Spin Labeling Theory and Applications / edited by Lawrence J. Berliner, Jacques Reuben.

We present this special topics volume on an area which has not received thorough coverage for over 12 years. Spin Labeling: Theory and Applications represents a complete update on new theoretical aspects and applications of the spin-label method. In the "line-shape theory" sections, we are...

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Bibliographic Details
Corporate Author:	SpringerLink (Online service)
Other Authors:	Berliner, Lawrence J. (Editor), Reuben, Jacques (Editor)
Format:	eBook
Language:	English
Published:	New York, NY : Springer US : Imprint: Springer, 1989.
Edition:	1st ed. 1989.
Series:	Biological Magnetic Resonance, 8 Springer eBook Collection.
Subjects:	Biochemistry. Biotechnology. Analytical chemistry. Biophysics. Biological physics. Electronic resources (E-books)
Online Access:	Click to view e-book
Holy Cross Note:	Loaded electronically. Electronic access restricted to members of the Holy Cross Community.

Table of Contents:

1 Calculating Slow Motional Magnetic Resonance Spectra: A User’s Guide
1. Introduction
2. General Theoretical Considerations
2.1. Terms Included in the Liouville and Diffusion Superoperators
2.2. Definitions of Coordinate Systems
2.3. Basis Vectors and Scalar Product in Operator Space
2.4. Construction of the Spin Hamiltonian
2.5. Matrix Elements of the Liouville Superoperator
2.6. Construction and Matrix Elements of the Diffusion Super-operator
2.7. Components of the Starting Vector
2.8. The High-Field Approximation
3. Magnetic Resonance Line Shapes and the Complex Symmetric Lanczos Algorithm
3.1. The Real Symmetric Lanczos Algorithm
3.2. The Complex Symmetric Lanczos Algorithm
3.3. The Real Symmetric Conjugate Gradients Algorithm
3.4. The Complex Symmetric Conjugate Gradients Algorithm
3.5. The Continued-Fraction Representation of the Spectral Function
3.6. Convergence of the Sequence of Approximate Spectral Functions
4. Computational Considerations
4.1. Naming Conventions for Files
4.2. Array Dimensions and Common Blocks
4.3. The Parameter Input Program: LBLL
4.4. Spectral Calculations: EPRLL and EPRCGL
4.5. Calculation of the Spectral Function: TDLL
4.6. “Field Sweep” Conjugate-Gradients Calculations: EPRBL and TNLL
4.7. Auxiliary Programs: D200, STVT, MATLST, and VECLST
4.8. Porting Programs to Other Machines
5. Example Calculations
5.1. Model Calculations and General Strategy
5.2. Examples from the Literature
Appendix: Parameters for Example Calculations
References
2 Inhomogeneously Broadened Spin-Label Spectra
1. Introduction
2. Experimental Determination of Hyperfine Coupling Constants
2.1. NMR and ENDOR
2.2. ESR Simulation
2.3. Solvent Dependence of Hyperfine Coupling Constants
3. Gaussian Contributions to Spin-Label Line Shapes
Example 1
4. The Voight Approximation and a One-Parameter Description of Line Shapes
Example 2
5. Line-Shape Comparisons
5.1. Unresolved Hyperfine Multiplets
5.2. A Universal Nitroxide
5.3. Gaussian-Lorentzian Sum Approximations
6. Correcting the Linewidth of an Inhomogeneously Broadened Line
6.1. Known Hyperfine Coupling Constants
Example 3. Solvent Dependence of ?HppG
Example 4. Dependence of ?HppGon Spin-Label Alignment in an Ordered Fluid
6.2. Unknown Hyperfine Coupling Constants
Example 5
6.3. Additional Broadening Method
7. The Relationship of Linewidth Ratios to Measured Line-Height Ratios
7.1. Rotational Correlation Times
Example 6
7.2. Linewidth Ratios Over a Broader Range
Example 7. Measuring Oxygen Concentrations Using Unresolved Spin-Label Spectra
8. Accurate Estimate of Relative Doubly-Integrated Spectral Intensities
Example 8. A Hypothetical Spin-Label Partitioning Experiment
9. Determining Spin-Exchange Frequencies of Spin Labels in Liquids of Low Viscosity
10. Deuterated Spin Labels
10.1. Gaussian Linewidth of Deuterated Spin Labels
10.2. Proton Contamination of a Deuterated Spin Label
Example 9
Example 10
11. Conclusions
References
3 Saturation Transfer Spectroscopy of Spin Labels: Techniques and Interpretation of Spectra
1. Introduction
2. Basic Principles of Saturation Transfer ESR
2.1. The Spin Hamiltonian
2.2. ESR Spectra of Immobilized Spin Labels
2.3. The Bloch Equations
2.4. Qualitative Explanation of ST-ESR
2.5. Spectral Displays of ST-ESR
2.6. Analysis of ST-ESR Spectra
3. Measurements of Saturation Transfer ESR Spectra
3.1. The Resonant Cavity
3.2. Effect of Sample on Cavity Properties
3.3. Phase-Sensitive Detection
3.4. Calibration Procedures
3.5. Standard Conditions for ST-ESR Spectroscopy
4. Analysis of Saturation Transfer ESR Spectra
4.1. Isotropic Motion
4.2. Anisotropic Motion
5. Future Developments
References
4 Nitrogen-15 and Deuterium Substituted Spin Labels for Studies of Very Slow Rotational Motion
1. Introduction
2. Overview of Rotational Diffusion Models
2.1. Definition of Rotational Correlation Times
2.2. Isotropic Rotational Diffusion
2.3. Anisotropic Rotational Diffusion in an Isotropic Medium
2.4. Uniaxial Rotational Diffusion in an Anisotropic Medium
3. Sensitivity of cw-ST-EPR Signals to Rotational Motion
3.1. Choice of Signal
3.2. Sensitivity to Motion
3.3. The Case of Isotropic Motion and Anisotropic Magnetic Tensors
3.4. Effects of Anisotropic Motion and Anisotropic Tensors
3.5. Geometric Considerations for Analyzing Anisotropic Motion
4. Analysis of cw-ST-EPR Data
4.1. Isotropic Model Systems
4.2. Anisotropic Model Systems
4.3. Anisotropic Motional Modeling by Computer Simulations
4.4. Overview of Theory for Computation of ST-EPR Spectra
5. Studies of Isotropic Motion with Nitrogen-15 Spin Labels
5.1. V1EPR Signals as a Function of ?r
5.2. Dependence of the V?2Signal on ?r
6. Effects of Anisotropic Rotational Diffusion on V?2Spectra
6.1. Sensitivity of V?2to Uniaxial Rotation
6.2. Effects of Labeling Geometry
6.3. Sensitivity of V’2to Anisotropic Rotational Diffusion of Axially Symmetric Ellipsoids in an Isotropic Medium
6.4. Relationship between Effective Correlation Times and Anisotropic Motion
7. Optimization of Sensitivity of V’2to Motion
7.1. Altering Sensitivity to Motion by Selection of v0
7.2. Altering Sensitivity to Motion by Selection of vm
8. Analysis of Overlapping Motional Species
8.1. One Fast and One Slow Motional Component
8.2. Two or More Slow Motional Components
9. Computer Modeling of Nitrogen-14 V’2Signals
9.1. Isotropic Motion Simulations
9.2. Anisotropic Motion Simulations
9.3. Signal-to-Noise Ratio and Motional Sensitivity of Nitrogen-15 versus Nitrogen-14 Spin Labels
10. Saturation Recovery EPR Studies with Nitrogen-15 Spin Labels
10.1. Overview of the Experiment
10.2. Spectrometer Variables
10.3. Strategies for Extraction of Motional Information
10.4. Theory of Saturation Recovery
10.5. Pseudosecular Terms
10.6. Isotropic Brownian Motion—Secular Terms Only
10.7. Results of Calculations of SR Curves for Isotropic Motion
10.8. Results of Calculations of SR Curves for Nonaxial Tensors
10.9. Effects of Pseudosecular Terms
10.10. Pseudosecular Terms using Nitrogen-14
10.11. Population Analysis: An Estimate of Amplitudes
11. Conclusions
References
5 Experimental Methods in Spin-Label Spectral Analysis
1. Introduction
2. Inhomogeneous Broadening
3. Fast Rotational Motion
4. Slow Rotational Motion
5. Anisotropic Rotation: Lipids/Membranes
6. Spin-Spin Interactions and Lateral Diffusion
6.1. Spin-Spin Exchange
6.2. Translational Diffusion and Bimolecular Collision Rate
6.3. Dipolar Spin-Spin Broadening
6.4. Separation of Exchange and Dipole-Dipole Interactions
7. Lipid-Protein Interactions
7.1. Spectral Subtraction/Addition
7.2. Measurements at 35 GHz
7.3. Analysis of Lipid-Protein Association
7.4. Two-Site Exchange Simulations
8. Saturation Transfer ESR
8.1. Power and Modulation Calibration and the Effects of Sample Shape, Size, and Dielectric Absorption
8.2. Anisotropic Rotation
8.3. Integral Method: Multicomponent Spectra
8.4. Dispersion Spectra: Difference Spectroscopy
References
6 Electron-Electron Double Resonance
1. Introduction
1.1. Definitions and Background
1.2. Historical Overview
2. Rate Equations
3. Spin-Label Relaximetry
4. Apparatus
5. Applications
5.1. Lateral Diffusion in Membranes
5.2. Studies Utilizing 14N: 15N Spin-Label Pairs
5.3. ELDOR in Cells
5.4. Comparison with Spin-Exchange Line Broadening
5.5. Further Application of 14N: 15N Methodology
6. Future Opportunities
References
7 Resolved Electron-Electron Spin-Spin Splittings in EPR Spectra
1. The Scope of Electron Spin-Spin Interactions
2. The Nature of Electron Spin-Spin Interactions
2.1. Dipolar Interaction
2.2. Exchange Interaction
2.3. Hamiltonian for Spin-Spin Interaction
2.4. Computational Approaches
3. Analogies between Nuclear-Nuclear, Electron-Nuclear, and Electron-Electron Spin-Spin Interactions and Long-Range Electron Transfer
4. Spin-1/2-Spin-1/2 Interaction
4.1. Spin-Spin Splitting
4.2. Half-Field Transitions
4.3. Geometrical Information
5. Spin 1-Spin 1/2
6. Spin 3/2-Spin 1/2
7. Spin 5/2-Spin 1/2
7.1. Mn(II) Interacting with S= 1/2
7.2. High-Spin Fe(III) Interacting with S= 1/2
8. Spin 7/2-Spin 1/2
9. Chemical Properties Revealed via Spin-Spin Interactions
9.1. Kinetics of Ligand Exchange for Cu(II) i.
9.2. Coordination Equilibria
9.3. Weak Orbital Overlaps
10. Spin-Spin Interactions in Biological Systems
10.1. Cobalt(II) - Radical Interaction
10.2. Mo(V) Interaction with Fe/S Cluster
10.3. Iron-Nitroxyl Interaction
10.4. Nitroxyl-Nitroxyl Interaction
11. Exchange Interaction through Multiatom Linkages
12. Quantitative EPR Measurements
13. Summary and Prognosis
References
8 Spin-Label Oximetry
1. Introduction
2. Physics
2.1. Bimolecular Collisions
2.2. Magnetic Interactions
2.3. The Absolute T1Method
2.4. The Absolute T2Method
3. Experimental Methods
3.1. TPX Gas-Exchange Sample Cell
3.2. T1Sensitive Methods
3.3. T2(Linewidth-Sensitive) Methods
4. Applications
5. Future Opportunities
References
9 Chemistry of Spin-Labeled Amino Acids and Peptides: Some New Mono- and Bifunctionalized Nitroxide Free Radicals
1. Introduction
2. Spin Labeling of Amino Acids and Peptides
2.1. Reagents for Labeling at the Amino Terminal
2.2. C-Terminal Spin-Labeled Amino Acids and Peptides
2.3. Amino Acids and Peptides Labeled in the Side Chain
3. Nitroxide Amino Acids
3.1. Imidazolinyl Nitroxide Amino Acids
3.2. Pyrrolidine Nitroxide Amino Acids
3.3.

Spin Labeling Theory and Applications / edited by Lawrence J. Berliner, Jacques Reuben.

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