Lecture10-complexseq - CHEM BCMB 4190/6190/8189 Introductory NMR Lecture 10-1 Introduction to Complex Pulse Sequences Beyond simple 1D spectra

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Unformatted text preview: CHEM / BCMB 4190/6190/8189 Introductory NMR Lecture 10 -1- Introduction to Complex Pulse Sequences Beyond simple 1D spectra: Simple 1D 1H and 13C spectra are not always sufficient for assigning even small organic compounds. The main problems are: 1) Assignment of the 1D spectra 2) Low S/N in spectra of insensitive nuclei with low natural abundance (e.g. 13C, 15N) Example: Neuraminic Acid derivative 1 O Ac = 1D 13C NMR Spectrum CH3 C -2- We would also like to use the following information: 1) 13C-1H correlations 2) The number of protons attach to one carbon 3) 1H-1H correlations 4) 13C-13C correlations etc. SOLUTION: Complex pulse sequences Use multiple pulses, delays and decoupling schemes • Various pulses: hard pulses: 90˚x, 90˚y, 180˚x, 180˚y, etc. selective pulses: 90˚x, 90˚y, 180˚x, 180˚y, etc. pulse field gradients fixed or variable delays for selective or broadband decoupling • Various delays: • Decoupling: -3- To analyze the effect of complex pulse sequences we use: A) Vector Diagrams: • They are EXTREMELY useful, but it is important to know that they have certain limitations i.e. difficult to explain 2nd order spectra, population transfer, zero or multiple quantum coherence, etc. • For ease of representation, usually in the rotating frame (x', y', and z) instead of the laboratory frame (x, y, and z) . Very important to know what is the frequency (ν) of the rotating frame. B0 z y' x' B) Energy Diagrams: • EXTREMELY useful for understanding energy transfer in certain experiments (e.g.: SPT, INEPT, HSQC) For 1H at equilibrium: β E (m = -1/2) Eβ = +1/2γhBo Nβ = (Nα + Nβ)/2 - δ = N Single quantum transition(∆m = 1) (m = +1/2) Eα = -1/2γhBo Nα = (Nα + Nβ)/2 + δ = N + ∆H α -4- Effect of a pulse on the longitudinal magnetization (Mz): • At equilibrium (Mz): ♦ Bulk magnetization along z caused by Bo ♦ Excess population in the α state • After 90˚, 270˚ pulses: Vector diagrams: B1 field brings Mz to the x'-y' plane 90˚x' z Mz 90˚-x' z Mz 270˚x' z Mz y' x' x' y' x' y' 90˚y' z Mz 90˚-y' z Mz y' y' x' x' Energy diagram: The populations of α and β are now equal For 1H: N E β 90˚, 270˚ N + ∆H/2 β N + ∆H α -5- N + ∆H/2 α • After 180˚ pulses: Vector diagrams: B1 field inverts Mz 180˚x' z 180˚-x' z Mz Mz y' x' 180˚y' x' 180˚-y' y' z Mz y' x' x' z Mz y' Energy diagram: The populations of α and β are inverted For 1H: N E β 180˚ N + ∆H β N + ∆H α -6- N α Effect of a pulse on the transverse magnetization (Mx', My'): • The transverse magnetization (Mx', My') is not at equilibrium ♦ Bulk magnetization in the x'-y' plane ♦ Equal populations in the α and β states • Effect of 90˚ and 180˚ x and y pulses on transverse magnetization with My' component only Vector diagrams: 90˚x' z My' 90˚-x' z 180˚x' z My' y' x' 90˚-y' My' y' x' 180˚y' y' x' 90˚y' z My' z My' z My' y' x' x' y' x' y' Energy diagrams: It all depends where the final magnetization ends up (See above). -7- • Effect of 90˚ and 180˚ x and y pulses on transverse magnetization with Mx' component only Vector diagrams: 90˚x' z 90˚-x' z 180˚x' z y' x' 90˚y' Mx' x' Mx' y' x' Mx' y' z 90˚-y' z 180˚y' z y' x' Mx' Mx' x' y' x' Mx' y' Energy diagrams: It all depends where the final magnetization ends up (See above). -8- • Transverse magnetization with Mx' and My' components: Where does it come from ? Lets consider a simple pulse sequence: 90˚x 1 H Delay Vector diagrams: A) Effect of Chemical Shift Evolution: example: νH = νrf + 200 Hz z Mz 90˚x' y' My' x' x' x' y' z Delay y' B) Effect of J coupling: example: νH = νrf z Mz 90˚x' y' My' x' x' x' -9- z Delay y' ν = νH - 1/2J y' ν = νH +1/2J • Effect of 90˚x pulse on transverse magnetization with Mx' and My' components Vector diagrams: Initial Magnetization: z My' component z Mx' component z y' x' = x' y' + x' y' After 90˚x' pulse: z z z y' x' = x' y' + x' y' After 90˚y' pulse: z z z y' x' = x' y' + x' y' - 10 - • Effect of 180˚ x and y pulses on transverse magnetization with Mx' and My' components Vector diagrams: 180˚x' y' y' 180˚y' y' x' 180˚x' y' x' 180˚y' y' x' y' x' x' 180˚y' y' x' 180˚x' y' y' x' x' x' - 11 - ...
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This note was uploaded on 11/13/2011 for the course CHEM 4190 taught by Professor Staff during the Fall '08 term at University of Georgia Athens.

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