Resolution of small molecules by passage through an open capillary

When a solute passes through an open capillary, in which a laminar flow is established, different peak profiles can be obtained according to its diffusion property under a working condition, i.e., the radius and length of the capillary and the flow rate of the carrier solution. If a solute diffuses over the entire cross section of the capillary before it is eluted, a Gaussian-shaped diffusion peak appears, which has an apex at the travel time of the average flow. Insufficient solute diffusion, which is realized, e.g., by increasing flow rates or capillary radius, produces a new peak having an apex at the travel time of the maximum flow. This implies that two solutes can be resolved simply by passing through a capillary. However, our previous study indicated that the diffusion coefficients of two solutes should be at least one order different for their resolution based on this principle, suggesting that its applicability is highly restricted. In the present paper, this concept has been extended to the resolution between dissolved solutes that have similar intrinsic diffusion properties. The incorporation of molecular aggregates in the carrier makes a solute less diffusive according to the extent of their interaction and allows the resolution of a dissolved molecule from other ones differing in the affinity to the molecular aggregates. Several examples of peak resolution for phenols, aromatic hydrocarbons, and inorganic anions are shown and discussed on the basis of the modification of the diffusion natures due to their interactions with micelles or vesicles.