Magic angle spinning
Encyclopedia
In nuclear magnetic resonance
, magic angle spinning (MAS) is a technique often used to perform experiments in solid-state NMR spectroscopy
.
By spinning the sample (usually at a frequency of 1 to 70 kHz) at the magic angle
θm (ca. 54.74°, where cos2θm=1/3) with respect to the direction of the magnetic field
, the normally broad lines become narrower, increasing the resolution for better identification and analysis of the spectrum.
In any condensed phase, a nuclear spin experiences a great number of interactions. The main three interactions (dipolar, chemical shift anisotropy, quadrupolar) often lead to very broad and featureless lines. However, these three interactions in solids are time-dependent and can be averaged by MAS. The nuclear dipole-dipole interaction, between magnetic moment
s of nuclei averages to zero only at the magic angle, θm . The chemical shift anisotropy, a nuclear-electron interaction, averages to a non-zero value. The quadrupolar interaction is only partially averaged by MAS leaving a residual secondary quadrupolar interaction. In liquids, e.g. a solution of an organic compound
, most of these interactions will average out because of the rapid time-averaged molecular motion that occurs. This orientation averaging in solution is mimicked by MAS of a solid. This causes the signal to become much narrower, giving rise to the isotropic value (which is of interest for structural determination of solid materials and compounds) and spinning sidebands which occur at multiples of the spinning speed and can be used to determine the chemical shift anisotropy of the nuclei.
The physical spinning of the sample is achieved via an air turbine mechanism. These turbines (or rotors) come in a variety of diameters (outside diameter), from 2.0-15.0 mm, and are usually spun on air or nitrogen gas. The rotors are made from a number of different materials such as ceramics e.g. zirconia, silicon nitride
or polymers such as poly(methyl methacrylate) (PMMA), polyoxymethylene
(POM). The cylindrical rotors are axially symmetric about the axis of rotation. Samples are packed into the rotors and these are then sealed with a single or double end cap. These caps are made from number of different materials e.g. Kel-F, Vespel, zirconia or boron nitride depending on the application required.
Magic-angle spinning was first described in 1958 by Edward Raymond Andrew, A. Bradbury, and R. G. Eades and independently in 1959 by I. J. Lowe. The name "magic-angle spinning" was coined in 1960 by Cornelis J. Gorter at the AMPERE congress in Pisa. Edward Raymond Andrew had numerous publications on the subject of MAS, including Knight shift
s in metals
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...
, magic angle spinning (MAS) is a technique often used to perform experiments in solid-state NMR spectroscopy
Spectroscopy
Spectroscopy is the study of the interaction between matter and radiated energy. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, e.g., by a prism. Later the concept was expanded greatly to comprise any interaction with radiative...
.
By spinning the sample (usually at a frequency of 1 to 70 kHz) at the magic angle
Magic angle
The magic angle is a precisely defined angle, the value of which is approximately 54.7356°. The magic angle is a root of a second-order Legendre polynomial, P_2=0 \,, and so any interaction which depends on this second-order Legendre polynomial vanishes at the magic angle...
θm (ca. 54.74°, where cos2θm=1/3) with respect to the direction of the magnetic field
Magnetic field
A magnetic field is a mathematical description of the magnetic influence of electric currents and magnetic materials. The magnetic field at any given point is specified by both a direction and a magnitude ; as such it is a vector field.Technically, a magnetic field is a pseudo vector;...
, the normally broad lines become narrower, increasing the resolution for better identification and analysis of the spectrum.
In any condensed phase, a nuclear spin experiences a great number of interactions. The main three interactions (dipolar, chemical shift anisotropy, quadrupolar) often lead to very broad and featureless lines. However, these three interactions in solids are time-dependent and can be averaged by MAS. The nuclear dipole-dipole interaction, between magnetic moment
Magnetic moment
The magnetic moment of a magnet is a quantity that determines the force that the magnet can exert on electric currents and the torque that a magnetic field will exert on it...
s of nuclei averages to zero only at the magic angle, θm . The chemical shift anisotropy, a nuclear-electron interaction, averages to a non-zero value. The quadrupolar interaction is only partially averaged by MAS leaving a residual secondary quadrupolar interaction. In liquids, e.g. a solution of an organic compound
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
, most of these interactions will average out because of the rapid time-averaged molecular motion that occurs. This orientation averaging in solution is mimicked by MAS of a solid. This causes the signal to become much narrower, giving rise to the isotropic value (which is of interest for structural determination of solid materials and compounds) and spinning sidebands which occur at multiples of the spinning speed and can be used to determine the chemical shift anisotropy of the nuclei.
The physical spinning of the sample is achieved via an air turbine mechanism. These turbines (or rotors) come in a variety of diameters (outside diameter), from 2.0-15.0 mm, and are usually spun on air or nitrogen gas. The rotors are made from a number of different materials such as ceramics e.g. zirconia, silicon nitride
Silicon nitride
Silicon nitride is a chemical compound of silicon and nitrogen. If powdered silicon is heated between 1300° and 1400°C in an atmosphere of nitrogen, trisilicon tetranitride, Si3N4, is formed. The silicon sample weight increases progressively due to the chemical combination of silicon and nitrogen...
or polymers such as poly(methyl methacrylate) (PMMA), polyoxymethylene
Polyoxymethylene
Polyoxymethylene , also known as acetal, polyacetal, and polyformaldehyde, is an engineering thermoplastic used in precision parts that require high stiffness, low friction and excellent dimensional stability....
(POM). The cylindrical rotors are axially symmetric about the axis of rotation. Samples are packed into the rotors and these are then sealed with a single or double end cap. These caps are made from number of different materials e.g. Kel-F, Vespel, zirconia or boron nitride depending on the application required.
Magic-angle spinning was first described in 1958 by Edward Raymond Andrew, A. Bradbury, and R. G. Eades and independently in 1959 by I. J. Lowe. The name "magic-angle spinning" was coined in 1960 by Cornelis J. Gorter at the AMPERE congress in Pisa. Edward Raymond Andrew had numerous publications on the subject of MAS, including Knight shift
Knight shift
The Knight shift is a shift in the nuclear magnetic resonance frequency of a paramagneticsubstance first published in 1949 by the American physicist Walter David Knight.The Knight shift is due to the conduction electrons in metals...
s in metals