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Chng 1
Trao i cht v nng lng sinh hc
1.1. Khi nim chung v trao i cht
Mi c th sng u tn ti trong mi trng v lin h mt thit vi
mi trng . Hin tng c th ly mt s cht t mi trng kin to
nn sinh cht ca mnh v thi ra ngoi nhng cht cn b c gi l s
trao i cht.
S trao i cht gii v sinh khc vi gii hu sinh. gii v
sinh, trao i cht lm cho cc cht hu c v v c b phn hu. V d,
vi (canxi carbonate) b xi mn v H
2
CO
3
c trong nc tc dng vi
vi thnh canxi bicarbonate, m b i ho thnh mt s cht khc l do tc
dng vi oxy.
th gii sinh vt, mi c th sng lun lun trao i cht vi mi
trng, ly thc n vo chuyn ho thnh cc cht s dng cho c th v
thi ra ngoi cc cht cn b. Qu trnh c thc hin l do cc bin
i ho hc lin tc xy ra trong c th. Ton b cc bin i ho hc
c gi l s trao i cht.
Qu trnh trao i cht gm nhiu khu chuyn ho trung gian. Mi
chuyn ho l mt mt xch ca mt trong hai qu trnh c bn: ng ho
v d ho.
ng ho v d ho l hai qu trnh i lp, nhng li thng nht vi
nhau trong mt c th: chng xy ra ng thi v lin quan mt thit vi
nhau. Cc cht c tng hp nn trong qu trnh ng ho l nguyn liu
cho qu trnh d ho (v d gluxit l sn phm ca qu trnh quang hp, l
nguyn liu cho qu trnh h hp). Nng lng gii phng ra trong qu
trnh d ho c s dng mt phn cho qu trnh tng hp.
1.2. Nng lng sinh hc
H thng sng cn nng lng chuyn ng, ln ln, tng hp
cc phn t sinh hc v vn chuyn ion, phn t qua mng.
Cc c th ly nng lng t mi trng sng v s dng nng
lng thc hin cc qu trnh sng c hiu qu.
nghin cu nng lng sinh hc i hi phi c hiu bit v
nhit ng hc, mt s nh lut, nguyn l m t ngun, trao i nhit,
nng lng v vt cht trong h thng nghin cu.
2
Nhit ng hc cho chng ta xc nh qu trnh ho hc v phn ng
c th t xy ra hay khng.
Mc d nhit ng hc l khi nim phc tp, nhng n da trn ba
nh lut tng i n gin v d hiu.
Mt vi nguyn l ca nhit ng hc c bn c a ra trong
chng ny bao gm phn tch ngun nhit, sn sinh entropy, hm nng
lng t do v mi lin quan gia entropy v thng tin.
Chng ny cng cp n ATP v nhng hp cht cao nng
khc.
Khi nim v nhit ng hc c bn
Bt k s quan tm no ca nhit ng hc cng phi phn bit gia
h thng v mi trng.
H thng l mt phn ca v tr m chng ta quan tm, trong khi
mi trng l gm tt c nhng g cn li. C ba trng thi c bn: h
thng c lp, h thng ng v h thng m.
H thng c lp: Khng c s trao i cht v nng lng vi mi
trng.
H thng ng: C trao i nng lng, nhng khng c trao i
cht vi mi trng.
H thng m: C trao i cht v nng lng vi mi trng.
C th sng l h thng m in hnh c trao i cht (dinh dng
v sn phm thi ra) v nng lng (nhit t trao i cht) vi mi trng.
nh lut 1: Nhit, cng v cc dng nng lng khc
Trc y trong s pht trin ca nhit ng hc ngi ta cho rng
nhit c th bin i thnh nhng dng nng lng khc v tt c cc
dng nng lng mt cch c bn c th bin i thnh mt s dng khc.
nh lut 1 ni rng: tng nng lng ca mt h thng c lp l
khng thay i.
Cc nh nhit ng hc m phng thnh mt hm ton hc
nghin cu s bin i nhit v s dng cng trong nhng h thng nhit
ng hc. Hm ny c gi l nng lng ni nng, thng k hiu l E
hoc U. Nng lng ny ch ph thuc vo trng thi hin ti ca mt h
thng v v vy c coi l hm trng thi. Nng lng ni nng khng
ph thuc vo h thng xy ra nh th no v v vy khng ph thuc vo
ng hng. Ni mt cch khc l chng ta c th thay i h thng
bng bt c con ng no v cho n khi no h thng tr v trng thi
ban u, nng lng ni nng s khng thay i.
Nng lng ni nng, E ca h thng c th thay i nu ngun
nng lng vo hoc ra khi h thng dng nhit hoc cng cho qu
3
trnh no bin i mt trng thi ny (1) sang mt trng thi khc (2) thay
i nng lng ni nng l:
E = E
2
- E
1
= q + w (1.1)
q l lng nhit c h thng hp th t mi trng
w l cng thc hin trn h thng do mi trng
Cng c hc c nh ngha l s chuyn ng t ch ny n ch
khc, gy ra do s dng lc. C hai phi xy ra cng mi c thc hin.
V d: Mt tu ch khch cha y khch nhng khng di
chuyn, theo nh ngha nhit ng hc cng khng c thc hin.
Trong h thng ho sinh hc v ho hc cng thng lin quan vi
p sut v th tch ca h thng. Cng c hc c xc nh w = -P V
Trong P l p sut, V l s thay i th tch, V = V
2
-V
1
Cng c th c thc hin nhiu dng: c hc, in, t v ho hc.
E, q, w phi c cng n v: calorie (cal) v kilocalorie (kcal) c s
dng theo truyn thng, nhng theo n v SI: Joule c ngh nn
dng.
Enthalpy: Hm c nhiu tin li cho h thng sinh hc
Nu nh ngha cng c gii hn bi cng c hc, trong trng
hp ny E ch l thay i nhit th tch khng i. V vy nu V khng
i, cng khng c thc hin. E = q. V vy E l mt nh lng rt
tin li trong qu trnh th tch khng thay i. E khng cn thit bng
bin i nhit. V l do ny cc nh ho sinh hc, ho hc xc nh mt
hm c bit ph hp cho qu trnh p sut khng i. N c gi l
enthalpy, H c nh ngha: H = E + PV (1.2)
Nu p sut khng thay i chng ta c:
H = E + P V = q + w + P V = q - P V + P V = q (1.3)
R rng H tng ng vi bin i nhit trong qu trnh p sut
khng i.
V cc phn ng ho sinh thng xy ra trong th lng hoc rn hn
l th kh nn thay i th tch l nh v enthalpy v nng lng ni nng
thng l nh nhau.
thun li khi so snh cc ch s nhit ng hc ca cc phn ng
khc nhau th ngi ta xc nh iu kin tiu chun. Mt dung dch
ho tan trng thi tiu chun, thng s dng n v n gin l nng
1M. Enthalpy, nng lng ni nng v nhng nh lng nhit ng
hc khc thng a ra hoc xc nh cho nhng iu kin tiu chun v
c k hiu l H
0
, E
0
...
Enthalpy thay i cc qu trnh ho sinh c th c xc nh
bng vic o nhit hp th (hoc to ra) bng mt calorimeter.
4
Mt khc cho bt k qu trnh no A B trng thi cn bng, s
thay i enthalpy trng thi tiu chun c xc nh t s ph thuc
vo nhit v h s cn bng:
d (ln K
eq
)
H
0
= ---------------- (1.4)
d (1/T)
Hnh 1.1 S thay i enthapy, H
0
ca 1 phn ng c xc nh
dc ca s RlnKeq ngc vi 1/T. minh ha phng php ny nhng
gi tr hai bn ca 327K (54,5
0
C) c nu ra. S liu c s dng tnh
H
0
54,5
0
C.
y R l hng s kh = 8.314 J/mol K
V d: trong s bin tnh nhit ca protein chymotripsinogen (qu
trnh thun nghch).
Trng thi nguyn thu (N) Trng thi bin tnh (D)
K
eq
= D / N
John F. Brandts o hng s cn bng cho s bin tnh ca mt s
protein mt s gi tr pH v nhit khc nhau (bng 1.1).
Gi tr H
0
c ngha g i vi bin tnh ca protein? Gi tr
dng ca H
0
biu din s b gy lin kt hydro cng nh gii phng
-3,21-(-17,63)
=14,42
1000
T
(K
-1
)
2,98 3,00 3,02 3,04 3,06 3,08 3,10
30
20
10
0
-10
-20
-30
R
l
n
K
e
q
3,04-3,067
=-0,027
54,5
o
C
5
nhng nhm a nc t bn trong phn t protein ban u trong qa trnh
bin tnh, nh vy s nng nng lng ca dung dch protein.
Bng 1.1 Cc ch s nhit ng hc cho s bin tnh protein
Protein
(v iu kin)
H
0
kJ/mol
S
0
kJ/mol.K
G
0
kJ/mol
G
p
kJ/mol.K
Chymotrypsinogen
(pH 3; 25
0
C)
164 0,440 31 10,9
b- Lactoglobulin (5 M
urea; pH 3; 25
0
C)
-88 -0,300 2,5 9,0
Myoglobin (pH 9;
25
0
C)
180 0,400 57 5,9
Ribonuclease (pH 2,5;
30
0
C)
240 0,780 3,8 8,4
nh lut th hai v entropy:
nh lut th hai ca nhit ng hc c m t v th hin trong
nhiu cch bao gm nhng im sau:
H thng c xu hng tin t trng thi trt t sang trng thi khng
trt t (tng entropy).
Entropy ca h thng + mi trng l khng i bi qu trnh thun
nghch. Entropy ca h thng + mi trng tng do qu trnh khng thun
nghch.
Tt c cc qu trnh xy ra trong t nhin hng ti trng thi cn
bng, l trng thi nng lng nh nht.
Mt s im ca nh lut 2 dn n khi nim entropy, l thc
o s mt trt t ca h thng, trong trng thi mt trt t l trng thi
c entropy cao.
Entropy c th c xc nh theo mt vi cch. Nu W l s cch
sp xp thnh phn ca mt h thng m khng thay i nng lng
ni nng hoc enthalpy ( l s lng ca trng thi knh hin vi c
a ra nhit , nh sng v tng vt cht). Entropy c tnh:
S = klnW (1.5)
k l hng s Boltzmann = 1,38.10
-23
J/K
nh ngha ny tin li cho tnh ton thng k, nhng dng ph bin
hn lin quan entropy n s bin i nhit trong mt qu trnh l:
dS
thun nghch
=
T
dQ
(1.6)
6
dS
thun nghch
l thay i entropy ca h thng trong mt qu trnh
thun nghch,
q l nhit c bin i, T l nhit s bin i nhit xy
ra.
nh lut 3: Ti sao0 tuyt i quan trng nh vy?
nh lut 3 ca nhit ng hc ni rng: entropy ca bt k cht no
hon ton c trt t, tinh th phi tin n 0. nhit tin n 0 K v T=
0 K entropy chnh xc = 0. Da trn iu ny c kh nng thit lp mt h
thng t l entropy tuyt i, s lng
S = Cp
T
0
dlnT (1.7)
Cp: kh nng bin i nhit p sut khng i. Kh nng nhit ca
mt cht l tng s nhit ca 1M c th d tr khi nhit ca cht
c nng ln 1 . i vi qu trnh p sut khng i n c m t
bng ton hc
Cp =
dt
dH
(1.8)
Nu kh nng nhit c th c tnh tt c nhit gia 0 K v
nhit no , entropy tuyt i c tnh i vi qu trnh sinh hc
thay i entropy c nhiu tin li hn entropy tuyt i. Thay i entropy
cho mt qu trnh c th c tnh nu thay i enthalpy v nng lng t
do bit.
Nng lng t do: Mt gi thuyt nhng l cng c tin li
Mt cu hi quan trng i vi nh ho hc, c bit i vi nh
ho sinh hc l: Phn ng s xy ra theo hng t phi sang tri? Gibbs,
mt trong nhng ngi xy dng nn nhit ng hc nhn thy cu tr li
cho cu hi ny nm trong s so snh thay i enthalpy v thay i
entropy mt nhit no , nng lng t do Gibbs c nh ngha
nh sau:
G = H - TS (1.9)
Cho bt k qu trnh A B nhit v p sut khng i.
S thay i nng lng t do c tnh:
G = H - T S (1.10)
Nu G gn = 0 qu trnh cn bng, khng i theo hng thun
hoc ngc li khi G = 0
S = H/T v thay i enthalpy v entropy l cn bng chnh xc.
Bt k qu trnh vi G khc 0 thc hin t ng n trng thi cui cng
7
c nng lng t do thp. Nu G m th qu trnh xy ra theo hng t
tri sang phi.
Nu G 0 phn ng xy ra theo hng ngc li (k hiu v gi
tr ca G cho php xc nh qu trnh s xy ra nhanh nh th no). Nu
qu trnh c G m th qu trnh t xy ra, nu G dng th qu trnh
khng t xy ra (hay t xy ra theo chiu nghch).
Thay i nng lng t do tiu chun
Thay i nng lng t do G cho bt k phn ng no ph thuc
vo cht tham gia phn ng v sn phm phn ng v cng b nh hng
bi iu kin phn ng k c nht , p sut v pH v nng ca cht
phn ng v sn phm.
Nu thay i nng lng t do cho mt phn ng l nhy cm vi
iu kin ho tan, iu g c bit c ngha cho s thay i nng lng
t do trng thi tiu chun. tr li cho cu hi ny xem xt mt phn
ng gia hai cht A v B to nn sn phm C v D
A + B C + D (1.11)
Thay i nng lng t do cho nng khng trng thi tiu
chun l
G = G
0
+ RT ln
[B] [A]
[D] [C]
(1.12)
[B] [A]
[D] [C]
= K
eq
trng thi cn bng G = 0
Chng ta c
G
0
= - RT ln K
eq
(1.13)
hoc logarit c s 10
G
0
= - 2,3 RT/ log
10
K
eq
(1.14)
N c bin i K
eq
=10
- G/2,3 RT
(1.15)
Trong bt c dng no mi lin h cho php xc nh thay i nng
lng t do tiu chun cho bt k qu trnh no nu hng s cn bng
c bit.
Quan trng hn, iu ni rng cn bng thit lp cho mt phn
ng trong dung dch l mt hm ca s thay i nng lng t do tiu
chun cho qu trnh, ngha l G
0
l cch vit khc ca hng s cn bng.
8
V d hng s cn bng xc nh bi Brandts mt s nhit vi
s bin tnh ca chymotrypsinogen c th c dng tnh s thay i
nng lng t do cho qu trnh bin tnh. V d h s cn bng 54,5
0
C l
0,27, nh vy
G
0
= - (8,314 J/mol. K (327,5K) ln (0,27)
G
0
= - (2,72 kJ/mol . ln (0,27)
G
0
= 3,56 kJ/mol
K hiu dng ca G
0
ngha l qu trnh bin tnh khng u th.
Dng gp l dng bn ca protein 54,5
0
C. Mt khc ln tng i
nh ca G
0
ngha l dng gp chim u th nh.
50 52 54 56 58 60 62
10
8
6
4
2
0
-2
-4
-6
-8
-10
G
,
k
j
/
m
o
l
Nhit
o
C
9
Hnh 1.2 S ph thuc ca G
0
vo nhit nhit trong qu trnh
bin tnh ca chymotrypsinogen
Hnh 1.2 ch s ph thuc ca G
0
vo nhit bin tnh pH = 3.
Tnh c H
0
v G
0
ca s bin tnh chymotrypsin, c th tnh S
0
s dng phng trnh (3.10).
S
0
=
T
) H G (
0 0
(1.16)
54,5
0
C (327,5 K)
S
0
= - (3560 - 533,000 J/mol) / 327,5 K
S
0
= 1,620J/mol.K
Hnh 1.3 biu din s ph thuc ca S
0
vo nhit bin tnh ca
chymotrypsin pH = 3. Gi tr dng S
0
ch rng dung dch protein
tr nn khng trt t khi protein b bin tnh. So snh gi tr 1,62 kJ/mol.K
vi gi tr S
0
bng 1.1 ch ra rng gi tr hin ti cho chymotrypsin
54,5
0
C l hon ton ln. ngha vt l ca ch s nhit ng hc cho s
bin tnh ca chymotrypsin s r hn trong phn sau.
ngha vt l ca c tnh nhit ng hc
Nhng ch s nhit ng hc cho ta bit nhng hin tng sinh ho
g? Cch tt nht tr li cu hi ny l mt ch s ring r (v d H
hoc G
) khng c nhiu ngha. Mt gi tr dng H
0
cho s bin tnh
ca mt protein c th phn nh hoc l s gy cc lin kt hydro trong
protein hoc s xut hin cc nhm a nc ra bn ngoi. Tuy vy s so
snh mt s ch tiu nhit ng hc c th cung cp nhng hiu bit bn
trong c ngha v mt qu trnh.
52 54 56 58 60
2,4
2,3
2,2
2,1
2,0
1,9
1,8
1,7
1,6
1,5
1,4
G
,
k
j
/
m
o
l
-
K
Nhit
o
C
10
Hnh 1.3 S ph thuc ca S
0
vo nhit trong qu trnh bin tnh ca
chymotrypsinogen
nh hng ca nng n thay i nng lng t do thc t
Phng trnh (3.12) ch ra rng thay i nng lng t do i vi
mt phn ng rt khc nhau so vi gi tr trng thi tiu chun nu nng
ca cht phn ng v sn phm khc vi nng hot ng (1M cho
dung dch).
Xem xt s thu phn ca phosphocreatine:
Phosphocreatine + H
2
O Creatine + Pi
Phn ng ny to nhit rt mnh v G
0
37
0
C l -42,8 kJ/mol
Nng sinh l ca phosphocreatine, creatine v Pi thng l gia 1
mM v 10 mM.
Cho rng nng 1 mM v s dng phng trnh (3.12) G
cho
thu phn phosphocreatine l
G
= - 42,8 kJ/M + (8.314J/M) (310 K)
] 001 , 0 [
] 001 , 0 ][ 001 , 0 [
ln
G
= - 60,5 kJ/M
37
0
C s khc nhau gia trng thi tiu chun v nng 1 mM
cho mt phn ng nh vy l khong -17,7 kJ/mol
Tm quan trng ca cc qu trnh kt hp trong c th sng
Nhiu phn ng cn thit gi t bo v c th chng li th nhit
ng hc, l theo hng G
dng.
Trong c s tng hp ATP v nhng phn t cao nng khc v
to nn gradient ion trong tt c t bo ng vt c v. Nhng qu trnh
ny c thc hin theo hng bt buc nhit ng hc.
11
Bng s kt hp vi cc qu trnh c kh nng t xy ra nhiu qu
trnh gn lin vi nhau c cp phn sau ca chng ny. Chng rt
quan trng trong trao i cht trung gian, phosphoryl ho oxy ho v vn
chuyn qua mng.
Chng ta c th on nhng cp phn ng kt hp s xy ra t ng
bng s thay i tng nng lng t do cho mi phn ng. V d, xem xt
phn ng t qu trnh ng phn lin quan n s bin i
phosphoenolpyruvic acid n pyruvat. S thu phn PEP gii phng nng
lng v c s dng phosphoryl ho ADP thnh ATP, mt qu trnh
m v mt nng lng khng t xy ra.
1.2.1 c tnh nng lng ca s trao i cht
Nng lng ca cc qu trnh trao i cht (nng lng sinh hc)
khc vi nng lng c thc hin trong bn cht khng sng ba c
im sau y:
c tnh th nht l s chuyn ho nng lng thnh cng v thnh
nhng dng khc m khng km theo s chuyn ho s b nng lng ny
thnh nhit nng. Xut pht t nguyn tc ny chng ta cn xem h thng
sng nh l mt ng c ho ng hc ch khng phi l ng c nhit.
c tnh th hai l vic gii phng nng lng trong cc qu trnh
oxy ho sinh hc sinh ra t t, tng phn mt, trong mt chui di cc qu
trnh k tip nhau cho n khi no tt c cc nguyn t hydro v cacbon
u bin thnh cc sn phm cui cng l CO
2
v H
2
O. V d s oxy ho
mt phn t gam ng gii phng ra 686 kcal. Nu nng lng ny c
gii phng ra cng mt lc th s gy ting n v h thng sng khng th
s dng ton b nng lng trong mt khong thi gian ngn nh vy.
12
Hnh 1.4 Tin trnh gii phng nng lng ho hc trong s trao i cht
c chia lm 3 giai on
c tnh th ba l nng lng ho hc c gii phng ra khi phn
gii glucid, lipid v nhng hp cht cao phn t khc u c th c tch
lu trong nhng hp cht tch tr nng lng c th, c gi l hp cht
cao nng.
Tin trnh ca vic gii phng nng lng ho hc c bn c chia
lm 3 giai on (hnh 1.4):
Giai on th nht cc hp cht cao phn t (tinh bt, glycogen,
proteine, lipid...) b thu phn thnh cc cht c phn t b
Protein Polysaccharide Lipid
Aminoacid ng n
Glycerin v
acid bo
Glucose
Pyruvate
Acetyl CoA
Giai on 1:
B gy cc i phn t
thnh cc n phn t
Giai on 2:
Phn gii cc n phn t thnh
Acetyl CoA, to ra ATP v NADH
mc nht nh
Giai on 3:
Oxy ha hon ton Acetyl CoA
thnh H
2
O v CO
2
, gii phng
mt lng ln NADH v ATP
ty th
Mng t
bo sinh
vt nhn
chun
Mng
ty th
Chu trnh
citric acid
13
(monosaccharide, amino acid, axit bo, glycerine...). Nng lng gii
phng ra trong giai on ny khng ng k, ch bng gn 1% d tr nng
lng t do ca cc cht ny c gii phng ra di dng nhit.
Giai on th hai l qu trnh ng phn, oxy ho cc axit bo v
cc amino acid. Nng lng gii phng ra trong giai on ny gn bng
1/3 nng lng t do d tr trong cc cht . Sn phm chnh ca giai
on ny l acetyl-CoA, -xetoglutaric acid v oxaloaxetic acid.
Giai on th ba l oxy ho tip tc cc cht trn trong chu trnh
Krebs. Khong 2/3 nng lng c gii phng ra giai on ny.
1.2.2 Cc hp cht cao nng
Nhng hp cht cao nng: Tt c s sng trn tri t ph thuc vo
nng lng mt tri, trong nhng dng sng c mt h thng th bc v
nng lng. Mt s tip nhn nng lng mt tri trc tip, mt s khc
nhn nng lng t nhm trn trong nhng qu trnh tip theo.
Nhng sinh vt hp thu nng lng nh sng trc tip c gi l c
th t dng. Nhng c th ny d tr nng lng mt tri trong cc phn
t hu c khc nhau. Nhng sinh vt s dng nhng phn t , gii
phng nng lng d tr trong mt lot cc phn ng oxy ho kh c
gi l sinh vt ho dng.
Mc d khc nhau c hai loi u c c ch chung v ti sinh mt
dng nng lng ho hc, nng lng c th c gii phng trong nhng
phn ng to nhit thc hin cc qu trnh sng a dng (cn nng
lng).
Mt nhm nh cc phn t l cht trung gian chuyn nng lng t
cc phn ng gii phng nng lng n cc phn ng cn nng lng ca
c th. Nhng phn t ny l coenzyme dng kh, nhng hp cht
phosphate c gi l cao nng nu chng gii phng ra nng lng t do
c gi tr m ln khi thu phn ( G
0
c gi tr m ln hn -25 kJ/M).
bng 1.2 sau y l danh sch nhng hp cht cao nng quan
trng nht, nhng phn t nh phosphoric anhydric (ATP, ADP), enol
phosphate (PEP), acyl phosphate (acetyl phosphate), guanidinophosphate
(creatine phosphate). C nhng hp cht thioeste, nh acetyl CoA khng
cha phospho nhng gii phng mt nng lng t do ln khi thu phn.
14
Bng 1.2 Nng lng t do gii phng khi thy phn mt s cht cao nng
Cc cht G
o
(kJ/mol) Cng tc cu to
Phosphoenolpyruvat (Pyruvate + P
i
) -62,2
3,5-Cyclic adenosin monophosphate -50,5
(5-AMP)
1,3-Bisphosphoglycerate -49,6
(3-phosphoglycerate + P
i
)
Creatine phosphate -43,3
(creatine + P
i
)
Acetyl phosphate (acetate + P
i
) -43,3
Adenosine-5 triphosphate -35,7
(ADP + P
i
)
Adenosine-5 triphosphate -30,5
(ADP + P
i
) (nng Mg
++
qu cao)
Adenosine-5 diphosphate -35,7
(AMP + P
i
)
P
15
Tng s nng lng chnh xc gii phng ra khi thu phn ph thuc vo
nng , pH, nhit ... nhng gi tr G
0
khi thu phn nhng hp cht
ny c gi tr dng ln hn ng k so vi nhng cht trao i khc.
Chng c hai c im quan trng:
Nhng cht phosphate cao nng (high- energy phosphate
compounds) khng phi l cht d tr nng lng lu di, chng l nhng
cht chuyn tip nng lng d tr, l cht mang nng lng t im ny
sang im khc, t mt h thng ny n mt h thng khc.
Nng lng hot ho c cung cp ng k t ATP khi thu phn
nhm -phosphat.
Nng lng lm gy lin kt O-P thng l 200-400 kJ/M, ln
hn ng k so vi 30,5 kJ/M khi thu phn ATP.
Cc nh ho sinh hc quan tm nhiu n nng lng gii phng
thc t.
Vai tr trung tm ca ATP trong nng lng sinh hc
ATP cha hai pyrophosphoryl (hnh 1.4). Nhng phn t c lin kt
anhydric, ADP, GTP, GDP v cc nucleoside triphosphate khc,
nucleotide-ng nh UDP-glucose v pyrophosphate v c th hin nng
Cc cht phosphate G
o
(kJ/mol) Cng tc cu to
nng lng thp hn
Glucose-1-P (glucose+ P
i
) -21,0
Fructose-1-P (fructose+ P
i
) -16,0
Glucose-6-P (glucose+ P
i
) -13,9
Glycerol-3-P (glycerol+ P
i
) -9,2
Adenosine-5 monophosphate -9,2
(adenosin + P
i
)
16
lng t do G
0
ln khi thu phn. Nguyn nhn ho hc ca gi tr G
0
m ln l do s khng bn vng ca cht phn ng do s cng lin kt gy
ra bi s y tnh in. S bn vng ca sn phm phn ng do s ion
ho, s cng hng v nhng yu t entropy gy ra do thu phn v s ion
ho tip theo.
Mc d PEP, cyclic AMP, 13 DPG, phosphocreatine,
acetylphosphate v pyrophosphate u c gi tr G
0
ln hn, nhng ATP
l duy nht nh v gia cc cht phosphate cao nng, (ATP c tng hp
khi phn gii cc cht hu c) v cc cht nhn nng lng (khi cc cht
ny c phosphoryl ho tham gia cc phn ng tip theo trong trao
i cht). Ni mt cch khc ATP l mt xch ni lin hai qu trnh ngc
nhau, l ng ho v d ho.
Vic hnh thnh tt c cc hp cht cao nng khc cng xy ra do s
tiu ph nng lng vn tch lu trong ATP.
ADP c th nhn c phosphate v nng lng t cc phosphate cao
nng.
ATP cho c gc phosphate v nng lng i vi cc phn t c
nng lng thp. Nh vy ATP c vai tr d tr nng lng cng nh tiu
hao nng lng.
Xt v c ch bin i v chuyn ho nng lng trong s phn gii ATP
v cc hp cht cao nng tng t ATP ta thy nng lng cn thit
thc hin phn ng ho hc c gii phng ra mt im, c th c
chuyn n mt im khc, y nng lng c s dng mt cch trc
tip. iu ny c ngha l trong c th sng khng nht thit phi tip xc
vi nhau bng cch va chm (c trng cho ngoi c th sng) gia cc
phn t cho v nhn nng lng.
17
Hnh 1.5 Chui ba gc phosphat ca ATP cha 2 lin kt pyrophosphat, c
hai lin kt ny gii phng nhiu nng lng khi thu phn
Cu hi 1. Nng lng sinh hc?
2. Cc ng hng tng hp ATP trong thc vt ?
3. Cc dng hp cht cao nng, cho v d?
Lin kt
Phosphoric anhydride
ATP
(adenosin-5-triphosphate)
Adenosine
AMP
ADP
ATP
1
Chng 2
Vitamin
Vitamin l nhng cht hu c c trng lng phn t b, c cu to
ho hc rt khc nhau v c hot tnh sinh hc nhm m bo cho cc qu
trnh ho sinh v sinh l trong c th tin hnh c bnh thng, v do
, c nh hng rt ln i vi s trao i cht.
Vitamin khng c tng hp ng vt bc cao, v vy chng
phi c tip nhn cng vi thc n. Nhiu vitamin l tin cht ca
cofactor (vitamin nhm B) tham gia vo cc phn ng enzyme, trong khi
nhng vitamin khc tham gia vo qu trnh nhn v iu khin s sao
chp (vitamin A), cc phn ng kh (vitamin C v E), to xng (vitamin
D), ng mu (vitamin K) v.v
Cc vitamin c cu to ho hc rt khc nhau. Thng chng c
phn loi da vo ho tan:
Nhm vitamin ho tan trong nc: B
1
, B
2
, B
6
, B
12
, C, folate,
pantothenate, biotin. Chng c tch lu ch vi lng t. Lng d tha
c thi ra qua nc tiu.
Nhm vitamin ho tan trong cht bo: A, D, E, K. Lng d tha
c tch ly v dn n hin tng tha vitamin (c bit vitamin A v
E).
2.1 Cc vitamin ho tan trong nc
2.1.1 Thiamin (vitamin B
1
)
Thiamin c pyrophosphoryl ho thnh coenzyme
thiaminpyrophosphate (TPP), tham gia xc tc phn ng kh carboxyl ho
bng cch oxy ho v phn ng chuyn nhm aldehyd hot ho. Phn ng
ny ng mt vai tr quan trng trong trao i cht.
TPP l nhm prostetic ca pyruvat-dehydrogenase, pyruvat-
decarboxylase, 2-oxoglutarat-dehydrogenase v transcetolase v nh vy
n tham gia vo qu trnh ng phn, chu trnh citrate, pentose-
phosphate v Calvin.
a. Decarboxylase: xc tc cho phn ng loi nhm carboxyl ca
pyruvic acid, -cetoglutaric acid.
b. Transcetolase: xc tc cho phn ng vn chuyn glycoaldehyd
(CH
2
OH-CO-). V d phn ng chuyn on 2C (C
1
v C
2
) ca
xylulose 5-phosphate n ribose 5-phosphate to thnh
sedoheptulose 7-phosphate v glyceraldehyd-3-phosphate.
2
Sinh tng hp
Hai thnh phn ca thiamine l pyrimidine v thiazol c tng hp
ring v sau c kt hp li vi nhau. Cc ng hng tng hp l
khc nhau sinh vt nhn s v sinh vt nhn chun.
Trong E.coli v S.thyphimurium 5-phosphoribosyl-5-aminoimidazol
(AIR) l tin cht ca pyrimidine. E.coli pyruvat v D-glyceraldehyd l
cc tin cht ca thiazol. Chng lng kt thnh 1-desoxy-D-xylulose, cht
ny c gn cc nguyn t C 4, 4, 5, 6, 7. Ngun gc ca C
2
v N
3
l
tyrosine, nguyn t S bt ngun t cysteine. Pyrophosphatester ca thnh
phn pyrimidine tham gia vo phn ng gn. Bng mt phn ng
pyrophosphoryl ho vitamin c chuyn thnh coenzyme.
B
1
c nhiu trong cm go, gan, thn, Mm ng cc v nm men
l ngun rt giu vitamin ny.
C th ngi hng ngy cn 1-1,5 mg vitamin B
1
. Thiu vitamin
ny nh hng n qu trnh trao i carbohydrate dn n bnh ph
thng, hay cn gi l bnh beri-beri, ri lon thn kinh v nh hng n
chc nng ca tim. B
1
ch bn vi nhit trong mi trng acid, cn trong
mi trng kim n b phn hu nhanh chng khi un nng. Khi oxy ho
B
1
chuyn thnh mt hp cht gi l thiocrome pht hunh quang. Tnh
cht ny c s dng nh lng vitamin B
1
.
Hm lng B
1
trong nguyn liu c th thay i tu thuc iu kin
bo qun v ch bin. V d: go xt k hm lng B
1
b gim 4 ln so vi
ban u. m khi bo qun nguyn liu (thc, go) cng cao, hm lng
vitamin B
1
b gim cng mnh.
2.1.2 Riboflavin (vitamin B
2
)
NH
2
N
H
3
C
CH
2
*
N
S
CH
2
CH
3
H
CH
3
Thiamin (vitamin B
1
)
3
Trc kia B
2
c gi l lactoflavin v ln u tin c tch ra t
sa. Bn cnh nicotinamid-nucleotide NAD
+
v NADP
+
flavin-nucleotide
FAD v FMN l nhng nhm vn chuyn hydro quan trng. Chng tham
gia hn 100 phn ng oxy ho kh. V d, qu trnh kh carboxyl ho
bng cch oxy ho pyruvic acid, oxy ho acid bo, kh amin ho bng
cch oxy ho amino acid... Coenzyme ny c to nn t riboflavin bng
phosphoryl ho (FMN) v tip theo adenyl ho (FAD).
Riboflavin (vitamin B
2
)
N H
3
C
N
NH
N
O
O
H
3
C
CH
2
HC-OH
HC-OH
HC-OH
CH
2
OH
Flavinmononucleotide (FMN)
N H
3
C
N
NH
N
O
O
H
3
C
CH
2
HC-OH
HC-OH
HC-OH
CH
2
OP
4
FAD
Sinh tng hp v bin i
Riboflavin c to nn t GTP v ribulose-5-P trong thc vt, nm
men v nhiu vi sinh vt.
Phn ng tng hp bt u bng vic m vng imidazol ca GTP v
tch ra mt gc pyrophosphate. Bng phn ng kh amin ho, phn ng
kh v tch ra gc phosphate cn li lm xut hin 5-amino-6-
ribitylamino-2,4-pyrimidindion. Phn ng ca cht ny vi 3,4-dihydroxy-
2-butanon-4-P (cht ny xut hin t ribulose-5-P) to nn phn t c hai
vng 6,7 dimethyl-8-ribityllumazin. Hp cht ny kt hp vi 5-amino-6-
ribitylamino-2,4-pyrimidindion thnh riboflavin. Phosphoryl ho
riboflavin to nn flavinmononucleotide (FMN). Bng phn ng adenyl
ho tip theo lm xut hin flavin-adenin-dinucleotide (FAD). S
phosphoryl ho riboflavin ng vt c iu khin chnh xc bng
hormone tuyn gip trng.
5
Thiu vitamin B
2
nh hng n qu trnh oxy ho kh lm nh
hng n qu trnh to nng lng cn thit cho s sinh trng v pht
trin ca c th. Thiu vitamin gy ra nhng ri lon v sinh trng v cc
bnh v da. Tuy nhin nhng bnh ny tng i him.
Nhu cu vitamin B
2
hng ngy ca ngi ln khong 1,4 - 2 mg.
Sn phm phn gii v sn phm thi ra ngi l riboflavin. Cc bc
phn gii khc (c bit vi khun) l hydroxyl ho cc gc methyl v
lm ngn chui ribityl.
Chc nng ho sinh
Guanosin
triphosphate
GTP
Hydrolase II
2-diamino-6-
ribosylamino-3 (3H)-
pyrimidine 3-P
3H
2
O
HCOOH
PP
i
5-diamino-6-ribosylamino-2,4
(1H,3H)-pyrimidinedione 5-P
Pirimidine
Desaminase
H
2
O
NH
3
NADPH
NADPH + H
+
5-diamino-6-ribotylamino-2,4
(1H,3H)-pyrimidinedione 5-P
NADPH + H
+
NADPH
NH
3
H
2
O
Uracil
reductase
5-diamino-6-ribotylamino-2,4
(1H,3H)-pyrimidinedione
H
2
O
P
i
Phosphatase
Ribulose-5-
phosphate
3,4-Dihydroxy-2-
butanone-4-P
6,7-Dimethyl-8-
ribityllumazine
Riboflavin (vitamin B
2
)
P
i
HCOOH
Formate
Mg
++
6,7-Dimethyl-8-
ribityllumazine
synthase
Riboflavin
synthase
6
Chc nng oxy ho kh ca FMN v FAD l do vng isoalloxazin
chu trch nhim. mt phn ng kh hon ton hai in t v hai proton
c tip nhn.
Dng oxy ho ca riboflavin l nhng tinh th vng da cam, hp th
bc sng 370 v 450 nm. Dng kh ca n khng mu v mt tnh hp
th 450 nm. Cc coenzyme flavin nucleotide dng kh cng c th b
oxy ho tr li khi c cc cht nhn in t nh xanh methylen, 2,6-
diclorophenolindophenol
FADH
2
+ xanh methylen FAD + xanh methylen
(dng oxy ho mu xanh) (dng kh khng mu)
C th s dng cc tnh cht trn theo di cc phn ng do flavin
dehydrogenase xc tc.
Tinh th vitamin B
2
dng kh tng i bn vi nhit hn vitamin
B
1
, tuy nhin vitamin ny khng bn di tc dng ca nh sng. Ngc
vi vitamin B
1
, hm lng vitamin B
2
trong go, tht, trng, sa bin i
khng nhiu trong qu trnh bo qun v ch bin.
2.1.3 Pyridoxin (vitamin B
6
)
Pyridoxin (pyridoxol), pyridoxal v pyridoxamine to nn nhm
vitamin B
6
. C 3 dng ny d dng chuyn ho ln nhau. Dn xut ca
vitamin B
6
l pyridoxalphosphate (PLP) l coenzyme ca nhiu enzyme.
Pyridoxal- v pyridoxamin-phosphate l coenzyme quan trng cng tc
ng mt s ln cc phn ng bin i amino acid, v d phn ng
transaminase, decarboxylase v dehydratase. Vitamin B
6
cng l thnh
phn cu to ca phosphorylase xc tc cho phn ng phn gii glycogen.
Ngoi ra vitamin B
6
cn c vai tr quan trng trong qu trnh sinh tng
hp NAD
+
, coenzyme A... Do thiu vitamin ny nh hng n nhiu
qu trnh trao i proteine, saccharide, lipid, dn n ri lon v thn kinh
v trao i amino acid.
Sinh tng hp v bin i
Mt s vi khun, nm men v thc vt tng hp c pyridoxine.
ng vt nhai li cng khng cn c vitamin B
6
trong thc n v vi sinh
vt trong rut ca chng c th tng hp vitamin ny cung cp cho
ng vt ch. Cc ng vt khc cn phi c cung cp vitamin ny t
bn ngoi.
Sn phm ngng t ca pyruvate v D-glyceraldehyd l 1-desoxy-D-
xylulose cung cp nguyn t C 2, 2, 3, 4 v 4. Erythrose 4-P c bin
7
i thnh 4-hydroxy-L-threonine. Hp cht ny cung cp nguyn t C 5,
5, 6 v N-1. Pyridoxine iu khin qu trnh tng hp bng c ch ngc.
Loi hydro ca pyridoxine thnh pyridoxal cho n nay ch c quan st
thy trong vi khun.
ng vt pyridoxine, pyridoxal v pyridoxamine sau khi hp th
c phosphoryl ho nh enzym kinase. Kinase ny b c ch bng sn
phm ca n. Bng phn ng oxy ho pyridoxinephosphate v
pyridoxaminephosphate bin i thnh pyridoxalphosphate. Phn ng ny
cng b c ch bng sn phm ca n.
Lng b sung hng ngy cn thit ngi ln khong 2 mg. S
phn gii bt u bng phn ng do phosphatase xc tc. S phn gii tip
theo ca vitamin ny thc hin bng mt phn ng oxy ho to thnh
carbonic acid-4-pyridoxat, cht khng c hot tnh sinh hc.
2.1.4 Cobalamin (vitamin B
12
)
Cobalamin l mt trong nhng phn t sinh hc khng trng hp
ln nht. Nguyn t coban trung tm gn lin hp vi 6 thnh phn: Bn
thnh phn l pyrrol ca vng corrin, mt thnh phn l nucleotide bt
thng dimethylbenzimidazol v thnh phn th su c th l gc
hydroxyl (vitamin B
12
), gc methyl (methylcobalamin), hoc gc 5-
desoxyadenosyl (desoxyadenosylcobalamin, coenzyme B
12
). Dng vitamin
B
12
trn th trng: thnh phn th 6 l mt gc cyanid.
Sinh tng hp coenzyme v phn ng kh vitamin
Coenzyme B
12
c tng hp nhiu bc trong vi sinh vt. Bc
th nht ging nhau gia hem v chlorophyll. Nhng phn ng tip theo
c nhiu bin i.
H
2
C-OH
HO
H
3
C
CH
2
-O-P
H
H
N
H-C=O
HO
H
3
C
CH
2
-O-P
H
H
N
H
2
C-NH
2
HO
H
3
C
CH
2
-O-P
H
H
N
Pyridoxamine-P
Oxydase
Pyridoxamine-P
Oxydase
O
2
H
2
O O
2
NH
3
H
2
O
2
8
Cobalamin
Sau nhiu bc methyl ho vng porphyrin bin thnh vng corrin.
Sau nhiu ln methyl ho tip theo v amid ho Co
++
c a vo v
c kh thnh Co
+
, ri kt hp vi adenosine. Tip theo -ribazol c
gn vo qua mt cu propionate-aminpropanol v to nn thnh phn th
6 ca Co. Co nm trong phc h lin hp l Co
+++
. ng vt c v nhu
cu B
12
( ngi 10 g/ngy) c p ng do vi khun rut.
hp thu vitamin B
12
t rut cn protein c hiu (50 kDa). Nu
thiu loi protein ny s dn n hin tng thiu vitamin B
12
trm trng
(thiu mu c tnh). vn chuyn trong mu B
12
lin kt vi nhiu
plasmglobulin khc nhau, c gi l transcobalamin. Phn ln B
12
c
tip nhn dng oxy ho (hydroxy-cobalamin, Co
++
). Sau hai bc phn
ng xut hin tr li dng desoxyadenosyl (coenzym B
12
).
Vitamin B
12
tham gia trong thnh phn cu to ca cc enzyme xc
tc cho cc phn ng:
- Phn ng chuyn ribonucleotide thnh desoxyribonucleotide
H
3
C
CH
3
CH
3
CH
3
CH
3
H
3
C
H
3
C
CH
3
H
3
C
NH
NH
2
CH
3
H
3
C
H
2
N
H
2
N
H
2
N
H
2
N
O
NH
2
O
O
O
O
O
O
O
-
O
O
P
N
N N
N
N
N
N
H
H
H
H
O
O HO
HO
Co
9
- Phn ng chuyn nhm methyl
- Sp xp li cc nhm th ca 2 carbon lin nhau trong phn t.
2.1.5 Vitamin H (Biotin)
Biotin l mt vitamin cn thit cho cc phn ng carboxyl ho, c
gn kt ng ho tr vi enzyme bng nhm -amin ca gc lysine.
Sinh tng hp v bin i
Qu trnh tng hp xy ra vi khun (c vi khun rut ca ng
vt), nm men v thc vt bc cao.
Phn t ban u l pimeloyl-CoA. Ngun gc ca phn t ny cha
c gii thch y , c th do s ngng t ca 3 phn t malonyl-CoA
v gii phng ra 2 phn t CO
2
. Tip theo n ngng t vi L-alanine tch
ra pyridoxal-pp, CO
2
v HS-CoA. 8-amino-7-oxopelargonat (7-KAP) xut
hin c bin i thnh 7,8-diaminopelargonate bng mt phn ng do
transaminase xc tc. phn ng ny, S-adenosylmethionine l cht cho
nhm amin (thay v chc nng thng xuyn l cht cho nhm methyl).
Bng s gn CO
2
vo (ph thuc vo ATP) vng imidazol c ng li.
Sau xy ra s gn S (t L-cysteine) v ng vng thiophan. Kt qu l
to nn (+)-Biotin.
S gn kt biotin vo enzyme tng ng cn hot ho bi ATP,
c xc tc bng enzyme c hiu biotin-ligase.
Ngi ln cn 100-200 g/ngy. Biotin c trong nhiu thc phm
v c tng hp bi vi khun ng rut, v vy t khi b bnh thiu
vitamin ny tr khi n nhiu trng sng c nhiu avidin kt hp rt cht
vi biotin, ngn cch vic hp thu n qua rut non.
Biotin
Phn gii bng vi khun
O
HN NH
S
OH
O
10
Pseudomonas c th lm ngn chui bng -oxy ho v nguyn t C
ca vng thiophan c tch ra. Gc ca vng imidazol c thi ra
nc tiu. ng vt c v ch c th tch chui bn v to nn hp cht
sulfoxid. Tuy nhin thnh phn chnh ca biotin c thi ra dng khng
bin i.
2.1.6 Ascorbate (vitamin C)
Vitamin C tham gia vo nhiu phn ng bin i cht v thng c
chc nng bo v.
Sinh tng hp v trao i cht
Vitamin C
Thc vt bc cao, to, nm men v phn ln ng vt c th tng
hp ascorbate. Mt s ng vt c v (ngi) cng nh cn trng, phn
ln cc loi c khng c kh nng ny. nhng ng vt c v cn cung
cp vitamin C, v thiu enzyme L-Gu-ionolacton-oxidase.
Sinh tng hp ng vt v phn ln thc vt t D-glucose v i
qua UDP-glucose, UDP-glucuronate, D-glucuronate, L-gulonate, L-
gulonolacton v 2-dehydro-L-gulonolacton. Vitamin C l sn phm oxy
ho ca cc ng. N c tng hp t glucose ( ng vt v thc vt),
t galactose ( mt s thc vt). Phn t vitamin C c cha en-iol, d
dng b loi hydro to thnh dehydroascorbic acid (cng c hot tnh
vitamin C). Vitamin C mt hot tnh khi vng lacton b thu phn. Trong
t nhin, vitamin C c th tn ti dng lin kt vi cc cht khc, gi l
ascorbigen l dng d tr vitamin C quan trng. Vitamin C ho tan tt
trong nc, dung dch c v acid, c tnh hot quang v c tnh kh mnh.
Ascorbic acid c kh nng kh dung dch Fehling, AgNO
3
. C th s dng
tnh cht ny nh lng ascorbic acid. Ngoi ra, cng c th s dng
vitamin ny lm cht chng oxy ho trong cng nghip thc phm.
Ascorbate i vo cng thc n c vn chuyn n cc c quan
khc nhau. mt s c quan s tip nhn l mt qu trnh ch ng, c
kch thch bi insulin. Nng ascorbate cao nht tm thy nang trn
O
O
OH
OH
HO
HO
11
thn, no thu, mt, gan, d dy v no. Bnh hoi huyt ngi c
ngn nga khi tip nhn 10mg ascorbate/ngy. Ngi ht thuc v ngi
c thai cn nhiu ascorbate hn. Ngi ta khng nh rng, mt liu lng
cao ascorbate tng cng h thng min dch, gim s mt mi v nguy c
bnh ung th. Tuy nhin s phn gii ascorbate xy ra mnh m, v vy
khi lng cn hng ngy l 50 mg th cn a vo c th l 1 500 mg.
Vitamin C c nhiu trong rau qu ti, c bit l cc loi: cam,
chanh, da chut... Vitamin C tham gia trong nhiu qu trnh quan trng
ca c th sng nh:
- Qu trnh hydroxyl ho do oxygenase. V d hydroxyl ho proline,
lysine trong phn t collagen. Thiu vitamin C, collagen mi c
to thnh khng c hydroxyl ho, khng to c dng xon ba
nn c bn km, do da b tn thng v thnh mch mu
mng manh d b v, gy ra bnh hoi huyt. Vitamin C tham gia
trong qu trnh chuyn ho protocollagen thnh collagen nn c tc
dng lm cho vt thng chng thnh so
- Vn chuyn hydro trong qu trnh oxy ho - kh thc vt
- Lm tng tnh khng ca c th i vi nhng iu kin khng
thun li ca mi trng ngoi, cc c t nhim trng. Ngoi ra
vitamin C cn tham gia trong nhiu qu trnh tng hp, chuyn ho
cc cht khc nhau.
- Duy tr cn bng gia cc ion Fe
2+
/Fe
3+
, Cu
+
/Cu
2+
Phn gii v s loi thi
loi linh trng (primat) mt phn ascorbate tn ti trong c th
c thi ra ngoi dng khng bin i qua nc tiu. Nhng sn phm
loi thi khc l oxalate v dioxogulonate (xut hin t dehydroascorbate
bng mt phn ng khng thun nghch v khng xc tc). Ascorbate c
th c oxy ho hon ton thnh CO
2
.
2.2 Cc vitamin ho tan trong cht bo
2.2.1 Retinol (vitamin A)
Vitamin A l tn thng gi cho ru retinol, aldehyd retinal v
retinic acid, chng l nhng isoprenoide c c tnh lipid. Chng tn ti
cc dng ng phn cis v trans khc nhau.
Sinh tng hp v bin i
Tin cht tng hp vitamin l provitamin -carotene, s tng hp
chng xy ra trong thc vt. ng vt c th tch carotene thnh retinal,
bng mt phn ng dioxygenase (xy ra trong rut) v s dng n nh
l vitamin.
12
Vitamin A c hp th vo cng vi cht bo v c tch lu
dng retinylpalmitat trong gan sau khi kh v ester ho. vn chuyn
n nhng c quan khc nhau ester c thu phn v retinol c a
vo mu, n c tip nhn bng mt protein kt hp c hiu vi
retinol. S bin i gia retinol, retinal v retinic acid c thc hin bng
nhng phn ng ph thuc NADP
+
.
Carotene c a vo cng vi thc n ca ngi c ngun gc
trc ht l t thc vt, trong khi retinol c ngun gc ng vt (du gan
c thu). Nhu cu hng ngy i vi ngi ln l khong 1 mg retinol hoc
6 mg -carotene. Thiu vitamin A rt ph bin nhm dn s suy dinh
dng, dn n chng qung g, c ch s pht trin ca xng v s
phn ho m biu b, hn ch s pht trin v chc nng sinh sn.
Chc nng ho sinh
Retinic acid l mt cht iu ho sao chp. Sau khi i qua mng t bo
phn t ny kt hp vi cht nhn c hiu: all-trans-retinic acid vi
RAR-receptor, 9-cis retinic acid vi RXR-receptor. Sau phc h
retinic acid -RAR-RXR kt hp vi hormone c to ra t DNA trong
nhn.
Thuc nhng gen c iu khin theo cch ny l gen m ho cho
protein kt hp vi retinol, enzyme PEP-carboxylase v apolipoprotein
A
1
. Retinic acid cng tham gia vo s iu khin s pht sinh phi v pht
sinh hnh thi ( liu lng nh vitamin A trong thi gian c thai l
nguyn nhn gy qui thai), pht trin, phn ho v kh nng sinh sn.
S bin i t 11-cis thnh all-cis-retinal nh nh sng l c s cho
qu trnh nhn ng vt. Trong vitamin nhm A c 2 dng quan trng l
vitamin A
1
v A
2
. Vitamin A
2
khc vi A
1
ch trong vng c thm mt
ni i gia C
3
v C
4
. Di tc dng ca enzyme retinoldehydrogenase
nhm alcol ca vitamin A d dng b oxy ho n aldehyd (all-cis-retinal,
vn c hot tnh vitamin A). Lin kt i gia C
11
v C
12
ca retinal c th
chuyn thnh dng cis (11-cis-retinal), 11-cis-retinal kt hp vi protein
opxin to nn sc t ca mt l rodopxin. y l protein nhn nh sng
(photoreceptor protein) c trong t bo hnh que ca mng li mt ngi
v ng vt c v. T bo ny hot ng trong nh sng yu, thch nghi
vi bng ti. Khi c nh sng, nhm thm ca rodopxin chuyn t dng
cis sang dng trans nn mt kh nng kt hp vi opxin. Ngc li trong
ti s ti to li dng 11-cis-retinal v rodopxin c tng hp tr li, lm
tng nhy cm ca mt trong nh sng yu.
13
Halobacterium s dng s bin i t all-trans thnh 13-cis-retinal
nh nh sng lm ng lc cho nhng bm proton ca chng.
Retinylphosphate tham gia vo qu trnh sinh tng hp cc
glycosaminoglycane trong cc t bo biu b, y n c chc nng
tng t nh dolicholphosphate. Bng cch ny n tham gia gin tip vo
s ton ven ca mng t bo v ty th, n nh biu b ca da v ca mng
nhy v gim nhng ri lon v pht trin.
2.2.2 Calciferol (vitamin D)
ng vt bc cao nhng sn phm hydroxyl ca vitamin D ng
mt vai tr trung tm trong trao i calcium.
CHO
CH
2
O
H
-carotene
-carotene-15,
15-Dioxygenase
Retinol
dehydrogenase
NADH + H
+
NAD
+
All-trans-Retinal
All-trans-Retinol
(Vitamin A)
Cholecalciferol
(Vitamin D
3
)
CH
3
CH
3
CH
3
CH
2
HO
CH
3
14
Thc t khi nim vitamin D l gm mt nhm cc cht h hng,
khc nhau v ngun gc. Nu ni cht ch th chng khng phi l
vitamin, v da c th tng hp mt trong chng (D
3
) t mt steroid (7-
Dehydrocholesterin, provitamin D) khi c nh sng t ngoi.
Sinh tng hp v s bin i
Cc vitamin D khc nhau c to nn t
5,7
-steroid (sn phm
trung gian tng hp zoo-, phyto- v mycosteroid) bng vic m vng B
nh nh sng. Chng ch khc nhau cc mch bn. Hai vitamin D u
tin sau y l quan trng nht:
- Vitamin D
2
(ergocalciferol): to nn t ergosterin, cht ny tn ti
trong thc vt v nm.
- Vitamin D
3
(cholecalciferol): to nn t 7-dehydrocholesterin, cht
ny c trong ng vt bc cao.
- Vitamin D
4
: xut hin t 22-dihydroergosterin, c trong thc vt
v nm
- Vitamin D
5
: to nn t 7-dehydrositosterin, c trong thc vt.
Tng hp ni sinh
Trong phn ng u tin khi chiu nh sng t ngoi dn n s
ng phn ho ng thi vi vic m vng B ca cu trc sterin, lm xut
hin provitamin D. di bc sng thch hp nht cho quang phn ng
l 295 nm. Chiu sng vi bc sng ln hn s to lumisterin, vi bc
sng ngn hn to tachysterin. nh sng mnh hn xut hin suprasterin
I v II. Vitamin D c to nn do s ng phn ho ph thuc vo nhit
. Vitamin D i vo mu v gn vi protein c hiu (DBP: vitamin D-
bindende-protein).
a vo cng vi thc n:
Mc d s chiu sng c th cung cp y lng vitamin D, vic
b sung thm vn l iu cn thit ( ngi ln 5 g/ngy, tr em 10
15
g/ngy). Sau khi hp th (c h tr bi acid mt) vitamin D c gn
vi chylomikronen hoc DBP v c vn chuyn n gan.
trong gan xy ra s hydroxyl ho C25 bng mt enzyme ph
thuc vo cytochrome P-450. Cht ny c chuyn n thn, y xut
hin hp cht c hot tnh sinh hc 1 , 25-Dihydroxycalciferol (calcitriol,
DHCC) do s hydroxyl ho tip theo v tr C
1
ca cholecalciferol.
S phn gii thc hin bng s hydroxyl ho v/hoc oxy ho nhm
hydroxyl thnh nhm carboxyl. Nhng hp cht ny phn cc mnh hn,
th hin hot tnh sinh hc thp, c thi ra qua phn hoc nc tiu.
Chc nng sinh ho
ng vt c v vitamin D (thc t l 1 25-Dihydroxycalciferol)
iu khin s trao i calcium v phosphate.
N hot ho trc tip s hp thu (ti hp th) Ca
++
v phosphate
rut, thn. Mt khc n gii phng Ca
++
t xng cho s iu chnh tm
thi mc Ca
++
trong mu.
Hiu qu sao chp c thc hin bi vitamin D-receptor. y
vitamin c vai tr nh mt hormon. trong rut, d dy v xng n
kch thch s sao chp ca cc gen m ho cho cc protein gn vi calcium
(CaBP, calbindin, osteocalcin...). Nhng protein ny tham gia vo s tip
nhn calcium v khong ho xng.
Lnh vc y hc: Nhng bnh gn lin vi mc vitamin D khng bnh
thng:
Cholecalciferol
(Vitamin D
3
)
CH
3
CH
3
CH
3
CH
2
HO
CH
3
Ca
++
Phosphate
Hydroxyl ha
C25 (gan)
Hydroxyl ha
C1 (thn)
1 , 25-Dihydroxycalciferol
(Calcitriol, DHCC)
HO
CH
3
CH
3
CH
2
H
3
C
CH
3
HO
OH
H
H
16
Ci xng: (khong ho xng thp, phn ln tr em) sinh ra do
s hp th Ca
++
gim khi thiu vitamin D, thnh thong cng do
tng hp khng calcitriol t calciferol.
Bnh long xng: xut hin khi tng hp calcitriol b ri lon, do
thn khng hot ng hoc mc ostrogen thp v n kch thch
bc hydroxyl ho.
2.2.3 Tocopherol (vitamin E)
Tocopherol (tocos = con chu, pherol = sinh ra) kh ph bin cy
xanh, rau x lch, ht ng cc, du thc vt, gan b, lng trng.
Nhm tocopherol gm 8 hp cht, bao gm vng 8 - chromanol v
mt chui bn isoprenoide Sn phm cui cng ca qu trnh sinh tng
hp l -tocopherol (5,7,8-trimethyltocopherol), th hin hot tnh sinh
hc cao nht. thc vt v ng vt tocopherol bo v lipid trc s thit
hi do oxy ho.
Cc tocopherol phn bit vi nhau bng s lng v v tr ca nhm
methyl vng v cc lin kt i trong chui bn. Tt c chng u a
lipid.
Tocopherol c tng hp dng ng nht ch thc vt, trc
ht trong lc lp ca l. ng vt v thc vt n mng t bo (mng ty
th, hng huyt cu, v lp th).
Lng b sung hng ngy i vi ngi ln l 8-12 mg. Cn lng
ln hn khi thc phm c cha nhiu acid bo cha no. Him khi thy
thiu vitamin ny, ngoi tr trng hp non v ri lon hp thu
lipid. Tuy nhin trong chn nui ch dinh dng cung cp khng y
th gy ra s thoi ho cc c quan v v sinh.
Chc nng ho sinh ca tocopherol l bo v lipid mng trc
phn ng peroxid-ho (c bit acid bo c nhiu lin kt cha no).
Tocopherol l ni ether ca cc hydroquinon. Chng l nhng cht nhn
gc v chuyn sang trng thi tocopheroxy (semiquinon). y l mt gc
phn ng yu vi thi gian bn hu l nhiu gi v lm gy cc phn ng
chui. Phn ng ny l thun nghch, c th ascorbate thc hin s kh tr
li thnh tocopherol. y n b oxy ho thnh monodehydroascorbate.
Gia hai vitamin ny c s ng tc dng. -carotene cng c coi l
cht kh cho tocopherol. Ngc li semiquinon c oxy ho tip tc
thnh quinon, cht ny dn n s m vng thun nghch.
CH
3
CH
3
H
3
C
HO
O
CH
3
CH
3
CH
3
CH
3
-Tocopherol
17
2.2.4 Phylloquinon v menoquinon (vitamin K)
Phylloquinon l mt thnh phn ca h thng quang ho ca thc
vt quang hp. Menoquinon ng mt vai tr trong h hp ym kh ca vi
khun. ng vt hai hp cht (vitamin K
1
cng nh vitamin K
2
) l
cofactor s cacboxyl ho ca glutamat. l monomethyl-
naphtochinon vi mt chui bn isoprenoid.
Phyllochinon v menachinon phn bit nhau ch s lng lin kt
i v chiu di ca chui bn.
Lng tip nhn hng ngy cn thit ngi ln 70-140 g. Lng
ny c p ng bng thc n v sn phm ca vi khun ng rut.
Trc khi c thi phn ln ch cc chui bn c lm ngn bng oxy
ho.
Chc nng ho sinh
ng vt chng l cofactor to nn -cacboxylglutamate trong
protein xy ra mng li ni cht (endoplamatische reticulum) th nh
enzyme carboxylase. Protein to nn c phn gii. Qu trnh bin i
sau l cn thit cho kh nng kt hp Ca
++
v cho s c nh protein
bng cc cu Ca
++
mng phospholipid (v d qu trnh ng mu).
qu trnh bin i protein ny vitamin-K-hydroquinon tch ra mt
proton ca glutamate, tip theo n c carboxyl ho. ng thi xut hin
mt vitamin K-quinon-2,3-epoxid (nhng chi tit vn cn cha bit).
Epoxid c kh bng quinon-epoxid-reductase gn vi dithiol thnh
quinon v sau thnh hydroquinon. Dn xut ca cumarine c th km
hm reductase, v d dicumarol v warfarin c tc dng l cht khng
ng.
CH
3
CH
3
H
2
C CH = C CH
2
CH
2
CH
2
C CH
2
H
H 3
O O
CH
3
Phyloquinon
18
Cu hi
1. Chc nng ha sinh ca cc vitamin?
2. Tng hp cc vitamin ha tan trong nc v ha tan trong cht bo?
CH
3
H
2
C CH = C CH
2
H
n
O
O
CH
3
Menoquinon
37
CHNG III
ENZYME V S XC TC SINH HC
sng v pht trin, c th sinh vt phi thng xuyn trao i
cht v trao i nng lng vi mi trng bn ngoi. Cc qu trnh ny
tin hnh c l nh cc phn ng ha sinh xy ra trong c th theo quy
lut c t chc v c lin quan cht ch vi nhau.
c im chung ca cc phn ng ny l c th xy ra mt cch
c hiu, d dng vi vn tc ln ngay trong iu kin mi trng sinh
l v nhit ca c th. S d cc phn ng tin hnh trong c th c
nhng c im trn chnh l nh cc cht xc tc c bit c kh nng
lm tng vn tc phn ng ln gp bi, l cc cht xc tc sinh hc.
Enzyme l cht xc tc sinh hc c bn cht protein lm nhim v
xc tc cho cc phn ng ha sinh xy ra trong c th sinh vt.
Enzyme tn ti trong tt c cc t bo sng ca ng vt, thc vt,
vi sinh vt. Cc phn ng do enzyme xc tc c th xy ra ngay trong c
th sng hoc ngoi c th. Hin nay tch c rt nhiu enzyme
khc nhau t ngun ng vt, thc vt, c bit l t vi sinh vt, trong
c nhiu loi c thu nhn vi thun khit cao. Xc tc enzyme c
nhiu u im hn hn xc tc thng thng nh cng lc xc tc ln,
tnh c hiu cao, khng c, c th tc dng trong iu kin nh nhng,
n gin. Hn na c th sn xut enzyme t cc nguyn liu gi r nhng
em li hiu qu kinh t cao, nh vy vic ng dng enzyme rng ri
trong cc ngnh cng nghip nh, cng nghip thc phm, nng nghip, y
hc v nghin cu khoa hc nhanh chng c nhng bc tin di v
ngy cng c nhiu trin vng tt p.
I KHI NIM V S XC TC NI CHUNG
Tc phn ng ha hc c xc nh bi gi tr nng lng hot
ha tc l nng lng cc cht tham gia phn ng phi t c trn mc
nng lng bnh thng ca chng ct t cc lin kt cn thit v hnh
thnh cc lin kt mi. Nng lng hot ha cc phn ng no cng ln
th tc phn ng cng chm v ngc li.
Vic a mt s cht no vo trong h thng vn c tc dng lm
tng tc phn ng ha hc c gi l s xc tc. Trong qu trnh xc
tc, cc cht xc tc lm gim nng lng hot ha ca phn ng ha
hc. Nng lng cn xy ra s va chm c hiu lc dn n phn ng
ha hc c gi l nng lng hot ha.
38
Trong qu trnh xc tc, cc cht xc tc ch tham gia vo cc phn
ng trung gian sau chng li c phc hi nhanh chng, cht xc tc
khng ng vai tr nh nhng cht tham gia phn ng.
Tc cc phn ng thun nghch cng c cc cht xc tc lm
tng theo c hai chiu.
iu ni ln rng: cht xc tc khng quyt nh chiu hng ca
phn ng, chng ch thc y cho phn ng t n cn bng mt cch
nhanh chng.
nh hng ca cht xc tc l lm gim nng lng hot ha. Trong
th sau: A l cht phn ng, B l sn phm ca phn ng.
II ENZYME L CHT XC TC SINH HC
Nhng lun c sau y chng minh bn cht xc tc ca enzyme:
a) Cng nh cc cht xc tc ni chung, enzyme lm tng nhanh tc
phn ng. Enzyme khng quyt nh chiu hng ca phn ng.
b) Enzyme khng ng vai tr l cht tham gia phn ng trong phng
trnh phn ng. Trong qu trnh xc tc, lng enzyme khng thay i.
c) Cng nh mi cht xc tc khc, enzyme lm gim nng lng hot
ha cn thit ca cc phn ng ha hc. Ni cch khc nng lng hot
ha phn ng c gim i nhiu khi c s xc tc ca enzyme.
Phn ng khng c
xc tc Nng lng
Nng lng hot ha
Phn ng c hot ha c
enzyme xc tc enzyme xc tc
A
B
AG
1
AG
2
Chiu phn ng
n
g
l
n
g
t
d
o
39
III - BN CHT HA HC CA ENZYME
3.1. Enzyme l nhng cht xc tc c bn cht protein.
Trong s pht trin ca ha sinh hc, bc nhy vt t c khi
ngi ta thc hin thnh cng vic tch rt cc cht xc tc sinh hc ra
khi t bo v nghin cu tnh cht ca chng, lc ngi ta nhn bit
rng enzyme c bn cht protein. Nm 1926, Sumner l ngi u tin thu
c urease dng kt tinh. Cho n nay c khong hn 150 enzyme
c rt ra dng tinh khit. Trong s cc enzyme , mt s c
bit trn vn v cu trc bc I nh ribonuclease, trypsin, chymotrypsin,
Ngy nay ngi ta xc nhn rng, cc enzyme chnh l nhm
protein quan trng. Chng c hnh thnh trong t bo nh cc protein
n gin (enzyme mt thnh phn) hoc nh cc protein phc tp (enzyme
hai thnh phn). Trong s cc enzyme th a s l enzyme hai thnh phn.
Dng hot ng ca enzyme hai thnh phn bao gm phn protein v
phn khng c bn cht protein gi l nhm prostetic (nhm ngoi, nhm
ghp, )
Enzyme mt thnh phn l cc protein n gin thc hin chc nng
xc tc. V d: Ribonuclease A v mt s enzyme thy phn protein v
mt s enzyme khc.
3.2. Cc nhm ghp, cc coenzyme
Bn cnh phn protein th enzyme hai thnh phn cn cha phn
khng c bn cht protein. Ngi ta gi phn khng phi protein cn thit
bt buc i vi hot ng ca enzyme l nhm ghp (nhm ngoi, nhm
thm, yu t ph, ) v phn protein vn lin kt vi nhm l
apoenzyme, phc hp ca hai thnh phn trn l holoenzyme (enzyme hai
thnh phn).
Trong trng hp nhm ghp l nhng cht hu c c trng lng
phn t b c lin kt vi phn protein th nhm ghp c gi l
coenzyme. Theo cch th:
Nu ng ring r th c coenzyme cng nh apoenzyme u khng c
kh nng xc tc. Ch c lc no 2 phn ny kt hp vi nhau th hot tnh
xc tc ca enzyme mi th hin.
Bn cht ha hc ca coenzyme rt khc nhau:
- Mt s loi ny chnh l cc vitamin. S lin quan v chc nng gia
cc vitamin v cc coenzyme c gii thiu bng sau:
Apoenzyme + Coenzyme Holoenzyme
40
Coenzyme Chc nng Vitamin tng
ng
NAD, NADP
FAD. FMN
Coenzyme A
Thiaminpyro(P)
Pyridoxal(P)
- Chuyn H
+
v e
-
- Chuyn H
+
v e
-
- Vn chuyn gc acyl
- Phn gii ho kh v tng hp
acid bo
- Kh carboxyl ha
- Chuyn nhm aldehyd
- Chuyn amine ha
- Kh carboxyl ha
PP
B
2
Pantotenic acid
(B
3
)
Thiamine(B
1
)
Pyridoxine(B
6
)
- Cc ion kim loi c vai tr cn thit bt buc cho s hot ng ca
enzyme. Cc ion (cation) c chc nng ging vi cc coenzyme.
Ngi ta gi cc ion kim loi l cc coenzyme n gin. Cc
enzyme cn ion kim loi cho vic thc hin chc nng ca mnh c gi
l metalloenzyme. Chc nng ca cc ion kim loi ni chung phn nhiu
l chng to ra cc phc hp kiu chelate gia mt nhm nht nh no
ca c cht v enzyme. Trc tin cc cation to phc ion kim loi c
cht, sau phc hp ny mi phn ng vi enzyme. Cc ion Ca, Cu,
Mg, Mn, Mo, Zn, u l nhng ion tham gia trong s hot ng ca cc
enzyme.
3.3. Tnh c hiu ca enzyme
Kh nng xc tc vi tnh c hiu cao l mt trong nhng c tnh c
bn v quan trng nht ca enzyme. Tnh c hiu ca enzyme th hin
ch: enzyme ch xc tc cho mt trong v s nhng chuyn ha c th c
c i vi cc cht. C hai loi c hiu c bn l c hiu phn ng
v c hiu c cht.
* Tnh c hiu phn ng: c th hin ch enzyme ch c kh
nng la chn mt dng phn ng trong s cc phn ng v xc tc cho
phn ng . iu thy r trong v d sau y:
41
Di tc dng ca oxidase, aminoacid b kh amine ha bng cch
oxy ha to ra cetoacid v NH
3
. Vi s c mt ca oxidase, mt phn
ng khc kh carboxyl ha li khng th xy ra. Vic xc tc ny i hi
phi c enzyme khc, l decarboxylase. Cng nh vy, phn ng
chuyn amine ha i hi phi c transaminase.
* Tnh c hiu c cht: Enzyme c th la chn i vi cc cht
tham gia phn ng. Khng phi mi c cht c kh nng phn ng u
c enzyme tip nhn nh nhau.
Mi enzyme ch chuyn xc tc cho mt hoc mt vi c cht nht
nh v mc c hiu ca n ty thuc vo tng loi enzyme. C 3
mc c hiu c cht ch yu:
a) c hiu tng i: Enzyme ch c th tc dng ln mt kiu
lin kt ha hc nht nh m khng ph thuc vo cc nhm ha hc nm
hai bn lin kt. V d cc esterase c th tc dng ln hng lot cc
ester ca phosphoric acid.
b) c hiu nhm: biu hin l enzyme ch c th tc dng ln mt
kiu lin kt ha hc nht nh v mt trong hai nhm nm hai bn lin
R
1
C COOH + NH
3
2H
oxidase O Cetoacid(1)
H
2
O
R
1
CH COOH decarboxylase R
1
CH
2
+ CO
2
NH
2
NH
2
Amine
Aminoacid (1) Transaminase
R
2
CH COOH
NH
2
Aminoacid (2)
R
2
C COOH R
1
C COOH
O O
Cetoacid (2) Cetoacid (1)
42
kt cng phi c cu to nht nh. V d carboxylpeptidase c kh nng
phn hy lin kt peptide gn nhm COOH t do, ngha l lin kt
peptide cui mch polypeptide,
c) c hiu tuyt i: Enzyme ch tc dng ln mt kiu lin kt
nht nh v cc nhm ha hc hai bn lin kt cng phi xc nh.
V d: Enzyme trypsine thy phn cc lin kt peptide gia lysine hoc
arginine vi bt c aminoacid no. Sn phm l nhng on peptide c
lysine hoc arginine cha nhm COOH t do pha tn cng ca peptide.
- Enzyme Trombine cn c tnh c hiu cao hn trypsine: n ch
thy phn lin kt peptide pha carboxyl ca gc arginine no c gc
glycine ng lin k sau n:
* Ngoi cc tnh c hiu trn nhiu enzyme cn biu hin rt cao
v tnh c hiu ha hc lp th (c hiu quang hc): Enzyme ch tc
dng ln nhng dng ng phn lp th no ca cc cht hu c.
V d: Enzyme L-lactatdehydrogenase ch tc dng ln L-lactic
acid m khng tc dng ln D-Lactic acid. Mun tc dng ln D-Lactic
acid phi c enzyme D-lactatdehydrogenase.
IV CC YU T NH HNG TI HOT TNH XC
TC CA ENZYME
O O
C NH CH C
R
V tr thy phn ca trypsine
Lysine hay
Arginine
O O
C NH CH C
V tr thy phn ca trombine
Arginine
Glycine
.. CH CONH CH COOH .. CH COOH + H
2
N CH COOH
R
1
R
2
R
1
R
2
43
4.1. Nhit
Trong phm vi l hc, tc ca phn ng tng ln cng vi s tng
ca nhit . Nhng khi vt qu phm vi no , cc phn ng c
enzyme xc tc b nh hng do s bin tnh ca phn t protein-enzyme.
Kt qu ny ph thuc vo nhit ti thch ca enzyme, l nhit m
ti tc phn ng enzyme t cc i.
Mi enzyme c nhit ti thch khc nhau. S khc nhau ny ty
thuc vo ngun gc ca cc enzyme, ty theo tng iu kin hoc tng
s khc nhau v tnh nhy cm vi nhit ca phn t protein-enzyme.
a s enzyme mt hot tnh xc tc nhit cao(>80
o
C), tr papain,
myokinase c th tn ti 100
o
C.
4.2. nh hng ca pH
Mi enzyme u c tr s pH ti thch no i vi hot tnh
ca chng. ngoi phm vi ca tr s ny hot tnh ca enzyme u b
gim thp.
Tr s pH ti thch ca mt s enzyme nh sau:
Enzyme pH ti thch
Pepsine
Amylase(mch nha)
Amylase(nc bt)
Trypsine
Arginase
Catalase
Peroxidase
1,5 2,5
4,6 5,0
6,8 7,2
7,8 9,5
9,8
6,8 7,0
6,0
Nhng nguyn nhn sau y c th dn ti s ph thuc vo pH
ca enzyme:
Hot
tnh
Nhit ti thch
20 30 40 50 60 70 80 t
o
C
44
a) Nu trong s cc nhm bn tham gia trc tip trong s hot
ng ca enzyme cha nhm c kh nng phn ly.
b) pH nh hng ti cc nhm phn ly khc ca protein-enzyme
vn c tc dng trong vic duy tr cu hnh c hot tnh ca enzyme.
c) S thay i pH ca mi trng c th nh hng ti cc nhm
phn ly ca c cht hay ca coenzyme vn c kt hp vi enzyme.
4.3. nh hng ca cht hot ha v cht km hm enzyme
Nhng cht no c kh nng lm tng hot tnh xc tc ca
enzyme th c gi l cht hot ha enzyme. Cc cht thng l cc
ion kim loi nh: K
+
, Na
+
, Mg
+2
, Ca
+2
, Co
+2
, Zn
+2
, Mn
+2
,
V d: Mg
+2
lm tng hot tnh phosphatase
Ca
+2
lm tng hot tnh lypase.
S hot ng ca cc enzyme u c th b km hm bi cc tc ng
gy bin tnh protein. Ngi ta phn bit cc hnh thc km hm enzyme
v phn bit cc cht km hm enzyme nh sau:
a) Cht km hm chung: cc cht ny km hm hot tnh xc tc
ca tt c cc enzyme. Cc cht ny l cc mui kim loi nng, cht
tannin.
b) Cht km hm ring: c tc dng km hm mt hay mt nhm
enzyme c cu to gn ging nhau. V d: cc cht cha nhm CN km
hm enzyme h hp.
4.4. Nng c cht v nng enzyme
Khi mi trng c y c cht th tc phn ng t l thun
vi lng enzyme. Khi nng c cht thp, khng li ko tt c
lng enzyme vo phn ng th tc phn ng tng t l thun vi nng
c cht. Tc phn ng t ti a khi tt c enzyme u kt hp vo
c cht.
V C CH XC TC CA ENZYME
Khi t vn nghin cu v c ch xc tc ca enzyme ngi ta
xut pht t gi thit cho rng trong cc phn ng c enzyme xc tc,
phc tm thi Enzyme C cht c to thnh. Qu trnh ny gm 3
giai on:
giai on 1 phn ng xy ra tng i nhanh, c cht (S) c lin
kt vi enzyme (E) nh cc lin kt yu. Lc ny s lin kt khng gian
E + S ES ES
*
E + P
1 2 3
45
gia cc phn t c cht v enzyme cha hiu qu i vi s xc tc
ca enzyme.
giai on tip theo xy ra s bin i ca c cht (S) c lin quan
ti vic ph v hay hnh thnh cc lin kt cng ha tr. giai on ny,
c cht c hot ha (mt hoc vi phc cht ES chuyn tip c hot
ha). y, cu trc bc 3 ca enzyme lun bin i to kh nng tip
xc gia cc nhm hot ng ca enzyme vi c cht ang bin i.
Enzyme lm bin i phn t c cht lm cho cc lin kt bn trong
phn t tr nn lng lo hn, do ch cn mt lng nng lng nh
cng lm cho c cht bin thnh cc sn phm (P) khc nhau.
Ngi ta chng minh rng trong khi hnh thnh phc cht ES c 2
qu trnh ng thi xy ra nhanh chng l:
a) S thay i mt in t gy nn s phn cc ha cc lin kt.
b) S bin dng v mt ha hc ca cc lin kt ko cng trong
phn t c cht.
C hai yu t ny (s bin hnh v s phn cc ha cc lin kt
ng ha tr) u lm tng th nng nhit ng hc ca cc lin kt ny,
ngha l xc tin vic vt qua hng ro nng lng hot ha ca qu
trnh chuyn tip phc Enzyme-C cht.
VI - NG HC CA PHN NG ENZYME
6.1. ng hc ca phn ng enzyme trong trng hp khng
c cht km hm.
6.1.1. giai on: E + S ES
K
+1
: hng s vn tc ca phn ng thun.
K
-1
: hng s vn tc ca phn ng nghch.
Gi V
1
l tc phn ng thun.
V
-1
l tc phn ng nghch.
[E]: nng enzyme.
[S]: nng c cht.
Ta c: V
1
= K
+1
([E]. [S])
V
-1
= K
-1
[ES] (1)
Khi phn ng t n cn bng (enzyme phn ng ht vi c cht)
th V
1
= V
-1
ngha l:
K
+1
([E]. [S]) = K
-1
[ES]
K
+1
E + S ES
K
-1
46
t ta c:
1
1
K
K
+
=
| | | |
| | S E
S E
Nu gi K
s
l hng s cn bng cc phn ng bc I, ta c:
s
K =
| || |
| | S E
S . E
s
K =
1
1
K
K
+
(2)
* Nu K
s
c gi tr ln th K
-1
s ln v K
+1
s nh. T ta thy
phc hp ES d phn gii thnh cc cht S v E. Phn ng enzyme tin
hnh chm.
* Nu K
s
c gi tr nh th tc to ES s nhanh ng thi phn
ng enzyme cng tin hnh nhanh. Vy nu K
s
cng nh th nng ES
cng cao.
giai on 1 ta tnh c:
s
K =
| | | |
| | S E
S E
Hay vit di dng khc l: [E] [S] = K
s
[ES] (3)
Nu gi [E
o
] l nng chung ca enzyme trc khi bt u tham
gia phn ng.
[E]: nng enzyme dng t do (khng to phc hp)
[ES]: nng ca phc h ES.
th nng enzyme khng to phc hp ( dng t do) l:
[E] = [E
o
] - [ES] (4)
Thay vo phng trnh (3), ta c:
([E
o
] - [ES]). [S] = K
s
. [ES]
Trin khai:
[E
o
] [S] - [ES] [S] = K
s
. [ES] hay l:
K
s
[ES] + [ES] [S] = [E
o
] [S] hay l:
[ES](K
s
+ [S]) = [E
o
] [S]
T
[ES] = [E
o
]
| |
| | S K
S
s
+
| |
| |
o
E
ES
=
| |
| | S K
S
s
+
(5)
Nh vy nng [ES] cng ln th tc phn ng enzyme cng
ln (v K
s
lc s nh). Tc s t ti ti a khi nng phc h
[ES] bng nng enzyme ban u [E
o
] ([ES] = [E
o
]) ngha l khi tt c
enzyme u c kt hp vi c cht th phn ng enzyme l ti a.
T c th lp thnh t l:
max
V
V
=
| |
| |
o
E
ES
V: tc phn ng enzyme ( giai on u)
V
max
: tc ti a.
47
T phng trnh (5) ta c:
| |
| |
o
E
ES
=
| |
| | S K
S
s
+
Vy
max
V
V
=
| |
| | S K
S
s
+
T : V = V
max
| |
| | S K
S
s
+
y l phng trnh Michaelis v Menten (1913) dng tnh tc
phn ng enzyme t E + S ES.
Nu K
s
= [S] th V =
2
1
V
max
6.1.2. giai on: ES
*
E + P
Khi ta c tc to ES l: V
+1
= K
+1
([E] [S])
Tc phn li ES theo phn ng nghch V
-1
= K
-1
[ES]
Tnh tc phn gii phc h ES to E + P, hng s tc ny
bng K
+2
Khi nng c cht [S] cao hn nhiu so vi nng [E] th s
t nhanh chng trng thi cn bng gia s hnh thnh ES v s phn gii
phc h ES .
Nh vy giai on ny ta c:
Hay l: (K
-1
+ K
+2
). [ES] = K
+1
[E] [S] (6)
T phng trnh (4): [E] = [E
o
] - [ES]
Thay vo phng trnh (6), ta c:
(K
-1
+ K
+2
). [ES] = K
+1
([E
o
] - [ES]). [S]
t :
K
+1
K
+2
E + S ES E + P
K
-1
K
-2
K
-1
[ES] + K
+2
[ES] = K
+1
[E] [S]
Tc phn gii Tc phn gii Tc to phc h ES
phc h ES E + S phc h ES E + P
48
1
2 1
K
K K
+
+
+
=
| | | | ( )| |
| | ES
S . S E E
o
=
| || | | || |
| | ES
S S E S E
o
t
1
2 1
K
K K
+
+
+
= K
m
K
m
=
| || | | || |
| | ES
S S E S E
o
K
m
c gi l hng s Michaelis (o bng mol/lit) (tnh theo khi
m s to [ES] v phn li [ES] bng nhau)
K
m
[ES] = [E
o
] [S] - [ES] [S]
K
m
[ES] + [ES] [S] = [E
o
] [S]
[ES](K
m
+ [S]) = [E
o
] [S]
[ES] =
| || |
| | S K
S . E
m
o
+
(7)
Mt khc tc phn ng tnh theo s hnh thnh sn phm P t
[ES] bng:
V = K
+2
[ES]
t : [ES] =
2
K
V
+
Thay vo (7) ta c:
2
K
V
+
=
| || |
| | S K
S . E
m
o
+
Vy V =
| || |
| | S K
S . E . K
m
o 2
+
+
(8)
Phng trnh ny cho php tnh c s ph thuc tc phn
ng vo nng ca enzyme v c cht.
V t cc i khi [ES] = [E
o
] ngha l khi E c kt hp hon
ton vi S.
max
V
V
=
| |
| |
0
E
ES
t phng trnh 7 ta c: ES =
| || |
| | S K
S E
m
0
+
Vy
max
V
V
=
| |
0
E
1
.
| || |
| | S K
S E
m
0
+
=
| |
| | S K
S
m
+
T : y l phng trnh
Michaelis v Menten dng
V = V
max
.
| |
| | S K
S
m
+
49
tnh tc phn ng t
ES
*
E + P
* Vy V =
2
1
.V
max
th
K
m
= [S]
Lc hng s Michaelis c o bng mol/lt
So snh gi tr K
m
v K
s
ta thy:
K
m
=
1
2 1
K
K K
+
+
+
m K
s
=
1
1
K
K
+
Vy K
m
= K
s
+
1
2
K
K
+
+
Khi K
+2
= K
+1
th K
m
= K
s
+ 1
T phng trnh (8) V = V
max
.
| |
| | S K
S
m
+
c th vit di dng
phng trnh:
Theo phng trnh ny th khi [S] tng th tc phn ng tng.
Nhng khi nng c cht [S] tng n mt mc no th t ti gi
tr tc cc i:V = V
max
. Sau th V khng tng theo nng c cht
[S] v V lun lun =V
max
.
l phng trnh biu din s ph thuc ca tc phn ng vi
nng c cht. C th biu din bng dng hiperbol:
C th gii thch ca ng biu din dng hiperbol nh sau:
Trong phn ng c enzyme xc tc s phn t c cht ln hn s phn t
| |
1
S
K
V
V
m
max
+
=
Tc
V
max C
2
V
max
B
0
K
m
[S]
50
enzyme rt nhiu (S>E). C cht ch c chuyn ho khi to thnh phc
h enzyme. Do tc phn ng ph thuc vo nng phc h [ES].
Nng [ES] 3 im A, B, C khng ging nhau. im A v B
cn vi phn t enzyme cha kt hp vi c cht, do nu tng hay
gim nng c cht [S] s lm tng hay gim s va chm gia E v S
ngha l lm tng hay gim nng [ES] v s nh hng ti tc phn
ng v tc l hm s ca nng c cht [S].
Ti im C tt c phn t enzyme kt hp vi S nn khi tng
nng c cht c th lm tng dn s va chm gia E v S nhng khng
lm tng tc phn ng.
V khng cn enzyme t do c th gn thm vo c cht v tc
t c l cc i.
im B ng
2
1
s phn t enzyme kt hp vi c cht,
tc =
2
1
V
max
v nng c cht tng ng vi im B bng
hng s K
m
.
T phng trnh Michaelis Menten
Nu V =
2
1
V
max
th K
m
= [S]. Nh vy ngha l hng s Michaelis
bng nng ca c cht khi m tc phn ng bng
2
1
V
max
.
* Phng trnh Michaelis cng c th vit di dng khc theo
ngh ca Lineweaver v Burk (1934) bng cch ly s nghch o:
V
1
=
| |
| | S . V
S K
max
m
+
V
1
=
max
m
V
K
.
| | S
1
+
max
V
1
Phng trnh c dng y = ax + b v ng biu din c dng
ng thng nh sau:
V = V
max
.
| |
| | S K
S
m
+
V
1
max
V
1
51
Qua th c th xc nh c V
max
v K
m
.
6.2. ng hc ca cc phn ng enzyme trong trng hp
c cht km hm
Trong trng hp c cht km hm cnh tranh hay khng cnh
tranh th gi tr V ca phn ng s bao gm c hng s K
i
(K
i
l hng s
phn li ca phc hp enzyme-cht km hm EI hay cn gi l hng s
km hm).
Hng s K
i
c tnh nh phng trnh sau:
K
i
=
1 i
1 i
K
K
+
=
| | | |
| | EI
I E
* Cc cht km hm cnh tranh: l cc cht thng c cu to gn
ging vi c cht. Cc cht km hm cnh tranh c tnh c hiu rt cao,
ngha l ch km hm mt enzyme ring bit.
V d: Malonic acid l cht km hm cnh tranh ca enzyme
succinat-dehydrogenase v n c cu to gn ging succinic acid.
Khi tng nng c cht th mt km hm cnh tranh.
* Cc cht km hm khng cnh tranh: l cc cht c tc dng km
hm hot ng ca enzyme bng cch gn vo cc v tr khc vi cc v tr
K
i+1
E + I EI
K
i-1
CH
2
COOH
COOH
Malonic acid
CH
2
COOH
CH
2
COOH
Succinic acid
52
gn c cht ca enzyme. Trong trng hp ny ch lm gim V cc i
ca phn ng ch khng nh hng g n hng s K
m
.
V d: Cc ion kim loi nng Ag
+
; Hg
+
; Trichloroacetic acid.
6.2.1. ng hc ca phn ng enzyme trong trng hp c cht km
hm cnh tranh.
Vic tnh ton V
i
s phc tp hn v ta c ng thi vi qu trnh gn
E vi c cht, cn c c qu trnh gn E vo cht km hm I.
Bng cch tnh ton nh trn ta c :
V
i
=
| |
| | | |
|
|
.
|
\
|
+ + I .
K
K
S K
S . V
i
m
m
max i
Phng trnh ny ging phng trnh Michaelis nhng c thm
| | I .
K
K
i
m
phn nh qu trnh km hm bi cc cht km hm cnh tranh.
* Cng c th tnh V
i
bng cch :
i
V
1
=
max i
V
1
.
| |
|
|
.
|
\
|
+
i
m
m
K
I . K
K .
| | S
1
+
max i
V
1
6.2.2. ng hc ca phn ng enzyme trong trng hp c cht
km hm khng cnh tranh:
Trong trng hp ny ngi ta thy rng cht km hm khng cnh
tranh c th gn vo enzyme t do v c vo phc h ES theo cc phn
ng sau:
K
+1
K
+2
E + S ES E + P
K
-1
K
i+1
E + I EI
K
i-1
K
+1
K
+2
E + S ES E + P
K
-1
53
Cch tnh phc tp hn:
- Gi thit rng K
+2
rt nh so vi K
+1
v K
-2
, v phc hp IES khng
to thnh sn phm tng ng v cc hng s cn bng c gi tr nh nhau
(tng ng vi cc phn ng ghi trn), bng cch tnh nh trn s c:
V
i
=
| || |
| | ( )
| |
|
|
.
|
\
|
+ +
+
i
s
o 2
K
I
1 . S K
S E . K
hoc tnh theo dng khc:
i
V
1
=
| |
|
|
.
|
\
|
+
i
K
I
1
| |
|
|
.
|
\
|
+
S
1
.
V
K
V
1
max
m
max
Khi so snh tc phn ng khng b km hm vi tc phn ng c
cht km hm khng cnh tranh ngi ta thu c t l sau:
i
o
V
V
=
| |
i
K
I
1+
V
o
l tc ban u ca phn ng enzyme khng c cht km hm.
V
o
=
| || |
| | S K
S E . K
s
o 2
+
+
t (8)
y K
s
thay vo ch ca K
m
v K
+2
rt nh so vi K
-1
ngha l
K
m
= K
s
. Nh vy c th thy rng: S bin i tng i ca hot tnh
K
i+1
E + I EI
K
i-1
K
i+2
ES + I IES
K
i-2
K
i+3
EI + S IES
K
i-3
54
enzyme c cht km hm khng cnh tranh ch ph thuc vo nng ca
cht km hm m khng ph thuc vo nng ca c cht [S].
* i vi cht km hm cnh tranh th t l
i
o
V
V
c dng:
i
o
V
V
= 1 +
| |
| | I
S K
K K
m
i m
+
t phng trnh ny ta thy s bin i ca
hot tnh enzyme khi c cht km hm cnh tranh ph thuc c vo nng
c cht v nng cht km hm.
C th biu din tc phn ng enzyme trong trng hp c cht
km hm cnh tranh v khng cnh tranh bng th:
Tm tt: (Tt c nhng phng trnh sau y ch dng cho trng hp
khi 1 c cht tham gia vo phn ng)
V V
V
max
= V
imax
V
max
V
imax
1 2 1 2
K
m
K
mi
[S] K
m
= K
i
[S]
V
1
2 1
V
1
2
max
V
1
=
max i
V
1
max i
V
1
1
max
V
1
m
K
1
mi
K
1
| | S
1
m
K
1
=
mi
K
1
| | S
1
1 c cht km hm.
2 khng c cht km hm.
C cht km hm cnh tranh C cht km hm khng cnh tranh
55
Khng c
cht km hm
C cht km hm
cnh tranh
C cht km hm
khng cnh tranh
Phng
trnh
V
1
=
max
m
V
K
.
| | S
1
+
max
V
1
i
V
1
=
max i
V
1
.
| |
|
|
.
|
\
|
+
i
m
m
K
I . K
K .
| | S
1
+
max i
V
1
i
V
1
=
| |
|
|
.
|
\
|
+
i
K
I
1 .
| |
|
|
.
|
\
|
+ +
S
1
V
K
V
1
max i
m
max i
on
thng trn
trc tung
ti im
max
V
1
max
V
1
max
V
1
max
V
1
.
| |
|
|
.
|
\
|
+
i
K
I
1
on
thng ct
trn trc
honh ti
im
| | S
1
m
K
1
| |
|
|
.
|
\
|
+
i
m
K
I
1 K
1
m
K
1
VII . CCH GI TN V PHN LOI ENZYME
Trong thi gian c ch tc dng ca enzyme cha c nu ra, ngi
ta t cho mt s enzyme nhng tn ring bit nh pepsine, trypsine,
chymotrypsine, papaine, bromeline,
Khi con s cc enzyme c bit ngy cng nhiu tn enzyme c
gi theo nguyn tc sau y: Tn enzyme = tn c cht m enzyme xc tc
+ loi phn ng m enzyme xc tc + tip v ng ase.
V d:
Ascorbat-
Ascorbic acid + O
2
Dehydroascorbic acid + H
2
O
oxidase
56
Vic phn loi enzyme l cng vic kh khn v s enzyme m c ch
xc tc ca n c hiu bit mt cch tng tn khng nhiu.
Vic phn loi enzyme c da theo nguyn tc l: ly c s kiu
phn ng do enzyme xc tc m Hip hi Ha sinh Quc t xut
nm 1964. Nm 1973 h thng phn loi ny li tip tc c hon thin
bi y ban danh php Ha sinh thuc Hip hi ha hc c bn v ng
dng Quc t (IUPAC). Trn c s tt c cc enzyme c phn chia 6
nhm ch yu sau:
1. Oxydoreductase 4. Lyase
2. Transferase 5. Isomerase
3. Hydrolase 6. Synthetase (Ligase)
Cc s thp phn trn bng phn loi c ngha nh sau:
- S th nht ch nhm chnh (V d nhm 2: transferase)
- S th hai qui nh mt s c tnh ca phn ng (V d: 2.1 cho bit
enzyme vn chuyn gc 1 carbon)
- S tip theo cho bit chi tit hn (V d 2.1.1: c ngha l enzyme
vn chuyn nhm methyl)
Tuy nhin cho n nay cc tn gi truyn thng ca enzyme vn cn
c s dng.
VIII. CC NHM ENZYME RING BIT
8.1. Oxydoreductase (cc enzyme oxy ha kh)
Cc enzyme nhm ny lm nhim v xc tc cho cc phn ng oxy
ha kh. Chng chuyn vn H
+
hay cc in t v xc tc cho s oxy ha
sinh hc. Cc enzyme ny c vai tr to ln trong qu trnh h hp v trao
i nng lng trong c th. S tng qut ca cc phn ng c xc
tc bi oxydoreductase nh sau:
Trong AH
2
l c cht; B l cht nhn H no , c th l O
2
.
Trong t bo oxydoreductase to nn cc h thng (c gi l
chui enzyme oxy ha kh), trong vic vn chuyn cc nguyn t
hydro (H
+
v e
-
) qua nhiu giai on, t c cht n cht nhn cui cng l
CH
2
COOH Succinat- CH COOH
+ FAD + FAD.H
2
CH
2
COOH dehydrogenase CH COOH
Succinic acid Fumaric acid
AH
2
+ B A + BH
2
oxydoreductase
57
O
2
. Kt qu l cc nguyn t hydro c vn chuyn n O
2
v s to
thnh H
2
O.
S h thng enzyme h hp v vic vn chuyn H
+
v e
-
c
trnh by tng qut sau y:
Ty theo kh nng ca oxydoreductase chuyn H
2
va ly c t c
cht (AH
2
) n O
2
ca khng kh, ngi ta chia oxydoreductase thnh hai
phn nhm:
- Dehydrogenase ho kh (oxidase)
- Dehydrogenase ym kh.
a) Dehydrogenase ym kh: l nhng enzyme khng c kh nng
vn chuyn H
+
v e
-
t c cht oxy ha n trc tip cho O
2
ca khng
kh, m chng s chuyn H
+
v e
-
cho cc cht vn chuyn trung
gian khc.
Nhm ghp ca dehydrogenase ym kh l dn xut ca vitamin
PP (B
5
) l NAD v NADP.
NH
2
O N N
C NH
2
(NAD
+
)
N
N
O CH
2
O (P)
-
O (P)
-
O CH
2
O
N
(+)
H H H H
2H
+
, 2e
-
2H
+
, 2e
-
AH
2
NAD NADH
2
FAD FADH
2
(NADP) (NADPH
2
) 2H
+
, 2e
-
Q
2H
+
QH
2
2e
-
2cytochrome b
2e
-
2cytochrome c
2e
-
2cytochrome a
O
-2
O
2
2e
- H
2
O
58
b) Dehydrogenase ho kh: l nhng enzyme c kh nng vn
chuyn H
+
v e
-
n trc tip cho O
2
ca khng kh. Chng cng l nhng
enzyme hai thnh phn. Nhm ghp ca chng l dn xut ca vitamin B
2
(Riboflavin) l FMN v FAD.
Cc enzyme cha FMN, FAD thng khng oxy ha trc tip c cht
m chng ly H
2
t NADH
2
(hoc t NADPH
2
) ri chuyn in t cho h
cytochrome.
O
N
H
3
C NH
NH
2
H
3
C
N N O
N N
CH
2
(CH OH)
3
N N FAD
CH
2
O (P) O (P) CH
2
O
H H
FMN H OH HO H
59
a s enzyme cha FMN khi tc dng trc tip vi O
2
khng kh s
to thnh H
2
O
2
. V d: enzyme glycolatoxidase xc tc cho phn ng oxy
ha glycolic acid theo s sau:
8.2. Nhm transferase (cc enzyme vn chuyn)
Cc enzyme nhm ny lm nhim v vn chuyn cc nhm ha hc t
hp cht ny sang hp cht khc m khng lm thay i ha tr ca cc
nguyn t.
S tng qut:
x: l nhm c vn chuyn.
Ty thuc vo x m ta c cc tn enzyme vn chuyn khc nhau.
V d: Acyltransferase: x l gc cc acid bo trong c gc acetic
acid. y l enzyme hai thnh phn trong nhm hot ng l HS-CoA
c cu to nh sau:
- Glycozyltransferase: Nu x l gc glycozyl.
- Aminotransferase: Nu x l nhm amin ( NH
2
).
- Methyltransferase: Nu x l nhm (CH
3
).
COOH Glycolatoxidase
CH
2
OH FMN H
2
O
2
Glycolic acid
O
C H FMNH
2
O
2
COOH
Glyoxilic acid
Ax + B A + Bx
transferase
NH
2
H
3
C CH
3
N N
O O SH
CH
2
O (P) O (P) O
O NH NH
N N H H OH
H H
OH O (P)
60
- Aldotransferase: Nu x l nhm aldehyd.
- Cetotransferase: Nu x l nhm cetone.
- Phosphotransferase: Nu x l gc H
3
PO
4
.
Enzyme ny cn c tn l:
a) Kinase: Nu xc tc cho phn ng chuyn gc H
3
PO
4
m ATP
l nhm hot ng ca enzyme ny. V d:
b) Mutase: l enzyme vn chuyn gc H
3
PO
4
trong ni ti phn t
ca 1 cht.
V d: Enzyme hexoso(P)-mutase xc tc cho phn ng sau:
8.3. Nhm hydrolase (cc enzyme thy phn):
Cc enzyme nhm ny xc tc cho cc phn ng thy phn. S
tng qut:
Da vo lin kt gia R
1
v R
2
m ta c tn cc enzyme thy phn
khc nhau:
- Peptidase: Thy phn lin kt peptide.
- Glycosidase: Thy phn lin kt glycoside.
- Esterase: Thy phn lin kt ester.
- Amidase: Thy phn amide.
Glycerine + ATP Glycerol(P) + ADP
Kinase
R
1
R
2
+ H
2
O R
1
H + R
2
OH
Hydrolase
R C NH
2
+ H
2
O R COOH + NH
3
Amidase
O
Amide
6 6
CH
2
OH CH
2
O (P)
5 O 5 O
H H H Hexoso(P) - H H H
4 1 4 1
HO OH H O (P) mutase HO OH H OH
3 2 3 2
H OH H OH
Glucoso-1(P) Glucoso-6(P)
61
V d:
8.4. Nhm Liase (cc enzyme phn ct)
Enzyme nhm ny phn ct mt nhm no ra khi mt hp cht m
khng c s tham gia ca H
2
O. C trng hp kt qu ca phn ng l to
lin kt i.
V d: * Decarboxylase: xc tc cho phn ng sau:
* Aldolase: xc tc cho phn ng thun nghch sau:
NH
2
C = O + H
2
O CO
2
+ 2NH
3
Urease
NH
2
Ure
H
2
N CH COOH H
2
N CH COOH
NH
3
CH
2
+ H
2
O CH
2
Asparaginase
CONH
2
COOH
Asparagin Aspactic acid
CO
2
R CH COOH R CH
2
Decarboxylase
NH
2
NH
2
Aminoacid Amine
Fructosodi(P) Aldehyd(P)glyceric + Phosphodioxiacetone
CH
2
O (P) O
C = O C H CH
2
OH
Aldolase
(CH OH)
3
CH OH + C = O
CH
2
O(P) CH
2
O(P) CH
2
O(P)
Fructoso 1,6 di(P) Aldehyd(P)glyceric Phosphodioxiacetone
62
* Hydratase (hydroliase): gm cc enzyme xc tc cho phn ng
loi tr v kt hp H
2
O.
8.5. Nhm Isomerase (cc enzyme ng phn ha):
Cc enzyme nhm ny xc tc cho phn ng chuyn ha cc cht hu
c thnh ng phn ca chng. V d chuyn ha gia dng cetone v
dng aldehyd. Gia dng L v dng D
V d: Enzyme trioso(P)isomerase xc tc cho phn ng sau:
Enzyme alaninracemase xc tc cho phn ng bin i L-alanine thnh
D-alanine v ngc li.
CH
2
COOH H
2
O CH
2
- COOH
C(OH).COOH C COOH
Aconitat-hydratase
CH
2
COOH CH - COOH
Citric acid Cis-aconitic acid
CH
2
COOH
H
2
O
CH COOH Aconitat-hydratase
CH.OH.COOH
Isocitric acid
COOH COOH
Alaninracemase
H
2
N C H H C NH
2
CH
3
CH
3
L-Alanine D-Alanine
O
CH
2
OH C H
C = O CH OH
CH
2
O(P) CH
2
O(P)
Phosphodioxiacetone Aldehyd(P)glyceric
63
8.6. Nhm synthetase (cc enzyme tng hp)
Cc enzyme nhm ny xc tc cho cc phn ng tng hp cc cht
hu c. Nhm ny ch xc tc khi c mt ca ATP v cc hp cht cao
nng khc. V cc phn ng tng hp i hi phi cung cp nhiu nng
lng. Mt s v d sau y:
Cu hi
1. nh ngha enzyme? Phn nhm enzyme v cho v d?
2. Cch gi tn enzyme v cho v d?
3. Mi lin quan gia enzyme v vitamin?
4. Ti sao ni: Enzyme l nhng cht xc tc c bn cht
protein?.
ATP ADP + H
3
PO
4
* Aspactic acid + NH
3
Asparagine
H
2
O
Asparaginsynthetase
ATP ADP + H
3
PO
4
* Glutamic acid + NH
3
Glutamine
H
2
O
Glutaminsynthetase
ATP AMP + H
4
P
2
O
7
* CH
3
COOH + HS-CoA CH
3
C ~ S.CoA
Acetic acid Acetyl-CoA-Synthetase
O
Acetyl-CoA
64
5. Cho bit s khc nhau (v mt chc nng) gia Trombin v Tripxin?
6. C ch tc ng ca enzyme?
7. Cc iu kin nh hng n tc phn ng ca enzyme?
56
CHNG 4
CARBOHYDRATE V S TRAO I
CARBOHYDRATE TRONG C TH THC
VT
4.1 Cu to, tnh cht v vai tr ca carbohydrate
Carbohydrate l nhm cht hu c ph bin kh rng ri trong c
th sinh vt. Nhn chung hm lng carbohydrate thc vt cao hn
ng vt. thc vt carbohydrate tp trung ch yu thnh t bo, m
nng v m d tr. Tuy nhin hm lng carbohydrate thay i tu
theo loi, giai on sinh trng, pht trin. Trong c th ngi v ng vt
carbohydrate tp trung ch yu trong gan.
Thc vt xanh c kh nng s dng nng lng nh sng tng
hp carbohydrate t CO
2
v H
2
O. Carbohydrate thc vt l ngun dinh
dng quan trng ca ngi v ng vt.
Trong c th sng carbohydrate gi nhiu vai tr quan trng nh:
- Cung cp nng lng cho c th, carbohydrate m bo khong
60% nng lng cho cc qu trnh sng.
- C vai tr cu trc, to hnh (v d: cellulose, peptidglican...)
- C vai tr bo v (mucopolysaccharide)
- Gp phn bo m tng tc c hiu ca t bo (polysaccharide
trn mng t bo hng cu, thnh t bo mt s vi sinh vt).
Da vo cu to, tnh cht carbohydrate c chia lm hai nhm
ln: monosaccharide v polysaccharide.
4.2 Cc monosaccharide
Monosaccharide l cc aldehyd hoc cetone c cha mt hoc nhiu
nhm hydroxyl. S lng carbon trong phn t monosaccharide t nht l
3, l glyceraldehyd v dihydroxyacetone. Chng c cng thc nh sau:
O H
C
HOCH
CH
2
OH
L-glyceraldehyd
O H
C
HCOH
CH
2
OH
D-glyceraldehyd
CH
2
OH
C = O
CH
2
OH
Dihydroxyacetone
57
Glyceraldehyd c cha 1 cacbon bt i (C*), c hai ng phn D
v L, cn dihydroxyaketone khng cha carbon bt i. S ng phn lp
th ca monosaccharide tnh theo cng thc X = 2
n
(n l s C* trong phn
t).
Nu s cacbon trong phn t monosaccharide l 4, 5, 6 hoc 7 chng c
tn gi tng ng l tetrose, pentose, hexose v heptose. Cng thc cu
to ca mt s monosaccharide thng gp c trnh by di y:
CHO
HCOH
HCOH
CH
2
OH
D-Erythrose
CHO
HCOH
HCOH
HCOH
CH
2
OH
D-Ribose
CH
2
OH
C = O
HC-OH
HCOH
CH
2
OH
D-Ribulose
CH
2
OH
C = O
HO-CH
HCOH
CH
2
OH
D-Xilulose
CHO
HCOH
HOCH
HCOH
HCOH
CH
2
OH
D-Glucose
CH
2
OH
C = O
HO-CH
HCOH
HCOH
CH
2
OH
D-Fructose
CH
2
OH
C = O
HO-CH
HCOH
HCOH
HCOH
CH
2
OH
D-Sedoheptulose
Khi nh s th t cc nguyn t carbon trong phn t
monosaccharide, bt u t carbon ca nhm carbonyl ca aldose, hoc
carbon u gn nhm carbonyl ca cc ketose.
Cn c vo v tr ca H v OH carbon bt i mang s th t ln
nht (carbon bt i xa nhm carbonyl) ging vi D hoc L-
58
glyceraldehyd xp monosaccharide vo dng D hoc L. Cc
monosaccharide c kh nng lm quay mt phng nh sng phn cc v
bn phi (k hiu du +) hoc bn tri (k hiu du -).
Trong ho sinh hc ng 6C v 5C c ngha ln. Mt s ng
v d 1,6 fructosediphosphate v ng ribose c nu trn. Hexose
v pentose c th tn ti dng thng hoc vng. Theo ngh ca
Harworth phn t ng c vit dng vng. y ngi ta tng
tng mt mt phng nm ngang c 6 hoc 5 gc, nhng gc ca n sp
xp pha trn hoc pha di nhng chui bn vung gc vi mt phng.
dng vng xut hin mt nhm hydroxyl glycoside, nhm ny c kh
nng phn ng cao, d dng to lin kt glycoside v c tnh kh.
Nhm hydroxyl glycoside l c trng ca ng kh, nhm ny c
th pha di hoc pha trn mt bng phn t. Nu n nm pha di th
ngi ta gi l dng , v d -glucose, nu pha trn th c gi l
dng . Glucose tn ti ch yu dng 6 cnh (pyranose), fructose v
pentose dng vng 5 cnh (furanose).
Mt lin kt glycoside xut hin khi mt phn t nguyn t H
c thay th bng mt gc ng (glycosyl), v d adenine c thay
th bi 1 ribosyl (gc ng ca ribose).
CH
2
OH
OH
HO
OH
OH
O
HO-CH
2
OH OH
OH
O
HO-CH
2
OH
HO
OH
O
CH
2
-OH
OH glycoside
- glucose
OH glycoside
- ribose
OH glycoside
- fructose
59
Hnh 4.1 Tng hp hexosephosphate t triosephosphate
Trong trng hp ny nguyn t N ni vi 2 thnh phn, v vy ngi
ta gi N-glycoside. Tng t nh vy S-glycoside v O-glycoside cng
c to nn. Trong trng hp th nht nguyn t H ca mt nhm SH,
trong trng hp th hai nguyn t H ca mt nhm OH c thay th
bi mt gc glycosyl.
N N
N N
H
NH
2
N N
N N
NH
2
HO-CH
2
OH OH
Ribosyl
O
R
HO-CH
2
OH OH
O
R-H
CH
2
OH
OH
HO
OH
O
O P
CH
2
-O P
OH
HO
OH
O
OH
P O-CH
2
OH
HO
OH
O
CH
2
-OH Isomerase
Isomerase
Glucose 1- phosphate Glucose 6- phosphate Fructose 6- phosphate
P O-CH
2
OH
HO
OH
O
CH
2
-O P
HOH
P OH
Phosphatase
PGA
DHAP
CH
2
- O P
C = O
H
2
C-OH
OCH
HCOH
CH
2
-O P
CH
2
- O P
C = O
H
2
C-OH
OCH
HCOH
CH
2
-O P
Aldolase
Bin i thnh
dng vng
Fructose 1,6-diphosphate
60
Tnh cht chung ca cc monosaccharide
Cc monosaccharide l nhng cht khng mu, phn ln c v ngt.
Chng ho tan tt trong nc, khng tan trong dung mi hu c khng
phn cc, tan trong dung dch ethanol 80%.
Tnh cht l hc c trng ca monosaccharide l tnh hot quang
ca chng, ngha l c kh nng lm quay mt phng ca nh sng phn
cc sang phi hoc sang tri. C th o c gc quay ny bng my phn
cc k.
Ho tnh quan trng ca monosaccharide l nhng tnh cht ca
nhm chc aldehyd hoc ketone, in hnh l tnh kh.
a) Tu iu kin oxy ho monosaccharide b oxy ho thnh cc acid
khc nhau
- Khi oxy ho nh bng dung dch clo, brom, iod trong mi trng
kim, hoc dung dch kim ca cc ion kim loi, nhm chc
aldehyd ca monosaccharide b oxy ho. Ion kim loi b kh thnh
dng c ho tr thp hn hoc n kim loi t do (vi d Cu
2+
Cu
+1
, Ag
+
Ag
0
).
CHO COOH
HCOH HCOH
HOCH Oxy ho nh HOCH
HCOH HCOH
HCOH HCOH
CH
2
OH CH
2
OH
D-glucose D-gluconic acid
- Khi cht oxy ho l HNO
3
c, c hai nhm aldehyd v alcohol
bc 1 ca monosaccharide u b oxy ho to thnh acid cha 2
nhm carboxyl gi l saccharic acid:
61
CHO COOH
HCOH HCOH
HOCH HNO
3
HOCH
HCOH HCOH
HCOH HCOH
CH
2
OH COOH
D-glucose Saccharic acid
b) Di tc dng ca cc cht kh nhm carbonyl ca
monosaccharide b kh to thnh cc polyol tng ng
tin hnh phn ng kh c th dng dng kh hydro c cht xc
tc l kim loi (hn hp Hg v Na). V d khi b kh fructose to thnh 2
polyol ng phn l sorbitol v mannitol. Sorbitol cng l sn phm ca
phn ng kh glucose.
CHO CH
2
OH
HCOH HCOH
HOCH HOCH
HCOH HCOH
HCOH HCOH
CH
2
OH COOH
D-glucose D-sorbitol
Trong c th sinh vt, glucose c th b kh to thnh polyol vng
gi l inosite, v d mezoinosite l yu t sinh trng ca cc m thc vt
nui cy. Estephosphoric ca n (fitin) l ngun d tr phospho trong ht.
CH
2
OH
OH
HO
OH
OH
O
62
c) Phn ng to este thng xy ra vi nhm alcohol bc 1, OH
glycosite ca monosaccharide. Cc este phosphat ca
monosaccharide l nhng sn phm trung gian quan trng nht ca
nhiu qu trnh trao i cht trong c th sinh vt.
d) Phn ng ca nhm OH glycosite to thnh cc hp cht glycoside
Nhm OH glycoside c th phn ng vi ru to thnh este tng
ng gi l glycosite. Tu theo v tr ca nhm OH ny m - hoc -
glycoside c to thnh. Trong phn t glycoside, phn khng phi
carbonhydrate c gi l aglicon.
C th phn bit cc kiu lin kt glycosite khc nhau:
- Lin kt O-glycoside: (G-C-O-A) gc aglicon (A) kt hp vi
carbonhydrate (G) qua O. Lin kt O-glycoside l dng lin kt ca i-,
tri-, oligo- v polysaccharide.
- Lin kt S-glycoside: (G-C-S-A) gc aglicon (A) kt hp vi
carbonhydrate (G) qua S
- Lin kt N-glycoside: (G-C-N-A) gc aglicon (A) kt hp vi
gluxit (G) qua N
- Lin kt C-glycoside: (G-C-C-A) gc aglicon (A) kt hp vi
carbonhydrate (G) qua C
Lin kt glycoside khng bn vi acid, tng i bn vi kim.
Di tc dng ca acid hoc cc enzyme tng ng, glycoside b thu
phn to thnh monosaccharide v aglicon.
4.3 Cc polysaccharide
Polysaccharide do nhiu gc monosaccharide kt hp vi nhau, c
khi lng phn t ln, do polysaccharide khng c tnh kh. Cc
monosaccharide c th thuc mt loi hay nhiu loi khc nhau. Cc lin
kt glycoside trong phn t polysaccharide c th l - hoc -glycoside.
Tn polysaccharide da theo tn ca monosaccharide cu to nn n
nhng i ui ose thnh ui an. V d D-glucane, D-fructane, D-
galactane. Sau y ch cp chi tit hn mt s polysaccharide ph bin
v quan trng.
Tinh bt l polysaccharide d tr thc vt ph bin nht, l mt hn
hp ca amylose v amylopectin, trong amylopectin chim khong
80%. Amylose l mt chui khng phn nhnh gm nhiu gc glucose. C
khong 200-300 gc glucose kt hp vi nhau theo kiu -glycoside. Lin
kt lun lun nm gia C
1
v C
4
. Ngc li amylopectin l chui phn
nhnh. S phn nhnh l do lin kt glycoside gia C
1
v C
6
. Amylopectin
63
c to thnh t amylose. Gc amylose (khong 40 gc glucose) c
gn kt vi mt chui amylose khc bng lin kt -1-6-glycoside. Ngi
ta cho rng chui amylose di v c nhng chui amylopectin ngn hn c
cu to xon.
C quan d tr tinh bt l v sc lp (amyloplast), tng t nh lc
lp v pht trin t tin lc lp. C quan cha t bo d tr (ht ng cc,
c khoai ty) gm cc v sc lp xp st nhau.
Amylose
Amylopectin vi s phn nhnh 1,6
64
Tinh bt c tch lu trong v sc lp v lc lp dng ht tinh bt
v to nn v tr tinh bt tp trung. Cu trc ny i vi tng loi thc vt
l khc nhau nh hnh 4.2. Ngi ta c th nhn dng ht tinh bt c
ngun gc t cc loi thc vt khc nhau. nhng v tr tinh bt tp trung
th hin s kt hp ca cc ht tinh bt dy hn hoc tha hn. S kt hp
dy hn th hin vo ban ngy, tha hn vo ban m. Tinh bt c nhiu
trong cc loi qu v c khc nhau, nh trong ht ng cc (60-70 %) trong
c khoai ty (15-20%).
Hnh 4.2 Cu trc ca cc ht tinh bt khc nhau
Trong lc lp tinh bt ch c tch lu tm thi v thc ra ch khi
hot ng quang hp mnh, vo ban ngy. Ban m nhng ht tinh bt
c phn gii thnh cc monosacaride, c bit l cc triose v c i ra
khi lc lp.
Glycogen l mt chui mch nhnh, i phn t c to nn t
nhiu gc glucose. Glycogen (tinh bt ca gan) l carbohydrate d tr ca
ng vt bc cao. N tn ti ch yu trong gan v trong m c. Nng
glycogen trong gan cao hn trong m c, tuy nhin v trng lng ca
m c ln hn trng lng ca gan nn m c c nng glycogen tng
s cao hn gan. Glycogen nm trong t bo cht dng ht nh, c
Khoai ty
La m
La
Ng
65
ng knh 10-40 nm. S tng hp glycogen thc hin t UDP-glucose.
N l cht cho gc glycosyl i vi enzyme tng hp glycogensynthetase.
Glycogen trong gan chu trch nhim iu khin nng ng trong
mu. Nng ng trong mu nm gia 4,5-7mM. Khi cung cp ng
qua thc n th glucose trong mu c tng hp thnh glycogen, khi cn
glucose, v d hot ng ca c th glucose c gii phng t glycogen.
Cellulose l mt thnh phn quan trng ca thnh t bo thc vt.
thnh t bo s cp n chim khong 30%, t bo gi thnh phn ny
cn cao hn. Cellulose l mt glucan, mt polysaccharide, c to nn t
cc gc glycosyl. Lin kt nm gia C
1
v C
4
v tng t lin kt trong
cellobiose. lin kt -glycoside nhm OH C
1
nm pha trn, trong
khi nhm OH C
4
nm pha di (cng thc Harworth). Nh vy
nhng nhm OH ca hai gc nh 2 pha i din nhau, ngi ta cho
rng mt bng ca phn t t quay 180
0
. Sau phn t cellulose c mt
hnh dng, m nguyn t C
6
lc nm pha trn v lc th pha di
ca phn t.
Cellulose (mt on ct)
CH
2
OH
OH
HO
OH
OH
O
CH
2
OH
OH
HO
OH
OH
O
CH
2
OH
OH
HO
OH
OH
O
CH
2
OH
OH
HO
OH
OH
O
180
o
CH
2
OH
O
CH
2
OH
O
O
CH
2
OH
O
CH
2
OH
O
O
O
66
C khong 36 chui cellulose ring bit kt hp vi nhau thnh 1 vi
si, y cc chui lin kt vi nhau bng lin kt hydro. Cc vi si ny
c nhng vng kt tinh v dng ny enzyme kh c th tc ng. Nhng
vi si kt hp li thnh si, v b si, nh bng vi l dng si tinh
khit. Cht cho glucosyl l UDP-glucose. Enzyme, cellulose synthetase,
c gian bo.
4.4. Ho sinh quang hp
4.4.1 Pha sng trong quang hp
Trong th gii sinh vt th quang hp l mt qu trnh c bn. Thng
qua quang hp m nng lng ca nh sng mt tri chiu xung c
bin thnh nng lng ho hc. Hu ht sinh vt ca hnh tinh chng ta
sng trc tip hoc gin tip nh nng lng nh sng mt tri. Nh vy
nng lng c tch lu l dng nng lng ho hc.
Phn ng tng qut ca qu trnh quang hp thng c biu din
bng phng trnh sau, mc d n th hin khng hon ton y .
6CO
2
+ 6H
2
O + Nng lng C
6
H
12
O
6
+ 6O
2
qu trnh quang hp nh nng lng nh sng mt tri m ng
c to thnh v quang hp thc vt gn lin vi vic gii phng
oxy.
Qu trnh quang hp c chia lm hai giai on:
- Phn ng sng
- S ng ho CO
2
Giai on th nht l qu trnh chuyn nng lng nh sng thnh
nng lng ho hc.
Giai on th hai l to ra dng nng lng ho hc bn vng v
d d tr hn.
67
Hnh 4.3 Cu trc ca dip lc a v b
nh sng cn cho qu trnh quang hp c tip nhn bi hai nhm
sc t: chlorophyll v carotenoid. mt s sinh vt bc thp hn cn c
phycobillin. Cu trc c bn ca dip lc l vng porphyrin, c to nn
t 4 vng pyrrol ring l (hnh 4.3). trung tm ca vng c mt nguyn
t Mg lin kt vi cc nguyn t nit bi hai lin kt ng ho tr v hai
lin kt phi tr. Nguyn t Mg c th c tch ra khi c tc ng ca
axit long. Phn t dip lc khng cha Mg c gi l pheophytin cng
c mt vai tr quan trng trong phn ng sng quang hp. Chui bn ca
phn t dip lc c tnh k nc v nh vy m ton b phn t c c
tnh k nc. Ngi ta bit nhng loi chlorophyll khc nhau: chlorophyll
a, chlorophyll b v chlorophyll vi khun. S khc nhau ca nhng loi ny
l do s khc nhau ca cc chui bn. chlorophyll b c nhm aldehyde,
nh hnh 4.3, c thay th bng nhm methyl chlorophyll a. iu th
v hn l chui bn di k nc c to nn t cc dn xut isopren.
68
chlorophyll a v b chui bn l mt phytol (ru) lin kt ester vi mt
chui bn ca vng porphyrine. mt s vi khun chlorophyll cha mt
farnesol (alkohol) c lin kt ester vi chui bn ca vng.
iu c ngha c bit hn l nhng lin kt i lin hp trong
vng porphyrine. Chng c kh nng hp thu nh sng v v vy nhng
lin i ny l yu t quan trng ca chlorophyll. Nhng lin kt lin hp
ca carotenoide cng hp thu nh sng. Cc cht thuc nhm carotenoide
c mu vng n mu da cam, thy r l cy vo ma thu, lc ny
dip lc b phn hu nn khng cn che ph sc t carotenoid.
hiu hn v qu trnh quang hp chng ta phi cp n c
quan m quang hp xy ra, l lc lp. Lc lp c hnh trn n
hnh bu dc, c ng knh khong 10 m. N c bao quanh bi
mng trong v mng ngoi, nhng mng ny c ngha i vi vic i
vo v i ra ca cc cht. Mng trong ca lc lp c to nn t h thng
mng ko dn, mt s v tr c dng xp chng ln nhau.
Hnh 4.4 S biu din mt lc lp
Nhng mng ny xut hin di knh hin vi in t nh nhng ti
dt. V vy ngi ta gi chng l thylacoid. Mng thylacoid bao quanh
mt khng gian bn trong gi l c cht ca lp th v to nn s ngn
cch gia bn trong thylacoid vi mi trng ngoi. S phn cch gia
bn trong thylacoid vi stroma l cn thit cho phn ng sng ca quang
Stroma
Bn trong
Thylakoid
Grana Thylakoid
Mng Thylakoid
Mng ngoi
Mng trong
Stroma - Thylakoid
69
hp. mt s v tr c nhiu thylacoid xp ln nhau thnh chng rt dy.
Chng xut hin di knh hin vi nh nhng ht (grana), v vy ngi ta
gi chng l grana-thylacoid. Chng c ni kt vi nhng thylacoid
ring l nh mng kp xuyn qua c cht lc lp. Chng c gi l
stroma-thylacoid (hnh 4.4).
Mng thylacoid l ni m nh sng c tip nhn bi cc sc t
m t trn v nh cc h thng oxy ho kh khc nhau m nng lng
nh sng mt tri c bin i thnh nng lng ho hc v thm thu.
Qu trnh ny phc tp v cha c gii thch chi tit.
Mng thylacoid cha ba cu thnh siu phn t, chng chim ton
b b rng ca mng v l thnh phn quan trng ca chui vn chuyn
in t trong quang hp. Ba phc h l h thng quang ho I, h thng
quang ho II v phc h cytochrome b/f (hnh 4.5).
Hnh 4.5 Cc phc h vn chuyn quan trng nht ca mng
thylacoid: H thng quang ho II (HTQHII), phc h cytochrome b/f, h
thng quang ho I (HTQHI)
H thng quang ho l v tr cha cc sc t hp th nh sng
(nhng anten). H thng quang ho I cha t nht l 13 loi protein khc
nhau, khong 200 phn t dip lc, mt s lng carotenoid cha bit v
ba phc h Fe-S. Nhng polypeptide kt hp v nh hng cc phn t
chlorophyll v carotenoid.
H thng quang ho II cha t nht 11 phn t polypeptide khc
nhau, khong 200 phn t dip lc a v 100 phn t dip lc b, hai phn t
pheophytin, quinon, 4 Mn cng nh Ca v chlorid. C hai h thng tip
nhn nh sng v chuyn ho chng trong s vn chuyn in t.
Chlorophyll
Carotenoide
Protein
Phc h Fe
2
-S
2
Chlorophyll
Carotenoide
Protein
Quinon
Phc h
Cyto-
chrome b,f
T bo cht
2NADP
+
+ 2H
+
2NADPH
4e
-
4e
-
Ferredoxin
Mng
Thylakoid
2H
2
O
4e
-
4H
+
+ O
2
HTQH II HTQH I
Plasto
cyanin
P682
P700
Pl.chinon
Pl.chinol
70
H thng quang ho II cn c nhim v l tch in t ra t H
2
O,
nh vy l oxy ho H
2
O. S oxy ho ny l qu trnh phc tp, gm 4
bc (mi bc 1e
-
c vn chuyn v y c s tham gia ca Mn vi
s thay i ho tr).
2H
2
O 4e
-
+ 4H
+
+ O
2
.
Qu trnh tch nc trong quang hp c gi l quang phn ly
nc, n gii phng ra O
2
v c trng cho quang hp sinh vt nhn
chun.
H thng quang ho I v II khng ch cha sc t tip nhn nh sng
m mi h thng cn cha mt phn t dip lc hon ton c bit th
hin v tr ca n, phn t dip lc ny khi tip nhn nh sng c kh
nng bn ra 1 in t. Qu trnh ny nh l s khi u cho s vn chuyn
in t trong quang hp. Phn t dip lc c bit ca h thng quang ho
I hp thu cc i nh sng c bc sng 700 nm. V vy gi l P700
(Pigment 700) v phn t dip lc c bit ca h thng quang ho II hp
thu cc i 682 nm.
bn ra 1 in t th phn t dip lc cn nng lng. Nng lng
c hp th dng nng lng nh sng t nhng sc t khc
(chlorophyll v carotenoid) ca mi h thng quang ho v c chuyn
n P682 cng nh P700 qua s cng hng in t. Bng cch ny hai
h thng quang ho to ra mt s vn chuyn in t khi c nh sng, s
vn chuyn in t ny i t H
2
O nh l ngun in t, qua h thng
quang ho II, plastochinone, phc h cytochrom b/f, plastocianin n h
thng quang ho I v cui cng n NADP
+
v n c kh thnh
NADPH.
NADP
+
+ H
+
+ 2e
-
NADPH
Trong chui kh ny h thng quang ho II v h thng quang ho I
khi ng k tip nhau. Plastochinone cng nh phc h cytochrome b/f
v plastocyanin c chc nng vn chuyn e
-
gia hai h thng quang ho
ny v chng nh v nhng v tr khc nhau. S vn chuyn e
-
lm
cho nng lng nh sng c bin i thnh nng lng ho hc, dng
kh NADPH (1 mol NADPH 220 kJ).
Thnh vin vn chuyn in t c bn trong chui vn chuyn l
phc cytochrome b/f, cng l protein c heme l nhm prostetic, v vn
chuyn in t l do s thay i ho tr ca Fe. Bn cnh phc
cytochrome b/f l plastocyanin, mt protein cha Cu (protein mu xanh)
vn chuyn in t gia phc cytochrome b/f v h thng quang ho I. S
vn chuyn ny c th l do s thay i ho tr ca Cu. H thng
71
plastochinon-plastochinol vn chuyn H t h thng quang ho II n
phc cytochrome b/f. Khong cch vn chuyn y ln hn. N khuch
tn trong vng ui ca lp mng kp lipid. Thnh phn mng cha
nhiu acid bo cha no th s khuch tn ca plastochinone d dng hn.
Sau y l phn t plastochinone v s kh n thnh plastochinol
(plastohydrochinone). c tnh k nc ca phn t l do cc nhm CH
3
v chui bn di vi 9 gc isopren. Phn ng kh vng chinone thc hin
qua s tip nhn ca 2e
-
v 2H
+
v vng quinone chuyn sang mt h
thng lin kt i ca bensoide.
H thng plastochinone/plastochinol vn chuyn H gia h thng
quang ho II v phc h cytochrome b/f. Phc h dng oxy ho-
plastochinon gn vo h thng quang ho II trc ht nhn 2e
-
v to
thnh semichinone (dng anion) v sau nhn 2H
+
ca h thng quang
ho II to thnh dng kh plastochinol. Sau n tch ra khi h thng
quang ho II v khuch tn n phc h cytochrome b/f. n y n b
oxy ho khi nhng 2e
-
v 2H
+
, to nn plastochinone v li khuch tn v
h thng quang II (hnh 4.5).
Chc nng c bn ca hai h thng quang ho l hp thu nh sng
v tp trung nng lng ca chng n P682 v P700, ri dn n qu
trnh quang ho, thc cht l bn ra 1e
-
. Chc nng ca 2 h thng tng
t nhau, tuy nhin nhng qu trnh chi tit hai h thng khc nhau, v v
chi tit cng cha c gii thch ht. S nhng 1 in t ca P682 lm
xut hin mt cht oxy ho rt mnh (phn t c kh nng oxy ho cht
khc) c th nng khong 1200 mV. P682 dng oxy ho (P
+
682) c kh
nng oxy ho H
2
O, ngha l tch e- ra khi H
2
O. Giai on quan trng
qu trnh ny l s tip nhn e
-
t P682 bn ra.
OH
OH
O
O
H
3
C
H
3
C
CH
2
CH
CH
3
C
CH
2
H
9
2e
-
2H
+
Plastochinone
Plastochinol
72
Ngy nay ngi ta cho rng, cht nhn in t bn ra l nhng
hp cht chinone. y chinone c kh thnh bn chinone
(semichinone mang in tch m). Semichinone l 1 radical, tip tc phn
ng nhanh, c th chuyn e
-
ca n n plastochinone. Dng semichinone
c kh to thnh plastochinone.
Pheophytin cng tham gia vo s vn chuyn e
-
. in t c bn ra
t P682 c th khng c tip nhn ngay, di tc dng ca nh sng
to nn rt nhanh l hng in t ca P682. Dng oxy ho ca P682
(P
+
682) tn ti rt ngn vi thi gian khong 10
-12
giy.
Nh c h thng quang ho II, di tc dng ca nh sng 1e
-
t
H
2
O c th nng oxy ho kh cao (th nng oxy ho kh tiu chun l
+800 mV) c chuyn n plastochinone c th oxy ho kh thp (th
kh tiu chun 100 mV). Nh vy kh nng kh ca e
-
c tng ln rt
nhiu.
Trong h thng quang ho I e
-
c bn ra t P700 c tip nhn
bi 1 phc h Fe-S. N chuyn e
-
ny tip tc n ferredoxin dng ho
tan nm trong stroma ca lp th. y cng thc hin mt phn ng
ngc chiu ca e
-
ngha l in t c chuyn n ni c in th m
ln hn, mt qu trnh cn nng lng, c thc hin nh nh sng mt
tri tip nhn c. Th kh tiu chun ca P700 nm khong +400 mV,
ca ferredoxin khong - 400 mV. Nng lng c nng ln r rt nh h
thng quang ho I. Ferredoxin kh c to nn l mt cht kh mnh, c
kh nng kh NADP
+
.
O
O
O
-
O
*
Semichinone
mang in m
(radical)
e
-
2x Ferredoxin Fe
II
2x Ferredoxin Fe
III
NADP
+
+ H
+
NADPH
73
hnh 4.6 a ra s c gi l s Z, ch ra hai s nng
nng lng c thc hin t h thng quang ho I v II trong chui vn
chuyn e ca quang hp. y e- ca H
2
O c chuyn n NADP
+
to nn NADPH l mt cht kh mnh cn cho nhiu qu trnh tng hp.
Hnh 4.6 S Z biu din s vn chuyn in t t in th dng n
in th m, s vn chuyn nng lng thc hin qua P682 v P700
Ferredoxin l mt cht kh mnh, c kh nng kh nhiu cht, c
ch ra hnh 4.7. Ngoi ra NADP
+
cn c ngha c bit trong vic kh
nitrite, sulfate v glutarate. Phn ng kh nitrite v sulfate l mt bc
quan trng trong s ng ho cc ion v c. V vy phn ng sng ca
quang hp khng ch l s ng ho CO
2
m cn ng ho c N v S.
Ferredoxin
NADP
+
-400
e
-
P700
Quang phosphoryl
ha vng
0
+400
+800
P682
H
2
O
e
-
Plasto-
chinone
e
-
Cyto-
chrome b,f
PC
e
-
e
-
Eo mV
74
Hnh 4.7 Nhng kh nng phn ng ca ferredoxin
Trong hnh 4.6 ch ra t ferredoxin e
-
khng nhng c th c
chuyn n NADP-reductase m cn tr v plastochinone. Nh vy to
nn mt dng in t khp kn. y in t li i qua cytochrome f v
plastocyanin tr v li P700 v t y li nh nng lng nh sng
c a n ferredoxin. Dng in t khp kn ny cng to nn s phn
tch proton v nh vy m tng hp ATP, dng in t khp kn ny c
gi l quang phosphoryl ho vng.
Quang phosphoryl ho vng ch sn xut ATP, quang phosphoryl
ho khng vng to nn ATP v NADPH. Bng cch ny qu trnh quang
hp c th t ph hp vi nhu cu ATP v NADPH. Qu trnh tng hp
tinh bt ch yu cn ATP, trong khi tng hp acid bo cn tng i
nhiu NADPH. ng ho CO
2
, cn ATP v NADPH theo t l 3:2.
Ferredoxin cng c th chuyn e
-
ca n n O
2
(hnh 4.7). Sau
H
2
O xut hin, v O
2
b kh lp tc phn ng vi H
+
trong mi trng
nc.
1/2O
2
+ 2e
-
O
2-
O
2-
+ 2H
+
H
2
O
Phn ng ny c ngha l tiu hao e
-
v trit tiu gradient H
+
. V vy
n lm quang phosphoryl ho tch ri s vn chuyn e
-
.
Tng kt chuyn ho nng lng quang hp ngi ta cho rng 4 mol
proton nh sng cn cho vic vn chuyn 2 mol e
-
v qu trnh quang
hp chui vn chuyn e
-
to nn 1 mol ATP v 1 mol NADPH.
Bng 4.1 Tng qut nng lng ca qu trnh quang hp
u vo:
4 Einstein (= mol proton) 710 x 10
3
J
Plastochinol
Nitrite
Sulfate
Glutarate
Cytochrome
O
2
e
-
Ferredoxin
HTQHI
NADP
+
e
-
e
-
e
-
e
-
e
-
e
-
e
-
75
u ra:
1 mol NADPH 220 x 10
3
J
1 mol ATP 32 x 10
3
J
Hiu sut: 35,5 % 252 x 10
3
J
Nh vy khong 35% nng lng nh sng hp thu c chuyn sang
dng nng lng ho hc.
4.4.2 Pha ti trong quang hp (chu trnh Calvin)
S kt hp CO
2
vo mt cht nhn hu c (s ng ho CO
2
) l mt
trong nhng qu trnh sinh hc quan trng nht. Nh qu trnh ny m
cacbon v c c a vo th gii sng. Phn ng c xc tc bi
enzyme ribulosediphosphate-carboxylase (RuDP-carboxylase), enzyme
ny c nhiu trong l xanh v n chim khong 30-50% protein ho tan
trong l. Enzyme gm 8 tiu n v ln v 8 tiu n v nh, trong ch
c cc tiu n v ln c hot tnh xc tc, cc tiu n v nh c chc
nng iu khin. Th v hn l thng tin di truyn ca cc tiu n v ln
nh v trn DNA ca lp th (DNA l cht mang gen).
xc tc enzyme cn nhng iu kin hon ton xc nh, l
gi tr pH (pH 8,3-8,6) v nng Mg
2+
tng i cao. C hai u b tc
ng bi s vn chuyn e
-
qua mng thylacoid. V vy enzyme ch hot
ng trong iu kin chiu sng. Phn ng ny gii phng nhit ( G
01
= -
40 x 10
3
J) v tng ng vi phng trnh sau:
RuDP + CO
2
+ H
2
O 2 phosphoglyceric acid.
H
2
C
O P
C=O
H C - OH
HC - OH
H
2
C - O P
H
2
C
O P
HC - OH
COO H
C O OH
HC - OH
H
2
C - O P
+ CO
2
+ H
2
O
RuDP Phosphoglycerate
76
Ngi ta cho rng carboxyl ho ribulosediphosphate (RuDP) dn n
to thnh mt hp cht trung gian c 6 nguyn t C vi enzyme, sau
c tch ra thnh hai phn t phosphoglyceric acid. Nh s trn CO
2
c tip nhn c mt trong phosphoglyceric acid pha trn v O t
phn t H
2
O c tip nhn th trong phosphoglyceric acid pha di.
Mt thi gian di ngi ta nh gi thp hot ng ca enzyme ny
v khi phn lp enzyme thng mt hot tnh. Kh khn na l CO
2
khng
nhng l c cht m cn nh hng trc tip n xc tc. Ngy nay ngi
ta bit hot tnh ca enzyme c c trng bi h s K
m
(CO
2
) t 10-
20 m l s ng ho CO
2
xy ra trong t nhin.
Sn phm carboxyl ho, phosphoglyceric acid c kh to thnh
aldehydphosphoglyceric. Qu trnh ny thu nng lng, cn ATP v
NADPH. C hai coenzyme tn ti stroma ca lc lp nh phn ng
sng. Khi khng c nh sng, nng ATP v NADPH thp th phn ng
xy ra ngc li, ngha l aldehydphosphoglyceric b oxy ho thnh
phosphoglyceric acid. Phn ng kh phosphoglyceric acid to ra sn phm
trung gian l 1,3 iphosphoglyceric acid. qu trnh ny bn cnh ATP
v NADPH cn c mt SH-enzyme-photphoglycerate-dehydrogenase
tham gia, c biu din s sau:
COOH
HCOH
H
2
C-O - P
Aldehydphospho-
glyceric
O
CO~ P H S Enzyme
HCOH
H
2
C-O - P
ATP
ADP
O
CH
HCOH
H
2
C-O - P
O
C~ S Enzyme
HCOH
H
2
C-O - P
NADP
+
NADPH + H
+
HS-Enzyme
P OH (=P
i
)
77
Aldehydphosphoglyceric l ng u tin xut hin qu trnh
ng ho CO
2
. N d dng chuyn sang dng ng phn
phosphodioxyaketone (PDOA). Cn bng phn ng nghing mnh v pha
phosphodioxyaketone (PDOA) v khong 90% triosophosphate nm
dng PDOA.
c s ng ho CO
2
lin tc th cht nhn CO
2
, RuDP phi c
to nn mt nng nht nh. ng 3C c to ra l
aldehydphosphoglyceric v phosphodioxyaketone c bin i mt phn
thnh RuDP. Trnh t phn ng l mt qu trnh khp kn. S ng ho
CO
2
v bin i ca triosephosphate c gii thch bi Calvin v cng s
ca ng. V vy chu trnh ny c gi l chu trnh Calvin hoc l chu
trnh kh pentosophosphate v s bin i t phosphoglyceric acid thnh
aldehydphosphoglyceric l phn ng kh.
C ba loi phn ng c trng cho chu trnh Calvin:
- Phn ng phosphatase
- Phn ng aldolase
- Phn ng transcetolase
Phn ng phosphatase c cp chng enzyme. Nhng
enzyme aldolase c th gn kt mt aldose vi mt cetose, v d
aldehydphosphoglyceric v photphodioxyacetone. Phn ng ny ch c
mt s bin i nh v nng lng, y l phn ng thun nghch, n
c biu din nh sau:
CHO
HCOH
H
2
C-O - P
Aldehydphospho-
glyceric (aldose)
H
2
C-OH
C=O
H
2
C-O - P
Phosphodioxy-
aceton (cetose)
78
phn ng transcetolase 2C ca cetose c chuyn ln mt aldose
(v d aldehydphosphoglyceric).
Bng cch tng t 2C ca fructosemonophosphate c chuyn ln
aldehydphosphoglyceric, to thnh mt pentosephosphate v mt
tetrosephosphate.
Chu trnh Calvin bt u vi mt phn ng aldolase (hnh 4.8). Khi
tn ti nhiu triosephosphate th aldehydphosphoglyceric phn ng vi
phosphodioxyacetone to nn fructose1,6 diphosphate.
Bng cch ny ng 6C u tin c to nn. T fructose1,6
diphosphate mt phosphate c tch ra nh enzyme phosphatase, lm
xut hin fructosemonophotphate. Fructosemonophosphate cng vi mt
CHO
HCOH
H
2
C-O - P
Phosphodioxy aceton (cetose) + Aldehydphosphoglyceric (aldose)
H
2
C-O P
C=O
HOCH
2
Fructose 1,6 diphosphate
HCOH
HCOH
H
2
C-O - P
H
2
C-O P
C=O
HOCH
CH
2
- OH
C=O
HOCH
HCOH
HCOH
CH
2
O P
Fructosemono-
phosphate
CHO
HCOH
H
2
C-O - P
Aldehydphospho-
glyceric
H
2
C-OH
C=O
HOCH
HCOH
H
2
C-O P
Pentose-
phosphate
CHO
HCOH
HCOH
H
2
C O P
Tetrose-
phosphate
Transcetolase
79
aldehydphosphoglyceric khc c bin i thnh mt ng c 4C
(erythrosephosphate) v mt ng c 5C (xylulosephosphate) bng phn
ng transcetolase. Erythrosephosphate phn ng vi mt triosephosphate
bng phn ng aldolase to thnh mt ng c 7C
(sedoheptulosediphosphate). T y mt phosphate c tch ra nh
enzyme phosphatase to nn sedoheptulosephosphate.
Sedoheptulosephosphate phn ng vi mt triosephosphate khc nh
enzyme transcetolase to thnh hai ng c 5C l xylulosephosphate
v ribosephosphate.
Trong phn ng tng qut th cn 5 ng triosephosphate to
nn 3 ng pentosephosphate, trong 1 ribosephosphate v 2
xylulosephosphate. Ba ng pentosephosphate c bin i sang dng
ng phn ca n l ribulosephosphate, ng ny c photphoryl ho
nh ATP to thnh ribulosediphosphate. Nh vy m cht nhn CO
2
c ti to.
Ba phn t ribulosodiphosphate c th kt hp vi 3 phn t CO
2
v
nh vy s to nn 6 phn t triosephosphate. y 5 phn t
triosephosphate cn ti to nn 3 phn t ribulosediphosphate. Mt
phn t triosephosphate cn li cho mc ch tng hp. Tng ng c
phng trnh nh sau:
3CO
2
+ 9 ATP + 6NADPH 1 triosephosphate + 9 ADP + 6NADP
+
T phng trnh trn ta thy kh mt phn t phosphoglyceric
acid cn 1 ATP v 1 NADPH. to nn 1 phn t ribulosediphosphate
t ribulosephosphate th cn thm mt phn t ATP. Chu trnh tng qut
cn 3 ATP v 2 phn t NADPH cho c nh 1 phn t CO
2
. Vi qu trnh
quang phosphoryl ho vng th h thng s to c nhiu phn t ATP
hn NADPH, ngha l t l yu cu theo l thuyt ATP/ NADPH ph hp
l 3/2.
80
Hnh 4.8 Chu trnh Calvin, PGA: phosphoglyceric acid,
PDOA: phosphodioxyacetone, FMP: fructosemonophosphate,
FDP: fructosediphosphate
4.4.3 H hp sng- Chu trnh Glycolate
Cy xanh khi c nh sng cn tip nhn O
2
v gii phng CO
2
. H
hp ph ny c gi l h hp sng. S tip nhn O
2
c th do nhiu qu
trnh v d ferredoxin tham gia vo quang hp chuyn e
-
ca n trc tip
n O
2
, nh vy H
2
O xut hin (hnh 4.7).
Warburg ch ra rng O
2
c ch s ng ho CO
2
. Enzyme xc tc
cho ng ho CO
2
l ribulosediphosphate-carboxylase th hin khng
nhng hot tnh carboxylase m cn hot tnh oxygenase. S th hin hot
tnh no l ph thuc vo nng CO
2
v nng O
2
. CO
2
c ch
oxygenase, O
2
c ch carboxylase. Carboxyl ho v oxy ho c cng trung
tm hot ho, l gc lysine. Nhng iu kin nh l Mg
2+
kch thch
carboxyl ho v gi tr pH cao kch thch s oxy ho.
NADP
+
+ P
i
NADPH + H
+
CO
2
+ H
2
O
Diphospho
glyceric acid
Triose-
phosphate
APG
AlPG
AlPG
AlPG
PDOA
ATP
PDOA
ADP
H
2
O
H
2
O
FMN
P
i
P
i
RuDP
1,6 FDP
Ribulose-
monophosphate
Sedoheptulose-
diphosphate
Erythroso-
phosphate
Xilulosophosphate
Sedoheptulose-
monophosphate
Xilulosephosphate
Ribosephosphate
1
2
3
4
5
81
Hnh 4.9 S cnh tranh gia CO
2
v O
2
vo cng mt v tr ca enzyme
ribulosephosphate-carboxylase-oxygenase
Cui cng th c hai phn ng c cng c cht, l
ribulosediphosphate. S cnh tranh gia O
2
v CO
2
vi phn t enzyme
c minh ha hnh 4.9.
S cnh tranh ca CO
2
v O
2
cng mt v tr ca enzyme to ra s
lin quan vi qu trnh quang hp. Khi cng quang hp cao th nng
O
2
trong t bo mesophyll tng ln do qu trnh quang phn ly nc,
trong khi s ng ho CO
2
th nng CO
2
gim. Nhng iu kin ny
thun li cho phn ng oxy ho. Nh vy nhng iu kin thun li cho
quang hp nh nhit thch hp, cng nh sng mnh kch thch s
oxy ho ribulosediphosphate. Phn ng c biu din nh sau:
y phn t O
2
c tch ra lm 2 nguyn t: mt nguyn t gn
vi gc 2C (phosphoglycolate), nguyn t oxy khc gn vi gc c 3C.
Phosphoglycolic acid l dn xut ca acetic acid. Bng phn ng
phosphatase t phosphoglycolic acid, glycolic acid s c to thnh.
CO
2
RuDP
O
2
RuDP
Carboxylase
Oxygenase
H
2
C
O P
C=O
H C - OH
HC - OH
H
2
C - O P
RuDP
COOH
HC - OH
H
2
C - O P
H
2
C - O P
COOH
H
2
C - OH
COOH
O
2
Oxygenase
Phosphoglycolate
H
2
O
P OH
Glycolate
Phosphoglycerate
82
S oxy ho ribulosediphosphate to nn chu trnh glyoxylate, y l
nhng phn ng quan trng ca quang h hp. Phn ng to thnh
phosphoglycolate v phn ng kh phosphoryl ho ca n c xc tc
bi enzyme phosphatase xy ra trong c cht ca lc lp. Hot tnh ca
glycolate-phosphatase c kch thch bi nng Mg
2+
v pH cao v
y l nhng iu kin thun li cho quang hp.
Glycolate t lc lp i n peroxisome l vi c quan t nm st cnh
lc lp, c bao bc bi mng v cha cc enzyme khc nhau nh
transaminase, oxidase v catalase.
Trong peroxisome glycolate b oxy ho to thnh glyoxilic acid
nh mt oxidase. H
2
O
2
xut hin c phn gii thnh H
2
O + 1/2 O
2
v
glyoxilic acid b bin i thnh mt amino acid, l glycine nh mt
transaminase. Transaminase s c cp k hn chng proteine,
y ch nu ln nguyn l ca n l nhm amin ca mt amino acid c
chuyn ln mt nhm ceto hoc nhm aldehyd. Amino acid tr thnh
cetoacid.
H
2
C - OH
COOH
CHO
COOH
Glycolic acid
O
2
H
2
O
2
Glyoxylic acid
CHO
COOH
Aminoacid
Glyoxylic acid
COOH
H
2
C NH
2
COOH
C=O
R
COOH
H
2
N -C H
R
Cetoacid
Glycine
83
Glycine i t peroxisome vo ty th, l c quan t m trong h
hp xy ra. Glycine b oxy ho di tc dng ca NAD
+
v sau b kh
amin ho (gii phng NH
3
), xut hin li glyoxylic acid.
NADH to ra phn ng kh v l c cht cho chui enzyme h
hp. Glyoxilic acid b kh cacboxyl ho v phn ng vi gc CH-OH t
do.
Tetrahydrofolic acid (THFA) kt hp vi mt gc hydroxylmethyl,
gc ny c chuyn n mt glycine, to nn aminoacid l serin v
THFA li tr v trng thi ban u ca n.
CHO
COOH
Glyoxylic acid
COOH
HC = NH
Iminoacid
COOH
H
2
C - NH
2
Glycine
NAD
+
NADH + H
+
H
2
O
NH
3
Hydroxymethyl
COO H
CHO = CH - OH
CO
2
THFA
H
THFA
H
2
C - OH
COOH
HC NH
2
H
Glycine
THFA
H
2
C - OH
THFA
H
COOH
HC NH
2
H
2
C - OH
Serine
+ +
84
Serine b kh amin ho to nn hydroxylpyruvate v cht ny c
th c bin i thnh phosphoglyceric acid bng phn ng kh v phn
ng phosphoryl ha.
Phn ng cn 1 NADH. Phosphoglyceric acid l mt cht trao i
ca chu trnh Calvin. Cht ny li i vo lc lp v n c s dng
to nn triosephosphat. Nh hnh 4.10 ch ra, chu trnh glyoxylate xy
ra trong cc c quan t khc nhau. Tng qut l c hai phn t glycolate
c s dng tng hp nn mt phn t phosphoglyceric acid.
COOH
HC NH
2
H
2
C - OH
Serine
COOH
C = O
H
2
C - OH
Pyruvic acid
COOH
HC - OH
H
2
C - O P
Phosphoglyceric acid
COOH
HC - OH
H
2
C - OH
Cetoacid
Aminoacid
ADP
ATP
Kinase
NADH + H
+
NAD
+
Hydroxypyruvic acid
Lc lp
Ty th
2x Glycolate
P-Glycerate
2x Glyoxylate
2x Glycine
Peroxisome
O
2
O
2
CO
2
NH
3
85
Hnh 4.10 Nhng cht trao i quan trng ca chu trnh glycolate cc c
quan t khc nhau
Chu trnh glycolate c mi lin h cht ch vi chu trnh Calvin qua
ribulosediphosphate-carboxylase-oxygenase. Tng qut ca chu trnh
glyolate l 2 v tr O
2
c tip nhn (phn ng oxygenase v phn ng
oxidase) v CO
2
v NH
3
c gii phng ra. Nh vy chu trnh glycolate
phn gii C v N hu c. ngha sinh l ca s phn gii ny vn cha
c gii thch r rng.
Quang h hp b nh hng bi nhiu yu t ngoi cnh. Nhng yu
t kch thch quang hp nh cng chiu sng cao, nhit thch hp
lm tiu hao nhiu CO
2
trong m l v sn sinh nhiu O
2
do quang phn ly
nc lm cho h hp sng xy ra mnh m. CO
2
v NH
3
gii phng ra
trong h hp sng li c ng ho. c bit l NH
3
.
Cht km hm t nhin ca chu trnh glyolate l glutamate, aspactate
v glycolate. nhng thc vt C4 h hp sng khng c ngha. y
c th do c ch ng ho CO
2
c bit m nng CO
2
tng i cao
trong lc lp, v vy m hot tnh oxygenase ca ribulosediphosphat-
carboxylase-oxygenase khng th hin.
4.4.4. Chu trnh Hatch v Slack
Ribulosediphosphate khng phi l cht nhn CO
2
duy nht cho
phn ng u tin ca s ng ho CO
2
. mt s loi thc vt, c bit
loi cy h c nhit i (ng, cao lng, ma) cht nhn CO
2
l
phosphoenolpyruvate (PEP). Qu trnh bt u bng phn ng kt hp
HCO
3
-
vo PEP. Bng cch ny nh enzyme PEP-carboxylase, mt hp
cht 4C- oxaloaxetic acid, c to thnh.
PEP
COOH
C O P
CH
2
COO
-
CH
2
C = O + P OH
COOH
Oxaloacetate
O
+ HO C O
-
86
Nh ch ra s , HCO
3
-
c tch ra thnh 1 gc hydroxyl v
1 gc carboxyl. Gc hydroxyl phn ng vi gc phosphoryl ca PEP
to nn phosphate v c (H
3
PO
4
). Gc carboxyl kt hp vi cht c 3C
(PEP) to nn cht c 4C (oxaloaxetic acid).
Hnh 4.11 S ng ho CO
2
theo chu trnh C
4
nh enzyme PEP-carboxylase
Phn ng ny gii phng nng lng, v lin kt cao nng trong PEP
c phn gii. Oxaloaxetic acid c to nn (anion oxalacetate) sau
tip tc b kh to thnh malate hoc b amin ho to thnh
aspartate. V nhng phn ng ny cha nhng hp cht c 4C, nn s
ng ho CO
2
nh PEP-carboxylase c gi l chu trnh C
4
. Nhng loi
thc vt m ng ho CO
2
u tin bng con ng ny, c gi l thc
vt C
4
ngc vi thc vt C
3
, l nhng cy ng ho trc tip CO
2
qua
PEP
COOH
C O P
CH
2
*
COO
-
CH
2
C = O
COOH
Oxaloacetate
COOH
H
2
N-CH
CH
2
COO
-
Aspartate
Aminoacid
COOH
H
2
N -C H
R
COOH
C=O
R
Cetoacid
H
+
CO
3
-
Pi
1
3
2
NADPH
+ H
+
NADP
+
COOH
C = O
CH
3
Pyruvate
*
COO H
CH
2
HCOH
COO
-
Malate
NADP
+
NADPH + H
+
+
CO
2
ATP + Pi
P ~ P
+ AMP
4
5
Chu trnh Calvin
87
chu trnh Calvin. Trnh t phn ng ca chu trnh C
4
c ch ra hnh
4.11.
Phn ng 1: HCO
3
-
c kt hp vi PEP to thnh oxalacetate.
Phn ng ny c xc tc bi enzyme PEP-carboxylase.
Phn ng 2: Oxalacetate b kh to thnh malate nh NADPH
Phn ng 3: Oxalacetate c bin i thnh aspartate bng phn
ng chuyn amin ho.
Phn ng 4: Nh cc malatenzyme m malate b kh carboxyl ho
v oxy ho to nn pyruvate. CO
2
c gii phng ra do kh cacboxyl
ho c a n chu trnh Calvin.
Phn ng 5: Pyruvate c bin i tr li thnh PEP bng phn
ng kh carboxyl ho. Phn ng cn ATP v photphate v c.
ATP c tch ra thnh AMP v pyrophosphate. Phn ng ny c
mt gi tr m G
01
cao, nn phn ng xy ra nhanh nn cht nhn CO
2
l
PEP c to ra nhiu. Enzyme xc tc gi l pyruvate-phosphat-
dikinase, gn vo enolpyruvate theo phn ng di y:
Trao i CO
2
ca thc vt C
4
c hiu khi ngi ta chia ra nhng
qu trnh ring l nhng m l khc nhau v nhn bit nhng v tr ca
t bo. Phn ln nhng thc vt C
4
c kiu gii phu Kranz c trng, mt
khi nim c Haberlandt (1904) ngh. y l nhng t bo xanh
bao quanh b mch dng xon kp xp st xung quanh nhng t bo b
mch, trong khi nhng t bo mesophyll nh hn sp xp lng lo hn
(hnh 4.12).
COOH
C - OH
CH
2
Enolpyruvate PEP
COOH
C O P
CH
2
ATP + P
i
AMP + P ~ P
88
Hnh 4.12 S sp xp ca cc t bo tht l v cc t bo b mch cu trc
Kranz ca thc vt C
4
1. Biu b trn, 2. T bo m giu cha lc lp, 3. Mch dn,
4. Khoang trng gian bo, 5. Biu b di vi kh khng.
Trong nhng t bo mesophyll CO
2
c ng ho nh PEP-
carboxylase v oxaloacetate c to ra b bin i thnh malate hoc
aspartate. Nhng t bo mesophyll ca thc vt C
4
khng cha RuDP-
carboxylase. Sn phm ng ho l malate v aspartate, loi ny l
malate v loi kia l aspartate, c vn chuyn qua gian bo n cc t
bo bao quanh b mch. y chng c kh carboxyl ho. Pyruvate
xut hin li tr v t bo mesophyll. Qu trnh ny xy ra hai loi t bo
v c ch ra hnh 4.13.
89
Hnh 4.13 S tng hp PEP, phn ng carboxyl ho, phn ng kh
oxaloacetate t bo tht l, s kh carboxyl ho v chu trnh Calvin xy ra
t bo b mch
loi cy malate pyruvate c to nn trc tip t malate bng
cch kh carboxyl ho oxy ho.
phn ng do malat-enzyme xc tc bn cnh CO
2
cn to nn
NADPH, l cht cn trong chu trnh Calvin. Vi malate khng nhng cc
nguyn t C m cn c cht kh c vn chuyn n chu trnh Calvin.
loi cy aspartate aspartate c kh carboxyl ho to thnh alanine.
Alanine c bin i thnh pyruvate nh phn ng chuyn amin ho.
Phn ng chuyn amin ho xy ra trong t bo cht ca t bo tht l.
Alanine c vn chuyn t t bo bao quanh b mch tr v t bo tht
l.
COOH
C = O
CH
3
Pyruvate
+ CO
2
COO H
CH
2
H C O H
COO H
Malate
NADP
+
NADPH + H
+
T bo bao quanh
b mch
T bo tht l
Malate
NADP
+
NADPH + H
+
ATP + Pi
AMP + Pyrophosphate
Oxaloacetate
NADPH
+ H
+
NADP
+
Pyruvate
Chu trnh
Calvin
CO
2
PEP
HCO
3
-
90
S phn chia cc phn ng ring l t bo cht v lc lp ca t
bo tht l tng ng vi t l nng lng. S phn chia ny c gii
thch trong hnh 4.14.
Pyruvate c a vo t bo tht l phi chui vo lc lp ca t bo
ny, v y c mt ca enzyme pyruvat-phosphate-dikinase v ATP,
ATP ny c to ra t quang hp. PEP to nn trong lc lp c vn
chuyn ra t bo cht bng s trao i vi phosphat v c. y PEP
cng vi CO
2
l c cht ca enzyme PEP-carboxylase. Oxalacetat c
to ra i vo lc lp ri b kh thnh malate nh NADPH. ATP v
NADPH c to ra trong lc lp l nh qu trnh quang hp.
Hnh 4.14 S vn chuyn nng lng v carbon gia lc lp v t bo cht
ca t bo tht l thc vt C
4
COOH
H
2
N-CH
CH
2
COO H
COOH
H
2
N-CH
CH
3
COOH
C = O
CH
3
Aspartate Alanine
Cetoacid
Aminoacid
Pyruvate
CO
2
Pyruvate
T bo
bao
quanh b
mch
T bo tht l
Malate
NADP
+
NADPH + H
+
Lc lp
ATP + Pi
Oxaloacetate
Pi
PEP
HCO
3
-
AMP ~ P ~ P
91
Malate sau c vn chuyn n t bo bao quanh b mch. T
bo tht l v t bo bao quanh b mch cha nhng lc lp c hnh thi
khc nhau: Lc lp ca t bo bao quanh b mch ln hn v khng c
grana v tch lu tinh bt. Lc lp ca t bo tht l nh hn v lun lun
cha grana.
u im ca s ng ho CO
2
thc vt C
4
l enzyme PEP-
carboxylase c trong t bo cht tip nhn CO
2
c trong m l v CO
2
t
qu trnh h hp tt hn s tip nhn CO
2
thc vt C
3
, v thc vt C
3
CO
2
trc ht phi chui vo lc lp. Tng ng im b CO
2
ca thc vt
C
4
c bn l thp hn thc vt C
3
, nm trong khong 0,5-1 l/LCO
2
,
im b CO
2
ca thc vt C
3
nm trong khong 3-5 l/LCO
2
. im b
quang hp l nng CO
2
m khng c s tch lu cht hu c.
Thc vt C
4
c kh nng gim nng CO
2
trong m l mnh hn thc
vt C
3
. V vy chng c kh nng s dng CO
2
trong khng kh c hiu
qu hn.
Hn na nng CO
2
cao c to ra trong t bo bao quanh b
mch nh qu trnh kh cacboxyl ho. Nh vy m im bo ho CO
2
ca
RuDP-carboxylase gn t c v hot tnh oxygenase ca enzyme b c
ch. V vy thc vt C
4
c kh nng s dng tt nh sng c cng
cao. V l do ny m chng thc t khng c im bo ho nh sng.
c im ny c th hin trn hnh 4.15. y ng cong ng ho
CO
2
ca hai cy trng C
4
l ma v ng tng cao hn ng cong ca thc
vt C
3
.
100 200 300 400
Cng nh sng Jm
-2
s
-1
50-
40-
30-
20-
10-
0
Ma
Ng
La m
C ci ng
Thuc l
C ci nc
M
g
C
O
2
-
1
0
0
c
m
-
2
.
h
-
1
92
Hnh 4.15 nh hng ca cng nh sng n s ng ho CO
2
mt s
cy trng
Tuy nhin thc vt C
4
cn nhiu nng lng cho s ng ho CO
2
,
v chu trnh C
4
khi ng trc chu trnh Calvin cn cho s kt hp 1 phn
t CO
2
hai phn ng phosphoryl ho (to nn hai lin kt cao nng)
tng hp nn ATP t AMP theo phng trnh sau:
AMP + ATP 2ADP
2 ADP + 2 phosphate 2ATP (quang phosphoryl ho)
-------------------------------------------------------------------
Tng qut: AMP + 2 phosphate 2ATP
Phn ln nhng thc vt C
4
c ngun gc t nhng vng c cng
nh sng mnh, v vy ATP c to nn nhiu nh quang phosphoryl
ho. i vi s ng ho CO
2
th cng nh sng l yu t t hn ch
hn so vi nng CO
2
. iu cng d hiu l trong qu trnh tin ho
mt s loi thc vt pht trin c ch ng ho CO
2
trong nhng iu kin
thi tit c bit. Do s thch nghi ny m enzyme pyruvate-phosphate-
dikinase mn cm vi nhit thp. V d iu kin kh hu Trung chu
u ma xun th hin s ngng pht trin v vng l ng, trong khi cc
loi ng cc khc (la m, la mch, yn mch, kiu mch) pht trin tt,
l do s mn cm ca enzyme pyruvate-phosphate-dikinase vi nhit
thp. Khi thi tit m ln th ng bt u pht trin vi tc nhanh, vt
nhiu so vi thc vt C
3
. Tc pht trin nhanh l do s ng ho CO
2
c hiu qu, v do thc vt C
4
s mt mt sn phm ng ho do h hp
sng thp hn thc vt C
3
.
Cu to gii phu kiu Kranz ca t bo l cng c mt ngha i
vi trao i nc. Nhng t bo xp st b mch c s trao i kh thp
hn v nh vy s mt nc do thot hi nc cng t hn. iu ny gii
thch ti sao thc vt C
4
c nhu cu nc tng i thp hn.
4.4.5 Quang hp theo chu trnh CAM (Crassulaceae Acid Metabolism)
Cc loi thc vt khc nhau ca h Crassulaceae v nhng i din
ca Agavaceae, Bromeliaceae, Cactaceae, Euphobiaceae, Liliaceae v
Orchideaceae c kh nng tip nhn CO
2
vo ban m nh kh khng m
v ban ngy th kh khng ng li trnh s mt nc. Tri vi a s
cc loi thc vt khc, kh khng ng li ban m v m ban ngy, kh
nng ny gn lin vi s trao i acid v CO
2
c bit, trc ht c
93
nghin cu loi Crassulaceae. Nhng thc vt c hnh thc trao i ny
c gi thc vt CAM.
Hnh 4.16 S ng ho CO
2
v trao i acid thc vt CAM
Nguyn l ca s trao i cht c bit ny c minh ha trong
hnh 4.16. Ban m CO
2
c tip nhn nh kh khng m, enzyme PEP-
carboxylase carboxyl ho PEP to thnh oxaloaxetate. Cht ny c
kh to thnh malate. Sau malate c d tr trong khng bo.
y nng malate c th ln n 100-200 mM, c bit nng ny cao
trong nhng gi u bui sng. Ban ngy khi kh khng ng, malate
trong khng bo c huy ng vo lc lp v y n c kh
carboxyl ho. CO
2
t do v NADPH to ra i vo chu trnh Calvin. Bn
cnh s ng ho CO
2
c cung cp bi ATP v NADPH c to ra
t quang hp. Sn phm ng ho ny mt phn c bin i thnh tinh
bt, tch lu trong lc lp. Ban m mt phn tinh bt ny c phn gii
to thnh PEP, l cht tip nhn CO
2
trong t bo cht. s kh
carboxyl ho oxy ho pyruvate c to thnh t malate, sau pyruvate
c bin i thnh PEP nh enzyme pyruvate-phosphate-kinase. Bn
cnh malate v oxaloaxetate th aspartate, glutamate, alanine, glycine bng
phn ng chuyn amin ho to nn nhng sn phm trung gian gn lin
vi s trao i cht ca thc vt CAM.
CO
2
(m)
Oxaloacetate
(m)
Malate
(m)
Malate
(ngy)
Khng bo
(m)
(m)
PEP
Tinh bt
Chu trnh Calvin
Lc lp
CO
2
+ NADPH
Pyruvate
(ngy)
94
S tch lu malate trong khng bo l mt qu trnh ch ng, c
iu khin bi sc trng ca khng bo. Th nc ca cy iu khin s
ng m kh khng. Ngi ta phn bit nhng thc vt CAM bt buc
v khng bt buc. Thc vt CAM khng bt buc ch thc hin theo
chu trnh CAM khi thiu nc, c bit l trong iu kin ngy di.
Kh khng ng ban ngy th s mt nc gim rt ng k, nh vy
m thc vt c kh nng vt qua c thi k kh hn. mt th nc
trong t l 2200 kPa, vt xa im ho ca cc cy trng khc, nhng
trong cc m ca loi cy ny vn duy tr c th nc t 500-1000 kPa.
4.4.6 Tng hp carbohydrate
Vi mt s phn ng tng i n gin thc vt c kh nng tng
hp cc hexosephosphate khc nhau, l nhng nguyn liu cn thit cho
tng hp oligo- v polysaccharide.
Nguyn l sinh tng hp l to nn lin kt glycoside trc ht c
gii thch bi Leloir. Nguyn l ny c ch ra v d tng hp glucan
(polysaccharide ca glucose) (hnh 4.17). phn ng ny c hai enzyme
tham gia: ADP-glucopyrophosphorylase v glucan- hoc ADP-gluco- -
glucan-4 -glucosyltransferase. Enzyme ADP- glucopyrophosphorylase
hot ho glucose1-phosphate nh ATP, vi s tch ra pyrophosphate xut
hin dng glucose hot ho, l ADP-glucose. phn ng ny nguyn
t H ca nhm phosphoryl c thay th bng nhm acyl ca
adenosinemonophosphate. Acyl tng ng gi l adenyl. Sau dng
glucosyl hot ho c chuyn ln chui glucan v thay th nguyn t H
ca nhm OH v tr C
4
(xem cng thc). Nh vy xut hin mt lin kt
glycoside gia C
1
ca glucosyl mi i vo v C
4
ca glucosyl chui
glucan. Lin kt nm pha di ca mt phng glucose v l lin kt
glycosidic. Theo nguyn tc ny mt chui di ca cc gc glucosyl c
to thnh.
Chui ko di theo hng C
1
C
4
. S tng hp polysaccharide
phn ln bt u bng mt phn t mi (primer), y glycosyl u tin
c nh vo. s tng hp tinh bt v glycogen th primer l 1
glycoprotein. Glucosyl l gc ng ca glucose, fructosyl ca fructose,
ribosyl ca ribose.
95
Hnh 4.17 Tng hp ADP-glucose nh enzyme ADP-glucose-
pyrophosphorylase v s chuyn glucosyl ln mt chui glucan
Bn cnh tinh bt, saccharose l sn phm quan trng khc ca qu
trnh quang hp. Triosephosphate c to nn t chu trnh Calvin i t
lc lp ra t bo cht, bin i thnh UDP-Glucose, Fructose 6-P v sau
thnh saccharose 6-P nh enzyme saccharose-P- synthase. Cui cng
phosphate c tch ra bng enzyme saccharose-P-phosphatase.
iu khin enzyme saccharose-synthase thc hin bc fructose-
1,6-disphosphate bi nng ca fructose 2,6-P
2
(xem gluconeogenese).
Mt v tr iu khin khc l saccharose-P-synthase c hot ho bi c
cht glucose 1-P v b c ch bng phosphate v c. Ngoi ra hot tnh
ca enzyme gim xung do qu trnh phosphoryl ho v tng ln do s
kh phosphoryl ho (tng t nh glycogen-synthase). Nng
saccharose li iu khin s tng hp tinh bt.
O
CH
2
OH
O
O
PO H
OH
O O O
HOP~OP~O~PO Aden
OH OH OH
O O
HOPO~POH
OH OH
Pyrophosphorylase
+
CH
2
OH
O
O
O O
PO~PO Aden
OH OH
CH
2
OH
O
O
CH
2
OH
O
O
CH
2
OH
O
O
CH
2
OH
O
H O
S tng hp glucan
96
Hnh 4.18 S tng hp saccharosephosphate v saccharose
Saccharose va l mt dng carbonhydrate vn chuyn va l tin
cht ca tinh bt (trong t bo, nm cch ra khi v tr quang hp) v ca
cellulose. Enzyme saccharose-synthase c tc dng thun nghch to nn
nucleosid - ng cn thit.
Saccharose + UDP = UDP-D-Glucose + Fructose
CH
2
OH
OH
HO
HO
O
HO-CH
2
OH
HO
O
O
CH
2
OH
CH
2
OH
P O-CH
2
OH
HO
O
O H
Saccharose
Saccharosephosphate
O
H
2
O
P
i
CH
2
OH
OH
HO
OH
UDP
O
CH
2
OH
OH
HO
OH
O
P O-CH
2
OH
HO
O
UDP
97
Tng t ATP l coenzyme ca ADP-pyrophotphorylase qu trnh
tng hp tinh bt, UTP cung cp nng lng cho s tng hp saccharose,
glycogen v cellulose. y UDP-pyrophosphorylase xc tc tng hp
UDP-glucose t glucose1-phosphate v UTP. s tng hp saccharose
mt glycosyl c vn chuyn t UDP-glucose n 1 fructosephosphate
to nn saccharosephosphate, t cht ny saccharose v phosphate v
c c tch ra. S tng hp saccharose sau khi ng ho CO
2
cng nh
s to nn saccharose t tinh bt trong ht ny mm c thc hin theo
con ng ny (hnh 4.18). Enzyme xc tc cho phn ng ny l
saccharosephosphat synthetase. Hng phn ng dch v pha
saccharosephosphate cng nh saccharose, v s to ra phosphate nh
phosphatase, l mt qu trnh thun li v nhit ng hc. Khng nn
nhm ln gia enzym saccharosephosphatsynthetase vi enzyme
saccharosesynthetase. Enzyme saccharosesynthetase ch tng hp
saccharose trong nhng trng hp ngoi l. Chc nng quan trng ca n
O O
H OP~OP~O
OH OH
CH
2
OH OH
O
N
N
O
OH
UDP Saccharose
HOCH
2
OH
HO
OH
O
CH
2
OH
CH
2
OH
OH
HO
OH
O
O
O O
P~OP~O
OH OH
CH
2
OH OH
O
N
N
O
OH
Fructose UDP-glucose
+
CH
2
OH
OH
HO
OH
O
CH
2
OH
HO
CH
2
OH
O
O
98
l to nn UDP-glucose t saccharose v UDP theo phng trnh phn
ng sau:
Saccharose + UDP UDP-glucose + fructose
Cn bng phng trnh ny dch v pha to UDP-glucose. Enzyme
ny l saccharose:UDP-glycosyltransferase, ng vai tr quan trng
trong m sinh trng v trong nhng c quan d tr ang ln (c, ht) m
saccharose c chuyn n tng hp UDP-glucose. Sau UDP-
glucose c s dng ch yu cho vic tng hp cc cht ca thnh t
bo, nh cellulose.
C ch ca phn ng ca saccharose:UDP-glycosyltransferase c
th hin s trn.
Nhng polysaccharide m t trn c cha nhiu nhm OH, nn
phn t c c tnh a nc v c kh nng to nn cc cu hydro. Cc
nhm acid, carboxyl, nhm sulfate lm cho phn t c tnh acid. Trong
iu kin pH sinh l (pH 5,5-7,5) cc proton c tch ra, v vy cc i
phn t mang nhiu nhm anion, nn tch in m v c kh nng kt hp
vi cc cht tch in dng, v d nhm amin b proton ho to lin
kt ion.
4.5 Ho sinh h hp
4.5.1 nh ngha h hp
H hp l qu trnh phn gii, oxy ho cc hp cht hu c phc tp
thnh cc sn phm cui cng l CO
2
v H
2
O, ng thi gii phng nng
lng cn thit cho c th sng.
Phng trnh tng qut ca h hp:
C
6
H
12
O
6
+ 6O
2
6CO
2
+ 6H
2
O + Nng lng
V bn cht h hp l qu trnh oxy ho sinh hc c thc hin
bng s tch cc nguyn t hydro ra khi c cht v vn chuyn n (H
+
v
e
-
) n nhng cht nhn khc nhau, cht nhn cui cng l O
2
. H hp xy
ra hai v tr khc nhau trong t bo. Giai on th nht xy ra t bo
cht (qu trnh ng phn), hoc bn trong ty th (chu trnh Krebs), l s
tch hydro ra khi c cht v chuyn n n NAD v/hoc FAD to
nn NADH
2
v FADH
2
. giai on th hai NADH
2
v FADH
2
b oxy
ho, l qu trnh chuyn H
+
v e
-
cho cc cht nhn trung gian v cui
cng n O
2
. Qu trnh ny xy ra mng trong ca ty th. Kt qu ca
qu trnh ny to ra cc phn t ATP v H
2
O.
H hp ho kh:
99
c tnh ca h hp ho kh l gii phng CO
2
v tip nhn O
2
. H
hp ym kh theo nh ngha trc y l gii phng CO
2
trong iu kin
khng c O
2
. Ho sinh hc nh ngha h hp ym kh l s phn gii
carbohydrate qua qu trnh ng phn v tip theo l s ln men ru.
Ton b qu trnh ny khng cn O
2
, CO
2
c gii phng ra trong qu
trnh ln men bng s kh carboxyl ho pyruvate.
H hp ho kh xy ra trong ty th. Khi qu trnh quang hp v h
hp ho kh c gii thch cng chi tit th s ging nhau gia chng
nh l my bin i nng lng cng nhiu. qu trnh quang hp
ngi ta bit matrix cha nhng enzym ca chu trnh Calvin, h hp
matrix ca ty th cha nhng enzyme ca chu trnh Krebs. H thng oxy
ho kh ca quang hp (chui vn chuyn e
-
trong quang hp) nh v
mng thylacoid ca lc lp, h thng oxy ho kh ca h hp nh v trn
mng trong ca ty th. S ging nhau gia hai my bin i nng lng
n l ngc nhin.
Hnh 4.19 Chui vn chuyn e
-
ca h hp vi nhng h thng oxy ho kh
quan trng v cc phc h vn chuyn mng
Chui vn chuyn e
-
trong h hp, v s nh v ca chng trong mng
trong ca ty th, c gii thch hnh 4.19. Chui vn chuyn e
-
gm c 4
phc h proteine vn chuyn ca mng v hai phc h protein nh hn,
cuccinate dehydrogenase (FAD) v cytochrome. Ngoi ra cn c
ubichinol/ubichinone trong chui vn chuyn. Cht kh tng ng l NADH
v FADH
2
, c hai u c to ra trong chu trnh Krebs, c i vo chui
h hp qua phc h FMN-protein cng nh qua phc h FAD-protein. Hai
Pha ngoi ty th (pH 5)
2H
+
H
+
O
2
+ 2H
+
H
2
O
ADP + P
i
ATP
FMN
FAD
NAD
+
NADH + H
+
Succinate
Fumarate
Matrix (pH 8)
ATP Syn-
thetase
Cyto-
chrome
b,c
1
Cyto-
chrome
a,a
3
Cyt c
Ubichinol
Ubi-
chinol
Ubichinone
Ubi-
chinone
P
r
o
t
o
n
e
n
-
k
a
n
a
l
100
phc h vn chuyn H ca n n ubichinone v kh n thnh ubichinol. H
thng ubichinone/ ubchinol v h thng plastochinone/plastochinol c cu to
v chc nng rt ging nhau (xem s ).
Ubichinone/ ubichinol c kh nng khuch tn rt nhanh vo mng
nh c tnh a lipid ca n. H s khuch tn nm 10
-8
cm
2
/sec. Ubichinol
kh phc h cytochrome b, c
1
, y dn n s tch H thnh H
+
v e
-
.
in t c tip nhn bi phc h cytochrome b, c
1
, trong khi
H
+
c thi ra pha ngoi mng. Phc h cytochrome b, c
1
, cn c
OH
OH
O
O
2e
_
2H
+
2x Cytochrome.Fe
3+
2x Cytochrome.Fe
2+
CH
CH
3
C
CH
2
H
n
O
O
H
3
CO
H
3
CO
CH
2
CH
3
2H
Ubichinol
Ubichinone
CH
CH
3
C
CH
2
H
n
OH
OH
H
3
CO
H
3
CO
CH
2
CH
3
101
gi cytochrome c-reductase, v n kh cytochrome c, in t ca n c
chuyn cho cytochrome c. y cng l 1 phc proteine nh hn, c th
khuch tn d dng ra pha mng ngoi. N chuyn e
-
n phc h
cytochrome a, cn c gi l cytochrome c-oxidase, v n oxy ho
cytochrome c. Phc h cytochrome a l thnh vin cui cng ca chui
vn chuyn e
-
. N chuyn e
-
n O
2
, ri phn ng vi H
+
ca h thng
to H
2
O. O
2
trong chui h hp c nhim v tip nhn e
-
cui cng.
Chui h hp trong hnh 4.19 lm r s vn chuyn H v e
-
qua
cc thnh vin ca chui dn n s chnh lch proton ca mng. S khc
bit ny xut hin s kh ca phc h cytochrom b, c
1
bi ubichinol. V
c s oxy ho NADH phc h FMN v s kh O
2
phc cytochrome a
lm cho matrix kim, v n lm gim H
+
, ngi ta c th nhn bit trn
hnh 4.19.
Bng cch ny m 1 th in ho c to nn. Matrix tch in m
v c mt nng H
+
thp (pH 8), ngoi mng tch in dng v c
nng H
+
tng i cao. S chnh lch th nng gia 2 mng c ln
l 200mV. Nng lng ca in th ho hc ny c s dng tng
hp ATP. Bn phc h vn chuyn mng c cha ATP-synthetase
(ATPase). Proton i qua cc knh vn chuyn ca phc h vn chuyn
mng t ngoi mng vo matrix, thc hin tng hp ATP. y c s
tng t nh sinh tng hp ATP trong quang hp.
Trc khi gii thch nng lng ca chui h hp, cn ni r hn h
thng oxy ho kh.
- Phc h FMN, NADH-dehydrogenase gm t nht 26
polypeptide khc nhau. N cha FMN trung tm phn ng v c
khong 20 nguyn t Fe v S linh ng/ FMN. Trng lng phn
t ca n l 850 kDa.
- Phc h FAD l cuccinate dehydrogenase, cha FAD v
phc Fe-S ho tr 2 v ho tr 4 trung tm phn ng.
- Phc h cytochrome b, c
1
cha cytochrome c
1
v 2 loi
cytochrome b, t nht 8 chui polypeptide ln hn v 1 phc Fe-S
c ho tr 2. Antimycin l 1 cht km hm ca phc h cytochrome
b, c
1
, n nh ch s vn chuyn e
-
gia cytochrome b v
cytochrome c
1
.
Cytochrome a, a
3
, cn c gi cytochrome c-oxidase gm 7 chui
polypeptide khc nhau. ng thi n tip nhn t cytochrome c 4 e
-
v
chuyn chng n 1 O
2
. s vn chuyn ny c s tham gia ca heme
trong cytochrome a
3
, cytochrome a v nguyn t Cu. Oxy dng kh (O
2
4-
)
phn ng vi 4H
+
c ngun gc t nc to H
2
O.
102
O
2
4-
+ 4H
+
H
2
O
Phn ng oxy ho kh cui cng ca chui h hp ny c gi l
s oxy ho cui cng. N s dng khong 90% nhu cu O
2
ca t bo.
S oxy ho ny b c ch bi CO
2
, cyanid v acid. Nhng cht ny kt
hp vi heme v phong to s kt hp ca hem vi O
2
, v vy chng l
cht c i vi h hp. Phc h vn chuyn mng, cha ATP-synthetase
gm nhiu chui polypeptide khc nhau, trong cha 1 knh proton,
thc hin s vn chuyn H
+
t pha mng ny sang pha mng khc. ATP-
synthetase ny rt ging ATP-synthetase trong mng thylacoid ca lc
lp v ATP- synthetase ca vi khun.
S vn chuyn e
-
trong chui h hp l s vn chuyn thun chiu,
theo th oxy ho kh tiu chun, nh trong hnh 4.20. Nng lng gii
phng ra y c bin i thnh nng lng thm thu, th hin s
chnh lch nng H (gradient H
+
). S chnh lch nng H
+
hai pha
ca mng to nn mt th in ho, m ln ca n c tnh theo
phng trnh sau y:
P -59 pH +
P lc
pH Grandient H
+
s khc nhau v in tch gia 2 mng
FMN FAD
Cytochrome
b, c
1
Cytochrome
c
Cytochrome
a, a
3
-400
-200
0
+200
+400
+600
+800
Ubichinone
e
-
e
-
1/2O
2
+ 2H
+
H
2
O
Th oxy ha kh tiu chun, mV
103
Hnh 4.20 S vn chuyn e
-
trong chui h hp ph thuc vo th oxy ho
kh tiu chun
Phng trnh ny ng vi mt nhit nht nh, m t lc di
chuyn proton ngha l lc y 1 H
+
t 1 pha mng nng H
+
cao
(pha ngoi mng) n 1 pha khc ca mng vi nng H
+
thp
(matrix). Lc ny c biu din mV l s chnh lch in th, y 1
n v pH tng ng vi 59 mV, v vy l h s ca phng trnh. Lc di
chuyn proton phi ln, mi tng hp c ATP. Vy bao nhiu H
+
phi i vo matrix, mi tng hp c 1 ATP? Ngi ta cho rng s
chnh lch th (lc t pH v , xem phng trnh) l 220 mV s vn
chuyn 1 mol H
+
t mng ngoi n matrix th nng lng t do gii
phng ra l 21.3kJ. Khi 2H t NADH trong chui h hp c a vo,
n tch ra 5H
+
m ngi ta c th rt ra t hnh 4.19. Ba H
+
cn trong
matrix, hai H
+
c i ra ngoi mng. Khi 5 mol H
+
tr v matrix, to ra 5
x 21,3 106.5 kJ nng lng t do vi iu kin chnh lch th l 220
mV. Gi s nng lng ny tng hp 3 mol ATP, v G
0
ca 1 lin
kt cao nng trong ATP l 30kJ. Hai nguyn t H, i vo chui enzyme h
hp qua phc h FMN, cn s oxy ho cui cng 1/2O
2
. th nng 220
mV c th tng hp t 2H (t NADH) 3 ATP vi s tiu hao 1/2 O
2
. Nh
vy t l P/O l 3, l s phn t ATP c tng hp/nguyn t O. Tuy
nhin gi tr thu c t thc nghim chnh lch nhiu so vi t l P/O
ny. iu ny d hiu v t l ch ng khi chnh lch th l 220 mV. Khi
tnh ton nng lng bin i ngi ta cho rng c cht h hp NADH +
H
+
to ra 3ATP, c cht l FADH
2
l 2ATP. Tuy nhin t l P/O vi
NADH v FADH
2
theo gii thch trn c th lch nhiu so vi gi tr thc
t. S chnh lch ny cn do nng lng t do tng hp ATP c tnh
trong iu kin tiu chun, m trong thc t phn ln cc trng hp
khng phi trong iu kin ny. Nng lng cn cho tng hp ATP hng
v trng thi cn bng phn ng:
ADP + Pi ATP
T l ATP/ADP iu khin h hp rt hiu qu v c ngha.
nng ADP cao, tng ng vi s thiu ATP th ATP c to nn
nhiu v nhanh vi tiu hao nng lng t, ngc li vi nng ATP cao
104
th s tng hp ATP cn nhiu nng lng. y l s thch nghi tt vi
nhu cu nng lng. Khi ATP c s dng nhiu cho cc qu trnh sinh
trng (tng hp protein, nucleic acid) hoc cho lao ng c bp, th
cng h hp tng ln, lc ny nng ATP thp v ADP cao. Trong
giai on c bp t hot ng nng ATP cao, tng ng vi cng
h hp thp.
nng ATP cao phn ng tng hp ATP c th theo chiu
ngc li. y ATP c tch thnh ADP v Pi v nh nng lng gii
phng ra m H
+
c bm ra pha ngoi mng. ATP-synthetase tr thnh
mt bm proton. V l do ny ngi ta gi ATP-synthetase ngc cng l
ATPase. Thc t l cc bm proton rt ph bin trong t nhin. Ngc vi
ATP-synthetase trong chui h hp, ATP-synthetase c trong mng
thylacoid khng th tch ATP.
H hp c chia lm hai loi: H hp ym kh v h hp ho kh.
C hai kiu h hp ny u c mt qu trnh chung l qu trnh ng
phn.
4.5.2 ng phn, s ln men ru v ln men lactic
Nh nhng enzyme thu phn k trn m chui carbohydrate
d tr c bin i thnh hexose, nu khng phi l glucose hoc
fructose, th chng cng d dng bin i thnh hai dng monosaccharide
ny. Glucose v fructose l nhng c cht trc tip ca qu trnh ng
phn (glycolyse).
Glycolyse c ngha l phn gii ng. Cc phn ng c gii thch
bi Gustav Embden v Otto Mayerhof. V vy qu trnh ny c gi l
s phn ng Embden- Mayerhof. S ny gm s phn gii ng v
polysaccharide ym kh cho n pyruvate. Nhng enzyme ca qu trnh
ny c mt t bo cht. Nh tc dng ca phosphorylase glucose1-
phosphate c tch ra l c cht trc tip ca qu trnh ng phn.
Chui phn ng gm nhng phn ng ring l nh sau:
1. T chui amylose nh phosphorylase m glucose1-phosphate
c tch ra.
2. Glucose1-phosphate c bin i thnh glucose-6-phosphate
nh isomerase.
3. Glucose-6-phosphate c bin i thnh fructose-6-phosphate
nh enzym isomerase.
105
4. Fructose-6-phosphate c phosphoryl ho nh ATP v
enzyme phosphofructokinase to thnh fructose-1,6-
diphosphate
5. Fructose-1,6-diphosphate nh enzyme aldolase c tch ra
thnh aldehydphosphoglyceric v phosphodioxyacetone.
Khi aldehydphosphoglyceric (AlPG) c s dng trong cc
phn ng tip theo th cht ny li c to thnh t
phosphodioxyacetone (PDOA). trng thi cn bng c hn 90% l
dng PDOA.
6. Aldehydphosphoglyceric (triosephotphate) c kt hp vi
mt HS-enzyme. Phc h HS-Enzyme ny cn kt hp vi
NAD
+
7. Bng vic nhng 2H cho NAD
+
, AlPG c oxy ho thnh
phosphoglyceric acid. S thay i trong phn t lm cho nhm
acyl giu nng lng c gn vo S ca phc h enzyme.
8. NADH gn vo phc SH-Enzyme c oxy ho, trong H v
e
-
ca n c chuyn ln mt NAD
+
t do.
9. Nh gc phosphate v c m phosphoglycerinacyl c tch ra
khi phc h. y nhm SH li xut hin khi to thnh 1,3
phosphoglyceric acid.
qu trnh ny phosphoric acid (P-OH) c tch ra 1 nguyn t H v
1 gc P-O- (xem s ). Gc P-O- c gn kt vo acyl ca
phosphoglyceric acid, trong khi H c kt hp vi nguyn t S ca
enzyme. Enzyme li tr li trng thi ban u.
P - O H
CO ~ S -
HCOH
CH
2
O P
O
C - O ~ P
C = O
CH
2
O P
E
n
z
y
m
e
E
n
z
y
m
e
HS -
106
10. Nhm phosphoryl mang nhiu nng lng ca 1,3
diphosphoglyceric acid c chuyn n ADP, tng hp nn
ATP.
11. 3-phosphoglyceric acid c bin i thnh 2-phosphoglyceric
acid nh enzyme isomerase
12. Nh enzyme hydratase H
2
O c tch ra t 2-phosphoglyceric
acid. Phosphoenolpyruvate c to thnh. Cu trc phn t
ca lin kt ny to nn nhm phosphoryl giu nng lng.
13. Nhm phosphoryl ca phosphoenolpyruvate c chuyn n
ADP. ATP c tng hp.
14. Enolpyruvate trng thi cn bng vi dng ceto ca pyruvic
acid (s ).
Hexose (glucose, fructose) cng nh triose (aldehydglyceric) c
phosphoryl ho nh kinase, trc khi chng tham gia vo phn ng ca
qu trnh ng phn.
Ton b qu trnh ng phn c chia lm 3 giai on:
1. Cc carbohydrate c bin i thnh triosephosphate do s
oxy ho ng.
2. Triosephosphate c bin i do s oxy ho thnh cc acid
hu c (glycerate).
3. Phosphoglycerate c bin i thnh pyruvate. Vi s gii
phng ra nng lng t do, ATP c tng hp.
COO H
C - OH
CH
2
Enolpyruvate
COO H
C = O
CH
3
Pyruvate
107
Hnh 4.21. Qu trnh ng phn
108
Tng qut: khi a vo 1 glucosephosphate v kt qu to ra 2 phn
t triosephosphate:
u vo u ra
1 glucosephosphate +1ATP + 2 NAD
+
ADP + 2NADH + 2H
+
+ 2 HS-Enzyme + 2HS- Enzyme +4ATP +2H
2
O
2 P-OH + 4 ADP + 2 pyruvic acid
Tng qut: glucosephosphate + 2 NAD
+
+ 3 ADP + 2 P-OH
2 pyruvic acid + 2 NADH + 2H
+
+ 3ATP +2 H
2
O
S tng qut ny lm r vai tr sinh l ca qu trnh ng
phn: hexosephosphate c phn gii thnh apyruvic acid. Nng lng
gii phng ra c dng tng hp ATP v kh NAD
+
. V vy qu
trnh ng phn v ngha sinh l tng ng vi phn ng sng ca qu
trnh quang hp. Qu trnh quang hp cn nng lng nh sng mt tri
tng hp ATP v NADPH, trong khi qu trnh ng phn th nng
lng ho hc c s dng tng hp ATP v NADH. S tng hp
ATP qu trnh ng phn xy ra trong iu kin ym kh. V vy ngi
ta gi phosphoryl ho ym kh, ngha l phosphoryl ho ADP tng hp
ATP khng cn O
2
.
4.5.3. Cc loi h hp
Pyruvate c coi l sn phm cui cng ca qu trnh ng phn.
N c th ln men ru to ethanol hoc ln men lactic to lactic
acid hoc c phn gii qua chu trnh Krebs to CO
2
v H
2
O.
s ln men ru trc ht pyruvate c kh cacboxyl ho thnh
acetaldehyde, sau di tc dng ca NADH n c kh thnh
ethanol.
NADH c ra trong qu trnh ng phn c s dng oxy
ho acetaldehyde, nh vy s ti to NADH l do oxy ho
aldehydphosphoglyceric (phn ng 8 ng phn) cung cp cho phn ng
ny.
Ethanol
COO H
C = O
CH
3
Pyruvic acid
NAD
+
NADH + H
+
CO
2
CHO
CH
3
CH
2
- OH
CH
3
Acetaldehyd
109
Qu trnh ln men ru gm qu trnh ng phn t carbohydrate
cho n pyruvic acid, t cht ny n acetaldehyde v ethanol l sn phm
cui cng. ng hexose (glucose, fructose) l nguyn liu ban u ca
qu trnh ln men, tng qut c biu din nh sau:
1 Hexose + 2ATP fructose-1,6-diphosphate
Fructose-1,6-diphosphate 2 aldehydphosphoglyceric
2 aldehydphosphoglyceric + 2 NAD
+
2 pyruvic acid + 4ATP +2NADH
2 pyruvic acid + 2 NADH 2 ethanol + 2 NAD
+
+ 2 CO
2
Cui cng: 1 hexose 2 ethanol + 2 CO
2
+ 2 ATP
Nhiu c quan nh r ca thc vt bc cao, c kh nng thc hin s
ln men ru trong iu kin ym kh. i vi cng ngh quan trng l
Saccharomyces cerevisiae, l mt loi men k kh khng bt buc, ngha
l n c th pht trin trong iu kin c hoc khng c O
2
. Khi khng c
O
2
s phn gii glucose xy ra nhanh hn. Ngi ta gi hiu ng ny l
hiu ng Pasteur. Pasteur pht hin ra rng, s phn gii ng trong
iu kin ym kh xy ra 7 ln nhanh hn so vi iu kin ho kh. Ngy
nay chng ta bit rng, hiu ng ny l do s iu khin bin i cu trc
(bin cu) ca enzyme fructosephosphatkinase. s phn gii ho kh th
ATP c to ra tng i nhiu, v khi nng ATP cao, n c ch hot
tnh ca fructosephosphatkinase lm cho s i vo ca glucosephosphat b
gim xung. Ngc li khi phn gii ng trong iu kin ym kh, nng
AMP cao, n kch thch hot tnh ca fructosephosphatkinase. ADP
c to ra nhiu phn ng do kinase xc tc, c bin i thnh ATP
v AMP nh sau:
2 ADP ATP + AMP
Ln men lactic cng gm qu trnh bin i t carbohydrate n
pyruvate, cht ny c kh to thnh lactic acid nh NADH c to
ra trong qu trnh ng phn.
Lactic acid
COO H
C = O
CH
3
Pyruvic acid
NAD
+
NADH + H
+
COO H
HCOH
CH
3
110
Qu trnh ny c tng qut nh sau:
1 glucose 2 lactic acid + 2 ATP
Nhng vi khun lactic quan trng thuc nhng chng loi sau:
Streptococcus khng mn cm vi O
2
Lactobacillus khng mn cm vi O
2
Clostridium ym kh nghim ngt
Vi khun streptococus v lactobacillus khng mn cm vi O
2
,
ngha l chng c enzyme superoxiddismutase, c kh nng lm mt c
tnh ca gc O
2
. Streptococcus v lactobacillus c kh nng s dng O
2
nhng khng phi cho s phn gii ho kh (h hp), v chng khng c
kh nng tng hp heme. Chng khng c cytochrome, l thnh phn
quan trng ca h hp. Clostridium sng nghim ngt trong iu kin ym
kh, nn O
2
l cht c i vi chng. Clostridium botulinum tng hp
c cht c t nhin mnh nht l botulinus-toxin. Mt lng rt nh
0.03 ng/kg trng lng c th gy cht.
Hu ht vi khun lactic khng mn cm vi nhit v pH thp.
qu trnh ln men lactic nhanh th pH mi trng gim nhanh v v nhiu
vi sinh vt mn cm vi pH thp, v d vi khun gy thi, nn chng
khng c c hi cnh tranh vi vi khun lactic, nh vy m nng sn c
bo v.
Khi sn xut thc n chua th s gy chua nhanh nh vi khun lactic
l mt iu kin c bn cho thnh cng ca ln men lactic v bo qun.
Ln men ch yu l nh lactobacillus plantarum, loi vi khun sng trn
l cy v bng cch no m c a vo cng vi nng sn. ln
men lactic nhanh iu quan trng l thc vt c carbohydrate, c bit
l saccharose. Nhng bp ci trng gi tho mn iu kin ny. Thc
phm xanh, non th hm lng carbohydrate t, v cy thc n giu m
th s ln men lactic xy ra chm, pH ch c gim rt t v nhng vi
khun khc, nh vi khun butyric c th phn gii thc phm xanh. Vic
cho thm mt vo c th hn ch nhc im trn, v mt cha nhiu
saccharose v raffinose, nhng cht ny sau khi thu phn c phn gii
nhanh bi vi khun lactic. Ng chn sa l nguyn liu ln men l tng,
v trong qu ca n cha nhiu carbohydrate d phn gii.
Khi sn xut phomat s ln men lactic cng c ngha quan trng.
Sa chua c gy ra phn ln l do streptococcus lactis v streptococcus
cremonis. pH thp dn n s kt ta protein (sa c li), c gi l
phomat trng. Phomat ny khng nhng cha protein m cn c cht bo
111
sa. Phomat ny l nguyn liu sn xut cc loi phomat khc nhau.
sn xut phomat cn c s tham gia ca cc vi khun lactic, streptococus,
lactobacillus, chng khng nhng to nn lactic acid m cn thu phn
protein, ngha l phn gii thnh peptide v aminoacid. Trong phomat
lactic acid cn c chc nng bo qun.
Nguyn l ca s phophoryl ho ym kh c nghin cu k. Nh
hnh 4.21 phn t c cht c bin i cho n nhm phosphoryl ca
n dng lin kt giu nng lng. Nhm phosphoryl ny c chuyn
n ADP, tng hp ATP. V vy ngi ta gi s phosphoryl ho ny l
phosphoryl ho c cht.
So snh hai giai on ca phn gii carbohydrate (h hp ho kh)
th nng lng thu c (ATP) t qu trnh ng phn ch chim khong
20% tng nng lng d tr trong phn t glucose. Phn nng lng ln
nht c to ra s giai on phn gii tip theo.
Qu trnh ng phn c iu khin bi enzyme
fructosephosphatkinase (phn ng 4 trong s ). cng l enzyme
quan trng ca qu trnh ng phn. Enzyme c 4 tiu n v b c ch
theo c ch tc ng bin cu bi ATP v citrate, ngc li c hot
ho bi AMP. V vy t l AMP/ATP cao kch thch v t l ATP/AMP
cao th c ch hot tnh ca enzyme. C ch ny rt c ngha, v khi
trong h thng c nhiu ATP th khng cn tng hp qua qu trnh ng
phn. Ngc li khi t l AMP/ATP cao biu hin s thiu ATP, xy ra
s tng hp ATP. Mt nng citrate cao l cht trao i cung cp cho
chu trnh Krebs. V qu trnh ng phn cung cp cc cht trung gian cho
chu trnh Krebs, nn s iu khin qu trnh ng phn qua hiu qu bin
cu ca citrate n fructosephosphatkinase l mt c ch rt c ngha.
4.5.4 H hp ho kh (chu trinh Krebs)
Chu trnh tricarboxylic, hay l chu trnh Krebs c gii thch bi
Hans Krebs, v Schueler Otto Warburg. Nh pht minh ny m Krebs
nhn c gii thng Nobel vo nm 1953.
Chu trnh ny xy ra trong ty th. C quan t ny c th so snh
c vi lc lp, thc ra n nh hn lc lp (ng knh 0.5-1 m), tuy
nhin v cu to v chc nng chng tng t nhau (hnh 4.22)
112
.
Hnh 4.22 S cu to ca ty th: hnh pha trn l s ct ngang qua
ty th, hnh pha di l ct mt phn ty th
Ngi ta cho rng cng nh lc lp, cc ty th xut hin trc
y khong 10
9
nm trong nhng c th c lp, trong qu trnh tin ho
chng c sinh vt nhn chun bt v ho nhp. Nhng t bo c s
bin i nng lng ln cha nhiu ty th, nh t bo m c hoc t bo
gan, chng c hn 1000 ty th trong mt t bo. Ty th xut hin di
knh hin vi l nhng ht nh hoc si.
Tuy nhin, di knh hin vi in t, ty th c bao bc bi mng
ngoi v bn trong l mt h thng mng ko dn vi nhiu s un cong
vo. Nh cu trc ny m mng trong c din tch b mt ln hn mng
ngoi khong 5 ln. Mng ngoi cho nhng phn t c trng lng ln
(n 10.000 Da) thm qua, v mng ny cha nhng protein nh l
nhng knh vn chuyn. Mng trong kh thm qua hn v vn chuyn cc
cht c tnh chn lc. Mng trong bao quanh stroma, trong stroma cha
cc enzyme ca chu trnh Krebs v enzyme phn gii cht bo (hnh 4.22).
Ngc li trn mng trong ty th c cc enzyme v h thng oxy ho.
y tng t nh lc lp, chui vn chuyn e
-
nh v trn mng thylacoid
v cc enzyme ca chu trnh Calvin trong matrix.
Mng ngoi
Mng trong
Matrix
Khong gia
hai mng
Khong gia
hai mng Matrix
Mng ngoi
Mng trong
113
C cht ca chu trnh Krebs, pyruvate l sn phm ca qu trnh
ng phn. N c vn chuyn t t bo cht qua mng trong ty th n
stroma v y n c kh carboxyl ho oxy ho nh enzyme pyruvate
dehydrogenase. Pyruvate dehydrogenase l mt v d v a enzyme, gm
mt phc h cha carboxylase, transacetylase v dehydrogenase. Bn cnh
trong phn ng cn c cc nhm prostetic l thyaminpyrophosphate,
liponic acid, coenzyme NAD
+
v Coenzyme A. Sau y l cc bc c
th ca chu trnh Krebs (hnh 4.23). Pyruvate b kh carboxyl ho oxy ho
trc khi i vo chu trnh.
Tng t qu trnh ng phn chu trnh Krebs l mt v d ni ln rng
trong c th sng cc phn ng phn gii cc cht cha nhiu nng lng
thc hin theo tng bc. mi chu trnh Krebs ly vo 1 phn t acetyl
CoA.
1. Pyruvic acid c chuyn thnh acetyl CoA bng phn ng kh
carboxyl ho oxy ho. phn ng oxy ho nng lng gii phng ra
c lin kt trong NADH v trong lin kt cao nng ca acetyl-CoA.
2. Nng lng cha trong lin kt cao nng ca acetyl-CoA gn
acetate vo oxaloacetate to thnh citrate.
3. Qua s ngng t ny 1 phn t c 6 nguyn t C c to nn. Phn
ng c xc tc bi enzyme citrate synthetase. Bng phn ng 3 v 4
citric acid c bin i thnh isocitric acid qua aconitic acid.
OH
CH
2
C CH
2
+ CoASH
COOH COOH COOH
Citric acid
+ H
2
O
Oxaloacetic acid
O
C
SCoA
O
CH
2
C + HCH
2
-
COOH COOH
CO ~ SCoA
CH
3
Acetyl - CoA
COO H
C = O
CH
3
Pyruvic acid
CoASH + NAD
+
NADH + H
+
+ CO
2
114
4. Di tc dng ca aconitase (hydratase) xy s kt hp vi nc.
trng thi cn bng citric acid chim 91%, aconitic acid 3% v
isocitric acid 6%.
5. hnh 4.23, phn ng 5 v 6 c thc hin bi enzyme isocitrate
dehydrogenase. Trc ht isocitric acid c oxy ho thnh
oxalosuccinic acid v sau c kh carboxyl ho thnh axit -
cetoglutaric acid.
6. C hai dng isocitrate dehydrogenase, 1 dng cng vi NAD
+
v 1
dng cng vi NADP
+
. ty th isocitrate dehydrogenase dng NAD
+
quan trng hn.
7. Bng phn ng kh carboxyl ho oxy ho - cetoglutaric acid c
bin i thnh succinyl-CoA. Enzyme xc tc l 1 phc h -
cetoglutarate dehydrogenase. Phn ng v enzyme tng t s kh
carboxyl ho oxy ho pyruvic acid.
COOH
CH
2
CH
2
O
C
SCoA
Succinyl-CoA
COOH
CH
2
CH
2
CO- COO H
NAD
+
NADH + H
+
+ CO
2 + CoA-SH
CH
2
- COOH
CH - COOH
H OC H - COOH
Isocitric acid
CH
2
- COOH
CH - COO H
O=C - COOH
Oxalosuccinic acid
COOH
CH
2
CH
2
C=O
COOH
-cetoglutaric acid
NAD
+
NADH + H
+
CO
2
CH
2
- COOH
CH - COOH
HOCH - COOH
Isocitric acid
CH
2
- COOH
HO C - COOH
H CH - COOH
Citric acid
CH
2
- COOH
CH - COOH
CH - COOH
Aconitic acid
- H
2
O + H
2
O
115
8. T succinyl-CoA, succinic acid c to thnh. Lin kt giu nng
lng ca succinyl-CoA c b gy, nng lng gii phng ra dng
tng hp guanosintriphosphate (GTP) t guanosindiphosphate
(GDP) v phosphate v c. Trong c th thc vt GTP c to thnh
tng t nh ATP.
9. Di tc dng ca FAD succcinate b oxy ho to thnh
fumarate.
Enzyme ny l mt flavoprotein, c nhm prostetic l FAD c gi
l succinate dehydrogenase. s oxy ho succinate thnh fumarate nng
lng gii phng khng kh NAD
+
. Tuy nhin n kh FAD
(xem th kh tiu chun).
10. Di tc dng ca H
2
O, fumarate bin thnh malate
COOH
CH
CH
COOH
Fumaric acid
COOH
HC H
HC H
COOH
Succinic acid
FAD
NADH
2
COOH
CH
2
CH
2
COOH
Succinic acid
GDP + P
GTP
COOH
CH
2
CH
2
O
C
SCoA
Succinyl-CoA
116
11. Malate dehydrogenase kh malate thnh oxaloacetate, l cht
khi u ca 1 chu trnh mi.
Nhng phn ng c bn trong chu trnh Krebs l s kh carboxyl
ho v phn ng oxy ho. Nu tnh phn ng t pyruvate n acetyl-CoA
vo chu trnh Krebs th c 3 v tr khc nhau CO
2
c gii phng (phn
ng 1,6,7) v 5 v tr khc nhau c cht b oxy ho (phn ng 1,5,7,9 v
11). nhng phn ng oxy ho lun lun c 1 coenzyme (NAD
+
) hoc 1
nhm prostetic (FAD) tham gia. Chng chuyn thnh dng kh bng phn
ng oxy ho. Nng lng c gii phng ra do s oxy ho c cht c
s dng cho vic kh coenzyme cng nh prostetic. Quan trng l nng
lng phn ng 8 c dng tng hp 1 phn t GTP, tng ng
vi 1 ATP, v GTP c th phn ng vi ADP nh sau:
GTP + ADP ATP + GDP
T hnh 4.23 rt ra rng, trong chu trnh, CO
2
c tch ra nhng O
2
khng c tip nhn vo. Nguyn t O c trong CO
2
khng phi l oxy
cho h hp. ngha ca chu trnh Krebs l cung cp nhng coenzyme kh
(NADH, FADH
2
), nhng cht kh ny l cn thit cho h hp. Ngoi ra
COOH
CH
2
HCOH
COOH
COOH
CH
2
C=O
COOH
NAD
+
NADH + H
+
Malic acid
Oxaloacetic acid
COOH
CH
2
HCOH
COOH
Malic acid
COOH
CH
CH
COOH
Fumaric acid
+ H
2
O
117
cc acid khc nhau ca chu trnh cn tham gia vo nhng qu trnh trao
i cht khc.
Hnh 4.23 Chu trnh Krebs
Qua chu trnh Krebs chui carbon t carbohydrate n trao i lipid
v trao i ca aminoacid, protein.
4.5.5 Chu trnh pentosephosphate- oxy ho trc tip glucose
Bn cnh qu trnh ng phn trong t bo cht cn xy ra mt
con ng khc, gi l chu trnh pentosephosphate v qu trnh phn ng
c phn tng t chu trnh Calvin. Phn ng bt u vi vic oxy ho trc
tip glucose-6-phosphate, v vy gi l oxy ho trc tip glucose. Enzyme
xc tc cho phn ng u tin l glucose-6-phosphate-dehydrogenase,
Oxaloacetate
Acetyl-CoA
Pyruvate
1
HSCoA + NAD
+
NADH+ CO
2
HSCoA
Citrate
H
2
O
H
2
O
Aconitate
H
2
O
Isocitrate
Oxalosuccinate
HSCoA + NAD
+
NADH+ CO
2
-cetoglutarate
CO
2
Succinyl-CoA
Succinate
Fumarate
Malate
H
2
O
NADH
NADH
NAD
+
NAD
+
FAD
FADH
2
GTP + HSCoA
GPP + phosphate
2
3
4
5
6
7
8
9
10
11
118
c Otto Warburg pht hin nm 1931. Cc bc oxy ho c ch ra
trong hnh 4.24.
- Phn ng 1: T glucose-6-phosphate 2 nguyn t H nh C
1
c tch ra nh enzyme glucose-6-phosphate dehydrogenase,
xut hin dng lactone. Glucose-6-phosphate dehydrogenase c
hiu i vi NADP
+
. i lc ca n i vi NADP
+
cao hn 1000
ln so vi NAD
+
.
Hnh 4.24 S oxy ho trc tip glucose trong chu trnh pentosephosphate
- Phn ng 2: Dng lactone c thu phn, to nn 6
phosphogluconic acid.
- Phn ng 3: 6-phosphogluconate c kh carboxyl ho oxy ho.
Enzyme xc tc l 6-phosphogluconate dehydrogenase.
CH
2
O P
OH
HO
OH
H
O
OH
CH
2
O P
OH
HO
OH
O
O
COOH
HC-OH
HOCH
HCOH
HCOH
CH
2
O P
6-phosphogluconic
acid
Glucose 6-
phosphate
Lactonphosphogluconic acid
NADP
+
NADPH + H
+
+ HOH
1
2
CHO
HC-OH
HC-OH
HC-OH
CH
2
O P Ribose 5-phosphate
CO
2
NADP
+
NADPH + H
+
3
119
Trong chu trnh ny 2 v tr (phn ng 1 v 3) NADP
+
c kh.
NADPH c to ra c th s dng cho phn ng tng hp, v d tng
hp cc acid bo. Ribulose-1-phosphate khng phi l sn phm cui cng
ca chui phn ng ny. N c bin i d dng thnh cc dng ng
phn nh ribose-5-phosphate hoc xylulose-5-phosphate, theo nh sau.
Chu trnh pentosephosphate cung cp nguyn liu cho cc qu trnh
tng hp khc. Ribose-5-phosphate tham gia tng hp nucleotide, nh vy
l tng hp cc nucleic acid v nhiu enzyme. Xylulose-5-phosphate cng
vi ribose-5-phosphate nh phn ng transcetolase to nn
sedoheptulosephosphate v aldehydphosphoglycic.
CHO
HC-OH
HC-OH
HC-OH
CH
2
O P
Ribose
5-phosphate
Xylulose
5-phosphate
Ribulose 5-
phosphate
Epimerase
Isomerase
CH
2
- OH
C=O
HCOH
HCOH
CH
2
O P
CH
2
- OH
C=O
HOCH
HCOH
CH
2
O P
120
Transcetolase vn chuyn 2 nguyn t C t ng ceto n aldose,
nhm prostetic ca chng l thiaminpyrophosphate, vng thiazol ca n
ng ceto c kt hp vo khi bt u phn ng.
Sedoheptulosephosphate phn ng vi aldehydphosphoglyceric trong mt
phn ng transcetolase to thnh erythrose-4-phosphate. phn ng
ny 3 nguyn t C c vn chuyn n aldehydphosphoglyceric.
CH
2
- OH
C=O
HOCH
HCOH
HCOH
CH
2
O P
Fructose 6-
phosphate
CHO
HOCH
HCOH
CH
2
O P
Erythrose 4-
phosphate
CHO
HCOH
CH
2
O P
Aldehydphospho-
glyceric
Sedoheptulose
7-phosphate
CH
2
- OH
C=O
HOCH
HCOH
HCOH
HCOH
CH
2
O P
+ +
CH
2
- OH
C=O
HOCH
HCOH
CH
2
O P
Xylulose
5-phosphate
CHO
HC-OH
HC-OH
HC-OH
CH
2
O P
Ribose
5-phosphate
CHO
HCOH
CH
2
O P
Aldehydphospho-
glyceric
Sedoheptulose
7-phosphate
CH
2
- OH
C=O
HOCH
HCOH
HCOH
HCOH
CH
2
O P
+ +
121
Fructose-6-photphate l cht trao i ca qu trnh ng phn, c
th i vo cc qu trnh khc. Erythrose-4-phosphate phn ng vi
xylulose-5-photphate to thnh fructose-6-photphate v
aldehydphosphoglyceric.
Phn ng ny cng vn chuyn 2C (transcetolase). Hai sn phm
ca phn ng l cht trao i ca qu trnh ng phn, c th c phn
gii tip tc trong qua trnh ny.
Ton b cc phn ng ca chu trnh pentosephosphate c biu
din trong hnh 4.25.
CH
2
- OH
C=O
HOCH
HCOH
CH
2
O P
CHO
HOCH
HCOH
CH
2
O P
CH
2
- OH
C=O
HOCH
HCOH
HCOH
CH
2
O P
CHO
HCOH
CH
2
O P
+
+
Xylulose
5-phosphate
Erythrose
4-phosphate
Fructose
6-phosphate
Aldehydphospho-
glyceric
122
Hnh 4.25. Chu trnh pentosephosphate
Cc bc oxy ho kh u tin dn n 2 v tr kh NADP
+
thnh
NADPH. Dng kh ca coenzyme cn cho phn ng tng hp v 1 H
c i vo cu to mt cht hu c. NADPH ng vai tr quan trng
trong tng hp cht bo. Nhng t bo trong acid bo c tng hp
nhiu th trao i cht theo chu trnh pentosephosphate xy ra mnh m, v
d trong cc m tuyn ca ng vt b sa. Ribulose-5-phosphate l tin
cht ca ribose-5-phosphate, l thnh phn ca nhiu nucleotide v nh
vy l ca nucleic acid. c bit nhng m sinh trng, tng hp nucleic
acid thng xuyn cn ribosephosphate, y trnh t phn ng ca chu
trnh cho n ribulose-5-phosphate thc hin vi tc ln. Erythrose-4-
phosphate l tin cht ca cc aminoacid thm (phenylalanine, tyrosine)
c s dng tng hp protein c bit trong cc m sinh trng. Khi
c nhu cu ln v NADPH th phn ng xy ra vi tc ln. T 6C ca
1 phn t glucose th 5C i vo qu trnh ng phn. Chu trnh
pentosephosphate c kh nng thch nghi vi nhu cu sinh l, tng t chu
trnh Krebs cung cp cho cc con ng trao i cht khc nhau vi chui
carbon hu c v cht kh tng ng.
Cu hi
6-phosphogluco-
lacton
6-phosphoglucuronate
Ribulose 5-phosphate
Nucleic acid
Ribose 5-phosphate
Pentose
-5 (P)
Glucose 6-phosphate
Fructose 6-phosphate
Glycolyse
Fructose 6-(P)
(P) Glyceraldehyde
Amino acid thm
Erythrose
4-phosphate
Xylulose 5-phosphate
Phospho-
Glyceraldehyde
Xylulose
5-phosphate
Ribulose
5-phosphate
Sedo 7-phosphate
H
2
O
CO
2
NADP
+
NADPH + H
+
NADP
+
NADPH + H
+
123
1. Quang hp; h hp l g ? Cc loi h hp?
2. Ni dung v c ch pha sng trong quang hp ?
3. C ch v ngha ca chu trnh C
3
v chu trnh C
4
?
4. Cho bit nhng im khc nhau gia chu trnh C
3
v chu trnh C
4
?
5. C ch v ngha ca qu trnh ng phn ?
6. C ch ca s bin i pyruvic acid trong iu kin ho kh.
7. C ch v ngha ca chu trnh KREBS ?
8. Ti sao ni: nh sng l iu kin cn thit cho qu trnh quang hp?
9. C ch v ngha ca h hp sng (Quang h hp) ?
131
CHNG V
LIPID V S TRAO I LIPID
TRONG C TH THC VT
Lipid l nhm cht hu c c cc c tnh ha l ging nhau, chng
khng tan trong nc, ch tan trong cc dung mi hu c nh ether,
cloroform, benzene, acetone, Khng phi tt c lipid u ha tan nh
nhau trong cc dung mi hu c ni trn m mi lipid ha tan trong dung
mi hu c tng ng ca mnh, nh c tnh ny ngi ta c th phn
tch ring tng loi lipid. V mt ha hc lipid l nhng ester gia ru v
acid bo, in hnh l triglycerid.
R
1
, R
2
, R
3
c th ging nhau,
c th khc nhau, c th bo
ha hoc cha bo ha.
Ngoi ru v cc acid bo, cc lipid phc tp (lipoid), trong phn
t ca chng cn cha cc dn xut c phospho, nit,
Vai tr ca lipid:
- L cht d tr nng lng, khi oxy ha mt gam lipid c th thu
c 9,3 Kcal.
- Lipid cu t ca t bo cht l thnh phn cu to ca t bo v cha
trong t bo vi s lng n nh. Lipid l thnh phn cu trc ca mng
t bo, mng ty lp th, Trong mng sinh hc lipid trng thi kt hp
vi protein to thnh hp cht lipoproteid. Chnh nh hp cht ny to
cho mng sinh hc c c tnh thm thu chn lc.
- Lipid di da ng vt c tc dng gi m v gi m cho c th.
- Lipid l dung mi cho nhiu vitamin quan trng (nh A, D, E, K).
- i vi loi ng vt ng ng, ng vt di c, cc loi su kn,
lipid cn l ngun cung cp nc, v khi oxy ha lipid cho mt lng
nc sinh ra.
- Cc ht cy trng khc nhau c hm lng lipid khc nhau.
V d: u tng (20 30%); go (2,2%); ng (4,9%); la m (1,9%);
cao lng (3,9%); lc (44 56%); thu du (50 60%).
CH
2
O CO R
1
CH O CO R
2
CH
2
O CO R
3
132
I - CU TO V TNH CHT CA LIPID
1.1. Cu to: Du, m c tng hp cc c th sng v ty theo
ngun gc m chng c phn ra du thc vt v m ng vt.
Glycerine l mt ru c 3 chc, do c th hnh thnh mono,
di hay triester. Cc ester ny c bit t lu vi cc tn mono, di v
triacylglycerid. Du, m c ngun gc t nhin lun l hn hp cc
triacylglycerid.
Cc acid bo ca du, m c ngun gc t nhin u c s nguyn
t carbon chn. Bi v cc acid bo u c tng hp t cc n v 2C
(gc acetyl).
Bn cnh cc acid bo bo ha, mt s acid bo khng bo ha
c tm thy trong du, m. Sau y l mt s acid bo bo ha
thng gp:
- Caproic acid (6C): CH
3
(CH
2
)
4
COOH
- Caprilic acid (8C): CH
3
(CH
2
)
6
COOH
- Caprinic acid (10C); lauric acid (12C); miristic acid (14C);
panmitic acid (16C); stearic acid (18C); arachidic acid (20C).
* Cc acid bo cha bo ha thng gp l:
- Oleic acid: CH
3
(CH
2
)
7
CH = CH (CH
2
)
7
COOH
- Linoleic acid:
CH
3
(CH
2
)
3
- [CH
2
CH = CH]
2
(CH
2
)
7
COOH
- Linolenic acid: CH
3
[CH
2
CH = CH]
3
(CH
2
)
7
COOH
- Eruxic acid: CH
3
(CH
2
)
7
CH = CH (CH
2
)
11
COOH
1.2. Tnh cht
a. Nhit nng chy: Ty thuc vo lng acid bo bo ha hay
cha bo ha chim u th trong thnh phn ca du m m nhit nng
chy khc nhau.
Nu trong thnh phn ca du, m c nhiu acid bo bo ha th
nhit nng chy cao, nu nhiu acid bo cha bo ha th nhit
nng chy thp v trng thi lng. a s du thc vt dng lng
nhit thng.
b. Ch s acid: l lng mg KOH cn thit trung ha cc acid bo
t do c trong 1 gam du, m. Ch s acid cng cao th lng acid bo t
do cng nhiu. Cht bo lu ngy, khng bo qun cn thn s c nhiu
acid bo t do. Ch s ny cho ta bit c cht lng ca cht bo.
c. Ch s x phng ha: l lng mg KOH cn thit trung ha cc
acid bo t do v cc acid bo kt hp vi glycerine khi x phng ha 1
133
gam cht bo. Ch s ny c trng cho phn t lng trung bnh ca
glyceride c trong du, m.
d. Ch s iod: l s gam iod c th kt hp vi 100 gam du, m.
Ch s ny dng m t mc khng bo ha ca cc acid bo c
trong thnh phn du, m. Ch s iod cng cao th du m cng long,
chng cng b oxy ha nhanh hn v cc acid bo b oxy ha d nht v
tr cc lin kt i.
S gn iod vo acid bo cha bo ha xy ra theo s sau:
Ch s iod ca m ng vt dao ng trong khong 30 70; cn ca
du thc vt trong khong 120 160.
e. S i ha du, m: Du, m lu ngy s c v hi, ng. Nguyn
nhn l do tc dng ca O
2
. Trng hp ny thng xy ra khi du m
cha nhiu acid bo cha bo ha. Oxy kt hp vo cc ni i ca acid
bo cha bo ha to thnh peroxid:
hoc O
2
kt hp vi nguyn t C bn cnh lin kt i to thnh
hydroperoxid:
Peroxid v hydroperoxid c to thnh lp tc b phn gii to thnh
aldehyd v cetone l nhng cht c mi v kh chu.
II. S PHN GII TRIGLYCERID
Du m l nhng cht dinh dng c gi tr nng lng cao, trong
ht cc cy ly du vn c t carbohydrate th du l cht d tr chnh v
C = C + I
2
C C
I I
C = C C + O
2
C = C C
O OH
Hydroperoxid
C = C + O
2
C C
O O
Peroxid
134
chng l ngun nng lng v ngun vt liu xy dng cho mm ang
pht trin.
Khi phn gii du ngi ta thy hm lng carbohydrate tng ln.
2.1. Phn ng thy phn triglycerid
2.2. Phn gii glycerine
Phn ng 1: do enzyme glycerolkinase xc tc.
Phn ng 2: do enzyme dehydrogenase xc tc.
- Phosphodioxiacetone di tc dng ca enzyme trioso(P)-isomerase
s chuyn thnh aldehydphosphoglyceric.
* Glycerine c quan h gn vi carbohydrate hoc l c s dng
tng hp fructose v carbohydrate khc hoc b phn gii nh
carbohydrate. Sau y l s cc ng hng trao i glycerine:
CH
2
O CO R
1
CH
2
OH R
1
COOH
lipase
CH O CO R
2
+ 3H
2
O CH OH + R
2
COOH
CH
2
O CO R
3
CH
2
OH R
3
COOH
Triglycerid Glycerine Cc acid bo
CH
2
OH CH
2
OH CH2 OH
ATP ADP NAD NADH
2
CH OH CH OH C = O
(1) (2)
CH
2
OH CH
2
O(P) CH
2
O(P)
Glycerine Glycerol(P) (P)dioxiacetone
CH
2
OH O
Trioso-(P) - C H
C = O
isomerase CH OH
CH
2
O(P)
(P)dioxiacetone CH
2
O(P)
Aldehyd(P)glyceric
Glycerine glycerol(P) (P)dioxiacetone Aldehyd(P)glyceric
Fructoso 1,6di(P) Pyruvic acid
Acetyl-CoA
Chu trnh Krebs
Carbohydrate khc
135
2.3. Phn gii acid bo
Mt acid bo mun c oxy ha phi tri qua mt s phn ng sau:
2.3.1. Hot ha acid bo:Nh h thng enzyme Acyl-CoA-Synthetase,
gm 2 bc sau:
Bc 1:
Bc 2:
Qu trnh ny c thc hin ngoi ty, lp th (t bo cht)
2.3.2. Gn Acyl-CoA vo carnitine to thnh acylcarnitine: Cht
ny i qua mng ty th. Trong ty th cc gc acyl ca acid bo c vn
chuyn li cho HS-CoA.
2.3.3. To Acyl-CoA tr li: qu trnh ny ngc li bc gn acyl
vo carnitine. Carnitine c gii phng v tr li mt ngoi ca ty th.
2.3.4. Qu trnh -oxy ha acid bo:
R CH
2
CH
2
COOH + ATP R CH
2
CH
2
CO AMP
-H
4
P
2
O
7
Acyl-AMP
R (CH
2
)
2
CO AMP + HS-CoA R CH
2
CH
2
CO ~ S.CoA
Acyl-AMP -AMP Acyl-CoA
R (CH
3
)
3
(CH
3
)
3
CH
2
+ N
+
Transferase N
+
CH
2
CH
2
-HS.CoA CH
2
CO ~ S.CoA CH OH CH O CO CH
2
Acyl-CoA
CH
2
- COOH CH
2
- COOH CH
2
Carnitine
R
Acylcarnitine
136
Trong c th sinh vt, s oxy ha acid bo xy ra bng cch oxy ha
nguyn t carbon v tr so vi nhm carboxyl, do qu trnh ny cn
c gi l qu trnh -oxy ha. Kt qu ca s -oxy ha l tng i
nguyn t carbon c tch ra di dng acetyl-CoA v acid bo mi to
thnh c mch carbon ngn hn trc 2 nguyn t carbon. S oxy ha
khng th t xy ra, c th tham gia phn ng, acid bo phi c hot
ha nh nng lng ca ATP, nhng y nng lng chuyn t ATP ti
cht bo khng thng qua con ng phosphoryl ha nh trong trng
hp oxy ha glucose m thng qua s to thnh hp cht acyl-CoA. Qu
trnh -oxi ha c Knoop (ngi c) a ra 1904, qu trnh ny xy ra
trong gian bo ty th.
Phn ng tng qut ca s to thnh acyl-CoA nh sau:
Sau acyl-CoA b oxy ha bi enzyme acyl-CoA-dehydrogenase
c nhm hot ng l FAD:
Di tc dng ca enzyme Enoyl-CoA-hydratase, phn t H
2
O kt
hp vo ni i v to thnh -oxyacyl-CoA:
Acyl-CoA-synthetase
R CH
2
CH
2
COOH + HS-CoA R CH
2
CH
2
C ~ S.CoA
ATP AMP + H
4
P
2
O
7
O
(1) Acyl-CoA
Acyl-CoA-dehydrogenase
R CH
2
CH
2
C ~ S.CoA R CH = CH C ~ S.CoA
O FAD FADH
2
O
Acyl-CoA (2) Enoyl-CoA
Enoyl-CoA-hydratase
R CH = CH C ~ S.CoA + H
2
O R CH CH
2
C ~ S.CoA
(3)
O OH O
Enoyl-CoA -oxyacyl-CoA
137
* -oxyacyl-CoA li b oxy ha ln th 2 di tc dng ca enzyme
-oxyacyl-CoA-dehydrogenase c coenzyme l NAD to thnh
-cetoacyl-CoA:
* -cetoacyl-CoA li phn ng vi HS-CoA to thnh acyl-CoA
mi v acetyl-CoA di tc dng ca enzyme -cetoacyl-CoA-thiolase:
Acyl-CoA mi to thnh ny cha gc acid bo c t hn acid bo ban
u 2 nguyn t carbon, n li c th tip tc tham gia cc phn ng 2, 3,
4, 5 to thnh acyl-CoA mi c mch carbon ngn hn 2 nguyn t
carbon v tch ra mt phn t acetyl-CoA na v qu trnh -oxy ha c
tip tc lp li nhiu ln cho n khi ton b phn t acid bo c
chuyn thnh cc acetyl-CoA.
S -oxy ha c Lynen m t di m hnh xon c.
Acetyl-CoA to thnh do kt qu ca s -oxy ha acid bo c th i
vo chu trnh Krebs, chu trnh glyoxilate hoc tham gia vo nhiu phn
ng khc.
NAD (4) NADH
2
R CH CH
2
C ~ S.CoA R C CH
2
C ~ S.CoA
-oxyacyl-CoA-
OH O dehydrogenase O O
-cetoacyl-CoA
(5)
R C CH
2
C ~ S.CoA + HS-CoA R C ~ SCoA + CH
3
C ~ S.CoA
-cetoacyl-
O O CoA-thiolase O O
Acyl-CoA(mi) Acetyl-CoA
138
Hnh 5.1 - S ca s -oxy ha acid bo (theo Lynen)
Hiu qu nng lng trong qu trnh -oxy ha acid bo:
V d -oxy ha hon ton palmitic acid (16C) t bo thu c ngun
nng lng nh sau: 7 vng quay to ra 7FADH
2
v 7NADH
2
v c 8
phn t acetyl-CoA.
Nhng v phi tiu tn 1 ATP hot ha acid bo nn s ATP to ra
khi -oxy ha palmitic acid l: 35ATP 1ATP = 34ATP.
Nu 8 phn t acetyl-CoA i vo chu trnh Krebs s to ra:
7FADH
2
7 x 2ATP = 14ATP
7NADH
2
7 x 3ATP = 21ATP
Tng cng : 35ATP
R CH
2
CH
2
COOH
ATP
HS-CoA
AMP
1) H
4
P
2
O
7
R CH
2
CH
2
C ~ S.CoA
CH
3
C ~ S.CoA Acyl-CoA O FAD
2)
O Acetyl-CoA FADH
2
O R CH = CH C ~ S.CoA
Acyl-CoA
R C ~ S.CoA 2C 2C 2C 2C
O Enoyl-CoA
HS-CoA 2CH
3
C ~ S.CoA 3) H
2
O
5) Acetyl-CoA
O
R C CH
2
C S.CoA R CH CH
2
C ~ S.CoA
4)
O O NADH
2
NAD OH O
-cetoacyl-CoA -oxyacyl-CoA
Chu trnh
Krebs
Chu trnh
glyoxilate
139
8 x 12ATP = 96ATP
Tng cng: 34ATP + 96ATP = 130ATP.
Ta c th p dng cng thc tnh sau:
A = 12 x
2
n
1 1
2
n
5
*---------------* * -------*
(-oxy ha) (Krebs)
A l s phn t ATP.
n l s nguyn t C (n: chn).
III. S PHN GII CC ACID BO CHA BO HA
i vi acid bo cha bo ha nh oleic acid, linolenic acid qu
trnh -oxy ha din ra bnh thng, cc phn t acetyl-CoA c tch
dn ra, cho ti gn lin kt i. Ti y, ty theo v tr ca lin kt i m
s phn gii c th c cc ng hng sau:
3.1. nhng acid bo cha bo ha m c lin kt i khng
gia C
v C
v C
v C
th n chu s
-oxy ha bnh thng.
3.2. Cc acid bo cha bo ha trc khi b oxy ha th chng
chuyn thnh acid bo ha bng cch gn thm H
2
v sau li chu s
-oxy ha nh bnh thng.
IV. S PHN GII CC ACID BO C S NGUYN T
CARBON L
S phn gii cc acid bo ny vn tin hnh bnh thng bng s -oxy
ha cho n khi hnh thnh (propionyl-CoA),
sau propionyl-CoA ( ty th thc vt v vi sinh vt) giai on u
ging nh s -oxy ha cho n khi hnh thnh -hydroxipropionyl-CoA.
CH
3
CH
2
C ~ S.CoA
O
140
Sau nguyn t C