VITAMINA D

H3C CH3 25
CH-CH=CH-CH-CH H3 C CH3
CH-CH=CH-CH-CH
CH3 CH3
CH3 CH3

oxidare
HO CH2

ergosterol
1
HO
vitamina D2 (ergocalciferol)

25
H3C CH3 H3C CH
CH-CH2-CH2-CH2-CH CH-CH2-CH2-CH2-CH CH3
CH3 3

oxidare

HO CH2

7-dehidrocolesterol HO 1

vitamina D3 (colecalciferol)

VITAMINA K
O O

H
O 3 O n-1
vitamina K1 (fitomenadiona) vitamina K2 (menachinona)

Carboxilarea resturilor de acid glutamic sub acţiunea vitaminei K

OH
OH

CH3 CH3
vitamina K-epoxidaza
O
R R

OH
O2 H2 O O-
OH
vitamina K redusa alcooxid
S anticoagulante glutamat
R
NAD+ cumarinice
S (-) vitamina K--glutamil-
vitamina K-reductaza carboxilaza
SH -carboxi-glutamat
R
SH NADH + H+

O O
(-)
CH3 H2O CH3
vitamina K-epoxid reductaza
O
R R

O S SH O
R R
vitamina K SH vitamina K epoxid
S

1
 VITAMINA B1

+ ATP AMP + CH3

CH3 N N
N N O
O
tiamin
H3C CH2- CH2-OH pirofosfokinaza H3C N NH2 S CH2-CH2-O-P-O-P-OH
N NH2 S
OH OH
tiamin pirofosfat (TPP)
tiamina

Mecanismul reacţiei de decarboxilate a acidului piruvic

+ CH3 H3C-C-COOH +
R N CH3
O R N
HO
S CH2-CH2-O-PP H3C-C CH2-CH2-O-PP
S
tiaminpirofosfat (TPP) COOH

+ CH3 + CH3
R N R N
- H3C-CHO
-CO2 HO
CH2-CH2-O-PP S CH2-CH2-O-PP
H3C-CH S

CH2-OH
CH2-OH CHO C=O
CHO
C=O H-C-OH HO-C-H
+ transcetolaza CH-OH
HO-C-H H-C-OH H-C-OH +
CH2-OPO3H2
H-C-OH H-C-OH H-C-OH
gliceraldehid-3-fosfat
CH2-OPO3H2 CH2-OPO3H2 H-C-OH
xilulozo-5-fosfat ribozo-5-fosfat CH2-OPO3H2
sedoheptulozo-7-fosfat

VITAMINA B2
O
H3C N
NH

H3C N N O

CH2-CH-CH-CH-CH2-OH
riboflavina OH OH OH

riboflavina FMN FAD

flavokinaza
flavinadenin
pirofosforilaza
ATP ATP PP
ADP

2
 O
H3C N
NH
FMN (flavinmononucleotid)
H3C N N O O
CH2-CH-CH-CH-CH2-O-P-OH
OH OH OH OH

O
H3C N
NH
NH2

H3C N N O O O N N FAD (flavinadenin dinucleotid)

CH2-CH-CH-CH-CH2-O-P-O-P-O-CH2
N
OH OH OH OH OH O N

OH OH

Reacţia de reducere a coenzimelor flavinice

O O
H
H3C N H3C N
NH NH
+ SH2 + 2e-
H3C O -S H 3C
N N N N O
H
R R
FMN (FAD) FMNH2 (FADH2)

FADH2 FAD

glutation
NAD+ reductaza NADH + H+

2 G-SH G-S-S-G

NAD(P)H-CYP450 reductaza AH + O 2 + FADH2 → A-OH + FAD + H2O

O O O
H2O, O2 H2O2 H2O, O2 H2O2 H
N N N
HN HN HN
O
xantin oxidaza xantin oxidaza
N N O N N O N N
H H H H H
hipoxantina xantina acid uric

R-CH-COOH + H2O + O2 aminoacid R-C-COOH + NH3 + H2O2

oxidaza
NH2 O
aminoacid cetoacid

3
 COOH COOH
FAD FADH2
CH2 H-C

CH2 succinat C-H

dehidrogenaza
COOH COOH
acid succinic acid fumaric

VITAMINA B3
NH2
CO-NH2
N N
(+) O O
N N
COOH CO-NH2 CH2-O-P-O-P-O-CH2 N
O O
OH OH

N N
acid nicotinic nicotinamida OH OH OH OH
(niacina) (niacinamida) +
NAD (nicotinamidadenin dinucleotid)
NH2
CO-NH2
N N
(+) O O
N
N CH2-O-P-O-P-O-CH2 N
O O
OH OH

OH OPO3H2 OH OH
+
NADP (nicotinamidadenin dinucleotidfosfat)

Reacţia generală de oxido-reducere a coenzimelor nicotinamidice

CO-NH2
CO-NH2
+ SH2
(+) + S + H+
N N
R
R

lactat dehidrogenaza
CH3-CH-COOH + NAD+ CH3-C-COOH + NADH + H+
OH O
acid lactic acid piruvic

alcool dehidrogenaza
CH3-CH2-OH + NAD+ CH3-CHO + NADH + H+
alcool etilic acetaldehida

4
 CH2-OPO3H2 CH2-OPO3H2
O O
glucozo-6-fosfat
OH + NADP+ dehidrogenaza OH O + NADPH + H+
HO OH HO
OH OH
D-glucozo-6-fosfat 6-fosfat-D-glucozo-1,5-lactona

OH OH
H NADPH + H+ NADP+ H
N N
N CH2-NH-R N CH2-NH-R
dihidrofolat
H2N N N H2N N
reductaza N
H
acid dihidrofolic
acid tetrahidrofolic

VITAMINA B5
H3C H3C
HO-CH2-C-CH-CO-NH-CH2-CH2-COOH HO-CH2-C-CH-CO-NH-CH2-CH2-CH2-OH
H3C OH H3C OH
acid pantotenic pantotenol (pantenol)
NH2

N N
O O H3C
N
N O CH2-O-P-O-P-O-CH2-C-CH-CO-NH-CH2-CH2-CO-NH-CH2-CH2-SH
OH OH H3C OH

OH OPO3H2 coenzima A

VITAMINA B6
CH2-OH CHO CH2-NH2
HO HO HO
CH2-OH CH2-OH CH2-OH

H3C H3C H3C

N N N
piridoxina piridoxal piridoxamina

Sinteza cofactorilor derivaţi de la vitamina B6

CHO
CHO
HO
CH2-OH HO
CH2-OPO3H2
piridoxal
H3C N kinaza
H3 C N
piridoxal
piridoxal-5'-fosfat
ATP ADP

5
 CH2-NH2
HO CH2-OH CH2-NH2
HO
CH2-OPO3H2
H3C
N piridoxal
piridoxamina kinaza
H 3C N
piridoxamin-5'-fosfat
ATP ADP

CH2-CH-COOH CH2-CH2-NH2
histidin
N N NH2 decarboxilaza + CO2
N N

histidina histamina

COOH COOH
(CH2)2 glutamat + CO2
decarboxilaza (CH2)2
CH-NH2 CH2-NH2

COOH GABA
acid glutamic (acid -aminobutiric)

HO CH2-CH-COOH HO CH2-CH2-NH2
5-hidroxi-triptofan
NH2 decarboxilaza
N N
H H
5-hidroxi-triptofan serotonina

CH2-CH-COOH serin CH2-CH-COOH

OH racemaza
NH2 OH NH
2
L-serina D-serina

Mecanismul reacţiei de transaminare

R1-CH-COOH R1-C-COOH
NH2 O

E-PLP-CHO E-PLP-CH2-NH2
CH2-OPO3H2 CH2-OPO3H2
transaminaza

R2-CH-COOH R2-C-COOH

NH2 O

6
 COOH COOH
COOH C=O COOH HC-NH2
TGP C=O + CH2
HC-NH2 + CH2
(ALT, ALAT)
CH3 CH2 CH3 CH2

alanina COOH acid piruvic COOH

acid -ceto-glutaric acid glutamic

COOH COOH
COOH COOH
C=O HC-NH2
HC-NH2 TGO C=O
+ CH2 (AST, ASAT) + CH2
CH2 CH2
CH2 CH2
COOH COOH
COOH COOH
acid aspartic acid oxalacetic
acid -ceto-glutaric acid glutamic

H2 O H2O NH3
CH2-CH-COOH CH3-C-COOH
CH2=C-COOH CH2=C-COOH
OH NH2 O
NH2 OH
serina acid piruvic

H2S H2O NH3 CH3-C-COOH

CH2-CH-COOH CH2=C-COOH
CH2=C-COOH
SH NH2 O
NH2 OH
cisteina acid piruvic

VITAMINA B7
O

HN NH
biotina

(CH2)4-COOH
S

ATP ADP + P
- acetil-CoA
CH3-CO-SCoA + HCO3 HCOO-CH2-CO-SCoA
carboxilaza
acetil-CoA malonil-CoA

ATP ADP + P
-
CH3-CH2-CO-SCoA + HCO3 propionil-CoA HCOO-CH-CO-SCoA
propionil-CoA carboxilaza CH3
metilmalonil-CoA
O O
O
HN NH ATP ADP + P
HN NH
HN N COO- CH3-C-COOH
biotin
carboxilaza O HOOC-CH2-C-COOH +
piruvat
- O
R HCO3 H2O carboxilaza R
S R acid oxalacetic
S S
biotina biotina
carboxibiotina

7
 CH2-NH2 CH2-NH-C-NH2
(CH2)2 ornitin (CH2)2 O
H2N-C-O-PO3H2 +
CH-NH2 carbamoil transferaza CH-NH2 +P
O
carbamoilfosfat COOH COOH
ornitina citrulina

VITAMINA B9
OH
N
N CH2-NH CO-NH-CH-COOH
CH2-CH2-COOH
H2N N N

Sinteza acidului tetrahidrofolic

OH
OH
N H OH
N CH2-NH-R N NADPH + H+ NADP+ H
NADPH + H+ NADP+ N CH2-NH-R N
N CH2-NH-R
H2N N N
folat H2N N N dihidrofolat
acid folic reductaza reductaza H2N N N
acid dihidrofolic H
acid tetrahidrofolic

Structura coenzimelor sintetizate din acid tetrahidrofolic

CH3 OH CH2 OH CH=NH

OH
N N
N N CH2-N-R
N CH2-NH-R N CH2-NH-R

H2N N N H2N N
H2N N N H N
H H
N5,N10-metilen-tetrahidrofolat N5-formimino-tetrahidrofolat
N5-metil-tetrahidrofolat

OH CHO OH CH OH CHO
(+) H
N N N
N CH2-NH-R N CH2-N-R N CH2-N-R

H2N N N H2N N N H2N

H H N N
H
N5-formil-tetrahidrofolat N5,N10-metenil-trahidrofolat N10-formil-tetrahidrofolat

8
 OH
H CH2
N CH2-CH-COOH OH
N CH2-NH-R N
H2O
OH NH N CH2-N-R
2
H2N N N
H H2N-CH2-COOH
H2N N N
acid tetrahidrofolic H
N5,N10-metilen-tetrahidrofolat
NADPH + H+
CH2-CH2-CH-COOH
metionin
sintaza NADP+
S-CH3 NH2 B12
OH CH3
L-metionina
N
N CH2-NH-R
CH2-CH2-CH-COOH

SH NH2 H2N N N
H
L-homocisteina
N5-metil-tetrahidrofolat

VITAMINA B12
O O
CH3-CH-C metilmalonil-CoA mutaza
(deoxiadenozil-cobalamin- HOOC-CH2-CH-C
S-CoA S-CoA
COOH mutaza)
L-metilmalonil-CoA succinil-CoA

N5-metil-tetrahidrofolat tetrahidrofolat

CH2-CH2-CH-COOH B12 CH2-CH2-CH-COOH

SH NH2 metionin sintaza S-CH3 NH2

L-homocisteina L-metionina

VITAMINA C
O O
C C
HO-C -2H O=C
O O
HO-C +2H O=C
HC HC
HO-CH HO-CH
CH2-OH CH2-OH
acid ascorbic acid dehidroascorbic

9
 O
O
CH2-CH2-NH2 C HO-CH-CH2-NH2
C
HO-C O=C
O O
HO-C + O2 dopamin-- + H2O
OH + monooxigenaza OH + O=C
HC HC
OH HO-CH OH HO-CH
dopamina CH2-OH noradrenalina CH2-OH
acid ascorbic acid dehidroascorbic

H3C + -butirobetain
H3C N-CH2-CH2-CH2-COOH + HOOC-CH2-CH2-C-COOH + O2 dioxigenaza
H3C
O
-butiro-betaina acid -ceto-glutaric

H3C +
H3C N-CH2-CH-CH2-COOH + HOOC-CH2-CH2-COOH + CO2
H3C
OH
acid succinic
carnitina

10