Fundamentals of Magnetic Resonance Flashcards

1
Q

Define nuclear spin, give its units and describe what values it takes in different nuclei.

A

Nuclear spin, I, is the total angular momentum of a nucleus. It is measured in units of ħ which is h/2π.

The nuclear spin can be an integer or an half-integer.

If the no. of protons and neutrons are even, spin is 0

If the no. of protons and neutrons are odd, spin is and integer

If one is odd and the other is even, the spin is a half-integer

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2
Q

How can the number of spin states for a nuclei be determined from the nuclei spin? How does this relate to the eigenvalue of the vector of the spin in the z direction?

A

Using m = 2I + 1 the number spin states can be determined. For 1/2, the states are -1/2 and 1/2.

The eigenvalues of Iz operator are mħ where m is the values determined above.

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3
Q

How does the nuclear spin affect the nuclear magnetic moment?

A

The nuclear magnetic moment, μ^, is given by γI^.

Where γ is the gyromagnetic ratio which is a property of the nucleus where γ/2π has the units of MHz T-1. γ is usually given in this form.

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4
Q

Describe the Zeeman interaction and how it can be described by a Hamiltonian. How can this be applied to the energy of the nuclei’s spin states?

A

The Zeeman interaction is the force when a nuclei is placed in a large magnetic field. The Hamiltonian is H^z = -μ^z • B0 = -γ I^z B0 where B0 is the magnetic field in the applied direction (defined as z).

Recalling that the eigenvalues are mħ, the energy of each spin state is:

Em = -γ B0 m ħ for various values of m.

Hence the difference between adjacent spin states is γ B0 ħ. And as the selection rule is ±1, this is always the energy gap.

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5
Q

How does the difference in energy between spin states relate to the frequency of the radiation to cause a transition between the states?

A

ω = γ B0 also know as the Larmor equation

ω = 2πv where v is the Larmor frequency.

Typical Larmor frequency values are 102 MHz

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6
Q

How are the number of nuclei in each state determined?

A

Via a Boltzmann distribution probability. At thermal equlibrium both states are very similar in population as they are close in energy. The difference in population at equlibrium is known as the nuclear polarisation, P. This depends on the field, B0, the gyromagnetic ratio and the temperature. This has a high temperature approximation.

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7
Q

Describe the coordinate system often used in NMR.

Describe how the magnetic moment is divided into these componants

A

Cylindical coordinates where z is the B0 axis, ρ is the distance in the xy plane from the origin and φ is the angle of the vector in the xy plane.

μz = μz, μx = μxycosφ, μy = μxysinφ

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8
Q

What is generated as a product of the magnetic field and the magnetic moment of a nuclei?

A

A torque which acts perpendicularly to both vectors. This causes the nuclei to precess about the magnetic field vector, at the Larmor frequency, ω = γ𝐵0.

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9
Q

Describe the nuclear spins in a sample and how they are oriented before and after a magnetic field is applied. Describe the net magnetisation.

A

Without a magnetic field, the nuclei point in any direction as none are preferred. Once the field is applied, the Zeeman interaction creates a preference for spin up nuclei and they will all precess about the B0 direction.

The sum of the magnetic moments is the net magnetisation, M. Mz is the sum of all z components of the magnetic moments. Mxy is the sum of the xy componants which depends on the phase of precession.

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10
Q

What determines the total magnetisatiation along the z axis?

A

The total magnetisation along z = P0 (the polarisation at equlibrium, asigns the difference in spin state population) • N (number of spins in the sample) • size of the magnetic moment (mγħ)

This therefore depends on the number of spins, the type of nucleus, B0 and temperature.

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11
Q

Describe the traverse magnetisation of the nuclei, Mxy.

A

As the nuclei precess, the phase will depend on time and the initial phase. This can be represented as a function of the two directions and converted to a more useful form using Eulers formula.

The phase of the nuclei at time t only depend on the phase when they were pointing at time t=0. At equlibrium these phases are random and on average they will cancel out for entropic reasons. Hence Mxy = 0.

There can only be magnetisation in the xy plane if there is initial phase coherence.

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12
Q

Describe the product of rotating the total magnetisation at equlibrium into the xy plane in terms of signal, phase coherence and polarisation.

A

As the magnetic moment is in sync, there is phase coherence. This means that when a coil is placed around the field, the precessing magnetic moment will generate an oscillating current. As there is no magnetisation along the z axis, there must be an equal population in both spin states. The rotation will be at the Larmor frequency.

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13
Q

Describe the basis of the rotating frame of reference.

A

To represent the precessing transverse vector, new axis of z’, x’ and y’ are used where x’ and y’ are rotating at the Larmor frequency. Since the vector is stationary in the rotating frame of reference, the field vector, B0, will dissapear.

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14
Q

Describe, using the rotating frame of reference, the RF pulse that induces transitions between energy states. Describe the RF pulse amplitude, frequency and duration and what effect this has on the magnetisation vector.

A

The RF pulse must have a magnetic field that rotates at the Larmor frequency (energy to move nuclei between states). This relates to a frequency in the radio range. The amplitude, B1, is in the mT range, smaller than B0. The duration is given by tRF.

In the rotating frame, the magnetisation vector will rotate perpendicular to the RF pulse. The pulse is applied perpendicular to the field so the vector will rotate in the plane of z and either x or y (depending on the RF pulse direction). The rotation will occur with the frequency ω1 = γB1.

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15
Q

When an RF pulse is applied to a vector, what determines the angle it is rotated to?

A

The angle, α = ω1tRF = γB1tRF.

Any angle from the z axis can be rotated to, it only depends on the time the RF pulse is applied for.

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16
Q

How is the RF pulse for an NMR spectrometer generated?

What part of the magnetisation is detected? What are the implications of this?

A

By passing an oscillating current through the coil that then detects the precession of the nuclei.

Only the magnetisation in the transverse plane is detected. This means that the signal has the magnitude of Mxy = M0sinα.

17
Q

What factors affect the NMR signal amplitude, S0?

A

The amplitude of the precessing magnetic moment, M0sinα, and the frequency of the precession. M0 can be further broken down to depend on temperature, γ, the nuclei and B0.

18
Q

Define and describe NMR receptivity, R.

A

NMR receptivity is the measure of how easy it is to detect the NMR signal for a given nucleus. It is given relative to another nucleus in the same field, at the same temperature. The receptivity depends on the natural isotope abundance, γ3 and has a small dependance on the spin state.

19
Q

Generally describe longitudinal (T1) relaxation and its causes.

A

Also known as spin-lattice relaxation, the equlibrium is established between spin up and down states with the lattice environment, B0, as the energy from the RF pulse decays to the surroundings. The equlibrium is established by transitions between the spin states which requires fluctuating magnetic fields, oscillating at the Larmor frequency. The fluctuations are caused by molecular motion on the timescale of the Larmor frequency.

Factors that affect T1: B0, temperature, sample viscosity, RMM and dipole-dipole coupling.

20
Q

Describe the uses and effects of longitudinal (T1) relaxation.

A

It can be used as a information source about the structure and dynamics of the system, such as MRI.

The rate of change of the z magnetisation = -T1-1 [Mz(t) - M0]. The relaxation rate, R1, is the reciprocal of the relaxation time. T1 is a function of the physical characteristics of the sample, such as temperature and viscosity.

The main role of T1 is the time used to determine how long between RF pulses so that enough of the sample has relaxed. This is described by the equation Meff = M0 (1 - exp(-TR/T1) where TR is the time between RF pulses. If 2T1 is waited, 86% of the sample will have relaxed. Enough time must be left so that integrals are accurate, for full accuracy, 5T1 are left.

21
Q

Generally describe transverse (T2) relaxation.

A

T2 relaxation is responsible for the decay of Mxy back to zero after phase coherence is applied. Therefore this must occur via de-phasing. This can occur by two ways:

  1. Random phase changes between spin up and down for a nucleus (also causes T1 due to the population change) or an exchange in energy between two nuclei leading to no population change.
  2. Differences in the Larmor frequency when there is fluctuations in the magnetic field, caused by the magnet or the sample.
22
Q

Describe the transverse (T2) relaxation rate dependancy and the effect this has on the NMR signal.

A

The rate of change of Mxy only depends on T2, a property of the sample. Therefore Mxy = M0exp(-t/T2). The Mxy moment causes the signal and T2 causes its decay.

In some cases Mxy will also decay due to reversible dephasing which along with local field differences and the differences in the sample will give rise to an effective relaxation time, T2*. This can then be compared with the fundamental T2 to find the field imhomogeneity.

A long T2* (close to T2) is optimal and gives rise to long signals/narrow peaks. Shimming is used to improve B0 homogeneity by applying small additional fields to remove variations.

23
Q

Summarise the longitudinal and transverse magnetisation with graphs for when B0 is initially applied, when a 90º RF pulse is applied and when the signal is detected.

A
24
Q

Describe the 5 magnetic interactions that the nuclear Hamiltonian depends on, and list them in order of strength in a strong magnetic field.

A
  • Strongest: Zeeman interaction, HZ: Direct interaction between the nuclei magnetic moments and B0.
  • Quadropolar interaction, HQ: Interaction between the nuclei magnetic moment and the electric field gradient of the nucleus, only occurs in I > ½ systems.
  • Dipole-dipole coupling, HDD: Direct magnetic coupling between two nuclei due to molecular dipoles.
  • Chemical shift, HCS: Indirect magnetic interaction between nuclei and B0 affected by electrons.
  • Weakest: J coupling, HJ: Indirect magnetic coupling between two nuclei by sharing electron density.
25
Q

Describe the principle behind isotropic chemical shift and how this affects the nuclei.

A

The principle is that the magnetic field, B0, is opposed by a magnetic field generated by the electrons. This is quantified by the magnetic shild tensor, which is multiplied by -B0 to find Bind. In solution the field is independent of molecular orientation.

The magnetic field experienced by the nuclei, Beff = B0 + Bind. This changes the Larmor frequency and the differences between ω0 and ωeff determine nuclei environments.

26
Q

Outline the basis of chemical shift.

A

Chemical shift is determined by the Larmor frequency over 2π, giving the frequency. This is then scaled with the reference by (ν - νref)/νref x 106 to give chemical shift in ppm.

This can be used in reverse to find the frequency of the signal.

27
Q

Describe a weak J coupling system, including the limits, the eigenvalues and how spin states can be converted between.

A

J coupling is the indirect interaction between two nuclei through the mediation of electrons. Weak coupling describes the nuclei individually with a JAB constant where JAB << |νA - νB|.

The eigenvalues contain 4 variations for the combinations of mA and mB which donate the spin states. The lowest spin state is where both spins align with B0. Then there is two degenerate states with one spin up and one spin down nucleus. The highest spin state is where both states oppose B0.

When converting between spins, the total change is ± 1 in observable NMR. ± 2 changes can occur but aren’t observable.

28
Q

Describe peak multiplicity in terms of active and passive spin.

A

When changing between the 4 spin combinations, one nuclei spin will change and the other will remain the same, denoting the active and passive spins respectively.

The active spin change generates the signal and as there is two ways the spin energy can change (depending on the other nucleis spin), hence a doublet is generated.

29
Q

Compare and contrast chemical and magnetic inequivalence.

A

Chemically inequivalent nuclei have different chemical shifts. Magnetic inequivalent nuclei couple differently to an external nucleus. An example of this is in aromatic systems such as pyridine, the nuclei adjacent to the N are not magnetically equivalent.

30
Q

Describe how decoupling occurs and the effect it has.

A

Decoupling removes couplings to other nuclei and is generally applied to a different nucleus such as 13C{1H}. This removes splitting so the signal to noise ratio is improved. It is done by repeatedly pulsating RF pulses at a specifc frequency at the sample to stop relaxation.

31
Q

For weak J coupling, how do you determine the number of lines?

A

2nI + 1

32
Q

Describe the change and conditions for strong to weak coupling.

A

A - νB| = 0: chemically equivalent, singlet seen unless there is some magnetic inequivalence.

A - νB| >> JAB: weak coupling, clean doublets seen, as JAB increases roofing will occur.

A - νB| ≈ JAB: strong coupling, can cause strange shaped ‘quartets’ or other signals which are actually due to different signals. 2nI + 1 cannot be used.

33
Q

What determines the value of the chemical shift tensor?

A

There is an isotropic part of the tensor and an anisotropic part (CSA) where the electron density around a nucleus is not symmetric. CSA depends on the molecular orientation relative to B0 which tend to average out due to entropic molecular orientations. It does contribute to relaxation however.

34
Q

What does the magnitude of dipole-dipole coupling depend on? What effects does it have?

A

The distance between nuclei and the orientation between the nuclei and B0. In liquids the interations average to zero but locally it drives relaxation. For spin ½ nuclei it is the main driver of relaxation.

35
Q

Define electric field gradients and state how it affects relaxation.

A

EFG are a molecular property that depends on molecular structure (symmetry) and the isotope. This is the driver of relaxation due to quadropolar nuclei and with certain isotopes the relaxation will be too fast to recieve any signal.

36
Q

Outline the mechanisms for liquid state relaxation.

A

Overall relaxation is caused by fluctuations of local magnetic fields. The difference sources are called relaxation mechanisms.

  • Dipole-dipole relaxation
  • Chemical shift anisotropy
  • Quadrupolar nuclei - affect NMR of I > ½ nuclei but also I = ½ nuclei coupled to quadrupolar nuclei
  • Paramagnetism
37
Q

Describe how solid-state NMR is taken and the effects this has on the spectrum.

A

The orientation based effects are not averaged out like in liquid NMR so lines are very broad. To counter this, the sample is spun at an angle from B0. The faster the rotation the thinner the lines but this must be smaller than the speed of sound. The normal rotation frequency is around 60 kHz.