Abstract
Dextrans from Leuconostoc ssp., α-1,6-linked glucans branched at O-3, were O-methylated in DMSO with lithium dimsyl and methyl iodide under various conditions. Methyl substituent distribution was comprehensively studied in the terminal, internal, and branched glucosyl units and along and over the dextran macromolecules. The order of reactivity was O-2 > O-4 ≥ O-3. The methyl pattern in the glucosyl units significantly deviates from a random distribution with enhanced amounts of un- and trisubstituted moieties. This deviation was found to proceed on macromolecular level by means of ESI-MS of perdeuteromethylated and partially depolymerized methyl dextrans. Heterogeneity was much more pronounced than for methyl amylose prepared under comparable conditions. DS gradients in and over the material are discussed with respect to dextran structure and the mechanism of Li dimsyl alkylation. For comparison, cyanoethyl dextrans were prepared by sodium hydroxide catalyzed addition of acrylonitrile. Monomer analysis of cyanoethyl dextrans revealed that this thermodynamically controlled reaction gave a random substitution pattern with 48% of cyanoethyl groups at O-2, 33% at O-4, and 19% at O-3.
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Acknowledgment
Financial support of A. Vollmer by Konrad-Adenauer Stiftung and of C. Bork by the Federal State of Lower Saxony is gratefully acknowledged. For technical assistance, we thank Silke Lehmann. For helpful discussion, we are very thankful to Prof. Dr. Walther Burchard, University of Freiburg, Germany.
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An extended version of the experimental part, more examples of cyanoethyldextrans (5, Fig. 2) as well as additional calculations on monomer methyl distribution (c 0–c 4, x i ) is available as electronic supplementary material (PDF 87 kb)
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Vollmer, A., Voiges, K., Bork, C. et al. Comprehensive analysis of the substitution pattern in dextran ethers with respect to the reaction conditions. Anal Bioanal Chem 395, 1749–1768 (2009). https://doi.org/10.1007/s00216-009-3013-4
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DOI: https://doi.org/10.1007/s00216-009-3013-4