NATURAL POLYMERS MU SCI 6 2018 1 NATURAL POLYMERS Polysaccharide I STARCH 1 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 – cellulose 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 POLYSACCHARIDES - DEFINITION January 2018/6 NATURAL POLYMERS MU SCI 6 2018 3 polysacharidy001.jpg Initial NONreducing unit End reducing unit Points of Branching Polysaccharides are polymeric carbohydrate molecules composed of long chains of monosaccharide units bound together by glycosidic linkages, and on hydrolysis give the constituent monosaccharides or oligosaccharides. They range in structure from linear to highly branched. Polysaccharides are often quite heterogeneous, containing slight modifications of the repeating unit. When all the monosaccharides in a polysaccharide are the same type, the polysaccharide is called a homopolysaccharide or homoglycan, but when more than one type of monosaccharide is present they are called heteropolysaccharides or heteroglycans. When the repeating units in the polymer backbone are six-carbon monosaccharides, as is often the case, the general formula simplifies to (C6H10O5)n, where typically 40≤n≤3000. LITERATURE BOOKS •Thermoplastic Starch –ISBN: 978-3-527-32528-3 •Starches –ISBN: 978-1-4200-8023-0 •Starch – Chemisty and Technology –ISBN: 978-0-12-746275-2 • • – • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 4 LITERATURE – JOURNALS •Starch ‐ Stärke •Journal of Carbohydrate Chemistry •Carbohydrate Polymers (Impact Factor: 5,1 !!!) • • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 5 1.Sorts of Starch 2. Production of Starch 3. Starch Chemistry 4. Starch utilisation 5. Starch Modification 6. Production of Dextrin 7. Dextrin use January 2018/6 NATURAL POLYMERS MU SCI 6 2018 6 Sorts of the Industry important Starches January 2018/6 NATURAL POLYMERS MU SCI 6 2018 7 img659.jpg Grain (Particles) shapes Two Sorts of Grains! The Characteristic shape of the STARCH GRAINS a) Potato, b) Wheat, c) Rice, d) Corn WHEAT STARCH January 2018/6 NATURAL POLYMERS MU SCI 6 2018 8 The Different Branching Two Sorts of Grains! Two Grain shapes January 2018/6 NATURAL POLYMERS MU SCI 6 2018 9 1280px-Wheat_starch_granules.jpg WHEAT STARCH – Two Sorts of Grains & Two Sizes of Grains Starch SEM – my own Work at MU 1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 10 Skrob brambor 200x.jpg Skrob brambor 2kxb.jpg Potato Starch You didn't see any Surface Wrinkling, as you can see on the Pictures drawn and taken from a Literature. The Reason IS PROBABLY IN THAT, because the Starch grains were not dried before taking the SEM Pictures. Starch SEM – my own Work at MU 2 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 11 Skrob brambor 5kx.jpg Skrob brambor 10kx.jpg Potato Starch Starch SEM – my own Work at MU 3 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 12 Skrob brambor 1kx M.jpg Potato Starch Starch SEM – my own Work at MU 4 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 13 Skrob kukurice 2kx M.jpg Corn (Maize) Starch Starch SEM – my own Work at MU 5 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 14 Skrob kukurice 200x.jpg Skrob kukurice 1kx.jpg Corn (Maize) Starch You didn't see any Surface Wrinkling, as you can see on the Pictures drawn and taken from a Literature. The Reason IS PROBABLY IN THAT, because the Starch grains were not dried before taking the SEM Pictures. Starch SEM – my own Work at MU 6 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 15 Skrob kukurice 5kx.jpg Skrob kukurice 10kx.jpg Corn (Maize) Starch Starch SEM –my own Work at MU 7 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 16 Corn (Maize) Starch X Potato Starch Skrob kukurice 1kx.jpg Skrob brambor 1kx b.jpg Starch SEM –my own Work at MU 8 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 17 Skrob kukurice 5kx.jpg Skrob brambor 5kx.jpg Corn (Maize) Starch X Potato Starch Starch SEM – WHEAT (taken form Literature) January 2018/6 NATURAL POLYMERS MU SCI 6 2018 18 Pšeničný škrob SEM GOOGLE 05112017.jpg A-Grain B Grain Sizes of Starch Grains (Particles) January 2018/6 NATURAL POLYMERS MU SCI 6 2018 19 •Potato : predominantly 10 – 70 mm (BROAD Grains’ sizes distribution) •Corn: predominantly 20 mm (NARROW Grains’ sizes distribution) •Wheat: Two Sorts of Grains –Size 1 – 10 mm > Starch B (Waste product, contains Proteins) –Size 10 – 25 mm > Starch B (PRODUCT) •Rice: predominantly approx. 5 mm (NARROW Grains’ sizes distribution) – STARCH - Production and Use (Data from the Years 1991 & 2011) •World Production (1991): 22 000 000 tons •World Production (2011): 70 000 000 tons •Corn STARCH : 15 000 000 tons •The most important plants utilized to STARCH production: CORN, Potato, Rise, Cassava •The principal STARCH Producers: USA (CORN), former USSR republics, Netherland, Germany, Poland (Potato) •Nutrition use: approx. 70 % •Modified STARCH :approx. 5 000 000 tons • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 20 World Production of the SYNTHETIC PLASTICS is approx 300 000 000 t/annual January 2018/6 NATURAL POLYMERS MU SCI 6 2018 21 img741.jpg Cassava January 2018/6 NATURAL POLYMERS MU SCI 6 2018 22 img739.jpg January 2018/6 NATURAL POLYMERS MU SCI 6 2018 23 img740.jpg World Production of the SYNTHETIC PLASTICS is approx 300 000 000 t/annual STARCH - Production from Potato 1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 24 •Potato contain 14 – 21 % w/w of Starch, which is not so much •It is possible to take approx. 4 tons of Starch from 1 ha of the Cultivated field •The Water Need is for the production, up to 3,5 – 8 m3/ton of Potato, but more modern Technologies can lower this Volume •Sušina škrobu je cca. 84 % hmot. •Ostatní složky jsou: img663.jpg Nitrogen compounds Lipids January 2018/6 NATURAL POLYMERS MU SCI 6 2018 25 img661.jpg Potato are transported by Water stream, so the Water Recycling must be done using Sedimentation Vessel to remove the Sand and Soil Potato Slicer (Pulper) WASTE Water with Proteins COAGULATION Of Proteins Potato Pulp Small Grain Starch Second Pulping „Classical“ starch factory 1.Potato Depot, 2. Washing machine, 3. Sedimentation Vessel, 4. Belt scales, 5. Potato hopper, 6. Potato slicer, 7. Centrifuge, 8. Wash out (Starch) machine, 9. Second Pulping, 10. Potato pulp Press, 11. Centrifuge, 12. Mesh, 13. Starch size sorting (Starch refining), 14. Filter, 15. Preheating, 16. Centrifuge, 17. Roller dryer A – Starch, B - Potato pulp, C – Clean Water, D – Waste Water, E – Dry protein, F – Liquid animal feed FROM THE STARCH TO ETHANOL •STARCH –ENZYME from the Grain malt •Monosaccharide – ENZYME from the Yeast »ETHANOL January 2018/6 NATURAL POLYMERS MU SCI 6 2018 26 STARCH - Production from Potato 2 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 27 •Starch factory is usually combined with Agricultural alcohol Distillery •Raw Materials for this Distillery: –Fine Fraction of Starch gained during so called STARCH SIZE SORTING (STARCH REFINING), –WASTE Water with Proteins gained during Centrifuging of the Starch Pulp –Potato pulp after Washing out the Starch by Water (It can be used as the Animal feed also) STARCH - Production from Wheat January 2018/6 NATURAL POLYMERS MU SCI 6 2018 28 •Wheat flour contains approx. 68 % w/w of Starch, what is really much, •It is possible to take approx. 4 tons of Starch from 1 ha of the Cultivated field, so it is the same Quantity as for Potato, •The Water Need is for the production, approx. 3,5 m3/ton of Wheat flour, •It is possible to utilize the Fraction B also and the Waste protein (Gluten) •Dry matter of this Starch is approx. 84 % w/w January 2018/6 NATURAL POLYMERS MU SCI 6 2018 29 img664.jpg Nothing goes to Waste here! Small Grains B Starch are separated and are processed in the Separate Branches I and J Wheat starch factory 1.Mill, 2. Washing machine, 3. Flour sifting machine, 4. Separator, 5. Separator, 6. Evaporator, 7. Mixer, 8. Water suction device, 9. Dryer, 10. Mill, 11. Animal feed Mixer, 12. Reactor for Hydrolysis, 13. Proteins Coagulation, 14. Evaporator A – Wheat, B - Water, C – Water, D – Flour, E – Water returning Stream, F – Starch, G - Wheat middlings, H – Starch, I – Gluten, J – Protein, K - Animal feed 1. STARCH - Production from Corn January 2018/6 NATURAL POLYMERS MU SCI 6 2018 30 •Corn Grain for the Starch production has the following Composition: • img666.jpg The Varieties has been cultivated, containing either mostly AMYLOSE or mostly AMYLOPECTIN The Top Varieties having in the Grain up to 90 % w/w of Starch The Water Need is for the production ( m3/ton of Corn) – I do not know Dry matter of this Starch is approx. 84 % w/w Water Starch Proteins Oil Fibre Ash Pentosans Other January 2018/6 NATURAL POLYMERS MU SCI 6 2018 31 img665.jpg Very similar to Wheat starch factory, up to SOAKING 1.Corn grain silo, 2. Soaking tank, 3. Sprout removing & Milling machine, 4. Sprout processing block, 5. Fine milling, 6. Fibre separation, 7. Liquid part separation, 8. Starch size sorting (Starch refining), 9. Filtration & Dryer, 10. Starch silo, 11. Sprout washing & Dryer, 12. Oil extraction, 13. Oil refining, 14.&15. Evaporator, 16. Drying, 17. Hopper A – Soaking Water, B - Animal feed, C – Sprout, D – Fibre, E – Corn oil, F –Gluten Water, G - Waste Water, H – Starch Suspension for Modification or Syrup, I – Corn eluate (infusion), J – Starch Nothing goes to Waste here! Corn starch factory Starch Products for Food Industry •Sweets, Jam and Marmalade, Drinks, Bakery products, Pastry etc. •Milk Products, Meat Products, Soup (especially dehydrated), Sauce, Salad dressing etc. •Ice cream, Children's nutrition … • • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 32 Starch Products for NONFood Industry •Paper Industry •SIZING IN THE MASS (MATTER), •SURFACE SIZING, •PASTING & PAINTING •TEXTILE Industry •Slashing, Printing, Final treatment, ….. •Gluing •Paperboard, Corrugated paperboard, Multilayer bags, Lamination, …………. • • • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 33 STARCH versus CELULLOSE 1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 34 img672.jpg STARCH is the a-D-glukopyranose polymer CELULLOSE is the b-D-glukopyranose polymer They differ in the Position of –CH2OH toward to -OH Dextrose STARCH versus CELULLOSE 2 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 35 img669.jpg cellobiosa & celulosa.jpg CELULLOSE C4 C1 C4 C1 Notice the Position of the Bond via Oxygen between the Glucose Units STARCH End reducing unit Initial NONreducing unit January 2018/6 NATURAL POLYMERS MU SCI 6 2018 36 img724.jpg STARCH (amylose - linear) versus CELULLOSE 3 STARCH versus CELULLOSE 4 NATURAL POLYMERS MU SCI 6 2018 37 STARCH CELULLOSE Ppolysaccharides Starch & Celullose 001.jpg Ppolysaccharides Starch & Celullose 002.jpg n = 1 > (1®4)-a-D-glukopyranosyl 1-a-D-glukopyranose Ţ MALTOSE n = 1 > (1®4)-b-D-glukopyranosyl 1-b-D-glukopyranose ŢCELOBIOSE n = 1000 ….. 7000 CELULLOSE n = 150 ….. 500 AMYLOSE n = 550 ….. 7500 AMYLOPECTIN, Branching (1®6) on the approx. Each 8 to 10 GLUCOSE unit AMYLOSE & AMYLOPECTIN 1 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 38 img660.jpg AMYLOPECTIN AMYLOSE AMYLOSE (Picture up) AMYLOPECTIN (Picture down) End reducing unit Initial NONreducing unit Point of Branching Separation AMYLOSE - AMYLOPECTIN 2 •Selective enzymatic BREAK DOWN AMYLOPECTIN to Saccharide •Different Solubility of the AMYLOPECTIN and AMYLOSE –Mixture of DMSO + Water > Different Solubilities –Water + NaOH > salt out by NaCl > AMYLOSE in the Solution and AMYLOPECTIN forms the Gel (Separation takes a longer time) • January 2018/6 NATURAL POLYMERS MU SCI 6 2018 39 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 40 Isolation (Separation) of AMYLOSE and AMYLOPECTIN Laboratory instructions Principle Starch is a universal storage Polysaccharide of Plants. It is present in the Form of Starch grains there. There is high Concentration of the Starch in some parts of Plants (Potato tuber, Corn Grain etc.). The Grains are formed from two Structures. AMYLOSE - linear polymer and AMYLOPECTINE - branched polymer. These Polymers is possible to separate on the basis of their different Solubility Isolation (Separation) of AMYLOSE from AMYLOPECTIN Pour to the Beaker of Volume 1000 cm3 360 cm3 0,2 mol.dm-3 of the NaOH solution in Water, 75 cm3. Add 5,3 g of the dry Starch mixed in 35 cm3 in Water and at Temperature 25 °C mix (stir) by glass Stick up clarifying the Solution. Add 125 cm3 of the NaCl Solution (5 % w/w) and neutralize by HCl Solution up to pH 6 – 7. Check the pH Value by test paper. Leave the system stay at laboratory Temperature 20 hours, avoid Sun light. AMYLOPECTIN is separated on the Bottom as the Gel, AMYLOSE remains in the Solution. It is possible to call this as the „SALT OUT “. It is visible influence of ions on the polymer solubility. REMARK: The separated AMYLOPECTIN is possible filter out and AMYLOSE precipitate as the Complex with Butanol. Add 12,5 ml of Butanol to 100 cm3 of the AMYLOSE Solution and leave it stay for 2 hours. AMYLOSE & AMYLOPECTIN 3 SIMILARITY TO Polyethylenes •LDPE •Branched •Higher Melt elasticity •HDPE •Linear •LOWER Melt elasticity January 2018/6 NATURAL POLYMERS MU SCI 6 2018 41 AMYLOPECTIN •Branched •Higher Melt elasticity in the Mixture of Starch - Glycerol AMYLOSE •Linear •LOWER Melt elasticity in the Mixture of Starch - Glycerol • AMYLOSE - AMYLOPECTIN 4 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 42 img669.jpg img671.jpg The Orthophosphoric acid could be bound on AMYLOPEKTIN, especially in the Potato starch. The Cations (K+, Ca+2, Mg+2 etc.) have then influence on the Viscosity of the Water solutions and/or Gels. img673.jpg AMYLOPEKTIN.jpg AMYLOSE - AMYLOPECTIN 5 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 43 Properties Comparision of AMYLOSE - AMYLOPECTIN Property AMYLOSE AMYLOPECTIN Complex with I-1 Colour Blue Red-vilolet Relative MW 103 – 106 107 - 108 Crystallinity by RTG Diffration High crystallinity Amorphous Solubility in Water Different Soluble According to Literature: Radley, J.A. (Editor): Starch and its Derivatives, Chapman and Hall, London 1968 AMYLOSE - AMYLOPECTIN 6 Relativ Average molar mass (MW) AMYLOSE AMYLOPECTIN Source, Remark M n 105 - 106 107 Czech Texbook M w It was not found M ??? n or w 105 - 106 107 - 108 Czech Book January 2018/6 NATURAL POLYMERS MU SCI 6 2018 44 Any case, these Figures are HIGH, at Level (Rank equally ) Synthetic polyolefis (PE, PP) AMYLOSE & AMYLOPECTIN 7 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 45 img269.jpg img270.jpg RETROGRADATION = from a Gel and/or Solution is precipitated POLYMER This Picture concerns WATER SOLUTIONS! AMYLOSE AMYLOPECTIN Bond type a(1®4) a(1®4) and a(1®6) Morphology Crystalline Amorphous, alternatively partly RETROGRADATION Considerable Low A possible structure of the AMYLOPEKTIN branching AMYLOSE & AMYLOPECTIN 8 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 46 TERMOPLASTICKÝ ŠKROB007.jpg TERMOPLASTICKÝ ŠKROB008.jpg G – glucose unit AMYLOSE & AMYLOPECTIN 9 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 47 • AMYLOPECTIN usually prevails in Ratio 4/1 • AMYLOPECTIN does not give BLUE Colour with Iodine • Some Starches, e.g. Pea Starch, contain AMYLOSE only • The other Starches, e.g. Corn cultivar called Waxy Corn (Maize), have MYLOPECTIN only • AMYLOPECTIN has higher MW • ………………. Starch MWD 1 (method GPC) January 2018/6 NATURAL POLYMERS MU SCI 6 2018 48 MWD škrobu scan 18112017001.jpg OXIDATION CRAKS THE MAIN CHAIN > MW LOWERING Starch MWD 2 (method GPC) January 2018/6 NATURAL POLYMERS MU SCI 6 2018 49 MWD škrobu scan 18112017002.jpg What can be done by DMSO, I do not know! VARIOUS Starches > VARIOUS MWD Starch MWD 3 January 2018/6 NATURAL POLYMERS MU SCI 6 2018 50 MWD škrobu scan 18112017003.jpg VARIOUS Starches > almost the Same MWD Starch is the je NATURAL POLYMER And so MWD is different for the same Plants’ Sources Possible deposition of the Fats molecules in the Cereal Starch January 2018/6 NATURAL POLYMERS MU SCI 6 2018 51 TERMOPLASTICKÝ ŠKROB006.jpg Molecule of Fat in the Amylose helix I do not like this Scheme, because Fats are TRIGLYCERIDES and here is only one Helix! There is not enough Space in the Helix of Amylose! SUPRAMOLECULAR STRUCTURE of STARCH January 2018/6 NATURAL POLYMERS MU SCI 6 2018 52 img675.jpg img674.jpg Linear AMYLOSE – Crystallize via Hydrogen bond Branched AMYLOPECTIN – the only enough long Branches can Crystallize. The Basic chain can go trough many such Crystalline parts. Crystalline parts are permeated by and connected by Amorphous parts (NONCrystalline ), as it is in synthetic SEMIKRYSTALLINE polymers Spherollitic Structure of the Starch Particle SUPRAMOLECULAR Structure of the Starch Particle according to Meyer: a)Structure of the Starch layer b)Framework of the branched part after Washing out the Amylose