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This document provides an overview of carbohydrate biochemistry. It defines carbohydrates as carbon compounds containing carbonyl carbon and hydroxyl functional groups. Carbohydrates are classified based on size of carbon chain, number of sugar units, and location of carbonyl carbon. Key topics covered include monosaccharide and disaccharide structure, isomerism, derivatives of monosaccharides, oligosaccharides, homopolysaccharides like starch and cellulose, and complex heteropolysaccharides.
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Biochemistry of Carbohydrates summary book harpers medicine
This document provides an overview of carbohydrate biochemistry. It defines carbohydrates as carbon compounds containing carbonyl carbon and hydroxyl functional groups. Carbohydrates are classified based on size of carbon chain, number of sugar units, and location of carbonyl carbon. Key topics covered include monosaccharide and disaccharide structure, isomerism, derivatives of monosaccharides, oligosaccharides, homopolysaccharides like starch and cellulose, and complex heteropolysaccharides.
This document provides an overview of carbohydrate biochemistry. It defines carbohydrates as carbon compounds containing carbonyl carbon and hydroxyl functional groups. Carbohydrates are classified based on size of carbon chain, number of sugar units, and location of carbonyl carbon. Key topics covered include monosaccharide and disaccharide structure, isomerism, derivatives of monosaccharides, oligosaccharides, homopolysaccharides like starch and cellulose, and complex heteropolysaccharides.
BIOCHEMISTRY OF CARBOHYDRATES UST FMS General Formula: C x (H 2 O) y or (CH 2 O) n Carbon compounds havi ng Carbonyl Carbon (C=O) and hydroxyl ( -OH) functi onal groups Carbonyl Functional Groups: Al dehyde (Pol yhydroxyal dehydes): 1 st C (C=O) Ketone (Pol yhydroxyketones): 2 nd C (C=O) Classification 1) Size of base Carbon chain Tri ose (3C), Tetrose (4C), Pentose (5C), Hexose (6C), Heptose (7C), Nanose (9C) 2) Number of sugar units Monosacchari de 1 CHO uni t Di sacchari de 2 CHO uni ts Ol i gosacchari de 3-10 CHO uni ts Pol ysacchari de >10 uni ts 3) Location of Carbonyl carbon Al dose Ketose Nomenclature
*Aldohexoses: ALL ALTruists GLadly MAke GUm IN GALlon TAnk. 2 nd C: alternate OH 3 rd C: alternate OH by 2 4 th C: 1 st 4 Right OH, Last 4 Left OH 5 th C: all OH at right side Ketoses
Ketotriose
Ketotetrose
Ketopentose
Ketohexose
Aldotriose Aldotetrose Aldopentose Aldohexose Marco Perikar R. Dimaano 1BMed Class 2015
Fischer Projection Sugars drawn i n strai ght chai n Perspective structural formula: 3D Fi sher Haworth Projection Cycl i c forms whi ch show the mol ecul es as cycl i c and pl anar wi th substi tuents above or bel ow the ri ng Boat and Chair conformation: more pl ausi ble bent forms Fischer projection Haworth projection Optical Activity Abi l i ty to rotate pl ane of pol ari zed l i ght Al l CHOs contai n assymetri cal (chi ral ) carbon and are, therefore, optically active. a. Dextrorotatory (+): D i somer o Rotates to ri ght o In Fi scher, -OH i s at the ri ght si de of penul ti mate Carbon o In Haworth, l ast Carbon i s above the ri ng b. Levorotatory (-): L i somer o Rotate to l eft o In Fi scher, -OH i s at the l eft si de of penul ti mate Carbon o In Haworth, l ast Carbon i s bel ow the ri ng *Assymetric or Chiral Carbon: carbon with 4 different substituents *Penultimate Carbon: chiral carbon farthest from functional group
Stereochemistry Isomers: same mol ecul ar formul a and bonds but di ffer i n spati al arrangement A. Constitutional Isomers Di fferent atom connecti vi ti es B. Stereoisomers Same atom connecti vi ty, di fferent spati al arrangement 2 types: Confi gurati onal and Conformati onal 1. Configurational Isomers o Interconverted onl y by breaki ng coval ent bonds (separabl e) o 4 types: Enanti omer, Di astereomer, Epi mer, Anomer a. Enantiomer Stereoi somers whi ch are non-superi mposabl e mi rror i mages of each other (Eg. D-gl ucose and L-gl ucose) b. Diastereomer Stereoi somers whi ch are non-superi mposabl e non-mi rror i mages of each other (Eg. D-gal actose and D-gl ucose) c. Epimer Stereoi somers whi ch di ffer i n one stereocenter (di fferent -OH posi ti on al ong 1 Carbon atom onl y) Exampl e: D-gl ucose, D-mannose and D-gal actose d. Anomer Stereoi somers whi ch di ffer onl y i n the confi gurati on around the carbon (anomeri c carbon, usual l y C1) whi ch was i nvol ved i n the i ntramol ecul ar nucl eophi l i c attack (Eg. and anomers) Fischer Projection: anomer (Cis): OH of anomeric Carbon and hemibridge on same side anomer (Trans): OH of anomeric Carbon and hemibridge on opposite side Haworth Projection: anomer (Trans): C6 up, -OH of C1 (anomeric carbon) down if in D isomer C6 down, -OH of C1 (anomeric carbon) up if in L isomer anomer (Cis): C6 up, -OH of C1 (anomeric carbon) up if in D isomer C6 down, -OH of C1 (anomeric carbon) down if in L isomer *Mutarotation: and are in equilibrium Marco Perikar R. Dimaano 1BMed Class 2015
2. Conformational Isomers o Rel ated by rotati on around si ngl e bond (bendi ng and twi sti ng) o Interchange wi thout breaki ng coval ent bonds o Boat and Chai r conformati on a. Boat conformation: l ess stabl e due to steri c hi ndrances b. Chair conformation: more stabl e *Axial Bond: perpendicular to plane *Equatorial Bond: parallel to plane
Monosaccharides
Glucose Central sugar i n metabol i sm Can cycl i ze through i ntermol ecul ar nucl eophi l i c attack of one of the OHs on the Carbonyl Carbon of the al dehyde Occurs i f stabl e 5 or 6 member ri ngs can form Furanose (5 member) or Pyranose (6 member) On nucl eophi l i c attack to form the ri ng, carbonyl O becomes an OH Fructose: 67% pyranose, 33% furanose Ribose: 25%pyranose, 75% furanose * Glucose is exclusively pyranose. Fructose and Ribose are exclusively furanose.
Monosaccharide Derivatives
1. Sugar Acids Oxi di zed forms i n whi ch al dehyde and/or al cohol functi onal groups are oxi di zed to carboxyl i c aci d ( Oxi dati on) a. Aldonic Acid o Al dehyde group i s oxi di zed (Eg. Gl uconi c Aci d) b. Uronic Acid o Termi nal al cohol i s oxi di zed (Eg. Gl ucuroni c Aci d) c. Aldaric Acid o Both al dehyde and termi nal al cohol are oxi di zed 2. Sugar Alcohol Reducti on of Carbonyl group to OH (-ol) (Eg. Dulcitol: excess causes cataract in galactosemia patients) 3. Phosphorylated Sugar Phosphate i s added by ATP formi ng phosphoester deri vati ves Eg. Gl ucose-6-Phosphate Glucose-6-Phosphate 4. Amino Sugars Ami no group repl aced hydroxyl group (-OH to -NH) Eg. Gl ucosami ne, Gal actosami ne 5. Acetylated Amine Derivative Sugars deri ved from ami no sugars Eg. N-acetyl gl ucosami ne, N-acteyl gal actosami ne 6. Lactone Forms Intramol ecul ar esters Hydroxyl group attacks Carbonyl carbon that was previ ousl y oxi di zed to Carboxyl i c aci d (Eg. Gl uconol actone) 7. Deoxysugars One or more Carbon atoms have been reduced, l osi ng hydroxyl group (-OH to -H) (Eg. Deoxyri bose)
Marco Perikar R. Dimaano 1BMed Class 2015
8. Condensation Products of Sugar Derivatives with Lactate and Pyruvate Forms Murami c Aci d (gl ucosami ne + l acti c aci d) Forms Neurami ni c Aci d (mannosami ne + pyruvi c aci d) N-acetyl murami c Aci d (MurNAc or NAM): Gl cNac + l acti c aci d (ether l i nk at C3) o found i n bacteri al cel l wal l s Sialic Acids: o Found on surface of al l cel l s o Invol ved i n cel l contact/communi cati on o Invol ved i n recogni ti on bacteri a (chol era) and vi ruses (i nfl uenza) o N-acetyl -neurami ni c Aci d (NANA): N-acetyl mannosami ne (ManNac) + pyruvi c aci d found onl y i n humans l ack hydrol ase gene (92 base pai rs of gene mi ssi ng) o N-gl ycoyl -neurami ni c Aci d: N-gl ycoyl mannosami ne + pyruvi c aci d Have hydroxyl ase
Neuraminic Acid
Oligosaccharides
Polysaccharides
Homopolysaccharides: pol ysacchari des wi th 1 type of repeati ng monosacchari de uni t Starch: found i n pl ants; composed of: o Amylose (20%) Li near chai n of Glc i n 1-4 l i nks (or repeati ng mal toses) o Amylopectin (80%) Branched chai n i n 1-6 l i nks o Major part: Glc chai n of 24-30 uni ts (amyl ose) then branches off (amyl opecti n) Glycogen o Mai n carbohydrate storage i n ani mal s o Composed of Glc resi dues i n 1-4 l i nks and 1-6 branches (greater than starch) o Synthesi zed on Glycogenin protei n pri mer o Reason why gl ycogen i s stored rather than gl ucose: Has l ess osmoti c pressure than gl ucose, therefore, does not easi l y reacts wi th water o Source: Muscl es (greatest source i n terms of total gl ycogen mass source) and l i ver (greatest source i n terms of grams gl ycogen per gram ti ssue) Marco Perikar R. Dimaano 1BMed Class 2015
Cellulose o Li near chai n of Glc resi dues i n 1-4 l i nks (or repeati ng cel l obi ose) o Hel d together by i ntra- and i nter-chai n H-bonds o Most abundant bi ol ogi cal mol ecul e i n nature; cannot be broken down by humans (l ack of cel l ul ase) Chitin o Li near chai n of GlcNAc i n 1-4 l i nks Heteropolysaccharides: pol ysacchari des wi th 2 di fferent monosacchari de uni ts Complex Oligosaccharide Units Mucopolysaccharides/Glycosaminoglycans (MPS/GAG) o Ami no sugar + negati vel y charged sul fate or carboxyl group (uroni c aci d: gl ucuroni c or i duroni c aci d) o Form matri x to hol d protei n component of ski n, connecti ve ti ssue and extracel l ul ar matri x o Often coval entl y attached to protei ns to form proteogl ycans o Hyaluronic Acid Hyaluronic Acid Dermatan Sulfate Gl ucuronate(1-3)Gl cNAc Water sol ubl e; found i n synovi al fl ui d Backbone for attachment protei ns o Dermatan Sulfate L-Iduronate(1-3)Gal NAc-4-Sul fate o Chondroitin Sulfate D-Gl ucoronate(1-4)Gal NAc-4or6-Sul fate o Heparin D-Gl ucoronate-2-Sul fate(1-4)Gl cNSul fo-6-Sul fate Chondroitin Sulfate Heparin Anti thrombi n, natural l y-occurri ng anti coagul ant o Keratan Sulfate D-Gal (1-4)Gl cNAc-6-Sul fate No uroni c aci d component o Syndecan Heparan Sulfate Bi nds through i ntracel l ul ar domai n to the cytoskel eton Interacts wi th fi bronecti n o Glypican Heparin Keratan Sul fate Attached to outer surface of pl asma membrane vi a phosphati dyl i nositol l i pi d Peptidoglycans o Bacterial Cell Walls Offer protecti on from hypotoni c condi ti on and hi gh i nternal osmoti c pressure Long chai n of GlcNAc(1-4)MurNAc (NAG,NAM) Gram (+) Bacteria Mul ti -l ayered; cel l wal l can be Gram stai ned (vi ol et) Chai ns are coval entl y connected by a Pentaglycine Bridge through the -Ami no group of tetrapepti de Lysi ne on one strand and D-Al ani ne on another strand Teichoic Acid Al ternati ng resi due of D-Al a and NAG i n C2 Gl ycerol or Ri bi tol Phosphate backbone Mul ti pl e gl ycerol s are l i nked through Phosphodi ester Bonds Often attached to C6 of NAM Make up 50% of cel l wal l dry wei ght Present a forei gn anti geni c surface to i nfected host Serve as receptors for bacteri ophages Marco Perikar R. Dimaano 1BMed Class 2015
Gram (-) Bacteria Cel l wal l cannot be Gram-stai ned (red) No pentagl yci ne bri dge; chai ns are connected by di rect ami de bond between the -Ami no group of tetrapepti de Lysi ne on one strand and D-Al ani ne on another strand Hydrophobi c protei n coval entl y attaches (through Lys ami de bond) to the l ast ami no aci d i n the tetrapepti de uni t of cel l wal l (actual l y di ami nopi mel i c aci d/DAP, whi ch repl aces 10% of D-Al a i n cel l wal l ) No tei choi c aci d; Cel l wal l sandwi ched between l i pi d bi l ayer; Peri pl asmi c space space between l i pi d bi l ayers Lipopolysaccharide (O anti gen) coats the outer membrane and determi nes anti geni ci ty of bacteri a Proteoglycans o GAG coval entl y O-l i nked to protei n (usual l y to Ser resi due of Ser-Gl y di pepti des) o May contai n N-l i nked ol i gosacchari de groups o Carbohydrates > Protei ns o Sol ubl e o CHO part provi des an i ncredi bl e vari ety of bi ndi ng structures (acts l i nke gl ue) i n connecti ng i ntra- and extracel l ul ar cel l functi ons o Syndecan: protei n + hepari n sul fate + chondroi ti n sul fate; bi nds through i ts i ntracel l ul ar domai n to the i nternal cytoskel eton of the cel l whi l e i nteracti ng wi th fi bronecti n i n the extracel l ul ar matri x o Aggrecan: protei n + Chondroi ti n sul fate + Keratan sul fate; bi nds hyal uroni c aci d; i mportant i n hydrati on of carti l ages o Versican: protei n + Chondroi ti n sul fate; bi nds hyal uroni c aci d i n extracel l ul ar matri x Glycoproteins/Glycosylated Proteins o Protei ns post-transl ati onal l y modi fi ed by attachment of carbohydrates o Usual l y attached through ei ther Asn or Ser si de chai ns o Invol ved i n recogni ti on of bi ndi ng mol ecul es, preventi on of aggregati on duri ng protei n fol di ng, protecti on from preoteol ysi s , i ncrease i n protei n hal f-l i fe, bl ood cl otti ng, i mmunol ogi c protecti on and ABO bl ood groups. o N-linked glycoproteins Carbohydrate attached to ei ther Gl cNAc or Gal NAc to an Asn i n a X- Asn-X-Thr sequence of protei n Core ol i gosacchari de: (Man) 3 (GlcNAc) 2 attached to Asn 3 types: Mannose, Compl ex, Hybri d o O-linked glycoproteins Carbohydrate usual l y attached from a Gal (1-3)Gal NAc to a Ser or Thr of a protei n Eg. Bl ood Group Anti gens Storage Polysaccharides: Starch, Gl ycogen Structural Polysaccharides: Cel l ul ose, Chi ti n, GAGs, Pepti dogl ycans Marco Perikar R. Dimaano 1BMed Class 2015
Hemiacetal and Hemiketal Formation
Al dehyde or ketone group of monosacchari des can cycl ize through i ntramol ecul ar nucl eophi l i c attack of a hydroxyl group ( -OH) at the Carbonyl carbon i n an addi ti on reacti on formi ng Hemi acetal or Hemi ketal , respecti vel y. On addi ti on of aci d: anomeri c OH i s protonated, formi ng water, a l eavi ng group Another al cohol can be added formi ng Acetal or Ketal
Reducing Property of Sugars
Reducing Sugars: sugars whi ch can form an al dehyde at C1 or have an -hydroxymethyl ketone group whi ch can i someri ze to an al dehyde under basi c condi ti ons, such as fructose o Eg. Al l common monosacchari des, mal tose o Eg. Lactose: Si nce Gl c i s attached through the OH on C4, i ts anomeri c carbon coul d revert to noncycl i c al dehyde form, whi ch i s suscepti bl e to oxi dati on , thus, subsequentl y reduced. Non-Reducing Sugar: sugars i n whi ch there are no al dehyde or ketone group to react; sugar ri ngs are l ocked or not capabl e of openi ng o Eg. Sucrose: Si nce the anomeri c carbons of both Gl c and Fru are l i nked, i t cannot be reduced (nei ther of the ri ngs can be opened). Tests for i denti fyi ng Reduci ng Sugars: o Benedicts: Copper Sul fate + Al kal i ne Ci trate; deep bl ue bri ck red ppt o Fehlings: Copper Sul fate + Al kal i ne Tartrate; deep bl ue bri ck red ppt o Tollens: Si l ver Ni trate + Aqueous Ammoni a; col orl ess si l ver mi rror