Metal Ions in Biological Systems: Metalloenzymes Involving Amino Acid-Residue and Related Radicals Book

	Preface to the Series	iii
	Preface to Volume 30	v
	Contributors	xiii
	Contents of Previous Volumes	xv
	Handbook on Toxicity of Inorganic Compounds	xxxii
	Handbook on Metals in Clinical and Analytical Chemistry	xxxiii
Chapter 1	Free Radicals and Metalloenzymes: General Considerations	1
1.	Introduction: A Survey of Biologically Relevant Free Radicals	2
2.	Necessity of Free Radicals and Metal Ions	4
3.	Reactivities of Free Radicals	7
4.	Summary of Free Radical-Dependent Metalloenzymes	11
	Abbreviations	21
	References	22
Chapter 2	Peroxidases: Structure, Function, and Engineering	25
1.	Introduction	26
2.	Peroxidase Crystal Structures	30
3.	Peroxidase Catalytic Mechanisms	48
4.	Peroxidase Engineering	56
5.	Conclusions	65
	Abbreviations	66
	References	67
Chapter 3	Photosystem II	77
1.	Introduction	78
2.	Identification and Spectroscopic Studies of the Tyrosine Radicals	83
3.	Electron Transfer Reactions of the Tyrosine Radicals--Both O[subscript 2]-Evolving and Inhibited Photosystem II	89
4.	Other Radicals in Photosystem II	95
5.	Concluding Remarks	99
	Abbreviations	100
	References	100
Chapter 4	Ribonucleotide Reductase in Mammalian Systems	109
1.	Introduction	110
2.	Mammalian Ribonucleotide Reductase	110
3.	Herpes Simplex Virus Ribonucleotide Reductase	115
4.	Comparison of Amino Acid Sequences and Spectroscopic Properties for Different Species	116
5.	Formation, Properties, and Stability of the Fe-Tyrosyl Radical Center	120
6.	Inhibitors; Radical Scavengers; Iron Chelators; Specific Peptides	121
7.	Subunit Interaction and Electron Transfer	124
	Abbreviations	125
	References	125
Chapter 5	Manganese-Dependent Ribonucleotide Reduction and Overproduction of Nucleotides in Coryneform Bacteria	131
1.	Introduction: The Diversity of Ribonucleotide Reductase Systems	132
2.	Effects of Manganese Depletion in Coryneform Bacteria	136
3.	The Manganese-Containing Ribonucleotide Reductase of Brevibacterium ammoniagenes	142
4.	Distribution of Manganese Ribonucleotide Reductases	153
5.	Concluding Remarks--Ribonucleotide Reduction: Universal but Not Uniform	156
	Abbreviations	158
	References	158
Chapter 6	Prostaglandin Endoperoxide Synthases	163
1.	Introduction	164
2.	PGH Synthase Isozymes	167
3.	Cyclooxygenase Catalysis	171
4.	Peroxidase Catalysis	179
5.	Cyclooxygenase-Peroxidase Interrelationships	184
6.	PGH Synthase Structure	186
	Abbreviations	192
	References	192
Chapter 7	Diol Dehydrase from Clostridium Glycolicum: The Non-B[subscript 12]-Dependent Enzyme	201
1.	Introduction	202
2.	Diol Metabolism in C. glycolicum	203
3.	Properties of Membrane bound Diol Dehydrase from C. glycolicum	206
4.	Characterization of Diol Dehydrase	209
5.	Conclusions	213
	Abbreviations	214
	References	214
Chapter 8	Diol Dehydrase and Glycerol Dehydrase, Coenzyme B[subscript 12]-Dependent Isozymes	217
1.	Introduction	218
2.	Purification, Properties, and Structures	219
3.	Catalytic Properties and Mechanism of Action	223
4.	Formation of Free Radicals	232
5.	Inactivation and Reactivation	240
6.	Physiological Roles	244
7.	Concluding Remarks	247
	Abbreviations	248
	References	249
Chapter 9	Adenosylcobalamin (Vitamin B[subscript 12] Coenzyme)-Dependent Enzymes	255
1.	Survey of Adenosylcobalamin-Dependent Enzymes	256
2.	Mechanisms of the Co-C Bond Cleavage	259
3.	Mechanisms of the Subsequent Reactions	269
4.	Conclusion	275
	Abbreviations	275
	References	276
Chapter 10	S-Adenosylmethionine-Dependent Radical Formation in Anaerobic Systems	279
1.	Introduction	280
2.	Pyruvate Formate Lyase-Activating Enzyme	280
3.	Lysine 2,3-Aminomutase	300
4.	Anaerobic Ribonucleotide Reductase	306
5.	Concluding Remarks	308
	Abbreviations	309
	References	309
Chapter 11	The Free Radical-Coupled Copper Active Site of Galactose Oxidase	315
1.	Introduction	316
2.	Historical Survey	318
3.	Recent Developments	322
4.	Model Reactions and the Role of the Radical in Catalysis	352
	Abbreviations and Definitions	356
	References	356
Chapter 12	Amine Oxidases	361
1.	Introduction	362
2.	Structural Properties of Amine Oxidases	365
3.	Catalytic Mechanism of Amine Oxidases	380
4.	Biological Roles of Amine Oxidases	392
5.	Conclusions and Prospects	395
	Abbreviations	396
	References	397
Chapter 13	Bacterial Transport of and Resistance to Copper	405
1.	Introduction	406
2.	Copper in Bacterial Nutrition	407
3.	Copper Transport and Uptake	409
4.	Bacterial Systems Conferring Resistance to Excess Copper	415
5.	Concluding Remarks	428
	Definitions and Abbreviations	429
	References	430
	Author Index	435
	Subject Index	469