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The large chemical shift range of 129Xe is the basis of many of the captivating studies described in the various chapters of this book. The only other stable noble gas isotope with nuclear spin I=1/2, 3He, lacks any appreciable chemical shift range. Beyond spin I=1/2, there are two stable noble gas isotopes, 83Kr (I=9/2) and 131Xe (I=3/2), that occur at sufficiently high natural abundance for practical applications. Unfortunately the usable chemical shift ranges associated with these isotopes are inferior to that of 129Xe. However, spin I>1/2 isotopes have a nuclear electric quadrupole moment that enables a host of supplementary magnetic resonance studies. The spin I>1/2 noble gas isotopes can all be hyperpolarized but their ‘quadrupolar’ relaxation times are fairly short causing rapid depolarization compared to hp 129Xe. This chapter reviews how this apparent disadvantage can be turned into a useful probe for surfaces in material sciences and biomedical research. This unique probe can ‘sense’ surfaces at far lower surface to volume ratios (S/V) than the 129Xe chemical shift. The underlying physical concept will be illustrated in the first part of the chapter using the ‘simpler’ I=3/2 isotope 131Xe that has 4 Zeeman energy levels rather than the 10 levels of 83Kr. The second part will focus on 83Kr, which strikes the best balance between achievable signal intensity and utility for novel, surface indicative MRI contrast.

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