Gelling polysaccharides • • What is a gel Look at – – – Alginates Pectin Carrageenans – Synergy • • • Notes can be found on ; sbw5f/APPS/APPS/WINAPPS/Data/ Slides and Lectures/SEHill/INDEX.HTM http://webct.nottingham.ac.uk/webct/ur w/lc4130001.tp0/cobaltMainFrame.do webct ?????????????????????? Xanthan LBG Mechanisms for gelation 1 X Gelation of proteins Polysaccharides • Said to occur when a small amount of solid is dispersed in a relatively large amount of solvent (usually water), by the property of mechanical rigidity. • Defined as a protein aggregation phenomenon – attractive and repulsive forces are so balanced that a well ordered tertiary network or matrix is formed. • Protein gels are composed of three dimensional matrices or networks of interwined, partially associated polypeptides in which water is entrapped. • Is a continuous network of macroscopic dimensions immersed in a liquid medium and exhibiting no steady flow. 2 Gels X 3 Structure and Gels Retorted gels 0.4% locust bean gum/0.4% carrageenan Total 0.8% polysaccharide Egg white ~12% protein 4 Gel structures Aggregates of spherical particles Physical gel with crystalline junctions Framework of Rod-like particles Chemical gel -covalent junctions 5 Structure of the polysaccharide • Change temperature • Change solvent quality • Change ionic environment It’s what happens to amylose 6 Carrageenan (E407) Red seaweed extract (Rhodophyceae) iota carrageenan lambda carrageenan kappa carrageenan 7 1- 4-linked- -D-galactopyranose 8 kappa lamda 1-3-linked-b-D-galactopyranose 9 Thermoreversible gels Kappa better gel former than iota 10 Agarose seaweed galactose residues sulfated more sulfate less well it gels 11 Importance of ions • General “salt” effect • Specific effects For example: K+, Rb+, Cs+ favour gelation of both kappa and iota Carrageenan 12 Ion 13 Gel Formation Association of chains (junction Zones) in order to produce a permanent network Diverse models for gel formation: Models proposed for carrageenan 14 Atomic force microscopy Image size 0.8 x 0.8 m 15 Alginate Guluronic acid Mannuronic acid 16 Gelation of alginates • High M-alginates form turbid gels low elastic modulus • High G alginates: stiff, transparent, brittle gels • Gelation depends on cation • Ba2+ > Sr2+ > Ca2+ > Mg2+ 17 18 Pectin a core chain of alpha (1,4)-linked D-galacturonic acid units interspersed with some L-rhamnose Branched structure Neutral sugars alternate R= rhamnose U= galacturonic acid About 40-100 19 20 galacturonic acid forming cells for cations 21 Pectin stable at low pH 22 Low ester pectin High ester pectin • Pectin with degree of esterification > 50% is referred to as high ester pectin. • Low ester pectins have DE < 50%. • High ester pectins gel in the presence of high concentrations of cosolutes (e.g. 60% sugar) and at pH values < 3.4. • Low ester pectins gel in the presence of calcium ions. The reactivity increases as DE decreases. • Rapid set pectins have DE ~70% and slow set pectins have DE ~65%. • Gelation occurs as a consequence of calcium ion crosslinking. • Gelation is believed to occur through association of the pectin chains by hydrophobic bonding. • Gels are thermally irreversible. 23 Mixed gels • Often more than one polymer exists • This can enhance to reduce gel quality 24 Two component gel types Swollen network Interpenetrating network 25 Phase separated network Coupled network 26 Gelation in Synergistic mixed polysaccharide gels Locust bean gum gelling with carrageenan 27 Xanthan galactomannan gels ? 28 Firm, Brittle Low Acyl Gellan Gum Agar k-Carrageenan High “G” Alginate Pectin High “M” Alginate Gelatin Xanthan/LBG High Acyl Gellan Gum Soft, Flexible 29 Useful references http://www.lsbu.ac.uk/water/ E-learning hydrocolloid program on Blackboard Journals: Food Hydrocolloids and Carbohydrate Polymers Series of Books: Gums and Stabilisers for the Food Industry Book :Functional Properties of Food Macromolecules (Chapter by Morris on gelation) Anything in the TX55-, QD4--, QP7-- section of the library 30