Ha hc Glucid (Carbohydrat)

BS. Chi Mai

Mc tiu
Trnh by c nh ngha, phn loi, danh php monosaccharid Trnh by c tnh cht kh ca monosaccharid Trnh by c cu to, tnh cht kh v ngun gc ca sucrose, lactose v maltose Trnh by c ngun gc, cu to, vai tr ca tinh bt, glycogen, cellulose

Glucid (Carbohydrat)

L cc hp cht hu c c nhiu nht trong t nhin

Ngun cung cp nng lng chnh trong ba n ca chng ta

Vai tr cu trc v bo v ca vch t bo vi khun v thc vt, m lin hp ng vt Bi trn cc khp xng, tham gia vo s nhn bit v kt dnh cc t bo. Kt hp vi lipid v protein to cc cht lin hp glucid Cu to bi cc nguyn t C, H v O

c tng hp t CO2, H2O

Saccharid, ngha l ng Nhn chung, cng thc tng qut l (CH2O)n vi n 3

Phn loi Carbohydrat

Monosaccharid
Khng th b thy phn thnh cc carbohydrat nh hn
ng n (Simple carbohydrates)

Carbohydrat phc tp:

Oligosaccharid: 2-14 monosaccharid Polysaccharid: > 14 monosaccharid: thun, tp

1.Monosaccharid

Khi nim v monosaccharid L cc dn xut aldehyd hoc ceton ca cc polyalcol. (Mt C l nhm carbonyl; cc C cn li gn vi OH) Khng phn nhnh c t 3-8 C Chng khng b thy phn thnh cc phn t nh hn Aldose C nhm aldehyd (carbon 1) Cetose CH2OH C nhm ceton (carbon 2) O

CHO
CHO HO H CH2OH

HO H H

H OH OH
CH2OH OH

HO H

H OH CH2OH

Cch gi tn monosaccharid

Danh php:s carbon + ose.

triose = 3 carbon tetrose = 4 carbon pentose = 5 carbon hexose = 6 carbon

Thm tip u ng aldo- hay ceto- biu th chc kh aldehyd hay ceton.

Aldohexose Cetohexose

Tn ring:

CH2OH O
CHO

Glucose (Aldohexose) Fructose (Cetohexose)

HO H H

H OH OH
CH2OH OH

CHO HO H CH2OH

HO H

H OH CH2OH

Test nhanh
Phn loi 2 monosaccharid sau:
CH2OH
CHO HO HO HO H H H CH2OH

O HO H H H OH OH CH2OH

Cng thc hnh chiu Fischer

Dng biu din cu to thng ca carbohydrat

C oxy ha cao nht v tr trn cng (C1)

Dng ng nm ngang cho cc lin kt v pha trc Dng ng thng ng cho cc lin kt v pha sau

ng phn D v L

Theo quy c, L ch cu trc c nhm OH ca C* cui cng v pha tay tri D ch cu trc c nhm OH ca C* v pha tay phi

D v L Monosaccharid

Ha lp th c xc nh bng C bt i xa

nhm carbonyl nht

Phn ln monosaccharid tm thy trong t nhin thuc dy D

CHO H H H OH OH OH CH 2OH D D-Ribose

O C H HO H H H OH H OH OH
D D-Glucose

O C OH HO H H HO H OH OH H

CH2OH

CH2OH L L-Galactose

Test nhanh

Hy ch ra ng phn dy D v L :
CHO HO HO HO H H H CH2OH
H HO CHO OH H CH2OH

CH2OH O HO H H H OH OH CH2OH

Ribose

Threose

Fructose

Cc ng phn epimer

Cc ng ch khc nhau 1 trung tm d lp th

D-Glucose

L hexose ph bin

nht, cn gi dextrose

C trong hoa qu, si r v mt ong

aldohexose c cng thc phn t C6H12O6

L ng c trong

mu

n v cu to ca nhiu disaccharid v

polysaccharid

D-Fructose

Cetohexose C6H12O6

Khc glucose C1 v C2 (v tr ca nhm carbonyl)

L carbohydrat c v ngt nht (th hai l sucrose) Tm thy trong nc qu v mt ong

CH2OH C O HO C H H C OH H C OH CH2OH D-Fructose

Sinh ra t thy phn sucrose

Chuyn thnh glucose trong c th

D-Galactose

Aldohexose

Khc D-glucose C4
Khng tm thy dng t do trong t nhin Sinh ra t lactose, mt disaccharid (trong sa) Vai tr quan trng trong mng t bo h thn kinh trung ng

CHO H C OH HO C H HO C H H C OH CH2OH D-Galactose

Hy ghi nh!

Ghi nh!

Hemiacetal hay hemicetal (bn acetal hay bn cetal)

Hemiacetal l g?Phn ng gia nhm aldehyd hoc ceton vi alcol to bn acetal Hemiacetal c to thnh nh th no?
O H CH3 C H
+

OH

CH3OH

CH3

C OCH3

Nu alcol v carbonyl trong ni phn t lin kt vi nhau s to thnh ci g? Bn acetal ni H phn t. H

O C HO H O O H+ O O C H H

HOCH2 H CH2OH O C HO H O O H+

HOCH2 H O O C

C H

Cu to vng ca monosaccarid

Cc monosaccarid c t 5 C tr nn thng c cu trc vng, thng to vng 5- hoc 6-cnh

Nhm Hydroxyl C5 phn ng vi aldehyd hoc ceton

Cng thc Haworth biu din cu trc vng

c biu din t cng thc hnh chiu Fischer

C1 pha bn tay phi

Cu trc vng ca ng phn dy D c nhm CH2OH cui cng pha trn mt phng vng(C6) Nhm OH bn tri trong cng thc thng(C3) pha trn Nhm OH bn phi trong cng thc thng (C2, C4) pha di

Pyranose

6 CH2OH 5
H H O H OH H

Ging nh nhn Pyran

O

1
OH

OH

3
H

2
OH

pyran

ng phn v ca D-Glucose

Cu trc vng ca Fructose

L cetohexose, fructose to cu trc vng khi nhm OH C5 phn ng vi nhm ceton C2 To vng 5 cnh O furanose: ging nhn furan
furan

CH2OH C O HO C H H C OH H C OH CH2OH D-Fructose OH CH2OH O CH2OH OH OH OH CH2OH O OH OH CH2OH

-D-Fructose

-D-Fructose

Pyranose v Furanose

S chuyn dng ca monosaccharid

Trong dung dch, cc dng cu trc vng v thng c th chuyn i qua li S chuyn i gia 2 dng ng phn alpha v beta gi l Mutarotation. Ch c mt lng rt nh saccharid dng mch thng
2/3

1/3

Tnh n nh ca cu trc vng

Vng Pyranose khng phi

dng phng Cu trc dng gh l n nh nht
HO OH OH H H H OH OH H O H H HO HO H OH H OH H OH H O

Test nhanh
Vit cu to vng ca -D-galactose:
H C H C OH HO C H HO C H H C OH CH2OH O

-D-galactose

Tnh cht ha hc ca monosaccarid

Oxy ha nhm aldehyd ca aldose

To acid aldonic

Kh nhm carbonyl ca aldose hoc cetose

Alditol

Phn ng gia nhm OH bn acetal vi alcol to acetal hoc cetal

Glycosid

Oxy ha Monosaccharid

Aldose acid aldonic

ng kh (Reducing Sugar)

Tt c cc monosacarid u c tnh kh (b oxy ha) Th nghim Benedict

Nhm Carbonyl b oxy ha thnh acid carboxylic Cu++ b kh

O C H C OH HO C H H C OH H C OH CH2OH D-Glucose + Cu2+ H O C H C OH HO C H H C OH H C OH CH2OH D-Gluconic acid + Cu2O(s) OH

Kh cc monosaccharid

S kh nhm carbonyl sinh ra cc polyalcol, hay cc alditol

D-Glucose b kh thnh D-glucitol (cn gi l sorbitol)

Tnh cht ha hc ca monosaccarid

S chuyn dng ln nhau ca monosaccarid: glucose, fructose v mannose c th chuyn dng ln nhau trong mi trng kim yu Dn xut este: cc este phosphat ng vai tr quan trng trong chuyn ha glucid.

Cc Glycosid v lin kt glycosid

Khi mt monosaccharid dng vng phn ng vi mt alcol:

To ra mt glycosid (acetal) Lin kt c to thnh l lin kt glycosid ( hoc )

CH2OH O OH OH + HOCH3 OH OH OH OH CH2OH O glycosidic bond O CH3

+ H2O

OH

-D-Glucose

Methanol

Methyl--D-glucoside

Disaccharid

L oligosaccharid

Bao gm 2 monosaccharid

Disaccharid

Maltose + H2O
Lactose + H2O Sucrose + H2O

H+

Monosaccharid

Glucose + Glucose
Glucose + Galactose Glucose + Fructose

Maltose

ng ko mch nha

Hai phn t Dglucose lin kt vi nhau bi lin kt -1,4-glycosid

Sinh ra t thy phn tinh bt

C tnh kh

Tn gi ca Disaccharid

Gi tn ng th nht

Thm furano hoc pyrano

Lin kt glycosid trong ngoc n(# #) Gi tn ng th hai

Lactose v Sucrose

Lactose

ng sa
Galactose v glucose Lin kt -1,4-glycosid C tnh kh ng n Glucose v fructose Lin kt ,-1,2glycosid Khng c tnh kh

Sucrose

 ngt ca cc cht c v ngt

ng v cc cht ngt nhn to khc nhau v ngt Mi cht ngt c so vi sucrose, c quy c gi tr l 100 Aspartame

L aspartyl phenylananyl metyl este.

Nguy him vi bnh nhn phenylketonuric
HO H2N O

O O NH

Polysaccharid

Cn gi l glycan L carbohydrat phc tp Cc monosaccharid lin kt vi nhau bi lin kt glycosid C th mch thng hoc phn nhnh Polysaccharid thun

Do 1 loi monosaccharid to nn > 1 loi monosaccharid Cc chui lp li

Polysaccharid tp

Cu trc c xc nh bng phng php thy phn (glycosidase) v NMR

Polysaccharid
1. Thun

Cu trc:

Cellulose Chitin

6 CH2OH 5
H H O H OH H

1
OH

D tr:

OH

3
H

2
OH

Tinh bt (Amylose v Amylopectin)

Glycogen

D-Glucose

2. Tp: Glycosaminoglycan

Cellulose

Thnh t bo thc vt Polyme mch thng C th ti 15000 gc Glc Lin kt -14 glycosid Dng si rt chc Khng tan trong nc B thy phn bi cellulase (chm)

C ng vt n c, mi, nm g

Cu trc ca Cellulose

Cc chui thng song song Cc lin kt H gia cc chui

Chitin

Tng t cellulose, tr OH C2 c thay bi acetamid

Dn xut osamin
Polyme ca N-acetyl-D-glucosamin

Rt cng Cu to b xng ca ng vt chn t

Tinh bt

Thnh phn chnh trong ba n ca ngi Ngun cung cp nng lng chnh trong nhiu loi thc phm

Cu to gm amylose (15-25%) v amylopectin (75- 85%)

Amylose

n v cu to l glucose Mch thng do lin kt -1,4 glycosid To xon tri Phn nhnh (~ 24- 30 gc c mt nhnh) Lin kt -1,4- to mch thng v lin kt -1,6-glycosid ch phn nhnh

Amylopectin

Glycogen
L dng tinh bt ng vt Cu trc tng t amylopectin, nhng phn nhnh nhiu hn, nhnh ngn hn

Thy phn polysaccharid

Enzyme trong nc bt v d dy (amylase, mt glycosidase) c th thy phn lin kt -1,4 glycosid trong tinh bt, nhng khng thy phn c lin kt -1,4 glycosid ca cellulose

Glycosaminoglycan (polysacharid tp)

To matrix ging nh gel bao quanh collagen sn, gn, xng Polysaccharid khng phn nhnh n hi v qunh cao Xen k acid uronic v hexosamine Thng cha cc nhm sulfat

Glycosaminoglycan

Summary of Polysaccharides

Mc lc, phn 2

Cc cht lin hp glucid (Glycoconjugates)

Glycolipid
Glycoprotein

Proteoglycan Peptidoglycan

Xc nh cu trc ca carbohydrat

Cc cht lin hp glucid (Glycoconjugates)

Lin kt ng ha tr gia carbohydrat v cc sinh phn t Glycoprotein Glycolipid Chc nng ca cc oilgosaccharid:

Cu trc

a nc (protein surface) Cu hnh hn ch Kt gn b mt v nh hng n tnh phn ng nh du cc protein Giao tip gia cc t bo

Tnh phn ng

Nhn bit b mt

Glycolipid

Lipid cu trc mng

u a nc l cc
oligosaccharid Cc v tr nhn bit

Glycoprotein
Protein lin kt vi carbohydrat Microheterogeneity

Thnh phn thay i Phn glucid c th chim 1-70% hoc hn Cu trc, vn chuyn, enzym, receptor... Thng ngn (oligosaccharid) C th phn nhnh c tng hp bng cc phn ng enzym Lin kt ng ha tr vi polypeptid

Nhiu chc nng khc nhau

Chui carbohydrat

Proteoglycans

S kt hp ca protein vi

glycosaminoglycan ngoi
t bo

Li l protein Oligosaccharid to lin kt glycosid vi O ca Ser hay Thr

Proteoglycan Aggregates

B khung

4000-40000 n phn t hyalurnoat C th ti 100 Many types N-linked O-linked Sulfonated Anionic Extended structure

Cc Protein

Oligosaccharides

Highly hydrated

High resilience

N- and O-linkages

-glycosidic bond -glycosidic bond

Peptidoglycan

Vch t bo vi khun
Lin kt ng ha tr gia polysaccharid v cc chui polypeptid

D-acid amin chng li tc dng thy phn ca peptidase

Lysozyme c th thoi ha vch t bo Penicillin c th c ch tng hp