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Mass spectrometry is a powerful and ubiquitous technique used to identify and quantify molecules via a measurement of the mass-to-charge ratio of ionized molecules and molecular fragments.  In biological applications, mass spectrometry is used to characterise a wide variety of biomolecules, including sugars, proteins, and oligonucleotides; for example, sequencing of proteins and peptides and identification of post-translational modifications.  While methods such as ion mobility spectrometry and H/D exchange techniques have been implemented in order to obtain additional structural information from mass spectra, none yield direct information on atomic connectivity within the structure.  We have recently developed a new technique known as Coulomb-explosion covariance-map imaging, a variation on the velocity-map imaging method employed widely within the field of chemical reaction dynamics.  While so far only applied to small molecules, our new approach provides direct structural information, and even promises the ability to follow structural change on the femtosecond timescale over which chemical change occurs.