Abstract: Vials for reducing the volume of sample that must be contained within the vial when interfacing with a variety of analytical instruments are provided herein, and particularly, for use in analytical instruments that interact with a sample via a “polar” or asymmetric probe, including in capillary electrophoresis, liquid chromatography, and gas chromatography, by way of non-limiting example. In accordance with various aspects of the present teachings, the vials can reduce the waste of expensive and/or scarce samples common in the round vials and vial inserts conventionally used in the art.