroxyphenylpropanoids. Phytochem Rev 3(1):29–60Google Scholar
  117. Rinaldi R, Jastrzebski R, Clough MT, Ralph J, Kennema M, Bruijnincx PCA, Weckhuysen BM (2016) Paving the way for lignin valorisation: recent advances in bioengineering, biorefining and catalysis. Angew Chem Int Ed 55:8164–8215Google Scholar
  118. Robert DR, Bardet M, Gellerstedt G, Lindfors E-L (1984) Structural changes in lignin during kraft cooking. Part 3. On the structure of dissolved lignins. J Wood Chem Technol 4(3):239–263Google Scholar
  119. Sakakibara A (1991) Chemistry of lignin. In: Hon DN-S, Shirashi N (eds) Wood and cellulosic chemistry. Marcel Dekker, New York, pp 111–175Google Scholar
  120. Santos RB, Jameel H, H-m Chang, Hart PW (2013) Impact of lignin and carbohydrate chemical structures on degradation reactions during hardwood kraft pulping processes. BioResources 8(1):158–171Google Scholar
  121. Sarkanen KV, Ludwig CH (eds) (1971) Lignins: Occurrence, Formation, and Reactions, Wiley, NY [Quoted pages refer to Russian translation: Лигнины Cтpyктypa, cвoйcтвa и peaкции/Пoд peд КB Capкaнeнa, КX Людвигa Пep c aнгл M: Лecн пpoм-cть, 1975]Google Scholar
  122. Sen S, Patil S, Argyropoulos DS (2015) Thermal properties of lignin in copolymers, blends, and composites: a review. Green Chem 17:4862–4887Google Scholar
  123. Shevchenko SM, Deineko IP (1983) Chemistry of anthraquinone pulping. Wood Chem (Riga) 6:3–32Google Scholar
  124. Shi R, Sun Y-H, Li Q, Heber S, Sederoff R, Chiang VL (2010) Towards a systems approach for lignin biosynthesis in Populus trichocarpa: transcript abundance and specificity of the monolignol biosynthetic genes. Plant Cell Physiol 51:144–163Google Scholar
  125. Shorygina NN, Reznikov VM, Yelkin VV (1976) Chemical reactivity of lignin. Nauka, MoscowGoogle Scholar
  126. Sjöström E (1981) Wood chemistry (Riga): fundamentals and applications. Academic Press, New YorkGoogle Scholar
  127. Srzić D, Martinović S, Lj Tolić Paša, Kezele N, Shevchenko SM, Klasinc L (1995) Laser desorption Fourier-transform mass spectrometry of lignins. Rapid Commun Mass Spectr 9:245–249Google Scholar
  128. Ten E, Vermerris W (2015) Recent developments in polymers derived from industrial lignin. J Appl Polymer Sci 132:42069–42082Google Scholar
  129. Thakur VK, Manju Kumari Thakur M, Raghavan P, Michael R, Kessler M (2014) Progress in green polymer composites from lignin for multifunctional applications: a review. ACS Sustain Chem Eng 2(5):1072–1092Google Scholar
  130. Vanholme R, Demedts B, Morreel K, Ralph J, Boerjan W (2010) Lignin biosynthesis and structure. Plant Physiol 153:895–905Google Scholar
  131. Weng J-K, Chapple C (2010) The origin and evolution of lignin biosynthesis. New Phytol 187:273–285Google Scholar
  132. Werthemann DP (1981) The xylophilicity/hydrophilicity balance of quinoid pulping additives. Tappi 64(3):140–142Google Scholar
  133. Werthemann DP, Huber-Emden H, Bersier PM, Kelemen J (1981) High catalytic activity of rosindone and related compounds in alkaline pulping. J Wood Chem Technol 1(2):185–197Google Scholar
  134. Wilder HD, Daleski EJ (1965) Part II of a series on kraft pulping kinetics. Tappi J 48(5):293–297Google Scholar
  135. Yamasaki T, Hosoya S, Chen C-L, Gratzl JS, Chang H-M (1981) Characterization of residual lignin in kraft pulp. In: Proceedings of international symposium on wood pulp chemistry Stockholm, Sweden, vol 2, pp 34–42Google Scholar
  136. Zakis GF (1987) Functional analysis of lignins and their derivatives. Zinatne, RigaGoogle Scholar
  137. Zhao Q, Dixon RA (2011) Transcriptional networks for lignin biosynthesis: more complex than we thought? Trends Plant Sci 16(4):227–233Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.St.-Petersburg State Forest Technical UniversitySt.-PetersburgRussia
  2. 2.TijerasUSA

Personalised recommendations