Chitin conformation

In addition, such an increase in enzymatic activity could result from changes in the conformation of the enzymatic molecules due to the high electrostatic activity of chitin (Dunand et al., 2002 Ozeretskovskaya et al., 2002). ft can be proposed that the PO sorption on chitin could not be considered to be a classic ion exchange process because both the anionic and cationic isoforms of the plant POs interact with chitin. Additionally, it contains 3 high anionic POs (3.5, 3.7, 4.0) but only 2 of them (3.5 and 3.7) adsorbed on chitin alongside with some cationic isoforms (Fig. 2). 

In one case, a small peptide with enzyme-like capability has been claimed. On the basis of model building and conformation studies, the peptide Glu-Phe-Ala-Ala-Glu-Glu-Phe-Ala-Ser-Phe was synthesized in the hope that the carboxyl groups in the center of the model would act like the carboxyl groups in lysozyme 17). The kinetic data in this article come from assays of cell wall lysis of M. lysodeikticus, chitin hydrolysis, and dextran hydrolysis. All of these assays are turbidimetric. Although details of the assay procedures were not given, the final equilibrium positions are apparently different for the reaction catalyzed by lysozyme and the reaction catalyzed by the decapeptide. Similar peptide models for proteases were made on the basis of empirical rules for predicting polypeptide conformations. These materials had no amidase activity and esterase activity only slightly better than that of histidine 59, 60). 

The crystal structure of a pentamer of GlcNAc residues, representing the chitin polymer (poly-/l-(l-4)-GlcNAc), boimd to the chitinase enzyme ChiB from Serratia marcescens, revealed a narrow, timnel-like active site in the center of the TIM barrel fold [167]. Several conserved residues near the center of the site, which are important in catalysis, interact with the substrate via hydrogen bonds, while interactions farther from the center depend on van der Waals interactions. The sugar in the - 1 subsite adopts a boat conformation, presumably due to interactions with these critical active-site residues. 

This subject has been of continuing interest for several reasons. First, the present concepts of the chemical constitution of such important biopolymers as cellulose, amylose, and chitin can be confirmed by their adequate chemical synthesis. Second, synthetic polysaccharides of defined structure can be used to study the action pattern of enzymes, the induction and reaction of antibodies, and the effect of structure on biological activity in the interaction of proteins, nucleic acids, and lipides with polyhydroxylic macromolecules. Third, it is anticipated that synthetic polysaccharides of known structure and molecular size will provide ideal systems for the correlation of chemical and physical properties with chemical constitution and macromolecular conformation. Finally, synthetic polysaccharides and their derivatives should furnish a large variety of potentially useful materials whose properties can be widely varied these substances may find new applications in biology, medicine, and industry. 

Formanek has concluded from the periodicities determined from X-ray diffraction data of the bacterial cell walls that the conformation of the polysaccharide backbone should be chitin-like with a twofold helical axis [241, 242],... 

Chitin is the 2-acetamido derivative of cellulose and serves as the fibrous component of skeletal tissues in many lower animals. At least two polymorphic forms of chitin have been recognized, (26) of which the a- and 0-forms are the best characterized. The unit cells and space groups of a- and 0-chitins are given in Table 1. Both have approximately the same fiber repeat as cellulose, and apparently have the same 2j helical conformation. 

It is well known that well-ordered (3-chitin (a polysaccharide) associated with a less ordered protein in the (3-sheet conformation is the main component of nacreous organic matrix in shell. The amino acid sequence of such proteins is very similar to those of silk fibroins. Indeed, the amino acid sequence of a major protein from the nacreous shell layer of the pearl oyster resembles that of spidroin (Sudo et al., 1997 Weiner and Traub, 1980). The question of whether silk-like proteins play an important role in shell formation is raised. When Falini et al. (1996) did the experiment with the proteins from the shell, they assembled a substrate in vitro that contained (3-chitin and natural silk fibroin and concluded that the silk fibroin may influence ion diffusion or the accessibility to the chi tin surface or both. Furthermore, cryo-TEM study of the structure of the Atrina shell nacreous organic matrix without dehydration... 

Comparing the solubility behavior of a- and p-chitins (although the later exists in a crystalline-hydrated structure, which is much looser than that of the ot-chitin), p-chitin shows lower solubility due to the penetration of wafer between the chains of the lattice. Based upon chitin molecule-solvent conformation and solubility mechanisms, p-chitin starts gelling at a lower concentration than a-chitin. Table 2.6 illustrates the solubility of chifin and structurally related compounds in a saturated CaCl2 2H20-methanol solvent system. 

Chitosan, a polymer of j8-(I 4)-linked 2-amino-2-deoxy-D-glucose residues, is formed on deacetylation of chitin. As pointed out already, this polysaccharide takes an extended conformation similar to that of cellulose. Deacetylation of chitin is very easily evaluated in view of the NMR spectra, as illustrated in Fig. 24.5. The three polymorphs of chitosan, ten-don-chitosan (from crab shell), L-2 (from shrimp shell), An-nealed (from crab shell chitosan annealed at 22°C in the presence of water) are easily distinguished, consistent with the data for the polymorphs as obtained by a powder X-ray diffraction data [38, 39]. The observed non-equivalence of two chitosan chains, as viewed from the splittings of the C-1 and C-... 

With the exception of cellulose and chitin, plant polysaccharides are usually hydrated. Hydration often occurs in the crystalline regions as well as in the amorphous areas. When water of hydration is found in the crystallites, it may or may not affect the conformation of the polysaccharide backbone and in most cases, it affects the unit-cell dimensions, while in a few cases, the water appears to have no effect on unit-cell dimensions. The structures of six hydrated neutral polysaccharides will be examined with regards to the state of water of hydration in the structure. It wi 11 be seen that water may occur as columns or as sheets in these structures. The structures that will be discussed are (1 4)-3-p-xylan, nigeran, amylose, galactomannan, (1 3)-3-p-gTucan and (1 3)-s-P-xy1 an. The chemical structures of these polysaccharides are shown in Figure 1. 

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