Evidence for gravity's influence on molecules at a solid-solution interface

Yoshimoto et al. [Anal. Chem. 2002, 74,4306-4309] reported that a quartz crystal microbalance or QCM changed its response to sucrose solutions according to its angle of immersion. The effect was tentatively attributed to gravity-caused stress on the viscous interface between the oscillator and the bulk solution. The present work reports results from QCM experiments carried out so that any effect of gravity on the interfacial region would be magnified. This permitted use of a lower-frequency, less-sensitive QCM. Molecules of DNA were tethered to a functionalized QCM surface and then extended in steps, via sandwich hybridization, to produce DNA of uniform and known length. This feature allowed both the effect of QCM immersion angle and the relationship between frequency and molecular length to be investigated simultaneously. Comparison of acoustic wave damping at 0degrees and 180degrees immersion angles offers compelling evidence that the interfacial region expands when the active face of the QCM is down and contracts when it is up. This is apparently a consequence of the interfacial region being more dense than the bulk solution. The results are consistent with (a) slow gravity-driven movement of molecules away from a down-facing QCM, (b) rapid hybridization-driven movement away from an up-facing QCM, and (c) a QCM frequency response that decreases according to a simple exponential function of the tethered molecules' radius of gyration.