4.

Granule size and shape Most of the granules of pulse starches are oval, although spherical, round, elliptical and irregularly shaped granules are also found (Table 3). Granules surfaces of pulse starches are generally smooth with no evidence of fissures or pin holes. Most of pulse starches are composed of simple granules. However, compound granules have been reported in smooth pea and wrinkled pea starches, Granules of wrinkled pea starch generally been shown to be extensively damaged resulting in splitting and exposure of the internal layering. 5. Molecular structure 5.1 Structure of amylose and amylopectin The two major components of starch are amylose and amylopectin. The ratio between amylose and amylopectin varies depending on the starch source. In normal starches, amylose constitutes about 15 30 % of total starch. Waxy starches have approximately 0 -5 % amylose, whereas the amylose contents of high amylose starches are in the range of 35 70 % . The degree of polymerization (DP) of amylose has been shown to vary from 690 to 6340 . The molecular weight of amylose has been shown to range from 1 x 10^5 to 1 x 10^6. Amylose forms helical complexes with iodine, fatty acids and monoglycerides. The location of amylose in a starch granule is still in dispute. The possible locations are listed as follows : (1) amorphous growth ring (2) amorphous lamellae, or (3) interspersed or co-crystallized with amylopectin molecules. The physicochemical characteristics of pulse amylose are presented in table4 . The structure of pulse amylose has not been well (characterized. The B-amyloses limit and the limiting viscosity ( not shown in table) are in the range 79 86,9 and 136 280, respectively. Amylopectin is the major component of all starches with a weight average molecular weight of the order 10^7 10^9. Amylopectin is composed of linear chains of a(1-4)-glucose residues connected through a(1-6) linkages (5 -6 %). The currently accepted amylopectin structure involves short amylopectin chains forming double helices and associating into clusters. These clusters pack together to form a structure which consists of alternating crystalline and amorphous lamellae. Hizukuri has calssified the amylopectin unit chains as A , B and C. The A chains are shortest (DP 6 12) and are linked by a single a(1-6) linkage to the amylopectin molecule. B chains are classified into B1, B2, B3, and B4 depending on their lenght and the number of clusters they span. The most exterior chains ( A and B1 ) have been shown to form double helices within the native granules, which are packed into lamellae crystallites. The B2 B4 chains act as connecting chains in the amylopectin molecule. The amylopectin average chain lenght and amylopectin chain length distribution of pulse starches are presented in Table 5. The data indicates that there is a dearth of information on the fine structure of amylose and amylopectin of pulse starches. C to onsequently, it is difficult to make any meaningful comparisons with the structure of amylose and amylopectins of cereal and tuber starches. 5.2 Crystallinity and polymorphic composition of pulse starches The amylopectin molecules inside starch granules have been shown to crystallize into either A-type (cereal starches), B-type (tuber, roots, high amylose cereal starches and retrograded starches) or a C-type (pulse starches). With the exception of wrinkled pea starch, most pulse starches exhibit a C-type X-ray diffraction (Table 6 ), which is intermediate between the A and B-types. Biogracheva, Morris, Ring, and Hedley (1998) have shown in studies on pea starches that the B polymorps are arranged centrally with the A-polymorph located peripherally within the granules. Wang, Yu, and Yu (2008) have shown by acid hydrolysis and microscopy data, that the armorphous regions of pea starch are mainly located in the central portion of the granule, while the crystalline areas mainly exist

in the peripheral regions. As shown in the Table 5, the B-polymorph content of man y pulse starches has not been determined. The crystallinity of pulse starches (Table 5) is in the range 17.0 34.0%. Crystallinity differences among pulse starches could be influenced by : (1) crystallite, (2) number of crystallites that are arranged in a crystalline array, (3) moisture content, and (4) polymorphic content. 6. Gelatinization characteristics Starch, when heated in the presence of excess water, undergoes an order-disorder phase transition called gelatinization over a temperature range characteristics of the starch source. The above phase transition is associated with diffusion of water into the granule, water uptake by the amorphous background region, hydration and radial swelling of the starch granules, loss of birefringence, uptake of heat, loss of crystalline order, uncoiling and dissociation of double helices and amylose leaching. The gelatinization transition temperatures and enthalpy of gelatinization have been shown to be influenced by the molecular architecture of crystalline region, which corresponds to the distribution of amylopectin short chain (DP 6-11) and not by the proportion of the crystalline region, which corresponds to the amylose to amylopectin ration. The above authors have shown a low T, T, T and H reflect the presence of abundant short amylopectin chains. Cooke and Gidley have postulated that H reflects the loss of double helical order rather than the loss double helical order rather than the loss of crystallinity. However, Tester and Morrison have postulated that H reflects the overall crystallinity of amylopectin. The gelatinization parameters of pulse starches determined using the differential scanning calorimeter (DSC) are presented in Table 7. In many of the above studies, only a single cultivar has been analyzed. Consequently, it is difficult to ascertain whether the DSC parameters truly represent the species in general. Furthermore, due to limited information on amylose chain length and amylopectin branch chain length distribution, it is not possible to discuss the influence of molecular structure on the DSC parameters of pulse starches. 7.Granular swelling and amylose leaching The extent of granular swelling has been reported as swelling factor and as swelling power. Pulse starches have been shown to exhibit a single stage restricted swelling and low extent of amylose leaching. This is indicative of strong interactions between starch chains that relax over one temperature and not over multiple temperatures. In most pulse starches, no measureable granule swelling or amylose leaching occurs at temperature below 60E C (Table 8). However, at temperature exceeding 700oC, there is a pronounced increase in both swelling and amylose leaching (Table8). We speculate that due to their high amylose content (Table 2), the amylose chains of pulse starches may be closely packed within the amorphous domains of the granule. This could result in strong interactions (via hidrogen bonding) between adjacent amylose chains. Consequently, a high input of thermal energy would be required to disrupt interactions between amylose chains. This seems plausible, since cereal starches having a lower amylose content and a higher bound lipid content exhibit a higher degree of granular swelling and more extensive amylose leaching than legume starches 8. Pasting properties A paste is defined as aviscous mass consisting of a continous phase of solubilized amylose and /or amylopectin and a discontinuous phase of granule ghosts and fragments. Pasting refers specifically to changes in the starch upon further heating after gelatinization has occured, including furhter swelling and leaching of polysaccharides from the starch granule, and increased viscosity which occurs with the application of shear forces. The Brabender viscoamylograph (BVA), and rapid viscoanalyzer (RVA) have been widely used to examine the pasting characteristics of pulse starches

(Table 9). The Pasting curves of these starches have been determined at different concentrations and by using either the BVA and RVA. Thus, it is difficult to make a meaningful comparison of the data presented in Table 9. Most pulse starches exhibit a high pasting temperature, the absence of peak viscosity, increasing viscosity during the holding period and a high set-back. The pasting properties of pulse starches probably reflect their high amylose content, the presence of only trace quantities of lipid complexed amylose chains, strong interaction between starch chains (amylose amylose and/or amylose amylopectin) within the native granule and the orientation of amylose chains relative to one another. It is likely that the pasting properties are also influenced by the amylose and amylopectin chain length. Our understanding of the rheology of pulse starches has come mainly from studies using the BVA and RVA, in which measurements are made under non-laminar flow conditions and, the starch paste is subjected to both thermal and mechanical treatment, thus making it difficult to relative viscous behavior to only one of these parameters. There is thus a need to extend the use of rheometers ( in which thermal treatments are separated from shear effects) to determine the rheological characteristics of pulse starches under well defined flow regimers.