Chng 1 CU TRC V CHC NNG CA CARBOHYDRATE

1.1. CC MONOMER CA POLYSACCHARIDE

Carbon: Tt c cc phn t sinh hc u cha C

Cng thc tng qut: (CH2O)n cha cc nguyn t

C, H v O theo t l 1:2:1 L ngun carbon v nng lng ca t bo

1.1.1 CU TRC MONOSACCHARIDE

Cha mt nhm aldehyde (-CHO) hoc keton (C=O)
Hai hay nhiu nhm hydroxy (-OH) Phn loi da vo s lng carbon, v bn cht ca

nhm carbonyl

c im ca ng n: C mt carbon lin kt vi oxygen bng lin kt i (carbonyl), cc carbon cn li, mi carbon lin kt vi mt nhm -OH Monosaccharide n gin nht l triose: glyceraldehyd (aldose) v dihydroxyacetone (ketose)

Glyceraldehyd (aldo triose)

Dihidroxyacetone (keto triose)

ng phn ha hc

Sn carbon thng t 3 n 7 carbon, mt vi ng n ph bin sau: Loi ng Triose Pentose Hexose S carbon 3 5 6 V d Glyceraldehyde Ribose Glucose

Cng thc lp th Fischer (Cu oxy)

Glyceraldehyde c mt carbon bt xng (k hiu C*), c hai ng phn dng D v L

S ng phn lp th: X = 2n (n l s C*)

nh s th t nguyn t C trong phn t monosaccharide bt u t nguyn t C ca nhm C=O, hoc C u gn vi nhm C=O ca cc ketose

1
2 3 4 5

1 2 3 4 5 6

D- Glucose

D- Fructose

S sp xp khng gian xung quanh sn carbon rt a dng, v d glucose v galactose l hai ng phn

ng phn epimer

Cu trc vng ca monosaccharide (cng thc Haworth)

Nhm carbonyl hnh thnh lin kt cng ha tr vi oxy ca mt nhm hydroxyl dc theo chui carbon

Phn ng gia OH v CHO (hoc C=O) to nn dn xut hemiacetal hoc hemiketal cha C bt xng

C O OH H OH OH

CHO
1 2 3 4 5 6

Dng thng

H C HO C H C H C

CH2OH

CH2OH

H
1 2

OH O

HO
1 2 3 4 5 6

H O

H
1 2 3 4 5 6

OH

HO
1 2 3 4 5 6

Dng cu oxy

3 4 5 6

CH 2OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH HOCH O OH H HO H H OH H

Cng thc

HOCH O H H HO Haworth OH H OH H

CH2OH O H H H OH H HO OH H OH

CH2OH O OH H H OH H HO H H OH

- furan

- furan

- pyran

- pyran

Mt s ng aldose ph bin

3 Carbon

4 Carbon

5 Carbon

6 Carbon

Mt s dng ng ketose ph bin

3 Carbon

4 Carbon

Dn xut ca monosaccharide

Sinh vt cha nhiu dn xut ca ng hexose

Mt nhm hydroxyl c thay bng nhm khc
Mt nguyn t C b oxy ha thnh nhm carboxyl

Glucosamine: -OH C-2 c thay th bng nhm amin, nhm amin thng lin kt vi acid acetic N-acetylglucosamine l thnh phn cu trc ca v t bo vi khun

N-acetylmuramic acid trong acid lactic hnh thnh lin kt ether vi oxy C-3 ca Nacetylglucosamine

Nhm OH C-6 ca L-galactose hoc L-mannose c thay th bng nhm CH3 to L-fucose hoc L-rhamnose, nhng ng dehydro ny c tm thy trong polysaccharides v trong glycoproteins v glycolipids.

S oxy ha carbon carbonyl (aldehyde) glucose to thnh gluconic acid, nhng ng aldose khc to aldonic acid tng ng khc

S oxy ha carbon khc ca chui carbon (C-6) ca glucose, galactose, mannose to thnh cc uronic acid: glucuronic, galacturonic, mannuronic acid. Aldonic acid v uronic acid to thnh cht trung gian n nh gi l lactone.

1.1.2. Tnh cht chung ca cc monosaccharide

1.1.2.1. Monosaccharide l mt cht kh
Monosaccharide c th b oxy ha bi cc cht oxy ha nh

Fe3+ hoc Cu2+. Carbon ca nhm carbonyl b oxy ha thnh nhm carboxyl. Glucose v nhng ng khc c kh nng kh ion st hoc ng c gi l ng kh.

 Khi oxy ha bng HNO3 c, c hai nhm chc CHO v

OH bc 2 ca monosaccharide u b oxy ha to thnh acid c cha hai nhm carboxyl gi l acid saccharic.
CHO HCOH HOCH HCOH HCOH CH2OH
COOH HCOH HOCH HCOH HCOH COOH

HNO3

D-Glucose

Acid Glucaric (Acid Saccharide)

1.1.2.2. Monosaccharide l mt cht oxy ha

Di tc dng ca cc cht kh, nhm carbonyl ca

monosaccharide b kh to thnh cc polyhydroxy alcohol tng ng, vi tn gi c ui -itol thm vo tn ca aldose ban u
CHO
CH2OH

CH2OH C O

CH2OH

CHO

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

D-Glucose

D-Sorbitol

D-Fructose

D-Manitol

D-Mannose

 Trong c th sinh vt di tc dng ca enzyme, glucose

b kh to thnh polyol vng gi l myo-inositol.

OH OH H OH H H OH H H OH OH H
P O H PO H P H O O H P P P

O H O H

Myo-inositol

Fitin

Ester phosphoric ca myo-inositol (Fitin) l ngun d tr phospho trong ht

1.1.2.3. Phn ng to ester

Phn ng to ester thng xy ra vi nhm alcohol bc 1

v OH glucoside ca monosaccharide. Quan trng nht l phn ng to thnh ester phosphate ca monosaccharide l nhng sn phm trung gian ca nhiu qu trnh trao i cht trong c th. V d:

D-Glyceraldehyd 3-phosphate D-Glucose 1-phosphate D-Glucose 1,6-diphosphate D-Fructose 1,6-diphosphae

1.1.2.4. Phn ng ca nhm glycoside

Nhm hydroxyl glycoside c th phn ng vi ru khan

to thnh ether tng ng gi l glycoside. Cc glycoside to thnh c th l - glycoside hoc -glycoside

CH2OH O H H OH H OH

D-Glucose

CH3OH HCl

CH2OH O H H OH H OH

OCH3

OH

OCH3

OH

-Methyl-D-Glucose

-Methyl-D-Glucose

1.1.2.4. Phn ng ca nhm glycoside

Trong phn t glycoside, phn khng phi l saccharide

gi l aglycone. Lin kt saccharide v aglycone gi l lin kt glycoside. Lin kt glycoside cng c to thnh gia cc monosaccharide to nn cc di-, oligo-, polysaccharide

Phn bit cc kiu lin kt glycoside khc nhau

-O-glycoside: Gc aglycone (A) kt hp vi saccharide (X) qua O -S-glycoside: Gc aglycone c kt hp qua S -N-glycoside: Gc aglycone c kt hp qua N -C-glycoside: Carbon ca aglycone kt hp vi C ca saccharide

1.1.2.5. Phn ng vi acid

un si pentose, hexose vi acid nng cao, cc

monosacchride ny loi i 3 phn t H2O to thnh furfurol, oxymethylfurfurol. Cc sn phm ny ngng t vi cc hp cht phenol to thnh hp cht mu c trng, cc phn ng ny thng c s dng nh tnh, nh lng cc monosaccharide.

1.1.2.6. Phn ng vi phenylhydrazine

Trong nhng iu kin xc nh, 1 phn t saccharide c

th phn ng vi 3 phn t phenylhydrazine to thnh tinh th osazone.

1.2. OLIGOSACCHARIDE
2-10 monosaccharide Monosaccharide lin kt bng lin kt O-glycoside

1.2.1. Disaccharide
Cng thc tng qut C12H22O11 Monosaccharide lin kt bng lin kt O-glycoside Disaccharide c th c tnh kh hoc khng

Ph bin Lactose, Maltose (14), Isomaltose

(16) isomer, Cellobiose (14) isomer

Kiu lin kt glycoside trong disaccharide

Kiu 1: Lin kt gia 2 nhm OH hemiacetal, loi b 1 phn t nc. Disaccharide trong trng hp ny khng cn OH hemiacetal t do nn khng cn tnh kh (non reducing end).

Non reducing end

Kiu lin kt glycoside trong disaccharide

Kiu 2: Lin kt gia 1 nhm OH hemiacetal ca mt monosacchride ny vi 1 nhm OH no (khng phi hemiacetal) ca monosaccharide khc, kt qu to mt disaccharide vn cn tnh cht kh (reducing end).

Reducing end

 Maltose (ng mch nha), c cu to t 2 phn t -D- Glucose. Maltose vn c cha mt nhm OH t do nn vn cn tnh kh Maltose b thy phn bi maltase, hoc acid nhit cao to thnh 2 gc -D-Glucose

 Lactose c cu to t 1 phn t -D- Galactose v D-Glucose. Lactose vn c cha mt nhm OH t do nn vn cn tnh kh

Cc loi disaccharid ph bin

Disaccharide Monomer (ng n) c im chung Ln men ru Hin din trong sa

Maltose Lactose

Glucose + Glucose Glucose + Galactose

Sucrose

Glucose + Fructose

do thc vt tng hp

Lactose: Gal--1,4-Glc; ch hin din sa, b thy phn bi lactase Sucrose: Glc--1,2-Fru; c thc vt xanh tng hp; enzyme thy phn l sucrase Maltose: Glc--1,4-Glc; sn phm thy phn bi tinh bt bi amylase Cellobiose: Glc--1,4-Glc; c ngun gc t cellulose

1.2.2. Trisaccharide
L oligosaccharide c cha 3 gc monosaccharide Trisaccharide ph bin l raffinose, raffinose c cu to t 3 monosaccharide l galactose, glucose, fructose Raffinose khng c tnh kh

1.2.2. Tetrasaccharide
L oligosaccharide c cha 4 gc monosaccharide Tetrasaccharide ph bin l stachyose, stachyose c cu to t 4 monosaccharide l 2 gc galactose, 1 gc -DGlucose, 1 gc -D-fructose Stachyose khng c tnh kh

1.3. Cu trc v chc nng ca polysaccharide

Polysacchride l polymer ca cc monosaccharide,

c t 10-15 gc monosaccharide, lin kt vi nhau bng lin kt glycoside Chui phn nhnh hoc khng phn nhnh dng si hay ht

Phn loi polysaccharide theo s loi monosaccharide

Hai loi polysaccharide: ng th v d th

1.3.1. Polysaccharide ng th (homopolysaccharide)

Gm mt loi monomer Tn gi da theo tn gi ca monomer nhng i ose

thnh an Polysaccharide ng th c vai tr d tr (tinh bt, glycogen) hay cu trc (cellulose, chitin)

 Tinh bt Amylose: Do cc -D-glucose lin kt nhau bng cu ni (14) glycoside to thnh si khng chia nhnh. Amylopectin: Do cc glucose lin kt nhau bng cu ni (14) glycosidic v (16) glycosidic to thnh si chia nhnh. 10- 30% amylose v 70- 90% l amylopectin Mi nhnh amylopectin l 12-30 phn t ng glucose Tinh bt c d tr t bo thc vt T bo ng vt c enzyme thy phn tinh bt

Amylopectin

Phytoglycogen (glycan) Polymer ca cc -D-Glucose, c cu trc tng t amylopectin nhng phn nhnh nhiu hn. Phytoglycogen ch mi tm c trong mt s t thc vt nh bp ng

 Glycogen

Do cc glucose kt nhau bng cu ni (14) glycosidic v (16) glycosidic to thnh si chia nhnh. c d tr c v gan ca t bo ng vt

Tinh bt

Glycogen

 Dextran

Do cc glucose kt nhau bng cu ni (16) glycoside v cc nhnh vi lin kt (13) glycoside v i khi (12) v c (14) glycoside, khi lng phn t c th n vi triu. Dextran l polysaccharide ca vi khun, nm men ng dng ca dextran:

Thay th huyt tng Chng ng mu, thay th heparin Dextran tng hp khng tan, c cc lin kt cho (sephadex) l tch ring cc phn t protein

Cellulose

Cellulose: Do nhiu phn t -glucose lin kt vi nhau bng lin kt (14) glycoside, to thnh si di khng chia nhnh Cellulose c nhiu t bo thc vt

Cellulose

Cellulose kt thnh si v t bo

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Cu trc ba chiu ca cc polysacchride

Chui polysaccharide bao gm cc vng pyranose c th

cun li nh cc tng tc yu nh lin kt hydro do trong chui cn nhiu gc OH t do, tng tc k nc, tng tc van der Waals v c tng tc tnh in nu polysaccharide c tch in.

S thy phn lin kt glycoside trong polysaccharide

Glycogen v tinh bt c ng vt tiu ha do enzyme -

amylase c tuyn nc bt v rut tit ra ct lin kt 1,4 glycoside gia hai glucose. a s ng vt khng th tiu ha cellulose v thiu enzyme thy phn lin kt -1,4 glycoside gia hai glucose. Mt s ng vt c vi sinh vt Trichonympha cng sinh tit cellulase, thy phn lin kt -1,4. Mt s nm v vi khun cng c th to enzyme ny.

Chitin:
Dn xut ca glucose (N-acetyl glucosamine) ni nhau bng cu ni -1,4 thnh si nh cellulose. C nhiu v gip xc, nm Si chitin c th l song song hoc i song song

1.3.2. Polysaccharide d th (heteropolysaccharide)

Thng c trong cht nn (matrix) t bo thc vt, vi khun, to, trong gian bo (extracellulose space) ca cc m lin kt , c bit l sn, gn, dy chng. Cht nn ngoi bo (extracellulose matrix, ECM) c tnh cht nh gel, l h thng chng cht cc heteropolysaccharide v cc protein hnh si, chon y khong khng gian ngoi bo cc m ng vt, gip cc t bo gn kt vi nhau, l mi trng O2 v cc cht dinh dng i vo mi t bo. Mt s heteropolysaccharide ph bin c vai tr quan trng trong thc vt l agar, hemicellulose, pectin, v ng vt l cc glucosaminoglycan.

1.3.2.1. Agar - Agarose

L polymer bao gm 600-700 n v cu trc lp li

(repeating unit, RU) kt hp vi nhau qua lin kt (13) glycoside. Mi RU bao gm D-Galactose kt hp vi 3,6 anhydroLGalactose.

 Mt loi to vch t bo cha agar c cu to t

sulfated heteropolysaccharide ca D-galactose vi mt dn xut ca L-galactose bng lin kt ether gia C-3 v C-6 Agar c hai dng chnh Agarose (Mr ~120.000): Polymer khng phn nhnh Agaropectin c mt nhnh

Trng thi lng

Dng gel ban u

Cu trc gel cui cng

Vch t bo vi khun v to cu to t polysaccharide d th

Thnh phn ca v t bo vi khun gm N-acetylglucosamine v N-acetylmuramic acid lin kt nhau bng lin kt (1-4) Cc si polymer nm cnh nhau lin kt nhau bng si peptide ngn: gip cc si polysaccharide dng phin v ngn cn s teo bo v v t bo do s thm thu ca nc

Enzyme lysozyme git vi khun do thy phn lin kt (1-4) glycoside gia N-acetylglucosamine v N-acetylmuramic acid Penicillin v cc khng sinh lin quan git vi khun do ngn cn qu trnh tng hp cc polypeptid, nn v t bo yu i vi qu trnh thm thu

Glycosaminoglycan l mt polysaccharide d th ca cht ngoi bo

Cht ngoi bo gm polysaccharide d th v cc protein

dng si nh collagen, elastin, fibronectin v laminin Polysaccharide l glycosaminoglycan l mt polymer do s lp li ca hai n v disaccharide

Mt monosaccharide lun lun l N-acetylglucosamine hoc Nacetylgalactosamine Monosaccharide cn li phn ln l mt trong cc uronic acid nh D-glucoronic acid hoc L-iduronic acid

Mt hoc nhiu nhm OH ca ng amino c ester

ha vi sulfate S kt hp ca nhm sulfate v carboxyl ca uronic acid lm cho glycosaminoglycan c t trng cao v tch in m

 S chuyn bit ca ng c sulfate ha hoc khng

trong glycosaminoglycan dn n s nhn din chuyn bit ca nhiu loi protein phi t (ligand) Glycosaminoglycan gn vi protein ngoi bo thnh lp proteoglycans

Hyaluronic acid
Cha mt gc bin i ca D-glucuronic acid v N-

acetylglucosamine Hyaluronate cng l thnh phn quan trng ca cht ngoi bo gn v sn

 Hyaluronidase l enzyme do mt s vi khun gy

bnh tit ra c th thy phn lin kt glycosidic ca hyaluronate m d b vi khun xm nhim Nhiu sinh vt c enzyme tng t trong tinh trng thy phn lp glycosaminoglycan ca t bo trng gip tinh trng xm nhp d dng

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Chondroitin sulfate
To sc cng cho dy chng, sn, gn v thnh ng mch Dermatan sulfate to nn tnh do ca da, hin din trong

mch mu v van tim. Nhiu glucuronate (GlcA) hin din trong chondroitin sulfate c thay th bi cc epimer ca n nh iduronate (IdoA)

Keratan sulfate
Khng c uronic acid Keratan sulfate hin din trong gic mc, gn, xng v

nhng cu trc sng nh sng, tc, mng, vut.

Heparin
L mt cht chng ng mu t nhin do t bo mast tit

v phng thch vo trong mu. Heparin lin kt vi protein antithrombin v c ch s ng mu

Proteoglycan, Glycoprotein, v Glycolipid

Tm tt mt s vai tr quan trng ca carbohydrate D tr: tinh bt, glycogen, dextran Cu trc: cellulose, chitin, peptidoglycans Cht mang thng tin: polysaccharide v oligosaccharide
Nh nhn cho mt s protein chuyn ch Cht trung gian (mediator) trong s tng tc gia cc t bo chuyn bit, gia t bo v cht ngoi bo Nhng phn t cha carbohydrate chuyn bit hot ng trong s nhn din t bo, s kt dnh t bo trong sut qu trnh pht trin, ng mu, p ng min dch Phn ln carbohydrate c chc nng thng tin, lin kt cng ha tr vi lipid hoc protein to glycoconjugate

Proteoglycan
i phn t ca b mt t bo hoc cht ngoi bo Mt hoc nhiu si glycosaminoglycan lin kt vi protein

mng hoc protein tit bng lin kt cng ha tr Proteoglycan l thnh phn chnh ca m lin kt nh sn. T bo ng vt c th to t nht 30 phn t thuc h proteoglycan Proteoglycan nh hng n s pht trin ca cc m chuyn ha, lin quan n nhiu yu t tng trng, iu ha cc yu t ca cht ngoi bo

Cu trc c bn ca mt proteoglycan
Mt proteoglycan gm mt li protein lin kt cng ha tr vi glycosaminoglycan

Glycosaminoglycan

Cu ni triglyceride

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Proteoglycan
Nhiu proteoglycan c tit vo bn trong cht ngoi

bo, mt s khc c protein hi nhp vi mng V d: syndecan l li protein (Mr 56.000), c mt domain xuyn mng v mt domain bn ngoi t bo

Domain bn ngoi t bo mang 3 si heparan sulfate v hai si chondroitin sulfate, mi si gn vi mt gc serin

Heparan sulfate trong proteoglycan gn vi nhiu loi ligand bn ngoi t bo iu chnh s tng tc gia ligand vi cc th th trn b mt t bo

Cu to ca mt heparan sulfate trong proteoglycan

[N-acetylglucosamine (GlcNAc) + Glucuronic acid (GlcA)]50 -200 ln

Enzyme epimase bin i GlcA IdoA Enzyme sulfotransferase gn gc sulfate C-2 ca IdoA v C-6 ca N-sulfated glucosamin 1 polymer vi nhiu domain c gn gc sulfate (S domain), 1 domain ch gm GlcNAc v GlcA gi l NA domain Enzyme N-deacetylase, N-sulfotransferase thay th mt s nhm acetyl bng nhm sulfate N-sulfated glucosamin (GlcN)

S domain ca heparan sulfate gn mt cch chuyn bit vi protein ngoi bo v nh hng n hot ng ca cc protein ny

Glycoprotein
Carbohydrate lin kt carbon anomeric vi nhm OH ca

Ser hoc Thr (O-linked) hoc lin kt N-glycosyl gn N ca gc amin ca Asn (N-linked).

Glycolipid v Lipopolysaccharide l thnh phn ca mng

Glycolipids
Lipid lin kt vi mt hoc nhiu oligosaccharide bng

lin kt cng ha tr Gangliosides l lipid mng ca t bo chn hch, c u phn cc pha bn ngoi mng l mt oligosaccharide cha sialic acid v nhng gc monosaccharide khc. Mt s gc oligosaccharide ca ganglioside gip xc nh nhm mu.

Lipopolysaccharide

Lipopolysaccharide l thnh phn ca v t bo vi khun

Gram m nh Escherichia coli v Salmonella typhimurium Lipopolysaccharide ca Salmonella typhimurium cha 6 acid bo lin kt vi hai gc glucosamine

Carbohydrate nh mt phn t mang thng tin: m ng (the sugar code)

T bo s dng nhng oligosaccharide chuyn bit m

ha nhng thng tin quan trng ca cc qu trnh bn trong t bo, bao gm: S tng tc t bo S pht trin m Tn hiu bn ngoi t bo

Lectin l protein c m ng v tham gia nhiu qu trnh sinh hc

Lectin l protein c th gn vi carbohydrate vi mt i lc

ln v chuyn bit. Lectin c vai tr ln trong s nhn din t bo (cell-cell recognition), s nh du (signaling), s gn (adhesion) t bo v s tng hp cc phn t protein mi.

Mt s hormone c chui oligosaccharide nh hng n s tun hon ca mu: Luteinizing v thyrotropin (v thng thn) c lin kt N-linked oligosaccharide lin kt u cui ca oligosaccharide vi hai ng n GalNAc4S (14)GlcNAc, phn ny c nhn din bi lectin (th th) ca t bo gan. S tng tc ca th th v hormone xy ra dn n s gim ca hormone ny trong mu (hormone ny tng ln trong mu l do vng v thng thn tit ra, v gim hoc b ph hy l do t bo gan).

Selectin
Cng l h lectin trn mng nguyn sinh cng c vai tr

trong s nhn din v s gn t bo. V d: Bnh lot d dy do vi khun Helicobacter pylori gn mt pha trong ca d dy do s tng tc lectin ca mng vi khun v ca oligosaccharide chuyn bit ca glycoprotein mng ca t bo biu m d dy

V tr gn c H. pylori nhn din l oligosaccharide Leb l mt phn trong cu trc ca nhm mu O nhng ngi mang nhm mu O b lot d dy nhiu hn mu A v B

 V d: c t cholera do vi khun Vibrio cholerae gy bnh

tiu chy. c t ny gn ln mt oligosaccharide ca phospholipid mng l ganglioside GM1 trn b mt t bo biu m rut nc khng c hp thu. c t pertussis do vi khun Bordetella pertussis, gy nn bnh ho khc khc. c t ny s tng tc vi mt hoc nhiu oligosaccharide c u tn cng l sialic acid s xm nhim ca vi khun vo t bo.

 Hiu bit v nhng oligosaccharide ny gip tng hp ra

nhng ng phn tng t vi c t (lectin) s dng trong vaccine. Nhng vaccine ny thiu v tr gn ca carbohydrate khng th i vo bn trong t bo nhng c th kch thch h min dich to ra khng th. Hoc tng hp nhng oligosaccharide ging vi b mt t bo, nhng oligosaccharide ny s gn vi lectin hoc c t ca t bo vi khun ngn cn s xm nhp ca vi khun vo t bo

CHN THNH CAM N