CH3410: Advanced Magnetic Resonance Spectroscopy: Principles and Applications

School Cardiff School of Chemistry
Department Code CHEMY
Module Code CH3410
External Subject Code 100417
Number of Credits 10
Level L7
Language of Delivery English
Module Leader Professor Damien Murphy
Semester Spring Semester
Academic Year 2015/6

Outline Description of Module

Magnetic resonance techniques, including NMR and EPR, are extremely powerful tools for investigating the structure and dynamics of molecules. This module offers the student the opportunity to study the underlying physical principles of NMR and EPR in both liquid and solid state, and the surrounding magnetic interactions that determine the appearance of the experimental spectra. Coverage of conventional principles in magnetic resonance, showing how the resonance frequency of a nucleus (or electron) is affected not only by the applied field but also by the electronic environment and surrounding nuclei, will be presented to the students. Subsequently the more modern versions of NMR and EPR, based on pulses of EM radiation, will be covered. The basic mathematical principles of the pulse sequences enabling more elaborate NMR experiments to be performed, will be treated, showing how these techniques are necessary to characterise particularly complex systems, such as those encountered in chemical biology. Particular emphasis will be devoted to NMR and EPR/ENDOR analysis of solid state spectra. The anisotropic interactions responsible for the broad and more complex spectral line shapes experienced in the solid state (compared to the isotropic profiles experienced in the liquid state) will be treated using a series of examples. The advanced methodology of angular selective ENDOR, used to analyse and extract structural information, for paramagnetic species in frozen solution, will also be treated.

On completion of the module a student should be able to

  • describe the behaviour of nuclear and electron spins in an applied magnetic field;
  • understand the role of spin angular momentum as the foundation stone in NMR and EPR;
  • understand the importance of bulk magnetization in NMR and EPR experiments;
  • describe the role of the rotating frame and free precession in magnetic resonance techniques;
  • understand the importance of the spin echo.
  • recall the detection of the NMR signals through Fourier transform NMR;
  • describe the importance of magnetic interactions, namely spin-spin coupling, as a vital source of information; 
  • describe the principles of pulsed-FT NMR and EPR;
  • appreciate the role and basic features of 2-dimensional NMR , to interpret more complex spin systems;
  • understand the nature of anisotropic interactions in the solid state, and how they dictate the shape of the spectra;
  • know how dynamic, as well as structural, information can be accessed in the solid state, and understand the importance of the time-frame of the NMR techniques in dynamic studies;
  • discuss the approaches taken to record NMR spectra in solid state;
  • describe how the ENDOR technique is performed and the role of saturation and relaxation phenomena in acquiring ENDOR signals with optimal amplitudes;
  • describe how the angular selective ENDOR methodology is applied to study paramagnetic systems in the solid state.

How the module will be delivered

The module will be delivered in 10 two-hour lectures, supplemented by 4 one-hour class tutorials.

Skills that will be practised and developed

On completion of the module a student should be able to:

  • link formal equations to observed NMR/EPR spectra;
  • interpret experimental observations in terms of the molecular and structural properties of the system;
  • select appropriate techniques for determination of structure in solution or solid state for a range of chemical situations;
  • assess the advantages/disadvantages of the different techniques for each particular purpose and chemical problem;
  • appreciate the steps involved in the analysis of modern magnetic resonance experiments;
  • understand how NMR/EPR may be used to study problems of general chemical interest;
  • use qualitative arguments to develop a theoretical description of magnetic resonance phenomena;
  • use quantitative measurements to verify or disprove theoretical models.

How the module will be assessed

The module will be assessed by a combination of coursework (20%) and written examination (80%). Coursework will be broken down into 3 short, problem-based pieces of work covering each of the three sub-topics.

Assessment Breakdown

Type % Title Duration(hrs)
Exam - Spring Semester 80 Advanced Magnetic Resonance Spectroscopy: Principles And Applications 2
Written Assessment 20 Written Assignments N/A

Syllabus content

Principles of NMR methodology: The vector model and product operators, building of complex pulse sequences from simpler blocks (eg., spin echo, INEPT, HSQC, 3D/4D multinuclear experiments), decoupling techniques, solvent suppression, the NOE, pulsed field gradients (leading into heavier PFG techniques and DOSY), shaped pulsed and selective excitation, relaxation experiments, protein NMR.

Foundations in Solid State NMR: This part of the course will provide an introduction to solid-state NMR spectroscopy, focusing initially on relevant theoretical background and experimental techniques. The discussion of background theory will highlight the significant differences between solid-state NMR and liquid-state NMR, focusing on the main anisotropic NMR interactions that are important in the solid state. The discussion of experimental strategies will then focus on the techniques for recording: (a) broad-line solid-state NMR spectra (in which the anisotropic NMR interactions are studied), and (b) high-resolution solid-state NMR spectra (in which the aim is to record narrow-line spectra that resemble those recorded in liquid-state NMR). The course will then build upon these foundations by discussing the applications of solid-state NMR to investigate structural and dynamic properties of solids, highlighting the scope and limitations of different types of solid-state NMR technique. Several recent examples of the application of solid-state NMR to solve problems in solid-state and materials chemistry will be presented. Students attending the course will emerge with an appreciation of the types of problem that can be tackled successfully by solid-state NMR, and the particular NMR technique (or combination of techniques) is most suitable for investigating each type of problem.

Angular Selective ENDOR: Finally, the theory and applications of angular selective ENDOR will be presented to the students. The basic principles underlying the EPR technique will be covered, including coverage of the form of the spin Hamiltonian for systems in the solid state. Anisotropy of the g and A hyperfine tensors, and the role of symmetry as manifested in the g/A frame will be presented to the students. Examination of the profiles of EPR spectra in the solid state will then be covered. The lectures will then cover the theory of ENDOR, with particular emphasis on the saturation and relaxation pathways important in this technique. The role of angular selection as a means of determining structural information for paramagnetic centres in the solid state will then be given. Examples of systems with low g anisotropy (no hyperfine interaction) leading to powder ENDOR patterns, and subsequently axial g anisotropy and axial hyperfine, leading so ‘single crystal-like’ ENDOR patterns will then be investigated. The students will then appreciate the experimental approaches taken to obtain EPR and ENDOR spectra of paramagnetic centres in the solid state (primarily in frozen solution) and the general methodologies subsequently involved in the analysis and understanding of the experimental data.

Essential Reading and Resource List

Owing to the advanced nature of the material covered in this module, many of the specialist textbooks are not readily available. Therefore an up-to-date reading list will be included in the course handbook. Many important monographs, and reviews pertaining to the module will be available to the students.

Background Reading and Resource List

Owing to the advanced nature of the material covered in this module, many of the specialist textbooks are not readily available. Therefore an up-to-date reading list will be included in the course handbook. Many important monographs, and reviews pertaining to the module will be available to the students.


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