PGS,TS.

NGUYEN PHC NHUAN

M C TIU
1. nh ngha glucid, monosaccharide, oligosaccharide, polysaccharide. Phan biet cac dang ong phan D va L, va ; cau truc vong 5 canh furanose va vong 6 canh pyranose cua monosaccharide Cong thc cau tao cua cac ng n pho bien : ribose, deoxyribose, glucose, galactose, fructose. Cong thc cau tao cua mot so ng oi co tnh kh va khong co tnh kh : saccharose, maltose, lactose, cellobiose. Cau truc va tnh chat cua polysaccharide thuan (tinh bot, glycogen va cellulose) va polysaccharide d the (hemicellulose, cac peatin, mucopolysaccharide). Lien ket glycosidic va lien ket hydrogen trong cau truc phan t glucid.

BI GI NG SINH HA H C
PH N I SINH HA H C TNH Chng 1- GLUCID

2. 3. 4. 5.

TP.HO CH MINH-2008

6.

Chng 1- GLUCID
1. AI CNG 2. MONOSACCHARIDE 3. DISACCHARIDE 4. POLYSACCHARIDE

1. AI CNG 1.1. NH NGHA : Glucid la mot lp chat hu c pho bien trong the gii ong vat, thc vat va vi sinh vat, vi cong thc phan t tong quat la Cn(H2O)n carbonhydrate. Ngi ta phan glucid lam 3 nhom ln : - Monosaccharide (ng n); - Oligosaccharide (ng nho, 2 10 goc ng n); - Polysaccharide (ng a) :
o Thuan nhat o Khong thuan nhat

1.2. VAI TRO Trong c the ong vat : ng n : glucose trong mau, ng oi : lactose trong sa, ng a : glycogen d tr trong gan va c. Cung cap cho c the ong vat 70-80% nhu cau nang lng. Tham gia cau tao mo bao trong phc hp vi protein la nhom glucoprotein (cac chat nhay trong niem dch, chat ciment gan ket mo bao .). Vai tro kh oc gan, thuoc ve acid glucuronic. Glucid la thanh phan chu yeu, chiem ty le 80-90% vat chat kho trong te bao thc vat (tinh bot, cellulose .)
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CH2- OH CH- OH CH2- OH Glycerol

C H CH - OH CH2- OH Glyceraldehyde

Nhom ch c aldehyde
ALDOSE

CH2- OH Nhom ch C=O CH2- OH Dihydroxyacetone

c ketone
KETOSE

2. MONOSACCHARIDE 2.1. NH NGHA La cac aldehyde hay ketone cua polyalcohol : - Aldehyde aldose - Ketone ketose - Tuy theo so C trong phan t ma phan biet : 3 C : triose 4 C : tetrose 5 C : pentose 6 C : hexose 7 C : heptose 8 C : octose

2.2.CAU TAO DANG THANG VA DANG VONG

Dang thang - Cac monosaccharide co C bat oi (C*) tao ra cac ong phan lap the khac nhau (x = 2n). - Quy c cau hnh ong phan l p th day D hay L cua monosaccharide da vao cau hnh cua glyceraldehyde: Cau hnh D : nhom OH c a C* canh nhom ru bac nhat ben phai truc thang ng; cau hnh L th ngc lai. Cau hnh L la hnh anh oi xng qua gng cua cau hnh D. ng n trong t nhien thng co dang D.
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- Them dau (+) e ch s quay mat phang tia phan cc ve ben phai, hay dau (-) ben trai.

CONG THC HNH CHIEU FISHER CHO H-C*- OH CH2OH D-glyceraldehyde O C-H H- C- OH HO-C- H H- C- OH H- C*- OH CH2OH D (+) Glucose CHO HO-C*-H CH2OH L-glyceraldehyde O C-H HO-C- H H -C- OH HO-C- H HO-C*- H CH2OH L (-) Glucose

O OH OH H- C H- C OH H- C H- C- OH H- C- OH H- C- OH HO-C- H HO-C- H - HOH HO-C- H O + HOH H- C- OH H- C- OH H- C- OH H- C- OH H- C- OH H- C CH2OH CH2OH CH2OH D-Glucose D-Glucose , D-Glucose (d ng th ng) (d ng vng 6 c nh) (d ng hydrate)

Dang vong : trong dung dch nhom aldehyde cua cac aldose hay nhom ketone cua cac ketose tac dung vi mot nhom OH trong cung phan t tao thanh dang hemiacetal. - Vong 5 canh : vong furanose Vong 6 canh : vong pyranose -Quy c : dang vong cua monosaccharide bieu dien theo nguyen tac cua Haworth : cac nhom H va OH nam ben phai trong cong thc hnh chieu Fisher c bieu dien pha di mat phang vong; neu ben trai -pha tren. - ong phan : nhom OH glycoside di mat phang ong phan - tren. - Moi cap ong phan tng ng cua mot chat (D-L, - )
goi la anomer
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CH2OH
5

O
1 2

HOCH2
5 4

O
HO
3 2

CH2OH OH

OH
3

OH

OH

OH ,D-Glucopyranose
(nguyn t c Haworth)

OH ,D-Fructofuranose

H- C- OH H- C- OH HO-C- H O H- C- OH H- C CH2OH , D-Glucose CH2OH OH OH OH

O C-H H- C- OH HO-C- H H- C- OH H- C- OH CH2OH D(+) Glucose (d ng th ng)

HO-C- H H- C- OH HO-C- H O H- C- OH H- C CH2OH , D-Glucose CH2OH OH OH OH OH

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1.3. TNH CHAT Tnh kh (b oxy hoa) : tao thanh acid - Nhom aldehyde b oxy hoa acid aldonic Glucose acid gluconic (C1OOH) - Nhom ru bac nhat b oxy hoa acid uronic Glucose acid glucuronic (C6OOH) Galactose acid galacturonic - Neu ca 2 nhom b oxy hoa acid saccharic

Nhom OH glycosid (OH hemiacetal)

OH , D-Glucopyranose

, D-Glucopyranose

ng n bi oxy ha (c tnh kh ) t o ra acid : 6

HOCH2
5 2

CH2OH
4

HOCH2
5

OH
4

OH OH
3

OH
3

CH2OH
1

OH , D-Fructofuranose

OH , D-Fructofuranose

O C-H H- C- OH HO-C- H H- C- OH H- C- OH CH2OH Glucose

H- C- OH HO-C- H H- C- OH H- C- OH CH2OH A. gluconic

1COOH

O C-H H- C- OH HO-C- H H- C- OH H- C- OH 6COOH A.Glucuronic

COOH H- C- OH HO-C- H H- C- OH H- C- OH COOH A.Glucaric

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 ng n c tnh oxy hoa (b kh nhan them 2H) ru Nhom aldehyde + 2H - CH2OH

CH2OH OH OH
Glucose

CH2OH OH + CH 3 OH
- H2 O

O C-H H- C- OH HO-C- H H- C- OH H- C- OH CH2OH Glucose

CH2OH H- C- OH HO-C- H H- C- OH H- C- OH CH2OH Sorbitol

Glucose Mannose Galactose Ribose Xilose

Sorbitol Manitol Dulxitol Ribitol Xilitol

OH

O CH3 OH Methyl -glycoside OH CH2OH

OH

CH2OH OH OH OH NH2 Glucosamine

OH

OH

OH NH-CO-CH3

N-acetyl glucosamine

Tao thanh glycoside : Nhom OH hemiacetal co the lien ket vi cac goc phi glucid (goi la nhom aglycone) tao thanh glycoside (TD: Methyl glycoside) Nhom OH hemiacetal lien ket vi nhom OH hemiacetal hay nhom OH bat ky cua monosaccharide khac tao thanh disaccharide, lien ket tao thanh goi la lien ket glycosidic. ay la nguyen tac e tao thanh di, tri , tetra polysaccharide. Tao thanh ng amine : Thng nhom OH C2 c the bi nhom amine NH2. N-Acetylneuraminic acid (Sialic acid Sia)
CH3 CH COOH HO NH CH2OH O O H H C CH3 O OH

N-Acetyl muramic acid (NAM)

COOC=O H -C H H C OH O H3CC- NH C H HO C H H C OH H C OH CH2OH

1 2 3 4 5 5 6 7 8 9 4 9 3 6 7,8

CH2OH O H - C NH C - R
1 2

H -C OH CH HC (CH2)12 CH3 SERAMIDE (N-Acyl sphingosine)

N-Acetyl neuraminic acid (Sialic acid SA) hp phan cua ganglioside, tp mang t/b

Gal NAc Gal

1,3

1,4

Gal

1,4

Glu

Ceramide

2,3

NAN (SA)

Ganglioside GM3 Ganglioside GM2 CAU TRUC GANGLIOSIDE GM1

2.4. CAC MONOSACCHARIDE PHO BIEN Hai nhom quan trong la pentose va hexose. Cac pentose thuoc nhom aldose : D-Ribose va D-Deoxyribose L- Arabinose va D-Arabinose; D-Xylose Cac pentose thuoc nhon ketose : D-Ribulose va D-Xylulose Cac hexose thuoc nhom aldose : Glucose , Galactose , Mannose Hexose thuoc nhom ketose : Fructose

Hnh 1.1 : Cac pentose thu c nhom aldose

O C-H H- C- OH HO- C- H HO- C- H CH2OH L-Arabinose

O C-H H- C- OH H- C- OH H- C- OH CH2OH D-Ribose O C-H HO- C- H H- C- OH H- C- OH CH2OH D-Arabinose

O C-H H- C- H H- C- OH H- C- OH CH2OH D-Deoxyribose O C-H H- C- OH HO- C- H H- C- OH CH2OH D-Xylose

CH2OH C=O H- C- OH H- C- OH CH2OH D-Ribulose Hnh 1.2 : Cc pentose thu c nhm ketose

CH2OH C= O HO- C- H H- C- OH CH2OH D-Xylulose

HOCH2
4 1 3 2

HOCH2
4 1 3 2

OH

Cac pentose quan trong thc vat

OH

H
5 H

H OH HO H 5 OH

OH OH -D-Ribofuranose HOCH2 -D-Deoxyribofuranose

4 5

OH

OH OH

-D-Ribofuranose OH
1 3 2

OH

OH , D-Xylose

OH OH

-L-Arabinose

OH

O C-H H- C- OH HO-C- H H- C- OH H- C- OH CH2OH Glucose

Hnh 1.4 : Cc hexose ph bi n

O C-H HO-C- H HO-C- H H- C- OH H- C- OH CH2OH Mannose

CH2OH C= O HO-C- H H- C- OH H- C- OH CH2OH Fructose O C-H H- C- OH HO-C- H HO-C- H H- C- OH CH2OH Galactose

Mot so dan xuat quan trong cua hexose :

H HO CH 5 3 OH OH

H
5 CH3

OH OH

OH OH
-L-Rhamnose (6-deoxy-L-mannose)

OH
-L-Fucose

(6-deoxy-L-galactose)

CH2OH
5 5

HOCH2
5

OH
4

NG T C A NG Ga tr dinh d ng c a ng c quy t nh do : - Kh nng c th tieu hoa, hap thu nhanh, cao; - Ga tr nng l ng cao. V m t c m quan (hng v ) ng t cung rat quan trong trong CNTP : - Saccharose - Fructose - Glucose : 100 : 173 : 74 - Xilose - Maltose - Rafinose - Lactose : 40 : 32 : 23 : 16

4 OH 1 OH 3 2 OH

OH
3

CH2OH
1

OH , D-Glucopyranose
6

OH ,D-Fructofuranose
6

CH2OH
5 5

CH2OH
5 5

HO

4 OH 1 3 2 OH

4OH HO 1 OH 3 2 OH

OH ,D-Galactopyranose

, D-Mannopyranose

- ng nghch ao : 130

ng t c a m t s hydrate carbon
Hydrate carbon -D-Fructose Saccharose -D-Glucose -D-Glucose -D-Galactose -D-Galactose -D-Mannose -D-Mannose -D-Lactose -D-Lactose -D-Maltose ng t trong dung d ch 100 175 100 40 79 30 40 27 67 59 ng 16 38 48 32 -46 ng t c a ch t k t tinh 180 100 74 82 32 21 32 ng 16 32 -

3. CAC DISACCHARIDE 3.1. DISACCHARIDE CO TNH KH La disaccharide con nhom OH glycoside t do : -Maltose : -glucose + -glucose LK (1 4)glycosidic -Lactose : -galactose + -glucose LK (1 4)glycosidic -Cellobiose : -glucose + -glucose LK (1 4)glycosidic 3.2. DISACCHARIDE KHONG CO TNH KH - Saccharose : -fructose + -glucose LK (1 2)glycosidic

Cac hp chat co v ngot, khi co s thay oi cau truc phan t du nho cung co the lam mat v ngot. Th du :

CH2OH OH
5 4 OH 1

CH2OH OH OH
5 4 OH 1

OH

O C NH SO2 Saccharin (rat ngot)

O C N CH3 SO2 N-Methyl saccharin (khong v)

OH , D-Glucose CH2OH OH
5 4 OH 1

OH , D-Glucose -H2O CH2OH O

5 4 OH 1

OH

OH OH MALTOSE v i LK (1 4) glycosidic

HO

CH2OH
5 1

CH2OH OH OH
5 4 OH 1

CH2OH OH
4 OH 5

CH2OH OH
4 OH 5

OH
1

4 OH

OH ,Galactose CH2OH HO 5
4 OH 1

OH , D-Glucose CH2OH O
4 OH 5 1

OH -Glucose CH2OH
5 4 OH

OH

OH -Glucose -H2O CH2OH O

5 4 OH

OH

OH

OH
1

OH LACTOSE, LK (1 4) glycosidic

OH

OH

OH

OH

CELLOBIOSE, LK (1 4) glycosidic

CH2OH
ng ngh ch o (quay triinvertin)

CH2OH OH -H2O
un v i acid; enzyme invertase

OH

5 4 OH

OH

4 OH

-Glucose

HO OH
1

OH O OH
2

HOCH2 H

HOCH2 H CH2OH
1

22 OH CH2OH

OH -Fructose

OH SACCHAROSE LK - (1 2) glycosidic

4. POLYSACCHARIDE 4.1. POLYSACCHARIDE ONG THE : phan t ch cha cac ng n. Neu ch gom ong nhat mot loai ng n th lay ten ng n + uoi AN : ARABINOSE ARABAN (1) Tinh bot (amidon) : dang d tr glucid trong hat, cu, qua. - Amylose : cha vai tram goc -glucose, lien ket (1 4) glycosidic, phan t dang xoan, tan trong nc, cho phan ng mau xanh vi iod. Chiem ty le 15-25% trong tinh bot. PTT : 20.00050.000. - Amylopectin : Cau truc phan nhanh vi iem phan nhanh co lien ket (1 6) glycosidic. un nong tao thanh ho, cho mau tm o khi tac dung vi iod. Chiem ty le 75-85% trong tinh bot. PTT : vai trieu. (2) Glycogen (tinh bot ong vat) : Phan nhanh day hn amylopectin. D tr gan (5%) va c (1%).

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CH2OH CH2OH
4 OH 5 1

CH2OH
1

CH2OH
1

CH2OH O
4 OH 5 1

CH2OH O
4 OH 5 1

5 4 OH

HO

OH

OH

OH

5 4 OH

5 4 OH

OH CH2OH O
5 4 OH 1

OH

OH

OH O
6CH
2

OH

Hnh 1.7 : M ch amylose v i lien k t (1 4) glycosidic

OH

5 4 OH

Hnh 1.8 : C u t o amylopectin V i LK (1 4) v (1 6) glycosidic

OH

CAU TRUC XOAN CUA MACH AMYLOSE

CAU TRUC HAT TINH BOT

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(3) Cellulose : Thanh phan chnh cua thanh te bao thc vat. Thng lien ket vi cac thanh phan khac : lignin, hemicellolse, pectin. Phan t chuoi dai khong phan nhanh, tao bi cac goc -glucose vi lien ket (1 4) glycosidic. (4) Dextran : tao bi cac goc -glucose vi LK (1 6) glycosidic. Co iem phan nhanh 1 2, 1 3 va 1 4. La dang d tr glucid cua nam men va vi sinh vat. Dung dch co o nht cao.

CAU TRUC PHAN T GLYCOGEN

2 2 1 4 2

Co the thanh lap cac lien ket hydrogen vi cac phan t cellulose khac tai cac iem C2 nay tao thanh bo si

Hnh 1.9 : C u t o cellulose

CAU TRUC PHAN T TINH BOT VA GLYCOGEN

v i lin k t (1 4) glycosidic

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CH
5

2 O

CH 2

O 1
2

4.2. POLYSACCHARIDE D THE

CH 2 2
5

O 1
2

Thanh phan ngoai ng n con co cac phan phi glucid nh goc acid acetic, phosphoric, sulfuric (1) Cac hp chat pectin : tp chu yeu : cac acid galacturonic, lien k t (1 4) glycosidic. - Pectin hoa tan (acid pectinic) : polygalacturonic acid, mot so nhom (-COOH) c methyl hoa (-COO-CH3). Khi co mat cac acid hu c chung co kha nang lam cac dung dch ng nong o cao keo s dung khi san xuat nc qua, mt. - Pectin khong hoa tan (protopectin) : polygalacturonic acid lien ket vi cac chat khac nh cellulose, galactan, araban. TV khi qua chn protopectin pectin hoa tan lam qua mem.

HO OH 3

1
2

HO OH 3

HO OH 3

OH

OH

OH

Hnh 1.10 : C u t o c a dextran v i LK(1 6) glycosidic, ay la dang d tr glucid cua nam men va VSV Dung dch dextran co o nht cao, trong y hoc c dung lam chat thay the huyet tng; cac dextran khac nhau co iem phan nhanh khac nhau, co the la 1 2 ; 1 3 hoac 1 - 4

HO CH 2 H OH

H O HO

2
CH 2

COOH

COOH O O O OH OH OH Petic acid O

COOH O OH OH O n

COOH O OH OH O

OH
HO CH 2
O OH

OH OH

Cac goc fructose lien ket vi nhau bi LK glycosidic 2-1, tan cung la goc saccharose

HO CH 2 H OH HO CH 2 H OH

O HO

nhom metoxi

1CH 2
O

COOCH3 O OH O OH

COOCH3 O OH OH O

COOCH3 O OH OH O

O HO

2
CH 2 n = 32 goc fructose O

Hnh 1 -11 : Cong thc cau tao cua inuline (fructosan)

Pectic acid : polygalacturonic acid, LK (1 4) glycosidic Pectinic acid : m t s nhm COOH b methyl ha Pectin ha tan : l pectinic acid c s l ng l n nhm CH3 Pectin khng ha tan (protopectin) : pectinic acid + cellulose, galactan, araban, tinh b t )

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2) Agar-agar (co trong rong bien) - Agarose : D va L-galactose lien ket (1 4), (1 3) - Agaropectin : D-galactose, mot so goc este hoa bi H2SO4
HO CH OH O OH
2

Acid hyaluronic COOH

CH2OH 1

5 4 OH

5 HO 3

CH2OH HO O O H OH O

D-Gluconate

OH

N-Acetylglucosamine

NHCOCH3

OH
Lien ket 1-3

Heparin

H 5 COOOH

CH2OSO35

CH2
3,6 anhydro galactose

HO O H

O
OSO3-

OH
NHOSO3-

OH

D-Iduronate-2-sulfate

N-sulfo-D-glucosamine-6-sulfate

3) Mucopolysaccharide : chu yeu co trong mo lien ket, mo nang (xng, sun), la thanh phan trong cac dch nhay. Th du nh: Acid hyaluronic : thuy tinh dch, dch khp xng .. Chondroitin sulfate : sun, cac mo bao ve, mo nang . Heparin : co nhieu gan, phoi, mau , la chat chong ong mau.

(4) Polysaccharide cua mang te bao ong vat : di dang glycoprotein, glycolipid, mucopolysaccharise acid. Mot so trng hp tnh khang nguyen cua mang te bao do thanh phan glucid mang quyet nh. Th du : khang nguyen nhom mau A : GalNAc Gal GlcNAc Gal Glc SERAMID Fucose (6-deoxy-L-galactose) nhom mau B GalNAc c thay bi galactose con nhom mau O khong co cac ng tren. (5) Polysaccharide thanh te bao vi khuan : lp vo boc ngoai cung cua te bao vi khuan la mot mang li cac phan t polysaccharide (ramnose, glucose va galactose hoac dan xuat amine cua chung) lien ket vi chuoi peptide ngan.

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