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BMB/CHEM 567 Bioinorganic Chemistry

Prerequisites:                        Graduate standing or consent of instructor.

Instructor:                              Michael Therien (333 Cret); e-mail:

therien@sas.chem.upenn.edu

Required Text:                      None

Course Material:                  Selected articles from the original scientific literature will be assigned throughout the semester.

Scheduled Lectures:                        Th       6:00 – 9:00

Make-up Lectures:               On occasion, there may be a need to schedule make- up lectures.  Potential times for such lectures will be discussed in class.

Material on Reserve:           1) Principles of Bioinorganic Chemistry,

                                                    by S. J. Lippard and J. M. Berg

                                                2) The Biological Chemistry of The Elements,

                                                    by J. J. R. Frausto da Silva and R. J. P. Williams

                                                3) Biochemistry, 2nd Edition, by D. Voet and J.                                                                             G. Voet

                                                4) Inorganic Chemistry, 4th Edition, by J. Huheey

                                                5) Bioinorganic Chemistry, by I. Bertini,

                                                     H. B. Gray, S. J. Lippard, and J. S. Valentine

                                                6) A variety of review articles will periodically                                                                             be placed on reserve as well.

Course Background             1) Biochemistry, 2nd Edition, by D. Voet and J. G. Material:                               Voet: Chapters 4, 6, and 7.

2) Inorganic Chemistry 4th Edition by J. Huheey: Chapters 5 and 11; (Note that this general information regarding bonding can be found in many advanced inorganic chemistry textbooks.)

Graded Assignments:          One midterm and one final exam.

Course Topics:                     O2 Transport

                                                O2 Activation

                                                O2 and O Atom Incorporation into Biological                                                                Substrates

                                                Metal-DNA Interactions

                                                Metalloproteins in DNA Biosynthesis

                                                Fe-S proteins and N2 Fixation

                                                Photosystems I and II

                                                Biological Electron Transport

Course Reading List            Publications: The scientific literature figures prominently in this course.  Many of the articles that will be assigned are classics in the field and several years old.  Examples of research articles that have been assigned as required reading in the past include:

A)        Metalloenzymes, Structural Motifs, and Inorganic Models, K. D. Karlin,     Science (Washington, D.C.) 1993,261, 701-708.

B)        Spin-State/Stereochemical Relationships in Iron Porphyrins:             Implications for the Hemoproteins, W. R. Scheidt and C. A. Reed, Chem. Rev. 1981, 81, 543-555

C)        Spectroscopic Studies for Tetraphenylporphyrincobalt (II) Complexes of CO, NO, O2, RNC, and (RO)3P, and a Bonding Model for Complexes of CO, NO, and O2 with Cobalt (II) and Iron (II) Porphyrins, B. B. Wayland, J. V. Minkiewicz, and M. E. Abd-Elmageed, J. Am. Chem. Soc. 1974, 96, 2795-2801.

D)        Binding of CO to Myoglobin from a Heme Pocket Docking Site to Form Nearly Linear Fe-C-O, M. Lim, T.A. Jackson, P.A. Anfinrud, Science, 1995, 269, 962-966.

E)        Probing Structure-Function Relations in Heme-Containing Oxygenases and Peroxidases, J. H. Dawson, Science  (Washington, D.C.) 1988, 240, 433-439.

F)         Key Elements of the Chemistry of Cytochrome P-450, Oxygen           Rebound Mechanism, J. T. Groves, J. Chem. Ed. 1985, 62, 928-931.

G)        Mechanism of Assembly of the Tyrosyl Radical-Dinuclear Iron         Cluster Cofactor of Ribonucleotide Reductase, J. M. Bollinger, Jr., D.          E. Edmondson, B. H. Huynh, J. Filley, J. R. Norton, J. Stubbe, Science       (Washington, D.C.), 1991, 253, 292-298.

H)        Mechanism of Aromatic Hydroxylation in a Copper Monooxygenase Model System.  1,2-Methyl Migrations and the NIH Shift in Copper Chemistry, M. Sarwar Nasir, B.I. Cohen, K.D. Karlin, J. Am. Chem. Soc., 1992, 114, 2482-2494.

I)          Metals and DNA: Molecular Left-Handed Complements, J.K. Barton, Science, 1986, 233, 727-734.

J)          A Metalloradical Mechanism for the Generation of Oxygen from Water in Photosynthesis, C.W. Hoganson, G.T. Babcock, Science, 1997, 277, 1953-1956.

K)        Architecture of the Photosynthetic Oxygen-Evolving Center, K.N. Ferreira, T.M. Iverson, K. Maghlaoui, J. Barber, S. Iwata, Science, 2004, 303, 1831-1838.

L)        Electron-Tunneling Pathways in Proteins, D.N. Beratan, J.N. Onuchic, J.R. Winkler, H.B. Gray, Science (Washington, D.C.), 1992, 258, 1740-1741.

M)       Electronic Tunneling in Proteins: Coupling Through a b Strand, R. Langen, I.-J. Chang, J.P. Germanas, J.H. Richards, J.R. Winkler, H.B. Gray, Science (Washington, D.C.), 1995, 268, 1733-1735.

Midterm Examination Date: TBA

Final Examination: Thursday December 13, 6:00 – 9:00 PM