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

4. HadeanArchean Proterozoic Mesozoic Cenozoic Paleozoic in the beginning… Nov. 11 2009 today 1 bya2 bya3 bya4 bya

5. 3.5 bya! Oldest fossils: stromatolites = Calcium carbonate deposits from blue-green algae or cyanobacteria.blue-green algae 0.5 bya N 2 + 3 H 2 --> 2 NH 3 BANG! Hadean 4.5 -3.8 bya Archean 3.8 -2.5 bya Oldest rocks? Most famous characteristic? Nitrogen “fixing” bacteria: 4.5 bya!

6. What do we find deep within cyanobacteria’s amazing N 2 -fixing machinery?

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

8. 540 mya Mesozoic 2.5 -0.6 mya Global catastrophe! Cenozoic 65 mya - today! “age of mammals” “age of dinosaurs” quagga Paleozoic 540 - 250 mya 250 mya65 mya Plants!! Animals!! Another extinction!! Has evolution moved on without #42 - Mo?

9. Grown without MoGrown with Mo

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

11. in the Beginning of Life… 1 bya2 bya3 bya4 bya Cyanobacteria Need Mo Plants Need Mo

12. What about the animals?

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

14. Why the correct oxidation state matters

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

16. The baby died because this reaction didn’t happen: SO 3 2- + H 2 O ---> SO 4 2- + 2H + + 2e- Sulfite Sulfate S 4+ S 6+ 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.

17. Oxidation SO 3 2- + H 2 O ---> SO 4 2- + 2H + + 2e- half reaction S 4+ in Sulfite S 6+ in Sulfate Reduction Mo 6+ + 2e- ---> Mo 4+ half reaction Net redox reaction SO 3 2- + H 2 O + Mo 6+ ---> SO 4 2- + 2H + + Mo 4+ A Redox Review of terms:

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

19. + Mo defective molybdoenzymes Human Molybdoenzyme Deficiencies: Cured with more Mo? Not repaired by adding Mo alone Non-functional enzyme More than just Mo is required

20. BioinorganicChemistry 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

21. BioinorganicChemistry Molybdenum EnzymesHemoglobin (Fe) Manganese Enzymes Zinc Enzymes (Zn) Auranofin (Au) arthritis Cis-platin (Pt) cancer Copper Enzymes (Cu) Vitamin B12 (Co) Iron enzymes Tungsten Enzymes Therapeutics V, Ti, Cr

22. BioinorganicChemistry Molybdenum EnzymesHemoglobin (Fe) Manganese Enzymes Zinc Enzymes (Zn) Aurial (Au) arthritis Cis-platin (Pt) cancer Copper Enzymes (Cu) Vitamin B12 (Co) Iron enzymes Tungsten Enzymes  Therapeutic s  V, Ti, Cr

23. 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

24. Mo Chemistry 1.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

25. 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

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

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

28. 1.Make starting material: MoO 2 detc 2 2.Make the “Purple Compound”, P 3.Make the “Yellow Compound”, Y 4.Recrystallize the starting material 5.Do IR’s if possible 6.Run NMR’s, if possible. This week:

29. 1.Write in the style of journal Inorganic Chemistry 2.Write a full paper, not a Communication 3.Will include synthesis description and reactivity 4.Will include spectroscopic data and interpretation 5.Will consist of these sections: 1.Introduction 2.Experimental 3.Results 4.Discussion 5.Conclusion Report on the Project

32. A proposed catalytic cycle for how Mo oxidizes SO 3 2-

34. Mo molybdopterin pterin dithiolene

35. Mo Ball and stick diagram Chemical structure diagram

36.    Protein structure destroyed Mo compound released (isolated) rapid decomposition