Ultra high throughput sampling and analysis systems and methods

A method of sampling a plurality of different compounds into a microfluidic channel, comprising:

• providing a sample substrate having at least a first surface, the substrate comprising a plurality of different compounds immobilized in a gridded array of one or more rows of different compounds, the different compounds being substantially uniformly spaced within the one or more rows whereby each compound is in a separate discrete region of the first surface of the substrate, the plurality of different compounds being present at a density of a least about 10 different compounds/cm2 of substrate surface;
• determining an approximate location of a plurality of the different compounds in the separate discrete regions of the first surface of the substrate which comprises locating at least first and second compound locations on the first surface of the substrate and interpolating an approximate location for substantially all of the different compounds between the first and second compound locations;
• separately solubilizing a first compound on the surface;
• drawing a portion of the solubilized first compound into a microfluidic channel disposed in a capillary element;
• and
• repeating the solubilizing and drawing steps with at least a second compound on the first surface of the substrate.