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Stochastic Aspects of Diffusion:
Single Molecules


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10.50 Homepage
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A single molecule in solution:


In class we dicussed the stochastic nature of diffusion. Usually it is very hard to directly 'see' simple molecules because of their small size (simple molecules are usually a few angstroms (10-10 m) in diameter). Some biomolecules, such as double stranded DNA, can be extremely long (lengths > 10's of microns (10-6m)) and can be directly visualized in solution using fluorescence microscopy.
Click here to view a single lambda-phage DNA molecule (length = 20 microns) in an aqueous solution (viscosity of solvent = 1 cp) . The image size is 12 microns x 12 microns and the counter is showing time in seconds. What you hopefully noticed are the large fluctuations in both the configuration of the molecule and the center of mass.
Aside: You also might have noticed that the apparent size of the DNA is much smaller than 20 microns! DNA is a polymer and due to entropic reasons will stay in a coiled configuration (this is beyond the scope of 10.50 and is discussed in detail in 10.537 and 10.668).

Molecular trajectories:


We can quantify the motion of the molecules by tracking the center of mass of the DNA as a function of time. The trajectories of 4 molecules during a 1 second time interval are shown in the figure to the right. Since this is a stochastic process we see that the trajectories of individual molecules are quite different!
[trajectories]
To analyze the system further we will calculate ensemble averaged quantities. The vectoral position of a molecule at time=0 is defined as ri(0). We monitor the displacement from this postion, ri(t)-ri(0). On taking the ensemble average over 100 molecules we arrive at < ri(t)-ri(0)> =0 which merely reflects the fact that there is no bulk flow in the experiment. However, the mean squared displacement (<[ri(t)-ri(0)]2>) is nonzero and grows linearly in time (cf. figure to the right). This is consistent with our discussion in class (section 2.9 of Deen).
[random
walk]
We add one technical note. In the experiment we are only able to track the in-plane motion of the molecule which is denoted here as the x-y plane. To extract the diffusion coefficent of the DNA we use the 2-dimensional analog of equation 2.9-21 in Deen: <[ri(t)-ri(0)]2> = 4 D t.


References
Analysis of Transport Phenomena, W.M. Deen, Oxford University Press, 1998
Professor Patrick S. Doyle
Dynamics and Rheology of Complex Liquids Group
MIT
pdoyle@mit.edu