Curdlans
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Introduction
The generic term « curdlan » refers to extracellular microbial polysaccharides having (1→3)-linked β-D-glucose residue as their repeating units.
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Fig. 1 Schematic representation of the repeating unit of Curdlan
It concerns also, a branched β-(1→3)-glucans with a few β-(1→6) glucose units groups among which is scleroglucan, lentinan, schizophyllan,….
These polysaccharides often form a triple helical conformation with a tendency to give a physical gel. Scleroglucan, lentinan, schizophyllan,…. all share similar structures and conformations. Their solubility increases in alkaline conditions, but an irreversible helix-coil transition occurs over pH > 12. Many of the polysaccharides belonging to this family are claimed to have anti-tumoral properties.
Curdlan is produced by the bacterium Alcaligens faecalis var. myxogens 10C3 strain. X-ray diffraction patterns from oriented specimens
,
,
have led to the identification of three distinct forms:
1. the native specimen (Curdlan I);
2. the hydrated form after annealing at 140° C (Curdlan II),
3. and the dehydrated form after annealing (Curdlan III).
They display significantly different 3-dimensional conformation and chain associations.
Curdlan-I
The elucidation of the 3D structure of native curdlan, has been under several investigations yielding somehow conflicting results. Previous investigations elicited the molecular structure as a six-fold
and seven-fold
triple helical models. Re-examination of these models based on the observation of a meridional reflection on the sixth layer line resulted in a model where the chain is a six-fold, right-handed single helix
.
(In this model, the pitch of the single helix is 22.8 Å. and the chain conformation is stabilized by a weak hydrogen bond between O4H…. O5 of 3.14 Å. The helices are oriented in a parallel fashion; they are fully hydrated as indicated by the large number of 250 water molecules per unit cell.
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Fig. 3 Schematic representation of the structural packing observed in native curdlan I
Curdlan-II
The hydrated form of Curdlan as analysed by fiber X-ray diffraction is organized as a triple helical structure of parallel right-handed strands (c value of 18.78 Å) packed in a triclinic unit cell
.
The core of the triple helix exhibits triad of interchain hydrogen bonds (O2H…O2 = 2.72 Å). Six water molecules have been located in the unit cell. These water molecules bridge adjacent helices through hydrogen bonds.
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Fig.4 3D representation of the structure of the packing observed in curdlan II
Curdlan-III
The dehydrated form of curdlan is structurally well organized and gives rise to an X-ray pattern that can be analysed as an hexagonal unit cell, with space group P63
.
The layer line spacing is consistent with a 6 fold parallel, triple helix whose pitch is 17.61 Å. The core of the triple helix exhibits triad of interchain hydrogen bonds (O2H…O2 = 2.72 Å) occurring at successive levels separated by distance of 2.94 Å.
The packing of the chains in the unit cell is maintained by a series of strong hydrogen bonds (having distance between 2.70 to 2.75 Å).