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    2D NMR Spectroscopy: Cosy: Jessica Thomaston

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    satheeshpharma6
    2D NMR spectroscopy techniques like COSY provide information about nuclear spin couplings in molecules. COSY uses a series of pulses separated by evolution times to produce spectra that indicate which nuclear spins are directly bonded through cross peaks. This technique has been widely used since the 1980s to determine the structures of proteins and other biological molecules by identifying spin-spin connectivities.

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    2D NMR Spectroscopy: Cosy: Jessica Thomaston

    Uploaded by

    satheeshpharma6
    55 views16 pages
    2D NMR spectroscopy techniques like COSY provide information about nuclear spin couplings in molecules. COSY uses a series of pulses separated by evolution times to produce spectra that indicate which nuclear spins are directly bonded through cross peaks. This technique has been widely used since the 1980s to determine the structures of proteins and other biological molecules by identifying spin-spin connectivities.

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    Cosy

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    2D NMR spectroscopy techniques like COSY provide information about nuclear spin couplings in molecules. COSY uses a series of pulses separated by evolution times to produce spectra that indicate which nuclear spins are directly bonded through cross peaks. This technique has been widely used since the 1980s to determine the structures of proteins and other biological molecules by identifying spin-spin connectivities.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    55 views16 pages

    2D NMR Spectroscopy: Cosy: Jessica Thomaston

    Uploaded by

    satheeshpharma6
    2D NMR spectroscopy techniques like COSY provide information about nuclear spin couplings in molecules. COSY uses a series of pulses separated by evolution times to produce spectra that indicate which nuclear spins are directly bonded through cross peaks. This technique has been widely used since the 1980s to determine the structures of proteins and other biological molecules by identifying spin-spin connectivities.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 16

    2D NMR Spectroscopy:

    COSY
    Jessica Thomaston
    Outline
    1. History

    2. Theory of 2D NMR

    3. Applications of COSY
    A brief history of 2D NMR
     In 1971, the idea of 2D NMR was proposed by Jean Jeener.
     The 1975 Ernst paper “Two-dimensional spectroscopy,
    application to nuclear magnetic resonance” utilized Jeener’s
    idea to produce spectra.

     1980s-present: application of NMR to protein structures


     In 1991 Ernst won a Nobel Prize in
    Chemistry for his contributions to
    Fourier Transform NMR
    Types of 2D NMR
     COSY: correlation spectroscopy
     HETCOR: heteronuclear COSY
     TOCSY: total correlation spectroscopy

     NOESY: Nuclear Overhauser effect


    spectroscopy
     EXSY: exchange spectroscopy
     J-Spectroscopy
    Experimental

     A series of equally-spaced t1 are used; 90˚ pulses occur at


    white circles

     Each spectrum measures the instantaneous state of the


    perturbed system after various t1
    General 2D FTS experiment
    1. At t = 0, the system is at ρ(0), an arbitrary nonequilibruim
    state

    2. During 0 < t < t1 the system develops under the influence of


    the time-independent Hamiltonian H

    3. At t = t1 the density operator is rotated by an rf pulse

    4. At t > t1 the system again develops under H and the spectrum


    is measured

    5. A Fourier transform is used to convert the time-dependent


    data to a 2D spectrum
    Theory
    The motion of the system is described by the density operator eqn:

    where H(t) = H(1) for 0< t<t1 and H(t) = H(2) for t>t1

    and r is the relaxation superoperator

    At t=t1+t2 the solution is:

    and the observed magnetization moment is:

    The observed spectrum is a 2D Fourier transform of the above.


    A pair of projection superoperators with the properties

    are used to obtain an expression for the observed magnetization that is separated into two
    terms:

    consists of magnetization components which show oscillatory behavior during the


    evolution period, and will be responsible for cross-peaks and dia-peaks in the 2D spectrum.

    The other term consists of components which do not oscillate and produces the axial peaks of
    the spectrum.
    Resulting 2D spectrum
     3 types of peaks

     Dia peaks are related to


    only one transition and
    occur at the main diagonal
    of the 2D spectrum

     Cross peaks correlate


    different transitions, are off-
    diagonal

     Axial peaks give information


    about spin-lattice relaxation
    processes
     Two pulse (90˚) 1H-1H experiment on 2,3-dibromothiophene.
    Absolute value spectrum shown.
    Cross and dia peaks
     Give information about:
     Connectivity of transitions in the energy level diagram:
    The rotation superoperator r couples transitions
     Transverse relaxation processes:
    Line shapes depend on transverse relaxation times
    T2k1
     The initial state of the spin system, ρ(0):
    Conventional NMR only measures allowed transitions,
    while all matrix elements ofρ(0) can be measured with
    2D NMR
    Uses

     Structural identification in organic and biological chemistry:


     Since its creation, 2D NMR has been useful for elucidating
    the structure of small molecules
     Advanced computing power now allows the structure of
    large, biological molecules to be solved

    Figure from Proc Natl Acad Sci U S A. 1999 January 19; 96(2): 332–334.
    Systematic application of two-dimensional 1H NMR
    techniques for studies of proteins,
    Wüthrich et al., Eur J of Biochem 114, 375-384
    (1981)

     Used COSY and NOESY to obtain individual


    assignments for each proton in the protein
    backbone in the β-sheet secondary structure of
    pancreatic trypsin inhibitor

     COSY spectra taken in 2H2O and H2O were


    combined to obtain sequential resonance
    assignments

     Additional experiments were carried out with t1 at


    different phases to cancel out axial peaks
    2D COSY 1H NMR for pancreatic trypsin inhibitor at 360 MHz
     COSY NMR was used to
    determine the J
    connectivities on the
    protein backbone
     NOESY was used to
    determine distance-
    dependent coupling,
    since NOE can only occur
    at distances of <5-6 Å
     A “β-snail” structure was
    observed for the protein
    Summary
     2D NMR uses a sequence of two pulses with a
    series of different evolution times to determine
    which nuclear spins are coupled to one another.

     COSY spectra indicate through-bond coupling, and


    can be used to gain structural information about
    molecules of a wide range of sizes.

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