1

Fe2+

hem B

CH=CH2

COOH

CH2

CH2

H3C

CH2

COOH

CH3

CH3

CH3 CH=CH2

CH2

N

N

NN

CH3

SH

Fe2+

hem C

CH2

CH2

COOH

CH3

CH3

CH3-CH-SH

CH2

H3C

CH3-CH

COOH

CH2

N

N

NN

Participarea coenzimei Q10 la reacţiile de oxido-reducere

FADH2

OH

OH

H3CO

H3CO CH3FMNH2

FMNFAD

citocromi2Fe2+ 2Fe3+2H+

NADH + H+ NAD+

coenzima Q10 oxidata

(CoQ)

coenzima Q10 redusa

(CoQH2)

O

O

H3CO

H3CO

CH3

(CH2-CH=C-CH2)10-H

CH3

(CH2-CH=C-CH2)10-H

CH3

COOH

acid lipoic

SS

H2N

O

N

N

N

NCH3

CH-CH-CH3

OH OHH

H

tetrahidrobiopterina

H

Hidroxilarea fenilalaninei sub acţiunea fenilalanin-4-hidroxilazei

O2 H2O

fenilalanina tirozina

NADP+

NADPH + H+

H2N

O

CH3

CH-CH-CH3

OH OHH

H

tetrahidrobiopterina

fenilalanin-4-hidroxilaza

H2N

O

CH3

CH-CH-CH3

OH OHH

H

tetrahidrobiopterin-4a-carbinolamina

OH

pterin-4a-carbinolamindehidraza

H2O

H2N

O

CH3

CH-CH-CH3

OH OH

H

dihidropterinreductaza

N

N

N

N

N

N

N

N

N

N

N

N

2

OH OH

HOOC-CH-CH2-CH2-S-CH2

NH2

CH3

NH2

N

N N

NO

S-adenozil metionina

VITAMINA A

retinol (vitamina A1)

CH2-OHH3C CH3

CH3

retinal (all-trans retinal)

CHOH3C CH3

CH3

11-cis-retinal

H3C

CHO

acid all-trans retinoic(acid retinoic)

COOH

H3C CH3

CH3

H3C CH3

CH3

Sinteza retinolului şi a acidului retinoic din β-caroten

caroten-

dioxigenaza

H3C

-caroten

H3C CH3

CH3

H3C CH3

retinal (all-trans retinal)

CHOH3C CH3

CH3

retinol

CH2-OHH3C CH3

CH3

acid retinoic

COOHH3C CH3

CH3

retinal reductaza retinol dehidrogenaza

3

Sinteza şi degradarea rodopsinei în procesul de vedere la întuneric

opsina

lumina

all-trans retinal

dehidrogenaza

+ 11-cis retinal

all-trans retinal

11-cis-retinol

nerv optic

impuls nervos

rodopsina

opsina

centri optici

all-trans retinollecitin retinol

aciltransferazaall-trans retinil ester

izomero-hidrolaza

11-cis-retinol

dehidrogenazaretinal

izomeraza

VITAMINA D

HO

ergosterol

CH-CH=CH-CH-CHCH3

CH3

vitamina D2 (ergocalciferol)

CH3

H3C

CH3

oxidare

HO

CH-CH=CH-CH-CH

CH2

H3C

CH3

CH3

1

25

7-dehidrocolesterol

HO

CH-CH2-CH2-CH2-CHCH3

CH3H3C

oxidare

vitamina D3 (colecalciferol)

HO

CH-CH2-CH2-CH2-CHCH3

CH2

H3C CH3

1

25

VITAMINA E

HO

-tocoferol (5,7,8-trimetil tocoferol)

5

78

O

HO

-tocoferol (5,8-dimetil tocoferol)

5

8O

4

-tocoferol (7,8-dimetil tocoferol)

HO

78

O

-tocoferol (8-metil tocoferol)

HO

8O

VITAMINA K

O

O

vitamina K1 (fitomenadiona)

3

O

O

vitamina K2 (menachinona)

n-1

H

Carboxilarea resturilor de acid glutamic sub acţiunea vitaminei K

vitamina K-epoxidaza

R

OH

O2

CH3

alcooxid

O

H2O O-

glutamat

OH

R

OH

CH3

OH

-carboxi-glutamat

OR

O

CH3

Ovitamina K epoxid

vitamina K-epoxid reductazaH2O

R

(-)

SH

SHR

S

S

R

O

CH3

O

vitamina K

NADH + H+

NAD+

RSH

SH

RS

Svitamina K-reductaza

(-)

anticoagulantecumarinice

vitamina K- -glutamil-

carboxilaza

vitamina K redusa

VITAMINA B1

ATP AMP

tiaminpirofosfokinaza

OHOH

OO

tiamin pirofosfat (TPP)

NH2

+

tiamina

CH3

CH2- CH2-OHH3C NH2

+ CH3

H3C CH2-CH2-O-P-O-P-OH

N

N

N

S

N

N

N

S

5

Mecanismul reacţiei de decarboxilate a acidului piruvic

H3C-C-COOH

O

-CO2

H3C-C

COOH

HO

- H3C-CHO

CH3

CH2-CH2-O-PP

+R

H3C-CH

HO

R+ CH3

CH2-CH2-O-PP

tiaminpirofosfat (TPP)

R+ CH3

CH2-CH2-O-PP

N

S

N

S

N

S

CH3

CH2-CH2-O-PP

+R N

S

xilulozo-5-fosfat

CH2-OPO3H2

C=O

HO-C-H

H-C-OH

CH2-OH

ribozo-5-fosfat

CH2-OPO3H2

H-C-OH

H-C-OH

CHO

H-C-OH+

sedoheptulozo-7-fosfat

CH2-OPO3H2

H-C-OH

H-C-OH

HO-C-H

H-C-OHCH2-OPO3H2

CH-OH

gliceraldehid-3-fosfat

transcetolaza

C=O

CH2-OH

+

CHO

VITAMINA B2

H3C

H3C

OH

CH2-CH-CH-CH-CH2-OH

O

O

OHOHriboflavina

H

N

N

N

N

riboflavina FMN FAD

ATP ADPATP PP

flavokinaza

flavinadenin

pirofosforilaza

FMN (flavinmononucleotid)

OH

O

H3C

H3C

OH

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

O

O

OHOH

H

N

N

N

N

6

FAD (flavinadenin dinucleotid)

OH

OH OH

NH2

O

OH

O

H3C

H3C

OH

CH2-CH-CH-CH-CH2-O-P-O-P-O-CH2

O

O

OHOH

H

ON

N N

N

N

N

N

N

Reacţia de reducere a coenzimelor flavinice

+ SH2

R

- S

+ 2e-

H

H

FMN (FAD) FMNH2 (FADH2)

H3C

H3C

O

O

H

R

H3C

H3C

O

O

H

N

N

N

N

N

N

N

N

FADH2

G-S-S-G

NAD+

2 G-SH

NADH + H+

FAD

glutationreductaza

NAD(P)H-CYP450 reductaza AH + O2 + FADH2 → A-OH + FAD + H2O

O

H

O

hipoxantina

H

xantin oxidaza

H2O2H2O, O2

H

O

xantina

H

H2O2H2O, O2

O

H

O

acid uric

H

O

H

H

xantin oxidaza

N

N

N

N

N

N

N

N

N

N

N

NH

R-CH-COOH

NH2aminoacid

+ H2O + O2aminoacid

oxidaza

O

R-C-COOH

cetoacid

+ NH3 + H2O2

COOH

acid succinic

FADH2

CH2

COOH

CH2

FAD

succinatdehidrogenaza

COOH

acid fumaric

C-H

COOH

H-C

7

VITAMINA B3

COOH CO-NH2

acid nicotinic (niacina)

nicotinamida(niacinamida)

N N

NAD+ (nicotinamidadenin dinucleotid)

OH

O

NH2

OH

O

OH OH

CH2-O-P-O-P-O-CH2

(+)

CO-NH2

OH OH

N

NN

N

O

N

O

OH

O

NH2

OH

O

OH OPO3H2

CH2-O-P-O-P-O-CH2

(+)

CO-NH2

OH OH

NADP+ (nicotinamidadenin dinucleotidfosfat)

N

NN

N

N

OO

Reacţia generală de oxido-reducere a coenzimelor nicotinamidice

CO-NH2

(+)

R

+ SH2CO-NH2

+ S + H+

R

NN

O

CH3-CH-COOH + NAD+

OH

lactat dehidrogenazaCH3-C-COOH + NADH + H+

acid lactic acid piruvic

acetaldehidaalcool etilic

CH3-CH2-OH + NAD+ alcool dehidrogenazaCH3-CHO + NADH + H+

+ NADP+

OH

OH

OH

CH2-OPO3H2

HO

D-glucozo-6-fosfat

NADPH + H+glucozo-6-fosfatdehidrogenaza +

OH

OH

CH2-OPO3H2

HO

6-fosfat-D-glucozo-1,5-lactona

OO

O

8

H

acid dihidrofolic

H2N

OH

H

HNADP+NADPH + H+

dihidrofolatreductaza

acid tetrahidrofolic

H2N

OH

N

N

N

N

N

N

N

N

CH2-NH-RCH2-NH-R

VITAMINA B5

HO-CH2-C-CH-CO-NH-CH2-CH2-COOH

H3C

H3C OH

acid pantotenic

HO-CH2-C-CH-CO-NH-CH2-CH2-CH2-OH

H3C

H3C

OH

pantotenol (pantenol)

coenzima A

H3C

H3C

OH

CH2-O-P-O-P-O-CH2-C-CH-CO-NH-CH2-CH2-CO-NH-CH2-CH2-SH

NH2

OH OPO3H2

OHOH

O O

O

N

N

N

N

VITAMINA B6

CH2-OH

H3C

HO

piridoxina

CH2-OH

N

CHO

H3C

HO

piridoxal

CH2-OH

N

CH2-NH2

H3C

HO

piridoxamina

CH2-OH

N

Sinteza cofactorilor derivaţi de la vitamina B6

CHO

H3C

HO

piridoxal

CH2-OH

N

piridoxalkinaza

ADPATP

CHO

H3C

HO

piridoxal-5'-fosfat

CH2-OPO3H2

N

CH2-NH2

H3C

HO

piridoxamina

CH2-OH

N piridoxalkinaza

ADPATP

H3C

HO

piridoxamin-5'-fosfat

CH2-OPO3H2

N

CH2-NH2

9

N N

CH2-CH-COOH

NH2

histidina

N N

CH2-CH2-NH2

histamina

histidindecarboxilaza + CO2

COOH

CH-NH2

COOH

(CH2)2

acid glutamic

COOH

CH2-NH2

(CH2)2

GABA

(acid -aminobutiric)

glutamatdecarboxilaza

+ CO2

5-hidroxi-triptofan

H

CH2-CH-COOH

NNH2

5-hidroxi-triptofandecarboxilaza

serotonina

H

CH2-CH2-NH2

N

HO HO

CH2-CH-COOH

NH2OH

D-serina

CH2-CH-COOH

NH2OH

L-serina

serinracemaza

Mecanismul reacţiei de transaminare

R1-CH-COOH

NH2

O

R2-C-COOHR2-CH-COOH

NH2

O

R1-C-COOH

CH2-OPO3H2

E-PLP-CHO

CH2-OPO3H2

E-PLP-CH2-NH2

transaminaza

COOH

HC-NH2

acid -ceto-glutaric

TGP(ALT, ALAT)

+

COOH

C=O

CH3

alanina

CH2

CH2

COOH

C=O

HC-NH2COOH

acid glutamic

+

COOH

CH3

acid piruvic

CH2

CH2

COOH

10

CH2

TGO(AST, ASAT)+

COOH

acid aspartic

CH2

COOH

acid oxalacetic

+

acid glutamic

COOH

HC-NH2

acid -ceto-glutaric

COOH

C=O

CH2

CH2

COOH

C=O

HC-NH2COOH

COOH

CH2

CH2

COOH

CH2-CH-COOH

NH2

H2O

O

CH3-C-COOH

OHNH2

NH3

CH2=C-COOH

H2O

OH

CH2=C-COOH

serina acid piruvic

CH2-CH-COOH

NH2

H2S

SHNH2

NH3CH2=C-COOH

H2O

OH

CH2=C-COOH

cisteina

O

CH3-C-COOH

acid piruvic

VITAMINA B7

O

H H

(CH2)4-COOH

N N

S

biotina

acetil-CoA

CH3-CO-SCoA HCO3-

+acetil-CoAcarboxilaza

HCOO-CH2-CO-SCoA

malonil-CoA

ATP ADP + P

propionil-CoA

CH3-CH2-CO-SCoA +propionil-CoA

carboxilaza

HCOO-CH-CO-SCoA

metilmalonil-CoA

CH3

HCO3-

ATP ADP + P

CH3-C-COOH

H2O

ATP ADP + P

HCO3-

O

H HCOO-

O

R

biotin

carboxilaza

O

H

R

N N

S

carboxibiotina

N N

S

biotina

piruvat

carboxilaza

HOOC-CH2-C-COOH +

O

O

H H

R

N N

S

biotina

acid oxalacetic

ornitina

CH2-NH2

CH-NH2

COOH

(CH2)2

carbamoilfosfatO

H2N-C-O-PO3H2+

citrulina

CH2-NH-C-NH2

CH-NH2

COOH

(CH2)2O

+ Pornitin

carbamoil transferaza

11

VITAMINA B9

H2N

OH

CH2-NH CO-NH-CH-COOH

CH2-CH2-COOH

N

N

N

N

Sinteza acidului tetrahidrofolic

acid folic

H

NADP+CH2-NH-RNADPH + H+

folat

reductaza

H2N

OH

acid dihidrofolic

H2N

OH

H

H

dihidrofolat

reductaza

acid tetrahidrofolic

H2N

OHN

NN

N

N

N

N

N

N

N

N

N

CH2-NH-R

CH2-NH-R NADP+NADPH + H+

Structura coenzimelor sintetizate din acid tetrahidrofolic

CH3

H

N5-metil-tetrahidrofolat

H2N

OHCH2

H

N5,N10-metilen-tetrahidrofolat

H2N

OH

CH2-NH-RCH2-N-R

N

N

N

N

N

N

N

N

CH=NH

H

N5-formimino-tetrahidrofolat

H2N

OH

CH2-NH-RN

N

N

N

CHO

H

N5-formil-tetrahidrofolat

H2N

OH

CH2-NH-RN

N

N

N

H(+)

HH2N

OH

CH2-N-R

N5,N10-metenil-trahidrofolat

CHCHO

H

N10-formil-tetrahidrofolat

H2N

OH

CH2-N-RN

N

N

N

N

N

N

N

CH3

H

H

acid tetrahidrofolic

H2N

OH

H

N5-metil-tetrahidrofolat

H2N

OH

CH2

H

N5,N10-metilen-tetrahidrofolat

H2N

OH

CH2-NH-R

CH2-NH-R

CH2-N-R

CH2-CH-COOH

NADPH + H+

OH

NADP+

NH2

H2N-CH2-COOH

B12

N

N

N

N

N

N

N

N

N

N

N

N

H2O

CH2-CH2-CH-COOH

SH NH2

L-homocisteina

CH2-CH2-CH-COOH

S-CH3

L-metionina

metioninsintazaNH2

12

VITAMINA B12

CH3-CH-C

O

COOHS-CoA

HOOC-CH2-CH-C

O

S-CoA

L-metilmalonil-CoA succinil-CoA

metilmalonil-CoA mutaza(deoxiadenozil-cobalamin-

mutaza)

CH2-CH2-CH-COOH

SH NH2

L-homocisteina

CH2-CH2-CH-COOH

S-CH3 NH2

L-metionina

N5-metil-tetrahidrofolat tetrahidrofolat

metionin sintaza

B12

VITAMINA C

-2H

HC

acid ascorbic

HO-CH

C

O

O

CH2-OH

HO-C

acid dehidroascorbic

HO-C

+2H

HC

HO-CH

C

O

O

CH2-OH

O=C

O=C

dopamin- -monooxigenaza

H2OO2

dopamina

CH2-CH2-NH2

OH

OH+++

noradrenalina

HO-CH-CH2-NH2

OH

OH +

HC

acid ascorbic

HO-CH

C

O

O

CH2-OH

HO-C

acid dehidroascorbic

HO-C

HC

HO-CH

C

O

O

CH2-OH

O=C

O=C

-butirobetaindioxigenaza

CO2

O2

-butiro-betaina

N-CH2-CH2-CH2-COOH

O

H3C

acid -ceto-glutaric

OH

++

+ HOOC-CH2-CH2-C-COOH

H3C

H3C

carnitina

N-CH2-CH-CH2-COOHH3C

acid succinic

++

+ HOOC-CH2-CH2-COOH

H3C

H3C