Solution

ID: past-exam-of-the-biological-physics-course-of-the-university-of-oxford/2022/5/c/solution

In atomic force microscopy, one end of the polyacrylic acid chain is attached to the substrate and the other to a compliant cantilever tip. Controlled separation displaces the cantilever; calibrated cantilever stiffness converts its deflection into force. The molecular extension is the tip–surface separation after correcting for cantilever deflection and instrumental offsets. A quasi-static interpretation requires relaxation to be fast compared with the pulling motion.
At low force a coiled polymer has many available configurations and extends mainly by changing segment orientations. This is the entropic spring regime. As the available contour is aligned, the loss of configurational entropy becomes steep. For an inextensible three-dimensional freely jointed chain,
where is the Langevin function. The limiting extension is the polymer contour length ; the ideal model approaches it only as . Real polymer backbone stretching permits extension beyond the fitted rigid-link contour, explaining why the experimental curve lies on the more extensible side at high force.
The original trace has a sharp force drop after its peak. Finite contour length explains the steep preceding rise, but does not itself cause that drop: release of an attachment, desorption or mechanical failure ends tensile loading. The graph alone does not distinguish these possibilities. If the intact chain is released from tension, thermal motion restores a coil with characteristic end-to-end distance of a polymer chain of order , because this macrostate has many more configurations. Recoil is reversible for an intact equilibrating chain; irreversible chain scission or attachment loss can prevent repetition of the same pulling curve.

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