NATURAL POLYMERS MU SCI 6 2018 1 NATURAL POLYMERS Polysaccharide I STARCH 3 Dr. Ladislav Pospíšil January 2018/6-3 Time schedule January 2018/6-3 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 Why do we modify the STARCH? January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 3 •HIGH VISCOSITY at even low Concentrations •LOW SOLUBILITY & DISPERSIBITY of the Starch particles •Strong Tendency to form stiff, threedimesional GEL (it is sometime advantageous, e.g. Cooking of a Blancmange (Pudding)) AMYLOSE & AMYLOPECTIN January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 4 img669.jpg img671.jpg Where are a Potential Reactions Centres in these MACROMOLECULES? BRANCHING MAIN CHAIN AMYLOPEKTIN.jpg January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 5 img742.jpg AMYLOSE •It forms the HELIX •Six GLUCOSE units are forming one Chain Spiral (Coil) •Bond 1 ® 4 via –OH • 300 – 1000 Units in a Macromolecule January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 6 AMYLOSE INTRAMOLECULAR HYDROGEN BONDS vodíkové můstky ve škrobu001.jpg These BONDS (Bridges) go via – OH Groups, no via Water Molecules. Water forms BONDS (Bridges) mainly between Macromolecules of Amylose, but not only there (AMYLOPECTIN is also employed). OXYGEN January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 7 img743.jpg AMYLOPECTIN •USUALLY doesn't form HELIX (ONLY HAVING VERY LONG BRANCHING CHAINS IS IT POSSIBLE) •Bond 1 ® 6 via –OH and via – CH2OH in the Point of Branching •Bond 1 ® 4 via –OH in the Main Chain and also in side Chains • 15 – 25 Units in the Branches Process of ENZYMATIC modification of Starch January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 8 img681.jpg RAPID DECREASE OF THE SOLUTION (PASTE) VISCOSITY Chain scission by Enzym Amylase Process of ENZYMATIC modification of Starch to MALTOSE img682.jpg January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 9 Chain scission to MALTOSE by Enzymes a and b AMYLASES MALTOSE is possible further scission up to GLUCOSE by Enzyme MALTASE Extent of Conversion accordingly it is possible classify these Products to: 1.Liquid syrups 2.Dried or thicken syrups 3.Glucose January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 10 img744.jpg AMYLOSE Chain scission by Enzymes (a, b, g Amylases, Phosphorylase, R-enzyme … Process of HYDROLYTIC modification of Starch img682.jpg January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 11 Acid catalysis using HCl or H2SO4 with Neutralisation after the end of Hydrolysis Extent of Conversion accordingly it is possible classify these Products to: 1.Liquid syrups 2.Dried or thicken syrups 3.Glucose It is possible to combine HYDROLYTIC and ENZYMATIC Chain scission Process of HYDROLYTIC modification of Starch January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 12 img684.jpg img683.jpg There are not valid Proofs, if this Process is random or are there some Bonds in the Chain preferred Chain scission – Chemical catalysis by H+ Chain scission – Chemical catalysis by H+ ENZYMATIC USE OF GLUCOSE from Saccharide to Alcohol January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 13 Alpha-D-Glucopyranose_svg.png 120px-Pyruvate.png 120px-Acetaldehyde-2D-flat_svg.png Ethanol-structure_svg.png Pyruvite of conjugated Base of the Pyruvic acid Vodka (in Russian) Gorilka (in Ukrainian) Schnaps (German) Whisky (ENGLISH) Rye whiskey, Grain alcohol (Czech) Potato Spirit > Domestic RUM ENZYMATIC (Xylose isomerase) isomerisation of GLUKOSE to FRUCTOSE January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 14 490px-D-Fructose_vs__D-Glucose_Structural_Formulae_V_1_svg.png GLUCOSE (ALDOSE) FRUCTOSE (KETOSE) D-xylose aldose-ketose-isomerisation FRUCTOSE is approx. of 1/5 more sweet then GLUCOSE. It is found mainly in the Fruit. GENERAL SORTING OF the POLYMER REACTIONS January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 15 •POLYMERANALOGIC REACTIONS –It doesn't occur any DESIRABLE Chain scission of the MAIN Macromolecules’ Chains •DESTRUCTION REACTIONS –It occurs a DESIRABLE Chain scission of the MAIN Macromolecules’ Chains Both Reactions are usual at POLYSACCHARIDES Summary of the STARCH MODIFICATIONS •Enzymatic •Thermal •Chemical –Hydrolysis –Oxidation –Esterification (several variants) –Starch Xanthate –Starch Carbamate –Starch ethers •Crosslinking •Grafting – January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 16 Principal Use of STARCH January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 17 STRACH PROPERTIES INDUSTRIAL BRANCH Viscosity increasing Food Industry Gels’ Formation Water Retention Adhesive Properties Paper Industry Film Forming Textile Industry Biodegradable Properties Biodegradable products, e.g. Bags etc. Protective Colloidal Films Polymer Dispersions Starch Modification 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 18 It could be MECHNICAL (sorting particle size accordingly) or in Solution (sorting AMYLOSE and AMYLOPECTIN) Classification of the Starch Modification technology according to the Chemical Connections Starch Fractionation AMYLOSE AMYLOPECTIN Substitution Starch Ether Starch Ester Crosslinked Starch Hydrolysis Oxidation Degradated Starch Oxidised Starch Thermal Modification Thermal Modified Starch Starch Modification 2 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 19 MODIFIKACE ŠKROBU 2.jpg It could be or is MECHNICAL (sorting Particle size accordingly) It is the case of mainly the Heterogeneous Reaction There is great Effort to do these Processes in the SUSPENSION! WHY? Basic Scheme of the Starch Modification Water Waste Water Waste Water Starch Starch Suspension Preparation Substances for Modification and Catalysts Chemicals to interrupt the Main Reactions Water Modification Reaction Interruption of the Reactions Rafination Fitration Drying Processing of the Dry Matter Starch Modification 3 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 20 1.Chemical Modification in the Water Suspension •Hydrolysed Starch •Oxidised Starch • Starch Ether • Starch Ester • Crosslinked Starch 2.Chemical Modification in the Water Solution •Hydrolysed Starch •Oxidised Starch • Starch Ether 3. 3.Chemical Modification in the Organic Solvent Solution • Starch Ether • Starch Ester 4. 4.Thermal Modification in Dry State • Degradated Starch • Oxidised Starch • Starch Ester • Crosslinked Starch 5. 5.Thermal Modification in presence of Water PREFERED Starch Thermal Modification – EXAMPLE 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 21 •Starch Water Suspension Cover on the heated Roll •Starch Paste formation, Hydrogen bonds between Starch Molecules breakage, •Water is so rapidly evaporated, that Hydrogen bonds between Starch Molecules can’t arise again •Dry Starch is formed from no-associated Macromolecules •Such Dry Starch is easy soluble in Water Starch Thermal Modification 2 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 22 termická modifikace škrobu 001.jpg Formation of Starch Paste and Hydrogen bonds between Starch Molecules breakage Water is so rapidly evaporated , that Hydrogen bonds between Starch Molecules can’t arise again Dry Starch is formed from no-associated Macromolecules ASOCIOATED Starch MOLECULES Starch Thermal Modification – Technology Diagram 3 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 23 img685.jpg The actual Process occurs here! Scrape away of the Dry Starch film The Classical Thermal Starch Modification 1) Dry Starch Hopper, 2) Automatic balances, 3) Mixer, 4) Metering pump, 5) Heated Roll, 6) Pregrinder, 7) Fan, 8) Cyclon, 9) Impact Mill, 10) Turnstile, 11) Dry product Hopper NONSELECTIV Oxidation of Starch 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 24 img687.jpg Oxidation of the CARBONYL GROUP in the OPEN FORM of GLUCOSE to -COOH Oxidation of the – OH in CYKLIC FORM of GLUCOSE to =C=O and then up to -COOH Oxidation of the CYKLIC FORM of GLUCOSE by opening between C2 a C3 C2 C3 C6 Oxidation of Starch January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 25 •The most Important Modification Reactions •It can be done in both low and high pH Regions •The most Important is the Oxidation by sodium hypochlorite in the pH Region approx. 8 – 9 (slightly basic conditions) •It is used mainly for the Potato Starch, having high Capillarity and low Tendency to Retrogradation • NONSELECTIV Oxidation of Starch –Technology Diagram January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 26 img686.jpg TYPICAL FORMULATION • pH = 8 – 9 • TEMPERATURE = 35 – 43 °C • Reaction time = 2 – 8 hours • activ chlorine (NaClO) = 3 – 45 g/kg Starch DEPOLYMERISATION in ALKALINE CONDITION > LOWERING of the MOLECULAR MASS (WEIGHT) Water Water Waste Water Waste Water Fitration Drying Rafination Starch Starch Suspension Preparation Oxidation Interruption of the Oxidation Neutralisation 3 % w/w Water Solution NaOH SELECTIV Oxidation of Starch on C 6 from –OH on – COOH using HNO3 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 27 Alpha-D-Glucopyranose_svg.png C 6 The Polymerisation Degree is not changing at such Oxidation – POLYMERANALOGIC CONVERSION SELECTIV Oxidation of Starch to Starch dialdehyde January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 28 img688.jpg The Polymerisation Degree is not changing at such Oxidation in the Ideal case – POLYMERANALOGIC CONVERSION Such Oxidation is performed by Periodic acid in the Special configuration so, that the Periodic acid is regenerating by Electrolysis Starch dialdehyde Starch Oxidation - SUMMARY January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 29 •Higher Oxidation > Higher Chain scission > Lower Viscosity •Higher Chain scission > Lower Binding ability •Higher Chain scission > Higher Dispersion Stability. It is lower Retrogradation Tendency •High Porosity (Capillarity) Starches are suitable for Heterogeneous Reaction, because having higher Surface able to be Reaction Site • DEXTRIN PRODUCTION 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 30 img689.jpg img690.jpg 12 – 24 hours, for going through of Acids and/or Bases & Solutions of Additives Starch Particles Chilling Starch Agein Neutralisation Predrying Solution of the Modification Substances Starch Impregnation by Modification Substances Roasting Potassium aluminum sulfate Classification by Sieve (screening) Solution of Substances for Neutralisation DEXTRIN PRODUCTION 2 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 31 img691.jpg It is fact STARCH HYDROLYSIS followed by POLYMERISATION (COMBINATION) of FRAGMENTS Starch Acid Catalysis Water Heat Acid Polymerisation Heat Acid Fragments of Hydrolysis DEXTRIN Starch to DEXTRIN January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 32 img113.jpg img114.jpg DEXTRIN PRODUCTION DIAGRAM DEXTRINATION CLASSICAL PAN heated by Gas DEXTRIN FACTORY: 1) Starch Hopper, 2) Acid Addition, 3) Agein, 4) Predrying, 5) Pans, 6) Dextrin Chiller, 7) Humidification Tower, 8) Homogesitation and Screening , 9) Dextrin Packaging, 10) Tank for Acid or Potassium aluminum sulfate Solution January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 33 DE – Dextrose Equivalent = GLUCOSE EKVIVALENT = %w/w reducing saccharides in dry dextrin Starch itself is not reducing SACCHARIDE DEXTRIN – BASIC CHARACTERISTICS Characteristic Starch DEXTRIN TYPE Approximate Production Conditions White Light yellow Yellow Yellowbrown T = 135 °C, 0,05 – 0,15 % w/w HCl T = 150 °C, 0,05 – 0,15 % w/w HCl T = 165 °C, 0,05 – 0,15 % w/w HCl T = 180 °C, 0,05 – 0,15 % w/w HCl MW AMYLOSE 30 000-160 000 & AMYLOPECTIN 100 000 - 1 000 000 20 – 30.103 15000 - 2000 8000 - 3000 Approx. 2000 Solubility in Water 0 30 – 70 % w/w Approx. 95 % w/w Approx. 97 % w/w Up to 99 % w/w DE 0 2 – 3 % w/w 2 – 5 % w/w 2 – 8 % w/w 2 – 5 % w/w ? Colour of the Iodine Complex Blue Blue -vilolet Red-vilolet Red No Colour Viscosity Decreasing DEXTRINS’ STRUCTURES January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 34 320px-Dextrin_skeletal_svg.png Process of so called „DEXTRINATION“ occurs also during e.g. baking of Bread! It is the brown Bread Crust DEXTRINS’ PROPERTIES & THE OTHER DEXTRIN TYPES •Colour from WHITE over Yellow to Brown •They are usually fully soluble in Water •OTHER TYPES OF DEXTRINS •Maltodextrin •is a shortchain starch sugar used as a food additive. It is produced also by enzymatic hydrolysis from gelled starch and is usually found as a creamy-white hygroscopic spraydried powder. Maltodextrin is easily digestible, being absorbed as rapidly as glucose, and might either be moderately sweet or have hardly any flavor at •all. •Cyclodextrin •The cyclical dextrins are known as cyclodextrins. They are formed by enzymatic degradation of starch by certain •bacteria, for example, Bacillus macerans. Cyclodextrins have toroidal structures formed by 6-8 glucose residues. January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 35 Energy Gels and Bars DEXTRINS’ USE January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 36 •Yellow dextrins •water-soluble glues in remoistable envelope adhesives and paper tubes, •in the mining industry as additives in froth flotation, in the foundry industry as green strength additives in •sand casting, as printing thickener for batik resist dyeing, and as binders in gouache paint. •White dextrins •a crispness enhancer for food processing, in food batters, coatings, and glazes, (E number 1400) •a textile finishing and coating agent to increase weight and stiffness of textile fabrics •a thickening and binding agent in pharmaceuticals and paper coatings. •As pyrotechnic binder and fuel, they are added to fireworks and sparklers, allowing them to solidify as pellets or "stars." •Due to the rebranching, dextrins are less digestible; indigestible dextrin are developed as soluble fiber supplements for food products. CYCLODEXTRINS January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 37 820px-Cyclodextrin_svg.png In CYCLODEXTRIN molecule can be absorbed ethanol (alcohol) and so is formed so called „alcohol in Powder“, which is releasing alcohol when pouring in Water DEXTRINS - SUMMARY January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 38 •PROBABLY the most Commonly used Product of the Starch Modification •It is substantial chemical transformation of Starch •Very wide Types’ Range of Use •Well sophisticated both continual and discontinuous technology •Process is employed at least since 19. Century Acetylation of Starch January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 39 img693.jpg img694.jpg Side Reaction lowering the Output January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 40 img695.jpg • The Result is ANIONIC STARCH with LOW SUBSTITUTION LEVEL (0,02 – 0,1 g substitution Agent per 1000 g dry Starch). That is enough for good Water solubility in the cold Water. • The Crosslinking can occur simultaneously, but where is HIGH SUBSTITUTION LEVEL (0,1 – 0,2 g substitution Agent per 1000 g dry Starch), sometimes even over 1 (Corn Starch no swelling even in the Boiling Water even) Sodium Monophosphate is employed here! Starch Monophosphate is resulting via the Following Reaction: Starch Monophosphate January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 41 Starch Xanthate img696.jpg Starch Xanthate Starch Xanthate is resulting via the Following Reaction of CS2 and Starch Starch alkylethers January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 42 Starch Carbamate img698.jpg img700.jpg Starch alkylether Starch Starch Starch Starch Starch Starch Starch Hydroxymetylether January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 43 Starch Carboxymettylether img699.jpg img701.jpg img702.jpg Starch Starch Starch Starch Starch Starch Starch Starch Starch Starch Starch Starch Reaction Mechanism is showing the following Equation: Starch Hydroxymetylether Glycolic acid Lactone 101px-Glycolic_acid_svg.png Cationic Starch 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 44 img705.jpg + Starch Starch Starch Starch Starch Starch Starch Starch Starch Quaternary Derivatives are resulting via Reaction of Starch with Halogen Quaternary Derivatives of amonium Base Cationic Starch 2 – PAPER PRODUCTION January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 45 škroby katio a anio v papírovině001.jpg From CELULLOSE! škroby katio a anio v papírovině002.jpg Addition of the CATIONIC STARCH improves Retention so called Extremely short Fibres, which arise from both waste Paper and Paper production Waste ANIONIC STARCH needs for acting Cation Al+3, usually from KAl(SO4)4 (Potassium aluminum sulfate) Diagram showing Influence of Ionogenic Starch Derivatives Cationic Starch Anionic Starch Cationic Starch Anionic Starch Crosslinked Starch 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 46 img706.jpg Starch Starch Starch Starch Starch Starch Starch Starch Starch Starch Diphosphate can results from the following Reaction also: Starch Diether results via the following Reaction of Starch and Epichlorhidrine in alkaline Medium : Crosslinked Starch 2 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 47 síťování škrobu trifosfátem sodným 001.jpg • Crosslinked Starch has HIGH SUBSTITUTION LEVEL sometimes even over 1 g substitution Agent per 1000 g dry Starch > Powdering agents in Pharmacy • ANIONIC STARCH can be formed simultaneously, but there is LOW SUBSTITUTION LEVEL (0,02 – 0,1 g substitution Agent per 1000 g dry Starch), Trisodium phosphate is used here! Graft & Block Starch copolymers January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 48 img710.jpg img709.jpg img708.jpg Starch Starch Starch grafting Diagram Starch Block Copolymerisation Diagram Starch Block Copolymerisation Diagram Use of the Modified Starches •Paper Production and Treatment •Food Industry •Textile Industry •Glues •Pharmacy •Flocculants for Waste Water Treatment •…………….. January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 49 Starch Glue (Adhesive) January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 50 škrob + NaOH.jpg lepidlo ze škrobu.jpg The Potato and Corn Starches Mixture is usually used by Industry Starch Starch Starch Starch Starch The Reactivity of Starch in Nucleofilic Substitutions is generally increased by Activation by Alkali via forming the alkali Salt, sometime formulated as STARCH – ALKALI COMPLEX LABORATORY EXAMPLE OF THE STARCH GLUE PREPARATION Approx. 20 g of Starch mix with 50 ml of cold Water and pour into approx. 200 ml of boiling Water containing 5 g NaOH. Boil at permanent mixing. The Glue is finished, when the Viscosity has increased and the Solution is clear enough. The Glue is finished then. Add approx. 10 Drops of Formaldehyde to avoid Moulding. Starch as the BIODEGRADABLE ADITIVE to Synthetic THERMOPLASTICS January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 51 •The Degradation is usually necessary „PUSH AHEAD“ by Thermo oxidation •What was done by me •BIODEGRADABLE LDPE films (up to 40 % w/w Corn Starch ) •The Inner part of the Shotgun shell •PP Fibres with Starch Polypropylene Fibres with Corn Starch 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 52 PP skrob 1kx.jpg PP skrob 2kx.jpg Polypropylene Fibres with Corn Starch 2 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 53 PP skrob 5kx b.jpg PP skrob 5kx M.jpg FIBRILATIONPP Fibres THERMOPLASTIC STARCH •Processing by Technologies used for the SYNTHETIC THERMOPLASTICS, but very difficult (UP TO NOW) •It is necessary to use so called PLASTICIZERS – usually WATER & GLYCEROL •Products are BIODEGRADABLE •If combined with NATURAL FIBRES (e.g. Flax) > BIODEGRADABLE COMPOSITS • • January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 54 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 55 Ewa Rudnik: Compostable Polymer Materials, ISBN: 978-0-08-045371-2 TERMOPLASTICKÝ ŠKROB010.jpg January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 56 TERMOPLASTICKÝ ŠKROB002.jpg TERMOPLASTICKÝ ŠKROB009.jpg PLASTICIZERS – usually WATER & GLYCEROL AGAR January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 57 AGAR & Food Industry • Clarifying (Fining) of the Wine and Fruit Juice • Thickening of Food AGAR & Medicine Bacterial and Mould culture/growth medium Agar consists of a mixture of agarose and agaropectin. Agarose, the predominant component of agar, is a linear polymer, made up of the repeating monomeric unit of agarobiose. Agarobiose is a disaccharide made up of D-galactose and 3,6-anhydro-L-galactopyranose. Agaropectin is a heterogeneous mixture of smaller molecules that occur in lesser amounts, and is made up of alternating units of D-galactose and L-galactose heavily modified with acidic side-groups, such as sulfate and pyruvate. pyruvic acid 1024px-Pyruvic-acid-2D-skeletal.png The other useful POLYSACCHARIDES 1 January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 58 Plantago ovata, known by many common names including blond plantain,[1] desert Indianwheat, blond psyllium, and ispaghul, is a medicinal plant native to Western Asia and Southern Asia. The plant can be found growing wild in the southwestern United States, where it is considered a possibly introduced species. It is a common source of psyllium, a type of dietary fiber. Psyllium seed husks are indigestible and are a source of soluble fiber which may be fermented into butyrate – a pharmacologically active short-chain fatty acid – by butyrate-producing bacteria. The other useful POLYSACCHARIDES 2A January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 59 arabinose.jpg glucose.jpg mannose.jpg xylose.jpg They are HETEROPLYSACCHARIDES PENTOSE HEXOSE Plant mucilages The other useful POLYSACCHARIDES 2B January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 60 They are HETEROPLYSACCHARIDES Plant mucilages is made of plant-specific POLYSACCHARIDES or long chains of sugar molecules.This polysaccharide secretion of root exudate forms a gelatinous substance that sticks to the caps of roots. Root mucilage is known to play a role in forming relationships with soil-dwelling life forms. Just how this root mucilage is secreted is debated, but there is growing evidence that mucilage derives from ruptured cells. As roots penetrate through the soil, many of the cells surrounding the caps of roots are continually shed and replaced. These ruptured or lysed cells release their component parts, which include the polysaccharides that form root mucilage. These polysaccharides come from the Golgi apparatus and plant cell wall, which are rich in plant-specific polysaccharides. Unlike animal cells, plant cells have a cell wall that acts as a barrier surrounding the cell providing strength, which supports plants just like a skeleton. January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 61 Building Unit Structure Unit 453px-Alginsäure_svg.png ALGINATE Molar mass 10,000 – 600,000 Alginic acid is a linear copolymer with homopolymeric blocks of (1-4)-linked β-D-mannuronate (M) and its C-5 epimer α-L-guluronate (G) residues, respectively, covalently linked together in different sequences or blocks. L-gulopyranuronic acid January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 62 Alginate absorbs water quickly, which makes it useful as an additive in dehydrated products such as slimming aids, and in the manufacture of paper and textiles. It is also used for waterproofing and fireproofing fabrics, in the food industry as a thickening agent for drinks, ice cream and cosmetics, and as a gelling agent for jellies.[citation needed] Alginate is used as an ingredient in various pharmaceutical preparations, such as Gaviscon, in which it combines with bicarbonate to inhibit reflux. Sodium alginate is used as an impression-making material in dentistry, prosthetics, lifecasting and for creating positives for small-scale casting. Sodium alginate is used in reactive dye printing and as a thickener for reactive dyes in textile screen-printing.[citation needed] Alginates do not react with these dyes and wash out easily, unlike starch-based thickeners. As a material for micro-encapsulation.[7] Calcium alginate is used in different types of medical products including skin wound dressings to promote healing[8] and can be removed with less pain than conventional dressings.[ January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 63 komplexa kationtu Ca+2 alginátem 05082017.jpg Complex of the Cation Ca+2 by Alginate – model „Egg in the Package“ January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 64 Building Unit Structure Unit Chondroitin_Sulfate_Structure_NTP.png Chondroitin Chondroitin is a glycosaminoglycan (GAG) composed of a chain of alternating sugars (N-acetylgalactosamine and glucuronic acid). It is usually found attached to proteins as part of a proteoglycan. A chondroitin chain can have over 100 individual sugars, each of which can be sulfated in variable positions and quantities. Chondroitin sulfate is an important structural component of cartilage and provides much of its resistance to compression.[1] Along with glucosamine, chondroitin sulfate has become a widely used dietary supplement for treatment of osteoarthritis. Chemical structure of one unit in a chondroitin sulfate chain. Chondroitin-4-sulfate: R1 = H; R2 = SO3H; R3 = H. Chondroitin-6-sulfate: R1 = SO3H; R2, R3 = H. b-D-glucopyranuric acid January 2018/6-3 65 NATURAL POLYMERS MU SCI 6 2018 Chondroitin - Medical use Although chondroitin is used in dietary supplements as an alternative medicine to treat osteoarthritis and also approved and regulated as a symptomatic slow-acting drug for this disease (SYSADOA) in Europe and some other countries, it is technically neither a medicine nor a disease-modifying treatment. See Clinical effects below. It is commonly sold together with glucosamine. Chondroitin and glucosamine are also used in veterinary medicine. Formulated with collagen and wound dressing matrix, one product that uses chondroitin sulfate is the veterinary wound gel Chondroprotec, which is applied over scrapes, burns, and lesions and serves to keep the wound moist and promote healing. Chondroitin, along with commonly used glucosamine, should not be used to treat patients who have symptomatic osteoarthritis of the knee as evidence shows that these treatments fail to provide relief for that condition. GUAR GUM - Plant gum January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 66 620px-Guaran_svg.png Chemically, GUAR GUM IS A POLYSACCHARIDE composed of the sugars galactose and mannose. The backbone is a linear chain of β 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short sidebranches. Thickening of Food, because having great influence on the Viscosity Increase, even at very low Concentration SCIENTIFIC (EXACT) Biodegradability Evaluation of Disposable PLASTIC shopping Bags in Compost January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 67 biodegradace ODNOSNÝCH PLASTOVÝCH TAŠEK 001.jpg It was done & published by: Mendel Agriculture and Forestry University in Brno, Faculty of Horticulture This Article was published in the Czech journal „ODPADY“ (WASTE) last year January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 68 „Bio plastics“ shopping Bags tested Sample Sample Denomination Material STATEMENT 1 100 % degradable shoping Bag KAUFLAND HDPE, TDPA – fully degradable plastic Additives 2 shoping Bag TESCO HDPE, PE Pllets + special Additives D2W 3 Compostable degradable shoping Bag A BIOflex 219 F 4 Compostable degradable shoping Bag B Starch, PCL - polylactone 5 Compostable degradable shoping Bag C Starch, PCL – polycaprolactone, Mater-Bi 6 „BIOBAG“ for dogs Excrements Starch, PLA 7 Mater-Bi Bioplastics Mixture, Corn Starch + Additives 8 shoping Bag COOP Oxo-degradable plastic, Fe, Mn and Co ions + Additive D2W January 2018/6-3 NATURAL POLYMERS MU SCI 6 2018 69 biodegradace ODNOSNÝCH PLASTOVÝCH TAŠEK 005.jpg Sample 7 (after 12 Weeks) Almost undestroyed Samples 2, 8 and 1 (after 6 Months) „Bio plastics“ shopping Bags tested Sample After 3 Months in the Compost After 6 Months in the Compost 1 Partly decomposed, approx. 10 % Partly decomposed, approx. 10 % and Brittle Material 2 Partly decomposed, approx. 10 % Partly decomposed, approx. 10 % and Brittle Material 3 Partly decomposed, approx. 10 %, some Cracks Partly decomposed, approx. 50 % 4 Partly decomposed, approx. 30 % Decomposed, 100 %, all Materials are Starch based 5 Decomposed, 100 % 6 Decomposed, 100 % 7 Decomposed, 100 % 8 Partly decomposed, approx. 5 % Partly decomposed, approx. 10 % and Brittle Material