CH3

CH=CH2

CH3-CH-SH

CH3

N H3C N CH2 CH2 COOH CH2 CH2 COOH CH3 CH3 Fe2+ N CH=CH2 N CH3-CH SH CH3 H3C N

N CH3 Fe2+ N CH2 CH2 COOH CH2 CH2 COOH

hem B

hem C

Participarea coenzimei Q10 la reaciile de oxido-reducere

O H3CO H3CO O (CoQ) CH3 (CH2-CH=C-CH2)10-H CH3 NADH + H+ FMNH2 FADH2 NAD+ FMN FAD OH H3CO H3CO + 2Fe2+ 2H 2Fe3+ citocromi CH3

coenzima Q10 oxidata

(CH2-CH=C-CH2)10-H CH3 OH coenzima Q10 redusa (CoQH2)

O HN

H N

OH OH CH-CH-CH3

COOH S S acid lipoic

H2N N N H

CH3

tetrahidrobiopterina

Hidroxilarea fenilalaninei sub aciunea fenilalanin-4-hidroxilazei

O N H2N N N H H N OH OH CH-CH-CH3 CH3 O2 NADP+ dihidropterin reductaza NADPH + H+ O N N H2N N N H H2O OH OH CH-CH-CH3 CH3 pterin-4a-carbinolamin dehidraza fenilalanin-4H N hidroxilaza H O 2 2 tirozina N N O OH H N OH OH CH-CH-CH3

fenilalanina

tetrahidrobiopterina

CH3 N H tetrahidrobiopterin-4acarbinolamina

NH2 CH3 HOOC-CH-CH2-CH2-S-CH2 NH2 O N N N N

OH

OH

S-adenozil metionina

VITAMINA A
H3C CH3 CH2-OH

H3C

CH3

CHO

CH3

CH3

retinol (vitamina A1)

retinal (all-trans retinal)

H3C

CH3 H3C CH3 CHO

H3C

CH3

COOH

CH3

11-cis-retinal

acid all-trans retinoic (acid retinoic)

Sinteza retinolului i a acidului retinoic din -caroten

H3C H3C CH3 H3C CH3 -caroten retinal reductaza CH3 carotendioxigenaza CH3 retinal (all-trans retinal) retinol dehidrogenaza H3C CH3 CHO

H3C

CH3

CH2-OH

H3C

CH3

COOH

CH3 retinol

CH3 acid retinoic

Sinteza i degradarea rodopsinei n procesul de vedere la ntuneric

opsina + 11-cis retinal rodopsina

11-cis-retinol dehidrogenaza

retinal izomeraza

lumina

11-cis-retinol opsina impuls nervos all-trans retinal izomero-hidrolaza all-trans retinal dehidrogenaza lecitin retinol aciltransferaza all-trans retinol centri optici

nerv optic

all-trans retinil ester

VITAMINA D
H3C CH-CH=CH-CH-CH CH3 CH3 CH3

25 H3C CH-CH=CH-CH-CH
CH3

CH3 CH3

oxidare HO ergosterol HO CH2

vitamina D2 (ergocalciferol)
H3C CH3 CH-CH2-CH2-CH2-CH CH3

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

oxidare HO 7-dehidrocolesterol HO CH2

vitamina D3 (colecalciferol)

VITAMINA E
HO 5
HO 5

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

-tocoferol (5,8-dimetil tocoferol)

HO

HO

8
-tocoferol (7,8-dimetil tocoferol)

-tocoferol (8-metil tocoferol)

VITAMINA K
O
O

O vitamina K1 (fitomenadiona)

O vitamina K2 (menachinona)

H n-1

Carboxilarea resturilor de acid glutamic sub aciunea vitaminei K

OH CH3 R OH vitamina K redusa R S S R SH SH O CH3 H2O R O vitamina K S S SH SH (-) vitamina K-epoxid reductaza CH3 O R O vitamina K epoxid NAD+ vitamina K-reductaza NADH + H+ (-) O2 H2O OOH alcooxid glutamat vitamina K- -glutamilcarboxilaza -carboxi-glutamat OH vitamina K-epoxidaza CH3 O R

anticoagulante cumarinice

VITAMINA B1
+ N N NH2 tiamina S CH3 ATP AMP N N NH2 + N S CH3 O O

N H3C

tiamin CH2- CH2-OH pirofosfokinaza H3C

CH2-CH2-O-P-O-P-OH OH OH tiamin pirofosfat (TPP)

Mecanismul reaciei de decarboxilate a acidului piruvic

R + N S CH3 CH2-CH2-O-PP H3C-C-COOH O R HO H3C-C COOH + N S CH3 CH2-CH2-O-PP

tiaminpirofosfat (TPP)

+ N S

CH3 - H3C-CHO CH2-CH2-O-PP

+ N S

CH3 CH2-CH2-O-PP

-CO2 HO H3C-CH

CH2-OH C=O HO-C-H H-C-OH CH2-OPO3H2 xilulozo-5-fosfat +

CHO H-C-OH H-C-OH H-C-OH CH2-OPO3H2 ribozo-5-fosfat transcetolaza

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

VITAMINA B2
O H3C H3C N NH N N O

CH2-CH-CH-CH-CH2-OH

riboflavina

OH OH OH

riboflavina flavokinaza

FMN

FAD

ATP

ADP

ATP

flavinadenin pirofosforilaza PP

O H3C H3C N NH N N O O FMN (flavinmononucleotid)

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

O H3C H3C N NH N N O O O N N N NH2 N FAD (flavinadenin dinucleotid)

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

OH

OH

Reacia de reducere a coenzimelor flavinice

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

FADH2

FAD

NAD+

glutation reductaza

NADH + H+

2 G-SH

G-S-S-G

NAD(P)H-CYP450 reductaza

AH + O2 + FADH2 A-OH + FAD + H2O

O HN N N N H hipoxantina H2O, O2 xantin oxidaza H2O2 HN O

O N N N H H xantina H2O, O2 xantin oxidaza H2O2 HN O

O H N O N N H H acid uric

R-CH-COOH + H2O + O2 aminoacid oxidaza NH2 aminoacid

R-C-COOH + NH3 + H2O2 O cetoacid

COOH CH2 CH2 COOH acid succinic FAD

FADH2

COOH H-C C-H COOH acid fumaric

succinat dehidrogenaza

VITAMINA B3
CO-NH2 (+) N O O O N N O NH2 N N

COOH

CO-NH2
N

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

acid nicotinic
(niacina)

nicotinamida
(niacinamida)

OH

OH OH + (nicotinamidadenin dinucleotid) NAD

NH2

OH

CO-NH2 (+) N O O O

N N N

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

OH

OPO3H2 OH OH + (nicotinamidadenin dinucleotidfosfat) NADP

Reacia general de oxido-reducere a coenzimelor nicotinamidice

CO-NH2 (+) N R + SH2 N R
lactat dehidrogenaza

CO-NH2 + S + H+

CH3-CH-COOH + NAD+ OH acid lactic

CH3-C-COOH + NADH + H+ O acid piruvic

CH3-CH2-OH + NAD+ alcool etilic

alcool dehidrogenaza

CH3-CHO + NADH + H+ acetaldehida

CH2-OPO3H2 O OH HO OH glucozo-6-fosfat + NADP+ dehidrogenaza HO

CH2-OPO3H2 O OH O + NADPH + H+

OH D-glucozo-6-fosfat

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

OH N H2N N

H N

NADPH + H+ CH2-NH-R

NADP+ N

OH

H N

CH2-NH-R

dihidrofolat reductaza

H2N

acid dihidrofolic

N H acid tetrahidrofolic N

VITAMINA B5
H3C HO-CH2-C-CH-CO-NH-CH2-CH2-COOH H3C OH
H3C HO-CH2-C-CH-CO-NH-CH2-CH2-CH2-OH H3C OH

acid pantotenic
NH2 N N N N
O

pantotenol (pantenol)

H3C

CH2-O-P-O-P-O-CH2-C-CH-CO-NH-CH2-CH2-CO-NH-CH2-CH2-SH OH OH H3C OH OPO3H2

OH

coenzima A

VITAMINA B6
CH2-OH HO CH2-OH N piridoxina
HO CHO CH2-OH N piridoxal

CH2-NH2 HO CH2-OH N piridoxamina

H3C

H3C

H3C

Sinteza cofactorilor derivai de la vitamina B6

CHO HO CH2-OH
N

CHO HO piridoxal kinaza CH2-OPO3H2

N

H3C

piridoxal ATP
CH2-NH2 HO CH2-OH

H3C ADP

piridoxal-5'-fosfat

CH2-NH2 HO CH2-OPO3H2
N

H3C

piridoxamina

piridoxal kinaza

H3C ADP

piridoxamin-5'-fosfat ATP

CH2-CH-COOH histidin NH2 decarboxilaza N histidina

CH2-CH2-NH2 N N histamina + CO2

COOH (CH2)2 CH-NH2 COOH acid glutamic

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

COOH glutamat decarboxilaza (CH2)2 CH2-NH2 GABA (acid -aminobutiric)

HO N H serotonina CH2-CH2-NH2

+ CO2

5-hidroxi-triptofan decarboxilaza

CH2-CH-COOH OH NH2 L-serina

serin racemaza

CH2-CH-COOH OH NH 2 D-serina

Mecanismul reaciei de transaminare

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

E-PLP-CHO CH2-OPO3H2 transaminaza

E-PLP-CH2-NH2 CH2-OPO3H2

R2-CH-COOH NH2

R2-C-COOH O

COOH COOH HC-NH2 CH3 alanina + C=O CH2 CH2 COOH acid -ceto-glutaric TGP (ALT, ALAT) COOH C=O +

COOH HC-NH2 CH2 CH2 COOH acid glutamic

CH3 acid piruvic

COOH HC-NH2 CH2 COOH acid aspartic +

COOH C=O CH2 CH2 COOH TGO (AST, ASAT) C=O +

COOH HC-NH2 CH2 CH2 COOH acid glutamic

CH3-C-COOH O acid piruvic
H2O NH3 CH2=C-COOH OH CH3-C-COOH O acid piruvic

COOH acid -ceto-glutaric

H2O CH2=C-COOH NH2

CH2 COOH acid oxalacetic

NH3

H2O CH2-CH-COOH OH NH2 serina

CH2-CH-COOH SH NH2 cisteina H2S CH2=C-COOH NH2

CH2=C-COOH OH

VITAMINA B7
O HN
NH

biotina (CH2)4-COOH

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

ATP CH3-CH2-CO-SCoA + HCO3 propionil-CoA ADP + P HCOO-CH-CO-SCoA CH3 metilmalonil-CoA
O N COOCH3-C-COOH O piruvat carboxilaza HN HOOC-CH2-C-COOH O acid oxalacetic + R S biotina NH

propionil-CoA carboxilaza

O HN NH ATP ADP + P HN

S biotina

biotin carboxilaza H2O R HCO3

R S carboxibiotina

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

CH2-NH-C-NH2 (CH2)2 O +P CH-NH2 COOH citrulina

10

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

Sinteza acidului tetrahidrofolic

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

CH2-NH-R

NADP+

H N

CH2-NH-R

acid dihidrofolic

N H acid tetrahidrofolic

Structura coenzimelor sintetizate din acid tetrahidrofolic

OH N H2N N N H
CHO N N H2N N N H CH2-NH-R H2N N N N H

CH3 N CH2-NH-R H2N N

OH N

CH2 CH2-N-R N H2N

OH

CH=NH N CH2-NH-R

N H

N5-metil-tetrahidrofolat
OH

N5,N10-metilen-tetrahidrofolat
OH CH CH2-N-R

N H N5-formimino-tetrahidrofolat N
OH N

(+) N

H N

CHO CH2-N-R

H2N

N H

N5-formil-tetrahidrofolat

N5,N10-metenil-trahidrofolat

N10-formil-tetrahidrofolat

OH
N

H
N

CH2-NH-R
N N

CH2-CH-COOH H2O OH NH 2 H2N-CH2-COOH

N

OH
N

CH2 CH2-N-R

H2N

H acid tetrahidrofolic

H2N

N5,N10-metilen-tetrahidrofolat NADPH + H+ CH2-CH2-CH-COOH S-CH3 NH2 metionin sintaza B12

N

NADP+ OH CH3
N

L-metionina CH2-CH2-CH-COOH SH NH2 L-homocisteina H2N

CH2-NH-R
N N

N5-metil-tetrahidrofolat

11

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

N5-metil-tetrahidrofolat CH2-CH2-CH-COOH SH NH2 L-homocisteina B12 metionin sintaza

tetrahidrofolat CH2-CH2-CH-COOH NH2 S-CH3 L-metionina

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

acid ascorbic
O CH2-CH2-NH2 C HO-C HO-C OH + HC OH dopamina HO-CH CH2-OH O

acid dehidroascorbic
O HO-CH-CH2-NH2 C O=C O + H2O

dopamin- + O2 monooxigenaza OH

OH + O=C HC HO-CH CH2-OH noradrenalina

acid ascorbic

acid dehidroascorbic

H3C + H3C N-CH2-CH2-CH2-COOH H3C -butiro-betaina

+ HOOC-CH2-CH2-C-COOH + O2 O acid -ceto-glutaric

-butirobetain dioxigenaza

H3C + H3C N-CH2-CH-CH2-COOH H3C OH carnitina

+ HOOC-CH2-CH2-COOH acid succinic

+ CO2

12