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به نام خدا Carbohydrates Photosynthesis: Sun’s energy becomes part of glucose molecule energy Carbon dioxide Water Chlorophyll گلوكز ,1% of body weight GLUCOSE 6 CO2 + 6 H20 + energy (sun) C6H12O6 + 6 O2 Carbohydrates -1کربوهیدراتها -2انواع کربوهیداتها - 3مونوساکاریدها (نامگذاری ،فرمول ،ایزومر نوری، DوLاپیمر ،انانتیومر،آنومر )، -4مشتقات مونوساکاریدها: قندهای دزاکسی ،قندهای آمین دار -3خواص مونوساکاریدها : گروه کربونیل(اکسیداسیون ،اثربازها ،اسیدها ،مواداحیا کننده ،هیروکسیل آمین ،اسید سیانیدریک) گروه هیدروکسیل(پیوند گلیکوزیدی ، تشکیل استر) -5الیگو ساکاریدها : دی ساکاریدها (مالتوز ،الکتوز،سلوبیلوز، ساکاروز،تره هالوز) -6پلی ساکاریدها: همو پلی ساکاریدها(نشاسته ،گلیکوژن،دکستران،سلولز،کیتین) هترو پلی ساکاریدها (اسید هیالورونیک ،هپارین ،کراتان،درماتان ،کنروئتین سولفات) Carbohydrates (glucides, Osides…) ساکاریدها،اوزیدها،گلوسیدها،کربوهیدارت ها (CH2O)n I or H - C - OH I Monosaccharides - simple sugars with multiple OH groups. Based on number of carbons (3, 4, 5, 6), a monosaccharide is a triose, tetrose, pentose or hexose. مونوساكاريد Oligosaccharides - a few monosaccharides covalently linked. (2-7) اوليگوساكاريد -Disaccharides - 2 monosaccharides covalently linked. دي ساكاريد -Trisaccharides - 3 monosaccharides covalently linked. تری ساكاريد Polysaccharides - polymers consisting of chains of monosaccharide or disaccharide units. ( 10…) پلي ساكاريد Monosaccharides • There are two families of monosaccharides: 1. 2. Aldose- containing an aldehyde functional group suffix –ose ( اوزRibose) , Aldotriose….. Ketose- containing a ketone functional group (suffix -ul ( ُالRibulose ) , Ketotriose….. aldose each have the same formulae C3H6O3 ketose مدل فیشر-ساختمان خطیساختمان قندها مدل هاوورث-ساختمان حلقوی- ساختمان خطي مونوساكاريد ها Linear Structure: Monosaccharides Aldoses (e.g., glucose) have an aldehyde group at one end. H O 1C H HO H H 2C 3C 4 5 OH Ketoses (e.g., fructose) have a keto group, usually at C2. :ایزومر عاملي تفا وت در گروه عامل- 1 CH2OH 2 C O HO 3 C H H C OH C OH 6 CH2OH D-glucose H 4C OH H 5C OH 6 CH2OH D-fructose D-ketoses -3تریوزها -4تتروزها -5پنتوزها -6هگزوزها -7هپتوزها D-aldoses مونوساكاريد ها: ايزومر Monosaccharides :Isomers Definition: Isomer 1-Functional isomers:. ایزومر عاملي 2-Ring isomers: ایزومر حلقه 3-Optical isomers: ایزومر نوری The number of isomers is 2n, where n is the number of asymmetric centers. (R- aldose n=m-1 , R- ketose , L-aldose n=m-2, L-ketose n=m-3 , m= number of carbon ) 1- D &L Isomeri 2-(Enantiomers, Racemic ) انانتيومر – راسميك 3-Epimerism Isomeri ايزومر اپي مر 4-Anomerism Isomeri ايزومر آنومري ايزومر D ,Lمونوساكاريدها Monosaccharides : D ,L Isomers قرار کرفتن گروه OHبر روي آخرین كربن نامتقارن با هم تفاوت دارد.اگر در سمت راست باشد قند از نوع Dو اگر در سمت چپ باشد از نوع Lاست.قندهای مهم از لجاظ بیولوژیک از نوع Dهستند.برای نشان دادن جهت انحراف نور از عالمت +و -استفاده می شود. H O H O C HO – C – H H – C – OH HO – C – H HO – C – H CH2OH C H – C – OH HO – C – H H – C – OH H – C – OH CH2OH L-glucose D-glucose CHO OH C CHO H CH2OH H C HO CH2OH D-glyceraldehyde L-glyceraldehyde )Dextro (right )Laevo (left انانتيومرها Monosaccharides :Enantiomers • : A special subset of isomers when 2 sugars differ only in the configuration around All carbon . بر روي تمام كربن هاي نامتقارن با هم تفاوت داردOH,H نحوه قرار گیري گروه Enantiomers اپي مرها Monosaccharides: Epimers : A special subset of isomers when 2 sugars differ only in the configuration around one carbon. بر روي یكي از كربن هاي نامتقارن با هم تفاوت داردOH,H نحوه قرار گیري گروه CHO H C OH HO C H H C H C CHO CHO HO HO C H H C OH C H HO C OH H C OH H OH H C OH H CH2OH D-glucose D-mannose CH2OH D-mannose is a C-2 epimer of D-glucose! CHO H C OH H HO C H C OH HO C H C OH H C OH CH2OH D-glucose CH2OH D-galactose D-galactose is a C-4 epimer of D-glucose! NOTE: D-mannose is NOT an epimer of D-galactose b/c configuration about 2 carbons is different. Ring Structures : اثبات ساختمان حلقوي • 1-Hemiacetal & hemiketal • formation اگر آلدئید با یك الكل واكنش دهد محصول آن نوعي استال است در حالیكه واكنش مونوساكاریدها با الكل فقط همي استال است R-OH Hcl H OR R C OR استال Acetal 2-Methylation واكنش متیالسیون glucose must be has 5 molecules methyl. In practical it has 4 molecules . Ring Structures • Monosaccharides with 5 or more carbon atoms in the backbone usually occur in solution as cyclic or ring structures. فوران O furan فورانوز O furanose پیران O pyran پیرانوز O pyranose الفا دي گلوكوپیرانوز بتا دي گلوكوپیرانوز Ring Structures When the ring forms, the –OH on the former carbonyl carbon can have two configurations, given the designations and . In Haworth projection, the - OH is down and the -OH is up. مدل هاوورث These isomers are called anomers, and the carbon atom is referred to as the anomeric carbon atom. ایزومر آنومري كربن آنومریك The interconversion between and forms occurs via the open-chain structure in a reaction called mutarotation. موتوروتاسیون CH2OH 1 HO H H 2C O C H C OH C OH 3 4 5 HOH2C 6 CH2OH 6 D-fructose (linear) H 5 H 1 CH2OH O 4 OH HO 2 3 OH H -D-fructofuranose Fructose forms either a 6-member pyranose ring, by reaction of the C2 keto group with the OH on C6, or a 5-member furanose ring, by reaction of the C2 keto group with the OH on C5. Properties of carbonyl group • Oxidation 1- aldehyde group اسید گلوكونیك اسید آلدونیك 2- Aldehyde & Alcoholic group 3- Alcoholic group CHO COOH H C OH HO C H OH H C OH OH H C OH H C OH HO C H H C H C CH2OH COOH D-gluconic acid D-glucuronic acid اسید گلوكورونیك اسید اورونیك )اسید گلوكاریك (ساکاریک اسید الداریك اسید موسیکGal اثرات عوامل احيائ كننده Effects of Reducing Agent: The reducing agent can reduce keto group and aldehyde group to hydroxyl group مانیتول D-Manose Ribose Galactose سوربیتول D-Glucose & fructose Ribitol ریبتول Dolcitol دولسیتول واکنش با فنیل هیدرازین : تولید اوزازوان شناسایی قند - کریستال Effects of diluted alkali : Tautomerization توتومریزاسیون Mannose Effects of Conc Acids: Pentose Furfural فورفورال Hexose Hydroxy metyl Furfural هیدروكسي متیل فورفورال Effects of HCN : اسید سیانیدریك Production of a new sugar with a addition carbon Effect of Hydroxyl Amine: هیدروكسیل آمین Production of a new sugar with lower a carbon Reducing Sugars • Monosaccharides are also known as reducing sugars, • Such reactions are used in the analysis of sugars, e.g. Benedict’s Solution RCHO + 2Cu2+ RCO2H + Cu2O (RED) معرف بندیكت Properties of Hydroxyl Groups • Hydroxy groups are modified in monosaccharides to give a number of important derivatives: Phosphorylation فسفوریالسیون Glycosides (elimination of water between anomeric hydroxyl group and hydroxyl of another compound) گلیكوزیدي Glycosidic Bonds The anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together, splitting out water to form a glycosidic bond: پیوند R-OH + HO-R' R-O-R' + H2O گلیكوزیدي E.g., methanol reacts with the anomeric OH on glucose to form methyl glucoside (methyl-glucopyranose). H OH H OH H2O H O HO HO H H H + CH3-OH H O HO HO H OH H OH -D-glucopyranose methanol H OH OCH3 methyl--D-glucopyranose Sugar derivatives CH2OH CH2OH O H H OH H H OH H OH OH H O H NH2 H H O OH OH H N C CH3 H -D-glucosamine الفا دي گلوكز آمین -D-N-acetylglucosamine ان استیل گلوكز آمین amino sugar - an amino group substitutes for a hydroxyl on C-2. An example is glucosamine. The amino group may be acetylated, as in N-acetylglucosamine. Sugar derivatives H O H3C C O NH R H COO H R= OH H HC OH HC OH CH2OH OH H N-acetylneuraminate (sialic acid) ان –استیل نورامنیك اسید –اسیدسیالیك N-acetylneuraminate (N-acetylneuraminic acid, also called sialic acid) is often found as a terminal residue of oligosaccharide chains of glycoproteins. Sialic acid imparts negative charge to glycoproteins, because its carboxyl group tends to dissociate a proton at physiological pH, as shown here. Sugar derivatives ریبوز دزاكسي ریبوز Structure of DNA ,RNA NADH ,ATP,…... فوكوزL- Fucose = 6- Deoxy-L- Galactose رامنوزL-Ramnose =6-Deoxy -L- Manose Oligosaccharides -2-7مونوساکارید با پیوندهای گلیکوزیدی به یکدیگر اتصال دارند. •دی ساکارید : -1احیائ کننده :مالتوز ،الکتوز ،سلوبیلوز -2غیر احیائ کننده :ساکاروز ،تره هالوز •تری ساکارید :مانند رافینوز(گلوکز-گاالکتوز-فروکتوز) Disaccharides • Two Monosaccharides are covalently linked to one another by glycosidic bonds that are acid labile, but base resistant. They are also hydrolyzed by specific enzymes. Writing the Structure of Disaccharides 1. the nonreducing end at the left. 2 The ring configuration is indicated by a suffix . ( osyl - ose) اوز- اوزيل 3. The atoms between which glycosidic bonds are formed are indicated by numbers in parentheses between residue designations. ( 1 4) CH2OH O CH2OH O + OH OH HO HO OH OH 6CH OH 2 5 O CH2OH H O H OH H H 4 O OH OH H 1 H OH 3 H OH H H H H 1 H O 2 OH مالتوز OH α -D-glucopyranosyl-(14)- α -D--glucopyranose.) Disaccharides: 6 CH2OH 6 CH2OH مالتوزMaltose, a cleavage H 5 O 5 H H O H H H 1 product of starch, is a 1 4 4 H H OH OH disaccharide with (1 4) O OH OH 2 2 3 3 glycosidic link between the OH H OH maltose H C1 OH & C4 OH of 2 α -D-glucopyranosyl-(14)- α -D--glucopyranose glucoses. 6 CH2OH 6 CH2OH It is the anomer (C1 O 5 5 O O OH H H points down). H H 4 OH OH H 1 O 4 OH H 3 H 2 OH 3 cellobiose H H 2 1 H OH β-D-glucopyranosyl-(14)- β -D--glucopyranose.) سلوبيوزCellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer . The (1 4) glycosidic linkage is represented as a zig-zag, but one glucose is actually flipped over relative to the other. الكتوزLactose, milk sugar, is composed of galactose & glucose, with β(14) linkage from the anomeric OH galactose. β -D-galactopyranosyl-(1 4)- β -D-glucopyranose ساكاروزSucrose, common table sugar, has a glycosidic bond linking the anomeric hydroxyls of glucose & fructose. α -D-glucopyranosyl-(12)- β -D-fructofuranoside. Disaccharides Maltose Glc(14)Glc Cellobiose Glc(14)Glc reducing maltase Plants (starch) Animals (glycogen) reducing cellulase Plants (cellulose dimer) reducing Lactase Milk (major energy source) Lactose Gal (14)Glc Sucrose Sucrase Fruits seeds Glc(12)Fru nonreducing (invertase) roots and honey Trehalose Glu (11) Glc non- reducing Fungi Polysaccharides 1-HomoPolysaccharides: هوموپلي ساكاریدها 2-HeteroPolysaccharides: هتروپلي ساكاریدها • The most important homopolysaccharides involve D-glucose monomers and are: 1. Glycogen- main storage polysaccharide of animal cells 2. Starch (amylose and amylopectin)- main storage polysaccharide of plant cells. 3. Cellulose- structural polysaccharide of plants 4. Chitin- major structural material in the exoskeletons of many arthropods and mollusks. (N-Acetyl Glucose Amine )n 1 4 5. Inolin ( D fructofuranose)n 1 2 Starch:نشاسته There are two forms of starch 1- آميلوز-amylose: D-glucose linked (14) with no branching,20-15 % ,60-600 Glu, 2-آمیلوپكتینamylopectin: D-glucose linked (14) and (16) with branching,80-85% ,600.00, 24-30 Glc Branching site -amylose amylopectin Glycogen:گليكوژن • • • . Glycogen is comprised of D-glucose monomers linked (14) and (16) Therefore, it is a highly branched structure. Glycogen is hydrolyzed by enzymes. located in animal cells. Cellulose: سلولز • Cellulose is comprised of D-glucose monomers linked (14). • 300-3000 unit. • Cellulose is hydrolyzed by the enzyme cellulase. • Vertebrates can not hydrolyze cellulose because they lack the enzyme cellulase. Microorgnisms in ruminants do produce cellulase and therefore cattle, sheep, goats, etc utilize cellulose indirectly. 2-HeteroPolysaccharides Glycoproteins and Proteoglycans گلیكوپروتئین ها Glycoproteins پروتئو گالیكن ها Proteoglycans Proteins conjugated to saccharides lacking a serial repeat unit Proteins conjugated to polysaccharides with serial repeat units گالیكوزوآمینوگالیكن هاGlycosaminoglycans موكوپلي ساكاریدهاMucopolysaccharides Protein >> carbohydrate Carbohydrate >> protein Repeat unit HexN and HexUA Glycoproteins • Oligosaccharides are covalently attached to proteins in one of two ways: 1. 2. • N-linked: CHO to Asn found within the protein sequence Asn-X-Ser(Thr) where X is almost any amino acid (except Pro, Asp or Glu). The CHO is most often GlcNAc and sometimes GalNAc. آسپارژين O-linked: CHO to Ser or Thr or hydroxylysine or hydroxylproline. The CHO is most often GalNAc. All blood group antigens are oligosaccharides O-linked to both proteins and lipids. سرين –تره اونين Oligosaccharides that are linked to proteins are generally called carbohydrate moieties Glycopeptide bonds CH2 OH O O H HN C NH2 CH2 CH Asn H Glc H OH H Type I Protein O H OH HN C CH3 NAc N-Glycosyl linkage to Asn CH2 OH NH2 O H O CH2 CH H Glc OH H O H OH H Type II COOH HN C CH3 NAc O-Glycosyl linkage to Ser (Thr) COOH Ser Protein گليکو ليپيد ها قند+چربي لیپید>قند :مانند لیپو پلي ساکارید باکتریها قند>لیپید:گلیکولیپیده (آنتي ژنهاي گروه خوني) Blood group antigen گروه خوني O گروه خوني A گروه خوني B موكوپلي ساكاريدها Glycosaminoglycans -1,3 COO - O H O O H H O H OH H H H H -1,4 CH2 OH OH H GlcUA HN C CH3 GlcNAc اسید گلوكورونیك اسید هیالورونیك Hyaluronate O H OH - استیل گلوكز آمین-N- No sulfate -1,3 glycosidic linkage Glycosaminoglycans اسید یدورونیك - استیل گاالكتوز آمین-N-1,4 -1,3 H CH2 OH O H O O OSO3 COO - Dermatan sulfate درماتان سولفات O H H OH H H H OH IdUA -1,4 O H H H HN C CH3 GalNAc -1,3 COO - CH2 OH O H H OH O H H H H H O O OSO3 OH O H H H HN C CH3 GalNAc GlcUA كند روتئین سولفاتChondroitin sulfate اسیدگلوكورونیك - استیل گاالكتوز آمین-N- Glycosaminoglycans گاالکتوز- استیل گلوكز آمین-N- -1,3 -1,4 CH2 OSO3 - CH2 OH O OH H O H H O H H OH H H H OH GlcUA O -1,4 O H H HN C -1,4 CH3 GlcNAc COO - CH2 OSO3 O H H Keratan sulfate كراتان سولفات OH O H H H OH H H O H IdUA OSO3 - H O H NHSO 3- GlcAmine هپارینHeparin اسیدیدورونیك- استیل گلوكز آمین-N Hemiacetal & hemiketal formation H An aldehyde can react with an alcohol to form a hemiacetal. C O + R' OH R' O R C OH R aldehyde alcohol hemiacetal R C A ketone can react with an alcohol to form a hemiketal. H R O + "R OH R' ketone "R O C R' alcohol hemiketal OH 6 CH2OH 6 CH2OH 5 H 4 OH H OH 3 H O H H 1 2 OH -D-glucose OH 5 H 4 OH H OH 3 H O OH H 1 2 H OH -D-glucose Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers are called anomers, & . Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1: (OH below the ring) (OH above the ring). H OH 4 H OH 6 H O HO HO H O HO H HO 5 3 H H 2 H OH 1 OH -D-glucopyranose H OH OH H -D-glucopyranose Because of the tetrahedral nature of carbon bonds, pyranose sugars actually assume a "chair" or "boat" configuration, depending on the sugar. The representation above reflects the chair configuration of the glucopyranose ring more accurately than the Haworth projection. Sugar derivatives CH2OH H C OH H C OH H C OH CH2OH D-ribitol sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol. sugar acid - the aldehyde at C1, or OH at C6, is oxidized to a carboxylic acid; e.g., gluconic acid, glucuronic acid. Polysaccharides 6CH OH 2 5 O CH2OH H O H OH H H 1 H O OH H 4 OH OH O H H OH H 1 O H H H OH H H O O H H O H OH H H O OH 2 3 H H CH2OH CH2OH CH2OH H H OH H OH H OH OH amylose Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch. Glucose storage in 6CHosmotic CH OH CH OH OH minimizes OH polymericCH form effects. 2 O 5 2 2 2 O H O H H Amylose is a glucose polymer with (14) linkages. It OH H H 1 H 1 O O O adoptsOH a helical conformation. 2 3 H H OH H OH H H H 4 OH H OH H H OH H OH H The end of the polysaccharide with an anomeric amylose C1 not involved in a glycosidic bond is called the reducing end. H 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 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 (14) linkages, but it also has branches formed by (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. 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 (16) branches. The highly branched structure permits rapid release of glucose from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants. CH2OH H O H OH H OH H 1 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 OH cellulose Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with (14) linkages. Every other glucose is flipped over, due to the linkages. This promotes intra-chain and inter-chain Hbonds and van der Waals interactions, that cause cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles called microfibrils. Monosaccharides can form ring structures O Furan O Pyran Glycosidic binds are between two sugars They can either be in the or configuration and can be linked through the 1-2, 1-4 or 1-6 linkage