Isoelectric points of small samples of proteins can now be measured using atomic force microscopy and substrates with a known charge.
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Walker, G. Net charge of trace proteins. Nature Nanotech 11, 739–740 (2016). https://doi.org/10.1038/nnano.2016.143
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DOI: https://doi.org/10.1038/nnano.2016.143