TY - JOUR
T1 - Roles of potassium ions, acetyl and l-glyceryl groups in native gellan double helix
T2 - an X-ray study
AU - Chandrasekaran, Rengaswami
AU - Radha, Akella
AU - Thailambal, Vadakkanthara G.
N1 - Funding Information:
We thank Dr . Ralph Moorhouse and Mr. Ross Clark for helpful discus Robert Werberig for photography . This work was supported in part by Kelco and he Industrial Consortium of the Whistler Center .
PY - 1992/2/7
Y1 - 1992/2/7
N2 - Native gellan, the natural form of the polysaccharide excreted by the bacterium Pseudomonas elodea, has a tetrasaccharide repeating unit that contains l-glyceral and acetate ester groups, and forms only weak and elastic gels. Based on X-ray diffraction data from well oriented and polycrystalline fibers of its potassium salt, the crystals structure of native gellan, including ions and water, has been determined and refined to a final R-value of 0.17. The molecule forms a half-staggered, parallel, double helix of pitch 5.68 nm which is stabilized by hydrogen bonds involving the hydroxymethyl groups in one chain and both carboxylate and glyceryl groups in the other. Two molecules are packed in an antiparallel fashion in a trigonal unit cell of side a = 1.65 nm. Although the gross molecular morphology and packing arrangements are isomorphous with those observed in the crystal structure of potassium gellan, which is devoid of any substitutions, native gellan exhibits exceptional changes in its ion binding characteristics with respect to gellan. In particular, the l-glyceryl groups do not allow the gellan-like coordinated interactions of the ions and the carboxylate groups, within and between double helices, which are necessary for strong gelation. These results at the molecular level explain, for the first time, the differences in the behavior of the polymer with and without substitutions.
AB - Native gellan, the natural form of the polysaccharide excreted by the bacterium Pseudomonas elodea, has a tetrasaccharide repeating unit that contains l-glyceral and acetate ester groups, and forms only weak and elastic gels. Based on X-ray diffraction data from well oriented and polycrystalline fibers of its potassium salt, the crystals structure of native gellan, including ions and water, has been determined and refined to a final R-value of 0.17. The molecule forms a half-staggered, parallel, double helix of pitch 5.68 nm which is stabilized by hydrogen bonds involving the hydroxymethyl groups in one chain and both carboxylate and glyceryl groups in the other. Two molecules are packed in an antiparallel fashion in a trigonal unit cell of side a = 1.65 nm. Although the gross molecular morphology and packing arrangements are isomorphous with those observed in the crystal structure of potassium gellan, which is devoid of any substitutions, native gellan exhibits exceptional changes in its ion binding characteristics with respect to gellan. In particular, the l-glyceryl groups do not allow the gellan-like coordinated interactions of the ions and the carboxylate groups, within and between double helices, which are necessary for strong gelation. These results at the molecular level explain, for the first time, the differences in the behavior of the polymer with and without substitutions.
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U2 - 10.1016/0008-6215(92)84088-A
DO - 10.1016/0008-6215(92)84088-A
M3 - Article
C2 - 1591755
AN - SCOPUS:0027113999
SN - 0008-6215
VL - 224
SP - 1
EP - 17
JO - Carbohydrate Research
JF - Carbohydrate Research
IS - C
ER -