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AminoAmino AcidsAcids MetabolismMetabolism

Prof Dr Mohammad Ibrahim Prof of Medical ١ http://osp.mans.edu.eg/medbiochem_mi •• CysteineCysteine

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٢ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine

SH NH2 CH CH COOH StructureStructure 2 •It is α-amino, β-thiol propionic NutrionalNutrional ValueValue •It is nonnon--essentialessential MetabolicMetabolic FateFate •It is glucogenicglucogenic amino acid

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٣ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine BiosynthesisBiosynthesis ofof CysteineCysteine NH2 NH2

CH2 CH COOH CH2 CH COOH OH Cystathionine Synthetase S NH2 + PLP CH CH CH COOH SH NH2 2 2 H O CH CH CH COOH 2 2 2 H O 2 PLP Cystathionase

Methionine OH NH2 SH NH2

CH2 CH2 CH COOH CH CH COOH + 2 Homoserine

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٤ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine MetabolicMetabolic FateFate 1. Incorporated in protein structure • Hormones • 2. of cystine 3. Synthesis of thioethanolamine 4. Biosynthesis of 5. It gives 6. Synthesis of 7. Biosynthesis of taurine 8. Bile acids and salts 9. Detoxication

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٥ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 22-- SynthesisSynthesis ofof cystinecystine

NH NH2 2

CH2 CH COOH CH2 CH COOH Cysteine reductase SH S SH NH + 2 S NH2 NAD+ NADH.H+ CH2 CH COOH CH2 CH COOH

2 Cysteine Cystine

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٦ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 33-- FormationFormation ofof thioethanolaminethioethanolamine

Decarboxylatione SH NH2 SH NH2 CH2 CH COOH CH CH CO2 2 2

Cysteine Thioethanolamine

CoA.SH

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٧ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 44-- BiosynthesisBiosynthesis ofof glutathioneglutathione O

COOH NH2 CH COOH C NH CH COOH CH2 CH H O + 2 γ Glutamyl cysteine 2 CH2 CH2 NH2 CH2 SH synthetase CH SH 2 CH HC NH γ Glutamyl cysteine 2 2 Cysteine HC NH2 COOH COOH COOH ATP ADP+Pi e tas e th yn s ATP e n O O io th C NH CH C NH ta lu CH2 CH2 G ADP+Pi CH2 CH2 SH COOH HC NH2 H2O COOH Glutathione (γ Glutamyl cysteinyl glycine)

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٨ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 55-- FormationFormation ofof pyruvicpyruvic acidacid

Desulfhydrase Desulfhydrase SH NH2 NH O

CH2 CH COOH CH3 C COOH PLP CH3 C COOH H2S Cysteine H O NH α imino propionic 2 3 Pyruvic acid

Transamination Sulpher SH NH2 SH O O CH CH COOH PLP CH C COOH 2 CH2 C COOH 3 α KG Glu 2H H2S Cysteine Thiolpyruvic Pyruvic acid

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٩ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 66-- GlucoseGlucose biosynthesisbiosynthesis Desulfhydrase Cysteine Pyruvic acid

Transamination Cysteine Thiolpyruvic Sulfinyl pyruvic Gluconeogenesis Oxidation Cysteine Cysteine sulfinic Glucose

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٠ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 77-- BiosynthesisBiosynthesis ofof taurinetaurine

SH NH2 SO2H NH2 Dioxygenase CH2 CH COOH CH2 CH COOH O Cysteine sulfinic Cysteine 2

O

NH2 CH2 CH2 SO3H

SO H NH 3 2 Decarboxylase SO3H NH2 CH CH 2 2 CH2 CH COOH Taurine CO2 Cysteic acid

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١١ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 88 –– ConjugationConjugation withwith bilebile acidsacids

NH CH CH SO H OH + 2 2 2 3 OH C S.CoA C NH CH2CH2 SO3H O O CoA.SH OH HO OH HO H H Taurocoholic Acid

Cholyl CoA Na K

Na taurocoholate K taurocoholate OH OH SO Na C NH CH2CH2 3 C NH CH2CH2SO3K O O

HO OH OH H HO H

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٢ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine Bromophenyl 99-- DetoxicationDetoxication ofof bromophenolbromophenol cysteine

S CH2 CH COOH NH2 NH2 HS CH2 CH COOH

Acetyl CoA + Br Br Bromophenol CoA.SH

S CH2 CH COOH O Bromophenyl HN CCH3 mercapturic Br

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٣ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine Naphthyl 99-- DetoxicationDetoxication ofof naphthalenenaphthalene cysteine

NH2 S CH2 CH COOH HS CH2 CH COOH NH2 + Acetyl CoA

Naphthalene CoA.SH

S CH2 CH COOH O Naphthyl HN CCH mercapturic 3

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٤ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine CatabolicCatabolic FateFate

1.1. NonoxidativeNonoxidative deaminationdeamination to pyruvic acid

2.2. TransaminationTransamination to Thiolpyruvic acid

3.3. DirectDirect oxidationoxidation to

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٥ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 11--NonoxidativeNonoxidative deaminationdeamination to pyruvic acid

Desulfhydrase Desulfhydrase SH NH2 NH O

CH2 CH COOH CH3 C COOH PLP CH3 C COOH H2S Cysteine H O NH α imino propionic 2 3 Pyruvic acid

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٦ http://osp.mans.edu.eg/medbiochem_mi 22--TransaminationTransamination to thiolpyruvic acid

SH NH2 Cysteine CH2 CH COOH

Transaminase

SH NADH.H+ O CH2 C COOH Thiolpyruvic 3 mercaptopyruvic Lactate Sulpher transferase 2H NAD+ O H2S SH OH CH3 C COOH Na Pyruvic acid CH2 CH COOH 3 mercaptolactic Sulphite oxidase

Sodium sulphate Na2SO4 Na2SO3 Sodium sulphite

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٧ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine 33-- DirectDirect oxidationoxidation to cysteine sulfinic acid

SO2H NH2

Dioxgenase CH2 CH COOH SH NH2 Cysteine sulfinic CH2 CH COOH O2 Cysteine α KG Taurine Cysteic acid

Glu O Desulfinase SO2H O CH3 C COOH CH2 C COOH Pyruvic acid -- SO3 Sulfinyl pyruvic

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٨ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine Inborn errors of cysteine

•• 11-- CystinuriaCystinuria

• Marked increase in urinary cystine,

, and .

• Defective renal tubular reabsorption of

these amino acids.

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ١٩ http://osp.mans.edu.eg/medbiochem_mi CysteineCysteine Inborn errors of

•• 22-- CystinosisCystinosis • Cystine accumulates in lysosomes • No transport to cytoplasm • Deposition of cystine crystals in tissues • Impaired renal functions • Generalized amino aciduria • Renal failure

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٢٠ http://osp.mans.edu.eg/medbiochem_mi SelenocysteineSelenocysteine

OH NH2 SeH NH2 CH CH COOH 2 CH2 CH COOH • Selenocysteine occurs at the active site of many enzymes: – Glutathione peroxidase – Deiodinase – Thioredoxin reductase • Selenocysteine-tRNA is first charged with serine • Subsequent replacement of the serine oxygen by selenium

Prof Dr Mohammad Ibrahim Prof of Medical Biochemistry ٢١ http://osp.mans.edu.eg/medbiochem_mi