1 In The Name of Gad
2 Goals of Biochemistry 1. Available1- جستجوي ترکيبات يا اجزائ متشكله سلول (جاندار)...... 2- شناخت چگونگي واكنشهاي بيوشيميايي در سلول .... تفاوت واکنش هاي بيوشيمائي و شيميائي. Chemical Elements in cells : Life depends primarily on which few elements C, O, N, H (99%) + S, P, Na, Cl, Ca, Mg, K + trace amounts various metals Why these? 1. Available 2. Suitable – C, H, O and N have strong tendencies to form covalent bonds Element (no. e-’s in outer shell) number of covalent bonds H (1) 1 O (6) 2 N (5) 3 C (4) 4 -Miler hypothesis
3 بيومولكولهاي موجود در موجودات آلي Organic Molecules – Four ClassesCarbohydrates Lipids Nucleic Acids Proteins Class Monomer (subunit) Polymer Carbohydrates Sugar Polysaccharides Lipids Fatty Acids Lipids, Phospholipids Proteins Amino Acids Proteins Nucleic Acids Nucleotides (DNA, RNA)
4 Nucleus Nucleolus اجزائ تشکیل دهنده سلول Mitochondria Rough ERLysosome Smooth ER Golgi Plasma membrane
5 گروهاي عملكردي در بيومولكولها Biomolecules: Functional Groupsهيدروكسيل كربونيل آمين آميد تيول استر آلكن
6 3 - مونوساکاریدها (نامگذاری ، فرمول، ایزومر نوری،Carbohydrates 1-کربوهیدراتها 2- انواع کربوهیداتها 3 - مونوساکاریدها (نامگذاری ، فرمول، ایزومر نوری، اپیمر ،انانتیومر،آنومر ،)LوD 3-خواص مونوساکاریدها : گروه کربونیل(اکسیداسیون، اثر بازها ،اسیدها ،مواداحیا کننده، هیروکسیل آمین ،اسید سیانیدریک) گروه هیدروکسیل(پیوند گلیکوزیدی ، تشکیل استر) -مشتقات مونوساکاریدها: 4 قندهای دزاکسی ، قندهای آمین دار 5- الیگو ساکاریدها : دی ساکاریدها (مالتوز، لاکتوز،سلوبیلوز، ساکاروز،تره هالوز) 6- پلی ساکاریدها: همو پلی ساکاریدها(نشاسته، گلیکوژن،دکستران،سلولز،کیتین) هترو پلی ساکاریدها (اسید هیالورونیک ، هپارین، کراتان،درماتان، کنروئتین سولفات)
7 گلوكز Photosynthesis: Sun’s energy becomes part of glucose molecule,1% of body weight گلوكز Carbon dioxide Water Chlorophyll GLUCOSE 6 CO2 + 6 H20 + energy (sun) C6H12O6 + 6 O2
8 Carbohydrates (glucides, Osides…)کربوهیدارت ها،گلوسیدها،اوزیدها،ساکاریدها 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
9 Monosaccharides ketose aldose -ساختمان خطی- مدل فیشر ساختمان قندهاThere are two families of monosaccharides: Aldose- containing an aldehyde functional group suffix –ose اوز ( Ribose) , Aldotriose….. Ketose- containing a ketone functional group (suffix -ul ُال ( Ribulose ) , Ketotriose….. each have the same formulae C3H6O3 ketose aldose -ساختمان خطی- مدل فیشر -ساختمان حلقوی- مدل هاوورث ساختمان قندها
10 ساختمان خطي مونوساكاريد ها Linear Structure: MonosaccharidesAldoses (e.g., glucose) have an aldehyde group at one end. Ketoses (e.g., fructose) have a keto group, usually at C2. ايزومر عاملي: تفا وت در گروه عامل- 1 2 3 4 5 6 1 2 3 4 5 6
11 D-ketoses D-aldoses تریوزها-3 4-تتروزها 5-پنتوزها 6-هگزوزها 7-هپتوزها
12 ايزومر :مونوساكاريد ها Monosaccharides :IsomersDefinition: Isomer 1-Functional isomers:. ايزومر 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
13 مونوساكاريدها D ,L ايزومر Monosaccharides : D ,L Isomersقرار کرفتن گروهOH بر روي آخرين كربن نامتقارن با هم تفاوت دارد.اگر در سمت راست باشد قند از نوع D و اگر در سمت چپ باشد از نوع L است.قندهای مهم از لجاظ بیولوژیک از نوع D هستند.برای نشان دادن جهت انحراف نور از علامت + و- استفاده می شود. CHO C CHO CH2OH C H HO OH H CH2OH L-glyceraldehyde Laevo (left) D-glyceraldehyde Dextro (right)
14 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 دارد OH,H نحوه قرار گيري گروه Enantiomers
15 اپي مرها Monosaccharides: Epimers: A special subset of isomers when 2 sugars differ only in the configuration around one carbon. بر روي يكي از كربن هاي نامتقارن با هم تفاوت دارد OH,H نحوه قرار گيري گروه C CHO H CH2OH OH HO D-glucose C CHO H CH2OH OH HO D-mannose C CHO H CH2OH OH HO D-glucose C CHO H CH2OH OH HO D-galactose D-mannose is a C-2 epimer of D-glucose! 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.
16 Ring Structures ساختمان حلقوي : اثبات1-Hemiacetal & hemiketal formation اگر آلدئيد با يك الكل واكنش دهد محصول آن نوعي استال است در حاليكه واكنش مونوساكاريدها با الكل فقط همي استال است H OR R-OH C Hcl R OR استال Acetal 2-Methylation واكنش متيلاسيون glucose must be has 5 molecules methyl. In practical it has 4 molecules .
17 Ring Structures پيرانوز پيران فورانوز فوران furan furanose pyranMonosaccharides with 5 or more carbon atoms in the backbone usually occur in solution as cyclic or ring structures. پيرانوز پيران فورانوز فوران O O O O furan furanose pyran pyranose الفا دي گلوكوپيرانوز بتا دي گلوكوپيرانوز
18 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. ايزومر آنومري كربن آنومريك The interconversion between and forms occurs via the open-chain structure in a reaction called mutarotation. موتوروتاسيون
19 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.
20 Properties of carbonyl groupOxidation 1- aldehyde group اسيد گلوكونيك اسيد آلدونيك 2- Aldehyde & Alcoholic group 3- Alcoholic group اسيد گلوكاريك (ساکاریک) اسيد الداريك اسيد گلوكورونيك اسيد اورونيك اسید موسیک Gal
21 اثرات عوامل احيائ كننده Effects of Reducing Agent:The reducing agent can reduce keto group and aldehyde group to hydroxyl group سوربيتول مانيتول D-Manose D-Glucose & fructose Ribose Ribitol ريبتول Galactose Dolcitol دولسيتول
22 Tautomerization توتومريزاسيون Mannose Effects of diluted alkali :Effects of Conc Acids: Pentose Furfural فورفورال Hexose Hydroxy metyl Furfural هيدروكسي متيل فورفورال Effects of HCN :اسيد سيانيدريك Production of a new sugar with a addition carbon Effect of Hydroxyl Amine:هيدروكسيل آمين Production of a new sugar with lower a carbon
23 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 بنديكت
24 Properties of Hydroxyl GroupsHydroxy groups are modified in monosaccharides to give a number of important derivatives: Phosphorylation Glycosides (elimination of water between anomeric hydroxyl group and hydroxyl of another compound) فسفوريلاسيون گليكوزيدي
25 Glycosidic Bonds پيوند گليكوزيديThe anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together, splitting out water to form a glycosidic bond: R-OH + HO-R' R-O-R' + H2O E.g., methanol reacts with the anomeric OH on glucose to form methyl glucoside (methyl-glucopyranose). پيوند گليكوزيدي
26 Sugar derivatives ان استيل گلوكز آمين الفا دي گلوكز آمينان استيل گلوكز آمين الفا دي گلوكز آمين 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.
27 Sugar derivatives ان –استيل نورامنيك اسيد –اسيدسياليكN-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.
28 Sugar derivatives دزاكسي ريبوز ريبوز Structure of DNA ,RNAدزاكسي ريبوز ريبوز Structure of DNA ,RNA NADH ,ATP,…... فوكوزL- Fucose = 6- Deoxy-L- Galactose رامنوز L-Ramnose =6-Deoxy -L- Manose
29
30 Oligosaccharides -2-7 مونوساکارید با پیوندهای گلیکوزیدی به یکدیگر اتصال دارند. دی ساکارید : 1- احیائ کننده : مالتوز ، لاکتوز، سلوبیلوز 2- غیر احیائ کننده: ساکاروز ،تره هالوز تری ساکارید: مانند رافینوز(گلوکز-گالاکتوز-فروکتوز)
31 Disaccharides + H مالتوز CH2OH CH2OH O O H2O OH OH HO HOTwo 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) اوزيل -اوز 3. The atoms between which glycosidic bonds are formed are indicated by numbers in parentheses between residue designations. ( ) OH HO O CH2OH OH HO O CH2OH + H2O H مالتوز α -D-glucopyranosyl-(14)- α -D--glucopyranose.)
32 α -D-glucopyranosyl-(14)- α -D--glucopyranose.)Disaccharides: مالتوزMaltose, a cleavage product of starch, is a disaccharide with a(1® 4) glycosidic link between the C1 OH & C4 OH of 2 glucoses. It is the a anomer (C1 O points down). α -D-glucopyranosyl-(14)- α -D--glucopyranose.) β-D-glucopyranosyl-(14)- β -D--glucopyranose.) سلوبيوز Cellobiose, a product of cellulose breakdown, is the otherwise equivalent b anomer . The b(1® 4) glycosidic linkage is represented as a zig-zag, but one glucose is actually flipped over relative to the other.
33 α -D-glucopyranosyl-(12)- β -D-fructofuranoside.لاكتوزLactose, milk sugar, is composed of galactose & glucose, with β(14) linkage from the anomeric OH galactose. β -D-galactopyranosyl-(1 4)- β -D-glucopyranose ساكاروز Sucrose, common table sugar, has a glycosidic bond linking the anomeric hydroxyls of glucose & fructose. α -D-glucopyranosyl-(12)- β -D-fructofuranoside.
34 Disaccharides Maltose Glc(14)Glc reducing maltasePlants (starch) Animals (glycogen) Cellobiose Glc(14)Glc cellulase Plants (cellulose dimer) Lactose Gal (14)Glc Lactase Milk (major energy source) Sucrose Glc(12)Fru non-reducing Sucrase (invertase) Fruits seeds roots and honey Trehalose Glu (11) Glc non-reducing Fungi
35 Polysaccharides 1-HomoPolysaccharides: هوموپلي ساكاريدها2-HeteroPolysaccharides: هتروپلي ساكاريدها The most important homopolysaccharides involve D-glucose monomers and are: Glycogen- main storage polysaccharide of animal cells Starch (amylose and amylopectin)- main storage polysaccharide of plant cells. Cellulose- structural polysaccharide of plants Chitin- major structural material in the exoskeletons of many arthropods and mollusks. (N-Acetyl Glucose Amine )n Inolin (b -D fructofuranose)n
36 Starchنشاسته: -amylose amylopectin There are two forms of starchآميلوز-1-amylose: D-glucose linked (14) with no branching,20-15 % , Glu, -amylose آميلوپكتين-2 amylopectin: D-glucose linked (14) and (16) with branching,80-85% ,600.00, 24-30 Glc Branching site amylopectin
37 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. .
38 Cellulose:سلولز Cellulose is comprised of D-glucose monomers linked (14). 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.
39 Glycoproteins and Proteoglycans2-HeteroPolysaccharides Glycoproteins and Proteoglycans گليكوپروتئين ها Proteins conjugated to saccharides lacking a serial repeat unit Glycoproteins Protein >> carbohydrate پروتئو گلايكن ها Proteins conjugated to polysaccharides with serial repeat units Proteoglycans Carbohydrate >> protein HexN: hexosamine HexUA: hexose uronic acid گلايكوزوآمينوگلايكن ها موكوپلي ساكاريدها Glycosaminoglycans Mucopolysaccharides Repeat unit HexN and HexUA
40 Glycoproteins Oligosaccharides are covalently attached to proteins in one of two ways: 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
41 Glycopeptide bonds Protein Protein Asn Glc NAc Type IN-Glycosyl linkage to Asn Protein Ser Asn: asparagine Glc: glucose NAc: N-acetyl Ser: serine Thr: threonine HOLys: 5-hydroxylysine Glc NAc Type II O-Glycosyl linkage to Ser (Thr)
42 گليکو ليپيد ها مانند ليپو پلي ساکاريد باکتريها: قند>ليپيد قند+چربيگليکوليپيده (آنتي ژنهاي گروه خوني):ليپيد>قند Blood group antigen O گروه خوني A گروه خوني B گروه خوني
43 موكوپلي ساكاريدها Glycosaminoglycansb-1,3 b-1,4 GlcUA GlcNAc -استيل گلوكز آمين اسيد گلوكورونيكN- GlcUA: glucuronic acid GlcNAc: N-acetylglucosamine No sulfate b-1,3 glycosidic linkage اسيد هيالورونيك Hyaluronate
44 Glycosaminoglycans -استيل گالاكتوز آمين - اسيد يدورونيكN-b-1,4 b-1,3 Dermatan sulfateدرماتان سولفات b-1,4 b-1,3 IdUA GalNAc IdUA: iduronic acid GlcUA: glucuronic acid GalNAc: N-acetylgalactosamine GalNAc GlcUA كند روتئين سولفاتChondroitin sulfate -استيل گالاكتوز آمين اسيدگلوكورونيكN-
45 Glycosaminoglycans -استيل گلوكز آمين - گالاکتوزN-b-1,3 b-1,4 a-1,4 a-1,4 GlcUA GlcNAc Keratan sulfate كراتان سولفات GlcNAc: N-acetylglucosamine Gal: galactose UA: uronic acid HexN: hexosamine GalNAc: N-acetylgalactosamine Ser: serine Thr: threonine GlcUA: glucuronic acid IdUA GlcAmine هپارين Heparin استيل گلوكز آمين - اسيديدورونيك-N
46
47
48 Hemiacetal & hemiketal formationAn aldehyde can react with an alcohol to form a hemiacetal. A ketone can react with an alcohol to form a hemiketal.
49 Cyclization of glucose produces a new asymmetric center at C1Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers are called anomers, a & b. Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1: a (OH below the ring) b (OH above the ring).
50 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.
51 Sugar derivatives 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.
52 Polysaccharides 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. It adopts a helical conformation. The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the reducing end.
53 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.
54 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 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.
55 Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with b(1®4) linkages. Every other glucose is flipped over, due to the b linkages. 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 called microfibrils. Botany online website
56 Monosaccharides can form ring structures
57
58
59 Glycosidic binds are between two sugarsThey can either be in the a or b configuration and can be linked through the 1-2, 1-4 or 1-6 linkage
60