Browsing by Author "Lopez-Rubio, A"

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    Effect of acid dextrinisation on enzyme-resistant starch content in extruded maize starch
    (Elsevier, 2010-05) Htoon, AK; Uthayakumaran, S; Piyasiri, U; Appelqvist, IAM; Lopez-Rubio, A; Gilbert, EP; Mulder, RJ
    The enzyme-resistant starch (ERS) content in processed high amylose and regular maize starches has been studied, with and without acid dextrinisation. The physicochemical and structural characteristics of the starches were analysed using a variety of techniques. The increase in ERS in high amylose maize starch with dextrinisation was related to the formation of a critical molecular weight fraction (MW ~ 20,000) that could rearrange structurally. Further dextrinisation reduced the processed starch MW to below where it could still form ERS. Regular maize starch containing less than 30% amylose did not increase its resistance to amylase digestibility with acid dextrinisation, probably due to impairment of amylose rearrangement by the numerous branched amylopectin chains. The ERS, which is likely to form during the enzyme-digestion process, is a linear molecule with a maximum degree of polymerisation (DP) of 30, irrespective of the starch source, processing conditions applied or type and amount of acid used. © 2010, Elsevier Ltd.
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    Effects of processing high amylose maize starches under controlled conditions on structural organisation and amylase digestibility
    (Elsevier, 2009-01-22) Htoon, AK; Shrestha, AK; Flanagan, BM; Lopez-Rubio, A; Bird, AR; Gilbert, EP; Gidley, MJ
    The amylase digestibility of high-amylose maize starches has been compared before and after thermo-mechanical processing. Starches were analysed for enzyme-resistant starch yield, apparent amylose content, crystallinity (X-ray diffraction), and molecular order (NMR and FTIR), both before and after treatment with (x-amylase. All samples had significant (>10%) enzyme-resistant starch levels irrespective of the type and extent of thermal or enzymic processing. Molecular or crystalline order was not a pre-requisite for enzyme resistance. Near-amorphous forms of high amylose maize starches are likely to undergo recrystallisation during the enzyme-digestion process. The mechanism of enzyme resistance of granular high-amylose starches is found to be qualitatively different to that for processed high-amylose starches. For all samples, measured levels of enzyme resistance are due to the interruption of a slow digestion process, rather than the presence of completely indigestible material. © 2008, Elsevier Ltd.
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    Enzyme resistance and structural organization in extruded high amylose maize starch
    (Elsevier, 2010-05-05) Shrestha, AK; Ng, CS; Lopez-Rubio, A; Blazek, J; Gilbert, EP; Gidley, MJ
    Gelose 80, a high amylose maize starch, was extruded in a twin screw extruder at different feed moistures, cooled, stored for 12 days at 4°C, and cryo-milled. The raw and extruded starches were analysed for in vitro enzyme-resistant starch content (ERS), morphology, in vitro digestibility, long range (X-ray diffraction) and short range (FTIR) molecular order. Extrusion markedly increased the rate of starch digestion and reduced the ERS content, irrespective of whether B-type or B- and V-type polymorphs were present. Increasing feed moisture and storage resulted in only slight increases in ERS content, with X-ray diffraction and FTIR also showing small changes in long and short range molecular order, respectively. Analysis of residues from in vitro digestion showed the mechanism of enzyme resistance of granular and extruded high amylose starch to be markedly different, both qualitatively and quantitatively. Enzyme digestion of granular high amylose maize starch showed initial disorganization in structure followed by slow reorganization at later stages of digestion. In contrast, molecular reorganization took place throughout the enzyme digestion of extruded high amylose maize starch. Higher levels of crystallinity were found in digested extrudates compared with digested granules, showing that there is no direct correlation between starch crystallinity and enzyme digestion rates. © 2009, Elsevier Ltd.
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    Influence of storage conditions on the structure, thermal behavior, and formation of enzyme-resistant starch in extruded starches
    (American Chemical Society, 2007-10-26) Chanvrier, H; Uthayakumaran, S; Appelqvist, IAM; Gidley, MJ; Gilbert, EP; Lopez-Rubio, A
    Starch structures from an extrusion process were stored at different temperatures to allow for molecular rearrangement (retrogradation); their thermal characteristics (DSC) and resistance to amylase digestion were measured and compared. The structure of four native and processed starches containing different amylose/amylopectin compositions (3.5, 30.8, 32, and 80% amylose content, respectively) before and after digestion was studied with small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD). Rearrangement of the amylose molecules was observed for each storage condition as measured by the DSC endotherm at around 145°C. The crystalline organization of the starches after processing and storage was qualitatively different to that of the native starches. However, there was no direct correlation between the initial crystallinity and the amount of enzyme-resistant starch (ERS) measured after in vitro digestion, and only in the case of high-amylose starch did the postprocess conditioning used lead to a small increase in the amount of starch remaining after the enzymatic treatment. From the results obtained, it can be concluded that retrograded amylose is not directly correlated with ERS and alternative mechanisms must be responsible for ERS formation. © 2007, American Chemical Society
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    Molecular rearrangement of starch during enzyme digestion as inferred by scattering techniques
    (Australian Chemical Institute, 2007-08) Lopez-Rubio, A; Htoon, AK; Gilbert, EP
    Resistant starch (RS) is defined as the fraction of starch that escapes digestion in the small intestine, serving as a fermentation substrate for the beneficial colonic bacteria. Understanding the structure that makes these fractions resistant to digestion is of outstanding importance as it assists in the design of food products with increasing RS content. Several studies have been focussed on the description of the RS fractions from several starch varieties, but little attention has been paid to the digestion process itself, which from the present work, seems to play a key role in the understanding of what is RS.
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    Molecular rearrangement of starch during in vitro digestion: toward a better understanding of enzyme resistant starch formation in processed starches
    (American Chemical Society, 2008-07) Lopez-Rubio, A; Flanagan, BM; Shrestha, AK; Gidley, MJ; Gilbert, EP
    Resistant starch (RS) is defined as the fraction of starch that escapes digestion in the small intestine, serving as a fermentation substrate for beneficial colonic bacteria. Several studies have been focused on the description of the RS fractions from different starch varieties, but little attention has been paid to the digestion process itself that, from the present work, seems to play a key role in the generation of enzyme-RS (ERS), as determined in vitro. High-amylose starch samples, extruded at two different processing conditions, have been characterized at different stages of in vitro digestion using scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS), infrared spectroscopy (FF-IR), solid state C-13 NMR spectroscopy, and X-ray diffraction (XRD). Control samples kept for 18 h in the digestion solution without starch hydrolyzing enzymes (alpha-amylase and amyloglucosidase) were used for comparison purposes. An increase in molecular order was favored by the hydrolytic action of the enzymes, reflected in an increase in double helical order observed by NMR, higher crystallinity measured by XRD, and corresponding changes in FT-IR spectra. An increase in the intensity of the scattering objects was also observed by SAXS as a function of digestion. SAXS from the dry ERS fractions reveals the 001 reflection of crystallites formed during the digestion process, corresponding to a characteristic dimension of the resistant crystalline fraction of similar to 5 nm. The changes found suggest that enzyme resistant starch does not refer to a specific structure present in predigested starches, but may in fact be formed during the digestion process through the rearrangement of amylose chains into enzyme-resistant structures of higher crystallinity. Therefore, the resistance to enzyme digestion of a specific processed starch is the result of a competition between the kinetics of enzyme hydrolysis and the kinetics of amylose retrogradation. © 2008, American Chemical Society
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    Neutron scattering: a natural tool for food science and technology research
    (Elsevier, 2009-12) Lopez-Rubio, A; Gilbert, EP
    Neutron scattering is a powerful tool for the study of soft condensed matter. The use of neutron techniques in combination with traditional characterisation techniques used in food science can provide a unique insight into novel food materials, providing the knowledge to develop new formulations. As these methods have traditionally been poorly utilised in food science research, this paper highlights the potential of neutron scattering techniques in this arena and provides some recent examples in its application across food components with an outlook of some potentially interesting applications. © 2009, Elsevier Ltd.
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    Novel approach for calculating starch crystallinity and its correlation with double helix content: a combined XRD and NMR study
    (Wiley-Blackwell, 2008-09) Lopez-Rubio, A; Flanagan, BM; Gilbert, EP; Gidley, MJ
    A peak fitting procedure has been implemented for calculating crystallinity in granular starches. This methodology, widely used for synthetic polymers, is proposed to better reflect the crystalline content of starches than the method normally used, in which it is assumed that relatively perfect crystalline domains are interspersed with amorphous regions. The new approach takes into account irregularities in crystals that are expected to exist in semicrystalline materials. Therefore, instead of assuming that the amorphous background extends up to the base of diffraction peaks, the whole X-ray diffraction (XRD) profile is fitted to an amorphous halo and several discrete crystalline diffraction peaks. The crystallinity values obtained from the XRD patterns of a wide range of native starches using this fitting technique are very similar to the double helix contents as measured by C-13 solid state NMR, suggesting that double helices in granular starches are present within irregular crystals. This contrasts with previous descriptions of crystalline and noncrystalline double helices that were based on the analysis of XRD profiles as perfect crystals interspersed in a noncrystalline background. Furthermore, with this fitting methodology it is possible to calculate the contribution from the different crystal polymorphs of starch to the total crystallinity. © 2008, Wiley-Blackwell.
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    Processing of novel elevated amylose wheats: functional properties and starch digestibility of extruded products
    (American Chemical Society, 2007-11-15) Chanvrier, H; Appelqvist, IAM; Bird, AR; Gilbert, EP; Htoon, AK; Li, ZY; Lillford, PJ; Lopez-Rubio, A; Morell, MK; Topping, DL
    Different types of novel wheat lines with different starch contents and amylose/amylopectin ratios, relating to defined alterations in the number and activity of starch synthase IIa genes, were processed by pilot-plant extrusion. Two types of products were produced: pure wholemeal products and breakfast cereals made from wholemeal/maize blends. Lower apparent shear viscosity was obtained in the extruder with lower starch content and higher amylose/amylopectin ratio flours (SSIIa-deficient line). The bulk density of the products decreased with increasing extrusion temperature and was always higher for the triple-null line. The bulk density was not completely explained by the melt shear viscosity, suggesting the importance of the fillers (fibers, brans) in the process of expansion and structure acquisition. The different mechanical properties were explained by the density and by the material constituting the cell walls. Enzyme-resistant starch (RS) content and hydrolysis index (HI) were not correlated to the extrusion temperature, but RS was higher in pure wholemeal products and in the SSIIa-deficient line. These results are discussed in terms of starch molecular architecture and product microstructure. © American Chemical Society
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    Structural characterization of acylated starches with increased delivery of short-chain fatty acids
    (Royal Australian Chemical Institute, 2007-08) Lopez-Rubio, A; Gilbert, EP; Topping, DL; Bird, AR; Cobiac, L; Clarke, JM
    Short-chain fatty acids (SCFA), mainly acetic, propionic and butyric acids, are produced during fermentation of carbohydrates in the human colon and are critical for the maintenance of bowel health and colonic function (Topping and Clifton, 2001). However, an increased delivery of specific SCFA to the large bowel can also be obtained by acylation of carbohydrates, using a CSIRO proprietary technology. Understanding the effects of structure on functionality is essential for the design and manufacture of acylated starches with specific health and therapeutic effects. The aim of the present study is to determine the effects of the level of acylation (degree of substitution), the molecular size of the esterified acid and the composition of the base maize starch on the structure of the acylated starch. Low and high amylose maize starches acylated with acetic, propionic and butyric acids at three degrees of substitution were compared with the structure of the unmodified maize starches.
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    Structural modifications of granular starch upon acylation with short-chain fatty acids
    (Elsevier, 2009-10) Lopez-Rubio, A; Clarke, JM; Scherer, B; Topping, DL; Gilbert, EP
    Low (LAMS) and high (HAMS) amylose maize starches acylated with acetic, propionic and butyric acids at three different degrees of substitution (DS) have been structurally characterized. SEM, XRD, SAXS and FT-IR were used to ascertain the effects of the molecular size of the esterified acid, the composition of the base maize starch and the DS on their structural properties. LAMS and HAMS did not differ significantly at the microscopic level. However, substantial differences were found at the nanostructural levels as a function of the esterified fatty acid, highlighting the importance of these length scales for the understanding of the macroscopic functional characteristics. Although the crystal unit cell remained practically unchanged, as deduced from the similar X-ray diffraction patterns, an increase in long-range order was observed with increasing fatty acid chain length. Conversely, shorter acyl chain lengths were related to greater decreases in the electron density difference between the amorphous and crystalline lamellae, suggesting the introduction of defects in the lamellar structure. From the SAXS results, it appears that the longer esterified chains are able to be accommodated within the crystalline lamellar regions so that the nanostructure is affected less by butyrylation than by the addition of acetyl or propionyl groups. © 2009, Elsevier Ltd.
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    Structure-function relationships in A and B granules from wheat starches of similar amylose content
    (Elsevier, 2009-02-11) Salman, H; Blazek, J; Lopez-Rubio, A; Gilbert, EP; Hanley, TL; Copeland, L
    Five wheat (Triticum aestivum L.) starches, from the varieties Sunco, Sunsoft, SM1118. and SM1028, with similar amylose content, and a waxy wheat were separated into large (A) and small (B) granules. The unfractionated starches, and isolated A and B granules, were characterized structurally and evaluated for their functional properties. The amylopectin chain length distribution revealed that A granules had a lower proportion of short chains with degree of polymerization (DP) 6-12 and a higher proportion of chains with DP 25-36 than B granules. X-ray diffraction (XRD) patterns showed predominantly A-type crystallinity for all of the starches. No differences in the crystallinity were found between unfractionated, A and B granules. Small-angle X-ray scattering (SAXS) patterns of the starches at 55% hydration showed that the lamellar repeat distance in A granules was larger than that of B granules for all the starches examined. However, the lamellar distances of both A and B granules from the waxy wheat were smaller than those of Sunco, Sunsoft, SM1118 and SM1028 starches. The swelling power of the B granules was greater than that of A granules from all five starches. The kinetics of digestion of A and B granules with α-amylase in vitro were complex, with B granules initially digested to a greater extent than A granules. After 4 h of incubation, A granules showed greater digestibility than B granules, except in the case of waxy starch where unfractionated and fractionated granules had similar in vitro digestibility. Correlations between structural and functional parameters were more significant for the isolated A and B granules than for the unfractionated starches. This study demonstrates that A and B granules differ in structure and functionality, and that some correlations between these properties could be masked in unfractionated starches with bimodal granule size distribution. © 2008, Elsevier Ltd.