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4/13/2015

I. GII THIU
Ha sinh hc ha hc & ha sinh: l khoa hc nghin cu

PH GIA POLYMER

thnh phn ha hc v nhng qu trnh bin i ha hc ca


c th sng (sinh vt).
Sinh ha tnh (static biochemistry) Ha hc: nghin cu
thnh phn cu to, tnh cht ha hc ca c th sng
POLYMER SINH HC.

1. PH GIA POLYMER
2. POLYMER SINH HC

II. LCH S HA SINH


Nhng kin thc sinh ha u tin c tch ly t ngn
xa, trn c s pht trin ha hu c, sinh l hc, y hc v
mt s ngnh khc.
Ha sinh tr thnh mt chuyn ngnh ring bit c lp i
vi cc ngnh khoa hc khc vo khong cui TK XIX.
Cc s kin lch s sinh ha chnh nh:
Wohler, 1828 tng hp urea bng con ng ha hc.
Na sau TK XIX, bit kh nhiu v cu trc nhng TPHH ch yu ca c
th sng.
Na u TK XX, xut hin nhng thnh tu v ha sinh dinh dng v
chuyn ha.
T nhng nm 50 n nay, nhiu thnh tu ng k trong nhin cu
cu trc phn t.

Sinh ha ng (dynamic biochemistry) Ha sinh: nghin cu


bn cht v c ch ha hc ca s trao i cht (metabolism).

III.
THNH
PHN
III.1. Thnh phn nguyn t

HA

C th sng c cu to
khong 30 loi nguyn t.
S c mt ca cc nguyn
t trong c th SV s c
mt ca cc nguyn t
ngoi c th.
Th gii SH - gi l th gii
ca cc hp cht C.
LK ca C vi cc nguyn t
khc rt bn so vi cc LK
khc.

HC

CA

SINH

VT

S phn b ca cc nguyn
t khng ng u phn
thnh 3:
Cc nguyn t a lng (>105): C, H, O, N, S, P, Cl, Ca, Na,
K, Mg, Fe, Zn
Nguyn t vi lng (10-8-10-5):
Cu, Co, Mo, B, F, Cr, I, Mn, Al,
Si
Nguyn t siu vi lng (<108): Hg, Au, U, Ra, Se

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III. THNH PHN HA HC CA SINH VT


III.2. Phn t sinh hc

From the Cell to Macromolecule

Cc phn t sinh hc nm trong 1 h thng kn l c


th SV c cc c im:
Cc phn t SH c kh nng t chuyn ha, t
phin m, t bin i v t iu khin cho cc
hot ng ca n.
Vai tr dinh dng ca cc phn t SH:
Nhm cht tham gia vo chc nng cu trc:
protein
Nhm cung cp NL: lipid, glucid
Nhm gi cc chc nng iu ha: enzyme, cc
ni tit t
Nhm cht vi dinh dng: vitamin, khong, acid
amin khng thay th, acid bo khng thay th
Nhm h tr dinh dng: nc, cht x

III. THNH PHN HA HC CA SINH VT


III.3. Thnh phn ha hc ca t bo
S phn b cc HCHC khc nhau gia V & TV
u c 2 thnh phn c bn: nc 60-80%, CK 30-40%.
HCHC

Protein

Glucid

Lipid

A.nucleic

ng vt

70%

< 5%

10%

15%

Thc vt

< 5%

50-70%

25%

10%

Macromolecules are abundant in cells

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TRAO I CHT & NNG LNG


1. Khi nim
Trao i cht (TDC - metabolism): l ton b
nhng chuyn ha ha hc xy ra trong c
th.
TDC gm 2 qu trnh c bn:

ng ha (anabolism): l qu trnh tng hp nn


cc cht hu c cho c th SV, cn cung cp nng
lng (t ATP)
D ha (catabolism): l qu trnh phn gii cht
hu c c phn t lng ln thnh cht hu
c n gin, gii phng nng lng (tch ly trong
ATP)

Ha dng

Quang dng
Thu nng lng
t nh sng

Photoautotrophs: T dng quang nng


Photoheterotrophs: D dng quang nng
Chemoautotrophs: T dng ha nng
Chemoheterotrophs: D dng ha nng

TRAO I CHT & NNG LNG


1. Khi nim
C ch ha sinh c bn sinh nng lng
H hp hiu kh (c O2) CO2 + H2O + nhiu ATP
(cht nhn e cui l O2)
H hp ym kh (KHNG O2) CHC hoc v c +
t ATP (cht nhn e cui KHNG l O2: NO3- , SO4-,
CO3-)
Ln men (KHNG O2) ethanol or acid, gas (CHC
l cht nhn e cui cng)
Sn phm cui u sinh ATP

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TRAO I CHT & NNG LNG


1. Khi nim

Basic reaction

: electron uptake

C ch ha sinh c bn sinh nng lng


H hp hiu kh CO2 + H2O (cht nhn e cui l
O2; O2 b kh to H2O)

ng vt, vi sinh vt gy bnh ngi


Nng lng: oxi ha CHC
Ngun carbon: Carbon t CHC
Qu trnh chuyn ha qua cc con ng
Qu trnh ng phn
Chu trnh Kreb hay chu trnh citrate
Chui h hp

: electron removal

Biological reaction

Qu trnh oxy ha kh sinh hc


c bn

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ATP

Enzymes

3 part molecule consisting of


adenine a nitrogenous base
ribose a 5-carbon sugar
3 phosphate groups

Removal of the terminal


phosphate releases energy

Adenosine Tri Phosphate


ADP + energy + phosphate
ATP contains energy that can be easily
released (high-energy or unstable energy
bond)
Required for anabolic reactions

Biological catalysts
Highly specific
Extremely efficient
Increase reaction rates 108-1010 times
High turnover numbers
Proteins or RNA (ribozymes)

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Chng II: PROTEIN

I. Khi nim chung

Protein l mt polymer
sinh hc to bi cc acid
amin
Trng lng phn t ln
C vai tr: to cu trc,
sinh hc (xc tc, iu
ha, min dch),vn
ng, vn chuyn, d
tr
Ngun thu nhn: ng
vt, thc vt, vi sinh vt

II. Cu to phn t protein


ACID AMIN
L n v c bn to nn mi protein t nhin

Pr = n x a.a
C 20 loi acid amin
Cc protein khc nhau: t l & s lng cc aa
Acid amin l dn xut ca acid carboxylic khi thay th
mt nguyn t H bng nhm amin (-NH2)

2. Phn loi acid amin


Da vo tnh acid hoc kim
Monoamin Monocarboxyl (aa. trung tnh)
Diamin Monocarboxyl (aa. kim tnh)
Monoamin Dicarboxyl (aa. acid tnh)

Da vo gi tr dinh dng
Acid amin khng thay th: Leu, Ile, Met, Val, Lys, Thr, Phe,
Trp (tr em: thm Arg, His).
Acid amin thay th

Da vo cu to ca nhm R

Hydrophilic
Mch bn c cc
Khng mang in (trung tnh):
Ser, Thr, Asn, Gln, Cys, Met, Tyr

Mang in dng (base): Arg, Lys,


His
Mang in m (acid): Asp, Glu

Hydrophobic
Mch bn khng cc
Mch h: Ala, Gly, Ile, Leu, Val
Mch vng: Phe, Trp, Pro

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1. Mch bn khng cc-k nc


Glycine (Gly)
L acid amin duy nht khng c tnh hot quang

3.Mch bn phn cc, khng tch in

2.Mch bn cha vng thm

4.Mch bn c cc,
tch in dng

5.Mch bn c cc,
tch in m

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3.1. Tnh cht chung ca acid amin (aa)

3. Tnh cht acid amin

Tinh th mu trng, bn 20-25oC


Tan trong nc vi mc khc nhau
Hu ht aa bn trong mi trng acid v nhit cao

Tnh cht chung


Tnh cht quang hc
Tnh lng tnh
Tnh cht ha hc

3.2. Tnh cht quang hc ca aa


Tr glycine, tt c cc aa cn li u c ng phn quang
hcth hin hot tnh quang hc, quay mt phng nh sng
phn cc
ng phn quang hc c gi bng danh php D-L hay R-S
Quay phi (+), tri (-)

gng

Danh php D-L

Da vo cu trc ca glyceraldehyde

L-Glyceraldehyde
tt c
cc
aa
trong
protein

- t ph bin
c xut hin
trong t
nhin
D-Glyceraldehyde mt s
peptide ca
VSV
- K c tiu
ha trong c
th ngi

L-Acid amin

Nhn t H C (b H)
Bt u t nhm COO, i theo chiu kim
ng h
i quang L- to thnh
ch CORN
i quang Dthnh ch CONR

to
L- Acid amin

D-Acid amin

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Danh php R-S


Xc nh th t u tin ca cc nhm th theo quy
tc Cahn-Ingold-Prelog
Nhn t C n nhm th c mc u tin thp nht
Th t u tin ca 3 nhm cn li: quay cng chiu
kim ng h R; quay ngc chiu kim ng h
S

3.3. Tnh cht lng tnh


Trong mi trng acid: tnh base
Trong mi trng base: tnh acid
ng dng tch cc acid amin

Mi trng pH tng dn

3.4. Tnh cht cm quan

3.5. Tnh cht ha hc

Acid amin tham gia to mi v cho nhng sn phm giu


protein qua x l bng qu trnh thy phn.
V ca acid amin ph thuc vo cu trc khng gian:
Dng L c v ng
Dng D c v ngt
Acid amin vi R mch vng c c v ngt v v ng
L-tryptophane v L-tyrosine c v ng nht
L-glutamic acid nng cao cho v ngt ca tht, nng
thp l cht tng v cho sn phm thc phm.
Methionine c mi sulfure
Cng v:
Ph thuc vo ngng nng
Ngng ny ph thuc vo tnh k nc ca mch R.

Cc phn ng c trng ca acid amin:


Phn ng vi formol
Phn ng vi HNO2
Phn ng vi Ninhydrin

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III. Peptide
1. Lin kt
peptide

2. Cch gi tn peptide
Ghp tn tt c cc acid amin theo th t
Acid amin c nhm COOH tham gia vo lin kt peptide: ui
i thnh -yl
Tu theo s lng acid min c: dipeptide, tripeptide,
tetrapeptide, polypeptide.
S ng phn peptide khng lp li to thnh t n acid amin =
n!
T Alanine T Glycine

T
Cysteine

3. Polypeptide
Cc polymer mch thng, di, to thnh do cc acid
amin ni vi nhau bng lin kt peptide c gi l
polypeptide.
Protein l cc phn t c cu to t mt hay nhiu
mch polypeptide.
Vasopressin ca ch nhi

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IV. PROTEIN

1. Cu to

n x acid amin
Ngoi lin kt peptide cn c cc lin kt khc:

2. Cc bc cu trc
Cu trc bc mt, bc hai, bc ba, bc bn

Lin kt hydro
Lin kt k nc
Lin kt disunfide (disunfua)
Lin kt ion
Lin kt Van der Waals

2.1. Cu trc bc mt
L trnh t sp xp ca cc acid amin trong mch
polypeptide ca protein
Glutamate
Glycine
Cysteine
Valine
Lysine

2.1. Cu trc bc mt V d
Glutamin, Histidine v Proline nu lin kt vi nhau theo th
t Glu His Pro s to thnh mt hormon kch thch tuyn
gip tit thyroxin, nhng nu 3 acid amin ny kt hp theo
mt trt t khc s khng c tnh cht chc nng.
Oxytocin v vasopressin l protein c 9 aa, ch khc nhau aa
th 3 v 8 chc nng hon ton khc nhau:
Oxytocin c tc dng trn c trn ca t cung v tuyn v,
gy co khi t cung sinh con v kch thch s tit sa khi cho
con b.
Vasopressin c tc dng chng li niu, tang cung ti hp
thu nuc thn, dng thi lm co mch, do d c tc dng
tang huyt p.

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2. Cu trc bc 2:
a s l protein cu trc
Do cc C* u bt i cu trc protein khng n nh
cc nhm R c th quay xung quanh nguyn t C
to nn dng xon.

Cu trc xon
Cu trc gp np
Cu trc xon 3 mch

2.2. Cu

trc bc hai Gp np beta

Cc mch polypeptide xp cnh nhau


Gia cc mch polypeptide c lin kt H
Cc nhm R hng ln trn hoc xung di mt phng
cha cc mch polypeptide
L cu trc ph bin ca cc protein si (Vd: t)

2.2. Cu trc bc hai - Xon anpha


L s sp xp 3 chiu ca cc acid
amin lm cho mch polypeptide c
dng xon c
c gi bi cc lin kt hydro gia
H ca nhm N-H v O ca nhm
C=O ca acid amin th t dc theo
mch polypeptide
Lin kt H song song trc xon
Nhn ging nh dy in thoi 3,6 aa
Xon : to bi 1 si polypeptide
c n nh bi v s LK H, a s
xon theo chiu kim ng h.
Cu trc gp np :

Cu trc gp np
i song

Song song

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2.2. Cu trc bc hai Xon 3 mch


3
mch
polypeptide an
vo nhau
Lin kt H gia cc
nhm OH gip
cu trc bn vng
Tiu
biu
l
collagen, m lin
kt, da, gn v sn

2.3. Cu trc bc ba
L dng cun gp ca mt mch polypeptide
Hnh dng tng th c trng ca mt protein
Cc lin kt ngang gia cc nhm R ca cc acid amin
trong mch

3. Cu trc bc 3:
a s l protein chc nng
Cu trc xon bc 2 c th t cun gp trong khng gian
hnh cu, ellip.
Cc protein hnh cu d ha tan, v cc gc acid amin k
nc quay vo trong, cc gc acid amin i nc ngoi.

disulfide
SS
Ion
COO ... H3N+
lin kt H
C=O HO
k nc
CH3 H3C

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Cu trc bc ba

Cc kiu cu trc bc ba
Cu

Nhiu acid amin


khng tan, protein
c xu hng gim
din tch b
mt/t l th tch
Insulin, Hemoglobin,
Enzyme, Khng th

Ri

Kt hp tt vi
nc v c cu hnh
ngu nhin

Si

Cu trc bc hai
mnh cho php
protein duy tr
hnh dng si.
Tc, Len, Da, Mng

2.4. Cu trc bc bn
L s kt hp ca nhiu n v bc ba
L cc protein c hai hay nhiu mch polypeptide
V d: Hemoglobin
o L protein mang oxy, c trong mu
o Phn t c 4 mch polypeptide
o Mi mch c mt nhm heme gn vi oxy

Common motifs

Common folds

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2.4. Cu trc bc bn

Insulin

Phn t Hemoglobin c cu trc bc 4, c chc nng vn chuyn


oxy, gm 2 mch xon v 2 mch xon .

4. Cu trc bc 4:
Cc protein hnh cu d dng kt hp vi nhau bng LK th cp
cu trc bc 4
Cc protein bc 4 d phn ly protome nh hng chc nng
sinh hc.
Protein l hp cht SH c cu trc bc ln nht, phc tp nht.
Protein thay i cu trc khng gian nh hng kh nng xt
p SH.

Phn loi protein


Protein n gin: Ch cu to bi cc acid amin
Protein phc tp: Acid amin + nhm ngoi
Loi Nhm ngoi V d

Lipoprotein - Lipid Chylomicrons


Glycoprotein - Carbohydrate Immunoglobulin
Phosphoprotein - Phosphate Caseine
Hemoprotein - Heme (St porphyrin) Hemoglobin
Flavoprotein- Flavin nucleotide - Succinate
Dehydrogenase
Metalloprotein - Fe, Zn, Ca, Mb, Cu -Ferritin (Fe)

Protein c phn loi da vo tnh ng th:


homoprotein v heteroprotein
Protein c chia thnh protein n gin v protein
phc tp gm:
Phosphoprotein

Cha cc gc ester vi acid phosphoric


Casein, phosvitin ca lng trng

Glycoprotein

Cha mt hoc nhiu monosaccharide, oligosaccharide


Nhiu thnh phn trong lng v lng trng trng, collagen ca
cc m kin kt, serum mt s loi c.

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Protein cu trc

Protein chc nng


Enzyme
Cht mang c vai tr d tr kim loi (apoferritine cha Fe),
c nh hoc vn chuyn kh (O2, CO2, NH3), vitamin
(flavoprotein i vi riboflavin)
Hormone iu chnh p sut cc ng mch, mu sc da,
iu tit cc dch (dch tiu ha, s tit sa), iu chnh s
chuyn ha nng lng.
Globulin min dch bo v c th chng cc cht l, cc vt
th l nh virus, vi khun (lysozyme).
Bo v cc c quan thc vt (anti-trypsin chng li hot
ng ca enzyme trypsin phn hy protein)
Vn chuyn nng lng ha hc v c hc (myosin v actin
ca cc m c ng vt).

Tham gia hnh thnh cc b khung, cc m, lin kt cc m vi


nhau trong c th ng vt.
V d:
Collagen c trong xng, gn v cc m lin kt (20-25% protein ca c
th ngi)
Elastin c nhiu trong cc m lin kt, thnh cc mch mu.
Keratin l thnh phn ch yu ca lng, tc, mng, sng
Fibrinogen, fibrin l thnh phn to cu trc cc m c.

Protein d tr
Protein ca trng, sa (casein), protein c trong v, ht
Polymer cha cc acid amin cn thit nui con (ng vt)
v cho cc qu trnh mc v nui mm, r (thc vt).

1. Protein n gin
Phn loi theo tnh cht ha
tan.
Albumin

M nh hoc trung bnh, d tan


trong nc, d bin tnh bi
nhit.
B hon ton bi (NH4)2SO4
bo ha
C mt hu ht cc t bo
vi t l khc nhau.
Do d tan nn albumin c
nhiu D quan trng.
D: tnh to bt.

Globulin

Protein hnh cu,


Khng tan hoc tan rt t
trong nc v acid long, d
tan trong mui long.
B bi dung dch (NH4)2SO4
bn bo ha, NaCl 4-10%.
Globulin ph bin trong TV v
c V (trong u, trng,
huyt thanh)
m nhn nhiu chc nng
SH quan trng. VD: E,
hormone

Prolamin
Khng tan trong nc hay trong dung dch mui
long, tan trong ru (ethanol, isopropanol 70-80%).
Ch yu c trong TV: bp (zein), u
Glutelin
Khng tan trong nc, trong dung dch mui long,
trong ru ethylic, ch tan trong dung dch kim long
hoc acid long.
Ch yu l protein ng cc: la m (glutenin cao bt
nho).

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Protamin

M nh, cu to n gin nht,


C tnh kim mnh, d tan trong nc, khng tan
trong dung dich amoniac long, khng ng t khi
un nng.

Histon

M nh 15000-25000
Kim tnh, d ha tan trong nc, khng tan trong
dung dch amoniac long, khng ng t khi ua
nng.
C trong nhn t bo.
C 5 loi Histon: H1, HA1, HA2, H3, H4
Chc nng: LK DNA to NST.

Hemoglobin

2. Protein phc tp
Phn loi theo bn cht
nhm ngoi.
Nucleoprotein
Phi protein: acid
nucleic.
C trong nhn t bo,
ribosome.
t c gi tr CNTP
D nhiu trong CNSH

Lipoprotein
Phi protein: lipid
Lipoprotein: mng t
bo,
Proteolipid: thnh phn
chnh ca t bo no b.

Glycoprotein
Myoglobin

Cromoprotein
Phi protein:
mang mu.
VD:

phc

Myoglobin,
hemoglobin,
cytochrom c, catalase
Flavoprotein

Thng gi chc
nng sinh hc quan
trng.

Phosphoprotein
Phi protein: H3PO4, gc
PO43 C vai tr quan trng
trong trao i gc
phosphate.
L protein d tr: casein
sa , , ; ovabumin
trng

Phi protein: glucid


L cc protein xuyn
Metaloprotein
mng, phn saccharide
Phi protein: kim loi
hng ra ngoi mi
trng
Thng l nhm protein
tham gia cu to
L thnh phn ca cc t
enzyme.
bo thn kinh

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Enzymes

Biological catalysts
Highly specific
Extremely efficient
Increase reaction rates 108-1010 times
High turnover numbers
Proteins or RNA (ribozymes)

Enzyme Components
2 Parts
1. Apoenzyme - protein portion
2. Coenzyme (cofactor) - non-protein

Holoenzyme - whole enzyme

Coenzymes

Enzyme components

Many are derived from vitamins


1. Niacin
NAD (Nicotinamide adenine dinucleotide)

2. Riboflavin
FAD (Flavin adenine dinucleotide)

3. Pantothenic Acid
CoEnzyme A

Cofactors may be metal ions


Cofactors may accept or donate atoms removed from the

substrate or donated to the substrate

Cofactors may act as electron carriers


Often derived from vitamins
e.g. NAD and NADP electron carries derived from nicotinic

acid

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c hiu tuyt i:

Nhim v
Coenzyme:
Thng LK vi c cht
Xc nh kiu phn ng vi E xc tc.
Lm tng bn ca apoE

Apoenzyme:
Quyt nh tnh c hiu ca E
Tng cng xc tc ca E.

Enzymes -

catalysts that speed up and direct


chemical reactions

A. Enzymes are substrate specific

Lipases
Lipids
SucrasesSucrose
Ureases Urea
Proteases
Proteins
DNases DNA

Naming of Enzymes - most are named by adding


ase to the substrate

Sucrose
Lipids
DNA
Proteins
removes a Hydrogen
removes a phosphate

Sucrase
Lipase
DNase
Protease
Dehydrogenase
phosphotase

E ch tc dng ln 1 c
cht nht nh
V hu nh khng tc
dng ln c cht no khc.

c hiu tng i:
E c kh nng tc dng ln
mt kiu LK ha hc nht
nh trong phn t c cht.
M khng ph thuc vo
cu to ca cc thnh
phn tham gia to thnh
mi LK .

c hiu nhm:
E c kh nng tc dng ln
1 kiu LK ha hc nht
nh
Vi iu kin: 1 trong 2
phn tham gia to thnh
LK phi c cu to xc
nh.

c hiu quang hc: E


ch tc dng vi 1 trong 2
dng ng phn quang
hc ca cc cht.

Naming of Enzymes
Grouped based on type of reaction they
catalyze
1. Oxidoreductases
oxidation &
reduction
2. Hydrolases
hydrolysis
3. Ligases
synthesis

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Types of enzymes
Oxidoreductase

Oxidation reduction in
which hydrogen or oxygen
are gained or lost

Cytochrome oxidase,
lactate dehydrogenase

Transferase

Transfer of functional
groups, e.g. amino, acetyl
or phosphate groups

Acetate kinase, alanine


deaminase

Hydrolase

Hydrolysis addition of
water

Lipase, sucrase

Lyase

Removal of atoms without


addition of water

Oxalate decarboxylase,
isocitrate lyase

Isomerase

Rearrangement of atoms
within a molecule

Glucose phosphate
isomerase, alanine
racemase

Ligase

Joining of two molecules

Acetyl-CoA synthetase,
DNA ligase

C CH TC DNG CA ENZYME
Qua 3 giai on (G):
E + S ES P + E
G1 to phc [ES]: E + S
bng LK yu phc ES
khng bn phn ng ny
xy ra rt nhanh.
G2 hot ha S: xy ra
s bin i S ko cng
v ph v cc LK ng ha
tr tham gia phn ng.
G3 hnh thnh P: to
thnh P, cn E c gii
phng ra di dng t do.

Cc loi LK ch yu c
to thnh gia E v S /
trong phc ES.
Tng tc tnh in
LK H
Tng tc VanderWaals
Mi loi LK i hi nhng
iu kin khc nhau v
chu nh hng khc nhau
khi c nc.

4
2

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Chymotrypsin mechanism - 7

IV. TNH CHT CA ENZYME

IV.1. Tnh cht l ha chung


E l protein chng c y tnh cht ca protein:
D bin tnh, d kt ta, d mt hot tnh SH, hot
tnh xc tc - khi chu nhng tc ng bn ngoi hoc
cc tc nhn ha hc.
Khng thm tch qua mng bn thm
C tnh lng tnh
Tan trong nc, dung mi hu c c cc khc, dung
dch mui long,
Hnh cu
M thng ln 2.000-1.000.000

IV.2. Cng lc xc tc
E l cht xc tc sinh hc

C y tnh cht ca mt cht xc tc


C cng lc xc tc mnh hn nhiu so vi xc tc thng
thng.

Nng lng hot ha: l nng lng cn thit chuyn


phn t cht tham gia phn ng t trng thi bnh
thng trng thi hot ng phn ng mi xy ra
c.
VD: H2O2 H2O + 1/2O2
Khng c xc tc NLHH 18.000kcal/mol
C xc tc v c (platin) NLHH 11.700kcal/mol
C catalase NLHH 5.500kcal/mol

20

4/13/2015

Gii thch tnh c hiu


Enzymes as Biological
Catalysts

Thuyt tng ng tnh:


S tng ng v cu trc phn t E & c cht l c sn
gii thch tnh c hiu tuyt i.
Thuyt tng ng ng:
Tn ti s tng ng v cu trc gia E & c cht, ch
khi c cht tc dng vi E.
S tng ng ch hnh thnh trong qu trnh
phn ng - ch khng c sn gii thch c tt c
cc tnh c hiu ca E.

Increase reaction rates


by over 1,000,000-fold
Two fundamental
properties

Increase the reaction


rate with no alteration
of the enzyme
Increase the reaction
rate without altering the
equilibrium

Reduce the activation


energy

V. CC YU T NH HNG
N VN TC PHN NG
ENZYME

V.1. Nng E

V.2. Nng S
M hnh Michaelis-Menten
c im quan trng nht ca m hnh ny l:
M u phn ng cn thit phi to thnh phc trung gian ES
Sau phc ES chuyn ha tip P cui cng ca phn ng v
E t do
E li kt hp vi phn t S khc bt u vng xc tc mi.

Trong iu kin tha S, vp ph


thuc tuyn tnh vo nng E.
v = k[E]
v: vn tc phn ng
[E]: l nng E

Cng c trng hp, khi nng


E qu ln vp tng chm.

v = k[E]

21

4/13/2015

Trng hp n gin nht, phn ng ch c 1 S v E


xc tc cho s chuyn ha n ch to thnh 1 sn
phm P.

k1: hng s vn tc phn ng thun to phc ES


k-1: hng s phn ng nghch phn ly ES
k2: hng s vn tc phn ng phn ly ES to sn phm P v
ti to E.

Vn tc phn ng:
Vp to phc [ES]:
Vp phn ly phc [ES]:
Vp to P:

v+1 = k+1[S][E]
v-1 = k-1[ES]
v+2 = k+2[ES]

k 1 [Eo][S]
[Eo][S]

k 1 k 2 k 1 [S] k 1 k 2 [S]
k 1
Mun phn ng cn bng
k 1 k 2
kM
th: v+1 = v-1 + v+2
t
k 1
[ ES ]

k+1[E][S] = (k-1 + k+2)[ES]


Vi [E] = [Eo] [ES]
[ES]: lng E c trong
phc
[E]: lng E s phn ng
[Eo]: lng E ban u

[ES]

[Eo][S]
k M [S]

v vmax

[S]
kM [S]

k+1[Eo][S] - k+1[ES][S] = (k-1 + k+2)[ES]


k+1[Eo][S] = (k-1 + k+2 + k+1[S])[ES]

Michaelis-Menten kinetics
Vn tc ca E t cc i khi ton b E ban u u
tham gia phn ng.
v = vmax [Eo] = [EoS]

v k 2[ES]

v vmax

k 2[Eo][S]
kM [S]

[S]
kM [S]

Vi:

[ES]

[Eo][S]
kM [S]

Vi: vmax = k+2[Eo]

Phng trnh Michaelis-Menten

k 1 k 2
kM
k 1
Hng s phn ly biu kin

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4/13/2015

Range of KM values

Lineweaver-Burk plot (double-reciprocal)

1 kM 1
1

v vmax [S] vmax

KM provides approximation of [S] in vivo for many enzymes

V.3. Cc cht km hm

Cc cht khi kt hp vi E lm
gim, lm yu, hay chm dt hot
ng xc tc ca E, nhng khng
b chuyn ha bi E: cht km
hm / cht c ch (inhibitor I).
Cc cht ny c th l nhng ion,
cc phn t v c, hu c
(protein).
Theo c ch tc dng ca cht
km hm:
Km hm thun nghch
Km hm canh tranh
Km hm khng cnh tranh

Km hm khng thun nghch E.

Enzyme inhibition

Km hm thun nghch E:
Khi c mt ca cht km hm
hot tnh E s b yu i.
Nhng khi loi b cht km
hm hot tnh E tr li
hot ng nh ban u.
2 dng
Km hm canh tranh
Km hm khng cnh tranh

Km hm bt thun nghch E:
Khi loi b cht km hm
hot tnh E khng tr li nh
ban u.

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4/13/2015

Cc cht km hm khng cnh tranh

Cc cht km hm cnh tranh


L nhng cht km hm thun
nghch E
C cu trc tng t cu trc S

C kh nng kt hp vo
TTH E chim ch kt hp
ca S.

Vmax unaltered, Km increased

Kt hp vi E ch khc vi TTH.
Lm thay i cu trc khng gian ca phn t E
theo hng khng c li cho hot ng xc tc ca
n lm v phn ng xc tc.
Sau khi kt hp vi cht km hm khng cnh tranh
E vn c th kt hp vi S phc EIS.
Km unaltered,
Vmax decreased

S kt hp ca I v S vo TTH
E c tnh cht loi tr ln nhau.

I cnh tranh v phn ng


xc tc.

Km hm bi sn phm ca phn ng
Km hm do tha c cht
Km hm d lp th (alosteric)
1 s E ngoi TTH, cn c trung tm d lp th
Alosteric l 1 phn ca E khi kt hp vi I cu trc E b
bin i TTH b bin i bin i hot tnh E.
th biu din s ph thuc gia V & S c dng Sigmoid
(khng cn dng Hyperbol)

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4/13/2015

Enzyme iu ha
Trong mi CT-TC, phi c t nht 1 E iu chnh tc p/ng ca
ton b CT E iu ha.
Trong phn ln cc CT chuyn ha, thng p/ng u tin c xt
bi E iu ha.
Hot tnh ca E iu ha, c iu chnh bi nhm cc cht iu
ha c MW nh (thng: cc cht trao i trung gian hoc
cofactor).
C ch iu ha:
E d lp th
E iu ha ci bin nh to LK ha tr thun nghch
Cc c ch iu ha hot tnh xt: nh gn hoc tch nhng phn t
protein c hiu, hot ha zymogen

Enzyme iu ha d lp th
Kiu iu ha ph bin ca E d lp th: iu ha c ch ngc (c
ch phn hi, feedback inhibition).
VD: chui p/ng bin i L-threonine L-isoleucine.
C 1/nhiu tm iu ha, c th nm cc tiu n v khc nhau
ca E E d lp th thng c cu trc khng gian phc tp v c
kch thc ln hn E bnh thng (thng c cu trc bc 4).
ng cong ng hc E d lp th c hnh Sigmoid (S) khc vi
ng Hyperbol ca E bnh thng. Th hin s phi hp tc ng
ca cc tiu n v trong phc E.

V.4. Cc cht hot ha


Lm tng hot xc tc ca
E, thng c bn cht ha hc
khc nhau.
Cc anion, ion kim loi
Cc cht hu c c cu to
phc tp hn lm nhim v
chuyn nhm, chuyn H
Cht c kh nng ph v 1 s
LK / phn t tin E,
Hoc nhng cht c tc dng
phc hi nhng nhm chc
trong TTH E.

Cht kch thch c kh nng


l v:

N c th tham gia vo thnh


phn cu to ca TTH.
N c th l cu ni gia E-S
N l 1 coE
N c th khi phc li cu
hnh khng gian ca TTH
Cht kch thch dn n s
phn ly ion ca E & S.

Tuy nhin, tc dng hot ha


ch gii hn nhng nng
xc nh, vt qu gii hn
ny c th lm gim hot
E.

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4/13/2015

V.5. Nhit
To l yu t quan trng nht nh hng v phn ng
E.
To thch hp i vi cc phn ng do E xc tc trong
gii hn 50-60oC.
To ph hy E gi l to ti hn 80-100oC.
To ng vi hot ng cao nht ca E (v = vmax): to ti
thch (optimum - Toopt),
Toopt t V l 40-50oC
Toopt t TV l 50-60oC

V=
vmax

toopt

V.6. pH mi trng
pH mi trng nh hng r rt n phn ng E. V:
N nh hng n mc ion ha ca E v S.
Khi pH thay i nh hng trc tip n TTH ca E
nh hng n bn protein E.

a s E bn trong gii hn pH 5-9.


pH m hot E mnh nht: pHopt

S mt hot tnh E do s pH mang tnh thun nghch.

26

4/13/2015

Enzyme

Ngun gc

-Pepsin
-Trypsin
-Chymotrypsin
-Amylase
-Lipase
-Phosphatase acid
-Phosphatase kim

-Dch v
-Dch ty
-Dch ty
-Dch ty, nc bt
-Dch ty
-Tuyn tin lit
-Xng, gan

pHopt
1,8
8
8,1-8,6
7
7-7,5
5-5,6
8,6-9,1

V.7. nh sng
nh sng thng c nh hng trc tip n v ca
nhng phn ng oxh-k.
V vy, nh sng cng l mt yu t iu chnh v phn
ng ca E oxh-k,
Trong cc bc x nh sng khc nhau nh hng
khc nhau.
VD:
Tia cc tm - nh hng nhiu nht hot tnh ca E / phn
ng oxh-k.
Tia hng ngoi t nh hng hn.

3. Tnh cht
Tnh phn ly
Tnh phn ly c trng bi pK v pI
Tnh acid ca nhm carboxyl v tnh base ca nhm
amin peptide thp hn so vi cc acid amin t do.

Hp th tia UV
OD ti 280nm c s dng nh tnh v nh
lng protein v peptide.

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4/13/2015

Tnh cht vt l
ha tan
Trong nc, ha tan ca cc acid amin rt khc nhau:

Proline, hydroxylproline, glycine, alanine, tan tt trong


dung dch.
Cystein v tyrosine hu nh khng tan
Cc acid amin khc c ha tan thp
Thm acid/kim tng ha tan ca cc acid amin.
Acid amin trong hp phn vi cc acid amin khc tan tt
hn khi ch c hn mt mnh.

Trong dung mi hu c,

ha tan thp do acid amin c tnh phn cc


Tt c cc acid amin khng tan trong ether, mt s t tan
trong ethanol.

28

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29

4/13/2015

Tnh cht cm quan


Dipeptide ca acid aspartic c v ngt lin quan n cu trc
dng D ca acid amin.
Cc peptide cn li c v ng hoc v dung.
V ca peptide khng ph thuc vo cu hnh khng gian dng
L hoc D.
Cng v ph thuc vo tnh k nc ca cc on mch
R v khng ph thuc vo trnh t acid amin.
V ng ca peptide c th xut hin khi thy phn mt phn
protein (v d: phomat khi chn cha hon ho c th b ng)
Cn ch khi s dng enzyme trong bin tnh protein.

Phn ng mu c trng (Phn ng


Biure)
L phn ng c trng
ca cc hp cht c t 2
lin kt peptide tr ln
Phn ng vi CuSO4
trong mi trng kim
To phc c mu t xanh
tm, tm n tm ty
thuc s lng lin kt
peptide
ng dng nh lng
protein.

Php th Biuret

4. Bin tnh protein


Ph v cu trc bc hai, bc ba, bc bn ca protein bng:
Nhit/Cht hu c: b gy lin kt H v ph v lc hp
dn k nc
Acid/Base: b gy lin kt ion v lin kt H gia cc
nhm R c cc
Ion kim lai nng: phn ng vi lin kt S-S to thnh
cc cht rn
Khuy trn: ko cng cc mch cho n khi cc lin kt
b t.

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4/13/2015

4.1. Bin tnh do nhit

Td

T nhin
Bin tnh

Cc yu t nh hng n
bin tnh nhit ca protein

Hm lng nc
Mui, ng
Thnh phn acid amin ca protein
pH

31

4/13/2015

4.2. Bin tnh do acid v base

S lng in tch cng du tng gy ra lc y ni phn t


S lng cp in tch tri du gim lm gim cc lc hp dn
ni phn t
Mt in tch b mt lm cho cc phn t protein khng b
y khi nhau.

Proton
ha
Tng tc tnh
in ni phn t

Protein bin tnh


c cu trc cun
ngu nhin

Nguyn nhn bin tnh acid/base

Bt u
bin tnh
Mt dung
mi lin kt

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4/13/2015

4.3. Bin tnh do x l c hc

4.5. Bin tnh do tng tc b mt

Do tc ng ca lc ct, lc ko
Lm gin mch protein, t lin kt

4.4. Bin tnh do dung mi hu c

6. Bin i protein
Thy phn (Protease; H+; OH-)
Thi ra (Enzyme, vi sinh vt)

6.1. Thy phn Protein

B gy lin kt peptide
Cn c acid hoc base, nc v nhit
Sn phm l cc peptide ngn hn v acid amin
Tng t nh s tiu ha protein bng enzyme
Xy ra trong t bo cung cp acid amin tng hp
thnh cc protein v m mi.

6.2. Cc phn ng thi ra protein

Kh amin
Kh carboxyl
Kh amin, kh carboxyl
To indol, scatol, phenol, t aa c nhn thm
To mecaptan
To di-, trimetylamin (t lipoprotein)
To phosphin

33

4/13/2015

Phn ng to trimetylamin
Phn lipid sau khi tch khi lipoprotein:
H3 C

CH3
N CH3

H3C N CH2 CH2 OH


H3 C

CH3

OH

+ O2
CH3
O = N CH3
(Oxytrimetylamin- tanh)

Phn ng to phosphin
Phosphoprotein & Nucleoprotein

CH3

S CHUYN HA PROTEIN
V:

Phn hy

H3PO4

Protein aa

VSV:

- 3O2

Tit cc protease ngoi bo protein aa, sau mi


hp thu aa.

PH3
(Thi, c)

Thc bo lysozyme tit E thy phn protein aa, sau


hp thu.

TV:
Ch yu tng hp protein ch khng phn gii.

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4/13/2015

S trao i protein
1) ngha
L mt QT chuyn ha c bn c tnh cht nng ct.

B) Cc ng hng chuyn ha aa: c 3 kiu p ca


aa trong c th

Mi dng trao i khc nh glucid, lipid u phc v


cho s trao i protein ny.

Kiu p/ nhm amin

S trao i protein s iu ha cc chuyn ha trn


to nn nhng iu kin ti u vi s tn ti ring ca
mnh.

Kiu p/ gc aa.

S trao i glucid, ngun cc chui C cho sinh tng


hp aa, l nguyn liu to nn protein.
S trao i lipid, cung cp NL trong ATP.

Sinh tng hp aa v protein


STH aa

Amin ha cc cetoacid theo ng hng kh


Amin ha trc tip cc acid cha no
Oxy ha cc cetoacid theo ng hng kh.
Sinh tng hp protein

Thuyt khun
Thuyt peptide

Kiu p/ nhm cacboxyl


Cc SP cui cng ca s phn gii aa
H2O s i vo cc QT trao i chung
CO2 s c bi tit ra khi c th
NH3 th ty tng loi VSV m c nhng chuyn ha
khc.

2. S chuyn ha acid amin


2.1. s oxy ha acid amin
a)
S oxy ha aa theo gc amin
Phn ng kh amin
Theo con ng thy phn
Theo con ng kh
Theo phn ng oxy ha ni phn
t
Theo phn ng oxy ha

2.2. S bin i aa c lin quan n


R

Ty theo gc R m aa c con
ng chuyn ha ring,
nhng nhn chung u l
oxy ha hay kh.

Phn ng chuyn amin ha


b)
S oxy ha aa theo gc
cacboxyl
Phn ng decacboxyl ha
Tng hp aminoacyladenylate
hot ha aa

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4/13/2015

3. Con ng chuyn ha cc sn phm cui ca trao


i acid amin Loi NH3

ng dng protein trong vt liu y sinh

TV: kt hp acid hu c mui amon.


VSV + 1 s TV: NH3 c ti s dng tng hp aa hoc tng
hp acid uric.
Ngi + V: chu trnh ure (ornithin).

Journal of material chemistry B 2014,2,3715

Journal of material chemistry B 2014,2,3715

Journal of material chemistry B 2014,2,3715

36

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Chng III: GLUCID

Journal of material chemistry B 2014,2,3715

I. KHI NIM CHUNG


1. Bn cht ha hc

2. Ngun phn b

N: Glucid l nhng HC polyalcol c cha nhm aldehyde


hoc cetone.

To thnh t qu trnh quang hp ca l cy xanh.


Glucid l nhng HCHC quan trng v phong ph, c trong
hu ht cc c th V, TV, VSV.
Thc vt: (chim 80-90% trng lng kh)

Gm: C, H, O (chu yu); S, N (m rng)


CTHH: Cx(H2O)y
carbonhydrate

Carbo = carbon, hydrate = water

Mt s cht quan trng:

ng ha tan
Tinh bt, glycogen
Cellulose
Pectin, chitin, agar

Tri cy chn: ng
Ng cc: tinh bt
ay, gai, bng: cellulose

ng vt: (chim < 2% trng lng kh)


Gan: glycogen
Tm, cua: chitin

Vi sinh vt
dextran

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4/13/2015

3. Chc nng sinh hc


Cung cp NL - vai tr dinh dng (70-80% nhu cu NL):
Ngi 50-70% khu phn NL t glucid. V > 70%.
Nhu cu glucid cho ngi: 5-7g/1kg th trng/ngy.

Gii phng NL & cc HC trung gian:


t 1g glucid 4,1calo
Cc HC trung gian l cc khung C tng hp cht HC.

Tham gia to cu trc (to hnh): l thnh phn cu trc c bn


ca tb TV, c th chim ti 70% KL kh tb TV.
D tr: di dng glycogen trong gan v c / c th V. Tinh
bt TV (ht, thn, c...).

S a dng v chc nng ca carbohydrate l nh vo


cc c im ha hc ca chng

Gluconeogenesis: qu
trnh tn to glucose
Glycolysis:
chu trnh ng phn

(1) Trong phn t c nhiu hn mt tm bt i xng


(lin kt vi 4 nhm khc nhau).
(2) C kh nng tn ti c hai dng mch thng hoc
mch vng.
(3) C kh nng to thnh polymer nh vo lin kt
glycoside.
(4) C kh nng to lin kt hydro vi nc hoc cc
phn t khc.

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4/13/2015

DA VO CU TO, GLUCIDE C CHIA LM 3 NHM

5. Phn loi
C3
C4
C5
C6
C7
C9

MONOSACCHARIDE

CARBOHYDRATE
- GLUCID

OLIGOSACCHARIDE

POLYSACCHARIDE

GLUCIDE
(Saccharide)

MONOSACCHARIDE (khng th thy phn c)


Triose: Glyceraldehyde, Dihydroxyaceton.
Tetrose: Erythrose
Pentose: Ribose, Ribulose, Xylulose
Hexose: Glucose, Fructose, Mannose, Galactose..
Heptose: Sedoheptulose
Nonose: Neuraminic acid

OLIGOSACCHARIDE ( 1-10 monosac.)


Maltose
Saccharose
Lactose
POLYSACCHARIDE

Thc vt: Tinh bt,


Cellulose
ng vt: Glycogen
Vi sinh vt

II. MONOSACCHARIDE
1. Cu to

Monosaccharide (ng n)
N: L dn xut aldehyde hoc cetone ca ru a
chc.
C3-9 (ph bin l C5 v C6)
Nhiu hp cht c hot tnh quang hc.
Khng b thy phn bi acid yu.

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4/13/2015

Monosaccharide mch thng


Tng qut:

2 nhm monosaccharide

Aldose
l
cc
monosaccharide c mt
nhm aldehyde v nhiu
nhm hydroxyl (-OH).
Cetose
l
cc
monosaccharide c mt
nhm cetone v nhiu
nhm hydroxyl (-OH).

Glycerine l polyol n gin nht khi oxi ho (mt 2H)


c 2 dng sau:
Aldose

CHO
CH OH

1 CH 2 OH
2 CH OH
3 CH 2 OH
Glixerin

-2H, C1

CH 2 OH

Aldehitglixerinic
(Aldotrioza)

-2H, C2

CH 2 OH
C

Cetose

CH 2 OH

Dihydroxyaxeton
(Xetotrioza)

- Aldehydglycerinic - cha nhm aldehyde (-CHO) Aldose


- Dihydroxyacetone - cha nhm cetone (C=O) Ketose

40

4/13/2015

Gi tn
S lng carbon
(Tn tng qut ca
monosaccharide)

3
(Triose)
4
(Tetrose)
5
(Pentose)
6
(Hexose)
7
(Heptose)

CU HNH MONOSACCHARIDE

Nhm chc
aldose

Nhm chc
cetose

Aldotriose

Cetotriose
Triulose
Cetotetrose
Tetrulose
Cetopentose
Pentulose
Cetohexose
Hexulose
Cetoheptose
Heptulose

Aldotetrose
Aldopentose
Aldohexose
Aldoheptose

Cu hnh tng i D, L

NG PHN MCH H

Trong cu to monosaccharide, c cc C bt i (C*).


S ng phn = 2n (n = s C*)
Danh php D L (so snh vi glyceraldehide)

D, L cho bit ta ang ni n ng phn bt i xng no.


Nu nhm OH gn trn nguyn t C cnh C di cng hng
sang bn phi th ng phn gi l ng phn D-; nu n
hng sang tri th l ng phn L-.

Carbohydrate t nhin thng dng ng phn D-.


ng phn D, L l mt cp i quang, ng phn D l
nh ca ng phn L qua gng.
ng phn epimer l cc monosaccharide ch khc nhau
v cu hnh ca Carbon s 2 (C2).

Dng D & L l 2
dng cu hnh
c bn ca C
bt i xng
glyceraldehyde.

C
H C OH
HO C H
H C OH
H C OH
CH2OH
D-glucose

C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose

S ng phn quang hc =
2n = 24 = 16

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ng phn khng i quang ng phn khng i quang

42

4/13/2015

Hnh chiu Rosanoff


D-Glycerose

OH

HO

D-Erythrose

D-Threose

OH

OH

OH

D-Ribose

D-Arabinose

D-Xylose

D-Lyxose

H
D-Allose D-Altrose D-Glucose D-Mannose D-Gulose D-Idose D-Galactose D-Talose

D & L designate absolute


configuration of the asymmetric
carbon atom farthest from the
aldehyde or ketone group

Aldotriose

Aldotetroses
Aldopentoses

Aldohexoses

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4/13/2015

Monosaccharide mch vng

S hnh thnh vng pyran v furan ca monosaccharide


Cng thc Haworth

Phu hp vi trng thi ha ly, c bit trong nc


S khp vng: phn ng ni phn t gia nhm ru
v nhm carbonyl to thnh 1 vng - tautomer.
Cc vng 6 cnh gi l pyranose
Cc vng 5 cnh gi l furanose

5
4

2 ng phn quang hc mi (Sinh ra mt C*1 -carbon


anomer)

1
3

2 anomer (- v -).

Cu hnh khng gian ba chiu

Dng thuyn (thng gp trong t nhin)


Dng gh

Nhm OH v tr /mi c kha nng phn ng cao: OH glycoside

V d v s tn ti 3 dng ca glucose

Khi tan trong nc, monosaccharide (glucose) c s


chuyn i gia 2 dng ng phn v
(mutarotation). im cn bng c khong 1/3 tn
ti dng , 2/3 tn ti dng v c t hn 1%
tn ti dng mch thng (open-chain form).

Hnh chiu Fischer


~ 35 %

~ 65 %
<1%

D va L c tnh cht vt ly khc nhau nhng c cng tnh


cht ha hc (ngoi tr phn ng di tc dng ca
enzyme)

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4/13/2015

Hnh chiu Haworth

Hnh chiu Haworth ca D-Glucose


Dy ng phn D: nhm CH2OH nm pha trn mt phng
V cc nhm OH bn phi (C2 v C4) hng xung,
V cc nhm OH bn tri (C3) hng ln, khi :
Nhm OH mi hnh thnh C1 s c 2 kh nng:
Hng xung ( anomer)
Hng ln ( anomer).

CU TO DNG MCH VNG


1

H
HO
H
H

2
3
4
5
6

CHO
C

OH

OH (linear form)

OH

D-glucose

CH2OH
6 CH2OH

6 CH2OH
5

H
4

OH

H
OH
3

Glucose
khi
C1
aldehyde ni vi C5
OH, to thnh mt
vng
6
cnh
pyranose.

OH

-D-glucose

OH

H
4

OH

H
OH
3

OH

OH

-D-glucose

VD: hin tng optical rotation:


-D-glucose + 112o
-D-glucose + 19o
im cn bng 53o

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4/13/2015

CH2OH

HO

2C

OH

OH

5
6

HOH2C 6
H

1CH2OH

O
HO

OH

OH

CH2OH

D-fructose (linear)

-D-fructofuranose

Fructose to vng theo 2 cch sau:


- Dng vng 6 cnh pyranose, bng phn ng gia nhm C2 ketone vi
nhm OH C6, hoc
- Dng vng 5 cnh furanose, bng phn ng ca nhm C2 ketone vi
OH C5.

Hnh th mch vng


Cng thc Reeves
V bn cht ca cc lin kt 4 ca C, ng pyranose thc t c
cu hnh dng gh "chair" hoc dng thuyn "boat".
H OH

H OH

4 6

H O

HO
HO

H O
HO
H
HO

5
3

OH 1
OH

-D-glucopyranose

OH
OH
H

-D-glucopyranose

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4/13/2015

2. Tnh cht

Tnh cht cm quan

Tnh cht cm quan


Tnh cht vt l
Tnh cht ha hc

V ngt
y l tnh cht cm quan quan trng nht,
Ph thuc vo tinh sch, nhit , pH,
S c mt ca cc ng hoc cht khng phi ng khc.

Cng v ngt
c nh gi bng ngng nng cm nhn ca ng,
c so snh vi mt ng chun khc (thng l ng
saccharose).

V d (dung dch ng 10%)


ngt ca saccharose l 100.
D-fructose 114, D-glucose 69, D-galactose 63, lactose 39,
maltose 46, D-sorbitol 51, ng nghch o 95, xylitol 102, Dmannitol 69

Tnh cht vt l
Tnh ht m ca cc ng n rt khc nhau ph
thuc:
Loi ng (cu trc),
tinh sch v trng thi ca ng (bt, kt tinh),
Kh nng gi m ca dung dch ng c ng dng trong
sn xut thc phm (bnh m).

Kh nng ha tan

ng n tan tt trong nc,


Tan mt phn trong ethanol,
Khng tan trong cc dung mi hu c nh ether, benzen,
chloroform

Tnh kt tinh

Khi c c dd monose kt tinh tinh th.


QT kt tinh cc monose, c th b nh hng bi hin
tng sonvat ho.
Hin tng sonvat ho: do monose tng tc vi cc dung
mi & hin tng chuyn ho h bin gia cc dng cu
to ca monose.

Kh nng quay

Chuyn t dng D sang dng L v ngc li.


Gc quay ph thuc cc dng -anomer, -anomer, dng
pyranose v furanose.

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Tnh cht ha hc
(Cc phn ng ha hc c trng)
Phn ng oxy ha: cc sn phm onic acid, -aric
acid v uronic acid,
Phn ng trong mi trng kim,
Phn ng trong mi trng acid,
Phn ng kh: chuyn glucose thnh glucitol,
mannose thnh mannitol (l cc ng ru
sugar alcohol),
Phn ng ether ha v ester ha,
Phn ng to glycoside,
Phn ng Maillard v Strecker,
Phn ng Caramel ha.

Phn ng oxi ha
Cc aldose c th b oxy ha thnh acid carboxylic
tng ng.

O
R

[O]

HO

O
R

ui ose hoc ulose i thnh onic acid, -aric


acid v uronic acid.

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4/13/2015

Oxyhoa sinh hc

Tc nhn oxi ha
Thuc th Tollens (Ag+/dung dch amoniac).

Thuc th Fehling (Cu2+/dung dch Natri Kali tactrate).

Thuc th Benedict (Cu2+/dung dch Natri citrate).

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Phn ng kh

Redox Reactions of Monosaccharides

Nhm carbonyl c th b kh thnh ru (tc nhn kh thng


dng l hydride kim loi NaBH4).
H

O
R

[H]

H
H

OH
R

Glucose b kh thnh sorbitol (D-glucitol).


Xylose c th b kh thnh xylitol.

ui ose hoc ulose i thnh itol.


Ngt nhng c hp thu chm; hot tnh km.

Phn ng ester ha

Acylation of Monosaccharides

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Phn ng ether ha

Phn ng to glycoside

OH ca ng + ru (methanol) ether (ng b


methyl ha).

ng + ng: ngt, khng c dc tnh.


ng + phi ng: khng ngt, c dc tnh.
O-glycoside

Alkylation of the OH Groups


Lin kt
glycoside

N-glycoside
S-glycoside
C-glycoside

Mechanism of Glycoside Formation

LIN KT GLYCOSIDE
H OH

H OH
H2O

H O
HO
HO

H
H

CH3-O H

H O
HO
HO

OH
H

OH

-D-glucopyranose

methanol

H
OH
OCH3

methyl--D-glucopyranose

Hydroxyl ca anomer v hydroxyl ca ng khc hoc vi hp cht khc c


th lin kt vi nhau, loi ra 1 phn t nc hnh thnh lin kt glycoside:
R-OH + HO-R' R-O-R' + H2O
Vd: methanol phn ng vi OH anomer trn glucose to thnh methyl
glucoside (methyl-glucopyranose).

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Phn ng trong mi trng kim


Formation of an N-Glycoside

Trong mi trng kim long cn c hin tng chuyn nhm


[Ca(OH)2, Ba(OH)2]

Phn ng trong mi trng acid


Monose bn / dd aicd v c long to cao tch ring, nh
lng cc monose to thnh khi thy phn polyose.
Trong acid m c, ng b dehydrate ha (tch nc)
furfural t pentose / oxymethylfurfurol t hexose.
Cc SP ny trng ngng vi 1 s cht khc cc phc mu
thng c s dng nh tnh, nh lng monose.

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Phn ng vi -Napthol trong acid cho phc mu tm

Phn ng caramel ha
un nng chy ng hoc khi un nng dung dch
ng trong mi trng acid hoc kim.

To ra cc cht c mu nu v mi caramel c trng,


Phn ng c th xy ra theo 2 hng to mi hoc to mu
nhiu hn.

Cc cht mi ch yu: dihydro-furanose,


cyclopentenolone, cyclohexenolone v pyrone.
un nng siro glucose vi acid sulfuric v c mt
ammonia:
Phc mu tm

Vi saccharose, phn ng caramen ho xy ra theo s phn


ng:
C12H22O11 H2O C6H10O5 + C6H10O5
Saccharose
glucozan levulozan
0
n 185-190 C s to thnh izosaccharozan:
Glucozan + levulozan izosaccharozan
C6H10O5 + C6H10O5 C12H20O10
Khi nhit cao hn s mt i 10% nc v to thnh caramelan
(C12H18O9 hoc C24H36O18) c mu vng:
2C12H20O10 2H2O (C12H18O9) hoc C24H36O18
Izosaccharozan
caramelan
Khi mt i 14% nc s to thnh caramelen:
C12H20O10 + C24H36O18 3H2O C36H48O24.H2O
V khi mt i 25% nc s to thnh caramelin c mu nu en.
Hu nh tt c cc sn phm caramen ho u c v ng.

Tng cng kh nng to ra cc hp cht polymer c mu


nu.

Phn ng Maillard
Phn ng Maillard (cn c gi l phn ng nu ha
phi enzyme) xy ra gia:
ng kh (glucose, frutose, maltose, lactose)
Gc amine ca protein (thng l cc gc -amine ca lysine)
peptide, acid amin

Phn ng ny s xy ra nhanh khi:


Nhit tng, pH trung tnh,
Hot tnh ca nc thp (aw 0,65-0,7),
Bo qun thc phm trong thi gian di.

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4/13/2015

CC DN XUT CA NG
Bn cht phn ng:
Tng t phn ng ca ng trong mi trng
acid hoc kim.
Cc hp cht N ng vai tr xc tc
Thc y phn ng xy ra vi tc nhanh hn,
Trong iu kin mi trng n gin hn rt nhiu.

Phn ng ny rt thng gp trong thc phm.

III. OLIGOSACCHARIDE
1. Cu to
Oligosaccharide c to ra:
Nh lin kt O-glycoside,
Gia nhm OH glycoside ca mt ng vi nhm OH bt k ca ng
khc.

Oligosaccharide c trn 10 gc ng gi l polysaccharide.


Oligosaccharide mch thng v mch nhnh.
Khi lin kt glycoside c to ra gia 2 nhm OH glycoside,
oligose to thnh l mt ng khng kh.
Khi lin kt c to thnh gia mt OH glycoside v mt nhm
ru OH mt carbon bt k, to thnh ng kh.

2. Tnh cht
Tnh cht vt l v cm quan ph thuc vo thnh phn cc
ng n.
Tnh cht ha hc ph thuc vo dng kh hay khng kh ca
ng.
Cc ng khng kh:
Thiu gc OH-glycoside.
Khng c phn ng c trng vi cc gc amin, alcohol, phn ng quay
quang hc

Cc ng oligo b thy phn trong mi trng acid hoc di


tc dng ca enzyme to ra cc ng n.

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Cu to phn t ca mt vi oligosaccharide tiu biu

Mt vi oligosaccharide t nhin khc

L thnh phn ca mt ong

C trong ht ca hoa hng


L cht gy v ng trong qu o, m

Mt vi dn xut ca oligo c hot tnh trong y hc


Mt vi oligosaccharide t nhin khc

L sn phm ca s thy phn tinh bt

L hp cht chng hnh


thnh khi u.

Mt vi loi aburamycin
c tc dng dit khun
v chng s hnh thnh
khi u.

ng dng trong sc k (phn tch)

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4/13/2015

Mt vi dn xut ca oligo c hot tnh trong y hc

IV. POLYSACCHARIDE
1. Cu to
L polymer ca monosaccharide,
Lin kt O-glycoside.
Cch c tn:
da vo thnh phn monomer
B ui ose thm an
VD:
polysaccharide to bi D-glucose: goi l D-glucan
Polysaccharide to bi galactose & glucose:
galactoglucan

gl

D-

2. Phn loi
Da vo thnh phn monosacchride:
Homopolysaccharide: cc monosaccharide ging
nhau (glucan, mannan,...)
Heteropolysaccharide: cc monosaccharide khc
nhau (2-4 loi ng n) (glucomannan,
fructogalactoglucan,...)

Da vo c trng ca mch polyglycoside:


Polysaccharide mch thng,
Polysaccharide mch nhnh.

Da vo ngun gc: polysaccharide thc vt,


ng vt, vi sinh vt.

Da vo chc nng:
Polysaccharide to hnh, to khung (cellulose,
hemicellulose
v
pectin
thc
vt;
chitin,
mucopolysaccharide ng vt).
Polysaccharide d tr (tinh bt, dextrin, inulin thc
vt; glycogen ng vt).
Polysaccharide c chc nng gi nc (agar, pectin
v alginate thc vt; mucopolysaccharide ng
vt).
Polysaccharide thc phm: n c, d tiu ha,
khng c.

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5. Cc polysaccharide tiu biu

4. Tnh cht
Tnh tan

H Gel

LK mnh vi nc =
tan,
LK mnh dc theo
chiu di polymer =
khng tan,
LK cc b, gii hn
vi polymer = to gel.

Tinh bt
Cellulose
Pectin
Agar
Alginate
Gum

Glycogen
Chitin

TINH BT

1. Cu to

Amylose Cu to

Amylose: Mch thng -1,4 glucose. PTL~106.


Amylopectin: Mch thng -1,4 vi mt mch nhnh 1,6 khong mi 20 n v glucose. PTL~108.
Amylose: amylopectin ~ 1:4.

Glucan vi lin kt -1,4

Tinh bt ging np cha hu nh l amylopectin (100%).


Mt s tinh bt cha n 70% amylose.

Lin kt -1,4
a1,6
a1,4

CH2OH
H

O
H
OH

H 1
O

OH
H

OH

6CH O H
2
5
O

4 OH
3

CH2O H
H

H 1

CH2OH

CH2OH
O

H
OH

OH

O
H
OH

OH

O
H
OH

OH

H
OH

OH

amylose

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4/13/2015

Amylose Tnh cht


Cun xon mch, mi vng xon 6 n v
glucose.

ha tan:

Am c ha tan cao, c bit trong dung dch


kim long nht dung dch Am cao.
Dung dch Am rt d to keo, ngay c khi to cao.

Tnh lu bin:

Trong dung dch Am tinh th.


Trong nc, Am hp th nc.

Kh nng to phc:
Amylose

Vng xon c Am tng tc vi Iod cho phc mu


xanh c trng.
Am c kh nng to phc vi nhiu hp cht hu
c c cc v khng cc.
Cc phc ny rt bn.

Amylopectin - Cu to
Glucan c lin kt -1,4 v cc nhnh gn vo
bng lin kt -1,6.

Amylopectin

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4/13/2015

Amylopectin Tnh cht


To phc vi iode mu tm .
Ho tan trong nc nng (60-80%) dung dch
c nht cao.
Ht tinh bt
Kch thc 0,02-0,12mm.
Hnh dng: trn, bu dc, a gic
Ht tinh bt / ht khc kch thc, hnh
dng khc nhau.
Cu trc xp hp th cc cht ha tan.

Tinh bt khoai ty

2. Tnh cht tinh bt

Dextrin v tnh cht ca


dextrin

Tnh tan

Amylosedextrin:

Khng tan trong nc lnh, ru.


To trng thi keo trong nc si to gel khi lm
ngui.

Phn ng thy phn tinh bt


Thy phn ha hc, thy phn sinh hc (bng
amylase)
iu kin: nhit, m, xc tc
Sn phm: maltose, glucose

To phc vi iod
Tnh cht chc nng

Bt trng tan trong


ethanol 25%, ta trong
ethanol 40%.
Cho mu tm xanh trong
dung dch Iod.

Eritrodextrin:

Achrodextrin:
Tan trong ethanol 70%.
Khng cho mu vi Iod.

Maltodextrin:
Khng ta trong ethanol.
Khng cho mu vi Iod.

Tan trong ethanol 55%,


ta trong ethanol 65%.

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4/13/2015

CC TNH CHT CHC NNG CA TINH BT

1. Tnh cht thy nhit v s h ha ca tinh bt

Ht tinh bt

Hp th
nc qua v

Ph v v ht,
t lin kt cc
phn t

Phn tn

Hydrate ha v
trng n

Trng n

Trng thi kh, si Am & AP xp xen k - to LK H


ni (kiu 1).
Khi c nc, LK H ngoi (kiu 2) hnh thnh gia
cc si tinh bt.
Nu to thp, tinh bt trng n mc no
dng li.

Dung dch keo


Kiu 1

Kiu 2

H ha tinh bt
N: Nhit ph v ht, chuyn tinh bt t trng
thi u c mc hydrate ha khc nhau thnh dung
dch keo gi l nhit h ha.
Cc ht nh c cu to cht, lin kt hydro kiu 1 rt
bn nn nhit h ha ht nh ln hn ht ln.
Do kch thc cc ht tinh bt rt khc nhau nn nhit
h ha tinh bt khng phi l mt im m l mt
khong.
nht tinh bt tng dn ln qua mt im cc i ri
gim xung.

Cc giai on ho tan ca tinh bt


1- nc, 2- tinh bt, 3- tinh bt +
nc, 4,5- nc + tinh bt,

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4/13/2015

Cc yu t nh hng n nhit h ha tinh


bt
To h ho, ph thuc vo:

NGUYEN LIEU

Tinh bot bap 5% 300C

Thnh phn amylose v amylopectin


Cc ion kim loi lin kt vi tinh bt
Cc mui v c, cc cht in ly.

C ngha quan trng i vi nhiu sn phm thc


phm:

Tinh bot bap 5% 600C

Tinh bot bap 5% 650C

Tinh bot bap 5% 700C

Lm tng gi tr cm quan ca cc thc phm ny


Tinh bt np thng cho h trong hn tinh bt t
ng lm tng trong cn cc cht nh ha gy c h
tinh bt.

Tinh bot bap 5% 800C

Tinh bot bap 5% 850C

Tinh bot bap 5% 900C

H ha tinh bt bp

Cc yu t nh hng
nht ca h tinh bt
ng knh biu kin ca cc ht tinh bt.
ng knh biu kin ph thuc:
c tnh bn trong: MW, kch thc, th tch, cu
trc,
Tng tc vi dung mi: nh hng n trng,
ha tan, cc cu hydrate ha bao quanh phn t,
Tng tc gia cc phn t tinh bt: nh hng n
kch thc ca s tp hp. Cc yu t: nng tinh
bt, pH, to, Ca2+, tc nhn oxy ha, ha cht ph hy
cu hydro.

pH:
pH kim: tng nht do ion ha phn t tinh bt lm tng kh
nng tp hp,
pH 4-7: khng nh hng nhiu n nht,
pH thp: dng tinh bt lin kt ngang ci thin n nh ca
nht.

Mui nng cao s chim mt cc phn t nc,


tng kh nng tp hp gia cc phn t tinh bt.
ng, acid bo lm tng gi tr cc i ca nht.
ng dng: ch, nc xt, xp, tng t, xt c chua,

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4/13/2015

2. Kh nng to gel
Khi ngui h tb cc p/t tng tc vi nhau
& sp xp li 1 cch c trt t gel.
Cc iu kin to gel:
Dung dch c nng va phi
c h ha chuyn tinh bt thnh dng ha tan,
ngui trng thi yn tnh to gel tinh bt c cu
trc mng 3 chiu.

Cc lin kt trong gel tinh bt:

S ng to gel vi protein:
Do cc tng tc Van der Waals v lin kt hydro
gia protein v tinh bt,
Kh nng gi nc, cng, n hi gel protein
tt hn.
Tinh cht ny c ng dng quan trng trong cc sn
phm nh gi la.

Lin kt hydro ni trc tip cc mch tinh bt hoc qua


cc cu phn t nc.

S thoi ha ca gel tinh bt


Nguyn l:

Khi mt thi gian di, cc


gel co li v tch nc. QT :
s thoi ha.

Cc giai on:

Mch tinh bt c un
thng li
Lp v hydrate b mt
Cc mch nh hng li
s/song vi nhau
Cc cu hydro c to thnh
gia cc nhm OH.

Yu t nh hng:

Am l thnh phn ch yu gy
thoi ha gel tinh bt
Thoi ha Am l khng khc
phc c
AP thoi ha c th phc hi
trng thi ban u khi un
nng 50-60oC.

Hu qu:

Tch nc v lm c li cc
sn phm na lng
Lm cng cc sn phm nh
bnh m,

Lm sn phm gin,
d gy, c nh gim

3. Kh nng to mng ca tinh bt


Nguyn l:
Cc phn t tinh bt (Am & AP) s dn phng ra
Sp xp li & tng tc trc tip vi nhau = LK H / gin tip
qua nc.

Phng php to mng:


Phn tn tinh bt trong nc n mt nng nht nh,
H ha s b to nht nht nh,
Khuy k v rt thnh mt lp mng ln b mt kim loi
phng v nhn c gia nhit thch hp.

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Yu t nh hng

Cc giai on to mng tinh bt


G1: S bc hi nc xy ra t b mt t do ca cht lng.
G2: Trn b mt mng to ra lp gel nht (nc phi thng
tr lc ca lp ny v p sut hi bo ha).
G3: Nng tinh bt tng ln, cc ht tinh bt dch li gn
nhau, phn tn, sp xp li thnh lp v hnh thnh cu trc.
G4: Nc nm gia cc ht bt u bc hi (nc solvat ha
lin kt bn)
Lc ny nc phi thng tr lc ca lp mng mi to ra,
Cc ht tip xc nhiu hn v bt u bin dng,
Sc cng b mt c khuynh hng lm co b mt ca h thng.

G5: Cc ht bt u th hin lc c kt, to nn cc tnh cht


c l ca mng.

dai, bn t ca ton si ph thuc vo:


Lc tng tc gia cc phn t
Lc tng tc ni phn t
Lin kt Van der Waals v lin kt hydro.

Tinh bt u xanh giu Am (>50%)


Mch di, thng
Lc tng tc gia cc phn t ln
Cc chui kh b t, si chc v dai.

Tinh bt giu AP
Phn nhnh v ngn
Lc tng tc gia cc phn t rt yu
Nhiu on mch ngn chp li d to ra khuyt
tt trong cc b si
Si tinh bt ro v d t.

Mng thu c gin v d


rch do:
Nc bc hi, gim dn th
tch tinh bt,
Cc ht tinh bt lin kt vi
nhau hnh thnh cc cu
trc cc b vng chc, xut
hin cc ng sut ni.

Nu ng sut ni < bn
ca cu trc hnh thnh th
s co ngt khng lm rch
mng.
Nu ng sut ni > bn
ca cu trc mng th gy
rch mng.

Khc phc:
Tng nhit to mng
tng chuyn ng nhit ca
cc ht, ph v cc cu trc
cc b.
Thm cc cht ha do
tng khong cch gia cc
phn t, gim lc Van der
Waals gim ng sut ni.

TINH BT BIN TNH


Cng ngh bin tnh c thc hin bng cc
phng php:
Ha hc
Vt l
Enzyme

Thng qua cc phn ng phn ct, kt hp, oxy


ha hoc thay th ha hc trong cc ht nh.
Nhm thay i c tnh tinh bt c c
nhng ng dng thit thc hn.

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4/13/2015

Tinh bt h ha trc

1. Bin tnh tinh bt bng PP vt l


Cc tc ng vt l:
Ct, trn
Nhit
m

Kt hp x l nhit v
ct thng c dng
sn xut cc sn
phm p n v bnh
snack.

V d mt s sn phm
tinh bt sn bin tnh:

TB h ha trc
TB x l nhit m
TB dng ht
Dextrin

Tinh bt p n (extrude starch)


Trong qu trnh p n, cu trc xon ca amylose (c th l
khong cch gia cc chui) c s thay i.
Tnh cht:
Tinh bt p n d phn tn
Tan tt
C nht thp hn tinh bt t nhin

S phn hy mt phn mch amylose cho thy cc thay i


v mt ha hc vn xut hin nhit cao ca qu trnh p
n (185-200oC).
Sn phm to ra c maltose, isomaltose, gentibiose,
sophorose v 1,6-anhydro-glcopyranose.

L cht kt dnh tan trong nc lnh v l cht


mang mu tt.
Tnh cht c trng:
trong cao
Khng c mi l
C nht cao ( nht ca dung dch TB sn
nng cht kh 6% khong 800BU).

2. Bin tnh tinh bt bng PP ha hc

Thy phn bng acid


Oxy ha
Ether ha
Ester ha
To lin kt ngang
Bin tnh kp

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4/13/2015

Tinh bt oxy ha
Tc nhn oxy ha:
HOCl, NaOCl (trong
mi trng kim).
Phn ng:
To cc gc carboxyl,
carbonyl; (1 gc/25
gc ng)
Ct t mch tinh bt
(ty vo nng ).

Tinh bt bin tnh bng acid


Tnh cht:
Mu rt trng
To mng, to gel
vi trong cao
C kh nng gi
nc v bn nht
tt
Tnh thoi ha gim.

ng dng:
Cng nghip giy
Thc phm

Tinh bt ester ha acetyl


ha
Tinh bt acetate (AS)
Vinyl acetate (max 7,5%) phn ng vi dung dch sa
tinh bt trong mi trng kim,

Tinh bt phosphate monoester


Tc nhn phn ng: orthophosphoric acid, sodium
orthophosphate.
Nhit phn ng: 120-170oC

Ngoi ra, tinh bt c th phn ng vi acid


succinic, acid bo, acid citric v cc mui ca
chng.

Quy trnh:
Acid (HCl) c cho vo dung dch tinh bt (khong
20-30% cht kh).
nhit thp hn nhit h ha
Dng phn ng v trung ha bng dung dch soda
C c, loi nc v sy kh.

Tnh cht:
C nht thp hn 30cPs (do p/ng thy phn)
pH khong 5,0-6,0
Tnh thoi ha thp

c tnh v ng dng ca tinh bt ester ha


nht cao, lm c tt
Paste tinh bt c trong
cao, to c mng trong
sut v n hi,
t b thoi ha, tnh cht
lnh ng/tan gi tt.

Tng nh ki nc
Tan tt trong dung mi HC
d ko mng, cn phim
C th thay i mc
acetyl ha (tng bn t
nhng c th phn hy bi
enzyme)
Gi c nh ko cng c
hc trong mi trng nc

65

4/13/2015

Tinh bt lin kt ngang


Di-tinh (di-starch) bt phosphate: 2 nhm hydro
trong phn t acid phosphoric H3PO4 hay mui ca
chng c thay th bng 2 phn t tinh bt.
Tinh bt c x l vi:
Sodiumtrimetaphosphate
Epichlorohydrin

c im v ng dng ca tinh bt lin kt


ngang
Bn nhit cao, pH, tc ng c hc
c ng dng trong thc n tr em (do bn khi
khuy v un nng).
Lm nhn trong bnh
Do duy tr c st khi lm lnh
Khng b ph hy nhit cao v khuy trn
Gel trong sut v bn

Tinh bt lin kt ngang nh tc nhn acid boric:


khng trng n khi gia nhit, c dng trong gng
tay phu thut.

Tinh bt dextrin ha
Dextrin l nhng phn t polymer ca ng Dglucose, c th hon ton mch thng, phn nhnh
t, nhiu hay mch vng.
Evans v Wurzburg phn loi dextrin thnh 3
nhm da trn cch sn xut ra chng:

Dextrin ha

Dextrin nhn c nh thy phn tinh bt bng acid hoc


enzyme.
Cyclodextrin nhn c nh tc dng ca enzyme t
B.macerans.
Dextrin nhn c bng tc dng ca nhit hay rang kh
tinh bt vi acid (pyrodextrin).

66

4/13/2015

ng dng ca dextrin

Tinh bt bin tnh bng enzyme

Do nht ca dextrin thp hn nhiu so vi tinh


bt:

Tinh bt dextrin MW cao dextrin MW thp


maltose glucose.
Cc sn phm chnh:

Chng c s dng nng cao


To cc loi mng mau kh vi bm tt

Maltosedextrin: s dng enzyme -amylase (qu trnh


dch ha).
Xi-r maltose, glucose: s dng enzyme -amylase v
glucoamylase.
ng glucose tinh th (s dng kt hp enzyme dch
ha v ng ha).
Xi-r HFS giu fructose: s dng glucoisomerase GI
chuyn glucose thnh fructose.
Cyclodextrin: s dng enzyme CDGTase.

Dextrin c tnh tan tt hn trong nc lnh


Dung dch nng cht kh cao cng n nh hn
so vi tinh bt
S dng trong sn xut keo dn, cc loi cht kt dnh tan
mt phn hay hon ton.

Trong cng nghip thc phm, dextrin c dng


nh cht kt dnh trong ngt, cht thay th cht
bo.

CELLULOSE Cht x - Fiber


Cu to:
-1,4 polyglucose
Phn t rt ln
C nhng vng kt tinh
(lin kt hydro) v nhng
vng khng kt tinh.

Phn b: l thnh phn


chnh ca thnh t bo
thc vt, cng vi pectin
v lignin.

Vai tr:
Do h tiu ha ca ngi & V (V nhai li) khng c h E
cellulase cellulose ch ng
vai tr duy tr nhu ng rut ca
h tiu ha.
Cc loi V nhai li c kh nng
tiu ha cellulose do h VSV c
kh nng sinh tng hp
cellulase.
Thiu cellulose / khu phn n
d gy to bn, ung th trc
trng.
Qu nhiu cellulose / khu phn
n gy s hp thu cht
dinh dng/ng rut.

CH2OH
H

O
H
OH

H 1

OH

OH

H
O
H

6CH OH
2
5
O

4 OH
3

CH2OH
H

H 1
2

OH

CH2OH

CH2OH
O

H
OH

OH

H
O

O
H
OH

OH

O
H
OH

OH

OH
H

cellulose

67

4/13/2015

Cc dn xut ca cellulose
Tnh cht b Thu phn:
Bng H2SO4/HCl c, to
cao b-glucose.
Trong iu kin nh hn
cellobiose.
Enzyme
cellulase

cellobiose + t -glucose.
V n c, c h vi khun
sinh enzyme cellulase.

D:

Cacboxymetylcellulose (CMC)

Trong CN si nhn to, da


nhn to, cht n, cht
do
Dng trong PP sc k
phn tch protein.
V dinh dng, tng nhu
ng rut, tng tiu ho

68

4/13/2015

Methylcellulose
Cu to
CMC l dn xut ca cellulose vi
chloroacetic acid.
Cell OH + NaOH Cell ONa + H2O
CTTQ: [C6 H7O2(OH)3-x(OCH2COOH)x]
CMC c th dng acid (H-CMC)
hoc dng mui (Na-CMC).
ng dng
L mt ph gia thc phm c
s dng trong nhn bnh, salad,
cc sn phm nu ng, kem, sa
chua, sir

Tnh cht
CMC c th c s dng dng
H hoc Na.
H-CMC khng tan trong nc,
ru, cetone, tan c trong
dung dch kim v cc h dung
mi dng ha tan cellulose.
Na-CMC c th ha tan trong mi
trng kim, tan trong nc.
nht dung dch CMC ph
thuc pH mi trng.
Khng to gel.

Ete ca cellulose, trong


nhm th c cha hydroxyl.
CTTQ:
[C6H7O2(OH)3-x(OCH2CH2OH)x]n

Tnh cht
- Ha tan trong nc lnh nh
lin kt vi nc thnh
hydroxyl.
[ R O+ CH3](OH)
- Khng tanHtrong nc nng.
- C th to gel khi tng nhit
.

ng dng
Trong
thc
phm,
metylcellulose c s dng
lm cht n nh v cht lm
c.

Pectin

Hydroxyetylcellulose
Cu to

Cu to

Tnh cht

ha
tan
Hydroxyetylcellulose
thuc mc th.

ca
ph

ng dng
Dng lm bn h nh tng.

69

4/13/2015

Ngun gc: Mng t bo thc


vt bc cao (v cy h citrus)
Tnh cht chc nng:
HMP s to gel khi c mt
acid v nng ng cao.

Cu trc: L polymer mch thng


ca acid polygalacturonic ni vi
nhau nh lin kt -1,4 vi cc
mc ester ha nhm metyl
khc nhau.
>50% b ester ha: pectin metyl
ha cao (HMP)

LMP s to gel khi c mt


Canxi.

<50% b ester ha: pectin metyl


ha thp (LMP)
Ngoi ra, trong thnh phn pectin
cn c rhamnose, D-galactan,
arabinan.

HMP v LMP
HMP

To gel vi Ca2+

To gel khi c acid


v hm lng nc thp

LMP

50

100

%DE ca Pectin

70

4/13/2015

Agar-Agar
Ngun gc: Trch ly t rong , thnh phn
chnh l agarose v agaropectin.
Cu trc:
Mch chnh l beta-D-galactopyranose v 3,6anhydro-anpha-L-galactopyranose lin kt vi nhau
bng lin kt -1,4 v -1,3 lun phin.
Mch chnh ny c ester ha mc thp bng
acid sulfuric. Trong agarosepectin c thm acid
pyruvic.

CU TO AGAROSE
Tnh cht chc nng: to
gel thun nghch nhit.
Ha tan trong nc si.
Hp th rt nhiu nc, to
gel nh cc lin kt hydro
nng rt thp (khong
0,4%).
Nhit nng chy 80-85oC,
ng li khi lm ngui n
40-50oC.
C kh nng to mng c
bn c hc cao v trong sut.

ng dng:
Thc phm n king;
Dng lm thch;
Thay th pectin trong mt
qu, thay gelatin trong cc
sn phm tht c;
Dng lm mi trng rn
nui cy VSV.

Gm 2 poly-sac: agarose v agaropectin


- Agarose: cu to t nhng n v -D v L-galactose,
LK vi nhau bng LK 1,4 v 1,3-O-glycoside.
- Agaropectin: cu to t nhng n v D-galactose.

71

4/13/2015

Alginate

Cu trc gel ca agarose

Ngun gc: Trch ly t to bin (to nu). MW 32-200kDa


Cu trc: polysaccharide mch thng cha hai loi gc (l
mt co-polymer) LK bng lin kt 1,4:

Cu trc gel ca alginate khi c


mt Ca2+

Acid -D-mannopyranosyluronic (M)


Acid -L-gulopyranosyluronic (G)

Tnh cht chc nng:


Nht trong dung dch nc: khc
vi agar, dung dch alginate
khng ng li ngay c khi lm
lnh ng.
To gel khi c mt Ca2+ (hoc pH
thp), nh cc tng tc tnh
in qua cu Ca2+.
Gel bn nhit: cc gel ny khng
thun nghch v t n hi.

ng dng: SP thng mi dng


Alginate Na
Lm c, lm dy trong thc
phm (trong kem, nc qu
c),
L thc phm n king,
L cht mang trong c nh t
bo.

Ca2+
Cc phn t acid
mannuronic (M)

Cc phn t acid
guluronic (G)

Ca2+

Ca2+
Ca2+

Ca2+

Ca2+

Ca2+

N cng c kh nng to mng


rt tt.

72

4/13/2015

Cc gum
Xanthan gum: l mt dn sut ca cellulose. Mch xanthan
gum cha cc lin kt 1,4 ca beta glucopyranose.
ng dng:
Quan trng ca xanthangum l da trn kh nng lm bn nh tng
v n nh kh nng l lng cc ht nh.
Do c tnh bn nhit cao nn c ng rt nhiu trong sn phm
hp.
Xanthan gum cng c ng dng trong sn xut bnh pudding n
lin.

Ngun gc: Gum to bin


Cu trc (gn ging agar):
Mch
thng
Dgalactopyranosyl vi cc lin
kt 1,3 v 1,4 lun phin.
Mt s gc c mt hoc hai
gc este sulfate (sulfate ha).
Ba loi cu trc lp li (, , v
carageenan)

Cargeenan
Tnh cht chc nng:
Carageenan c kh to gel
nh to cu trc bc 3, bc 4
t cc xon kp ca phn t
carageenan.
To c khng ph thuc pH.
Dng xon i hay
carageenan c th dn ti
vic to gel.

S to gel ca
Carageenan

ng dng: -carageenan trong


cc thc phm t sa, trong
ung c chocolate, thc
phm n king

Gum Arabic
Ly t cy Acacia
nht thp, khng
to gel.
To phc vi mt
glycoprotein - hot tnh
b mt.

Gum Adragante

Gum Karaya

Thu nhn t cy Astregalus (Th


Nh K, Syrie, Iran).
L polymer ca acid galacturonic,
ng thi c cha D-galactose, Lglucose, D-xylose v L-arabinose.

L nha ca cy thuc h rau.


Cu trc ha hc cha r. Thnh
phn chnh gm: D-galactose, Lrhamnose, Acid galacturonic.

Gum Ghatti

Gum Guar

L nha cy Anogeissus Latfolia.


L polymer c mch chnh cha
cc gc -D galactose, acid
galacturonic v rhamnose.

Trch t ht ca cy Guar (n ,
M, Pakistan).
L galactomannnan
T l galactose/mannose = 1/2

73

4/13/2015

Gum Guar

Caroube

Mch thng ca -D mannose


lin kt 1,4 vi cc nhnh ch gm
1 gc -D galactose lin kt 1,6.

Trch ly t ht Caroube
L galactomannan
Cu to tng t gum Guar,
nhng t l galactose/mannose =
1/4.

Gum Xanthan

Gum Gellane

Ngun gc: Sn phm ca vi


khun Xanthomonas campestris.

Ngun gc: Sn phm ln men vi


sinh vt (Pseudomonas).

Cu trc: Mch chnh ging


cellulose (-1,4-poly-glucose) vi
cc nhnh trisaccharide (cc gc)
ti cc v tr monome lun phin
trn mch chnh mang cc gc
acid carboxylic.

Cu trc: n v lp li l mt
tetra-saccharide gm glucose,
acid glucuronic v rhamnose.

Tnh cht chc nng: Tan trong


nc, nht, khng to gel.
nht ch ph thuc rt yu vo
nhit .

CH 2OH

Xanthan: Cu trcchc nng

H
OH

OH

CH 2OH

Phn t

mch
thng

OH

OH

H
O

O
H
OH
H

H
OH

H
O

glycogen

H
1
O
6 CH 2
5
H
OH
3
H

CH 2OH
O
H
2
OH

H
1
O

CH 2OH
O

H
4 OH
H

H
O
OH

O
H
OH

H
OH

OH

Glycogen, glucose d tr dng polymer ngi & V

Cu to: tng t nh cu trc amylopectin, nhng


glycogen c nhiu nhnh (16) hn.

Cu trc phn nhnh cao hn cho php glucose gii


phng nhanh t glycogen d tr, vd: c trong qu trnh
tp th dc.

Kh nng lm glucose gii phng nhanh s dng V


th cn thit hn so vi TV.

Xon

ngu
nhin

H
OH

OH

pH thp

CH 2OH
O

H
OH
H

OH

Glycogen

CH 2OH
O

Tnh cht chc nng: C th cho


bin i ha hc thay i tnh
cht to gel (gel do thnh gel
dn).

74

4/13/2015

Chitin - Chitosan
Chitin l g?

Cu to ca chitin

L polymer (homopolysaccharide) hu c phong ph th


hai trn tri t sau cellulose.
Cu trc tuyn tnh gm cc n v N-acetyl--D glucosamine
ni vi nhau nh cu ni -1,4 glucoside.
C cu hnh tng i cht ch do cc cu ni glycoside c
bit.
D to mng v c coi l vt liu c cc c tnh c hc rt
tt.
Cng thc phn t: (C8H13O5)n
Phn t lng: Mchitin =(203.09)n

75

4/13/2015

Chitosan l g?

Tnh cht ca Chitin


Mu trng
Khng tan trong nc, mi
trng kim, acid long, cc dd
hu c nh este, ru.
Tan trong dd c nng ca mui
trung tnh thyoxyanate liti v
thyoxyanate canxi, to thnh dd
keo.
n nh vi cht chng oxy ha
nh: KMnO4, nc javen, NaClO.
Kt tinh dng tinh th v nh
hnh.
C kh nng hp th tia hng
ngoi bc sng 884-890cm.

L polysaccharite ngun gc t
nhin, c hot tnh sinh hc cao,
c tnh ha hp sinh hc v t
phn hy trn da.
B men lyozyme mt loi men
ch c trn c th ngi, phn
gii thnh monome N-acetyl-DGlucosamine.
Khi un nng trong HCl m c
to thnh 88,5% D-Glucosamin v
21,5% acid acetic.
Khi un nng trong NaOH m
c th chitin b mt gc Acetyl
to thnh chitosan (C6H11O4)n.

Tnh cht ca Chitosan


Khng ha tan trong nc, trong dd kim ti pH >6.5
Tan c trong dd long ca hu ht cc acid hu c bao gm
a.formic, a.tartaric, a.acetic v a.citric.
Ha tan c gii hn trong cc acid v c long nh
a.phosphoric v a.sulfuric.
c xem nh mt polymecationic c kh nng bm dnh vo
b mt tch in m.
Phn ng vi acid m c to thnh mui kh tan.
Tc dng vi iod trong mi trng H2SO4 cho phn ng ln
mu tm.

L dng N-deacetyl ca chitin, khi deacetyl chitin bng kim


c ta thu c chitosan.
L mt polymer ha c c cu trc tuyn tnh t cc n v D-glucosamine lin kt vi nhau nh cu ni -1,4
glucoside.
Cng thc phn t: (C6H11O4N)n
Phn t lng: MChitosan= (161,07)n

Cng thc cu to ca chitosan

Ngun gc ca Chitin

Thng c nhiu trong v ca cc loi gip xc v ng vt


thn mm.
Trong xng sng ca mc ng.
Trong biu b ca cn trng.
Hin din trong to.
C trong t bo ca mt s loi nm.

Hm lng Chitin (%) trong mt s loi cua


Loi
Cua bin
Cua ng

Tht
0.07
0.04

V
8.2
4.4

(Ngun: Sachindra NM, Studies on some crustaceans of tropical


water with special reference to pigments, 09/2003)

76

4/13/2015

Hm lng Chitin (%) trong mt s loi tm


Loi
Penaeus monodon
Penaeus indicus
Metapenaeus dobsoni
Parapenaeopsis stylifera
Solonocera indica
Aristeus alcocki
Macrobrachium rosenbergii

Tht
0.13
0.1
0.07
0.04
0.05
0.01
0.04

u
3.6
4.1
3.5
4.2
4.2
3.3
4.4

Hm lng Chitin (%) trong mt s loi nm


V
5.0
5.0
4.9
5.2
6.3
4.4
5.8

Loi
Nm men
Nm mc

Allomyces
macrogynus
Phycomyces
blakesleeanus

Hm lng
0.45
58
91

(Ngun: Eugene Khor, Chitin: Fulling a biomaterials promise,


05/2001)

(Ngun: Sachindra NM, Studies on some crustaceans of tropical water


with special reference to pigments, 09/2003)

Trong cng nghip


Vi col dng cho may mc.
Vi chu nhit, chng thm.
Vi Chitosan dng cho may qun
o dit khun trong y t.
Lm tng bn ca giy.
Dng lm thu knh tip xc.
Gp phn tng tnh bn ca hoa
vi.
S dng trong sn xut sn chng
mc v chng thm.

Trong nng nghip


Bo qun qu, ht ging mang li
hiu qu cao.
Dng nh mt thnh chnh trong
thuc tr nm bnh (o n, kh
vn).
Dng lm thuc kch thch sinh
trng cy trng cho la, cy cng
nghip, cy n qu, cy cnh
Trong phim nh
Phim Chitosan c nt cao.
Khng tan trong nc.
Tan trong acid long nh acid
acetic.

Trong cng ngh in n


Dng lm mc in cao cp
trong cng ngh in.
Tng cng bm dnh
ca mc in.
Trong cng ngh mi trng
X l nc thi cng nghip
rt hiu qu.
X l nc thi trong cng
nghip nhum vi.
X l nc trong cng
nghip nui tm, c.

Trong cng ngh sinh hc


Cht mang c nh enzyme
v c nh t bo.
Trong cng ngh thc phm
Sn xut ra mng mng
bao gi thc phm.
Thay th cho PE.
Mng Chitosan d phn hy
trong mi trng t nhin.

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4/13/2015

MT S HETEROPOLYSACCHARIDE

Glycosaminoglycan v
proteoglycan

L thnh phn cht nn ngoi bo, dng gel nm gia cc m V cu to t


heteropolysaccharide v si protein.
n v cu to ca heteropolysaccharide l: N-acetylglucosamine / Nacetylgalactosamine v uronic / glucuronic acid. Ngoi ra, cc nhm OH
ca nhn glycosaminoglycan thng b sulphate ha chng c mt
in tch m kh ln.
Mt s glycosaminoglycan ph bin:

CH 2 O H

D -glucuronate

6 COO

H
4

H
OH
3

OH

NH COCH 3

N-acetyl-D -glucosamine

hyaluronate
Glycosaminoglycans (mucopolysaccharides) l polymer ca
disaccharide lin hon.
Cu to cc monosaccharide hng ti lm thay i, vi
nhm acid, nhm amino, sulfated hydroxyl v nhm amino
Glycosaminoglycans c khuynh hng mang in tch m, v
cha nhiu nhm acide.

6CO

1 O

OH

CH 2OH

D-glucuronate

O
H

Hyaluronic acid: l thnh phn cht nn ngoi bo nm gia cc m V. Cu to t


D-glucuronic acid v N-acetylglucosamine. Thng ng vai tr lm cht bi trn khp
ni v l thnh phn chnh ca sn v gn.
Proteoglycan: glycosaminoglycan thng LK vi protein ngoi bo, l thnh phn
quan trng th 2 ca cht nn ngoi bo. Cu to: cc si glycosaminoglycan ngn
(keratan sulfate, heparn sulfate, dermatan sulfate, chondroitin sulfate) cng gn ln si
protein li. Sau cc si ny gn ln si hyaluronate. To thnh mt khi c
ngm nc cao. Chc nng: lm gi cho gian bo v nh hng cho m V pht
trin.

H
4

H
OH
3

O
H
2

OH

OH
O

1 O

NH COCH 3

N-acetyl-D-glucosamine

hyaluronate
Hyaluronate (hyaluronan) l mt glycosaminoglycan
vi disaccharide lin hon gm 2 dn xut glucose l
glucuronate (glucuronic acid) & N-acetyl-glucosamine.
Lin kt glycoside l (13) & (14).

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4/13/2015

CH 2OH

D-glucuronate
6COO

heparan sulfate
glycosaminoglycan

core
protein

H
4

H
OH
3

transmembrane
-helix

Proteoglycans l glycosaminoglycans lin kt ng


ho tr vi serine ca protein li ring bit.
Chui glycosaminoglycan c tng hp bng cch
thm tun t ng cn li vo protein li.

H
O

OSO3

OH

1 O

NH COCH 3

N-acetyl-D-glucosamine

Mt vi proteoglycans ca matrix ngoi bo ni khng


ng ho tr vi hyaluronate qua protein domains gi l
lin kt modules.
Nhiu bn sao ca aggrecan proteoglycan kt hp
vi hyaluronate trong sn to thnh phc hp ln.
Versican, proteoglycan khc, ni vi hyaluronate
matrix ngoi bo ca nhng m lin kt mm.

H
OH

NHSO3

H
H

OH

Glycoprotein v glycolipid

CH2OSO3

O
H

N-sulfo-glucosamine-6-sulfate

iduronate-2-sulfate

COO
OH

hyaluronate

cytosol

heparin or heparan sulfate - examples of residues


Heparan sulfate lc u c tng hp trn mt mng dnh vo
protein li nh l polymer ca N-acetylglucosamine lun phin v
glucuronate cn li.
Sau , trong cc phn on ca polymer, cc phn cn li ca
glucuronate c th thay i thnh ng sulfate iduronic acid,
trong khi N-acetylglucosamine residues c th deacetylated
v/hoc sulfated.

Phc oligopolysaccharide gn ha tr protein v lipid (ch yu:


protein v lipid mng, protein bi tit) glycoprotein v glycolipid.
Phn oligopolysaccharide do mang nhiu in tch m nh hng
ln s gp np v cun khc gip protein trnh b protease phn
gii.
Oligopolysaccharide nh hng rt nhiu n tnh c hiu SH
ca glycoprotein v glycolipid.
VD: phn oligopolysaccharide ca glycoprotein mng t bo thng
cha khong 14 n v ng n khc nhau LK glycoside 1-2, 1-3,
1-4, 1-6, 2-3, 2-6. Mt s dng , s khc dng . S kt hp a
dng ny mt s lng khng l cc vng tip xc v trao i
thng tin gia cc t bo v m

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4/13/2015

3 con ng chuyn
ha chnh ca glucose

Con ng ng phn (glycolyse),


Embden Meyerhof Parnas (EMP)
Gm 5 G
GI: hot ha G G6P (p 1 tn 1ATP)
GII: bin i G6P (6C) 2Glyceraldehyde-3P (3C) c kh
nng b oxy ha (p 2,3,4,5 tn 1ATP)
GIII: oxy ha 2Glyceraldehyde-3P 2Glycerate-3P (p 6,7
sinh 2ATP + 2NADH)
GIV: bin i 2Glycerate-3P 2Pyruvate (p 8,9,10 sinh
2ATP)
GV: kh 2Pyruvate 2Lactate (p 11 s dng 2NADH t
GIII)

GI: hot ha G G6P (p 1 tn 1ATP)


(1) Hot ha G G6P vi E xc tc Hexokinase, phn ng
ny khng thun nghch.
6 CH 2OH
5

H
4

OH

H
OH

H
2

OH

glucose

6 CH OPO 2
2
3

ATP ADP
H
H
1

OH

Mg2

5
4

OH

H
OH
3

H
2

H
1

OH

Hexokinase H
OH
glucose-6-phosphate

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GII: bin i G6P (6C) 2Glyceraldehyde-3P (3C) c


kh nng b oxy ha (p 2,3,4,5 tn 1ATP)
(2) ng phn ha G6P F6P, phosphoglucose
isomerase
6 CH OP O 2
2
3
5
O

H
4

OH

H
OH

Phosphofructokinase

6 CH OP O 2
2
3

1CH2OH

OH

HO

3 OH

(4) Phn ct phn t C6 2C3, aldolase

HO 3C
H 4C

OH

2C

OH

6CH2OPO 3

fructose-1,6bisphosphate

C H2OPO 32
3
O

1CH2OH
2

dihydroxyacetone
phosphate

HO

3 OH

Mg2+

HO

3 OH

OH

fructose-6-phosphate

1CH 2OP O32

ATP ADP

fructose-1,6-bisphosphate

(5) 2 triose chuyn ha ln nhau, ch yu to thnh


Glyceraldehyde-3P l sn phm c oxy ha,
triosephosphate isomerase

Aldolase

6 CH OPO 2
2
3

1CH 2OH

OH

Phosphoglucose Isomerase
glucose-6-phosphate
fructose-6-phosphate

2C

6 CH OPO 2
2
3

OH

OH

1CH2OPO 3

(3) Phosphoryl ha ln 2 Fru-1,6-biP, phosphofructose


kinase, tiu tn ATP ln 2, phn ng khng thun
nghch, quyt nh tc ng phn.

Triosephosphate Isomerase

1C

H 2C OH
2
3 CH2OPO 3

glyceraldehyde-3phosphate

Triosephosphate Isomerase

H
H

OH

H+ H+

CH2OPO 32

dihydroxyacetone
phosphate

OH
C
C

H+ H+

OH

CH2OPO 32

enediol
intermediate

O
C

OH

C H2OPO 32

glyceraldehyde3-phosphate

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GIII: oxy ha 2Glyceraldehyde-3P 2Glycerate-3P (p


6,7 sinh 2ATP + 2NADH)
(6) Oxy ha Glyceraldehyde-3P hnh thnh ni ~P
1,3BiPG + NADH + H+, glyceraldehyde 3 phosphate
dehydrogenase

(7) S dng trc tip gc ~P ca c cht ATP


(phosphoryl ha mc c cht, khng qua chui h
hp), phosphoglycerate kinase

Phosphoglycerate Kinase

Glyceraldehyde-3-phosphate
Dehydrogenase
H

O
1C

OH

3 CH2OPO3

1C

OPO 32
+ H+ O
NAD+ NADH
C
1
+ Pi
H C OH

glyceraldehyde3-phosphate

3CH 2OPO 3

O
C
1

H 2C OH
2
3 CH2OPO 3

3-phosphoglycerate

H 2 C OPO3
3 CH2OH

OH

O
C

C
1
H 2C OPO 3
3 CH2OH

3-phosphoglycerate

(9) Phn ng kh nc, edolase c s sp xp li cc


lin kt trong phn t to ~P.

Enolase
Phosphoglycerate Mutase

H 2C OH
2
3 CH 2OPO 3

Mg2+

1,3-bisphosphoglycerate

1,3-bisphosphoglycerate

GIV: bin i 2Glycerate-3P 327 2Pyruvate (p


8,9,10 sinh 2ATP)
(8) Phn ng ng phn ha chuyn gc P t C3 ln C2,
phosphoglycerate mutase

H 2C OH
2
3 CH2OPO 3

OPO 32 ADP ATP O

O
1

OPO3

CH2OH

2C

OPO32

3 CH2

2-phosphoglycerate enolate intermediate phosphoenolpyruvate

2-phosphoglycerate

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(10) Phn ng thnh lp ATP ln th 2 trong ng phn,


pyruvate kinase pyruvate (SP trung gian quan trng)

GV: kh 2Pyruvate 2Lactate (p 11 s dng


2NADH t GIII)

Lactate Dehydrogenase

Pyruvate Kinase
O

ADP ATP

OPO 3

3 CH 2

phosphoenolpyruvate

3 CH 3

pyruvate

Kt lun
V tr xy ra ca QT EMP: t bo cht
PTTQ: glucose 2pyruvate + 2ATP + 2NADH
Tc QT EMP c iu ha bi 2 E cha kha:
phosphofructokinase-1 v pyruvate kianase nhm duy tr
s cn bng v n nh [ATP]/t bo.

NADH + H+ NAD+

O
C
HC

OH

CH3

CH 3

pyruvate

lactate

Chu trnh Krebs, chu trnh TCA (acid


tricacboxylic), acid citric
y l con ng chung ca s oxy ha cc cht hu c
to ATP cung cp cho cc hot ng ca c th.
Chu trnh ny xy ra trong ty th, oxy ha acetylCoA CO2 +
H2O + gii phng ton b nng lng d tr.

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Cc G ca chu trnh acid citric


1. Ngng t acetyl-CoA vi acid oxaloacetic
P 1: nh s xt ca E citrate synthetase, acetyl-CoA i vo chu trnh
Krebs bng p ngng t vi acid oxaloacetic (dng enol) v nc
to thnh acid citric, NL ngng t do LK cao nng ca acetyl-CoA
cung cp.
P 2: acid citric bin i thnh dng ng phn ca n l acid isocitric,
QT ny c xt bi cng 1 E l aconitate hydratase v qua dng trung
gian acid cis aconitic.

2. ng phn ha acid citric i xng thnh acid isocitric khng


i xng qua SP trung gian l acid cis acotinic.
P 3: l s oxh a.isocitric di tc dng ca E isocitrate
dehydrogenase 2 nguyn t H ca a.isocitric b kh c chuyn cho E
NADP+ kt qu l NADPH2 v a.oxalosuccinic c to thnh. Ngay sau
a.oxalosuccinic li b kh C bin thnh a.cetoglutaric. gd ny 1
phn t CO2 c tch ra.

5.

Oxh a.succinic thnh a.fumaric


P 7: a.fumaric c hydrate ha s to thnh a.malic nh tc dng ca fumartate
hydratase.

7.

Hydrate ha a.fumaric thnh malic


P 8: a.malic va c to thnh s b oxh thnh a.oxaloacetic di tc dng ca
mt E oxh-k l malate dehydrogenase c CoE l NAD+.

8.

P 4: a.cetoglutaric li b kh C oxh do phc h E cetoglutarate


dehydrogenase xt. P ny cng tng t oxh a.ppyruvic gd trn v
cn cc CoE nh TPP-a.lipoic CoA v NAD+ tham gia p. SP ca p l
dn xut ca a.succinic: succinyl-CoA.

4. Kh cacboxyl oxh acid -cetoglutaric to thnh succinylCoA.


P 5: NL ca LK cao nng trong succinyl-SCoA c chuyn thnh LK
cao nng ca GTP (guanosintriphosphate) nh tc dng ca E
succinate thiokinase, cui cng NL c chuyn t GTP cho ADP
tng hp nn ATP.

A.succinic c to thnh t succinyl CoA


P 6: a.succinic b oxh thnh a.fumaric nh tc dng ca succinate dehydrogenase
c CoE l FAD khi nhn H t c cht s tr thnh FADH2 v hydro FADH2 c
chuyn cho h thng vn chuyn in t to thnh nc v tng hp 2ATP.

6.

3. Kh cacboxyl oxh a.isocitric to thnh acid -cetoglutaric.

Oxh a.malic thnh a.oxaloacetic


Nh vy, chu trnh c khp kn v a.oxaloacetic li tip tc ngng t vi acetylCoE v chu trnh mi li bt u.

Qua chu trnh Krebs, gc acetyl c oxh thnh kh CO2


v H2O.
Do s xut hin trong chu trnh Krebs cc acid di v
tricacboxylic nn chu trnh Krebs c gi l chu trnh di,
tricacboxylic.
Qua chu trnh Krebs ta nhn thy rng:
Khi oxh 1 gc acetyl s loi ra 2 phn t CO2.
ng thi xy ra 1 s kh 4 phn t H2 c chuyn vn trn
2NAD, 1NADP v 1FAD (dng HH tb).
Gd t a.isocitric ti a.oxalosuccinic cho 3ATP,
Gd t a.-cetoglutaric ti a.succinic cho 4ATP,
Gd t a.succinic ti a.fumaric cho 2ATP,
Gd t a.malic ti a.oxaloacetic cho 3ATP.
T acetyl-CoA, 1 vng ca chu trnh cung cp 12ATP.

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Nhn vo s chu trnh acid citric ta thy:

2 nguyn t C i vo chu trnh di dng acetyl-CoA.


2 nguyn t C i ra chu trnh di dng 2 phn t CO2.
Trong chu trnh acid citric cn phi c mt s p oxh-k.
C 4 gd xy ra p oxh-k,
C 3 gd c NAD tham gia,
C 1 gd c FAD tham gia.
Mi gd chuyn vn 2 nguyn t hydro (2 proton v 2
electron).
QT chuyn vn electron t chu trnh acid citric ti oxy s
cung cp cho c th 12ATP.

Chng IV: LIPID


I. I CNG V LIPID

1. nh ngha
Lipid l dn xut ca cc acid bo cao phn t v
cc alcohol.
L HCHC t nhin, thng gp l du TV v m V.

2. c im
Trong phn t lipid khng c hoc c rt t cc
nhm ho nc (-OH, -NH2, -COOH), trong khi
li giu nhm k nc.
Lipid khng ha tan hoc ha tan rt t trong nc,
n tan nhiu trong dung mi hu c (ester, benzen,
chloroform, ru).

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4. Vai tr lipid - Gi tr dinh dng


Trong m t bo, lipid 2 dng:
Dng t do, l nhng lipid d tr, l m m V, TV,
ht du trong TV. Cc dng lipid t do ny c th
chit rt ra bng dung mi hu c.
Dng lin kt, l lipoprotein, lipopolysaccharide,
phospholipid tham gia cu to cc mng nguyn
sinh cht v mng ca cc bo quan. y l thnh
phn c bn ca t bo, thng c vi mt lng
khng i v thnh phn xc nh.

Lipid l ngun NL quan trng (1g lipid 9,3cal), 15%


NL khu phn n.
Nhu cu 36-42g/ngi/ngy, 6kg/ngi/nm.
Khi ch bin nhit, SP c thm lipid lm tng v v
dinh dng.
To cm gic hp dn cho TP.
Lu gi trong d dy lu to cm gic no .

Khi c th bnh hay i ch s dng lipid t


do.

Vai tr ca lipid trong c th ngi


L cht dinh dng c m nhit cao nht.
L dung mi ha tan cc vitamin khng phn
cc nh A, D, E, K.
L ngun cung cp vitamine tan trong du
m, cc acid bo cha no nhiu ni i
(acid bo cn thit), cc phosphatide
(leucithin).

Phn lipid khng dng n c d tr


nhm mc ch:
Cung cp nng lng khi cn thit.
Bo v c th, l cht m cho cc ni
quan.
Gim mt nhit cho c th.

NL kin to: thnh phn cu to mng t


bo v cu trc di t bo (lipoprotein).
c bit t bo m thn kinh.

- Gi tr sinh hc ca lipid
L dung mi ca vitamin A, D
Tham gia vo thnh phn nguyn sinh cht ca t bo.
L m m gi nhit cho c th.
Phosphatide l thnh phn cu trc t bo thn kinh, no, tim,
gan, tuyn sinh dc
Cholesterol l thnh phn cu trc t bo v tham gia mt s chc
nng chuyn ho quan trng nh:

L tin cht ca acid mt


Tham gia tng hp cc ni tit t v thng thn
LK cc c t tan mu v c t tan mu ca VK, k sinh trng.

Du TV (acid bo khng no) c tc dng lm tng s chuyn ha


chloesterol cholic.
C th V khng tng hp acid bo khng no phi thu nhp t
thc n.

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5. Tnh cht lipid

6. Phn loi (ty theo cu to ha hc)

nhit 15-20oC

Lipid n gin

Cht bo th rn m
Cht bo th lng du

B: dng ch cht bo c ly ra t sa ca V c v. i vi
cht bo c ngun gc TV c c gn ging b b magarine.
T trng nh hn nc, 15oC l 0,866-0,973
Khng tan trong nc khi trn ln vi nc tch thnh 2 lp.
(b) Unsaturated fat and
Fatty acid
cis double bond
causes bending

Stearic acid

Trong thnh phn ch c C, H,


O
Khi thy phn cho ra ru v
cc acid bo
3 nhm:
Glyceride:
ester
ca
glycerine v acid bo
Seride (sp): ester ca
ru bc cao.
Steride: ester ca ru
a vng.

Lipid phc tp
Ngoi 3 nguyn t C, H, O cn
cha P, N, S
Khi thy phn cho ra ru,
acid bo, v mt s cht khc
nh acid amin, H3PO4, glucid
Cc phn nhm:
Phospholipid: H3PO4
Proteolipid
protein

(lipoprotein):

Glucolipid: glucid

(a) Saturated fat and fatty acid

II. Acid bo (fatty acid)


Lipid trung tnh

Lipid phn cc

Acid bo (>C12)

Glycero-phospholipid

Mono-, di-, triacyl-glycerol

Glycero-glycolipd

Sterol v sterol ester

Sphingo-phospholipid

Carotenoid, tocopherol

Sphingo-glycolipid

Sp

Lipid c cha acid bo

Lipid khng cha acid bo

Lipid n gin

Cc Steroid

Du, m (triglyceride)
Sp

Lipid phc tp
Phospholipid

- Khi nim

1. Gii thiu chung

L acid hu c, n
chc, bc cao.
Mch C thng (c th
c mch phn nhnh)
S C l s chn C4C24 (nhiu nht l
C16-C24) (c th c
s C l s l).
C hoc khng c ni
i.

- Acid bo quyt nh
Cht lng ca cht bo.

- Tnh cht ca lipid:


Acid bo no, acid bo
cha no.

Sphingolipid

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- Acid bo Phn loi


Cng thc ca cc acid
bo chnh

Nhit nng chy ca


mt s acid bo

Lauric 12:0
Myristic 14:0
Palmitic 16:0 (11% trong t
nhin)
Stearic 18:0 (4%)
Oleic 18:1 (9) (34%)
Linoleic 18:2 (9, 12) (34%)
Linolenic 18:3 (9, 12, 15)
(5%)
Arachidonic 20:4

Acid stearic 18:0 69oC


Acid oleic 18:1 (9) 13,4oC
Acid elaidic 18:1 (trans 9)
46oC
Acid linoleic 18:2 (9, 12) 5oC
Acid linolenic 18:3 (9, 12,
15) -11oC
Acid arachidonic 20:4 (5,
8, 11, 14) -49,5oC

Da trn tnh cht no hay khng no: acid bo no v


acid bo khng no.
Da trn chiu di mch: acid bo mch ngn v acid
bo mch di.
Da trn s lng, v tr v cu hnh ca cc ni i.
S xut hin ca cc nhm chc dc theo chiu di
mch (him khi c nhm chc khc).

Acid bo no - Tnh cht


Ch cha lin kt n C C
Xp cht,

2. Acid bo no

Gia cc mch c lc hp dn mnh,


Nhit nng chy cao,
L cht rn nhit thng.

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3. Acid bo cha no
Acid bo no
(Ch c ni n)
Acid bo cha no
(1 ni i)
Acid bo cha no
(Nhiu ni i)

Acid bo khng no Danh php omega,


delta
V tr ni i c tnh t u -CH3 cc acid bo ny
c xp vo nhm .

3 (linolenic type)
6 (linoeic type)
9 (oleic type)
Nhm 6 khng c tng hp trong c th ngi, c coi l
cc acid bo khng thay th cn thit cho qu trnh to mng
sinh hc cho t bo.

V tr ni i c tnh t u -COOH cc acid bo


ny c xp vo nhm .

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Acid bo cha no - Tnh cht


Cha mt hoc nhiu ni
i C=C,
C mch gp khc nn
cc phn t khng th
xp cht,
Lc hp dn gia cc
mch yu hn.
Nhit nng chy thp,
L cht lng nhit
thng.

Acid bo khc
Acid bo mch nhnh: him, thng tm thy trong cht bo
sa; c th l acid no hay khng no.
Acid bo mch vng:
- A.hydrocacpic: C16H28O2
Tonc = 59,5oC
- A.chaulmogric: C18H32O2
Tonc = 71oC

(CH2)10

COOH

(CH2)10

COOH

4. Tnh cht vt l
acid ca nhm carboxyl: ph thuc vo s phn ly
proton H+ v to nhm carboxylate COO-.
im nng chy: ph thuc vo s sp xp cc on acyl
trn li tinh th.
Nhit nng chy gim, khi cc ni i tng ln.
Cu trc tinh th: cc acid bo sp xp do tng tc k
nc.
Khng ha tan trong nc.
C kh nng hp th tia UV.

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Hydrophobic forces

C
C
H

O
H

H
H
H

C
C

C
H

H
C

C
H

Cc phn ng ca aicd bo khng no:

O
H

H
H

O
H

O
H

H
H

H
H
H
C
H

H
H
C

C
H

R-COOH + CH2N2 R-COOCH3 + N2

H
C

H
C

H
C

H
C

H
C

H
O

H
C

Methyl ha cc nhm carboxyl: diazomethane

H
O

H
H

H
O

H
O

6. Tnh cht ha hc

O
H

P/ vi cc gc halogen,
P/ isomer ha - H ni i khng lin hp b isomer ha
thnh h ni i lin hp khi c mt kim (KOH).
P/ to phc khng tan v thun nghch -complex vi
Ag+ - tch cc acid bo khng no.
P/ hydrogen ha, khi c mt xc tc Ni, H2 c gn
thm vo v tr cc ni i. P/ ny c s dng to
ra cc cht bo cng (m) dng trong cng nghip thc
phm.

Hydrophobic interactions are primarily entropy effects

Phn ng hydro ha

Cc hp cht khng no phn ng vi H2


Xc tc Ni hay Pt
Lin kt C=C Lin kt CC
Qu trnh hydro ha chuyn cc ni i trong cc loi
du thnh ni n. Cc sn phm rn c dng lm
margarine hay lm cc sn phm khc.

Cc dn xut ca acid bo
[1] Hydroxy acid
Ricinoleic

C18 : 1

(12 - OH)

COOH

OH
Cha trong tinh du hi ly, mi thm d chu.
D-2-hydroxy acid t C16: 0 n C25: 0 (mch C chn v l) c nhiu trong
l xanh v cc loi rau.

[2] Oxo acid (ceto)


t ph bin hn hydroxy acid.
Lipid sa cha 1% oxo acid no (C10C20), nhm C=O gn C5C13
CH3

(CH2)4

CH

[3] Furan acid


C trong du gan c (16%); mt
vi loi c nc ngt (25%); du
TV; b; chanh, du, bp ci,
khoai ty, nm,

CH

CH2

CH2

(CH2)7

COOH

CH3
CH3

(CH2)4

CH3
O

(CH2)4

COOH

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