Abstract
Polysaccharides are formed by repeated glycosylations between a sugar donor and a sugar acceptor. This chapter reviews the in vitro synthesis of polysaccharides by “enzymatic polymerization.” As catalyst, a hydrolase enzyme is used where the monomer was designed based on the concept of a “transition-state analog substrate” (TSAS), sugar fluoride monomers for the polycondensation, and sugar oxazoline monomers for the ring-opening polyaddition. Enzymatic polymerization enabled the first in vitro synthesis of natural polysaccharides such as cellulose, xylan, chitin, hyaluronan, and chondroitin, and also of unnatural polysaccharides such as a cellulose-xylan hybrid, a regularly methylated cellulose, and derivatives of hyaluronan and chondroitin. The polymerization mechanism is discussed here. Mutant enzymes were effective for polysaccharide synthesis, where only polycondensation of monomers was induced by suppressing the hydrolysis activity. The polymerization principle was extended to a stepwise synthesis of oligosaccharides. By using characteristics of the polymerization to produce a polysaccharide by a single step, in situ observations of the polymerization reaction by TEM, POM, SEM, and SANS revealed the formation of various high-order molecular structures from the polysaccharide molecules.
Preview
Unable to display preview. Download preview PDF.
Abbreviations
- Ala:
-
alanine
- BTH:
-
bovine testicular hyaluronidase
- CBD:
-
cellulose binding domain
- Ch:
-
chondroitin
- Chi-oxa:
-
chitobiose oxazoline monomer
- DMF:
-
dimethylformamide
- DMSO:
-
dimethyl sulfoxide
- DP:
-
degree of polymerization
- ECM:
-
extracellular matrix
- EG:
-
endoglucanase
- GAG:
-
glycosaminoglycan
- GalNAc:
-
N-acetyl-d-galactosamine
- GlcA:
-
d-glucuronic acid
- GlcNAc:
-
N-acetyl-d-glucosamine
- Glu:
-
glutamic acid
- HA:
-
hyaluronic acid (hyaluronan)
- MALDI-TOF:
-
matrix-assisted laser desorption ionization time-of-flight
- OTH:
-
ovine testicular hyaluronidase
- POM:
-
polarization optical microscopy
- SANS:
-
small-angle neutron scattering
- SEM:
-
scanning electron microscopy
- TEM:
-
transmission electron microscopy
- TSAS:
-
transition-state analogue substrate
- UDP:
-
uridine 5′-diphospho-
- α-CF:
-
α-cellobiosyl fluoride
- β-CF:
-
β-cellobiosyl fluoride
- α-LF:
-
α-lactosyl fluoride
- β-LF:
-
β-lactosyl fluoride
- α-MF:
-
α-maltosyl fluoride
- β-XF:
-
β-xylobiosyl fluoride
References
Kobayashi S (1997) Introduction. In: Kobayashi S (ed) Catalysis in precision polymerization. Wiley, Chichester, UK, p 1
Kobayashi S, Shoda S, Uyama H (1995) Adv Polym Sci 121:1
Kobayashi S, Shoda S, Uyama H (1996) Enzymatic polymerization. In: Salamone JC (ed) The polymeric materials encyclopedia. CRC Press, Roca Raton, FL, p 2102
Kobayashi S, Shoda S, Uyama H (1997) Enzymatic catalysis. In: Kobayashi S (ed) Catalysis in precision polymerization. Wiley, Chichester, UK, p 417
Ritter H (1997) In: Arshady R (ed) Desk reference of functional polymers, synthesis and applications. American Chemical Society, Washington, DC, p 103
Kobayashi S, Uyama H (1998) Biocatalytical routes to polymers. In: Schlueter AD (ed) Material science and technology-synthesis of polymers. Wiley, Weinheim, Germany, p 549
ACS Symposium Series (1998) Gross RA, Kaplan DL, Swift G (eds) American Chemical Society, Washington, DC, Vol 684
Kobayashi S (1999) J Polym Sci Part A Polym Chem 37:3041
Kobayashi S, Uyama H, Ohmae M (2001) Bull Chem Soc Jpn 74:613
Kobayashi S, Uyama H, Kimura S (2001) Chem Rev 101:3793
Gross RA, Kumar A, Karla B (2001) Chem Rev 101:2097
Kobayashi S, Sakamoto J, Kimura S (2001) Prog Polym Sci 26:1525
Kobayashi S, Uyama H (2002) Enzymatic polymerization. In: Kroschwitz JI (ed) Encyclopedia of polymer science and technology, 3rd edn Web site. Wiley, New York
Kobayashi S (2005) J Polym Sci Part A Polym Chem 43:693
Fischer E (1894) Ber Chem Dtsch Chem Ges 27:2985
Pauling L (1946) Chem Eng News 24:1375
Kollman PA, Kuhn B, Donini O, Perakyla M, Santon R, Bakowies D (2001) Acc Chem Res 34:72
Kennedy JF, White CA (1979) In: Barton D, Ollis WD, Haslam E (eds) Comprehensive organic chemistry. Pergamon, Oxford 5:755
Koenig W, Knorr E (1901) Ber Chem Dtsch Chem Ges 34:957
Schmidt RR, Michel J (1980) Angew Chem Int Ed Engl 19:731
Schmidt RR (1986) Angew Chem Int Ed Engl 25:212
Mark H (1980) Cellul Chem Technol 14:569
Klemm D, Heinze T, Wagenknecht W (1997) Acta Polym 48:277
Heinze T (1998) Macromol Chem Phys 199:2341
Kobayashi S, Uyama H (2003) Macromol Chem Phys 204:235
Schlubach HH, Luehrs (1941) Liebigs Ann Chem 547:73
Huseman E, Mueller GJM (1966) Macromol Chem 91:212
Kochtkov NK (1987) Tetrahedron 43:2389
Uryu T, Yamaguchi C, Morikawa K, Terui K, Kanai T, Matsuzaki K (1985) Macromolecules 18:599
Nakatsubo F, Takano T, Kawada T, Murakami K (1989) In: Kennedy JF, Phillips GO, Williams PA (eds) Cellulose, structural and functional aspects. Ellis Horwood, Sussex, UK, p 201
Kobayashi S, Kashiwa K, Kawasaki T, Shoda S (1991) J Am Chem Soc 113:3079
Davies GJ, Dauter M, Brozowski AM, Børnvad ME, Andersen KV, Schuelein M (1998) Biochemistry 37:1926
Saxena IM, Brown RM Jr, Fevre M, Geremia RA, Henrissat B (1995) J Bacteriol p 1419
Brown RM Jr, Saxena IM, Kudlicka K (1996) Trends Plant Sci 1:149
Delmer DP (1999) Annu Rev Plant Physiol Plant Microbiol 50:245
Nakamura I, Yoneda H, Maeda T, Makino A, Ohmae M, Sugiyama J, Ueda M, Kobayashi S, Kimura S (2005) Macromol Biosci 5:623
Gardner KH, Blackwell J (1974) Biopolymers 13:1975
Kolpak FJ, Blackwell J (1976) Macromolecules 9:273
Kobayashi S, Shoda S, Lee J, Okuda K, Brown PM Jr, Kuga S (1994) Macromol Chem Phys 195:1319
Lee JH, Brown RM Jr, Kuga S, Shoda S, Kobayashi S (1994) Proc Natl Acad Sci USA 91:7425
Kobayashi S, Okamoto E, Wen X, Shoda S (1996) J Macromol Sci Pure Appl Chem 33:1375
Kobayashi S, Shoda S, Wen X, Okamoto E, Kiyosada T (1997) J Macromol Sci Pure Appl Chem 34:2135
Kobayashi S, Hobson LJ, Sakamoto J, Kimura S, Sugiyama J, Imai T, Ito T (2000) Biomacromolecules 1:168,509
Tanaka H, Hashimoto T, Kurosaki K, Ohmae M, Kobayashi S, Koizumi S (2003) Polym Prepr Jpn 52:1873
Kobayashi S, Kawasaki T, Obata K, Shoda S (1993) Chem Lett 685
Karthaus O, Shoda S, Takano H, Obata K, Kobayashi S (1994) J Chem Soc Perkin Trans I 1851
Shoda S, Chigira Y, Mitsuishi (1999) Glycoconjugate J 16:S18
Mackenzie LF, Wang Q, Warren RAJ, Withers SG (1998) J Am Chem Soc 120:5583
Fort S, Boyer V, Greffe L, Davies GJ, Morez O, Christiansen L, Schuelein M, Cottaz S, Bringuez H (2000) J Am Chem Soc 122:5429
Carpita NC, Gibeaut DM (1993) Plant J 3:1
Woodward JR, Fincher GB, Stone BA (1983) Carbohydr Polym 3:207
Faijes M, Imai T, Bulone V, Planas A (2004) Biochem J 380:635
Samain E, Lancelon-Pin C, Ferigo F, Moreau V, Chanzy H, Heyraud A, Driguez H (1995) Carbohydr Res 271:217
Kobayashi S, Shimada J, Kashiwa K, Shoda S (1992) Macromolecules 25:3237
Ziegast G, Pfannemueller B (1987) Carbohydr Res 160:185
Kobayashi S, Wen X, Shoda S (1996) Macromolecules 29:2698
Muzzarelli RAA, Jeuniaux C, Gooday G (1986) Chitin in nature and technology. Plenum, New York
Kiyosada T, Takada E, Shoda S, Kobayashi S (1995) Polym Prepr Jpn 44:660
Kiyosada T, Shoda S, Kobayashi S (1995) Polym Prepr Jpn 44:1230
Kobayashi S, Kiyosada T, Shoda S (1996) J Am Chem Soc 118:13113
Sato H, Mizutani S, Tsuge S, Ohtani H, Aoi K, Okada M, Kobayashi S, Kiyosada T, Shoda S (1998) Anal Chem 70:7
Kobayashi S (1990) Prog Polym Sci 15:751
Sakamoto J, Kobayashi S (2004) Chem Lett 33:698
Terwisscha van Scheltinga AC, Armand S, Kalk KH, Isogai A, Henrissat B, Dijkstra BW (1995) Biochemistry 34:15619
Tews I, Terwisscha van Scheltinga AC, Perrakis A, Wilson KS, Dijkstra BW (1997) J Am Chem Soc 119:7954
Brameld KA, Shrader WD, Imperiali B, Goddard III WA (1998) J Mol Biol 280:913
Brameld KA, Goddard III WA (1998) J Am Chem Soc 120:3571
Bramed KA, Goddard III WA (1998) Proc Natl Acad Sci USA 95:4276
Kiyosada T (1998) PhD Thesis, Tohoku University
Tominaga Y, Tsujisaka Y (1976) Agric Biol Chem 40:2325
Watanabe T, Suzuki K, Oyanagi W, Ohnishi K, Tanaka H (1990) J Biol Chem 265:15659
Watanabe T, Kobori K, Miyashita K, Fujii T, Sakai H, Uchida M, Tanaka H (1993) J Biol Chem 268:1856
Sakamoto J, Watanabe T, Ariga Y, Kobayashi S (2001) Chem Lett 1180
Minke R, Blackwell J (1978) J Mol Biol 120:167
Dweltz N (1961) Biochim Biophys Acta 51:283
Keller A, Waring JRS (1955) J Polym Sci 17:447
Keith HD, Padden FJ Jr (1959) J Polym Sci 39:123
Marchessault RH, Morehead FF, Walter NM (1959) Nature 184:632
Revol JF, Marchessault RH (1993) Int J Biol Macromol 15:329
Sakamoto J, Sugiyama J, Kimura S, Imai T, Itoh T, Watanabe T, Kobayashi S (2000) Macromolecules 33:4155,4982
Shoda S, Fujita M, Lohavisavapanichi C, Misawa Y, Ushizaki K, Tawata Y, Kuriyama M, Kohri M, Kuwata H (2002) Helv Chim Acta 85:3919
Iozzo RV (1998) Annu Rev Biochem 67:609
Bernfield M, Götte M, Park PW, Reizes O, Fitzgerald ML, Lincecum J, Zako M (1999) Annu Rev Biochem 68:729
Prydz K, Dalen KT (2000) J Cell Sci 113:193
Bullock SL, Fletcher JM, Beddington RSP, Wilson VA (1998) Genes Dev 12:1894
Perrimon N, Bernfield M (2000) Nature 404:725
Lin X, Wei G, Shi Z, Dryer L, Esko JD, Wells DE, Matzuk MM (2000) Dev Biol 224:299
Lander AD, Selleck SB (2000) J Cell Biol 148:227
Chudo H, Toyoda H (2001) Seikagaku 73:449
Habuchi O (2001) Cell Technol 20:204
Maeda N (2001) Cell Technol 20:1074
Selleck SB (2000) Trend Genet 16:206
Maccarana M, Sakura Y, Tawada A, Yoshida K, Lindahl U (1996) J Biol Chem 271:17804
Feyzi E, Saldeen T, Larsson E, Lindhal U, Salmivirta M (1998) J Biol Chem 273:13395
Kobayashi S, Morii H, Itoh R, Kimura S, Ohmae M (2001) J Am Chem Soc 123:11825
Ochiai H, Mori T, Ohmae M, Kobayashi S (2005) Biomacromolecules 6:1068
Kobayashi S, Fujikawa S, Ohmae M (2003) J Am Chem Soc 125:14357
Kobayashi S, Ohmae M, Fujikawa S, Ochiai H (2005) Macromol Symp 226:147
Meyer K, Palmer JW (1934) J Biol Chem 107:629
Itano N, Kimata K (2002) IUBMB Life 54:195
Weigel PH (2002) IUBMB Life 54:201
Selleck SB (2000) Trend Genet 16:206
Doege K, Sasaki M, Horigan E, Hassell JR, Yamada Y (1987) J Biol Chem 262:17757
Zhuo L, Kimata K (2001) Cell Struct Funct 26:189
Salustri A, Yanagishita M, Underhill CB, Laurent TC, Hascall VC (1992) Dev Biol 151:541
Fulop C, Salustri A, Hascall VC (1997) Arch Biochem Biophys 337:261
de la Motte CA, Hascall VC, Calabro A, Yen-Lieberman B, Strong SA (1999) J Biol Chem 274:30747
Thome RF, Legg JW, Isacke CM (2004) J Cell Sci 117:373
Evanko SP, Wight TN (1999) J Histochem Cytochem 47:1331
Tammi R, Rilla K, Pienimäki J-P, MacCallum DK, Hogg M, Luukkonen M, Hascall VC, Tammi M (2001) J Biol Chem 276:35111
Lapčík L Jr, Lapčík L (1998) Chem Rev 98:2663
Dahl LB, Laurent TC, Smedsrod B (1988) Anal Biochem 175:397
Curvall M, Lindberg B, Lonngren J (1975) Carbohydr Res 41:235
Karst NA, Linhardt RJ (2003) Curr Med Chem 10:1993
Blatter G, Jaquinet JC (1996) Carbohydr Res 288:109
Frost GI, Csóka T, Stern R (1996) Trends Glycosci Glycotechnol 8:419
Marković-Housley Z, Miglierini G, Soldatova L, Rizkallah PJ, Müller U, Schirmer T (2000) Structure 8:1025
Ochiai H, Mori T, Ohmae M, Kobayashi S (2004) Polym Prepr Jpn 53:1882
Bulik DA, Wei G, Toyoda H, Kinoshita-Toyoda A, Waldrip WR, Esko JD, Robbins PW, Selleck SB (2000) Proc Natl Acad Sci USA 97:10838
Faissner A, Clement A, Lochter A, Streit A, Mandl C, Schachner M (1994) J Cell Biol 126:783
Watanabe H, Kimata K, Line S, Strong D, Gao LY, Kozak CA, Yamada Y (1994) Nat Genet 7:154
Clement AM, Nadanaka S, Masayama K, Mandl C, Sugahara K, Faissner A (1998) J Biol Chem 273:28444
Maeda N, Noda M (1998) J Cell Biol 142:203
Kitagawa H, Uyama T, Sugahara K (2001) J Biol Chem 276:38721
Kitagawa H, Izumikawa T, Uyama T, Sugahara K (2003) J Biol Chem 278:23666
Sato T, Gotoh M, Kiyohara K, Akashima T, Iwasaki H, Kameyama A, Mochizuki H, Yada T, Inaba N, Togayachi A, Kudo T, Asada M, Watanabe H, Imamura T, Kimata K, Narimatsu H (2003) J Biol Chem 278:3063
Uyama T, Kitagawa H, Tanaka J, Tamura J, Ogawa T, Sugahara K (2003) J Biol Chem 278:3072
Kusche-Gullberg M, Kjellén L (2003) Curr Opin Struc Biol 13:605
DeAngelis PL, Padgett-McCue AJ (2000) J Biol Chem 275:24124
Ninomiya T, Sugiura N, Tawada A, Sugimoto K, Watanabe H, Kimata K (2002) J Biol Chem 277:21567
Sugahara K, Mikami T, Uyama T, Mizuguchi S, Nomura K, Kitagawa H (2003) Curr Opin Struct Biol 13:612
Takagaki K, Nakamura T, Majima M, Endo M (1988) J Biol Chem 263:7000
Fujikawa S, Ohmae M, Kobayashi S (2004) Polym Prepr Jpn 53:1880
Saitoh H, Takagaki K, Majima M, Nakamura T, Matsuki A, Kasai M, Narita H, Endo M (1995) J Biol Chem 270:3741
Takagaki K, Ishido K (2000) Trends Glycosci Glycotechnol 12:295
For example, see the following review and cited references therein: DeAngelis PL (2002) Anat Rec 268:317
De Luca C, Lansing M, Martin I, Crescenzi F, Shen GJ, O'Regan M, Wong CH (1995) J Am Chem Soc 117:5869
DeAngelis PL (2003) J Biol Chem 278:35199
Okamoto E, Kiyosada T, Shoda S, Kobayashi S (1997) Cellulose 4:161
Ochiai H, Ohmae M, Kobayashi S (2004) Carbohydr Res 339:2769
Ochiai H, Ohmae M, Kobayashi S (2004) Chem Lett 33:694
Fujita M, Shoda S, Kobayashi S (1998) J Am Chem Soc 120:6411
Driguez H (1997) Top Curr Chem 187:86
Moreau V, Driguez H (1996) J Chem Soc Perkin Trans 1 p 525
Uryu T (1993) Prog Polym Sci 18:717
Tramontano A, Kim DJ, Lerner RA (1986) Science 234:1566
Pollack SJ, Jacobs JW, Schultz PG (1986) Science 234:1570
Lerner RA, Benkovic SJ, Schultz PG (1991) Science 252:659
Borman S (2004) Chem Eng News February 23:35
Matsuura K, Yamamoto K, Shinohara H (1994) Biochem Biophys Res Commun 204:57
Hifumi E, Okamoto Y, Uda T (1999) J Biosci Bioeng 88:323
Uda T, Hifumi E (2004) J Biosci Bioeng 97:143
Author information
Authors and Affiliations
Corresponding author
Editor information
Rights and permissions
About this chapter
Cite this chapter
Kobayashi, S., Ohmae, M. Enzymatic Polymerization to Polysaccharides. In: Kobayashi, S., Ritter, H., Kaplan, D. (eds) Enzyme-Catalyzed Synthesis of Polymers. Advances in Polymer Science, vol 194. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_032
Download citation
DOI: https://doi.org/10.1007/12_032
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-29212-8
Online ISBN: 978-3-540-32451-5
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)