UNIVERSIDAD NACIONAL SAN ANTONIO ABAD DEL CUSCO ESCUELA DE POST GRADO MAESTRIA EN CIENCIA Y TECNOLOGIA DE ALIMENTOS COMPOSICION Y ANÁLISIS DE ALIMENTOS EPA 01ACT CARBOHIDRATOS – Polisacaridos Dra. Celina Luízar Obregón Polisacáridos Polisacáridos Clasificación de los Polisacáridos Homopolisacáridos de glucosa: • enlace a: almidón, glucógeno (reserva energía) • enlace b: celulosa (fibras pared celular) Heteropolisacáridos: Ej., proteoglicanos de la matriz extracelular Clasificación de los Polisacáridos Clasificación de los Polisacáridos Posición reductora y no reductora Polisacáridos Polisacáridos Almidón Starch is used for energy storage in plants ◦ it can be separated into two fractions; amylose and amylopectin. Each on complete hydrolysis gives only Dglucose ◦ amylose is composed of continuous, unbranched chains of up to 4000 D-glucose units joined by a-1,4glycoside bonds ◦ amylopectin is a highly branched polymer of D-glucose. Chains consist of 24-30 units of D-glucose joined by a1,4-glycoside bonds and branches created by a-1,6glycoside bonds CH2OH H O H OH H H H 1 O OH 6CH OH 2 5 O H 4 OH 3 H OH H H H H 1 O H OH CH2OH CH2OH CH2OH H H H O H OH H O O H H O H OH H O OH 2 OH H OH H OH H amylose Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch. Glucose storage in polymeric form minimizes osmotic effects. Amylose is a glucose polymer with a(14) linkages. The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the reducing end. H OH Amilosa Soluble starch, polymer of D-glucose. Starch-iodide complex, deep blue. => Chapter 23 15 AMILOSA Amylopectin Branched, insoluble fraction of starch. => Chapter 23 17 AMILOPECTINA Almidón y glucógeno CH2OH CH2OH O H H OH H H O OH CH2OH H OH H H H OH CH2OH O H OH H OH OH H H O H OH H H O O H OH H H OH H O amylopectin H 1 O 6 CH2 H 5 H 4 OH 3 H CH2OH O H 1 2 OH H H O CH2OH O H 4 OH H H H H O OH O H OH H H OH H OH Amylopectin is a glucose polymer with mainly a(14) linkages, but it also has branches formed by a(16) linkages. Branches are generally longer than shown above. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can occur. Gránulos de almidón en un embrión de judía Gránulos de almidón en un embrión de judía Celulosa Cellulose is a linear polymer of D-glucose units joined by b-1,4-glycoside bonds ◦ it has an average molecular weight of 400,000, corresponding to approximately 2800 Dglucose units per molecule Both rayon and acetate rayon are made from chemically modified cellulose CH2OH H O H OH H H 1 OH O H H OH 6CH OH 2 5 O H 4 OH 3 H H H 1 2 OH O O H OH CH2OH CH2OH CH2OH H H O O H OH H OH O H O H OH H OH OH H H H H H H H cellulose Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with b(14) linkages. Every other glucose is flipped over, due to b linkages. OH This promotes intra-chain and inter-chain H-bonds and van der Waals interactions, that cause cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles - microfibrils. Schematic of arrangement of cellulose chains in a microfibril. Celulosa b-Glucanos: Celulosa n Celulosa O CH2OH O HO Acetato celulosa O OH n O - CH3COOH O CH2O C CH3 O CH3CO O COCH3 O C O CH3 O O C O CH3 n Nitro celulosa Si de algodón y menor grado de esterificación = algodón pólvora o piroxilina O O CH2OH CH2O NO2 HNO3- H2SO4 O HO O O O O NO2 OH n O NO2 n Celuloide O CH 2O Celulosa NO2 CH 3 C CH 3 O O O O NO2 O NO2 CH 3 n Piroxilina (Grado de nitración 2) Alcanfor Mezcla gelatinizada Primer plástico moldeable de principios siglo pasado Descubierto por John Wesley Hyattt Sustituto del marfil para bolas de billar (explosivas) Carboxi Metil celulosa Carboxymethylcellulose; carmellose; E466 Se trata la celulosa con NaOH concentrada y caliente (cadenas de menor Pm) y después tratar con un R-Cl Espesante y cambiador de cationes Carboxi Metil celulosa Carboxi Metil celulosa Carboxymethylcellulose; carmellose; E466 Carboxymethyl cellulose (CMC) or cellulose gum [1] is cellulose derivative with carboxymethyl groups (-CH2-COOH) bound to some of the hydroxyl groups of the glucopyranose monomers that make up the cellulose backbone. It is often used as its sodium salt, sodium carboxymethyl cellulose. Dietilaminoetil celulosa Diethylaminoethyl cellulose (DEAE or DEAE-C) is a positively charged resin used in ion exchange chromatography, a type of column chromatography, used in protein and nucleic acid purification/separation. Gel matrix beads are derivatized with DEAE and lock negatively charged proteins or nucleic acids into the matrix, until released by increasing the salt concentration of the solvent. DE52 has a pKa of 11.5. DEAE-Dextran (DEAE-D) is also used for transfecting animal cells with foreign DNA. It is added to solution containing DNA meant for transfection. It binds and interacts with negatively charged DNA molecules and via a largely unknown mechanism brings about the uptake of nucleic acids by the cell. This procedure is highly suited for transient transfection used for various molecular biology studies. Dietilaminoetil celulosa Farmacia - laxante Si R= -CH2 -CH2 –N(CH2 –CH3 )2 Espesante y cambiador de aniones Muy utilizado como cambiador de aniones Glycogen Glucose polymer, similar to amylopectin, but even more highly branched. Energy storage in muscle tissue and liver. The many branched ends provide a quick means of putting glucose into the blood. => Chapter 23 51 CH2OH CH2OH O H H OH H H OH H O OH CH2OH H H OH H H OH H H OH CH2OH O H OH O H OH H H O O H OH H H OH H H O 4 glycogen H 1 O 6 CH2 5 H OH 3 H CH2OH O H 2 OH H H 1 O CH2OH O H 4 OH H H H H O OH O H OH H H OH H OH Glycogen, the glucose storage polymer in animals, is similar in structure to amylopectin. But glycogen has more a(16) branches. The highly branched structure permits rapid glucose release from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants. Glucógeno Glycogen is the reserve carbohydrate for animals Like amylopectin, glycogen is a nonlinear polymer of D-glucose units joined by a1,4- and a-1,6-glycoside bonds bonds The total amount of glycogen in the body of a well-nourished adult is about 350 g (about 3/4 of a pound) divided almost equally between liver and muscle Glucógeno Gránulos de glucógeno en el citoplasma de un hepatocito Almidón y glucógeno a Ramificación: amilopectina, 4%; glucógeno, 10% Chitin Polymer of N-acetylglucosamine. Exoskeleton of insects. Chapter 23 57 Chitin Chitin is a long-chain polymer of a N-acetylglucosamine, a derivative of glucose, and is found in many places throughout the natural world. It is the main component of the cell walls of fungi, the exoskeletons of arthropods such as crustaceans(e.g., crabs, lobsters and shrimps) and insects, the radulas of mollusks, and the beaks ofcephalopods, including squid and octopuses. In terms of structure, chitin may be compared to the polysaccharide cellulose and, in terms of function, to the protein keratin. Chitin has also proven useful for several medical and industrial purposes Chapter 23 58 Quitina Quitina Chitin is used in industry in many processes. It is used as an additive to thicken and stabilize foods and pharmaceuticals. It also acts as a binder in dyes, fabrics, and adhesives. Industrial separation membranes and ion-exchange resins can be made from chitin. Processes to size and strengthen paper employ chitin Pectinas Pectin (from Greek πηκτικός pektikos, "congealed, curdled"[1]) is a structural heteropolysaccharide co ntained in the primary cell walls of terrestrial plants. It was first isolated and described in 1825 by Henri Braconnot.[2] It is produced commercially as a white to light brown powder, mainly extracted from citrus fruits, and is used in food as a gelling agent particularly in jams and jellies. It is also used in fillings, sweets, as a stabilizer in fruit juices and milk drinks and as a source of dietary fiber. Pectina Pectins are a family of complex polysaccharides that contain 1,4-linked α-D-galactosyluronic acid residues. Three pectic polysaccharides have been isolated from plant primary cell walls and structurally characterized. These are: Homogalacturonans Substituted galacturonans Rhamnogalacturonans Pectina Pectins are the major components of most higher plant cell walls; they are particularly prevalent in fruits and vegetables. Commercial pectins are prepared mostly from some by-products of the food industry, such as apple pulp, citrus peels, and sugarbeet pulp. Pectins are the most complex class of plant cell wall polysaccharides. They comprise of two families of covalently linked polymers, galacturonans and rhamnogalacturonans (type I) Gomas Exudate gums are polysaccharides produced by plants as a result of stress, including physical injury and/or fungal attack. Gum arabic, gum tragacanth, gum karaya, and gum ghatti have been used by humans for many thousands of years in various food and pharmaceutical applications. Generally, these gums are structurally related to arabinogalactans, galacturonans, or glucuronomannans .They all contain a high proportion of glucuronic or galacturonic acid residues (up to 40%). Gomas Gomas Goma Arábiga (goma acacia) La goma arábiga (E-414) es un polisacárido de origen natural que se extrae de a resina de árboles subsaharianos (Acacia senegal y Acacia seyal) como parte del proceso de cicatrización de éstos (gummosis). La resina de color ámbar se recolecta normalmente a mano una vez seca. Es un polisacárido con cantidades variables de D-galactosa, L-arabinosa, Lramnosa y algunos ácidos derivados como el ácido D-glucorónico o el 4O-metil-D-ácido glucorónico. Se trata de una sustancia de color amarillento a pardo, inflamable aunque con un elevado punto de inflamación (>250 ºC), buena solubilidad en agua (aprox. 500 g/l) y con un LD50 > 16.000 mg/kg. Goma Guar The guar plant is an annual plant known as 'Cyamopsis Tetragonaloba'. The important source of nutrition to human and animals is the legume, it regenerates soil nitrogen and the endosperm of guar seed is an important hydrocolloid widely used across a broad spectrum of industries. Guar Gum mainly consists of hydrocolloidal polysaccharide with a high molecular weight, which consists of galactopyranose- and mannopyranose- units in glycoside linkage which can be chemically described as galactomannan. Goma Guar Goma Guar Tragacanth Gum (Goma tragacanto) La goma tragacanto es un polisacárido obtenido por incisión de tallos de varias especies de Astragalus, que se encuentran en regiones montañosas de Turquía, Siria,Irak, Irán y Rusia It is collected by hand, then graded, milled, and sifted to remove impurities. Tragacanth gum contains a water-soluble fraction and a water-insoluble fraction and the water-soluble fraction is accounted for 30 to 40% of the total gum. Astragalus gummifer Labillardiere Tragacanth Gum (Goma tragacanto) La goma es de color blanco o blanco amarillento muy pálido, traslúcida y córnea. Se rompe con fractura breve, es inodora y tiene ligero sabor. Cuando se pone en agua, la goma tragacanto se hincha, dando una masa gelatinosa, pero sólo se disuelve una pequeña porción. The water soluble fraction is a highly branched neutral polysaccharide composed of 1→6-linked D-galactosyl backbones with L-arabinose side chains joined by 1→2-, 1→3- and/or 1→5-linkages. The water-insoluble fraction (~60 to 70%), is tragacanthic acid which is consisted of D-galacturonic acid, Dgalactose, L-fucose, D-xylose, L-arabinose and L-rhamnose. It has a (1→4)linked α-D-galacturonopyranosyl backbone chain with randomly substituted xylosyl branches linked at the 3 position of the galacturonic acid residues. Tragacanth Gum (Goma tragacanto) La formación de la goma tragacanto es completamente distinta a la de la goma arábiga, pues la goma exuda inmediatamente después de herir el árbol y, por tanto, estará preformada en la planta, mientras que la goma arábiga se produce lentamente después de la herida. Un corte del tallo de la planta muestra que las membranas celulares de la médula y radios medulares se transforman gradualmente en goma, proceso denominado gomosis. La goma absorbe agua y da lugar a una considerable presión dentro del tallo