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Quartz
crystal
microbalance, or QCM, relies on
the ability of quartz crystals to change shape in response to the
applied voltage (reverse piezoelectric effect).
In
particular, quartz crystals cut in a certain way will oscillate in
shear-thickness mode in response to the applied voltage,
sending shear waves into the surrounding media. In the image on the
left,
such a crystal is shown schematically. It has a rectangular
cross-section at rest. Top and bottom surfaces will
move in opposite directions when voltage is applied. |
In a typical QCM
measurement, the resonance frequency and bandwidth (half
width of the resonance peak at half height) of a quartz crystal are
measured. Measurements
can be done in the frequency
domain (e.g., with an
impedance analyser) or the time domain (exciting the crystals
intermittently and measuring the decay of oscillations; this is the
approach Q-sense took with their QCM-D system). Both approaches result
in two parameters (per overtone): resonance frequency and bandwidth.
The two kinds of measurements are related to each other via a Fourier
transform (see the diagram on the right).
These two parameters depend on the environment of the crystal. For
example, a crystal in air
will oscillate at one frequency, while the same crystal in liquid - at
another (red and blue curves in the diagram on the right). Note, that
the widths of the resonance peaks also change. The change in the
resonance frequency, as well as the change in bandwidth, upon transfer
of a crystal from air to liquid is described by the well-known
Kanazawa-Gordon relation, which states that both are proportional to
the square root of the liquid density times liquid viscosity.
More information about QCM can
be found here.
Below, the results of a typical measurement are shown.
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The frequency/bandwidth in
air (blue) and the frequency/bandwidth in liquid (red) are related
to each other via liquid viscosity and density through the so-called
Kanazawa-Gordon relationship (see Borovikov 1976 Instruments and
Experimental Techniques 19,
223-224; Kanazawa and Gordon 1985 Anal.
Chem. 57, 1771-1772). A
frequency-domain
measurement (left) is related to the time-domain measurement (right)
via a Fourier-transform. Bandwidth is defined as half-width
of the resonance peak at half-height.
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A typical QCM
experiment - adsorption of liposomes to a surface and bilayer
formation:
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In this experiment,
the resonance frequency and bandwidth
of a quartz crystal are monitored as a function of time. The plots show
the difference in the resonance frequency (left) and bandwidth (right)
relative to that of the bare crystal in liquid. Since initially, there
is only a bare crystal in liquid, this difference is zero. At time 0, liposomes were injected. The frequency
goes down, while the bandwidth increases, corresponding to adsorption
of liposomes to the surface. After reaching the respective extrema, the
signals return: bandwidth returns to ~ zero, frequency shift returns to
~ - 25*n Hz, where n is the overtone order. Lines of different color
represent measurements done on different overtones, where fn ~ n*f0, with f0 = 5 MHz the
fundamental frequency of the quartz crystal used in this experiment.
Dissipation is related to bandwidth as D = 2Γ/f.
This type of
response (extrema in frequency and bandwidth shifts) has
been interpreted by Keller and Kasemo (Biophys.
J. 75, 1397, 1998) as
adsorption of liposomes and their subsequent decomposition to form a supported lipid bilayer:
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A
supported lipid bilayer is formed at the end of the process. Note, that
the frequency shifts at this stage are the same on all overtones, so Δf/n ~ constant,
and the bandwidth shifts are ~ zero. Therefore, the Sauerbrey
relationship can be applied to
calculate the mass of the
adsorbed layer from the frequency shifts: Δf/n = - (layer density)*(layer
thickness) / constant. With Δf/n
~ -25 Hz, the Sauerbrey constant = 18.8 ng/cm2/Hz, and
density ~ 1 g/cm3, the thickness comes out ~ 5 nm, which is in good
agreement with what is expected for a lipid bilayer.
On the other hand, the Sauerbrey relationship
can not be used to accurately determine the mass of the adsorbed
liposomes, because the bandwidth shift is not zero and Δf/n is not constant. You can learn
more about interpretation of QCM data in heterogeneous films here and here.
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