This review covers methods for modifying the structures of polysaccharides. The introduction of hydrophobic, acidic, basic, or other functionality into polysaccharide structures can alter the properties of materials based on these substances. The development of chemical methods to achieve this aim is an ongoing area of research that is expected to become more important as the emphasis on using renewable starting materials and sustainable processes increases in the future. The methods covered in this review include ester and ether formation using saccharide oxygen nucleophiles, including enzymatic reactions and aspects of regioselectivity; the introduction of heteroatomic nucleophiles into polysaccharide chains; the oxidation of polysaccharides, including oxidative glycol cleavage, chemical oxidation of primary alcohols to carboxylic acids, and enzymatic oxidation of primary alcohols to aldehydes; reactions of uronic-acid-based polysaccharides; nucleophilic reactions of the amines of chitosan; and the formation of unsaturated polysaccharide derivatives. 1. Introduction With increasing oil prices and forecasts of a future lack of availability, renewable non-petrochemical-based alternatives to materials synthesis could become more important. Polysaccharides are the products of a natural carbon-capture process, photosynthesis, followed by further biosynthetic modifications. Some are produced on a very large scale in nature, and some have industrial relevance with, for example, materials and food applications, either in their native or chemically modified forms. This review covers methods for the chemical modification of polysaccharides. The topic of general modification of polysaccharides has been reviewed previously [1], and several more specific reviews are referenced later. In this review, I have limited myself to discussing the synthesis of modifications whereby the polymeric chain remains intact—or at least while degradation may take place to some extent, the products are still polysaccharides. The conversion of polysaccharides into small molecules has been reviewed elsewhere [2, 3] and is not covered here. Chemical modification can change the character of the polysaccharides, for example, rendering them hydrophobic [4]. Some such processes, such as the formation of cellulose esters (including nitrocellulose, celluloid, cellulose acetate), are very well known and have been carried out at an industrial level for more than a hundred years. The object of this review is not to cover such well-known processes in detail but rather to describe published
References
[1]
M. Yalpani, “A survey of recent advances in selective chemical and enzymic polysaccharide modifications,” Tetrahedron, vol. 41, no. 15, pp. 2957–3020, 1985.
[2]
A. Corma, S. Iborra, and A. Velty, “Chemical routes for the transformation of biomass into chemicals,” Chemical Reviews, vol. 107, no. 6, pp. 2411–2502, 2007.
[3]
S. Van de Vyver, J. Geboers, P. A. Jacobs, and B. F. Sels, “Recent advances in the catalytic conversion of cellulose,” ChemCatChem, vol. 3, no. 1, pp. 82–94, 2011.
[4]
A. G. Cunha and A. Gandini, “Turning polysaccharides into hydrophobic materials: a critical review. Part 2. Hemicelluloses, chitin/chitosan, starch, pectin and alginates,” Cellulose, vol. 17, no. 6, pp. 1045–1065, 2010.
[5]
T. L. Vigo and N. Sachinvala, “Deoxycelluloses and related structures,” Polymers for Advanced Technologies, vol. 10, no. 6, pp. 311–320, 1999.
[6]
T. Heinze and T. Liebert, “Unconventional methods in cellulose functionalization,” Progress in Polymer Science, vol. 26, no. 9, pp. 1689–1762, 2001.
[7]
T. Liebert and T. Heinze, “Interaction of ionic liquids wlth polysaccharides 5. Solvents and reaction media for the modification of cellulose,” BioResources, vol. 3, no. 2, pp. 576–601, 2008.
[8]
M. Gericke, P. Fardim, and T. Heinze, “Ionic liquids-promising but challenging solvents for homogeneous derivatization of cellulose,” Molecules, vol. 17, no. 6, pp. 7458–7502, 2012.
[9]
S. Murugesana and R. J. Linhardt, “Ionic liquids in carbohydrate chemistry-current trends and future directions,” Current Organic Synthesis, vol. 2, no. 4, pp. 437–451, 2005.
[10]
A. W. T. King, J. Asikkala, I. Mutikainen, P. J？rvi, and I. Kilpel？inen, “Distillable acid-base conjugate ionic liquids for cellulose dissolution and processing,” Angewandte Chemie International Edition, vol. 50, no. 28, pp. 6301–6305, 2011.
[11]
A. Takaragi, M. Minoda, T. Miyamoto, H. Q. Liu, and L. N. Zhang, “Reaction characteristics of cellulose in the LiCl/1,3-dimethyl-2-imidazolidinone solvent system,” Cellulose, vol. 6, no. 2, pp. 93–102, 1999.
[12]
A. Isogai, A. Ishizu, and J. Nakano, “Preparation of tri-O-benzylcellulose by the use of nonaqueous cellulose solvents,” Journal of Applied Polymer Science, vol. 29, no. 6, pp. 2097–2109, 1984.
[13]
A. Isogai, A. Ishizu, and J. Nakano, “Preparation of tri-O-substituted cellulose ethers by the use of a nonaqueous cellulose solvent,” Journal of Applied Polymer Science, vol. 29, no. 12, pp. 3873–3882, 1984.
[14]
A. Isogai, A. Ishizu, and J. Nakano, “Preparation of tri-O-alkylcelluloses by the use of a nonaqueous cellulose solvent and their physical characteristics,” Journal of Applied Polymer Science, vol. 31, no. 2, pp. 341–352, 1986.
[15]
C. L. McCormick and P. A. Callais, “Derivatization of cellulose in lithium chloride and N,N-dimethylacetamide solutions,” Polymer, vol. 28, no. 13, pp. 2317–2323, 1987.
[16]
L. Petrus, D. G. Gray, and J. N. BeMiller, “Homogeneous alkylation of cellulose in lithium chloride/dimethyl sulfoxide solvent with dimsyl sodium activation. A proposal for the mechanism of cellulose dissolution in LiCl/Me2SO,” Carbohydrate Research, vol. 268, no. 2, pp. 319–323, 1995.
[17]
J. Asikkala, Acta Universitatis Ouluensis 502, 2008.
[18]
M. S？derqvist Lindblad and A.-C. Albertsson, “Chemical modification of hemicelluloses and gums,” in Polysaccharides: Structural Diversity and Function, S. Dumitriu, Ed., p. 491, CRC Press, New York, NY, USA.
[19]
J. N. BeMiller and R. E. Wing, “Methyl terminal-4-O-methylmalto-oligosaccharides,” Carbohydrate Research, vol. 6, no. 2, pp. 197–206, 1968.
[20]
R. Pieters, R. A. De Graaf, and L. P. B. M. Janssen, “The kinetics of the homogeneous benzylation of potato starch in aqueous solutions,” Carbohydrate Polymers, vol. 51, no. 4, pp. 375–381, 2003.
[21]
T. Umemura, M. Hirakawa, Y. Yoshida, and K. Kurita, “Quantitative protection of chitin by one-step tritylation and benzylation to synthesize precursors for chemical modifications,” Polymer Bulletin, vol. 69, no. 3, pp. 303–312, 2012.
[22]
O. Somorin, N. Nishi, S. Tokura, and J. Noguchi, “Studies on chitin-2. Preparation of benzyl and benzoylchitins,” Polymer Journal, vol. 11, no. 5, pp. 391–396, 1979.
[23]
N. Teramoto, T. Motoyama, R. Yosomiya, and M. Shibata, “Synthesis and properties of thermoplastic propyl-etherified amylose,” European Polymer Journal, vol. 38, no. 7, pp. 1365–1369, 2002.
[24]
M. Shibata, R. Nozawa, N. Teramoto, and R. Yosomiya, “Synthesis and properties of etherified pullulans,” European Polymer Journal, vol. 38, no. 3, pp. 497–501, 2002.
[25]
K. Petzold, K. Schwikal, and T. Heinze, “Carboxymethyl xylan-synthesis and detailed structure characterization,” Carbohydrate Polymers, vol. 64, no. 2, pp. 292–298, 2006.
[26]
L. J. Tanghe, L. B. Genung, and J. W. Mensch, “Cellulose acetate,” in Methods in Carbohydrate Chemistry, Vol III, Cellulose, R. L. Whistler, Ed., pp. 193–212, Academic Press, New York, NY, USA, 1963.
[27]
C. L. McCormick and P. A. Callais, “Derivatization of cellulose in lithium chloride and N,N-dimethylacetamide solutions,” Polymer, vol. 28, no. 13, pp. 2317–2323, 1987.
[28]
C. Grote and T. Heinze, “Starch derivatives of high degree of functionalization 11: studies on alternative acylation of starch with long-chain fatty acids homogeneously in N,N-dimethyl acetamide/LiCl,” Cellulose, vol. 12, no. 4, pp. 435–444, 2005.
[29]
F. Belmokaddem, C. Pinel, P. Huber, M. Petit-Conil, and D. Da Silva Perez, “Green synthesis of xylan hemicellulose esters,” Carbohydrate Research, vol. 346, no. 18, pp. 2896–2904, 2011.
[30]
M. Gr？ndahl, A. Teleman, and P. Gatenholm, “Effect of acetylation on the material properties of glucuronoxylan from aspen wood,” Carbohydrate Polymers, vol. 52, no. 4, pp. 359–366, 2003.
[31]
R. C. Sun, J. M. Fang, J. Tomkinson, and C. A. S. Hill, “Esterification of hemicelluloses from poplar chips in homogenous solution of N, N-dimethylformamide/lithium chloride,” Journal of Wood Chemistry and Technology, vol. 19, no. 4, pp. 287–306, 1999.
[32]
T. Heinze, T. F. Liebert, K. S. Pfeiffer, and M. A. Hussain, “Unconventional cellulose esters: synthesis, characterization and structure-property relations,” Cellulose, vol. 10, no. 3, pp. 283–296, 2003.
[33]
J. Wu, J. Zhang, H. Zhang, J. He, Q. Ren, and M. Guo, “Homogeneous acetylation of cellulose in a new ionic liquid,” Biomacromolecules, vol. 5, no. 2, pp. 266–268, 2004.
[34]
T. Heinze, K. Schwikal, and S. Barthel, “Ionic liquids as reaction medium in cellulose functionalization,” Macromolecular Bioscience, vol. 5, no. 6, pp. 520–525, 2005.
[35]
J. E. Sealey, G. Samaranayake, J. G. Todd, and W. G. Glasser, “Novel cellulose derivatives. IV. Preparation and thermal analysis of waxy esters of cellulose,” Journal of Polymer Science B, vol. 34, no. 9, pp. 1613–1620, 1996.
[36]
S. N. Pawar and K. J. Edgar, “Chemical modification of alginates in organic solvent systems,” Biomacromolecules, vol. 12, no. 11, pp. 4095–4103, 2011.
[37]
M. E. I. Badawy, E. I. Rabea, T. M. Rogge et al., “Fungicidal and insecticidal activity of O-acyl chitosan derivatives,” Polymer Bulletin, vol. 54, no. 4-5, pp. 279–289, 2005.
[38]
S. R. Labafzadeh, J. S. Kavakka, K. Siev？nen, J. Asikkala, and I. Kilpel？inen, “Reactive dissolution of cellulose and pulp through acylation in pyridine,” Cellulose, vol. 19, no. 4, pp. 1295–1304, 2012.
[39]
K. Arai, S. Sano, and H. Satoh, “Preparation of cellulose stilbene-4-carboxylate and its application to thin-layer chromatography,” Journal of Materials Chemistry, vol. 2, no. 12, pp. 1257–1260, 1992.
[40]
K. Arai and S. Sano, “Preparation of cellulose 2-methylstilbene-5-carboxylate and photoregulation of its properties,” Journal of Materials Chemistry, vol. 4, no. 2, pp. 275–278, 1994.
[41]
C. M. Buchanan, N. L. Buchanan, J. S. Debenham et al., “Preparation and characterization of arabinoxylan esters,” ACS Symposium Series, vol. 864, pp. 326–346, 2004.
[42]
T. Iwata, A. Fukushima, K. Okamura, and J. Azuma, “DSC study on regioselectively substituted cellulose heteroesters,” Journal of Applied Polymer Science, vol. 65, no. 8, pp. 1511–1515, 1997.
[43]
E. Pascu, “Halogenation,” in Methods in Carbohydrate Chemistry, Vol III, Cellulose, R. L. Whistler, Ed., p. 259, Academic Press, New York, NY, USA, 1963.
[44]
K. Rahn, M. Diamantoglou, D. Klemm, H. Berghmans, and T. Heinze, “Homogeneous synthesis of cellulose p-toluenesulfonates in N,N-dimethylacetamide/LiCl solvent system,” Angewandte Makromolekulare Chemie, vol. 238, pp. 143–163, 1996.
[45]
S. C. Fox, B. Li, D. Xu, and K. J. Edgar, “Regioselective esterification and etherification of cellulose: a review,” Biomacromolecules, vol. 12, no. 6, pp. 1956–1972, 2011.
[46]
Y. Morita, Y. Sugahara, A. Takahashi, and M. Ibonai, “Preparation of chitin-p-toluenesulfonate and deoxy(thiocyanato) chitin,” European Polymer Journal, vol. 30, no. 11, pp. 1231–1236, 1994.
[47]
A. F. Kolova, V. P. Komar, I. V. Skornyakov, A. D. Virnik, R. G. Zhbanov, and Z. A. Rogovin, Cellulose Chemistry and Technology, vol. 12, p. 553, 1978.
[48]
G. Mocanu, M. Constantin, and A. Carpov, “Chemical reactions on polysaccharides, 5. Reaction of mesyl chloride with pullulan,” Die Angewandte Makromolekulare Chemie, vol. 241, no. 1, pp. 1–10, 1996.
[49]
D. Klemm, T. Helme, B. Philipp, and W. Wagenbiecht, “New approaches to advanced polymers by selective cellulose functionalization,” Acta Polymerica, vol. 48, no. 8, pp. 277–297, 1997.
[50]
A. Koschella, D. Fenn, N. Illy, and T. Heinze, “Regioselectively functionalized cellulose derivatives: a mini review,” Macromolecular Symposia, vol. 244, pp. 59–73, 2006.
[51]
J. W. Green, “Triphenylmethyl ethers,” in Methods in Carbohydrate Chemistry, Vol III, Cellulose, R. L. Whistler, Ed., p. 327, Academic Press, New York, NY, USA, 1963.
[52]
R. L. Whistler and S. Hirase, “Introduction of 3,6-anhydro rings into amylose and characterization of the products,” Journal of Organic Chemistry, vol. 26, no. 11, pp. 4600–4605, 1961.
[53]
J. Holappa, T. Nevalainen, P. Soininen et al., “N-chloroacyl-6-O-triphenylmethylchitosans: useful intermediates for synthetic modifications of chitosan,” Biomacromolecules, vol. 6, no. 2, pp. 858–863, 2005.
[54]
D. Klemm and A. J. Stein, “Silylated cellulose materials in design of supramolecular structures of ultrathin cellulose films,” Journal of Macromolecular Science A, vol. 32, no. 4, pp. 899–904, 1995.
[55]
A. Koschella and D. Klemm, “Silylation of cellulose regiocontrolled by bulky reagents and dispersity in the reaction media,” Macromolecular Symposia, vol. 120, pp. 115–125, 1997.
[56]
A. Koschella, T. Heinze, and D. Klemm, “First synthesis of 3-O-functionalized cellulose ethers via 2,6-di-O-protected silyl cellulose,” Macromolecular Bioscience, vol. 1, no. 1, pp. 49–54, 2001.
[57]
D. Klemm, B. Heublein, H. Fink, and A. Bohn, “Cellulose: fascinating biopolymer and sustainable raw material,” Angewandte Chemie International Edition, vol. 44, no. 22, pp. 3358–3393, 2005.
[58]
D. Xu, B. Li, C. Tate, and K. J. Edgar, “Studies on regioselective acylation of cellulose with bulky acid chlorides,” Cellulose, vol. 18, no. 2, pp. 405–419, 2011.
[59]
J. Zhang, J. Wu, Y. Cao, S. Sang, J. Zhang, and J. He, “Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid,” Cellulose, vol. 16, no. 2, pp. 299–308, 2009.
[60]
A. Stein and D. Klemm, “Syntheses of cellulose derivatives via O-triorganosilyl celluloses, 1. Effective synthesis of organic cellulose esters by acylation of trimethylsilyl celluloses,” Die Makromolekulare Chemie, Rapid Communications, vol. 9, no. 8, pp. 569–573, 1988.
[61]
A. Koschella, T. Leermann, M. Brackhagen, and T. Heinze, “Study of sulfonic acid esters from 1→4-, 1→3-, and 1→6-linked polysaccharides,” Journal of Applied Polymer Science, vol. 100, no. 3, pp. 2142–2150, 2006.
[62]
R. Dicke, K. Rahn, V. Haack, and T. Heinze, “Starch derivatives of high degree of functionalization. Part 2. Determination of the functionalization pattern of p-toluenesulfonyl starch by peracylation and NMR spectroscopy,” Carbohydrate Polymers, vol. 45, no. 1, pp. 43–51, 2001.
[63]
D. M. Clode and D. Horton, “Preparation and characterization of the 6-aldehydo derivatives of amylose and whole starch,” Carbohydrate Research, vol. 17, no. 2, pp. 365–373, 1971.
[64]
J. Ren, P. Wang, F. Dong, Y. Feng, D. Peng, and Z. Guo, “Synthesis and antifungal properties of 6-amino-6-deoxyinulin, a kind of precursors for facile chemical modifications of inulin,” Carbohydrate Polymers, vol. 87, no. 2, pp. 1744–1748, 2012.
[65]
H. N. Cheng and Q. M. Gu, “Enzyme-catalyzed modifications of polysaccharides and poly(ethylene glycol),” Polymers, vol. 4, no. 2, pp. 1311–1330, 2012.
[66]
F. F. Bruno, J. A. Akkara, M. Ayyagari et al., “Enzymatic modification of insoluble amylose in organic solvents,” Macromolecules, vol. 28, no. 26, pp. 8881–8883, 1995.
[67]
J. Xie and Y. Hsieh, “Enzyme-catalyzed transesterification of vinyl esters on cellulose solids,” Journal of Polymer Science A, vol. 39, no. 11, pp. 1931–1939, 2001.
[68]
S. Chakraborty, B. Sahoo, I. Teraoka, L. M. Miller, and R. A. Gross, “Enzyme-catalyzed regioselective modification of starch nanoparticles,” Macromolecules, vol. 38, no. 1, pp. 61–68, 2005.
[69]
A. Alissandratos, N. Baudendistel, S. L. Flitsch, B. Hauer, and P. J. Halling, “Lipase-catalysed acylation of starch and determination of the degree of substitution by methanolysis and GC,” BMC Biotechnology, vol. 10, p. 82, 2010.
[70]
K. Yang and Y. J. Wang, “Lipase-catalyzed cellulose acetylation in aqueous and organic media,” Biotechnology Progress, vol. 19, no. 6, pp. 1664–1671, 2003.
[71]
K. Yang, Y. J. Wang, and M. I. Kuo, “Effects of substrate pretreatment and water activity on lipase-catalyzed cellulose acetylation in organic media,” Biotechnology Progress, vol. 20, no. 4, pp. 1053–1061, 2004.
[72]
A. Rajan, V. S. Prasad, and T. E. Abraham, “Enzymatic esterification of starch using recovered coconut oil,” International Journal of Biological Macromolecules, vol. 39,, no. 4-5, pp. 265–272, 2006.
[73]
A. Rajan and T. E. Abraham, “Enzymatic modification of cassava starch by bacterial lipase,” Bioprocess and Biosystems Engineering, vol. 29, no. 1, pp. 65–71, 2006.
[74]
A. Rajan, J. D. Sudha, and T. E. Abraham, “Enzymatic modification of cassava starch by fungal lipase,” Industrial Crops and Products, vol. 27, no. 1, pp. 50–59, 2008.
[75]
V. Sereti, H. Stamatis, E. Koukios, and F. N. Kolisis, “Enzymatic acylation of cellulose acetate in organic media,” Journal of Biotechnology, vol. 66, no. 2-3, pp. 219–223, 1998.
[76]
C. Altaner, B. Saake, M. Tenkanen et al., “Regioselective deacetylation of cellulose acetates by acetyl xylan esterases of different CE-families,” Journal of Biotechnology, vol. 105, no. 1-2, pp. 95–104, 2003.
[77]
R. S. Tipson, “Sulfonic esters of carbohydrates,” Advances in Carbohydrate Chemistry, vol. 8, pp. 180–215, 1953.
[78]
J. W. H. Oldham and J. K. Rutherford, “The alkylation of amines as catalyzed by nickel,” Journal of the American Chemical Society, vol. 54, no. 1, pp. 306–312, 1932.
[79]
S. S. Shaik, “The α- and β-carbon substituent effect on SN2 reactivity. A valence-bond approach,” Journal of the American Chemical Society, vol. 105, no. 13, pp. 4359–4367, 1983.
[80]
K. Petzold-Welcke, N. Michaelis, and T. Heinze, “Unconventional cellulose products through nucleophilic displacement reactions,” Macromolecular Symposia, vol. 280, no. 1, pp. 72–85, 2009.
[81]
P. R. Skaanderup, C. S. Poulsen, L. Hyldtoft, M. R. J？rgensen, and R. Madsen, “Regioselective conversion of primary alcohols into iodides in unprotected methyl furanosides and pyranosides,” Synthesis, no. 12, pp. 1721–1727, 2002.
[82]
A. L. Cimecioglu, D. H. Ball, D. L. Kaplan, and S. H. Huang, “Preparation of 6-O-acyl amylose derivatives,” in Proceedings of the MRS Symposium, pp. 7–12, December 1993.
[83]
D. H. Ball, B. J. Wiley, and E. T. Reese, “Effect of substitution at C-6 on the susceptibility of pullulan to pullulanases. Enzymatic degradation of modified pullulans,” Canadian Journal of Microbiology, vol. 38, no. 4, pp. 324–327, 1992.
[84]
H. Tseng, K. Takechi, and K. Furuhata, “Chlorination of chitin with sulfuryl chloride under homogeneous conditions,” Carbohydrate Polymers, vol. 33, no. 1, pp. 13–18, 1997.
[85]
M. Sakamoto, H. Tseng, and K. Furuhata, “Regioselective chlorination of chitin with N-chlorosuccinimide-triphenylphosphine under homogeneous conditions in lithium chloride-N,N-dimethylacetamide,” Carbohydrate Research, vol. 265, no. 2, pp. 271–280, 1994.
[86]
K. Furuhata, N. Aoki, S. Suzuki, M. Sakamoto, Y. Saegusa, and S. Nakamura, “Bromination of cellulose with tribromoimidazole, triphenylphosphine and imidazole under homogeneous conditions in LiBr-dimethylacetamide,” Carbohydrate Polymers, vol. 26, no. 1, pp. 25–29, 1995.
[87]
K.-I. Furuhata, K. Koganei, H.-S. Chang, N. Aoki, and M. Sakamoto, “Dissolution of cellulose in lithium bromide-organic solvent systems and homogeneous bromination of cellulose with N-bromosuccinimide-triphenylphosphine in lithium bromide-N,N-dimethylacetamide,” Carbohydrate Research, vol. 230, no. 1, pp. 165–177, 1992.
[88]
Y. Matsui, J. Ishikawa, H. Kamitakahara, T. Takano, and F. Nakatsubo, “Facile synthesis of 6-amino-6-deoxycellulose,” Carbohydrate Research, vol. 340, no. 7, pp. 1403–1406, 2005.
[89]
H. Tseng, K. Furuhata, and M. Sakamoto, “Bromination of regenerated chitin with N-bromosuccinimide and triphenylphospine under homogeneous conditions in lithium bromide-N,N-dimethylacetamide,” Carbohydrate Research, vol. 270, no. 2, pp. 149–161, 1995.
[90]
T. Hasegawa, M. Umeda, M. Numata et al., “‘Click chemistry’ on polysaccharides: a convenient, general, and monitorable approach to develop (1→3)-β-d-glucans with various functional appendages,” Carbohydrate Research, vol. 341, no. 1, pp. 35–40, 2006.
[91]
G. N. Smirnova, L. S. Gol’braikh, A. I. Polyakov, and Z. A. Rogovin, “Synthesis of 2, 3-anhydro-6-O-tritylcellulose,” Chemistry of Natural Compounds, vol. 2, no. 1, pp. 1–3, 1966.
[92]
S. Immel, K. Fujita, H. J. Lindner, Y. Nogami, and F. W. Lichtenthaler, “Structure and lipophilicity profile of 2,3-anhydro-α-cyclomannin and its ethanol inclusion complex,” Chemistry A, vol. 6, no. 13, pp. 2327–2333, 2000.
[93]
Z. A. Rogovin and T. V. Vladimirov, Chimi？eskaja Nauka i Promy？lennost, vol. 2, p. 527, 1957.
[94]
Z. A. Rogovin and T. V. Vladimirov, Chemical Abstracts, vol. 52, p. 4167, 1958.
[95]
T. R. Ingle and R. L. Whistler, “3,6-anhydroamylose by nucleophilic displacement,” in Methods in Carbohydrate Chemistry, Vol 5, General Polysaccharides, R. L. Whistler, Ed., p. 411, Academic Press, New York, NY, USA, 1963.
[96]
I. Cumpstey, J. Frigell, E. Pershagen et al., “Amine-linked diglycosides: synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays,” Beilstein Journal of Organic Chemistry, vol. 7, pp. 1115–1123, 2011.
[97]
T. Heinze, A. Koschella, M. Brackhagen, J. Engelhardt, and K. Nachtkamp, “Studies on non-natural deoxyammonium cellulose,” Macromolecular Symposia, vol. 244, pp. 74–82, 2006.
[98]
C. Liu and H. Baumann, “Exclusive and complete introduction of amino groups and their N-sulfo and N-carboxymethyl groups into the 6-position of cellulose without the use of protecting groups,” Carbohydrate Research, vol. 337, no. 14, pp. 1297–1307, 2002.
[99]
Y. Matsui, J. Ishikawa, H. Kamitakahara, T. Takano, and F. Nakatsubo, “Facile synthesis of 6-amino-6-deoxycellulose,” Carbohydrate Research, vol. 340, no. 7, pp. 1403–1406, 2005.
[100]
T. Takano, J. Ishikawa, H. Kamitakahara, and F. Nakatsubo, “The application of microwave heating to the synthesis of 6-amino-6-deoxycellulose,” Carbohydrate Research, vol. 342, no. 16, pp. 2456–2460, 2007.
[101]
C. Xiao, D. Lu, S. Xu, and L. Huang, “Tunable synthesis of starch-poly(vinyl acetate) bioconjugate,” Starch-St？rke, vol. 63, no. 4, pp. 209–216, 2011.
[102]
G. Zampano, M. Bertoldo, and F. Ciardelli, “Defined chitosan-based networks by C-6-azide-alkyne “click” reaction,” Reactive and Functional Polymers, vol. 70, no. 5, pp. 272–281, 2010.
[103]
A. L. Cimecioglu, D. H. Ball, S. H. Huang, and D. L. Kaplan, “A direct regioselective route to 6-azido-6-deoxy polysaccharides under mild and homogeneous conditions,” Macromolecules, vol. 30, no. 1, pp. 155–156, 1997.
[104]
J. Shey, K. M. Holtman, R. Y. Wong et al., “The azidation of starch,” Carbohydrate Polymers, vol. 65, no. 4, pp. 529–534, 2006.
[105]
S. Knaus, U. Mais, and W. H. Binder, “Synthesis, characterization and properties of methylaminocellulose,” Cellulose, vol. 10, no. 2, pp. 139–150, 2003.
[106]
C. Liu and H. Baumann, “New 6-butylamino-6-deoxycellulose and 6-deoxy-6-pyridiniumcellulose derivatives with highest regioselectivity and completeness of reaction,” Carbohydrate Research, vol. 340, no. 14, pp. 2229–2235, 2005.
[107]
G. R. Saad and K.-I. Furuhata, “Dielectric study of β-relaxation in some cellulosic substances,” Polymer International, vol. 41, no. 3, pp. 293–299, 1996.
[108]
A. Koschella and T. Heinze, “Novel regioselectively 6-functionalized cationic cellulose polyelectrolytes prepared via cellulose sulfonates,” Macromolecular Bioscience, vol. 1, no. 5, pp. 178–184, 2001.
[109]
N. Aoki, K. Koganei, H. Chang, K. Furuhata, and M. Sakamoto, “Gas chromatographic-mass spectrometric study of reactions of halodeoxycelluloses with thiols in aqueous solutions,” Carbohydrate Polymers, vol. 27, no. 1, pp. 13–21, 1995.
[110]
N. Aoki, K. Furuhata, Y. Saegusa, S. Nakamura, and M. Sakamoto, “Reaction of 6-bromo-6-deoxycellulose with thiols in lithium bromide-N,N-dimethylacetamide,” Journal of Applied Polymer Science, vol. 61, no. 7, pp. 1173–1185, 1996.
[111]
G. Wenz, P. Liepold, and N. Bordeanu, “Synthesis and SAM formation of water soluble functional carboxymethylcelluloses: thiosulfates and thioethers,” Cellulose, vol. 12, no. 1, pp. 85–96, 2005.
[112]
N. Aoki, K. Fukushima, H. Kurakata, M. Sakamoto, and K. Furuhata, “6-Deoxy-6-mercaptocellulose and its S-substituted derivatives as sorbents for metal ions,” Reactive and Functional Polymers, vol. 42, no. 3, pp. 223–233, 1999.
[113]
G. R. Saad and K. Furuhata, “Effect of substituents on dielectric β-relaxation in cellulose,” Polymer International, vol. 42, no. 4, pp. 356–362, 1997.
[114]
D. Horton and D. H. Hutson, “Developments in the chemistry of thio sugars,” Advances in Carbohydrate Chemistry C, vol. 18, pp. 123–199, 1963.
[115]
D. Trimnell, E. I. Stout, W. M. Doane, and C. R. Russel, “Preparation of starch 2-hydroxy-3-mercaptopropyl ethers and their use in graft polymerizations,” Journal of Applied Polymer Science, vol. 22, no. 12, pp. 3579–3586, 1978.
[116]
E. Mentasti, C. Sarzanini, M. C. Gennaro, and V. Porta, “Nitrilotriacetic acid, thiourea and cysteine ligands immobilized on cellulose for the uptake of trace metal ions,” Polyhedron, vol. 6, no. 6, pp. 1197–1202, 1987.
[117]
I. Cumpstey, “Neodisaccharide diglycosyl compounds: ethers, thioethers and selenoethers. A survey of their synthesis and biological activity,” Comptes Rendus Chimie, vol. 14, no. 2-3, pp. 274–285, 2011.
[118]
V. Fournière and I. Cumpstey, “Synthesis of non-glycosidically linked selenoether pseudodisaccharides,” Tetrahedron Letters, vol. 51, no. 16, pp. 2127–2129, 2010.
[119]
K. A. Kristiansen, A. Potthast, and B. E. Christensen, “Periodate oxidation of polysaccharides for modification of chemical and physical properties,” Carbohydrate Research, vol. 345, no. 10, pp. 1264–1271, 2010.
[120]
S. Coseri, G. Biliuta, B. C. Simionescu, K. Stana-Kleinschek, V. Ribitsch, and V. Harabagiu, “Oxidized cellulose-Survey of the most recent achievements,” Carbohydrate Polymers, 2012.
[121]
Van Bekkum, “Studies on selective carbohydrate oxidation,” in Carbohydrates as Organic Raw Materials, F. Lichtenthaler, Ed., p. 289, VCH, Weinheim, Germany, 1990.
[122]
G. O. Aspinall and A. Nicolson, “Paper 505. The catalytic oxidation of European larch ε-galactan,” Journal of the Chemical Society, pp. 2503–2507, 1960.
[123]
D. L. Verraest, J. A. Peters, and H. Van Bekkum, “The platinum-catalyzed oxidation of inulin,” Carbohydrate Research, vol. 306, no. 1-2, pp. 197–203, 1998.
[124]
G. O. Aspinall, “Reduction of uronic acids in polysaccharides,” in Methods in Carbohydrate Chemistry, Vol 5, General Polysaccharides, R. L. Whistler, Ed., p. 397, Academic Press, New York, NY, USA, 1963.
[125]
A. E. J. de Nooy, A. C. Besemer, and H. van Bekkum, “Highly selective tempo mediated oxidation of primary alcohol groups in polysaccharides,” Recueil des Travaux Chimiques des Pays-Bas, vol. 113, no. 3, pp. 165–166, 1994.
[126]
A. E. J. De Nooy, A. C. Besemer, and H. Van Bekkum, “Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans,” Carbohydrate Research, vol. 269, no. 1, pp. 89–98, 1995.
[127]
P. S. Chang and J. F. Robyt, “Oxidation of primary alcohol groups of naturally occurring polysaccharides with 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion,” Journal of Carbohydrate Chemistry, vol. 15, no. 7, pp. 819–830, 1996.
[128]
A. Isogai and Y. Kato, “Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation,” Cellulose, vol. 5, no. 3, pp. 153–164, 1998.
[129]
R. A. A. Muzzarelli, C. Muzzarelli, A. Cosani, and M. Terbojevich, “6-Oxychitins, novel hyaluronan-like regiospecifically carboxylated chitins,” Carbohydrate Polymers, vol. 39, no. 4, pp. 361–367, 1999.
[130]
P. L. Bragd, A. C. Besemer, and H. Van Bekkum, “Bromide-free TEMPO-mediated oxidation of primary alcohol groups in starch and methyl α-d-glucopyranoside,” Carbohydrate Research, vol. 328, no. 3, pp. 355–363, 2000.
[131]
K. Maurer and G. Drefahl, “Oxydationen mit stickstoffdioxyd, I. Mitteil.: die Darstellung von glyoxyls？ure, glucurons？ure und galakturons？ure,” Berichte der Deutschen Chemischen Gesellschaft, vol. 75, no. 12, pp. 1489–1491, 1942.
[132]
E. C. Yackel and W. O. Kenyon, “The oxidation of cellulose by nitrogen dioxide,” Journal of the American Chemical Society, vol. 64, no. 1, pp. 121–127, 1942.
[133]
K. Parikka and M. Tenkanen, “Oxidation of methyl α-d-galactopyranoside by galactose oxidase: products formed and optimization of reaction conditions for production of aldehyde,” Carbohydrate Research, vol. 344, no. 1, pp. 14–20, 2009.
[134]
K. Parikka, A. -S. Lepp？nen, L. Pikt？nen, M. Reunanen, S. Willf？r, and M. Tenkanen, “Oxidation of polysaccharides by galactose oxidase,” Journal of Agricultural and Food Chemistry, vol. 58, no. 1, pp. 262–271, 2010.
[135]
E. Frollini, W. F. Reed, M. Milas, and M. Rinaudo, “Polyelectrolytes from polysaccharides: selective oxidation of guar gum-a revisited reaction,” Carbohydrate Polymers, vol. 27, no. 2, pp. 129–135, 1995.
[136]
M. Yalpani and L. D. Hall, “Some chemical and analytical aspects of polysaccharide modifications. 3. Formation of branched-chain, soluble chitosan derivatives,” Macromolecules, vol. 17, no. 3, pp. 272–281, 1984.
[137]
S. Dumitriu, Polysaccharides: Structural Diversity and Functional Versatility, Marcel Dekker, New York, NY, USA, 2005.
[138]
J. Yang, Y. Xie, and W. He, “Research progress on chemical modification of alginate: a review,” Carbohydrate Polymers, vol. 84, no. 1, pp. 33–39, 2011.
[139]
M. D. Cathell, J. C. Szewczyk, and C. L. Schauer, “Organic modification of the polysaccharide alginate,” Mini-Reviews in Organic Chemistry, vol. 7, no. 1, pp. 61–67, 2010.
[140]
S. Pelletier, P. Hubert, F. Lapicque, E. Payan, and E. Dellacherie, “Amphiphilic derivatives of sodium alginate and hyaluronate: synthesis and physico-chemical properties of aqueous dilute solutions,” Carbohydrate Polymers, vol. 43, no. 4, pp. 343–349, 2000.
[141]
C. S. Pappas, A. Malovikova, Z. Hromadkova, P. A. Tarantilis, A. Ebringerova, and M. G. Polissiou, “Determination of the degree of esterification of pectinates with decyl and benzyl ester groups by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and curve-fitting deconvolution method,” Carbohydrate Polymers, vol. 56, no. 4, pp. 465–469, 2004.
[142]
G. A. Morris, Z. Hromadkova, A. Ebringerova, A. Malovikova, J. Alf？ldi, and S. E. Harding, “Modification of pectin with UV-absorbing substitutents and its effect on the structural and hydrodynamic properties of the water-soluble derivatives,” Carbohydrate Polymers, vol. 48, no. 4, pp. 351–359, 2002.
[143]
J. S. Yang, H. B. Ren, and Y. J. Xie, “Synthesis of amidic alginate derivatives and their application in microencapsulation of λ-cyhalothrin,” Biomacromolecules, vol. 12, no. 8, pp. 2982–2987, 2011.
[144]
F. Vallée, C. Müller, A. Durand et al., “Synthesis and rheological properties of hydrogels based on amphiphilic alginate-amide derivatives,” Carbohydrate Research, vol. 344, no. 2, pp. 223–228, 2009.
[145]
A. Synytsya, J. Copikova, M. Marounek et al., “Preparation of N-alkylamides of highly methylated (HM) citrus pectin,” Czech Journal of Food Sciences, vol. 21, pp. 162–166, 2003.
[146]
A. Sinitsya, J. Copikova, V. Prutyanov, S. Skoblya, and V. Machovic, “Amidation of highly methoxylated citrus pectin with primary amines,” Carbohydrate Polymers, vol. 42, no. 4, pp. 359–368, 2000.
[147]
A. Synytsya, J. Copikova, M. Marounek et al., “N-octadecylpectinamide, a hydrophobic sorbent based on modification of highly methoxylated citrus pectin,” Carbohydrate Polymers, vol. 56, no. 2, pp. 169–179, 2004.
[148]
I. Ugi, “Recent progress in the chemistry of multicomponent reactions,” Pure and Applied Chemistry, vol. 73, no. 1, pp. 187–191, 2001.
[149]
J. P. Zhu, “Recent developments in the isonitrile-based multicomponent synthesis of heterocycles,” European Journal of Organic Chemistry, no. 7, pp. 1133–1144, 2003.
[150]
P. Slobbe, E. Ruijter, and R. V. A. Orru, “Recent applications of multicomponent reactions in medicinal chemistry,” Medicinal Chemistry Communications, vol. 3, pp. 1189–1218, 2012.
[151]
R. V. A. Orru and E. Ruijter, Synthesis of Heterocycles via Multicomponent Reactions, Springer, Berlin, Germany, 2010.
[152]
I. Ugi, R. Meyr, U. Fetzer, and C. Steinbrückner, “Versuche mit Isonitrilen,” Angewandte Chemie, vol. 71, no. 11, pp. 386–388, 1959.
[153]
I. Ugi and C. Steinbrückner, “über ein neues Kondensations-Prinzip,” Angewandte Chemie, vol. 72, no. 7-8, pp. 267–268, 1960.
[154]
H. Bu, A. L. Kj？niksen, K. D. Knudsen, and B. Nystr？m, “Rheological and structural properties of aqueous alginate during gelation via the Ugi multicomponent condensation reaction,” Biomacromolecules, vol. 5, no. 4, pp. 1470–1479, 2004.
[155]
J. Desbrieres, C. Martinez, and M. Rinaudo, “Hydrophobic derivatives of chitosan: characterization and rheological behaviour,” International Journal of Biological Macromolecules, vol. 19, no. 1, pp. 21–28, 1996.
[156]
M. E. I. Badawy, “Chemical modification of chitosan: synthesis and biological activity of new heterocyclic chitosan derivatives,” Polymer International, vol. 57, no. 2, pp. 254–261, 2000.
[157]
E. I. Rabea, M. E. I. Badawy, T. M. Rogge et al., “Enhancement of fungicidal and insecticidal activity by reductive alkylation of chitosan,” Pest Management Science, vol. 62, no. 9, pp. 890–897, 2006.
[158]
K. T？mmeraas, S. P. Strand, W. Tian, L. Kenne, and K. M. V？ruma, “Preparation and characterisation of fluorescent chitosans using 9-anthraldehyde as fluorophore,” Carbohydrate Research, vol. 336, no. 4, pp. 291–296, 2001.
[159]
S. Hirano, K. Nagamura, M. Zhang et al., “Chitosan staple fibers and their chemical modification with some aldehydes,” Carbohydrate Polymers, vol. 38, no. 4, pp. 293–298, 1999.
[160]
D. de Britto, R. C. Goy, S. P. C. Filho, and O. B. G. Assis, “Quaternary salts of chitosan: history, antimicrobial features, and prospects,” International Journal of Carbohydrate Chemistry, vol. 2011, Article ID 312539, 12 pages, 2011.
[161]
V. ？. Rúnarsson, J. Holappa, S. Jónsdóttir, H. Steinsson, and M. Másson, “N-selective “one pot” synthesis of highly N-substituted trimethyl chitosan (TMC),” Carbohydrate Polymers, vol. 74, no. 3, pp. 740–744, 2008.
[162]
A. B. Sieval, M. Thanou, A. F. Kotzé, J. C. Verhoef, J. Brussee, and H. E. Junginger, “Preparation and NMR characterization of highly substituted N-trimethyl chitosan chloride,” Carbohydrate Polymers, vol. 36, no. 2-3, pp. 157–165, 1998.
[163]
P. L. Dung, M. Milas, M. Rinaudo, and J. Desbrières, “Water soluble derivatives obtained by controlled chemical modifications of chitosan,” Carbohydrate Polymers, vol. 24, no. 3, pp. 209–214, 1994.
[164]
Z. Jia, D. Shen, and W. Xu, “Synthesis and antibacterial activities of quaternary ammonium salt of chitosan,” Carbohydrate Research, vol. 333, no. 1, pp. 1–6, 2001.
[165]
S. Hirano and Y. Yagi, “The effects of N-substitution of chitosan and the physical form of the products on the rate of hydrolysis by chitinase from Streptomyces griseus,” Carbohydrate Research, vol. 83, no. 1, pp. 103–108, 1980.
[166]
S. Hirano, Y. Ohe, and H. Ono, “Selective N-acylation of chitosan,” Carbohydrate Research, vol. 47, no. 2, pp. 314–320, 1976.
[167]
K. Y. Lee, W. S. Ha, and W. H. Park, “Blood compatibility and biodegradability of partially N-acylated chitosan derivatives,” Biomaterials, vol. 16, no. 16, pp. 1211–1216, 1995.
[168]
C. Y. Choi, S. B. Kim, P. K. Pak, D. I. Yoo, and Y. S. Chung, “Effect of N-acylation on structure and properties of chitosan fibers,” Carbohydrate Polymers, vol. 68, no. 1, pp. 122–127, 2007.
[169]
T. Ishii, “Facile preparation of deoxyiodocellulose and its conversion into 5,6-cellulosene,” Carbohydrate Research, vol. 154, no. 1, pp. 63–70, 1986.
[170]
D. Horton and M. H. Meshreki, “Synthesis of 2.3-unsaturated polysaccharides from amylose and xylan,” Carbohydrate Research, vol. 40, no. 2, pp. 345–352, 1975.
[171]
Z. Liu, B. Classon, and B. Samuelsson, “A novel route to olefins from vicinal diols,” Journal of Organic Chemistry, vol. 55, no. 14, pp. 4273–4275, 1990.
[172]
B. Classon, P. J. Garegg, and B. Samuelsson, “A facile preparation of 2′,3′-unsaturated nucleosides and hexopyranosides from acetylated halohydrins by reductive elimination,” Acta Chemica Scandinavica B, vol. 36, p. 251, 1982.
[173]
M. J. Robins, J. S. Wilson, D. Madej, N. H. Low, F. Hansske, and S. F. Wnuk, “Nucleic acid-related compounds. 88. Efficient conversions of ribonucleosides into their 2′,3′-anhydro, 2′(and 3′)-deoxy, 2′,3′-didehydro-2′,3′-dideoxy, and 2′,3′-dideoxynucleoside analogs,” Journal of Organic Chemistry, vol. 60, no. 24, pp. 7902–7908, 1995.
[174]
L. Alvarez de Cienfuegos, A. J. Mota, C. Rodriguez, and R. Robles, “Highly efficient synthesis of 2′,3′-didehydro-2′,3′-dideoxy-β-nucleosides through a sulfur-mediated reductive 2′,3′-trans-elimination. From iodomethylcyclopropanes to thiirane analogs,” Tetrahedron Letters, vol. 46, no. 3, pp. 469–473, 2005.
