Lecture 2 - Chemistry 312 Inorganic Chemistry Tracy...

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Chemistry 312 Inorganic Chemistry Tracy Furutani
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Course Goals: Develop the Fundamentals to Understand How Antioxidants and Metalloenzymes Work Chapter 27 coordination complex in a protein electron transport Chapter 5 e Chapters 6, 7, 19, 20
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Metalloenzymes contain metal ions attached to proteins via amino acid ligands Histidine (amino acid) ligand Cysteine (amino acid) ligand
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4 Antioxidants Antioxidants replenish the bodies source of reductants (high energy e ) are found in fruits and veggies protect against disease states such as Alzheimer s, Parkinson s, and cancer
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N N Electron Transfer Reactions M +n ne CO 2 ....one of the most important reactions in biology! 6e , 6H + CO + H 2 O substrate O O 2 NH 3 4e , 4H + 2 H 2 O 2e , 2H + Chapter 5
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ferredoxin NADH FAD Cytochrome b Cytochrome c 1 Cytochrome c Cytochrome c oxidase O 2 –400 E 1/2 +800 (+815 mV) +500 +300 0.0 (+60 mV) (–320 mV) (+260 mV) E Besides promoting redox reactions, electron transfer is intimately connected with energy storage in mitochondria (as ATP), via the e l e ctr on–transpo r t c hain G= –52.6 kcal/mol Chapter 5
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NAD + FAD mitochondrial matrix inner mitochondrial membrane O 2 e e e e e e cytosol H + H + H + H + [H + ]= small [H + ]= larger Directional electron transport Directional electron transport occurs across a membrane in the occurs across a membrane in the mitochondria mitochondria = metalloprotein active site = metalloprotein active site
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8
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Chapters 19, 27
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From Electronic Structures of Metal Sites in Proteins and Models: Contributions to Function in Blue Copper Proteins, Solomon, E., et. al. Chem. Rev . 2004 , 104 , 419-458 S met N His N His S cys N his Cu S cys N his S met blue copper E 1/2 = +370 mV Chapter 27
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From Electronic Structures of Metal Sites in Proteins and Models: Contributions to Function in Blue Copper Proteins, Solomon, E., et. al. Chem. Rev . 2004 , 104 , 419-458 The SOMO (singly occupied molecular orbital) of The SOMO (singly occupied molecular orbital) of the blue copper site is highly delocalized the blue copper site is highly delocalized Chapters 2, 6, 20
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Electron transfer pathways Electron transfer pathways Electrons fed via the sulfur orbitals plastocyanin multicopper oxidases Chapters 2, 6, 20
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M +n e electrode surface ....studied in the lab under more  controlled conditions. ..
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Lecture 2 - Chemistry 312 Inorganic Chemistry Tracy...

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