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What is the answer to Life, the Universe and Everything?

What is the answer to Life, the Universe and Everything?. Proterozoic. Hadean. Archean. Paleozoic. Mesozoic. Cenozoic. Nov. 11 2009. in the beginning…. 4 bya. 3 bya. 2 bya. 1 bya. today. Hadean 4.5 -3.8 bya. Archean 3.8 -2.5 bya. Oldest rocks?. BANG!. 4.5 bya!. 3.5 bya!.

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What is the answer to Life, the Universe and Everything?

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  1. What is the answer to Life, the Universe and Everything?

  2. Proterozoic Hadean Archean Paleozoic Mesozoic Cenozoic Nov. 11 2009 in the beginning… 4 bya 3 bya 2 bya 1 bya today

  3. Hadean 4.5 -3.8 bya Archean 3.8 -2.5 bya Oldest rocks? BANG! 4.5 bya! 3.5 bya! 0.5 bya Oldest fossils: stromatolites = Calcium carbonate deposits from blue-green algae or cyanobacteria. Most famous characteristic? Nitrogen “fixing” bacteria: N2 + 3 H2 --> 2 NH3

  4. What do we find deep within cyanobacteria’s amazing N2-fixing machinery?

  5. (Greek ‘molybdos’ ) lead-like # 42 Mo Molybdenum “Moly” The Answer to Life, the Universe, and Everything (?)

  6. quagga Cenozoic 65 mya - today! Paleozoic 540 - 250 mya Mesozoic 2.5 -0.6 mya “age of dinosaurs” Plants!! Animals!! Another extinction!! Global catastrophe! 250 mya 65 mya 540 mya “age of mammals” Has evolution moved on without #42 - Mo?

  7. Grown with Mo Grown without Mo

  8. Tobacco plants (Arabidopsis thaliana) Healthy (wild type) Sick (mutant) Nitrate Nitrite Proteins All plants require the molybdoenzyme Nitrate Reductase nitrate nitrite

  9. Cyanobacteria Need Mo Plants Need Mo in the Beginning of Life… 4 bya 3 bya 2 bya 1 bya

  10. What about the animals?

  11. enzyme in mammalian milk xanthine oxidase Got Mo? two enzymes in livers of mammals and avians sulfite oxidase aldehyde oxidase

  12. Why the correct oxidation state matters

  13. MRI of brain of deceased baby with Sulfite Oxidase Deficiency MRI of healthy brain

  14. The baby died because this reaction didn’t happen: SO32- + H2O ---> SO42- + 2H+ + 2e- Sulfite Sulfate S4+ S6+ The baby has a genetic defect in the enzyme that catalyzes this reaction. Babies with this genetic disease die shortly after birth. The enzyme is Sulfite Oxidase. You have it in your liver.

  15. A Redox Review of terms: Oxidation SO32- + H2O ---> SO42- + 2H+ + 2e- half reactionS4+ in Sulfite S6+ in Sulfate Reduction Mo6+ + 2e- ---> Mo4+ half reaction Net redox reaction SO32- + H2O + Mo6+ ---> SO42- + 2H+ + Mo4+

  16. xanthine dehydrogenase sulfite sulfate xanthine uric acid hypoxanthine xanthine sulfite oxidase aldehyde oxidase Human Molybdenum Cofactor Disorder: Combined Oxidase Deficiency • xanthinuria • (gout) • No detoxification • of heterocycles • Mental/motor retardation • Epileptic seizures • Brain atrophy • Dislocated ocular lens • death

  17. defectivemolybdoenzymes Not repaired by adding Mo alone + Mo Non-functionalenzyme Human Molybdoenzyme Deficiencies: Cured with more Mo? More than just Mo is required

  18. 1. Not having the structure or organization of living bodies 2. Not characterized by vital processes 3. Not fundamental or related; extraneous 4. Pertaining to compounds that are not hydrocarbons 5. Mineral 1. (Gr. “bios” ‘life, course or way of living’). In compounds formed in Greek itself, as biography; and in modern scientific words in which bio- is extended to mean ‘organic life.’ 2. A prefix meaning “life” Websters, OED Bio inorganic Chemistry

  19. Bio inorganic Chemistry Molybdenum Enzymes Hemoglobin (Fe) Zinc Enzymes (Zn) Vitamin B12 (Co) Iron enzymes Copper Enzymes (Cu) Manganese Enzymes Tungsten Enzymes V, Ti, Cr Therapeutics Auranofin (Au) arthritis Cis-platin (Pt) cancer

  20. Bio inorganic Chemistry Cis-platin (Pt) cancer Molybdenum Enzymes Hemoglobin (Fe) Zinc Enzymes (Zn) Vitamin B12 (Co) Iron enzymes Copper Enzymes (Cu) Manganese Enzymes Tungsten Enzymes V, Ti, Cr 3 Therapeutic s 4 Aurial (Au) arthritis

  21. Questions asked of molybdoenzymes and their model compounds: • What is the redox potential ( energy of) Mo redox reactions? • What are the structural details? What is bond order? • (angles, bond distances) • How well do models mimic reactions of Mo in enzymes? • in structure • in reactivity

  22. Mo Chemistry • Oxidation states • Mo occurs in oxidation states from 0  +6 • This Molybdoenzyme Project will generate complexes in oxidation states +4, +5 and + 6, • same as enzymes

  23. Mo Chemistry 2. Geometries: Mo complexes have Coordination Numbers from CN 4  8 This Molybdoenzyme Project uses reagents or makes products with CN 4  7

  24. Mo Chemistry 3. Reaction Chemistry Mo S; dtc ligand Mo O; Mo=O ligands

  25. Molybdenum, atomic # 42: is it the answer to Life, the Universe and Everything? Sure looks like it! What’s the Ultimate Question? Adams speculates in “The Restaurant at the End of the Universe”: What do you get if you multiply nine by six?

  26. This week: • Make starting material: MoO2detc2 • Make the “Purple Compound”, P • Make the “Yellow Compound”, Y • Recrystallize the starting material • Do IR’s if possible • Run NMR’s, if possible.

  27. Report on the Project • Write in the style of journal Inorganic Chemistry • Write a full paper, not a Communication • Will include synthesis description and reactivity • Will include spectroscopic data and interpretation • Will consist of these sections: • Introduction • Experimental • Results • Discussion • Conclusion

  28. A proposed catalytic cycle for how Mo oxidizes SO32-

  29. dithiolene pterin molybdopterin Mo

  30. Mo Ball and stick diagram Chemical structure diagram

  31. Mo compound released (isolated) rapid decomposition Protein structure destroyed & & &

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