Control of calcium-protein interactions in designing casein-based food structures with novel functionality

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Title: Control of calcium-protein interactions in designing casein-based food structures with novel functionality
Authors: McIntyre, Irene Margaret
Advisor: O'Riordan, Dolores; O'Sullivan, Michael
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Date: 2017
Online since: 2017-07-20T13:57:18Z
Abstract: AbstractThis thesis evaluated the basis of calcium-protein interactions in casein systems in order to develop novel casein-based food matrices with different structures and functionalities. Initially, in Chapter 2 the effects of calcium chelating salts (CCS) (disodium phosphate and trisodium citrate) on calcium-ion activity (ACa++), calcium distribution and protein solubility were investigated in model CaCl2 solutions (50 mmol L-1) and rennet casein dispersions (12 % w/w). In both model systems, adding trisodium citrate either alone or as part of a mixed chelating salt system resulted in high levels of dispersed “chelated” calcium; conversely, disodium phosphate addition resulted in lower levels, while the ACa++ decreased with increasing concentration of both CCS. Addition of either salt resulted in only a modest increase in soluble protein. Hence, the results suggested that CCS may play a more subtle role in modulating hydration during manufacture of casein-based matrices than simply solubilising calcium or protein. Therefore, despite the fact that the rennet casein dispersion used was relatively concentrated, an even more concentrated protein system was required to clarify the role of calcium chelators in casein hydration and matrix formation during manufacture of concentrated casein-based food matrices e.g. processed and analogue cheese.Hence, this work was further built upon in Chapter 3, where a small-scale manufacturing protocol for concentrated casein-based food matrices was developed using a Thermomix. Manufacture was stopped at various time-points, and the matrix formed and any free liquid still remaining were collected. The dispersed and insoluble phases were separated by centrifugation and the calcium (total calcium and ACa++) and protein contents of the dispersed phase analysed. The levels of calcium in the dispersed phase increased and ACa++ decreased during manufacture of casein matrices formulated with CCS; ~23 % of the total calcium was solubilised by the end of manufacture. In the absence of CCS, the levels of calcium solubilised were significantly (P < 0.05) lower at equivalent processing times and remained unchanged as did ACa++, throughout manufacture. The level of protein in the dispersed phase was low (≤ 3 % of total protein), but was significantly (P < 0.05) higher for the matrices containing CCS. The results obtained strongly suggested that the role of CCS was mainly to deplete colloidal calcium by partial solubilisation, which reduced calcium-mediated cross-linking sufficiently to allow adequate protein solubilisation to occur for fat emulsification. All of which contributed to successful matrix formation and stabilisation. The results generated suggested that only ~23 % of colloidal calcium needed to be solubilised to form a hydrated and functional casein-based food matrix. This lead us to believe that a similar attenuation of calcium mediated cross-links might possibly be achieved by simply reducing the total calcium concentration of these matrices by a similar proportion.Therefore in Chapter 4 casein-based food matrices with different calcium levels (1080-37 mg.100 g-1) were manufactured by mixing rennet and acid casein. At intermediate calcium levels (673-358 mg.100 g-1) homogeneous matrices were formed without CCS after relatively short processing times. However, homogeneous matrices with high (≥ 775 mg.100 g-1) or low (≤ 37 mg.100 g-1) calcium levels could not be produced without CCS. On cooling the CCS-free matrices with intermediate calcium levels formed functional cheese-like structures although they had lower hardness, flow on melting and G values at 25 C than conventionally formulated high-calcium matrices made from rennet casein with CCS. The results obtained demonstrated that by manipulating total calcium concentration, it was possible to form hydrated casein matrices to meet a range of functional and compositional requirements suitable for different end-use applications, without the use of CCS. The elimination of CCS provided a means of reducing the sodium content of these casein matrices by up to 60 % and also presented the opportunity to formulate end-products with cleaner labels.The sensory acceptability of casein matrices with low levels of calcium (357 mg.100 g-1) manufactured without CCS was investigated in Chapter 5. These matrices were flavoured with different types of enzyme modified cheeses (EMCs) and of those examined; Emmental was the most preferred by sensory panellists. The sensory acceptability of EMC flavoured casein matrices with different fat levels was also investigated. Firstly, the results of this study demonstrated that it was possible to produce full, half and reduced fat casein matrices without CCS. Furthermore, the results showed that although full-fat flavoured matrices were most preferred by sensory panellists and were rated higher in terms of their texture, flavour and overall liking; there were no significant differences (P > 0.05) detected between matrices containing half or reduced fat levels for any of these attributes.In Chapter 6 CCS-free casein-based matrices prepared with different types of lipid (i.e. milk fat or rapeseed oil) were formulated with high (774 mg.100 g-1) or low (357 mg.100 g-1) calcium levels again by blending rennet and acid casein. Their physico-chemical characteristics (i.e. composition, texture, microstructure and water mobility) and in vitro digestibility were compared to conventionally formulated high-calcium (723 mg.100 g-1) casein matrices made from rennet casein with CCS. The CCS-free, high-calcium matrices were significantly (P < 0.05) softer than those with low calcium levels and showed the highest rates of disintegration during simulated gastric digestion. Despite having a higher moisture-to -protein ratio, the high-calcium matrices containing CCS had broadly similar hardness values to those of high-calcium concentration prepared without CCS, but had higher cohesiveness. The high-calcium matrices containing CCS had quite a different microstructure and increased water mobility compared to those made without CCS and showed the slowest rate (P < 0.05) of disintegration in the gastric environment. Gastric resistance was shown to be unaffected by the type of lipid phase present in the matrix. Conversely, fatty acid release was similar for all casein matrices prepared from milk fat, however, high-calcium matrices (CCS-free) prepared from rapeseed oil showed higher lipolysis. The results demonstrated that modifying the composition (i.e. calcium concentration, moisture to protein ratio, inclusion of CCS) and consequently the physical characteristics (e.g. texture, microstructure and water mobility) of casein-based food matrices affects their behavior during in vitro digestion. In particular, the results obtained showed that the physical properties of such matrices could be modified to alter resistance to gastric degradation which may have consequences for the kinetics of nutrient release and delivery of bioactives sentitive to the gastric environment.
Type of material: Doctoral Thesis
Publisher: University College Dublin. School of Agriculture and Food Science
Qualification Name: Ph.D.
Copyright (published version): 2017 the author
Keywords: CalciumCaseinDigestionFunctionalityMilk Protein
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Language: en
Status of Item: Peer reviewed
This item is made available under a Creative Commons License:
Appears in Collections:Agriculture and Food Science Theses

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