I HC NNG

TRNG I HC BCH KHOA

KHOA HA






HA SINH II
Bi ging

Bin son: TS. ng Minh Nht


















Nng, 2007
CHNG 1 - KH NNG CHUYN HO CA PROTEIN, GLUXIT, LIPIT
1.1 CC BIN I CA PROTEIN TRONG QU TRNH SN XUT V
BO QUN
1.1.1 BIN I DO NHIT
Cc qu trnh ch bin thc phm bao gm un nng, lm lnh, sy, s l
ho cht, ln men, chiu bc x v cc qu trnh x l khc. Trong , un nng l
qu trnh ch bin c s dng ph bin nht.
Thng thng, un nng c thc hin nhm mc ch v hot vi sinh vt
v cc enzym ni sinh (endogenous enzyme) gy cc phn ng oxy ho hoc thu
phn khng mong mun khi bo qun hoc bin i hn hp cc thnh phn
nguyn liu thc phm khng hp dn thnh sn phm thc phm c kt cu ng
nht v c sc li cun v mt cm quan. Hn na, mt s protein nh -
lactoglobulin v -lactalbumin t sa b v protein t u nnh c th gy d ng,
tr thnh v hi nh qu trnh ny.
Tuy nhin, cc nh hng c li nh qu trnh un nng thc phm giu
protein ni chung thng i km vi mt s nh hng xu, lm gim gi tr dinh
dng v cc tnh cht chc nng ca protein.
Gia nhit va phi
Gia nhit va phi ch lm protein bin tnh v gip ci thin gi tr dinh
dng ca sn phm, do:
- lm mt c tnh ca cc c t c bn cht protein (nh enterotoxin cu
Staphyloccocus aureus) hoc ca cc cht km hm cc enzym ng tiu ho (nh
antitripxin Kunitz v Bowman c trong ht u tng).
- lm v hot cc enzym (protease, polyphenoloxidase, lipoxydase) vn
xc tc phn ng ph hu cc vitamin.
- lm tng kh nng tiu ho ca mt s protein do lm dui mch peptit ca
chng, gii to cc gc axit amin trc y b vi trong phn t, do to iu kin
cho protease tc dng c thun li hn.Vd.: colagen, glixinin u tng,
ovalbumin
Thanh trng
Gia nhit kiu thanh trng nhit ln hn 110-115
o
C cc sn phm giu
protein nh tht, c, sa s gy ph hu mt phn cc gc xistin, xistein hnh thnh
nn H
2
S, dimetylsulfua, axit xisteic v hp cht bay hi khc khin cho cc sn
phm ny c mi c trng.
Gia nhit khan
Gia nhit khan protein nhit trn 200
o
C (nhit rn tht v c) to ra
, hoc cacbolin do phn ng vng ho ca tryptophan:
N
H
R
NH
2
-cacbolin
(R=H hay CH
3
)
N
H
N
R
R N
H
NH
2
CH
3
R
-cacbolin
(R=H hay CH
3
)
-cacbolin
(R=H hay CH
3
)

Gia nhit nhit cao
Gia nhit nhit cao (hn 200
o
C) thc phm giu protein c pH trung
tnh hoc kim tnh s xy ra:
Thu phn cc lin kt peptit v ng phn ho cc gc axit amin, to ra hn
hp raxemic do lm gim gi tr dinh dng i 50%, do cc ng phn D c
to thnh kh b tiu ho hn;
Ph hu mt s axit amin: nh arginin s b chuyn thnh ornitin, ure,
xitrulin v amoniac. Xistein b chuyn thnh dehydroalanin. Gia nhit mi trng
kim, serin, treonin v lizin cng b ph hu;
To cu ni ng ho tr kiu lyzinoalanin, ornitinoalanin hoc lantionin lin
kt gc dehydroalanin (DHA) chui polypeptit ny vi cc gc lyzin, ornitin hoc
gc xistin chui polypeptit khc.
Gc DHA c to ra do phn ng loi gc xistein hoc phosphoserin:
NH HC
CH
2
X
C
O
OH
-
NH
C
-
CH
2
X
C
O
NH C
CH
2
C
O
+
X
-

(X l SH hoc PO
3
H
2
) gc DHA
Mch polypeptit c ch gc lizin, gc ornitin hoc gc xistein s kt hp
vi mch polypeptit c ch gc DHA theo s sau:
NH CH C
O
(CH
2
)
4
NH
2
NH CH C
O
(CH
2
)
3
NH
2
NH CH C
O
CH
2
SH
NH CH C
O
CH
2
NH CH C
O
CH
2
NH CH C
O
CH
2
NH CH C
O
(CH
2
)
4
N H
N
H
CH C
O
(CH
2
)
3
NH
N
H
CH C
O
CH
2
S
NH CH C
O
CH
2
NH CH C
O
H
2
C
NH CH C
O
H
2
C

Khi x l nhit tht hoc c nhit cao hn nhit thanh trng th cn
to ra cu ng ho tr kiu izopeptit gi gc lizin cu chui peptit ny vi gc
glutamic hoc gc aspartic cu chui peptit khc:
CH
2
N H
C
(CH
2
)
4
NH C
O
(CH
2
)
2
HC
NH
C O
O

Cu izopeptit

V phng din dinh dng, vic to ra cu ng ho tr izopeptit trong cng
mt phn t hoc gi cc phn t s lm gim tiu ho cu nit, gim h s s
dng protein v gi tr sinh hc cu protein. Hn n do hiu ng khng gian cc
cu ng ho tr (glutaminlizyl hoc aspartyl-lizyl) s ngn cn khng cho cc
protease n c vng c hiu thu phn do lm cho qu trnh tiu ho
protein b chm li.
1.1.2 BIN I DO ENZYM
Trong qu trnh bo qun cc thc phm giu protein thng xy ra hin
tng i thi lm mt gi tr dinh dng cu thc phm. Nguyn nhn l do tc
dng cu enzym c sn trong thc phm, cng nh cu vi sinh vt xm nhp t mi
trng ngoi vo. Khi protein b chuyn ho theo nhng phn ng c bn sau:
a) Phn ng kh amin:
R CH COOH
NH
2
+
O H
2
R CH COOH
OH
+
NH
3
R CH COOH
NH
2
+
H
2
R CH
2
COOH
+
NH
3
enzym cua
vi sinh vat hieu khi


b) Phn ng kh nhm carboxyl:
R CH COOH
NH
2
R CH
2
NH
2 +
CO
2

Phn ng ny to thnh cc amin khc nhau. T lizin to thnh cardaverin, t
histidin to thnh histamin, l nhng cht c.
c) Phn ng kh amin kh carboxyl:
R CH COOH
NH
2
+
1/2 O
2 R CH COOH
O
+
NH
3
R CH COOH
O
R CH O
+
CO
2
R CH COOH
NH
2
+
O H
2 R CH COOH
OH
+
NH
3
R CH COOH
OH
R CH OH
+
CO
2
decarboxylase

d) Phn ng to thnh mercaptan. Thng xy ra i v cc axit amin
c ch lu hunh:
CH
2
CH COOH
NH
2
S H
CH
2
CH
3
S H
+ +
CO
2
NH
3
+2H
etylmercaptit

e) Phn ng to thnh scatol, crezol, phenol: do cc vi sinh vt gy thi r
thng gp trong ng rut v trong qu trnh ct gi protein chuyn ho cc axit
amin vng thnh cc sn phm c c mi kh chu nh: scatol, indol, crezol,
phenol.
- Phn ng to scatol, indol:
COOH CH CH
2
NH
2
N
H
+
O H
2
COOH CH CH
2
OH
N
H
+
NH
3
tryptophan
axit indoloxypsopinic
COOH CH CH
2
OH
N
H
+
O
2
COOH CH
2
N
H
+
O H
2 +
CO
2
axit indolaxetic

COOH CH
2
N
H
CH
3
N
H
+
CO
2
CH
3
N
H
scatol
+
3/2 O
2
N
H
indol
+ +
O H
2
CO
2

- Phn ng to thnh crezol, phenol:
COOH CH CH
2
NH
2
O H
CH
2
OH OH
crezol
phenol
tyrosine

f) Phn ng to thnh di- trimethylamin t cc lipoprotein.
Phn lipit sau khi tc t lipoprotein s b chuyn ho thnh cc di-
trimethylamin:
V d:
C H
3
N
C H
3
C H
3
CH
2
CH
2
OH
OH
C H
3
N
CH
3
CH
3
CH
3
N
C H
3
CH
3
O
colin
trimetyl amin
oxytrimetylamin (mui tanh)
[O]
g) Phn ng to thnh phosphin: Xy ra vi phosphoprotein v
nucleoprotein. Ngun to thnh phosphin l cc axit phosphoric c trong protein
c gii phng ra khi phn hu. Phosphin l kh khng mu, mi thi, rt c

1.2 KH NNG CHUYN HO CU CARBOHYDRAT
1.2.1 S PHN GII CU DISACARIT V POLYSACARIT
S phn gii cu disacarit v polysacarit thc hin theo hai kiu: thu phn
v phosphoryl phn.
a) Thu phn: l qu trnh phn gii c s tham gia cu nc.
Di tc dng cu nhiu loi enzym:
Polysaccarit oligosaccaritmonosaccarit
V d: tinh bt, glycogendextrinmaltoseglucose; qu trnh phn gii ny
c thc hin nh cc enzym -amylase, -amylase v -amylase (glucoamylase).
b) Phosphoryl phn: qu trnh phn gii, trong axit phosphoric ng vai
tr cu nc trong qu trnh thu phn, xy ra di tc dng cu enzym
phosphorylase.
Phosphorylase ch tc dng vo lin kt 1,4 cu phn t tinh bt v s dng
li khi ti lin kt 1,6. Tc dng cu n ch tip tc c sau khi lin kt 1,6 c
gii phng nh enzym amylo-1,6-glucosidase. C th coi phosphorylase l enzym
glucosyl transferase, v n xc tc cho s chuyn gc glucose ti gc axit
phosphoric. Qu trnh phn ng c tip din ln lt v to nn hng loi phn t
glucose-1-phosphat.
S phn gii glycogen cng tin hnh tng t v cng to nn glucose-1-
phosphat. Cc disacarit cng c th b tc dng cu enzym phosphorylase tng
ng v to nn dn xut phosphat cu monosacarit ng thi gii phng mt
monosacarit th hai.
V d enzym maltosephosphorylase xc tc cho qu trnh phn gii maltose
thnh glucose-1-phosphat v glucose nh s tham gia cu H
3
PO
3
.
Phn ng phosphorylase ni trn l thun nghch nn c th xc tc cho s
phn gii cc polysacarit v oligosacarit cng nh s ti t hp chng.
1.2.2 S CHUYN HO CU CC MONOSACARIT
V bn cht qu trnh ny bao gm cc phn ng oxy ho kh sinh hc c
thc hin bi mt lot cc enzym c trong ti th. Kt qu l phn t hexose (ch
yu l glucose) b oxy ho hon ton to ra cc sn phm v c l kh CO
2
v nc,
cn nng lng m cht hu c gii phng ra c tch lu trong lin kt cao nng
ATP.
Tu thuc vo iu kin khng c hay c oxy m s phn gii glucose xy ra
theo hai hng chnh:
- Phn gii k kh: bao gm giai on ng phn v s ln men k kh.
- Phn gii ho kh (cn gi l qu trnh h hp): bao gm c giai on
ng phn, s oxy ho axit pyruvic v chu trnh Crep.
Nh vy hai qu trnh trn u c chung chui phn ng t glucose n axit
pyruvic.
1.2.2.1 S ng phn
Qu trnh ny c pht hin bi Embden, Meyerhof v Parnas. y l qu
trnh phc tp, c xc tc bi nhiu enzym v khng c s tham gia cu oxy.
Phn t ng ln lt tri qua cc giai on: hot ho, ct i phn t hexose (6C)
to thnh 2 phn t ng triose (3C), loi hydro cu triose-phosphat to thnh
phospho glycerat, chuyn sn phm trn thnh axit pyruvic.
a) Giai on hot ho phn t hexose: gm 3 phn ng
- phn ng to thnh glucose-6-phosphat nh enzym phospho-gluco-kinase
vi s tham gia cu Mg
2+
:
O
OH
H
H
H
O H
OH
H OH
H
H
2
C OH
ATP
ADP
O
OH
H
H
H
O H
OH
H OH
H
H2C
O P
Glucose
Glucose-6-phosphat
Mg
2+

- Phn ng ng phn ho do enzym isomerase xc tc:
O
OH
H
H
H
O H
OH
H OH
H
H2C
O P
Glucose-6-phosphat
O
CH
2
OH
H
O H
OH
H
H
O
OH
P
Fructose-6-phosphat

Cu to dng vng furan c lin kt km bn vng hn, do mch cacbon
d b ct hn.
- Fructose-6-phosphat tip tc b phosphoryl ho ln th hai nh enzym
phospho fructose kinase vi s tham gia cu phn t ATP (adenosin triphosphat)
Fructose-1,6-di
-
phosphat
O
CH
2
OH
H
O H
OH
H
H
O
OH
P
Fructose-6-phosphat
O
P
O
H
2
C
H
O H
OH
H
CH
2
H
O
OH
P
ADP ATP
Mg
2+

Do cu to i xng, n d b ct mch cacbon im gia.
b) Giai on ct mch cacbon:
Fructose-1,6-di
-
phosphat
O
P
O
H
2
C
H
O H
OH
H
CH
2
H
O
OH
P
H
2
C
C
H
2
C
O
O
OH
P
O P
CH
HC
CH
2
OH
O

Aldolase l enzym xc tc s phn ly fructose-1,6-diphosphat thnh hai phn
t triose phosphat (dihydroxy axeton phosphat v glyxeraldehyd-3-phosphat). Hai
triose phosphat ny c th chuyn ho ln nhau nh enzym ng phn (triose-
phosphat-isomerase). Cn bng cu phn ng ny lch v pha to thnh
glyxeraldehyt-3-phosphat. Bi vy, t 1 phn t fructose-1,6-diphosphat s to
thnh 2 phn t glyxeraldehyd-3-phosphat.
c) Giai on oxy ho:
c thc hin nh glyxeraldehyt-3-phosphat dehydrogenase. Enzym ny c
coenzym l NAD
+
, trong trung tm hot ng c nhm -SH.

Trong phn ng ny gc phosphat cao nng cu axit 1,3-diphosphoglyxeric
chuyn cho ADP. cng l kiu phosphoryl ho ADP thnh ATP. Phn ng ny
rt c ngha v nng lng gii phng trong qu trnh oxy ho c tch ly trong
phn t ATP, bo m cung cp nng lng cho hot ng t bo trong iu kin
khng c oxy. Phn ng do enzym 3-phospho glyxerat kinase xc tc v to thnh
axit 3-phospho glyxeric:

Axit 3-phospho glyxeric bin i thnh axit 2-phospho glyxeric nh enzym
phospho glyxerat mutase:

d) S to thnh axit pyruvic: bao gm
- qu trnh loi nc nh enolase xc tc to thnh axit phospho
enolpyruvic, c ch lin kt cao nng.

- Qu trnh chuyn gc phosphat cao nng cho ADP to thnh axit enol
pyruvic v ATP:

Dng enol cu axit pyruvic khng bn v n s chuyn thnh dng xeton bn
hn.

e) S chuyn ho cc sn phm cui cng cu qu trnh ng phn.
Nh vy, sau qu trnh ng phn, ngoi ATP sn phm to thnh s l
NADH v pyruvat. S chuyn ho tip theo cu chng ph thuc vo cc con
ng chuyn ho khc nhau t bo. NADH phi c chuyn ho tr li v dng
NAD
+
, nu khng s lm hn ch qu trnh ng phn. NADH c th quay li
dng NAD
+
tr li bng con ng hiu kh v k kh. C hai u con ng u
gn vi s chuyn ho tip theo cu pyruvat. S phn cu pyruvat trong t bo s
ph thuc vo s c mt cu oxy.
Trong iu kin hiu kh, pyruvat b oxy ho trong chu trnh axit xitric, to
thnh CO
2
v ng thi to ra thm NADH (v FADH
2
) v trong iu kin hiu kh
cc phn t NADH c to ra t qu trnh ng phn v chu trnh axit xitric s b
oxy ho tr li thnh NADH
+
qua chui vn chuyn electron ty th.
Trong iu kin k kh, pyruvat s c chuyn ho theo cch khc.
- S to thnh axit lactic: di tc dng cu lactat dehydrogenase, axit
pyruvic b kh thnh axit lactic:

Phn ng xy ra trong m c ng vt th to thnh axit L-lactic, cn trong
qu trnh ln men lactic do cc vi sinh vt gy ra th to thnh D-lactic.
- Ln men ru: mt s vi sinh vt nh nm men c kh nng bin i axit
pyruvic thnh ru etylic. Qu trnh xy ra theo hai bc. Bc u axit
pyruvic b kh nhm carboxyl thnh CO
2
v axetaldehyt nh enzym pyruvat
decarboxylase c coenzym l thiamin pyrophosphat (cha vitamin B
1
) v
Zn
2+
. Bc hai, axetaldehyt b kh thnh etanol. Phn ng c xc tc bi
alcohol dehydrogenase:

- S to thnh -glyxerophosphat v glyxerin
S ln men glucose cu nm men lun km theo to thnh mt lng nh
glyxerin:

Tt c cc phn ng kh axit pyruvic trn u gip NADH chuyn ho tr
li dng NAD
+
cn thit cho qu trnh ng phn.
Qu trnh ng phn v ln men c tm tt bng sau:

Qu trnh oxy ho k kh 1 phn t glucose to thnh 2 phn t axit pyruvic
s dng 2 ATP v to ra c 4 ATP, nh vy tch lu c 2 ATP. So vi nng
lng d tr cu phn t glucose, qu trnh ny ch gii phng mt phn nh nng
lng. Phn ln nng lng vn cn tng tr trong sn phm cui cng (axit lactic,
etanol v.v.). Nh vy i vi cc vi sinh vt k kh, bo m nng lng cho
cc hot ng sng, chng phi phn gii mt lng ln ng, to thnh mt
lng ln sn phm cui cng l nhng hp cht hu c (ru, axit hu c v.v.).
Ngi ta li dng iu sn xut ru, bia, cn, axit hu c v.v.
f) S tham gia cu cc c cht khc vo qu trnh ng phn

1.2.2.2 Chu trnh Crep
Qu trnh phn gii ho kh glucose xy ra theo 4 giai on chnh:
- T glucose n axit pyruvic: cc phn ng ging vi s ng phn k
kh
- T axit pyruvic n axetyl-CoA
- Oxy ho axetyl-CoA qua chu trnh Crep
- Oxy ho cc coenzym kh qua chui h hp
Trong iu kin c oxy, axit pyruvic b oxy ho hon ton n CO
2
v
H
2
O v gii phng ton b nng lng cn li. Cc phn ng cu qu trnh ny xy
ra theo mt chu trnh, mang tn nh bc hc pht hin ra n gi l chu trnh Crep
(Krebs).
a) S kh carboxyl oxy ho axit pyruvic thnh axetyl-CoA:
Trc khi tham gia vo chu trnh, axit pyruvic b kh nhm carboxyl
ng thi b oxy ho di tc dng cu mt phc h a enzym c tn l pyruvat
oxydase hay pyruvat decarboxylase.
Phng trnh tng qut cu giai on ny nh sau:

b) Cc phn ng trong chu trnh Crep
- Giai on 1: nh xc tc cu enzym citrat syntase, nhm axetyl cu axetyl-
CoA s c chuyn cho axit oxaloaxetic to thnh axit axetic, ng thi gii
phng coenzym A.
- Giai on 2: axit xitric b bin i thnh dng ng phn cu n l axit
izoxitric, qu trnh ny c xc tc bi enzym aconitase.
- Giai on 3: xy ra s oxy ho axit izoxitric di tc dng cu enzym
izoxitrat dehydrogenase. Axit izoxitric b kh hydro, 2 nguyn t hydro cu n
c chuyn cho coenzym NADP
+
. Kt qu to thnh NADPH+H
+
v axit
oxaloxucxinic. Ngay sau , axit oxaloxucxinic li b kh carboxyl bin thnh
axit -xetoglutaric. Mt nguyn t carbon li c tch ra khi c cht di dng
CO
2
.
- Giai on 4: axit -xetoglutaric li b kh carboxyl oxy ho do phc h
enzym -xetoglutarat dehydrogenase xc tc. Phn ng ny cng tng t nh s
oxy ho axit pyruvic giai on trn v cn cc coenzym nh tiamin pyrophosphat,
axit lipoic, coenzym A v NAD
+
tham gia. Sn phm cu phn ng l axit
dicarboxylic dng hot ng, l xucxinyl coenzym A (c ch lin kt tio-este
giu nng lng) v mt nguyn t cacbon b tch ra giai on ny l phn t
CO
2
.
- Giai on 5: Nng lng trong lin kt cao nng cu xucxinyl-coenzym A
c chuyn thnh lin kt cao nng cu GTP, nh tc dng cu enzym xucxinat-
tiokinase, cui cng nng lng c chuyn t GTP cho DP tng hp nn
ATP. y l phn ng duy nht trong chu trnh Crep xy ra s tch lu nng lng
trong ATP.
- Giai on 6: axit xucxinic b oxy ho thnh axit fumaric nh tc dng cu
xucxinat dehydrogenase. Enzym ny c coenzym l FAD, khi nhn hydro t c cht
s tr thnh FADH
2
. Hydro cu FADH
2
c tip tc chuyn cho h thng vn
chuyn in t to thnh nc v tng hp c 2 ATP.
- Giai on 7: axit fumaric c hydrat ho s to thnh axit malic nh
enzym fumarat hydratase.
- Giai on 8: axit malic v c to thnh s b oxy ho thnh axit
oxaloaxetic di tc dng cu enzym malat dehydrogenase c coenzym l NAD
+
.
Khi phn t axit oxaloaxetic ban u tham gia vo chu trnh c ti to th chu
trnh khp kn. y khng phi hon ton l phn t axit oxaloaxetic ban u,
bi v trong cc phn ng n nhng 2 nguyn t cacbon dng CO
2
v c b
sung bng hai nguyn t cacbon mi t axetyl-coenzym A. Phn t oxaloaxetic mi
ny li tip tc ngng t vi phn t axetyl-coenzym A v chu trnh c lp li.
Nh vy qua mt vng cu chu trnh Crep, gc axetyl hot ng to ra 2
phn t CO
2
. T axit pyruvic th to ra c 3 phn t CO
2
. Cc phn t CO
2
c
to thnh t chu trnh Crep c th c s dng vo cc qu trnh khc nhau trong
c th (s carboxyl ho, tng hp ure, tng hp nucleotit. (hnh v)
Qua s trn c th thy rng, khi oxy ho hon ton 1 phn t axit
pyruvic, c 5 cp nguyn t hydro c tch khi c cht to thnh cc coenzym
kh: 1 [NADPH+H
+
], 3[NADH+H
+
] v 1 FADH
2
. Trong thnh phn, phn t axit
pyruvic ch ch 4 nguyn t hydro, nh vy cc nguyn t hydro cn li l cu
phn t nc trong mi trng t bo tham gia vo. Phng trnh tng qut cu s
oxy ho axit pyruvic nh sau:
C
3
H
4
O
3
+ 3 H
2
O 3 CO
2
+ 5 H
2
O
S to thnh 5 phn t H
2
O trong phng trnh trn l kt qu cu s oxy
ho cc coenzym kh nh h thng vn chuyn in t, ng thi thng qua qu
trnh ny cng tng hp c mt s ln lin kt cao nng.
c) Tng kt nng lng khi oxy ho hon ton mt phn t glucose
Nng lng trong phn t glucose ch yu c gii phng giai on phn
gii ho kh. C 1 vng cu chu trnh Crep gii phng c 12 ATP cc giai on
phn ng.
Tuy nhin, trc khi i vo chu trnh Crep, phn t glucose phi tri qua cc
phn ng cu giai on ng phn v phn ng kh carboxyl oxy ho axit pyruvic.
Ho nng cu glucose gii phng cac giai on phn ng c tng kt nh sau:
Glucose
-ATP
Glucose-6-phosphat

Fructose-6-phosphat
-ATP
Fructose-1,6-diphosphat

2 Glyxeraldehyt-3-phosphat
2NADH+H
+
+6 ATP
2 1,3-diphosphoglyxerat + O
2
H
2
O
+2 ATP
2 3-phosphoglyxerat

2 2-phosphoenol pyruvat
+2 ATP
2 pyruvat
2 CO
2
2 NADH+H
+
+6 ATP
2 axetyl-CoA + O
2
H
2
O
+ O
2
Chu trnh Crep v +24 ATP
chui h hp
4 CO
2
+ 4H
2
O Tng cng: 38 ATP

Khi oxy ho hon ton 1 phn t gam glucose s thu c 686 kcal. Nhng
tng hp ATP t ADP v P
i
cn cung cp 8-10 kcal/mol. Bi vy nu ton b
nng lng c phn gii mt mol glucose u c dng tng hp ATP th s
thu c 686/976 mol ATP.
Thc t ch to c 38 mol ATP, chin 50% tng s nng lng. Nh vy
cn 50% c gii phng dng nhit nng
chui h hp
chui h hp
d) nghi cu chu trnh Crep
Thng qua chu trnh ny, phn t glucose b oxy ho hon ton n CO
2
,
H
2
O v gii phng ton b nng lng mt phn di dng ho nng trong ATP v
mt phn dng nhit nng c tc dng gi m t bo. T ATP c th tng hp nn
GTP, XTP, UTP l ngun ngn lng cn thit cho cc qu trnh sinh tng hp cc
cht khc nahu tng c th.
Chu trnh Crep to ra nhiu coenzym kh. Cc coenzym kh ngoi vai tr
to thnh ATP cn dng kh cc lin kt kp, cc nhm carbonyl, nhm imin
trong cc phn ng cn thit cho t bo.
Chu trnh Crep cn l ngun cacbon cho cc qu trnh tng hp khc nhau.
V d axetyl-CoA c th dng tng hp cc axit bo, steroit, axetoaxetat hoc
axetyl colin. CO
2
dng tng hp e, tng hp mi AMP v trong cc phn ng
carboxyl ho khc. Mt s xetoaxit trong chu trnh nh -xetoglutaric v
oxaloaxetic thng l nguyn liu tng hp cc axit amin glutamic v aspartic.
Cng v vy chu trnh Crep l mt xch lin hp, l im giao lu cu nhiu
ng hng phn gii v tng hp cc cht khc nhau trong t bo, ng thi cng
l ng hng chnh phn gii cc hp cht hu c.
1.2.2.3 S oxy ho trc tip glucose. Chu trnh pentose phosphat
c th sinh vt cn c mt kim phn gii glucose thnh CO
2
v H
2
O
nhng khng tri qua qu trnh ng phn v chu trnh Crep. Trong qu trnh ny,
cc phn ng cng to thnh mt chu trnh m cc sn phm trung gian ch yu l
cc pentose phosphat. V vy ngi ta gi l chu trnh pentose phosphat. Ngoi
ra, cn c vo cht ca ng cu chu trnh l glucose-6-phosphat, ngi ta cn gi
l chu trnh hexose monophosphat. y l qu trnh oxy ho trc tip glucose v s
oxy ho xy ra ngay giai on hexose ch khng phi qua triose nh qu trnh
ng phn. Chu trnh ny do Dickens-Horecker nghin cu v pht hin.
a) Cc phn ng: gm 2 giai on phn ng
- Giai on oxy ho glucose glucose-6-P
Glucose-6-P l cht u tin gia nhp vo chu trnh. N b oxy ho di tc
dng cu enzym glucose-6-P dehydrogenase (c coenzym l NADP
+
), bin thnh
axit 6-P-gluconic. Tuy nhin, giai on ny c to thnh mt sn phm trung gian l
6-P-glucono--lacton, cht ny sau b thu phn thnh axit 6-P-gluconic.
Qu trnh oxy ho ln th 2 di tc dng cu enzym 6-P-gluconat
dehydrogenase (c coenzym NADP
+
) to thnh axit 3-xeto-6-P-gluconic, ri sau
cht ny b kh carboxyl to thnh D-ribulose-5-P.
Trong ton b chu trnh ch xy ra 2 lt oxy ho (phn ng 1 v 3) nh
nu trn. Kt qu l t 1 hexose phosphat qua 1 vng cu chu trnh to ra 1
pentose phosphat, 1 phn t CO
2
v 2 (NADP+H
+
)
- Giai on ti to hexose phosphat
s oxy ho c tip tc, pentose phosphat va to thnh cn tri qua
nhng bin i ti to li hexose phosphat, khp kn chu trnh. Nhng bin i
ny c th chia thnh 2 bc sau:
Bc 1: S ng phn ho cu ribulose-5-P
Ribulose-5-P l mt xetopentose, n c th chuyn thnh dng aldose l
ribose-5-P nh tc dng cu phosphoribo isomerase. Mt khc, ribulose-5-P c th
bin i thnh dng ng phn epime ( v tr cacbon th 3) l xilulose-5-P nh tc
dng cu enzym phospho-xetopento-epimerase. Hai phn ng ny c v tr quan
trng, n c coi l im ni gia giai on u v giai on tip theo cu chu
trnh.
Bc 2: S bin i tng h gia cc pentose-P v cc hexose-P
C hai kiu phn ng quan trng tng giai on ny. l s chuyn aldol
ho v s chuyn xetol ho.
S chuyn aldol ho l s chuyn mt nhm 3 nguyn t ccbon (dihydroxy
axeton) ca mt ketose phosphat (v d: fructose-6-P hoc xetoheptulose-7-P) cho
cht nhn l mt aldose phosphat (v d, glyxeraldehyt-3-P hoc erytrose-4-P).
S chuyn ho xetol ho l s chuyn mt nhm 2 nguyn t cacbon (xetol
hoc glycolaldehyt) cu cht cho l xetose phosphat cho cht nhn l mt aldose
phosphat.
C 6 phn t glucose-6-P tham gia vo chu trnh th 5 phn t c ti to, 1
phn t b oxy ho hon ton n CO
2
v to thnh 12 coenzym kh (NADPH+H
+
).
Qu trnh oxy ho glucose-6-P qua chu trnh pentose phosphat c trnh by
hnh v.
b) Tng kt nng lng: phng trnh tng qut mt vng chu trnh nh
sau:
6 glucose-P + 12 NADP
+
5 glucose-6-P + 6 CO
2
+ P
v
+ 12 NADPH + 12 H
+

Hoc vit dng n gin:
1-glucose-6-P + 12 NADP
+
6 CO
2
+ P
v
+ 12 (NADPH + H
+
)
C mi phn t glucose-6-P b oxy ho hon ton trong chu trnh to ra c
12 phn t NADPH + H
+
. Nu hydro c chuyn qua h thng vn chuyn in
t, cho php to thnh 36 ATP. Do cn 1 ATP phosphoryl ho glucose ban u
thnh glucose-6-P, nn cn thu c 35 ATP. l s nng lng tng ng vi
s oxy ho hon ton 1 phn t glucose qua s ng phn v chu trnh Crep (38
ATP). ng thi, cng hn hn mc nng lng do s phn gii glucose trong iu
kin k kh (qu trnh ng phn ch to ra 2 ATP).
c) nghi cu chu trnh pentose phosphat:
- Chu trnh cung cp cc pentose phosphat l nguyn liu cn thit cho s
sinh tng hp nucleotit, c trong thnh phn cu to cu cc coenzym v axit
nucleic.
- Cung cp NADPH cn thit cho cc phn ng khc nhau, nht l trong s
tng hp axit bo v steroit.
Trong iu kin cc NADPH b oxy ho qua chui h hp s to thnh mt
lng ng k ATP.
- Chu trnh cho php cc c th quang hp tng hp c xacarit v cc cht
hu c khc t CO
2
.
Tm li, trong c th sinh vt, s phn gii ng c th tin hnh theo
nhiu kiu khc nhau. Cc kiu ny b sung cho nhau c th xy ra song song cng
nhau hoc mt vi kiu chim u th nhng iu kin nht nh. iu cng ni
ln s phong ph cu cc qu trnh thch nghi cu vi sinh vt i vi mi trng
sng, v qu trnh phn gii ng cung cp nng lng ch yu cho mi hot ng
sinh sng cu c th.

1.3 CHUYN HO CA LIPIT
1.3.1 Kh nng chuyn ho cu lipit
Trong iu kin bo qun cng nh trong c th, lipit c th b chuyn ho
to thnh nhng phm vt khc nhau. Cc qu trnh chuyn ho ny rt phc tp,
di tc dng cu mt lot cc nhn t v c enzym hoc khng c enzym xc tc.
1.3.1.1 S i ho
Khi bo qun lu, di tc dng cu nhiu nhn t nh nh sng, khng kh,
nhit , nc v vi sinh vt..., lipit b thay i trng thi, mu sc v c mi v kh
chu. Thng ngi ta gi qu trnh tng hp ny l s i ho. Thc cht cu s i
ho l qu trnh oxy ho. Tuy vy, nu da vo c ch phn ng th c th phn ra
i ho do thu phn v i ho do oxy ho.
a) i ho do phn ng thu phn
Phn ng thu phn lipit cng c th xy ra, khi c enzym cng nh khng
c enzym xc tc.
Trng hp th nht xy ra trong pha bo v ch c nc ho tan trong
lipit (du, m) mi tham gia phn ng, ngha l phn ng tin hnh trong mi
trng ng th. Khi trong lipit c mt nc vi mt lng ng k, nhng nhit
thng, th vn tc phn ng cng rt b. V l nhit thng vn tc phn
ng thu phn rt chm. Hn na kh nng khng ho tan cu pha nc trong pha
bo cng ngn cn s tip xc cn thit gia chng.
Trng hp thu phn do enzym xc tc thng xy ra trn b mt tip
xc gia lipit v nc. Enzym lipase xc tc phn ng thu phn c th c trong
nguyn liu cng nh do vi sinh vt mang vo.
Chng ta u bit lipase l mt globulin. N xc tc khng nhng phn ng
thu phn m c phn ng tng hp na. Do cn bng phn ng ph thuc vo
tng iu kin c th m c th chuyn dch v phi cng nh v tri. Khi hm m
cao th s thu phn u th hn s tng hp. Ngc li, trong ht kh th s tng
hp li u th hn. Lipase c trong ht v trong cc c quan dinh dng cu cy.
Lipase c nhiu trong ht thu du. Tc dng ti u cu lipase cu ht l 35-38
o
C.
Hot cu n gim xung mt cch ng k khi ch bin thu nhit cc ht cng
nh khi p nng cc ht c du. Phn ng thu phn lipit s tng mnh khi ht b
nghin c hc hoc b tn thng do cn trng. Lipase c c hiu thp so vi cu
trc cu lipit nhng li c c hiu quang hc cao i vi nhng c cht c hot
quang. Ni chung i vi nhng c cht khng mang in tch th di cu mch
cacbon cu axit bo tham gia trong lipit c nghi ln i vi hot cu lipase.
Trng hp n gin nht cu s i ho do phn ng thy phn thng thy
khi bo qun b v margarin. Khi s gii phng ra axit butyric l axit c mi rt
kh chu.
Trong ch bin lng thc, bo qun c ht, bt v tm, vai tr quyt
nh l nhit v thy phn. Chng hn bt khi nhit di 5
o
C vn bo qun
c tt ngay c khi c hm m cao. Ngi ta nhn thy rng khi bo qun bt c
hm m cao hn 15% th phn ng thu phn ch yu l do emzym ca nm mc.
Khi axit cng tng lin do tch t cac axit hu c ho tan v bt s c mi v
kh chu. Ngi ta cn nhn thy i vi bt kh, nm mc khng pht trin c,
axit cng tng nhng khng c mi v axit, v ch yu l to ra nhng axit bo
khng ho tan trong nc.
b) i ho do phn ng oxy ho kh
i ho theo kiu ny l ph bin nht trong bo qun cc lipit. Thng ngi
ta phn bit hai loi: i ho ho hc v i ho sinh hc.
i ho ho hc l qu trnh t oxy ho. Khi xy ra s tn cng cc gc
axit bo t do cng nh kt hp bi oxy phn t. p sut ca oxy v lng ni i
trong phn t axit bo c nh hng n tin trnh phn ng. Sn phm u tin l
hydro peroxit. T to nn aldehyt no v khng no, xeton, axit mono- v
dicarboxylic, aldoaxit, xetoaxit, epoxyt v.v. Ngoi ra cn c th trng hp ho cc
sn phm oxy ho na.
a s nhng cht ny c vai tr quyt nh trong vic pht trin mi v.
i ho sinh ho hc li bao gm s i ho do enzym lipoxygenase v s i
ho xeton. Kiu i ho th hai ny thng c trng i vi lipit c cha axit bo
no vi phn t lng trung bnh v thp, khi c hm m ng k. Khi axit bo b
-oxy ho v decarboxyl ho, kt qu s l tch t cc alkylmetylxeton c mi kh
chu.
Khi lipit b i ho, thng b mt hot tnh vitamin. V l khi cc axit bo
khng no cao phn t cng nh cc vitamin u b ph hu bi cc phm vt oxy
tch t trong lipit.
Cc sn phm oxy ho ca lipit thng lm v hot enzym v c bit lm
gim hot ca suxinoxydase, xitocromoxydase v colinoxydase.
Sn phm oxy ho cn c kh nng phn ng cao vi protein. Hp cht to
thnh ny bn vng, khng ho tan trong nc cng nh trong dung mi hu c v
cng khng b phn ly bi enzym.
Ngi ta cn cho rng s pht trin ca bnh va x ng mch l do s to
thnh phc gia sn phm oxy ho ca lipit vi protein c trong thnh phn ca
thnh huyt qun.
Lipit b oxy ho cn km hm s pht trin ca ng vt.
C ch ca qu trnh i ho ho hc
Qu trnh i ho ho hc l phn ng chui nn thng c 3 thi k sau:
- Pht sinh:
u tin, phn ng c khi mo bng vic mt vi phn t lipit (RH) b
oxy ho to thnh gc t do:

R

: gc ca axit bo no hoc khng no t do hoc gc ca axit bo trong
phn t glyxerit;
H

: nguyn t H C

so vi ni i, hoc nguyn t H ca nhm metylen

bt k trong axit bo no.
to thnh gc, ngha l t lin kt C-H trong phn ng trn i hi
nng lng l 70-100 kcal/mol.
Tuy nhin khi c oxy ho tan th tng tc gia RH ban u vi oxy s xy
ra mt cch mnh m hn. V l s to thnh gc theo phn ng lng phn di
y i hi nng lng ch l 47 kcal/mol.
RH + O
2
R

+ HO
2

Trng hp khi nng RH cao th c th xy ra phn ng tam phn:
RH + O
2
+ HR
1
R

+ H
2
O
2
+ R
1

Phn ng ny i hi nng lng cn b hn phn ng lng phn.
Gc t do cng c th pht sinh khi c ion kim loi giao chuyn:
M
3+
+ RH M
2+
+ R

+ H

M
2+
+ ROOH M
3+
+ RO

+ OH

Pht trin
Gc t do R

hoc RO

c to thnh do qu trnh khi mo s bt u
chui chuyn oxy ho:
R

+ O
2
RO
2


(1)
RO
2

+ RH ROOH + R

(2)
Phn ng (1) c bit nhanh, thc t khng cn nng lng hot ho. Cn
nng lng hot ho ca phn ng (2) l 4-12 kcal/mol. T y ta thy gc RO
2

l
gc ch o trong mch oxy ho v phn ng c ngha quyt nh vn tc pht
trin ca qu trnh t oxy ho l phn ng tng tc gia gc RO
2

vi phn t lipit
(phn ng (2)).
T hydroperoxit s phn mch cho nhng gc t do theo ng hng
sau:
ROOH RO
2

OH (3)
Hoc 2 ROOH RO
2

+ H
2
O + RO

(4)
Hoc ROOH + RH RO

+ H
2
O + R

(5)
Vic t lin kt O-O to thnh hai gc t do theo phn ng (3) i hi
nng lng hot ho 30-35 kcal/mol.
S lin hp cc hydroperoxit thnh dime theo phn ng (4) s thun li khi
nng hydroperoxit ln. Vic to nn dime (do lin kt hydro) s lm yu lin kt
O-H v O-O, do lm gim bi nng lng phn gii dime thnh cc gc.
Hydroperoxit c th phn gii theo phn ng (5) i hi nng lng hot ho
b hn phn ng n phn (3).
Cn ch rng gc peroxit c xu hng phn ng vi sn phm b oxy
ho hn l vi phn t cha b oxy ho do ch trong sn phm b oxy ho thng
cha cc lin kt C-H c kh nng phn ng hn.
Gc peroxit cng c th t nguyn t H - c bit v tr do qu trnh ni
phn v cng c th kp hp vi ni i olefin. V vy vic chuyn ho cc gc
peroxit s a ti to nn khng nhng hydroperoxit m c peroxit polyme, peroxit
vng, oxit, aldehyt v cc sn phm khc.
Do qu trnh pht trin ca chui phn ng oxy ho vi cc phn ng phn
mch (3), (4), (5) nn tch t gc alcoxyl RO

, peroxit ROO

v hydroxyl

OH.
T gc alcoxy c th to nn nhng sn phm th cp nh ru, xeton,
aldehyt v.v.: RO

+ RH ROH + RO

ru gc t do
Tng tc ca hai gc alcoxyl:

Tng tc ca gc alcoxyl vi gc alkyl:

Hoc

Hoc t hydroperoxit v gc alkyl cng to ra xeton:


Aldehyt cng c th c to thnh t xeton bng cch oxy ho chng n
-xetohydroperoxit ri n aldehyt v axit:

Ngoi ra, trong lipit b oxy ho cn c th to thnh cc sn phm trng hp
cao phn t:

Hoc
Kt thc:
Vic t mch, ngha l mt cc gc t do xy ra ch yu do kt qu tng
tc ca cc gc theo c ch lng phn:
R

+ R

+ RO
2

sn phm phn t
RO
2

+ RO
2

Nng lng hot ho ca cac phn ng ny rt khng ng k (1-2 kcal/mol)
do vn tc phn ng rt ln.
Cc yu t nh hng n vn tc oxy ho
Cc yu t kch thch
nh hng ca axit bo t do: axit bo t do c tc dng xc tc qu trnh
oxy ho, lm tng nhanh s phn gii hydroperoxit thnh cc gc.
nh hng ca oxy: vn tc t oxy ho ph thuc vo lng oxy trong mi
trng. V s pht sinh chui phn ng ch yu ph thuc vo RH + O
2
.
nh hng ca nhit : nhit c nh hng ln n vn tc phn ng
ho hc. Tng nhit , lng peroxit to thnh tng. nhit 40-45
o
C v cao
hn, s phn gii hydroperoxit s tng.
nh hng ca trng thi lipit: b mt tip xc ca cht bo vi khng kh
cng ln th vn tc oxy ho cng cao. Vn tc t oxy ho cn ph thuc vo chiu
dy ca lp. Khi lp dy th oxy xm nhp kh. Gim nhit n lc cht bo
chuyn sang trng thi rn th vn tc oxy ho cng gim.
nh hng ca ion kim loi chuyn tip: cc ion cng nh cc hp cht ca
kim loi chuyn tip c tc dng xc tc s oxy ho lipit. Thc nghim cho thy
rng khi c mt st trong du vi lng 0,2-10 mg/kg st s lm gim bn ca
du i vi oxy ho 20-50%. Vi Cu ch cn 0,05-0,2 mg/kg s lm gim bn
ca du i vi oxy ho 20-50%.
Ion kim loi chuyn tip c cc electron c thn v thc cht l gc. Nhng
tnh cht gc chng th hin yu do chng c th tn ti trong dung dch vi
nng ln. Tuy nhin chng c th chuyn hoc ly electron t mt ht bo ho
ho tr no to thnh gc t do hot ng hoc gc ion.
M
n+
+ RO

M
(n+1)+
+ RO
-

M
n+
+ RO
2

M
(n+1)+
+ RO
2
-

M
(n+1)
+ RO
2

M
n+
+ R
+
+ O
2

nh hng ca nng lng mt tri v tia ion: nng lng nh sng c bit
l tia cc tm v tia ngn ca quang ph nhn thy c tc dng xc tc qu trnh oxy
ha lipit. C l nng lng nh sng s quang phn hydroperoxit thnh cc gc t
do.
nh hng ca nc: ngi ta nhn thy rng nc c tc dng lm tng
tnh n nh ca cht bo sa i vi s oxy ha nhit 95
o
C v khng c nh
hng g n m ln 50
o
C.
nh hng ca yu t km hm
Vn tc phn ng RO
2

+ RH c th c lm gim bng cch hng cc

phn ng ca gc peroxit theo chiu khc.
iu t c bng cch a vo trong lipit cht chng oxy ha InH
2
,
ngha l cht c kh nng phn ng d dng vi gc RO
2

hn:
InH
2
ROOH +

InH
RO
2


RH
Kt qu l thay gc peroxit RO
2

bng gc ca cht chng oxy ha In

l gc
yu khng th tng tc vi phn t lipit. Cc gc In

s b v hot do s t hp:
RO
2

+ InH
2
In

In

+ In

In-In
RO
2

+ In

ROOIn
iu kin tha mn c bng cch a vo nhng cht chng oxy ha
c bn cht phenol hoc amin v.v. Phenol c nng lng lin kt ca nguyn t
hydro trong nhm hydroxyl rt b (60-70 kcal). Mt cch khc gim nng
RO
2

l lm gim vn tc phn ng pht sinh ra chng.

Km hm s oxy ha bng cch lm t mch
C ch tc dng ca nhng cht chng oxy ha loi ny (nh phenol, amin)
c th nh sau:
RO
2

+ InH
2
ROOH +

InH

InH +

InH

In + InH
2

gc khng hot ng
hoc RO
2

+ InH
2

[RO
2
InH
2
]

[RO
2
InH
2
] + RO
2

sn phm bn
hoc RO
2

+ InH
2
ROOH +

InH

InH + RO
2

sn phm bn
Km hm s oxy ho bng cch lm gim vn tc pht sinh mch
V d, cc sulfua c kh nng ph hu hydroperoxit:
ROOH + R
1
SR
2
ROH + R
1
SOR
2

ROOH + R
1
SOR
2
ROH + RSO
2
R
2

Cc sulfua kiu ny nh tiuam (tetration, tetrametyltiuramdisulfua)

V hot cc hp cht ch kim loi c hot ng xc tc
Cc kim loi chuyn tip c th tng tc vi hydroperoxit to thnh gc
t do, ng thi kim loi chuyn sang ho tr khc:
Fe
2+
+ ROOH Fe
3+
+ RO

OH
Fe
3+
+ ROOH Fe
2+
+ RO
2

+ H
+

V vy phi chn nhng cht chng oxy ho c kh nng to phc vi ion
kim loi qu m phong to c s chuyn electron t mc N ti mc M,
nghi l loi tr c kh nng chuyn ha tr. Nhng cht chng oxy ho loi ny
nh axit xitric, axit malic, axit fitinic...

Axit carboxymetylmercaptosucxinic c tnh nng kh mnh thng c
dng bo qun du u, du bng.
Trong bo qun lipit, ngi ta c th dng cng tnh cu hai cht lm tng
hiu qu cu cht chng oxy ho. Cht lm tng tnh cht chng oxy ho cu cht
kia gi l cht hip tr. Cht hip tr ny c hoc khng c tnh cht chng oxy
ho. Bn cht cu chng c th l v c hay hu c. Axit phosphoric, axit ascorbic,
axit xitric v mui cu chng, polyphosphat, axit amin, xephalin l nhng cht
thuc loi . C ch hip tr cu chng l ch chng l nhng cht cho hydro
kh cc dng cht km hm b oxy ho. Chng hn km hm s oxy ho cht bo
bng hn hp axit ascorbic v quinon. Axit ascorbic chuyn hydro n quinon
cho cht ny c tc dng c vi gc peroxit. Qu trnh chuyn hydro cng c
coi l s hip tr cu axit ascorbic vi tocoferol. Tc dng hip tr cu -alanin n
hydroquinon trong chng oxy ho cho du hng dng l ch khi b deamin ho
n axit pyruvic th ng thi cng kh c hydroquinon b oxy ho.
Cc cht nh tocoferol, xemazol, phosphatit, gossipol, quercetin...l nhng
cht chng oxy ho t nhin, v thng ch trong trong cc ngun lipit t nhin.
Trong qu trnh khai thc v tinh luyn, nhng cht ny c th b mt i, do
nhng ngun lipit ny d b i ho. Mt s cht chng oxy ho cng c tn to
khi gia cng cc ht c du nh melanoidin, gossiphosphatit,
melanophosphatit...Hin nay ngi ta cn s dng nhiu cht chng oxy ho tng
hp nh butyloxyanizol, butyloxytoluen, dodexigalat v.v. trong bo qun du m.
c) C ch cu qu trnh i ho sinh hc
i ho do enzym lipoxydase
Trong qu trnh khai thc cng nh bo qun, lipit v c bit l du m, c
th b oxy ho di tc dng xc tc cu enzym lipoxydase to thnh nhng sn
phm khc nhau.
Lipoxydase hay lipoxygenase l enzym oxyhoas kh, thng c tn h thng
l linoleat:O
2
oxydoreductase (1.13.1.13). Enzym lipoxygenase xc tc s oxy ho
cc axit bo khng no ch 2-3 ni kp (hoc nhiu hn) nh axit linoleic,
linolenic, axit arachidic. im c bit l lipoxygenase ch oxy ho dng cis-cis cn
dng cis-trans hoc trans-trans th hon ton khng c tc dng. C 3 axit ny u
b oxy ho vi vn tc nh nhau. im khc l cc hydro peroxit c to thnh
y c hnh th cis-trans v c hot ng quang hc. C ch tc dng cu
lipoxygenase nh sau:

T hydroperoxit s chuyn ho mt cch bnh thng to ra epoxit,
aldehyt, xeton v nhng phm vt oxy ho khc.
Nhiu hp cht hu c l nhng cht km hm cu lipoxygenase.
Propylgalat, dephenylamin v oxyquinolin l nhng cht km hm lipoxygenase.
Tc dng km hm cu nhng cht ny l ch lm gim vn tc oxy ho linoleat
v hp th oxy.
Lipoxygenase c nhiu trong ht u tng v trong ht ho tho. pH ti u
cu lipoxygenase cu u tng l 9,0 v cu cc cy khc l 7,0. Lipoxygenase cu
ng vt c pH ti u t 4-7.
i ho xeton
i ho xeton thng c trng i vi lipit ch axit bo no, phn t lng
trung bnh, thp. Chng hn, trong bo qun b v margarin khi b nhim nm mc
(Aspergillus, Penicillium) thng xy ra kiu i ho ny. Di tc dng cu cc
enzym cu vi sinh vt, axit bo b -oxy ho v decarboxyl ho m kt qu l to ra
cc alkylmetylxeton c mi kh chu.
S phn ng nh sau:

d) S oxy ho cc axit bo trong c th sinh vt
Trong m ng vt cng nh thc vt, cac axit bo cn b chuyn ho oxy
ho theo mt ng hng ring, thc hin theo tng nc, mi nc axit bo li b
ct ngn i mt mnh hai cacbon ra khi phn t. Cc axit bo cha no, trc tin
phi c kh thnh axit bo no, sau mi b oxy ho theo con ng . Qu
trnh oxy ho axit bo theo ng hng ny cng c tn l -oxy ho. Lc cc
phn ng cu qu trnh -oxy ho axit bo bao gm 5 phn ng:
- Phn ng 1: l phn ng hot ho axit bo nh axyl coenzym A CoA-SH,
ATP v s xc tc cu enzym axyl-CoA-syntetase:
Pyrophosphat v to thnh s b phn gii thnh axit phosphoric (khi c
enzym pyrophosphatase xc tc) do cn bn g ph n gs chuyn dch v phi
phi.
- Phn ng 2: l phn ng oxy ho axyl CoA nh enzym axyl CoA
dehydrogenase. Enzym ny l mt flavoprotein c nhm ngoi l FAD:
Cc enzym ny khc nhau v tnh cht l hc v v tnh cht c hiu theo
di cu mch carbon cu c cht.
- Phn ng 3 do enzym enoyl-CoA-hydratase xc tc:
- Phn ng 4 do enzym -oxyaxylCoA dehydrogenase ch nhm ngoi l
NAD xc tc:
- Phn ng 5 bao gm vic chuyn nhm axyl cu phn t -xetoaxylCoA
ln mt phn t coenzym A mi. Enzym xc tc phn ng ny l -xetoaxylCoA
thiolase

Nh vy c qua 5 phn ng th phn t axit bo li ngn i hai nguyn t
cacbon to thnh axetyl CoA. Qu trnh c th c lp i lp li nhiu ln cho
n khi ton b sn phm cui cng l axetyl CoA. T Axetyl CoA s i vo chu
trnh Krebs (hoc chu trnh glyoxylic) cung cp nng lng cho c th sinh vt.
Khi oxy ho mt phn t lipit n gin (v d tristearin) th s cung cp cho
c th 458 mol ATP.
Nh vy cng vi carbohydrat, lipit l ngun nng lng d tr to ln cu c
th.
CHNG 2: CC CHT MU
2.1 NGHA CA CC CHT MU TRONG SN XUT THC PHM
Cht lng cu cc sn phm thc phm khng nhng bao hm gi tr dinh
dng m cn bao hm c gi tr cm quan cu chng n. Mu sc l mt ch s
quan trng cu gi tr cm quan. Mu sc cu cc sn phm thc phm khng ch c
gi tr v mt hnh thc m cn c tc dng sinh l rt r rt. Mu sc thch hp s
gip cho c th ng ho thc phm d dng. V vy trong k thut sn xut thc
phm ngi ta khng ch bo v mu sc t nhin m cn cho thm cht mu mi,
to ra nhng mu sc thch hp vi tnh cht v trng thi cu sn phm.
C th thc hin c iu bng nhng cch sau:
- Xy dng mt quy trnh gia cng nguyn liu, bn thnh phn bo ton
c ti a cc cht mu c sn trong nguyn liu;
- Tch ra, c c v bo qun cc cht mu t chnh nguyn liu thc vt
hoc t cc nguyn liu khc giu mu sc y. Sau t cc cht mu t nhin
c c ny c th dng nhum mu cho chnh nguyn liu m t ta thu
c cht mu hoc cho nhng dng nguyn liu hon ton khc.
- Tng hp nhn to cc cht mu ging nh cc mu t nhin cu sn phm
thc phm ri dng chng nhum mu cho cc sn phm khc m dng t
nhin khng mnh hoc b mt mu ban u do qu trnh ch bin.
- Dng cc bin php k thut thch hp iu chnh cc phn ng theo
chiu to ra nhng cht mu mi t nhng hp phn c trong nguyn liu.
Da vo qu trnh hnh thnh c th chia cht mu thnh hai loi:
- cc cht mu t nhin
- cc cht mu hnh thnh trong qu trnh gia cng k thut.
2.2 Cc cht mu t nhin
Cc cht mu t nhin thng gp ch yu trong cc nguyn liu thc vt,
c th chia lm ba nhm chnh:
- Clorofil, dip lc hay cht mu xanh l cy;
- Cc carotenoit c trong lc lp, trong qu v rau mu da cam, mu vng
v i khi mu
- Cc cht mu flavonoit c trong cc khng bo, c mu , xanh v vng,
2.2.1 Clorofil
Mu xanh l cy cu thc vt l do c mt clorofil. Cht mu ny ng rt
quan trng trong qu trnh quang hp. N khng nhng cho mu xanh m cn che
m cc cht mu khc. Clorofil c trong lc lp hoc ht dip lc, phn tn
nguyn sinh cht. N chim khong 1% cht kh.
Clorofil c hai dng: clorofil a v clorofil b. Clorofil b c mu nht hn. T
ln gia clorofil a v clorofil b trong thc vt khong 3:1.
Mg
+
N N
N N
X
CH
2
CH
2
CH
3
O
COOCH
3
CH
2
CH
2
COOC
20
H
39
C H
3
C H
3
CH C H
2

Hnh 7.1 Cu to ca clorofil a v b:
a X l CH
3
; b X l CHO
Tnh cht
a) Di tc dng ca nhit v axit cu dch bo mu xanh b mt i, mt
mt l do protein ng t lm v t bo b ph hu, mt khc l do lin kt gi
clorofil v protein b t lm cho clorofil d dng tham gia phn ng 7.1 takp ra
feofytin c mu xanh oliu:
Clorofil + 2 HX Feofytin + MgX
2
(7.1)
b) Khi cho tc dng vi kim nh nh cacbonat kim, kim th th chng s
trung ho axit v mui axit cu dch t bo v to nn mi trng kim lm cho
clorofil b x phng ho cho ru phytol, metanol v axit clorofilinic.
Clorofil a + kim (C
32
H
30
ON
4
Mg)(COONa)
2
+ CH
3
OH + ru phytol
Clorofil b + kim (C
32
H
28
O
2
N
4
Mg)(COONa)
2
+ CH
3
OH + ru phytol
Cc axit (C
32
H
30
ON
4
Mg)(COONa)
2
v (C
32
H
28
O
2
N
4
Mg)(COONa)
2
thu c
do x phng ho clorofil a v b uwojc gi l clorofilin hoc clorofilit. Cc axit
cng nh mui cu chng u cho sn phm mu xanh m.
Trong mt s cy cn c enzym chlorophyllase cng c th thu phn c
cc lin kt este ny gii phng ra phytol v metanol. Enzym ny thng c
nh v trong cc sc lp, kh bn vi nhit v ch c hot ho trong thi gian
chn.
c) Clorofil cng c th b oxy ho do oxy v nh sng (quang oxy ho), do
tip xc vi cc lipit b oxy ho hoc do tc dng ca enzym lipoxydase. Cc qu
trnh oxy ho ny c th xy ra trong cc rau (nht l rau sy) bo qun m
tng i di 30%; cn khi m tng i cu khng kh cao hn th clorofil li
b bin i thnh feofytin (phn ng 7.1). Mt s hp cht bay hi c th lm tng
(etylen) hay lm chm (kh CO
2
) s bin ho cu clorofil.
d) Di tc dng cu Fe, Sn, Al, Cu th Mg trong clorofil s b thay th v s
cho cc mu khc nhau sau:
- Vi Fe s cho mu nu;
- Vi Sn v Al cho mu xm;
- Vi Cu s cho mu xanh sng.
Trong sn xut thc phm, c bit l trong sn xut hp rau, ngi ta
thng dng cc bin php sau y bo v c mu xanh dip lc:
- Gia nhit nhanh trong mt lng nc si ln (3-4 l/kg) gim hm
lng axit. Axit lc ny s b bay i cng vi hi nc;
- Gia nhit rau xanh trong nc cng, cacbonat kim th s trung ho mt
phn axit cu dch bo.

Trong thc t, bo v mu xanh cu u ng hp, ngi ta cho vo hp
mt t dinatri glutamat hoc nhum mu xanh cho u vng, ngi ta dng
clorofylin (clorofil + kim). Clorofil d b hp th trn b mt cu ht u v gi
c bn mu trn b mt lm cho mu ht rt p.
2.2.2 Carotenoit
Carotenoit l nhm cht mu ho tan trong cht bo lm cho rau v qu c
mu da cam, mu vng v mu . Nhm ny gm t 65-70 cht mu t nhin, tiu
biu l caroten, licopen, xantofil, capxantin v xitroxantin. Carotenoit c trong a s
cy (tr mt s nm) v hu nh c trong tt c c th ng vt. Hm lng
carotenoit trong l xanh chim khong 0,07-0,2% cht kh, tng trng hp hn
hu ngi ta thy nng carotenoit rt cao, v d trong bao phn cu nhiu loi
hoa loa kn c nhiu xantofil v anteracxantin.
Tt c carotenoit khng ho tan trong nc, rt nhy i vi axit v cht
oxy ho, nhng li bn vng v kim. Mt trong nhng c im cu carotenoit l
c nhiu ni i lun hp to nn nhng nhm mang mu cu chng. Mu cu
chng ph thuc vo nhng nhm ny.
Tt c carotenoit t nhin c th xem nh dn xut cu licopen.
2.2.2.1 Licopen
Licopen c trong qu c chua v mt s qu khc. Mu cu c chua chn
ch yu do c mt licopen mc d trong c chua cng mt lot cc cait khac n
nh: fitoflutin, -caroten, -caroten, -caroten, licopen. Trong qu trnh chn, hm
lng licopen trong c chua tng ln 10 ln. Tuy nhin, cht mu ny khng c hot
tnh vitamin. Licopen c cu to nh sau:
CH
3
CH
3
C H
3
CH
3
CH
3
C H
3
C H
3
CH
3 CH
3
CH
3

licopen
Bng cch to thnh vng mt u hoc c hai u cu phn t licopen th
s c cc ng phn . , -caroten. Mu da cam cu c rt, m ch yu l do
caroten. Caroten c cu to nh sau:
CH
3
CH
3
C H
3
CH
3
CH
3
C H
3
C H
3
CH
3 CH
3
CH
3

-caroten
CH
3
C H
3
CH
3
CH
3
C H
3
C H
3
CH
3 CH
3
CH
3

-caroten
CH
3
C H
3
CH
3
CH
3
C H
3
C H
3
CH
3 CH
3
CH
3
CH
3

-caroten
Tt c nhng carotenoit t nhin khc u l dn xut cu licopen v caroten.
Chng c to thnh bng cch a nhm hydroxyl, carbonyl hot metoxy vo
mch, nh phn ng hydro ho hoc oxy ho.
2.2.2.2 Xantofil
Xantofil c cng thc C
40
H
56
O
2
v c c bng cch gn thm hai nhm
hydroxyl vo phn t -caroten, do c tn 3, 3-dihydroxy -caroten v 3, 3-
dihydroxy -caroten vi t l 2:1. Xantofil cng vi caroten c ch trong rau xanh
v cng vi caroten v licopen cu c chua.
CH
3
C H
3
CH
3
CH
3
C H
3
C H
3
CH
3 CH
3
CH
3
CH
3
O
O H
O
OH
Xantofil
2.2.2.3 Capxantin
Capxantin c cng thc C
40
H
58
O
3
l cht mu vng c trong t .
Capxantin chim 7/8 tt c cht mu cu t. Capxantin l dn xut cu caroten,
nhng c mu mnh hn cc carotenoit khc 10 ln. Trong t c cc carotenoit
nhiu hn trong t xanh 35 ln.
2.2.2.4 Criptoxantin
Criptoxantin c cng thc nguyn C
40
H
58
O
3
(3- hoc 4- hydroxy -caroten).
Mu da cam cu qut, cam ch yu l do criptoxantin.
2.2.2.5 Birxin
Birxin l cht mu c trong qu cy nhit i tn l Bixa orellana, birxin
c dng nhum mu du, margarin v cc sn phm thc phm khc. Birxin l
sn phm oxy ho cu cc carotenoit c trong 40 nguyn t cacbon.
2.2.2.6 Xitroxantin
Xitroxantin c cng thc C
40
H
50
O. Xitroxantin c trong v qu chanh.
Xitroxantin c c khi kt hp vo phn t -caroten mt nguyn t oxy to
thnh cu trc furanoit.
2.2.2.7 Astarxantin
Astarxantin cng l dn xut cu caroten v c tn gi l 3, 3-dihydroxy -
4,4-dixeto--caroten.
Trong trng cu loi gip xc c cht mu xanh ve gi l ovoverdin c th
coi nh l mui dng endil cu astarxantin v nhm amin cu protein (kt hp cu
astarxatin v protein).
Trong mai v gip cu cua, tm astarxantin cng tham gia vo thnh phn
cu lipoprotein gi l xianin.
Trong qu trnh gia nhit do protein b bin tnh v astarxantin b tch ra
di dng cht mu .
2.2.3 Cc cht mu nhm flavonoit
Cc chtmu ny ho tan trong nc v ch trong cc khng bo. Trong
rau, qu v hoa, s lng cng nh t l cac flavonoit khc nhau, do lm cho
chng c nhiu mu sc khc nhau: t mu n mu tm. flavonoit l nhng dn
xut cu croman v cromon. Croman v cromon l nhng phenylpropan v c ch
b khung cacbon C
6
-C
3
. Khi croman hoc cromon ngng t vi mt vng phenol
n th c dn xut c tn l flavan.
O
O O
croman
cromon
flavan

Da vo mc oxy ho (hoc kh) ca d vng, c th chia flavonoit ra cc
nhm c dng cu trc ch yu nh sau:
O
OH
catesin (flavanol-3)
O
OH
OH
leucoantoxianidol
(flavandiol-3,4)
O
+
OH
antoxianidol

O
O
flavanon
O
O
flavanon
O
OH
O
flavanodol

O
O
OH
flavonol
izoflavon
O
chalcon
O
O

O
CH
2
O
auron

2.2.3.1Antoxian
Antoxian hay l antoxianozit l mono- diglucozit do gc ng glucose,
galactose hoc rhamnose kt hp vi gc aglucon c mu gi l antoxianidin. Do
, khi thu phn antoxian th c ng v antoxianidin (antoxianidol). Antoxian
ho tan trong nc, cn antoxianidol th khng ho tan trong nc. Cc
antoxianidol v cc antoxian l nhng cht to nn mu sc cho hoa v qu. Cc
antoxianidol c mu , xanh, tm hoc nhng gam mu trung gian.
Tt c antoxianidol u c ch trong vng pyran oxy ho tr t do. Tuy
nhin ngi ta cha bin c chc chn nguyn t no: oxy hay cacbon mang in
tch dng t do. Do antoxianidol thng c biu din di dng cng thc
trung tnh:
O
+
OH
O
OH
Cl
-

Cng thc thng Cng thc trung tnh
Nh in tch dng t do ny m cac antoxianidol trong dung dch axit tc
dng nh nhng cation v to mui c vi cc axit. Cn trong dung dch kim th
antoxianidol li tc dng nh anion v to mui vi baz.
Thng gp ba antoxianidol chnh l: pelargonidol, xianidol v delfinidol.
Cn apigenidol th t gp hn.
O
+
OH
O H
OH
OH
O
+
O H
OH
OH
pelargonidol
apigenidol

O
+
OH
O H
OH
OH
OH
O
+
O H
OH
OH
OH
OH
OH
xianidol
delfinidol

O
+
OH
O H
OH
OH
OCH
3
O
+
O H
OH
OH
OCH
3
OCH
3
OH
xianidol
xirinhidol (malvidol)
Tnh cht cu antoxian
Ni chung cc antoxian ho tan tt trong nc v trong dch bo ho. Khi
kp hp vi ng lm cho phn t antoxian cng ho tan hn.
Mu sc cu cc antoxian lun lun thay i ph thuc vo nhit , cc cht
mu c mt v nhiu yu t khc,...Khi tng s lng nhm OH trong vng benzen
th mu cng xanh m (trong vng benzen c th c 1-2 hoc 3 nhm OH)
Mc metyl ho cc nhm OH trong vng benzen cng cao th mu cng
. Nu nhm OH v tr th 3 kt hp vi cc gc ng th mu sc cng s thay
i theo s lng cc gc ng c nh vo nhiu hay t.
Cc antoxian cng c th to phc vi cc ion kim loi cho cc mu khc
nhau: chng hn mui kali s cho vi antoxian mu mu, cn mui canxi v
magie s cho vi antoxian phc c mu xanh ve. Hoc ngi ta cng thy phc bn
t en s chuyn sang mu xanh, cn anh o th chuyn sang mu tm khi c mt
thic, anh o cng s c mu tm khi c mt nhm, nhng nhm li khng nh
hng n mu cu nho . Cc antoxian cu nho ch thay i ng k khi c Fe,
Sn hoc Cu. im ng ch l mu sc cu cc antoxian ph thuc rt mnh vo
pH mi trng.
Thng thng, khi pH>7, cc antoxian cho mu xanh v khi pH<7, cc
antoxain c mu . Chng hn, rubrobraxinin clorua l antoxian cu bp ci , l
mt triglucozit cu xianidin.
Khi pH=2,4-4,0 th c mu thm; pH=4-6 th c mu tm; pH=6 th c
mu xanh lam; pH l kim th c mu xanh l cy.
Hoc nh xianin c trong hoa hng, mu sc s thay i khi pH cu dch bo
thay i.
Mu sc cu antoxian cn c th thay i do hp th trn polysacarit.
Khi un nng lu di cc antoxian c th ph hu v mt mu, c bit l cc
antoxian cu du ty, anh o, c ci. Ngc li, cc antoxian cu phc bn t en
cng trong iu kin li khng b thay i. Nhn chung khi gia nhit, cac cht
mu d dng b ph hu, cn cht mu vng th kh hn.

Cc mu sc khc nhau cu hoa c c l do t hp cc antoxianidin v cac
este metylic cu chng vi axit v baz.
Tm li, trong mi trng axit, cc antoxian l nhng baz mnh (oxonium)
v c th to mui bn vng vi axit. Antoxian cng c kh nng cho mui vi
baz. Nh vy chng c tnh cht lng tnh. Mui vi axit th c mu , cn
mui vi kim c mu xanh.
Trong sn xut hp, bo v mu sc t nhien, ngi ta c th cho thm
cht chng oxy ho, v d, thm rutin bo v mu cu anh o v mn, thm
tanin, axit ascorbic bo v mu cu du v anh o. Mt bin php khc c th
bo v c mu t nhin cu cc hp rau qu l thm enzym glucooxidase,
chng hn nh thm gluco oxidase gi mu t nhin cu nc qu c...
Cc dn xut cromon ng ch hn c l flavanon v flavonol
2.2.3.2 Flavanon
So vi cc flavonoit khc th cc flavanon t gp hn. Hesperidin v naringin
l hai flavanon c trong v cam qut bn cnh cc catesin c hot tnh vitamin P.
Aglucon cu cc glucozit ny l hesperetol v naringenol:
O
+
O H
OH
OCH
3
OH
O
O
+
O H
OH
OH
O
hesperetol
naringenol

Naringin l diholozit (vi glucose v rhamnose) thng gy ra v ng cu
bi nht l bi trc khi chn.
O
O H
OH
OH
O
OH
R'
R

O
O
OH
OH
O
O
H
H
H
O H
OH
H O
H
CH
2
OH
O
CH
3
OH
OH OH
naringin

Naringin l mt flavonoit khng mu, t tan trong nc, d dng kt tu di
dng cc tinh th nh do gy kh khn cho sn xut nc qu cng nh puree
cam qut. Khi qu chn, enzym nariginase phn ct lin kt glucose-rhamnose do
mt v ng.
2.2.3.3 Flavonol
Flavonol l glucozit lm cho rau qu v hoa c mu vng v da cam. Khi
flavonol b thu phn th gii phng ra aglucon mu vng. Cc glucozit nhm
flavonol rt nhiu, nhng thuwofng gp hn c l nhng aglucon dn xut sau y:

Kempherol R=R=H
Querxetol R=OH, R=H
Mirixetin R=R=OH

Astragalin l 3-glucozit cu kempherol, c trong hoa t vn anh, hoa d
nga, trong l ch v trong hoa hng. Querxetol c trong v si, l ch, to, nho,
thuc l, ho huplng (hoa bia).
Rutin l 3-rhamnoglucozit cu querxetol rt thng gp trong cy. Rutin
c ng dng rng ri trong y hc lm thuc b mao mch.
Cc flavonol u ho tan trong nc. Cng mu cu chng ph thuc
vo v tr nhm OH: mu xanh nht khi OH v tr orto.
Flavonol tng tc vi st cho ta phc mu xanh l cy, sau chuyn sang
mu nu. Phn ng ny thng xy ra khi gia nhit rau qu trong thit b bng st
hoc bng st trng men b dp.
Vi ch axetat, flavonol cho phc mu vng xm. Trong mi trng kim,
flavonol rt d b oxy ho v sau ngng t to thnh sn phm mu .
2.3 Cc cht mu hnh thnh trong qu trnh gia cng k thut
Trong cc nguyn liu a vo ch bin thc phm, thng cha mt t hp
cac cht khc nhau. Trong qu trnh gia cng c nhit, chng s c tng tc vi
nhau to thnh nhng cht mu mi c nh hng tt hoc xu n thnh phm.
Cc phn ng to mu trong thc phm thng phc tp v a dng. Chng
hn nh mu sc cu nc ch l do phn ng oxy ho cc polyphenol bng enzym,
mu sc xut hin khi sy malt, khi nng bnh m hoc trong cc sn phm ch
bin ht khc li hu nh ch yu do phn ng ozamin. Nu nh trong cc sn
phm bnh ko, mu c to nn ch yu l do phn ng caramen ho cc ng
th trong ch bin rau qu mu c hnh thnh nn cn do mt lot cc phn ng
khc na.
Chung quy li, cc phn ng to mu l nhng phn ng oxy ho v nhng
phn ng c enzym xc tc khng c enzym xc tc. l phn ng trng hp ho
cc phm vt oxy ho cu polyphenol v phn ng gi bisflavonoit vi axit amin.
Chng gm c:
- phn ng gia ng v axit amin;
- phn ng dehydrat ho cc ng hay l phn ng caramen ho;
- phn ng phn hu axit ascorbic, axit limonic, axit maleic, axit tartric v
mt s axit hu c khc;
- phn ng oxy ha cc hp cht cu st v to thnh phc c mu;
- phn ng to nn cc sulfua kim loi c mu.
2.3.1 To mu mi do phn ng caramen
Phn ng caramen ho c nh hng ln n mu sc cu cc sn phm giu
ng nh bnh, ko, mt...Phn ng xy ra mnh m nhit nng chy cu
ng. Chng hn, vi glucose 146-150
o
C, fructose 95-100
o
C, saccharose
160-180
o
C, lactose 223-252
o
C. Tuy nhin, ph thuc vo nng ng, thnh
phn pH cu mi trng, thi gian un nng,...ngi ta vn tm thy cc sn phm
cu s caramen nhit thp hn im nng chy cu ng. V d, saccharose
c th bt u bin i ny khi nhit 135
o
C.
Giai on u cu phn ng to nn cc anhydrit cu glucose, fructose,
saccharose nh glucozan, fructozan, sacarozan l nhng hp cht khng mu. Sau
, bn cnh s dehydrat ho cn xy ra s trng hp ho cc ng ng
dehydrat ho to thnh cc phm vt c mu nu vng.
Chng hn, vi saccharose, s phn ng caramen nh sau:
C
12
H
22
O
11
C
6
H
10
O
5
+ C
6
H
10
O
5
+ H
2
O
n 185-190
o
C s to thnh izosacarozan:
glucozan + levulozan izosacarozan
C
6
H
10
O
5
+ C
6
H
10
O
5
C
12
H
20
O
10

Khi nhit cao hn s mt i 10% nc v to thnh caramelan
(C
12
H
18
O
9
hoc C
24
H
36
O
18
) c mu vng:

2
C
12
H
22
O
10
(C
12
H
18
O
9
) hoc C
24
H
36
O
18
+
2
H
2
O
izosacarozan caramelan
Khi mt i 14% nc s to thnh caramelen:
C
12
H
22
O
10
+ C
24
H
36
O
18
C
36
H
48
O
24
.H
2
O + 3 H
2
O
V khi mt i 25% nc s to thnh caramelin c mu nu en.
Cn ch rng tt c cc sn phm caramen ho u c v ng.
2.3.2 S to mu mi do phn ng melanoidin
Phn ng ozamin, cacbonylamin, aminoza hay phn ng melanoidin l phn
ng c vai tr c bit qun trng trong k thut sn xut thc phm. Cc hp phn
tham gia phn ng l protein (hoc cc sn phm phn gii cu chng) v
carbohydrat.
iu kin phn ng xy ra c l cht tham gia phn ng phi c nhm
carbonyl. Khc vi phn ng caramen ho, phn ng ozamin i hi nng lng
hot ho b hn, nhng tin hnh phn ng bt buc trong mi trng phn ng
phi c nhm amin hoc amoniac.
Da vo mc v mu sc cu cc sn phm c th chia thnh ba giai on
k tip nhau. Sn phm cu giai on u khng mu v khng hp th nh sng
cc tm. Giai on ny bao gm hai phn ng: phn ng ngng t carbonylamin v
phn ng chuyn v Amadori. Sn phm cu giai on th hai khng mu hoc c
mu vng, nhng hp th mnh nh sng cc tm. Giai on ny bao gm phn ng
kh nc cu ng, phn hu ng v cc hp cht amin. Sn phm cu giai
on cui c mu m. Giai on ny gm c phnng ngng t aldol, trng hp
ho aldehytamin v to thnh hop cht d vng ch nit.
Thc t trong hn hp phn ng c ch ng thi tt c cc sn phm,
nhng t lng cu sn phm ny hay sn phm khc chim u th l ph thuc
mc tin hnh cu phn ng.
2.3.2.1Cc giai on cu phn ng to melanoidin
a) Giai on u cu phn ng to melanoidin
Phn ng ngng t cacbonylamin
Giai on u tin ca s to thnh melanoidin l s ngng t ng vi axit
amin. Trong iu kin nhit sinh l th to thnh baz Schiff (hp cht hu c c
nhm -HC=N-) hoc glycoside:
CH
2
OH
O
H OH
O H H
H OH
H OH
+
N H
2
R
-H
2
O
+H
2
O
C
CH
2
OH
N
H OH
O H H
H OH
H OH
R
C
CH
2
OH
N
H OH
O H H
H OH
H
R
O
Glucose
bazo schiff
N-glucoside

Trong iu kin sn xut khi nhit cao, phn ng c bt u khng
phi t N-glycoside m t sacaroamin (ng amin) theo s :
C
C
R'
O
H OH
H
COOH
C
H
N R" H
H
+
C
C
R'
O
H
H
COOH
C
H
N R"
H

ng hp cht amin phc ng amin
Phc ng amin c to thnh khng mu v khng c tnh cht no cu
melanoidin c.
Phn ng ny c th tin hnh ch lnh v qua mt vi gi th t c cn
bng. Nhng c th tng rt nhanh khi un nng hn hp phn ng.
Phn ng chuyn v Amadori
Khi nhit cao th phc ng amin b ng phn ho hay ngi ta cn
gi l b chuyn v ni phn Amadori. Kt qu l gia nguyn t cacbon th nht v
th hai pht sinh ra ni kp v to thnh 1-amin-1dezoxy-2-ketose:
C 1
C
2
R'
O
H
H
COOH
C
H
N R"
H
C
2
R'
O
CH
2
1
COOH
C
H
NH R"
C R'
OH
CH
2
COOH
C
H
NH R"

Phc ng amin 1-amin-1-desoxy-2-ketose dng enol
ca 1-amin-1-desoxy-2-
ketose
Phm vt cu s chuyn v Amadori l hpo cht c kh nng phn ng v l
cht khi u to thnh polyme c mu sm gi l melanoidin.
b) Giai on trung gian cu phn ng melanoidin
giai on ny xy ra s kh nc cu 1-amin-1-desoxy-2-ketose to thnh
cc sn phm phn ly khc nhau. Ph thuc vo iu kin cu mi trng v nhit
m giai on trung gian c th tin hnh bng mt vi con ng. S kh to
thnh furfurol hoc hydroxymetylfurfurol l mt trong nhng con ng kh nc
cu desoxyketose. Mt con n gkhc l to thnh reducton mch h. Con ng
thc ba l phn hu hp phn ng to thnh aldehyt, eton, diaxetyl. Con
ng th t l to thnh ozon.
To thnh furfurol v ozon
Nu cu t u tin cu s to thnh melanoidin l glucose, th sn phm
chuyn v Amadori khi un nng s chuyn sang dng furan v sau thnh baz
Schiff cu hydroxymetylfurfurol:
C
C
C
C
C
CH
2
OH
N H
OH
O H H
H OH
H OH
R
-H
2
O
O
CH
C
CH OH O H
CH NH R H
2
C O H
-H
2
O
C
O
HC
C
CH
CH NH R H
2
C O H
1-amin-1-desoxy-2-ketose baz shiff ca
hydroxymetyl
furfurol
Nu ng khi u khng phi l hexose m l pentose th to thnh baz
Schiff cu furfurol.
Sau ny khi b thu phn, baz Schiff cu hydroxymethylfurfurol hoc cu
furfurol c th b phn hu to thnh hydroxymetylfurfurol hoc furfurol v axit
amin t do theo s :
C
O
CH
C
CH
CH NH R H
2
C O H
+H
2
O
C
O
CH
C
CH
C H
2
C O H
H
O
N H
2
R
+
hydroxymetylfurfurol axit
amin
i khi baz Schiff cu hydroxymetylfurfurol v cu furfurol cng c th
ngng t to thnh melanoidin ch nit. Trong mi trng axit hoc trung tnh
v nhit cao th furfurol v cc dn xut cu n s to thnh trc tin.
Mt s tc gi tm thy mt con ng kh nc khc cu desoxyxetose.
Ban u desoxyketose phn ng vi phn t glucose to thnh difuranozamin.
Sau difuranozamin b phn hu to thnh 3-dezoxyglucozon, cac ozon khng
no dng cis v trans:
C
C
C
C
C
CH
2
OH
OH
O
H H
H OH
H
O
C
C
C
C
C
CH
2
OH
OH
O
H
H
H
O
C
C
C
C
C
CH
2
OH
OH
O
H
H
H
O

3-dezoxyglucozon glucozon khng no dng cis glucozon khng no dng trans
Hydroxymetylfurfurol cng c th c to thnh. Cc tc gi ny cho rng
cc sn phm v k trn l nhng cht tin thn c bn cu cc polyme c mu nu
sm.
To thnh reducton c 6 cacbon
Cc aminodezoxyketose c to thnh khi chuyn v Amadori, c th b
kh i hai phn t H
2
O to thnh cc reducton c 6 cacbon.
Reducton l nhng hp cht hu c c tnh cht chung l kh mnh do c
mt nhm endiol:
C C
O H OH

Theo thng l, nhm endiol cu reducton c lin kt vi gc aldehyt
hoc gc axit. V d:
CH C C
O H O H
H
O

Do , nhng hp cht ny rt nhy vi phn ng oxy ho v kh.
Chng hn, reducton n gin nht l triozoreducton:
CH C C
O H O H
H
O

Cht ny thc cht l enol cu hydroxymetylglyoxal:
CH
2
C C
O H O
H
O
CH C C
O H O H
H
O

Hydroxymetylglyoxal reducton hay l enolaldehyd
ca axit tartric
S t hp cu nhm endiol vi nhm carbonyl lm cho cc cht ny c kh
nng nhy cm c bit vi phn ng oxy ha v kh.
Kh nng phn ng cu reducton c th dn n s kh hydro chuyn
nhm endiol thnh nhm carbonyl
CH C R
2
O H O H
R
1
2H
C C R
2
O O
R
1

reducton dehydroreducton
D nhin, reducton c th d dng kt hp vi oxy v chnh l iu rt
quan trng cho s bn vng cuc cvat.
Reducton khng kh dung dch Fehling li d dng kh iot v 2,6-
diclophenolindophenol.
Axit dehydroascorbic c th coi l mt v d cu reducton c su cacbon.
Khng phi ch ring reducton m cac dng dehydro cu chng cng tham
gia vo vic to nn mu nu.
Phn hu ng
Mt trong nhng giai on trung gian cu phn
ng to melanoidin l s phnhu cu t ng cun
phm chuyn v Amadori to thnh cc phm vt khc
nhauL triozoreducton, aldehyt pyruvic, axeton, axetoin,
diaxetyl.
Mt s cht to thnh kh phn hy ng c mfui
vi v v d chu do quyt nh cht lng cu sn
phm.
Phn hu cc hp cht amin
Trong qu trnh to nn melanoidin th CO
2
, aldehyt v NH
3
l nhng phm
vt cu phn ng khi nhit cao. Nguyn do cu hin tng ny l s phn hu
Strecker theo nhng hng khc nhau:
1/ Phm vt chuyn v Amadori c th kt hp vi axit amin thot ra CO
2

v H
2
O:
CH NH
2
COOH
R
+
CH CH
2
O
R
1
CH NH
COOH
R
2
CH CH
2
R
1
CH NH
COOH
R
2
CH
2
N R
-CO
2
-H
2
O

C
C
C
C
C
CH
2
OH
O
O
O H
O
O
H
Axit dehydroascorbic
Baz Schiff c to thnh b phn ly thy phn thnh aldehyt v hp cht
amin. Chnh hp cht amin ny s cho cc phm vt ch ni t v c mu nu sau
ny. Cn aldehyt c to thnh trong phn ng ny, so vi axit amin tham gia
tng tc vi aminodezoxyketose th c t hn 1 cacbon.
C
N
C
C
N
C
H
R
H
H
R
1
H
H
R
2
COOH
H
H
2
O
R C
H
O
NH
2
C
C
N
C
H
H
R
1
H
H
R
2
COOH
H
+

2/ Gi furfurol hoc hydroxymetylfurfurol v axit amin c th xy ra s
tng tc oxy ho:
C
O
CH
C
CH
C
H
O
O
2
C
O
CH
C
CH
C
OOH
O

furfurol axit furfurolic
C
O
CH
C
CH
C
OOH
O
HC NH
2
COOH
R
+
C NH
COOH
R
C
O
CH
C
CH
C
OH
O
+
+
O H
2

axit amin axitimin axit furfurolic
C NH
COOH
R
+
O H
2
C O
COOH
R
+
CO
2 +
NH
3

aldehyt
Kt qu l t axit amin to thnh aldehyt c t hn mt nguyn t cacbon.
3/ Aldehyt cng c th c to thnh do kt qu cu s chuyn amin gi
axit amin vi reducton
HC NH
2
COOH
R
+
C C R
2
O O
R
1
C O
H
R
+
CH C R
2
N H
2
O
R
1 +
CO
2

Gi s, do s chuyn amin m dn n hnh thnh nn aldehyt l phn ng
ch yu, th r rng l do kt qu cu phn ng m ni t tham gia vo polyme
mu nu. Phn ln CO
2
thot ra trong qu trnh to mela
nu do axit amin b phn hy Strecker. Cc aldehyt to thnh ng vai tr
quan trng trong vic hnh thnh hng v cu sn phm thc phm khi ch bin
nhit.
c) Giai on cui cng cu phn ng to melanoidin
Giai on cui cng ny bao gm rt nhiu phn ng phc tp. C th chia
thnh hai kiu phn ng:
- Phn ng ngng t aldol vi s to thnh polyme mu nu khng ch
nit;
- Phn ng trng hp ho aldehytamin vi s to thnh cc hp cht nito
d vng.
S ngng t aldehyt axetic c th cng l v d v s ngng t aldol:
H
3
C C
H
O
H
2
CH C
H
O
+
H
3
C C
OH
CH
2
C
H
O

aldehyt axetic aldol
Khi nguyn t hydro cu nhm metyl cu mt phn t aldehyt ny c
lin kt vi nguyn t oxy cu nhm carbonyl cu phn t aldehyt th 2.
S trng hp ho v oxy ho ng thi cc aldehyt aminoaxetic dn n to
thnh pyrazin.
NH
2
CH
2
CHO
+
NH
2
CH
2
CHO
+O
2
N
N
+
O H
2
3

Pyrazin c mi d chu nhng yu, ho tan trong nc.
Khi trng hp ho dehydroreducton vi amoniac v aldehyt s to thnh hp
cht phc tp c ch vng imidazol:
C
C R
2
O
O
R
1
+
NH
3
NH
3
R
3
C
H
O
C
N
H
C
C
N
R
3
R
2
R
1
+
O H
2
3

imidazol dn xut
Ngoi nhng hp cht k, do kt qu cu phn ng ngng t aldehyt,
pyridin v pyrol cng c th c hnh thnh.
S ngng t aldol ch tin hnh c khi caramen ho dung dch ng
thun khit. Khi c mt cc hp cht amin mc du ch l vt cng xy ra ng thi
c hai kiu phn ng.
Giai on cui cng cu phn ng melanoidin s to nn u tin l cc
polyme khng no ha tan c trong nc, sau n l cc polyme khng no v
khng ho tan c trong nc, nhng u c mu m v c cng tn gi chung l
melanoidin.
Cc melanoidin hp th mnh tia cc tm (<220 nm), khng kh c dung
dch Fehling, nhng kh c iot v 2,6-diphenolindophenol. Kh nng ho tan cu
melanoidin ph thuc vo nhit v phn ng tin hnh.
Khi nhit cao th qu trnh xy ra mnh lit hn, nhng melanoidin to
thnh c hng thm km hn v t ho tan trong nc hn. Cc melanoidin khng
ho tan v tnh cht th gn ging humin.
2.3.2 iu kin tin hnh cu phn ng melanoidin
a) nh hng cu axit amin v ng
Nh thy trn, cng sm mu cu phn ng ph thuc vo bn cht
cu axit amin, bn cht cu ng, nng cht kh ni chung trong dung dch,
nhit , pH v mt lot yu t khc.
Qua c ch phn ng, ta thy mt trong nhng phn ng cu giai on trung
gian l to thnh furfurol v oxymetylfurfurol c km theo s ti to li axit amin
vn tham gia tng tc vi ng t phn ng u tin. Nh vy, axit amin c
th xem nh mt cht xc tc trong giai on u. Mt khc, melanoidin - sn
phm cui cng cu phn ng li l cht c ch nit. Mt phn axit amin tiu tn
cho s tn to aldehyt v thot ra NH
3
. NH
3
tng tc vi ng v to ra
melanoidin.
Cc axit amin tham gia phn ng khc nhau ph thuc vo nhit , pH v
lng nc. Cng phn ng ph thuc vo loi axit amin.
Protein, peptit, amin, amon v mt s cht ch nit khc cng c kh nng
phn ng vi ng kh to thnh cht c mu sm.
Cng cu phn ng melanoidin cng ph thuc vo bn cht cu ng
kh v nng ng. Glucose phn ng mnh lit hn c, sau n galactose v
lactose. T l gia axit amin v ng thch hp nht l 1/2 hoc 1/3. Ni chung
phn ng c th tin hnh ngay c khi nng axit amin khng ng k v t l
axit amin/ng rt b 1/40, thm ch 1/300.
b) nh hng cu nc
phn ng Maillard tin hnh cc i th xung quanh mi phn t protein
phi to nn lp n phn glucose v lp n phn nc. Nh vy, s c mt cu
nc l iu kin cn thit tin hnh phn ng. Nng cht tc dng cng cao,
lng nc cng t th to thnh melanoidin cng mnh.
c) nh hng cu nhit v pH mi trng
0
o
C v di 0
o
C, phn ng melanoidin khng xy ra. Cng vi s tng
nhit , vn tc phn ng tng ln rt mnh m. cc nhit khc nhau, cc sn
phm to thnh cng khc nhau. Ngi ta nhn thy khi nhit t 95-100
o
C,
phn ng s cho cc sn phm c tnh cht cm quan tt hn c. Khi nhit qu
cao th cc melanoidin to c s c v ng v mi kht. V vy trong sn xut
thu c malt mu, ngi ta thng khng ch phn ng melanoidin 160
o
C (mc
d lng cht mu s cc i khi nhit 190
o
C). V l nhit trn 160
o
C
cc melanoidin to thnh s khng ho tan trong nc, do lm gim kh nng
cho mu v trch ly cu malt thu c.
Phn ng Maillard c th tin hnh trong mt khong pH kh rng, tuy nhin
trong moi trng kim phn ng nahnh hn. Trong khi mi trng axit (pH<3) qu
trnh to melanoidin th hin rt yu v ch yu l s phn hy ng. Cng vi s
tng nhit phn ng s c tng nhanh ngay c khi trong mi trng axit
(pH=2).
d) Cht km hm v cht tng tc phn ng melanoidin
Phn ng caramen ho, oxy ho v melanoidin l nhng phn ng c tham
gia cu c hp cht carbonyl. V vy cht km hm l nhng cht phn ng c
vi nhm carbonyl nh dimedon, hydroxyamin, bisulfit. Nhng cht ny s kt hp
vi cc cht khc nhau pht sinh ra trong giai on trung gian, do lm ngng
cc qu trnh tip theo cu phn ng. Chng hn dimedon kt hp ;uc vi aldehyt
nen c th lm ngng hn phn ng to melanoidin. Khi sulfur, axit sulfur hoc
mui cu n (bisulfit cu natri v kali) l nhng cht kfm hm rt mnh m phn
ng to mu melanoidin. Tc dng km hm cu axit sulfur c lin quan vi cc
reducton:

Bng cch un nng dung dch glucose v sulfit 100
o
C, ngi ta thu
c hp cht 3,4-didezoxy-4-sulfohexozon (III). Cc dn xut cu axit sulfuric l
nhng hp cht rt bn vng, thm ch bng phng php thu phn ngi ta vn
khng th thu li c SO
2
khi chng ct. Do , cc sn phm trung gian tng t
cu phn ng melanoidin u khng c chuyn ho thnh cc hp cht mu cui
cng.
Ngoi ra, khi kt hp nhm ru bc 2 glucozon khng no dng trans, axit
sulfur cn gt b kh nng vng ho sau ny cu glucozon (khi tng tc vi
amoniac).
Axit sulfur cn th hin tc dng khng khun mnh m v l cht chng
oxy ho. Axit sulfur n nh c axit ascorbic dng hydroascorbic trong cc
sn phm. Ngi ta nhn thy rng, trong mt s sn phm (nc chanh, nc nho,
nc to) khi lng axit ascorbic b gim th cng sm mu tng ln, lng axit
amin v ng kh b gim xung cn hm lng furfurol li tng ln. C l do
tnh kh cu axit ascorbic v kh nng phn ng cu n vi cc sn phm thc
phm s lm yu s to thnh cc melanoidin. Tuy cht km hm axit ascorbic ny
lm tng gi tr sinh hc cu sn phm, nhng nghi thc tin li hn ch, v axit
ascorbic cng nh nhng axit hu c khc, khi phn hu s cho hp cht c mu
sm. Ngoi ra, axit ascorbic l mt reducton, nghi l mt sn phm trung gian cu
phn ng melanoidin m sau ny s tng tc vi axit amin to thnh cht c
mu sm.
Cn thy rng, trong cc sn phm c mu m do antoxian truyn cho, th
di tc dng cu vitamin C, mu t nhin s b nht i. Nh vy dng axit ascorbic
km hm s sm mu l khng c gi tr vn nng. Ngi ta ch c th ng dng
n i vi tng sn phm c th khi nghin cu k thnh phn ho hc cu n.
Cht km hm phn ng melanoidin tt nht l dimedon
(dimetyldihydroreorxin). N c kh nng lin kt cc furfurol v aldehyt do lm
ngng s to thnh melanoidin.
Dimedon trong nhng iu kin nht nh c th lm kt tu hon ton
furfurol bng cch to ra sn phm ngng t (furfuroldimedon) (hai phn t). Cc
cht oxy ho (KmnO
4
, H
2
O
2
, quinhydron) v cc cht kh (H
2
SO
3
, natri hyposulfit,
hydroquinon, hydro mi sinh) u km hm phn ng to melanoidin nhng vi
cng khc nhau:

Gn y, ngi ta cn dng este cu axit pyrocacbonic lm cht km hm
phn ng melanoidin. Este c cu to nh sau:

R
1
v R
2
c th l gc alkyl, aryl hoc cc gc d vng (furfuryl).
Trong mt s sn phm thc phm ngi ta cn dng cc anhydrit cacbonic
cu cc -hydroaxit nh sau:

V phng din l thuyt, hiu qu km hm cu pyrocacbonat cng nh cu
anhydrit cacbonic th hin ch chng tng tc vi nhm amin t do. Do , axit
amin tr nn khng c kh nng phn ng vi nhm cacbonyl cu ng.
Cc cht tng tc phn ng melanoidin c axit lactic v phosphat. Mui cu
axit lactic lm tng nhanh vn tc phn ng ny rt mnh. Dung dch m phosphat
khng nhng lm tng nhanh vn tc phn ng gi axit amin v glucose m cn
lm tng phn ng nu ho dung dch glucose tinh khit.
2.3.2.1Tnh ph bin cu phn ng Maillard
Nh nu trn, phn ng gi axit amin v ng xy ra trong iu kin
rt d dng, do phn ng ny rt ph bin trong sn xut v bo qun cc sn
phm thc phm. Tu thuc vo yu cu v tnh cht cm quan cu tng sn phm
m ngi ta hoc to iu kin tng cng phn ng n ti a hoc km hm
phn ng n mc ti thiu.
Mt tng nhng qu trnh to iu kin phn ng ny pht trin ti a l
sn xut bnh m. Mu sc cu v bnh m hu nh do phn ng ny quyt nh. V
vy nhng bin php k thut tng ng trong quy trnh sn xut ln men to
axit amin t do, ng kh, iu chnh nhit tng giai on nng u nhm
mc ch .
Trong sn xut bia (v cvat) mu sc v hng v cu bia phn ln do malt
quyt nh. Cc bin php k thut tng sn xut malt nhm iu ho phn ng
melanoidin. thu c malt vng, ngi ta chomc mm trong mt thi gian
ngn, lm mt nc nhanh thu c lng axit amin v t ng lm kh khn
cho phn ng carbonylamin. Theo Manxev, do thu phn axit amin v protein m
tch t nhng hp cht c kh nng to thnh cht thm. Malt sy nhit thp
qu s nh huworng xu n v cu bi, cn khi sy nhit qu cao, bia s c v kht.
V vy, khi sn xut bia vng cn phi kim tra s to thnh melanoidin v hn ch
thi gian un si dung dch ln men.
Tri li trong sn xut ru ngi ta tm cch km hm phn ng Maillard
mt cch trit . V phn ng s gy tn tht tinh bt v ng, n gthi
melanoidin to thnh c tc dng km hm hot ng cu enzym.
Trong sn xut thuc l, qu trnh sy, trc khi ln men v ln men cng do
phn ng Maillard quyt nh. Vic lm gim m cu mi trng s to iu
kin thun li cho phn ng v tng cng mu sm. Nguyn nhn c bn cu
s t m ho thuc l l phn ng melanoidin c km theo thot nc. Khi t l
gi axit amin v ng bng 1/2 th lng m thot ra l cc i v lng cht kh
l cc tiu. Thay i t l ny s c nh hng nhanh chng n lng nc thot
ra trong phn ng.
Trong sn xut ng, khi c c, ng b sm mu cng l do phn ng
melanoidin. Phn ng melanoidin cn c nh hng ln n vic ch bin rau qu
cng nh bo qun chng. Ngi ta thy rng do phn ng gi ng nghch
o v axit amin hoc mui amon m tt c sir v nc qu c c u b sm mu
khi bo qun, nht l nhit cao. Trong hp qu v rau, ngi ta c khuynh
hng bo v mu t nhin v hng thm cu chng. Phn ng Maillard lun lun
lm xu i khng nhng tnh cht cm quan m c gi tr thc phm cu sn phm
n.
Tm li, phn ng melanoidin rt ph bin trong mi sn phm thc phm
c lin quan vi gia nhit v thi gian bo qun di.
2.3.3 S to thnh cc cht mu do phn ng oxy ho polyphenol
Bn cnh phn ng melanoidin, cn c phn ng to mu do oxy ho cc
polyphenol c enzym v khng enzym tham d. Ngi ta cng gi l phn ng sm
mu do enzym.
2.3.3.1 Cc c cht phenol
Hp cht phenol l nhng cht m phn t c cha vng benzen, trong c
mt, hai hoc nhiu hn hai nhm hydroxyl. Da vo c trng cu b xng
cacbon, cc hp cht phenol t nhin c th chia ra lm ba nhm chnh:
- nhm hp cht phenol C
6
-C
1
(axit galic)
- nhm hp cht phenol C
6
-C
3
(axit cafeic)
- nhm hp cht phenol C
6
-C
3
-C
6
(catechin v flavonoit)
Kh nng phn ng to mu mnh hay yu ph thuc vo cu trc cu
phenol cng nh vo ngun enzym xc tc phn ng oxy ho ny. Chng hn, cc
metadiphenol thng l nhng c cht xu.
Cc c cht phenol ch yu cu phn ng to mu do enzym xc tc nh
sau:
1/ Pyrocatechol v cc dn xut (ngoi tr gaiacol hay o-metoxyphenol)

2/ 3,4-dihydroxyphenylalanin (DOPA)

3/ 3,4-dihydroxyphenyletylamin hay dopamin

l cht chnh lm cho chui b sm mu.
4/ Axit galic


l axit c nhn thm, khi b oxy ho th cho mu sm, ho tan c trong
nc.
5/ Axit clorogenic, c trong to, khoai ty v l, l cht c kh nng to ra
cht mu xanh en khi phn ng vi st trong qu trnh nu khoai ty.

Khi gim pH xung nh hn 4 hoc dng cc tc nhn to phc c vi Fe
nh phosphat hoc axit etylendiamintetraaxetic (EDTA, trong iu kin cho php)
th c th trnh c phn ng to mu ny.
6/ Cc flavonoit, trong c antoxian, flavon v flavanol l nhng hp cht
nguyn thu c mu.
Catechin v leucoantoxianidol l nhng hp cht khng mu, d dng b oxy
ho (nht l khi gia nhit trong mi trng axit), mt nc chuyn thnh nhng
sn phm (antoxianidol) c mu khc nhau.
Catechin hay catechol l tn gi chung cho cc phenol c dng flavanol-3

Quan trng nht trong nhm ny c catechin v galocatechin ch nhiu
trong l ch:
- Catechin (3,5,7,3,4-pentahydroxyflavan)

- Galocatechin (3,5,7,3,4,5-hexahydroxyflavan)

Trong phn t catechin v galocatechin c hai nguyn t cacbon bt i
xng v tr C
2
v C
3
do to ra nhiu ng phn quang hc (24 ng phn).
7/ Tanin khng nhng l c cht cu phn ng sm mu do enzym xc tc
m cn gp phn to ra kt cu v to v cho cc t chc thc vt. Ngi ta thng
phn bit hai nhm tanin: tanin thu phn v tanin ngng t:
- Tanin thu phn (tanin pyrogalic) l este cu ng glucose vi cc axit
polyphenolic khc nhau (axit galic, axit digalic, axit egalic, axit luteic). Este cu
glucose vi axit galic l galotanin, cu glucose vi axit egalic l egalotanin. Di
tc dng cu axit, kim hoc enzym chng b thu phn thnh cc cht ban u.

Chng hn nh tanin Trung Quc l -pentadigaloylglucose.

Tanin c tnh cht thuc da l hp cht c khi lng phn t t 500-3000,
l este cu axit digalic v glucose.
- Tanin ngng t (hay tanin catechic) l hp cht do cc catechin ngng t
vi nhau theo kiu u ni ui (C
6
-C
8
vi catechin) hoc kiu ui ni ui
(C
6
-C
6
, vi galocatechin) hoc kiu u ni u (C
4
-C
8
vi flavandiol -3,4) to
thnh. Tan nin ngng t khng b phn gii bi axit v c cng nh bi enzym.
2.3.3.2 Tnh cht chung cu cc hp cht polyphenol
a) Phn ng oxy ho kh
Di tc dng cu enzym polyphenoloxydase, cac polyphenol b oxy ho
to thnh cc quinon, S phn ng nh hnh bn.
Bn thn cc ortoquinon cng l nhng cht oxyhoas. Nu c cc cht kh
khc nh vitamin C, glucose, chng s ngng t vi nhau v s oxy ho cc cht
theo s sau:

b) Phn ng cng
Khi c mt cc axit amin th cc ortoquinon c to thnh s tin hnh
phn ng cng hp vi axit main:

Cc sn phm c to thnh cu phn ng cng li c th b oxy ho to
nn cc ortoquinon tng ng.
c) Phn ng ngng t
Cc ortoquinon cng d dng ngng t vi nhau to nn cc sn phm c
mu gi chung l flobafen
Polyphenol + O
2
ortoquinon (1)
Ortoquinon + glucose polyphenol + CO
2
+ H
2
O (2)
n (ortoquinon) flobafen (3)
Trong iu kin h hp bnh thng th phn ng (1) v (2) chim u th.
Tri li, trong iu kin sn xut th phn ng (1) v (3) chim u th.
2.3.3.3 Chc nng cu cc polyphenol
Cc polyphenol c tc dng c ch nm. Ngi ta thng dng phenol (axit
cacbovic) lm cht kh trng cng vi nghi . Thc ra bnh thng trong
thc vt, tc dng th hin tng i yu, nhng s tng lnmt cch mnh m
trong qu trnh polyphenol b oxy ho bi enzym. Thm ch, mt s polyphenol vi
mt nng nht nh c tc dng kch thch s pht trin cu k sinh trng, cn
tc dng km hm ch th hin ra trong qu trnh oxy ho chng bi enzym. Tuy
nhin, ng vai tr quan trng trong hin tng min dch thc vt ny khng phi
ch mt mnh polyphenol m l h polyphenol-polyphenoloxydase. Ngi ta
chng minh rng trong nhiu cy b dp c hc hay b nhim trng th hm lng
polyphenol v hot polyphenoloxydase u tng ln. ch m b dp nt bt
u to thnh hp cht polyphenol mi v km theo s ngng t oxy ho trong lp
b mt. Sn phm ngng t to thnh lp bo v.
Nhiu polyphenol c hot tnh sinh t P, nghi l c kh nng lm tng
n hi v chun ho tnh thm cu vi ti huyt qun. Trong s , catechin c hot
tnh vitamin P cao hn c. Cn ch rng, tt c flavonoit c hot tnh sinh hc u
bt buc phi c hai nhm ortohydroxyl , trong hydro cu mt nhm c th c
thay th bng gc bt k. Vng chnh l florogluxin, vng ph l pyrocatechic.
Polyphenol l nhng cht chuyn hydro (electron) trong chui h hp bnh
thng nh c ty th. Ubichinon (coenzym Q) l mt trong nhng cht ny.
Nhiu polyphenol l nhng cht chng oxyho, do chng c ng dng trong
cng nghip thc phm lm bn cht bo. Hot tnh chng oxy ho cu chng c
th do:
- phenol to phc bn vng vi cc kim loi nng, do lm mt tc dng
xc tc cu chng.
- phenol l cht nhn cc gc t do tc l c kh nng dp tt cc qu trnh
to ra gc t do.
7.3.3.4 Enzym xc tc phn ng oxy ho phenol
Phn ng to mu do enzym thng gm cc giai on sau:

S hydroxyl ho cc monophenol v oxy ha cc diphenol l hai tc ng
khc nhau v tch bit nhau. Tuy nhin i khi cng mt enzym cng c th xc tc
c hai phn ng. Ni chung, cc enzym c ngun gc khc nhau s c t s hot
lng hydroxyl hot ho lng oxy ho cng nh hm lng Cu
+
v Cu
2+
khc
nhau.
Enzym xc tc giai on u c tn l monophenolase hoc creosolase, cn
enzym xc tc giai on hai c tn l polyphenolase hoc catecholase. Tn gi h
thng cu enzym m trch giai on oxy ho l orthodiphenoloxy oxydoreductase
(E.C.1.10.3.1). y oxy phn t ng vai tr cht tip nhn hydro.
Polyphenoloxydase l metaloenzym c ch khong 0,2% Cu tng phn
t. Chng hn nh polyphenoloxydase l ch c khi lng phn t bng 144 000
Da v c ti 7 mol ng/mol.
Phng trnh phn ng oxy ho cc diphenol vi polyphenol oxydase c th
nh sau:

Ta thy phng (7.1) to ra polyphenol oxydase dng kh (ch Cu
+
) do
c th a tc ng hydroxyl ho monophenol vo phng trnh tng cho y
hn:

Nh vy, theo (7.4), chnh diphenol c tc dng xc tc s hydryl ho cc
monophenol.
Cc quinon to ra do hu qu tc dng cu polyphenoloxydase cng c th
oxy ho cc cht c th oxy ho kh b hn quinon:

Cc cht nh vitamin C, NADH
2
, glutation dng kh, xistein, cac
antoxianidol...c th kh cc quinon thnh diphenol.
Nh vy, polyphenol oxydase c th oxy ho c nhiu c cht khc nhau:

Do , v mt ny polyphenol oxydase cng c vai tr tng t nh enzym
xitocromooxydase (cng ch Cu) cui chui h hp.

7.3.3.5 C ch chung cu phn ng to mu do enzym
Cc cht mu c to thnh do phn ng ku ny thng c tn gi chung
l melanin. Thc ra thut ng melanin l phng theo tn gi cu mt sn phm c
mu do s oxy ho tyrozin bi enzym to ra. Cc cht mu cu phn ng sm mu
enzym cn c tn n l flobafen.

Ni chung sn phm cui cng, thng c mu nu, mu en hoc cc gam
mu trung gian nh: hng, , nu, xanh en, v.v.Phn ng to thnh cc cht mu
c bt u t quinon v khng c enzym tham gia.
u tin quinon phn ng vi nc to ra trihydroxybenzen, tip cc
trihydroxybenzen li phn ng vi cc quinon khc hnh thnh ra cc
hydroxyquinon v cui cng chnh cc hydroxyquinon ny li l ni ngng t
oxy ho ( giai on ny cn tiu th oxy) dn n to thnh cc polyme theo s
trn.
- Cc quinon cng c th tc dng vi nhm SH v NH
2
cu protein, axit
amin v amin theo c ch sau:

Quinonimin l phc gi quinon v axit amin thng c mu nu . Khi to
thnh phc ny, axit amin kt hp vi cacbon v tr para cu mt trong hai nhm
quinon. Nu c hai v tr para ca cc nhm quinon u b thay th th axit amin s
khng kt hp vo v phc quinon s khng c to thnh. Nhiu th nghim
chng t mu c to thnh mt cch mnh m ch khi hp cht nit tham gia
vo phc c ch nhm amin bt hai (prolin). Nu hp cht c nhm amin bc 1 th
phc to thnh c mu da cam, t m hn.
- Phc gi quinon v polypeptit hoc protein th c mu nu. Cht mu nu
c to thnh trong l thuc khi sy kh trong khng kh l mt phc thuc kiu
ny.
- Phc quinoimin khng nhng c tc dng to mu m cn c tc dng oxy
ho lng axit amin tha (khng c enzym) tham gia, phn ly n n amoniac v -
xetoaxit hoc aldehyt tng ng theo s sau:

7.3.3.7 Mt s bin php phng nga phn ng sm mu do enzym xc tc
Phn ng sm mu do enzym xc tc l phn ng rt thng xy ra trong
qu trnh ch bin cc sn phm thc phm c ngun gc thc vaajt nh rau qu,
cac sn phm dod hp rau qu, cc sn phm ch, thuc l,v.v. C nhi unhn t
nh hng n pahrnng ny nh cc nhn t sau:
- nng c cht phenol;
- hm lng v trjang thi cu polyphenoloxydase
- nng oxy;
- nng quinon;
- pH v.v.
Trong thc t ngng ng phn ng ngi ta thung ahy dng nhn
gbin php k thut tong ng sau:
- Trnh ng dp gy tn hi cc m, renzym khng c iu kin tip xc
vi c cht to mu;
- V hot enzym polyphenol oxydase bng nhit (chn, thanh trng) rt c
hiu qu, nhng c th lm thay i tnh cht cm quan cu sn phm do khng
th p dng cho mi trng hp;
- Thm cc ph gia c tnh kh chuyn ho qui non tahfnh phenol, do
cng lm chm hoc ngng cn s sm mu. Ngi ta hay dng vitamin C cho vao
cc nc qu v cc sn phm qu, ct lt cng vi mc hc . Khi liu lng
vitamin C cao (c th t 0,5-1% so vi khi lng sn phm) enzym polyphenol
oxydase c th b v hot hon ton trc khi lng vitamin ny bin ht trong mi
trng;
- Nhng ngp qu sau khi ct lt hoc sau khi gt v va trong dung dicjh
nc mui njhat, dung dch saccharose hoc dung dch glucose hn ch oxy xm
nhp vo qu cng nh ngn cn qu hp th oxy. Khi ng xm nhp vo m
cng c tc dunng lm qu chc li do tng p sut thm thu. Ni chung cc qu
lnh ng thong c bao bn gsi r (c th dng mt phn si r c nn g 30 -
50% saccharose cho 3-7 phn qu). Trong trng hp ny, ng v c tc dng
nh mt cht bo v lanh v cht gi hng thm cho qu.
- Dng axit xitric lm gim pH lm chm phn ng sm mu;
- Ly oxy trong cc m cu qu bng chn khg hac bng cc cht c kh
nng s rudjng oxy nh axit ascorbic, hoc nh enzym glucooxydase v catalase:

Glucose + O
2
axit gluconic + H
2
O
2


H
2
O
2
H
2
O + O
2

Tuy nhin cn trnh lm ym kh cc m thc vt m bo hot ng sinh
l bnh thng cho chng. Cn ch l vic kh oxy phi i km ngay vi x l
bo qun v phi bao gi bng bao b khng thm oxy.
- SO
2
v bisulfit cng c tc dng c ch phn ng sm mu do enzym xc
tc. Hp cht ny chng nhng c tc dng st trng (nhng khng phi vi liu
lng dng chng phn ng sm mu) m cn c kh nng lin kt vi cc nhm
carbonyl cu cc ng cng nh phn ng vi cc quinon. Nhng c th SO
2
tc
dng trc tip n polyphenol oxydase. Ngi ta cn nhn thy rng axit ascorbic
v tiamin c th lm gim liu lng bisulfit. SO
2
cn c tc dng bo v mu sc
t nhin cho qu, c bit l qu sy (chui sy).
Trong thc t, vi nhng qu nhm bo qun lnh ng, th u tin ngi ta
nhng (ngm) 45 giy trong dung dch NaHSO
3
0,25%, tip ngm 5 pht trong
mt dung dch K
2
HPO
4
0,2%. Chnh K
2
HPO
4
l tc nhn lm gim kh nng phn
ng cu polyphenol.
2.3.1 MT S CHT MU T NHIN V TNG HP DNG TRONG
THC PHM
Trong thc t, ngi ta c th dng cc cht mu t nhin hoc tng hp
to mu cho cc thc phm lm tng gi tr cm quan cu chng. Cc cht mu
v mu vng thng c s dng nhiu hn. Carotenoit l nhm cht mu t
nhin c s dng nhiu nht.
Cu trc v cch s dng cu mt s cc cht mu t nhin v tng hp quan
trng trong thc phm c trnh by bng 7.2:



glucooxydase
catalase
CHNG III: CC CHT THM
3.1 NGHA CA CC CHT THM TRONG SN XUT THC
PHM
Cng nh mu sc, hng thm l mt tnh cht cm quan quan trng ca
thc phm, v chng c nhng tc dng sinh l rt r rt. Cht thm c nh hng
n h tun hon, n nhp p cu tim, n h hp, n nhp th, n s tiu ho,
n thnh gic, th gic v c xc gic na. V vy trong sn xut thc phm, ngi
ta tm mi bin php k thut bo v nhng cht thm t nhin, mt khc ngi
ta cn tm cch iu khin cc phn ng to ra nhng hng thm mi.
Thng thng, ngi ta thc hin mt trong ba bin php sau to cho sn
phm c hng thm:
- Cht thm vn d bay hi v thng khng bn; v vy ngi ta dng cc
bin php k thut v thit b phc tp thu hi cac cht thm bi tc ra khi sn
phm trong qu trnh gia nhit (un hoc c c), to iu kin gi chng li, hp
th tr li vo thnh phm cc cht thm t nhin vn c trong nguyn liu ban
u;
- Chng ct v c c cc cht thm t nhin t cc ngun giu cht thm,
sau dng cc cht thm ny cho vo cc sn phm thc phm khc nhau;
- Tng hp cc cht thm nhn to c mi thch ng cho vo cc sn
phm thc phm.
3.2 Vi nt v mi
Trong hn hai triu cht hu c, th 400.000 cht c mi nhiu hoc t. a
s cht thm c mi c trng ring cu mnh. Mi cu chng do nhng nhm
nguyn t c bit gi l nhm mang mi quyt nh. Tuy nhin nu tng s nhm
mang mi tng mt phn t ln th khng lm tng mi m li lm yu mi v i
khi cn lm tt mi hon ton.
Nhng nhm mang mi c bn thng l nguyn t O, S, N, P, As, Se. Cc
nhm mang mi hu c l:
C-OH;
C th tng mnh hac lm yu mi ny bng mt mi khc, hoc cho mi
mi m i khi khng ging v hon ton bt ng. Chng hn, mi x hng cu
trinitrobutyltoluen hon ton mt i khi thm vo mt lwng nh quinin sulfat l
cht vn khng c mi.
Mi cu cao su, iot, long no v g b hng khi phi hp s trit tiu ln
nhau hon ton. Mi cu vani trong lnh s mt hon ton qua mt vi pht,
nhng nu thm mt t cumarin th hng cu vani s cm thy c rt lu.

Cc cht rt ging nhau v cu to v tnh cht c th c mi khc nhau.
Chng hn, cng thc cu hai cht h hng eugenol v dihydroxyeugenol ch khc
nhau mch bn.
Nhng eugenol l thnh phn ch yu cu du inh hng v c mi inh
hng mnh, cn dihydroxyeugenol li hu nh khng c mi.
Vanilin v izovanilin ch khc nhau v tr cu nhm th. Nhng vanilin l
hng liu ni ting nht c mi d chu, cn izovanilin ch bt u c mi khi un
si.
Ngc li, cc cht hon ton khc nhau c th c mi ging nhau. Chng
hn, cng thc cu x hng v cc cht thay th n khng ging nhau nhng li
cho mi ging nhau.
i khi mi cn ph thuc vo nng cu cht trong khng kh. Chng
hn, mi cu ionon m c ging b hng, nhng khi trng thi long th ionon
li c mi cy hoa tm.
Cn thy rng, nhiu hin tng lin quan n mi khng th gii thch c
mt cch chc chn, v cha c mt quan nim y v khu gic lm vic nh
th no v ti sao mt cht no li c mi.
3.2.1 Thuyt ho hc v mi

3.2.2 Thuyt l hc v mi

3.3 Cc cht mi t nhin
3.3.1 Tinh du v nha
Cc cht mi thng gp trong t nhin l tinh du v nha. Tinh du v
nha thuc nhm hp cht izoprenoit, nghi l nhng hp cht c coi nh l dn
xut cu izopren. Nhm hp cht izoprenoit bao gm rt nhiu cht: ngoi tinh du
v nha, cn c steroit, carotenoit v cao su. Cc cht thuc nhm izoprenoit c c
tnh chung l khng ho tan trong nc m ho tan trong cc dung mi hu c.
Tinh du v nha c to thnh v thot ra trong cc c quan c bit cu
cy: trong lng tuyn v vy i vi tinh du v trong ng nha i vi nha. Tinh
du v nha c hng thm nht nh quyt nh mi cu nhiu cy, cu hoa v
qu.
V bn cht ho hc, tinh du (v nha) thng l mt hn hp cac chc
khc nhau: hydrocacbon, ru, phenol, aldehyt, xeton, axit, este...Tuy nhin quan
trng v thng gp hn c trong hp phn tinh du l terpen v cc dn xut ch
oxy cu terpen.
Terpen l hydrocacbon mch thng hoc vng c cng thc chung l
(C
10
H
16
)
n
.
n=1 ta c monoterpen
n=1,5 ta c sesquiterpen
n=2 ta c diterpen
n=3 ta c triterpen
n=4 ta c tetraterpen
Cc dn xut cha oxy cu terpen thng l ru, aldehyt, xeton v.v...
3.3.1.1 Monoterpen
Cc monoterpen thng tiu biu l myrcen, oxymen v cc dn xut ch
oxy cu chng l linalol, geraniol, xitronelol, xitronelal v xitral.
Myrcen c trong mt lot tinh du. Trong tinh du cu hoa huplng c 30-
50% myrcen.
Linalol, geraniol v xitronelol u l ru:

Linalol c trong hoa lan chung, trong qut v trong cy mi. Linalol c
dng trong hng phm, di nguyn dng hay di dng este axetat. Ngi ta cho
rng hng thm cu o l do cc este khc nhau cu formiat, valerianat cu
linalol quyt nh.
Geraniol gp trong t nhin trng thi t do cng nh di dng este.
Geraniol c trong tinh du khuynh dip v cng vi xitronelol l thnh phn ch
yu cu tinh du hoa hng.
Xitronelol c trong tinh du hoa hng, phong l v cc tinh du khc.
Xitronelol c mi hoa hng.
Xitral c cha trong tinh du h cam qut v tng cc tinh du khc. Xitral
tng tc vi axeton to thnh ionon l hp cht vng c trong thnh phn cu phn
t caroten. Ionon v ng phn cu n l iron c ng dng rng ri trong cng
nghip hng phm. Xitral l hn hp cu hai ng phn hnh hc: dng cis gi l
dng a v dng trans hay l dng b.
Xitronelal gp trong t nhin di dng hai i quang.
Monoterpen n vng ph bin v quan trng hn c l limonen v cc dn
xut ch oxy cu n l menton, piperitenon, piperiton v carvon, v.v...
Limonen c trong nha, thng, trong tinh du cam, chanh v th l:

Piperitenon, piperiton, pulegon, menton v mentol hp thnh nhm menton
c trong tinh du bc h.
Piperitenon l cht khng hot quang do khng c tm bt i xng. Menton
c hai tm bt i xng v mentol c 3 tm bt i. Mi lin quan tng h v c
cu gia limonen v cac dn xut cha oxy cu n c th biu din bng s nh
hnh bn:
Trong s cc monoterpen hai vng c pinen v camphen ch trong tinh du
chanh v dn xut oxy cu chng l borneol v camphor.
Phn t pinen l t hp vng su cnh v bn cnh gm hai ng phn - v
-pinen. Pinen l hp phn cu nhiu tinh du v l cu t ch yu cu du thng.
N cho du thng mfui c trng, d dng b oxy ha trong khng kh chuyn
thnh sn phm dng nha.
Camphen c cu to i xng v gm hai vng nm cnh. Camphen c cha
trong tinh du chanh, tinh du loi lavng, tinh du h hoa trc bch, tinh du linh
sam v trong nhiu tinh du khc.

Borneol l ru bc 2 c cha trong tinh du long no, lavng, h
Rosmarinus. Borneol th rn. Khi oxy ho borneol th to thnh camphor.
Camphor c trong tinh du cu nhiu tho mc.
Cng nh borneol, camphor th rn. Camphor c trong g v l cy long
no. Camphor c ng dng rng ri trong y hc lm cht kch thch hot ng
cu tim. Trong cng nghip ho hc, camphor dng ch to xenluloit v thuc n
khng khi.
3.3.1.2 Sesquiterpen
Sesquiterpen c th xem nh hp cht do ba n v izopren to nn, c cng
thc chung l C
15
H
24
. Sesquiterpen cng chia ra mch thng v mch vng. a s
sesquiterpen l hp cht n vng hoc a vng. Nhng sesquiterpen thng v vng
tiu biu l farnezen, xinhiberen, humulen, cardinen v -xantalen. Trong , c
bit l xinhiberen c nhiu trong tinh du gng, humulen c trong tinh du huplng.

Trong s dn xut ch oxy cu sesquiterpen c farnezol, nerolidol,
xantonin.

Farnezol rt ph bin trong t nhin. Farnezol c trong tinh du cam, chanh,
hoa hng v trong mt s tinh du khc.
Nerolidol c trong tinh du cu hoa cam v trong nha thm Pru. Nerolidol
c ng dng quan trng trong k ngh nc hoa vi danh nghi l cht c nh mi,
nghi l cht c kh nng lm gim c bay hi cu cht c nhit si thp v
d dng bay hi khi trn vi n. Cc cht c nh mi c mi thm tng t nh
nerolidol c coi l qu.
Xantonin c trong h thu du. Xantonin c dng rng ri lm thuc ty
giun sn. Khi ho tan trong kim, xantonin to thnh mui cu axit xantonic. Khi
axit ho mi trng th li c xantonin.

3.3.1.3 Diterpen
Diterpen c cng thc chung l C
20
H
32
. Trong t nhin, diterpen bao gm
mt s hp cht khng ln. Diterpen hon ton khng b bay hi cng vi hi nc.
c bit ph bin rng ri trong cc nha l axit nha.
Khi chch mt ch trn v thng th s cho thng tit ra mt th nha m
nu chng ct hi nc th s c phn bay hi v phn khng bay hi. Khi lm
ngui phn khng bay hi, ta s c mt th thu tinh mu nu gi l canifol.
Phn bay hi cu du thng ch yu l pinen. Cn cafinol chnh l hn hp phc
tp cc axit, c cng thc chung l C
19
H
29
COOH v c tn chung l axit nha.
Axit abietic l cht tiu biu cu axit nha chim phn chnh trong canifol.
So vi cc axit nha khc, axit abietic tng i bn vng, mc d n rt d
dng b oxy ha trong khng kh. Tuy nhin trong nha nguyn thu axit abietic
ch chim mt lng rt nh. Trong qu trnh hnh thnh nn canifol, axit abietic
mi c to nn t mt lot cc cht tin thn linh ng khc c tn gi chung l
galipot. Axit levopimaric nm trong galipot . Khi gia nhit cng nh di tc
dng cu axit, axit levopimaric chuyn thnh axit abietic. Axit levopimaric khc vi
axit abietic v v tr cu ni i.
3.3.1.4 Triterpen
Triterpen thng gp trong thc vt di dng t, glucozit hoc trng thi
t do. Tiu biu cho triterpen l squalen. Squalen c trong cht bo cu gan c mp,
cng nh trong cc c khc.
Mt triterpen khc c bit t lu l axit masticadienic. Axit ny c
dng lm sn bng.
Tnh cht chung cu tinh du
Ni chung, tinh du ho tan rt t trong nc v ho tan nhiu trong ru
m c. ho tan cu hai cht lng cng nhiu khi c cc cu phn t chng
cng ln. Khi u tch in dng cu mt phn t ny gn u tch in m cu
phn t kia th chng s ht ln nhau v dn n lin hp cc phn t. ho tan
tng h cng c tng mnh khi hng s in mi cng gn nhau v cc yu t
lin hp cu cht cng gn nhau. Ru etylic l dung mi c cc mnh v hng
s in mi cu n rt ln (=27). Do c cc mnh nn n c th ho tan trong
nc theo tt c cc t l v c kh nng ho tan c nhiu cht hu c trong
c cc cu t ca tinh du.
Di tc dng cu oxy, mt phn tinh du ch yu l cc hp cht khng no b oxy
ho v cho mi nha.
Ni chung mi thm cu tinh du l do este, phenol, aldehyt, xeton v nhng hp
cht hu c khc quyt nh. Tng lng cu nhng cht ny thng ch chim n
10% lng tinh du, 90% cn li l nhng cht m. Sesquiterpen l cht n nh
(cht m) .
Cc cht thm hnh thnh nn trong qu trnh gia cng k thut
Nh chng ta u bit, sau cc qu trnh gia cng k thut, khng nhng
trng thi, mu sc m hng v cu cc sn phm thc phm cng b thay i. C
nhng nguyn liu hay bn thnh phm qua nhng qu trnh gia cng k thut no
(chng hn gia nhit) th mi thm b yu i hoc mt i hon ton. Ngc li,
cng c khng t trng hp, cc sn phm sau khi qua mt s gia cng k thut
no th hng thm cu chng li mnh thm, hoc thm ch sn phm t ch
khng c mi chuyn sang c mi thm hon ton mi.
Nghin cu nhng cht thm mi c tn to ra trong cc qu trnh gia
cng k thut cu nhiu sn phm thc phm, ngi ta thy rng chng thng l
nhng hp cht c nhm carbonyl. V l khi cho nhng cht lin kt c vi nhm
aldehyt nh imeon, natri sulfitvo cc sn phm u dn n lm tt mi.
Vy th t nhng hp cht nguyn thu no v bng con ng no tn
to nn c nhng cu t aldehyt ny?
3.4.1 Phn ng Maillard l ngun to ra aldehyt
Trong qu trnh gia nhit, cc axit amin tng tc vi ng v to thnh cc
aldehyt v reducton.
Bn thn cc furfurol v oxymetylfurfurol cng l nhng aldehyt vng c
mi c trng.
Furfurol c mi to v do ng pentose to thnh. Oxymetylfurfurol c mi
tht d chu v c to thnh t ng hexose.
Hai furfurol ny c th c to thnh do tng tc cu ng vi axit amin
qu phc hp trung gian 1-amin, 1-ketose. Tuy nhin chng cng c th c to
nn bng con ng dehydrat ho cc ng.
Ngoi furfurol v oxymetylfurfurol, cc aldehyt khc c th c tn to do
tng tc cu axit amin vi furfurol hoc vi cc reducton theo s phn ng sau:

Vi reducton th s phn ng tng qut nh sau:

T s phn ng ta thy cc aldehyt R
1
CH=O c tn to ra c mch
cacbon ngn hn axit amin nguyn thu mt cacbon. Cc aldehyt ny do bn cht
cc axit amin nguyn thu quyt nh. Nh vy cng c nghi l hng thm cu
cc bn thnh phm hay thnh phm l do cc axit amin quyt nh.
Thc nghim cho thy rng t lxin s cho aldehyt c mi thm cu bnh
m, t glyxin s cho aldehyt c mi mt v mi thm bia, t valin v phenylalanin
s cho aldehyt c mi thm du cu hoa hng v.v.
3.4.2 Phn ng quinonamin l ngun tn to ra cc aldehyt
Cc aldehyt cn c tn to nn do tng tc cu axit amin vi polyphenol
khi c s xc tc cu enzym polyphenoloxydase hoc trong iu kin nhit cao.
S phn ng nh trong hnh 3.2. T y chng ta thy aldehyt c tn to nn
c mch cacbon b hn mch cacbon cu axit amin nguyn thu mt nguyn t
cacbon. Nh vy, trong trng hp ny axit amin cng ng vai tr quan trng
trong vic to ra hng mi cu sn phm.
Trong thc t, khi ch bin nhit, cc bn thnh phm ch cha c ln
men, ngi ta nhn thy rng hm lng cc axit amin nh alanin, phenylalanin,
valin, lxin, izolxin b gim i, trong khi hm lng cc aldehyt: axetaldehyt,
phenylaxetic, butyric v valerianic tng ln mt cch tng ng.
Trong iu kin khng gia nhit, nhng c s xc tc cu enzym
polyphenoloxydase, phn ng ny cng xy ra mt cch d dng. l trng hp
khi ln men cc l ch qua gia on v.
3.4.3 Tng tc gi axit amin v axit ascorbic l ngun tn to cc aldehyt
Ngi ta cn nhn thy rng, cc aldehyt c th c hnh thnh nn do
tng tc cu axit amin vi axit ascorbic khi c mt catechin (polyphenol), ion Cu
2+

hoc khi gia nhit n 80-90
o
C. y r rng cng l phn ng oxy ho deamin
ho cc axit amin. Chng ta u bit, di tc dng cu Cu
2+
, nhit axit
ascorbic b oxy ho n axit dehydroascorbic. Axit dehydroascorbic cng l mt
reducton, do c th tng tc vi cc axit amin tn to ra cc aldehyt khc
nhau:

Phn ng Maillard c vai tr rt quan trng trong sn xut bnh m v sn
xut bia. Cc bin php k thut tng ng khi nng bnh m cng nh khi sy
malt u nhm to ra hng thm c trng cho nhng sn phm .
Chng hn, hng thm cu bnh m c tn to nn sau khi nng l mt
hn hp gm 70 cu t thm, trong quan trng l furfurol, oxymetylfurfurol v
aldehyt valerianic.
Trong sn xut ch th phn ng quinonamin li c bit quan trng. Ngi
ta thy rng mi thm c th c tn to trong giai on lm ho v (ln men).
Nhng mi thm c trng cu cc sn phm ch th c tn to trong giai on
sy. Chng hn, trong sn phm ch ngi ta tm thy 34 cu t thm khc nhau,
trong c aldehyt phenylaxetic, aldehyt izovalerianic, geraniol, ru benzylic
Cc cht thm tng hp
Mt s cht thm tng hp sau y thng c dng to hng thm
cho cc sn phm thc phm:

3.5 Cc hnh thm (t hp thm)
3.5.1S to ra hnh thm
Mt hn hp cc cu t tng tc hi ho vi nhau qua mi cu cc cu
t n th b bin i i tn to ra mt mi thm nht nh, gy cho khu gic
mt cm gic d chu gi l mt hnh thm.
Trong mt hnh thm, hm lng v vai tr cu cc cu t khng ging
nhau. C nhng cu t cn c mt vi mt lng nhiu nhng cng c cu t thm
ch ch cn dng vt. C nhng cu t c vai tr quyt nh hng thm ch yu
cu hnh thm gi l cht nn thm. Cht nn thm trong mt hnh thm c th l
mt cu t thm n th (v d, ionon cho mi hoa tm) hoc l hn hp cu mt s
cht thm n th hoc l t hp mt vi mi n gin. C nhng cu t thng
vi lng rt nh nhng c tc dng lm tng hay gim hng, lm cho hnh thm
c ho hp hon ton, nghi l to ra s hi ho cho hnh thm. Nhng cht ny
thng l indol, scatol, metylheptylxetol, phenyletylaxetatNgoi ra li c cu t
ng vai tr cht nh hng to kh nng gi c mi thm cu hnh thm. Cht
nh hng thng l cc nha v bazam (nha benzoic, styrat), mus v xibec
(ng vt, tinh du tuyt i, cc cht hu c kt tinh (vanin, mus nhn to), cc
cht tng hp (dietylphtalat, benzylbenzoat). Cc cht nh hng dng nha lm
cho dung dch c nht cao. Chng li l h keo phn tn nn c kh nng hp th
nng lng, khin cho s di chuyn cu dung mi v cc cht d bay hi ln b
mtj cu dung dicjh b cn tr v khng nng lng thng ma st ni ti. Cn
nhng cht nh hng dng tinh th c kh nng hp th mt lng ln cht thm
d bay hi ln b mt mng tnh th. Nh vy, chung quy cht nh hng c tc
dng lm thay i p xut ring cu hn hp v iu chnh s bay hi cu cc cu
t.
Chng hn hnh thm cu hoa nhi gm 15 cu t khc nhau.
3.5.2 Cc tng tc to ra hnh thm
Trong qu trnh phi hp cc cu t tn to ra hnh thm, cc tng tc l
hc hoc ho hc c vai tr quan trng.
Tng tc l hc gy ra hin tng to cn v lng xung.
Tng tc ho hc xy ra gia cc cu t thm vi dung mi v gia cc cu
t thm vi nhauCc tng tc ho hc c th biu din di dng nhng
phn ng sau.
3.5.2.1 Phn ng cu dung mi vi cu t thm
Dung mi thng l ru, nn c th phn ng vi aldehyt, xeton v este.
V d:

3.5.2.2 Phn ng oxy ho
Phn ng oxy ho rt quan trng c nh hng n cht lng cu hnh
thm.


Chng hn do phn ng oxy ho xitral v aldehytdexylic m mi cu tinh
du chanh b thay i v nht tng ln do axit to thnh xc tc cho qu trnh
polyme ho cc terpen v sesquiterpen.
Cc aldehyt cng c th oxy ho kh di tc dng cu vt kim to ra
este:

C trng hp phn ng oxy ho c nh hng tt n hng:

3.5.2.3 Phn ng ngng t
Xy ra khi trong hnh thm c cc cht cha cc nhm nh chc khc nhau
(hoc cng cha nhm nh chc c kh nng phn ng)

3.5.2.4 Phn ng chuyn este:

Qu trnh tn to ra mt hnh thm c th chia thnh ba giai on:
- Giai on u hay giai on tui tr, lc ny mi cu hnh thm cha
hon chnh, cng v sc thi km, mi khng chnh xc;
- Giai on pht tri, lc ny mi cu hnh thm hon chnh, n nh v
cc i, hon ton p ;
- Giai on gi, giai on ny mi v gim v xu i.
Trong thc t, da vo kinh nghim ngi ta to ra c nhng hnh
thm thch ng dng cho nc hoa, phn sp, x phng thm v thc phm. c
bit, cc hnh thm dng cho thc phm (ko, bnh, nc gii kht) i hi cc
cu t phi c tinh khit cao.