NATURAL POLYMERS MU SCI 6 2018 1 NATURAL POLYMERS Polysaccharide I STARCH 2 Dr. Ladislav Pospíšil January 2018/6 Time schedule January 2018/6 NATURAL POLYMERS MU SCI 6 2018 2 LECTURE SUBJECT 1 Introduction to the subject – Structure & Terminology of nature polymers, literature 2 Derivatives of acids – natural resins, drying oils, shellac 3 Waxes 4 Plant (vegetable) gums, Polyterpene – natural rubber (extracting, processing and modification), Taraxacum_kok-saghyz 5 Polyphenol – lignin, humic acids 6 Polysaccharides I – starch 7 Polysaccharides II – celullosis 8 Protein fibres I 9 Protein fibres II 10 Casein, whey, protein of eggs 11 Identification of natural polymers Laboratory methods of natural polymers’ evaluation SOLUBILITY versus SWELLING January 2018/6 NATURAL POLYMERS MU SCI 6 2018 3 rozpust verus botnání.jpg 1.Biopolymer molecule 2.Polymer Chain 3.Water molecule or other Solvent (solvation agent) 4. DISSOLVING OF STRACH January 2018/6 NATURAL POLYMERS MU SCI 6 2018 4 • NATIV STARCH is not soluble in the Cold Water, having Water in the in the Capillaries and Hydrogen bonds only, approx. 14 – 16 % w/w of Water • NATIV STARCH after pouring to Water at the Laboratory Temperature – the only the other Pores are filled by Water • NATIV STARCH in the Water at Temperature increasing to approx. 50°C – it is SWELLING, Hydrogen bonds are destroyed a DISPERSION OF SWOLLEN (hydrated) Particles in Water • THE FULL HYDRATATION occurs (maximal for the particular Starch) after taking another Water and a Gel are arising (AMYLOPECTIN) or High Viscosity Solution (AMYLOSE) • THE RESULTING STATE IS CALLED GELATION STARCH Behaviour of Starch in Water •Laboratory Temperature: the Reversible filling of the Capillaries in the Starch Particle only •Temperature Increasing: the steady Hydratation and Destruction of the Hydrogen bonds, AMYLOSE DISOLVING, the only Swelling of the AMYLOPECTIN •Temperature Increasing & Mixing: Hydrogen bonds are destroyed and so called „ GELATION STARCH (GELLING) POINT (Peptisation)“ •GELATION STARCH (GELLING) POINT is characteristic for each type native or modified Starch January 2018/6 NATURAL POLYMERS MU SCI 6 2018 5 STARCH GELLING Curves of Starch in Water January 2018/6 NATURAL POLYMERS MU SCI 6 2018 6 •Suited for starch and flour •Usage for acid and lye •Small sample size (5 - 15 g) •Short measuring times •Speed (0 - 300 min-1) •Temperature measurement within the sample •Heating / cooling rates of up to 10°C / min •No follow-up costs •Evaluation in BU, mPas, cP or cmg img676.jpg Modified ROTATION VISCOSIMETER ROTATION VISCOSIMETER January 2018/6 NATURAL POLYMERS MU SCI 6 2018 7 img676.jpg 472px-Rotationsviskosimeter.jpg Standard ROTATION VISCOSIMETER Modified ROTATION VISCOSIMETER January 2018/6 NATURAL POLYMERS MU SCI 6 2018 8 Sol-Gel_Scheme_svg WIKI ENG 09112016.png It is related to STARCH January 2018/6 NATURAL POLYMERS MU SCI 6 2018 9 SolGelCartoon WIKI ENG 09112016.png SOL –big Particles in Solution Solid GEL is formed by Calcination STARCH GELLING Curves of Starch in Water – in GENERAL January 2018/6 NATURAL POLYMERS MU SCI 6 2018 10 STARCH GELLING POINT mazovatění Google 05112017.jpg RETROGRADATION STARCH GELLING Curves of various sorts of Starch in Water 2 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 11 img677.jpg STARCH GELLING POINT img678.jpg Viscosity curves of native Starches: 1) Wheat Starch, 2) Potato Starch, 3) Corn Starch Swelling characteristics of Various Starches Potato Starch Corn Starch STARCH GELLING Curves of Starch in Water1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 12 Micro-Visco-Amylo-Graph-Diagramm_01.jpg •Suited for starch and flour •Usage for acid and lye •Small sample size (5 - 15 g) •Short measuring times •Speed (0 - 300 min-1) •Temperature measurement within the sample •Heating / cooling rates of up to 10°C / min •No follow-up costs •Evaluation in BU, mPas, cP or cmg BU = Brabender Unit Brabender is the German manufacturer of such Devices Take notice of the COURSE TEMPERATURE MEASUREMENT and Points its Changes! STARCH GELLING POINT STARCH GELLING Curves of Starch in Water 3 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 13 Micro-Visco-Amylo-Graph-Diagramm_01.jpg Gradual dissolving of the Shorter chains and their Diffusion to Water > VISCOSITY INCREASING STARCH GELLING POINT RETROGRADATION = viscosity Increasing with Temperature Decreasing > GEL FORMING Coast along (INCREAS) after Temperature switching to Constant Temperature Hydrogen bonds Destruction between Starch chains and hydratation of the all Starch particle, Three-dimensional network > GEL Releasing of the Smaller Hydrated Structures > SOL STARCH GELLING Curves of Starch in Water 4 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 14 STARCH GELLING POINT MAZOVATĚNÍ RŮZNÝCH ŠKROBŮ foods-05-00030-g003_05112017.png RETROGRADATION STARCH GELLING Curves of Starch in Water 5 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 15 MAZOVATĚNÍ ŠKROBU KŘIVKY 001.jpg STARCH GELLING POINT RETROGRADATION January 2018/6 NATURAL POLYMERS MU SCI 6 2018 16 MAZOVATĚNÍ ŠKROBU KŘIVKY 002.jpg STARCH GELLING POINT RETROGRADATION STARCH GELLING Curves of Starch in Water 6 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 17 STARCH GELLING POINT želatice škrobu scan 18112017001.jpg RETROGRADATION STARCH GELLING Curves of Starch in Water 7 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 18 stages_of_starch_conversion 05112017.gif Dough Gradual Cleavage (Chain Scission) by Enzymes STARCH GELLING POINT STARCH GELLING Curves of Starch in Water 8 Another type of the Viscosimeter for Maesurement of the STARCH GELLING POINT 1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 19 img645.jpg img647.jpg January 2018/6 NATURAL POLYMERS MU SCI 6 2018 20 img652.jpg VISCOSITY IS GIVEN IN THE SI UNITS! Various Sorts of Corn (Maize) Starch Transition GEL > SOL Another type of the Viscosimeter for Maesurement of the STARCH GELLING POINT 2 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 21 STARCH GELLING POINT - various Starches Starch GELLING POINT Temperature (°C) Starting Final Middle Potato 59 60 63,5 Corn (Maize) 62 72 67 Wheat 58 64 60 Rye 57 70 61 Rice 68 78 74,5 Pea 55 70 65 Waxy Corn (Maize) 63 72 65 Amylose Corn (Maize) 67 Full Gelling in the boiling Water 80 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 22 STARCH GELLING POINT - various Additives to Water Corn (Maize) Starch GELLING POINT Temperature (°C) Additives Starting Final Middle 5 % w/w Saccharose 60,5 72,5 67 10 % w/w Saccharose 60 74 67 20 % w/w Saccharose 65,5 78 74 40 % w/w Saccharose 72 85 79,5 60 % w/w Saccharose 84 96,5 90,5 0,2 % w/w NaOH 55,5 69,5 64 0,3 % w/w NaOH 49 65 59 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 23 STARCH GELLING POINT - various Additives to Water Corn (Maize) Starch GELLING POINT Temperature (°C) Additives Starting Final Middle 5 % w/w Na2CO3 64 72 70 10 % w/w Na2CO3 67 76 72 20 % w/w Na2CO3 77,5 87 82 30 % w/w Na2CO3 92 103 98 1,5 % w/w NaCl 67,5 77 72 3 % w/w NaCl 69,5 78,5 74 6 % w/w NaCl 75 82,5 79,5 STARCH GEL BEHAVIUOR in Water •Decreasing Temperature: gradual Regeneration of the Hydrogen Bonds, mainly at AMYLOSE, the Starch having high Content of the AMYLOPECTIN (Branched macromolecule) has lower Tendency to RETROGRADATION •They precipitate from the Solution as the Flakes at low Concentration, up to approx. 3 % w/w •The Gel is formed at high Concentrations, having High Viscosity •This Process is called RETROGRADATION and it possible to retard it by Addition of e.g. Glucose, Fats or Inorganic Salts (e.g. NaNO3) • • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 24