John Wiley & Sons, Inc. 2002. - 356 p.
Bioinorganic chemical knowledge grows more interesting and more complex with each passing year. As more details about the usage and utility of metals in biological species and more mechanistic and structural information becomes available about bioinorganic molecules, more biologists, chemists, and physicists will become interested in the field. Senior-level undergraduates in chemistry, biology, and physics, as well as beginning graduate students, will do well to educate themselves in this diverse and fascinating chemical area.
This introductory text will be catalytic for students, whetting their appetites for more information and encouraging them to join research groups engaged in the search for new knowledge in the continually expanding bioinorganic field.
Contents
Preface
Acknowledgments
Inorganic Chemistry Essentials
Introduction
Essential Chemical Elements
Metals in Biological Systems: A Survey
Inorganic Chemistry Basics
Biological Metal Ion Complexation
Thermodynamics
Kinetics
Electronic and Geometric Structures of Metals in Biological Systems
Bioorganometallic Chemistry
Electron Transfer
Conclusions
References
Biochemistry Fundamentals
Introduction
Proteins
Amino Acid Building Blocks
Protein Structure
Protein Sequencing and Proteomics
Protein Function Enzymes and Enzyme Kinetics
Nucleic Acids
DNA and RNA Building Blocks
DNA and RNA Molecular Structures
Transmission of Genetic Information
Genetic Mutations and Site-Directed Mutagenesis
Genes and Cloning
Genomics and the Human Genome
Zinc-Finger Proteins
Descriptive Examples
Conclusions
References
Instrumental and Computer-Based Methods
Introduction
Analytical Instrument-Based Methods
Spectroscopy
X-Ray Absorption Spectroscopy (XAS) and Extended X-Ray Absorption Fine Structure (EXAFS)
Theoretical Aspects and Hardware
Descriptive Examples
X-Ray Crystallography
Introduction
Crystallization and Crystal Habits
Theory and Hardware
Descriptive Examples
Electron Paramagnetic Resonance
Theory and Determination of g-Values
Hyperfine and Superhyperfine Interactions
Descriptive Examples
Nuclear Magnetic Resonance
Theoretical Aspects
Nuclear Screening and the Chemical Shift
Spin–Spin Coupling
Techniques of Spectral Integration and Spin–Spin Decoupling
Nuclear Magnetic Relaxation
The Nuclear Overhauser Effect (NOE)
Obtaining the NMR Spectrum
Two-Dimensional (D) NMR Spectroscopy
Two-Dimensional Correlation Spectroscopy (COSY)
Nuclear Overhauser Effect Spectroscopy (NOESY)
Descriptive Examples
Moёssbauer Spectroscopy
Theoretical Aspects
Quadrupole Splitting and the Isomer Shift
Magnetic Hyperfine Interactions
Descriptive Examples
Other Instrumental Methods
Atomic Force Microscopy
Fast and Time-Resolved Methods
Stopped-Flow Kinetic Methods
Flash Photolysis
Time-Resolved Crystallography
Introduction to Computer-Based Methods
Computer Hardware
Molecular Modeling and Molecular Mechanics
Introduction to MM
Molecular Modeling Molecular Mechanics and
Molecular Dynamics
Biomolecule Modeling
Molecular Modeling Descriptive Examples
Quantum Mechanics-Based Computational Methods
Introduction
Ab-Initio Methods
Density Function Theory
Semiempirical Methods
Computer Software for Chemistry
Mathematical Software
World Wide Web Online Resources
Nomenclature and Visualization Resources
Online Societies Literature Materials
Equipment Web Servers
Summary and Conclusions
References
Iron-Containing Oxygen Carriers and Their Synthetic Models
Introduction
Myoglobin and Hemoglobin Basics
Structure of the Prosthetic Group
Analytical Techniques
Mechanism for Reversible Binding of Dioxygen and
Cooperativity of Oxygen Binding
Behavior of Dioxygen Bound to Metals
Structure of the Active Site in Myoglobin and Hemoglobin: Comparison to Model Compounds
Model Compounds
Cobalt-Containing Model Compounds
Iron-Containing Model Compounds
Binding of CO to Myoglobin Hemoglobin and Model Compounds
Conclusions
References
Copper Enzymes
Introduction Occurrence Structure Function
Discussion of Specific Enzymes
Azurin
Plastocyanin
Superoxide Dismutase
Hemocyanin
Model Compounds
Introduction
Type I Copper Enzyme Models
Type II Copper Enzyme Models
Type III Copper Enzyme Models
Karlin Group Tridentate Model Compounds
Tolman Group Tetradentate Model Compounds
Kitajima Group Tetradentate Model Compounds
Karlin Group Tetradentate Model Compounds
Summary
Conclusions
References
The Enzyme Nitrogenase
Introduction
Detailed Mechanistic Studies
Iron–Sulfur Clusters
Fe–Protein Structure
MoFe–Protein Structure
Overview
Details of the P-Cluster
Details of the M Center
Nitrogenase Model Compounds
Structural Models
Functional Models
Conclusions
References
Metals in Medicine
Introduction
Inorganic Medicinal Chemistry
Metal Toxicity and Homeostasis
Therapeutic Compounds
Superoxide Dismutase Mimics
Vanadium-Based Diabetes Drugs
Introduction
Examples of Vanadium Compounds Tested as Insulin Mimetic Agents
The Role of Chromium
Platinum-Containing Anticancer Agents
Cis- and trans-Dichlorodiammineplatinum(II)
Mechanism of cisDDP Antitumor Activity
Drug Resistance and DNA Repair Mechanisms
A New Nonclassical Platinum Antitumor Agent
Other Platinum-Containing Anticancer Compounds
Conclusions
Diagnostic Agents
Technetium Imaging Agents
Introduction
‘‘Technetium Essential’’ Radiopharmaceuticals
‘‘Technetium Tagged’’ Radiopharmaceuticals
Gadolinium MRI Imaging Agents
Introduction
Magnetic Imaging Considerations Kinetics and Thermodynamics of Complexes
Selected Drugs in Usage or in Trials
Metal Transport and Metallochaperones
Introduction
The Atx Metallochaperone
Hah or Atox Metallochaperone
Superoxide Dismutase Metallochaperones
Copper Toxicity Disease States and Treatments
Familial Amyotrophic Lateral Sclerosis (FALS)
Wilson and Menkes Diseases
Conclusions
Metals in Medicine (MIM)
Summary Goals; Past Present and Future
MIM Development
References
Index
Bioinorganic chemical knowledge grows more interesting and more complex with each passing year. As more details about the usage and utility of metals in biological species and more mechanistic and structural information becomes available about bioinorganic molecules, more biologists, chemists, and physicists will become interested in the field. Senior-level undergraduates in chemistry, biology, and physics, as well as beginning graduate students, will do well to educate themselves in this diverse and fascinating chemical area.
This introductory text will be catalytic for students, whetting their appetites for more information and encouraging them to join research groups engaged in the search for new knowledge in the continually expanding bioinorganic field.
Contents
Preface
Acknowledgments
Inorganic Chemistry Essentials
Introduction
Essential Chemical Elements
Metals in Biological Systems: A Survey
Inorganic Chemistry Basics
Biological Metal Ion Complexation
Thermodynamics
Kinetics
Electronic and Geometric Structures of Metals in Biological Systems
Bioorganometallic Chemistry
Electron Transfer
Conclusions
References
Biochemistry Fundamentals
Introduction
Proteins
Amino Acid Building Blocks
Protein Structure
Protein Sequencing and Proteomics
Protein Function Enzymes and Enzyme Kinetics
Nucleic Acids
DNA and RNA Building Blocks
DNA and RNA Molecular Structures
Transmission of Genetic Information
Genetic Mutations and Site-Directed Mutagenesis
Genes and Cloning
Genomics and the Human Genome
Zinc-Finger Proteins
Descriptive Examples
Conclusions
References
Instrumental and Computer-Based Methods
Introduction
Analytical Instrument-Based Methods
Spectroscopy
X-Ray Absorption Spectroscopy (XAS) and Extended X-Ray Absorption Fine Structure (EXAFS)
Theoretical Aspects and Hardware
Descriptive Examples
X-Ray Crystallography
Introduction
Crystallization and Crystal Habits
Theory and Hardware
Descriptive Examples
Electron Paramagnetic Resonance
Theory and Determination of g-Values
Hyperfine and Superhyperfine Interactions
Descriptive Examples
Nuclear Magnetic Resonance
Theoretical Aspects
Nuclear Screening and the Chemical Shift
Spin–Spin Coupling
Techniques of Spectral Integration and Spin–Spin Decoupling
Nuclear Magnetic Relaxation
The Nuclear Overhauser Effect (NOE)
Obtaining the NMR Spectrum
Two-Dimensional (D) NMR Spectroscopy
Two-Dimensional Correlation Spectroscopy (COSY)
Nuclear Overhauser Effect Spectroscopy (NOESY)
Descriptive Examples
Moёssbauer Spectroscopy
Theoretical Aspects
Quadrupole Splitting and the Isomer Shift
Magnetic Hyperfine Interactions
Descriptive Examples
Other Instrumental Methods
Atomic Force Microscopy
Fast and Time-Resolved Methods
Stopped-Flow Kinetic Methods
Flash Photolysis
Time-Resolved Crystallography
Introduction to Computer-Based Methods
Computer Hardware
Molecular Modeling and Molecular Mechanics
Introduction to MM
Molecular Modeling Molecular Mechanics and
Molecular Dynamics
Biomolecule Modeling
Molecular Modeling Descriptive Examples
Quantum Mechanics-Based Computational Methods
Introduction
Ab-Initio Methods
Density Function Theory
Semiempirical Methods
Computer Software for Chemistry
Mathematical Software
World Wide Web Online Resources
Nomenclature and Visualization Resources
Online Societies Literature Materials
Equipment Web Servers
Summary and Conclusions
References
Iron-Containing Oxygen Carriers and Their Synthetic Models
Introduction
Myoglobin and Hemoglobin Basics
Structure of the Prosthetic Group
Analytical Techniques
Mechanism for Reversible Binding of Dioxygen and
Cooperativity of Oxygen Binding
Behavior of Dioxygen Bound to Metals
Structure of the Active Site in Myoglobin and Hemoglobin: Comparison to Model Compounds
Model Compounds
Cobalt-Containing Model Compounds
Iron-Containing Model Compounds
Binding of CO to Myoglobin Hemoglobin and Model Compounds
Conclusions
References
Copper Enzymes
Introduction Occurrence Structure Function
Discussion of Specific Enzymes
Azurin
Plastocyanin
Superoxide Dismutase
Hemocyanin
Model Compounds
Introduction
Type I Copper Enzyme Models
Type II Copper Enzyme Models
Type III Copper Enzyme Models
Karlin Group Tridentate Model Compounds
Tolman Group Tetradentate Model Compounds
Kitajima Group Tetradentate Model Compounds
Karlin Group Tetradentate Model Compounds
Summary
Conclusions
References
The Enzyme Nitrogenase
Introduction
Detailed Mechanistic Studies
Iron–Sulfur Clusters
Fe–Protein Structure
MoFe–Protein Structure
Overview
Details of the P-Cluster
Details of the M Center
Nitrogenase Model Compounds
Structural Models
Functional Models
Conclusions
References
Metals in Medicine
Introduction
Inorganic Medicinal Chemistry
Metal Toxicity and Homeostasis
Therapeutic Compounds
Superoxide Dismutase Mimics
Vanadium-Based Diabetes Drugs
Introduction
Examples of Vanadium Compounds Tested as Insulin Mimetic Agents
The Role of Chromium
Platinum-Containing Anticancer Agents
Cis- and trans-Dichlorodiammineplatinum(II)
Mechanism of cisDDP Antitumor Activity
Drug Resistance and DNA Repair Mechanisms
A New Nonclassical Platinum Antitumor Agent
Other Platinum-Containing Anticancer Compounds
Conclusions
Diagnostic Agents
Technetium Imaging Agents
Introduction
‘‘Technetium Essential’’ Radiopharmaceuticals
‘‘Technetium Tagged’’ Radiopharmaceuticals
Gadolinium MRI Imaging Agents
Introduction
Magnetic Imaging Considerations Kinetics and Thermodynamics of Complexes
Selected Drugs in Usage or in Trials
Metal Transport and Metallochaperones
Introduction
The Atx Metallochaperone
Hah or Atox Metallochaperone
Superoxide Dismutase Metallochaperones
Copper Toxicity Disease States and Treatments
Familial Amyotrophic Lateral Sclerosis (FALS)
Wilson and Menkes Diseases
Conclusions
Metals in Medicine (MIM)
Summary Goals; Past Present and Future
MIM Development
References
Index