Of chitin

For a review of the isolation of chitin from natural sources and some of its uses see the November 1990 issue of the Journal of Chemical Education (pp 938-942)... 

Liquid crystalline behavior occurs in the exocuticle of certain classes of beetles. The bright iridescent colors that are reflected from the surface of Scarabaeid beetles originates from a petrified chiral nematic stmctural arrangement of chitin crystaUites in the exocuticle (38). It is suggested that this chiral nematic texture forms spontaneously in a mobile, Hquid crystal phase that is present during the initial stages of the exocuticle growth cycle. 

Nikkomycins. The nikkomycins (141—159), isolated from S. tendae are nucleoside-peptide antibiotics (1,4,244,245) as shown in Table 8. Nikkomycins X and Z are stmcturaHy identical to neopolyoxins A and C, respectively. Compound (141) is a competitive inhibitor of chitin synthetase. Two new nikkomycins, nikkomycin pseudo-Z and pseudo-J (158, 159), contain a C-glycosidic bond between C-5 of uracil and C-1 of... 

It iaterferes with the synthesis of the hyphal walls, the biosynthesis of nucleic acids, and the synthesis of chitin. The iateraction with microtubules has also been described. The sensitivity of a cell seems to depend particularly on the abiUty to form griseofulvin—nucleic acid complexes. Further information concerning griseofulvin is available (21). 

Element stmctures of chitincontaining sorbents are determined using standard methods. Behind the data of an element stmcture the contents of chitin in ChCS was calculated. The analysis of morphological frame of ChCS was conducted by a electron-microscopic method on a raster supermicroscope at increase from 500 up to 1000 times. For matching is samples ChCS were conducted IR reseai ch in the field of 400 - 4000 cm f... 

Chitosan, having a similar chemical backbone as cellulose, is a linear polymer composed of a partially deacety-lated material of chitin [(l-4)-2-acetamide-2-deoxy-/3-D-glucan]. Grafting copolymer chains onto chitosan can improve some properties of the resulting copolymers [48-50]. Yang et al. [16] reported the grafting reaction of chitosan using the Ce(IV) ion as an initiator, but no detailed mechanism of this initiation has been published so far. 

Amino-sugars and Related Compounds. Part IV. Isolation and Properties of Oligosaccharides Obtained by Controlled Fragmentation of Chitin, S. A. Barker, A. B. Foster, M. Stacey, and J. M. Webber, J. Chem. Soc., (1958) 2218 - 2227. 

Fig. 5.—Parallel packing arrangement of the 2-fold helices of chitin I (3). (a) Stereo view of two unit cells approximately normal to the hc-plane. The two comer chains (open bonds), separated by b, in the back are hydrogen bonded to the comer chains (tilled bonds) in the front, (b) Projection of the unit cell along the c-axis with a down and b across the page. The diagonal orientation of the sugar rings facilitates interchain hydrogen bonds involving the JV-acetyl moieties along the a-axis.

The present chapter, therefore, will present certain topics based on a selection of references, mainly in view of providing a perception of the current developments and great potential of chitin today. The reader is referred to books and reviews [1-17] where basic information and specific subjects are treated in a more systematic way. These polysaccharides are described not only in encyclopaedias, handbooks, monographs and articles, but also in the American Standard Testing Materials standard guides and in the Pharmacopoeias of various coimtries [10,16,17]. 

A number of articles considered the association of chitosan with polylactic acid or similar compounds [47-49] another group of articles presented new data on highly cationic chitosans [ 50 - 55]. More data have also been made available on the delivery of growth factors [56] and ophthalmic drugs [57,58], on the activation of the complement, macrophages [59-61] and fibroblasts [62], on mucoadhesion [63] and functionalization of chitin [64]. The development of new carriers for the delivery of drugs, and the interactions of chitosans with living tissues seem therefore to be major topics in the current research on chitosan. Therefore, this chapter will place emphasis on these aspects. 

Most commonly, chitin means the skeletal material of invertebrates. At least 1.10 kg of chitin are constantly present in the biosphere. Q -Chitin occurs in the calyces of hydrozoa, the egg shells of nematodes and rotifers, the radulae... 

The solubility of chitin is remarkably poorer than that of cellulose, because of the high crystallinity of chitin, supported by hydrogen bonds mainly through the acetamido group. Dimethylacetamide containing 5-9% liCl (DMAc/IiCl), and N-methyl-2-pyrrohdinone/LiCl are systems where chitin can be dissolved up to 5%. The main chain of chitin is rigid at room temperature, so that mesomorphic properties may be expected at a sufficiently high concentration [67,68]. 

Recent progress of basic and application studies in chitin chemistry was reviewed by Kurita (2001) with emphasis on the controlled modification reactions for the preparation of chitin derivatives. The reactions discussed include hydrolysis of main chain, deacetylation, acylation, M-phthaloylation, tosylation, alkylation, Schiff base formation, reductive alkylation, 0-carboxymethylation, N-carboxyalkylation, silylation, and graft copolymerization. For conducting modification reactions in a facile and controlled manner, some soluble chitin derivatives are convenient. Among soluble precursors, N-phthaloyl chitosan is particularly useful and made possible a series of regioselective and quantitative substitutions that was otherwise difficult. One of the important achievements based on this organosoluble precursor is the synthesis of nonnatural branched polysaccharides that have sugar branches at a specific site of the linear chitin or chitosan backbone [89]. 

The accessibility of chitin, mono-O-acetylchitin, and di-O-acetylchitin to lysozyme, as determined by the weight loss as a function of time, has been found to increase in the order chitin < mono-O-acetylchitin < di-O-acetylchitin [120]. The molecular motion and dielectric relaxation behavior of chitin and 0-acetyl-, 0-butyryl-, 0-hexanoyl and 0-decanoylchitin have been studied [121,122]. Chitin and 0-acetylchitin showed only one peak in the plot of the temperature dependence of the loss permittivity, whereas those derivatives having longer 0-acyl groups showed two peaks. 

The subject of fiber production from chitin and chitosan has been reviewed considering the interest in the exploitation of chitin as a textile material [246-251]. The production of fibers, however, is a challenging and difficult task. 

Nontoxic and noncorrosive solvent systems can be used when chitosan is considered instead of chitin for the manufacture of fibers. Improvements of the fiber quality rely mostly on technical shrewdness for instance the use of potassium hydrogen phthalate at pH 4-5 imparted better mechanical properties [255]. 

Cross-linking agents have been proposed for the improvement of chitin fibres in the wet state. Epichlorohydrin is a convenient base-catalysed crosslinker to be used in 0.067 M NaOH (pH 10) at 40 °C. The wet strength of the fibres was considerably improved, whereas cross-hnking had neghgible effect on the dry fibre properties. Of course, the more extended the chemical modification, the more unpredictable the biochemical characteristics and effects in vivo. Every modified chitin or modified chitosan fibre should be studied in terms of biocompatibiUty, biodegradabiUty and overall effects on the wounded tissues. 

Peculiar characteristics of chitins and chitosans are hemostatic action, anti-inflammatory effect, biodegradability, biocompatibihty, besides antimicrobial activity, retention of growth factors, release of glucosamine and M-acetylglucosamine monomers and oligomers, and stimulation of cellular activities [11,12,295-297]. 

A number of important papers could not be cited in this chapter, due to the length limitations and the specific target of the chapter. For example, the antimicrobial activity of chitosans [349], the chitinolytic enzymes, the preparation of cosmetics, and the occurrence of chitin in fungi [350] are some of the subjects not dealt with specifically here, notwithstanding their importance. 

UrbanczykGW (1997) In Goosen MFA (ed) Applications of Chitin and Chitosan. Technomic, Basel, p. 281... 

A contrasting picture is seen for chitosans. Chitosans—as considered in detail in the following Chapter—are derivatives of chitin (after an alkali extraction procedure) and are available in large quantities from the shells of crabs, lobsters and other crustaceans. Pure chitin is poly-N-acetylglucoasmine. The N-acetyl groups are de-acetylated in chitosan to an extent represented by ei-... 

Chitinases are responsible for the breakdo vn and recycling of chitin. With several gigatons of chitin being produced annually, it is the second most abundant polymer... 

Unit of chitin, mucoproteins and mucopolysaccharids, obtained by hydrolysis with HCI. 

Table 1. Analysis of chitin-specific isoperoxidases in plant species...

We found that the PO activity in all the plants tested increased in the presence of chitin as compared with the activity in crude extracts. This activation was not only found in chitin-eluted fraction but also in that fraction not adsorbed on chitin. This data confirms the... 

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). 

We observed the activation of chitin-specific PO during infection with the causative agents of a number of diseases in wheat under the influence of Btpolaris soroktntana and the elicitors (Fig. 4), Septoria nodorum (Yusupova et al, 2006) and Tilletia caries (Khairullin et al., 2000) in potato infected by Phytophthora infestans (Maksimov et al., 2011), and in Aegilops umbellulata infected by Septoria nodorum (Maksimov et al, 2006). 

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