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5. SACCHARIDES sugars classification according number of sugar molecules monosaccharides oligosaccharides (2-10 monosacharides) polysaccharides ( 10 monosacharides) conjugated (complex) saccharides free bound homoglycosides, heteroglycosides, aglycons (non-sugar components) Monosaccharides polyhydroxyalkyl substituted aldehydes a ketones and derived compounds main nutrients, biological and sensory activites content (book 1, tab. 4.4, 4.5) structure and classification according to type of carbonyl group aldoses ketoses H C O C O according to number of C atoms (3-8) trioses 1 CH O 2 H C * OH 3 CH2OH CH O CH O * OH H C* OH CH2OH CH2OH H CH O D-(+)-glyceraldehyde (D-glycero-triose) optical isomers (enantiomers) D/L, HO C* H CH2OH L-(-)-glyceraldehyde R/S d/l, +/- CH2OH C O CH2OH 1,3-dihydroxyacetone (1,3-dihydroxypropane-2-one, glycerone) tetroses pentoses, hexoses CH O H HO H H C* OH C* H C* OH C* OH CH2OH CH2OH C O HO C* H H C* OH H C* OH CH2OH D-glucose (D-gluko-hexosa) D-fructose (D-arabino-hex-2-ulose) dextrose, grape sugar levulose, fruit sugar according to chain linear chain branched chain according to type of lactol 2 2 R OH 1 1 R OH O H OR 2 OR aldehyde 2 R CH R CH R CH O OR 1 semiacetal acetal furanose pyranose CH2OH O OH OH * O 5 OH * 1 OH HO OH HO CH2 -D-fruktopyranosa -D-glukofuranosa OH CH2OH HO CH2 O O HO * HO * CH2OH OH OH OH OH -D-fruktopyranosa -D-glukofuranosa CH2OH HO * OH OH O OH HO * OH OH * OH HO OH -D-glukopyranosa O CH2OH HO * 2 OH HO OH -D-glukopyranosa HO HO HO HO OH 5 CH2OH CH2OH CH2OH -D-fruktofuranosa -D-fruktofuranosa mutarotation anomers, anomeric C, anomeric OH -pyranosa -pyranosa acyklická forma -furanosa -furanosa conformation furanoses (envelope E, twist T) pyranoses (chair 4C1, 1C4) acyclic forms (cik-cak) occurrence present in all food less typical monosaccharides CH2OH CH2OH H HO CH O HO OH H CH2OH CH2OH HO O O HO H H HO H OH H OH H H OH CH2OH CH2OH D-apiose L-sorbose D-manno-hept-2-ulose branched sugar root vegetables rowanberries ketoheptose avokado 2 abbreviations glucose fructose mannose apiose sorbose Glc Fru Man Api Sor furanose pyranose acid -D-glukopyranose f p A -D-Glcp derivatives of monosaccharides formation oxidation (or rearrangement) sugar acids ketoaldoses, diketoses suger alcohols deoxysugars anhydrosugars glycosides ethers esters amino sugars reduction dehydration reaction with other compounds sugar acids content in malt and chicory (book 1, tab. 4.10) aldonic Ca-gluconan (medicine), -laktone (fermented salami, 0,1 %) alduronic polysaccharidy: D-GlcA6 (glycoproteins), D-GalA6 (pectins), D-ManA6 a L-GulA6 (alginates) aldaric, for example tartaric and malic acids ketoaldoses, diketoses main products of Maillard reaction and oxidation 3-deoxyglycosuloses 1-deoxyglycodiuloses 4-deoxyglycodiuloses CH O CH3 C O C O CH2 C C OH H H C O H C OH OH H C CH2OH OH CH2OH o 3-deoxy-D-erythro-hexos-2-ulosa 1-deoxy-D-erythro-hexo-2,3-diulosa CH O CH2OH C O C C O O HO C H CH2 H C OH H C OH H C OH CH2OH CH2OH 4-deoxy-D-glycero-hexo-2,3-diulosa -arabino-hexos-2-ulosa D sugar alcohols 3 alditols, glycitols (homologues of glycerol) reduction content (book 1, tab. 4.7 a 4.8) CH2OH CH2OH H C OH CH2OH H C OH H C H C OH HO C H C OH H C CH2OH ribitol CH2OH HO C OH H HO C H HO C H H H C OH H C OH OH H C OH H C OH CH2OH CH2OH xylitol CH2OH D-glucitol D-mannitol natural components of food ribitol riboflavin arabinitol mushrooms xylitol mushrooms D-glucitol plums, rowanberries, pears D-mannitol mushrooms, rowanberries, celery, green coffee galactitol mushrooms, fermented milk products synthetic (reduction H2/catalyst., NaHgx, sweetners) xylitol, D-glucitol cyclitols content (book 1, tab. 4.9) cyclohexane-1,2,3,4,5,6-hexols (inositols, cycloses) OH OH OH OH 2 OH 1 6 OH OH HO OH 3 4 HO OH HO HO OH HO 5 OH OH myo-inositol ( meso-inositol) OH 1D-(+)-chiro-inositol 1L-(-)-chiro-inositol OH OH OH OH OH OH OH OH HO OH HO HO HO OH scyllo-inositol (scyllitol) HO OH OH neo-inositol allo-inositol OH OH OH OH OH OH OH HO OH HO OH HO epi-inositol OH HO OH HO HO myo-inositol pseudooligosaccharides o OH muko-inositol cis-inositol widespread” phospholipids, fytates pulses myo-inositol D-galaktosa CH2OH HO OH 5 O 6 OH 1 OH 1 O 2 OH HO 4 3 OH OH galaktinol deoxysugars reduction of primary / secondary hydroxyl natural 4 Maillard reaction 2-deoxysugars CH2OH O 2 H OH OH H 2-deoxy-D-ribose (thyminose) deoxyribonucleic acids 6-deoxysugars (6-deoxyhexose = methylpentose) CH3 6 HO 6 O CH3HO OH 6 O CH3 HO O OH OH OH HO OH OH OH OH L-fucose L-rhamnose D-chinovose 6-deoxy-L-galactose 6-deoxy-L-mannose 6-deoxy-D-glucose milk oligosaccharides heteroglycosides heteroglycosides anhydrosugars sugar anhydrides, glycosans water elimination, mostly poloacetal and other OH natural components of polysaccharides CH2 HO O O OH OH 3,6-anhydro--D-galactopyranose (carageenan) 3,6-anhydro--L-galactopyranose (agar) products of thermal reactions O CH2 O OH HO OH 1,6-anhydro--D-glucopyranose (-glucosan, levoglucosan) (caramel) glykosides, ethers, esters and other derivatives O CH2OH CH2OH O O R R C O CH2 O OH OH O OH OH HO OH HO HO OH O-glykosid ether CH2OH O S OH OH O R ester CH2OH CH2OH R O OH O NH R OH OH HO HO HO OH S-glykosid OH N-glykosid NH2 2-amino-2-deoxycukr 5 O-glykosides ethers esters S-glycosides N-glycosides aminodeoxysugars C-glycosides widespread 4-O-methyl-D-GlcpA (hemiceluloses) 2-O-methyl-D-Xylp (pectins) natural (phosphates, acetates, benzoates etc.), synthetic (fatty acids, emulgators) glucosinolates in brassica vegetables natural (ATP, NADH), Maillard reaction (glycosylamines) natural (chitosamine), Maillard reaction (Amadori products) OH O HO CH2OH O OH HO OH OH CO OH OH O CH3 karminovÿá kyselina (anthrachinony) carminic acid Oligosaccharides homoglycosides pentoses, hexoses, sugar acids and other derivatives furanoses, pyranoses classification according to number of monosaccharides (2-10) disaccharides (bioses) – decasacharides (decaoses) according to semiacetal OH reducing (glycosides) non-reducing (glycosylglycosides) according to major monosaccharids (backbone) glucooligosaccharides maltose, maltooligosaccharides fructooligosaccharides saccharose galactooligosaccharides lactose, -galactosides according to digestability digestible non-digestible according to biological effects prebiotic effects (stimulate growth and metabolisms of desirable microorganisms) probiotic effects (with fibre influence and regulate peristaltic activity) symbiotic effects (simultaneously prebiotic and probiotic effects) 6 CH2OH O OH 1 OH CH2OH O CH2OH O 4 1 OH HO 4 + OH OH CH2OH O OH OH -D-glukopyranosa -D-glukopyranosa O -trehalosa -H2O 1 OH HO OH 1 HO CH2OH O 4 1 OH HO CH2OH 4 1 OH HO 4 + OH 1 OH OH OH OH -D-glukopyranosa OH maltosa - H2O HO OH OH O HO -D-glukopyranosa OH 1 OH HOH2C OH O 1 O CH2OH CH2OH O CH2OH O OH 4 1 OH + 4 -trehalosa 1- OH HO HO H2O OH OH OH -D-glukopyranosa CH2OH O -D-glukopyranosa OH O 1 OH 4 HO 4 1 OH HO + 4 CH2OH O OH 1 - H2O OH -D-glukopyranosa OH cellobiosa HO CH2OH O OH OH OH O CH2OH OH CH2OH O OH OH OH O CH2OH O OH O OH HOH2C OH O -D-glukopyranosa O 1 OH OH 1 HO OH HOH2C OH O OH -trehalosa terminology maltose ,-trehalose glucooligosaccharides maltose -D-glucopyranosyl-(14)-D-glucopyranose 4-O--D-glucopyranosyl-D-glucopyranose -D-Glcp-(14)-D-Glcp -D-glucopyranosyl--D-glucopyranoside -D-Glcp-(11)--D-Glcp -D-Glcp-(14)-D-Glcp CH2OH O CH2OH O 1 OH HO malt sugar 4 O OH OH OH OH occurrance (book 1, tab.4.11 a 4.12) product of starch hydrolysis, reversion of glucose malt, bread (1,7-4,3 %), honey (2,7-16 %) production maltose sirups (85 %), glucose sirups (acids, enzymes) maltose isomeration on maltulose, -D-Glcp-(14)-D-Fruf reduction on maltitol, -D-Glcp-(14)-D-glucitol 7 fructooligosaccharides saccharose -D-Glcp-(12)--D-Fruf CH2OH O OH HO HO CH2 O 1 O CH2OH OH OH occurrance (book 1, obr. 4.14) fruits vegetables green coffee (roasted) sugar beet sugar cane maple sirup date sirup HO 2 up to 8 % 0,1-12 % 6-7 % (0,2 %) 15-20 % 12-26 % saccharose saccharose production (from sugar beet) extraction of sugar beet slices (diffusion) cleaning (epuration) of crude juice, clarification by Ca(OH)2 saturation by CO2 filtration, light juice thickening heavy juice (61-67 % saccharose, 68-72 % dry matter) crude (brown) sugar 96 % saccharose, 2-3 % non-sugars, 1-2 % water (1,0-1,2 % organic, 0,8-1,0 % inorganic matters) afinade rafinade molasses (folder, substrat for fermentation processes) production of invert suger, other products galactooligosaccharides lactose -D-Galp-(14)-D-Glcp milk sugar HO CH2 HO CH2 HO O OH O 4 OH OH O 1 OH OH occurrance (book 1, tab.4.15, 4.16) cow milk 4-5 % human milk 5,5-7 % production (from whey) ultrafiltration thickening, crystalisation production of galactose, galactitol, lactulose, lactitol other -galactooligosaccharides of milk 8 -galactooligosaccharides of pulses content (book 1, tab.4.17) HOCH2 HO sacharosa O 1 OH 6 O CH2 1 HO CH2 O O OH n 1 OH HO raffinosa (n = 1) verbaskosa (n = 2) stachyosa (n = 3) ajugosa (n = 4) O HO 2 OH CH2OH OH REACTIONS OF SACCHARIDES complex of enzymatic and nonenzymatic reactions carbonyl, anomers OH, primary OH, secondary OH nonenzymatic browning reactions reaction of saccharides Maillard reaction (reaction with proteins, amino acids) caramelisation Reaction of saccharides reactants reducing mono- and oligosaccharides non-reducing oligo- and polysaccharides after hydrolysis main reactions of monosaccharides (acid-basic catalysed) in acid medium (futher factors: temperature, time) in alcali medium mutarotation formation (hydrolysis) of glycosides dehydration reductone formation mutarotation isomeration fragmentation rearrangement oxidation formation and hydrolysis of glycosides reaction of poloacetals OH CH2OH O H CH2OH O + HO H + OH CH2OH O R OH OH + -H H OH OH CH2OH O + O R OH O R OH HO HO HO karbeniový kation monosacharid + OH OH OH CH2OH O CH2OH O - H2O O H OH OH OH HO + HO OH glykosid (hetero- nebo homoglykosid) 9 hydrolysis (inversion) production of starch hydrolysates invert sugar galactose formation (reverse, Fischer reaction) side products of inversion (starch sirup: 5-6 %) side products of caramelisation low energy products indicaters of edulteration dehydratation reactions reaction of semiacetal OH and other OH semiacetal OH / and other OH anhydrosugars (glycosans) other OH / other OH deoxysugars anhydrosugars -D-Glcp 1,6-anhydro--D-Glcp (-glucosan) 6 O CH2 O OH 1 HO OH ketoses dimericanhydrides (tricyclic compounds) CH2OH O HO 1 2 O , 1 2 O , HO CH2OH O OH OH (-D-fruktofuranosa)-( -D-fruktofuranosa)-1,2´:1´,2-dianhydrid deoxysugars 1,2-enolisation (series of isomeration and dehydratation) H C OH H C O CH O C OH H C OH C O HO C H HO C H CH2 H C OH H C OH H C OH H C OH H C OH CH2OH CH2OH CH2OH -glukosa 1-en-1,2-diol D - H2O H C OH 3-deoxy-D-erythro-hexos-2-ulosa CH O C O CH - H2O CH H C OH - H2O HO CH2 O CH O CH2OH 3,4-dideoxy-D-glycero-hex-3-enos-2-ulosa 5-hydroxymethylfuran-2-karbaldehyd o 10 D-glukosa HO CH2 O O CH 5-hydroxymethylfuran-2-karbaldehyd D-fruktosa o CH2OH O O 2-hydroxyacetylfuran pentosy, L-askorbová kyselina O CH O furan-2-karbaldehyd 6-deoxyhexosy (methylpentosy) CH3 O CH O 5-methylfuran-2-karbaldehyd 2,3-enolisation CH2OH CH2 OH CH2 CH3 C O C OH C O H C O HO C H H HO C O C C OH H C OH H C OH CH2OH -fruktosa - H2O H C OH H C OH H C OH H C OH CH2OH CH2OH CH2OH 1-deoxy-D-erythro-hexo-2,3-diulosa 2-en-2,3-diol D C O H C OH O OH CH3 CH3 C O C O C O H C O - H2O C OH H C O H CH2OH C OH O CH3 maltol - H2O OH H C CH2OH O COCH3 isomaltol caramel aroma reductone formation Antioxidants (reduction of organic substances, metal ions) R1 C O R -2H C OH C OH R 2 redukton 1 C O C O 2H C O R 2 triulosa isomerisation aldose ketose aldose aldose (epimeration) 11 H CH O CH OH C OH C OH HO C H HO C CH O HO C H HO C H H H C OH H C OH H C H C OH H C OH H C OH CH2OH CH2OH CH2OH 1-en-1,2-diol D-mannosa D-glukosa OH CH2OH C O HO C H H C OH H C OH CH2OH disaccharides isomeration lactose -D-Galp-(14)-D-Glcp D-fruktosa lactulose -D-Galp-(14)-D-Fruf epilactose -D-Galp-(14)-D-Manp rearrangement to acids 1-en-1,2-diol, Cannizzaro reaction, benzyl rearrengement fragmentation formation of reactive componds retroaldolisation R R CH CH=O aldolizace OH R CH CH C CH=O OH OH OH retroaldolizace oxidadation (after isomeration, dehydration) 12 CH O CH O H C OH H C OH CH2OH CH2OH -glyceraldehyd D H HO CH2OH H C OH CH2OH -glyceraldehyd CH2OH -glyceraldehyd 1,3-dihydroxyaceton D D CH O CH OH CH2OH CH2OH C OH C OH C O C OH C H HO HO C H H C OH H C OH H H CH O C O C H HO C C OH H C OH H C OH C OH H C OH H C OH CH2OH CH2OH CH2OH CH2OH -glukosa 1-en-1,2-diol D CH O H CH O formaldehyd 2-en-2,3-diol -fruktosa D HO C H CH2OH CH O CH O H C OH H C OH H C OH glykolaldehyd H C OH CH2OH -arabinosa D CH2OH -erythrosa D MAILLARD REACTION non-enzymatic browning reaction reactants sugars (carbonyl compounds) monosaccharides and reducing oligosaccharides (nonreducing oligosaccharides, polysaccharides, glycosides) triose …. pentose hexose (acyclic forms) aldose ketose -dicarbonyls aldehydes ketones saccharides proteins (amino compounds) -NH2 Lys, N-ending NH2, guanidyl Arg, SH Cys free amino acids, amines, ammonia -NH2 …. -NH2 -NH2 NH3 R-NH2 amino acids reaction conditions water activity (aw 0,3-0,7) pH (9-10) others (temperature, time of reaction, other components) concequences: positive, negative formation of aroma compounds formation of yelow, brown, black pigments melanoidins decrease of nutritive value formation potentially toxic products reaction in vivo (glykosylation of proteins) 13 mechanism of reaction 3 stages initial stage formation of glykosylamines (Amadori rearrangement) and formation of aminodeoxysugars (Amadori products) central stage decomposition of saccharides, glycosylamines, aminodeoxysugars (dehydratation, fragmentation) decomposition of amino acids (Strecker degradation) final stage reaction of degradation products, formation of aroma, taste and colour products (melanoidins) glycosylamines and aminodeoxysugars NH R N R CH O CHOH CH H C OH H C OH R NH2 HO C H - H2O HO C H HO C H H C OH H C OH H C OH H C OH H C OH H C OH CH2OH CH2OH CH2OH D-glukosa + H + NH R OH NH R NH R CH CH CH2 C OH C O H C OH -H HO C H HO OH HO C H D-glukosylamin O CH2 NH R HO HO C H HO H C OH H C OH H C OH H C OH H C OH H C OH CH2OH CH2OH CH2OH D-glukosylamin OH NH R + NH R OH HO imin (Schiffova báze) karbinolamin CH2OH O CH2OH O H C OH OH OH kation Schiffovy D-fruktosamin (1-amino-1-deoxy- D-fruktosa) cyklická forma enolforma oxoforma báze totally utilisable form non-utilisable form ketose ketosylamine aldosamine (2-amino-2-deoxyaldose), Heyns rearrangement mechanisms (reaction of acyclic forms) decomposition of aminodeoxysugars 1,2-enolisation in acidic medium 2,3-enolisation in neutral and alkali medium formation of glycosuloses and glycodiuloses (aldoketoses a diketoses) 1,2-enolisace CH NHR C OH + CH NHR + H C OH C H H2O C H R CH2 NHR - H2O C OH + HO C H CH O CH NR R R enaminol H2O C O - H + CH2 produkty - R NH2 R 3-deoxy-D-erythro-hexos-2-ulosa C O HO C H R -fruktosamin 2,3-enolisace CH NHR C OH D H + + CH2 NH2R CH2 CH3 C OH C OH C O C O C O R R HO C H O C R R endiol -H + - R NH2 produkty o 1-deoxy-D-erythro-2,3-hexo-2,3-diulosa analogy with reaction of sugars but: lower activation energy products contain N a S qualitativelly and quantitativelly more products 14 important heterocyclic products OH CH3 O O HO CH3 O O CH3 CH2 SH O isomaltol (caramel) furaneol (strawberry, pineapple) furfurylthiol (coffee) O O N CH3 OH S CH3 CH3 CH3 N CH3 N CH3 O maltol (caramel) 2,4-dimethylthiophene 2-acetyl-1-pyrroline 2,6-dimethylpyrazine (fried anion) (bread) (chocolate, nuts) Maillard reaction in important food commodities positive and negative consequences, desirable and undesirable reactions technology (aroma, taste, colour, nutritive value) roasting boiling, frying , backing drying extrusion, microvawe heating milk, milk products Lys losses: 10-30 % traditional drying, 3 % sprey drying cereals, vcereal products Lys losses: 70 % bread crust, 10 % total meat, meat products mutagenes fruits, vegetables coffee, cocoa, nuts reaction during processing of milk non-utilisable (blocked) Lys (example) NH CH2 NH [CH 2 ]4 CH NH CH2OH O HO OH O NH2 [CH2]4 CH CH2OH C O + O HN CH R OH OH O C OH H C HN O CH2OH protein 2 H2O OH OH H C OH OH laktosa C O C O HO C H HCl OH HOH2C O 1-lysino-1-deoxylaktulosa -N-deoxylaktulosyllysin) CH2 NH [CH2]4 CH COOH C O NH2 O C O C CH 2 NH [CH 2 ]4 CH COOH O CH2 furosin H C OH NH 2 CH 3 CH2OH O HO N [CH 2 ]4 CH COOH NH 2 pyridosin 15 isomeration lactose lactulose + epilactose lysinoalanine inhibition of Maillard reaction unfavourable conditions water content (activity), lower temperature, regulation of pH removal of one reaction partner use of inhibitors SO2 + H2O H+ + HSO3- H2SO3 - SO3 CH=O CHOH - HSO3 H C OH H C OH o aldehyd sulfonová kyselina CARAMELISATION sugars (saccharose, glucose, fructose, starch sirup, invert sugar) temperature: 150-190oC (240oC) reaction time: 5-10 hours catalysts caramel = solid product, couler = liquid product class I CP name of couler additives matter utilisation caustic Na2CO3, K2CO3, NaOH, KOH, alcoholic beverages H2SO4, acetic citric acid, (high content of alcohol) II CCS caustic sulphite SO2, H2SO4, Na2SO3, K2SO3, NaOH, vinegar, beer, alcoholic KOH, beverages, aromatised wine III AC ammonium NH3, (NH4)2SO4, Na2CO3, H2SO4, beer, alcoholic beverages, NaOH, KOH acid food IV SAC ammonium-sulphite NH3, SO2, (NH4)2SO3, Na2SO3, acid food, non-alcoholic K2SO3, Na2CO3, K2CO3, NaOH, beverages KOH, H2SO4, 16