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A 13C NMR in DMSO-d6 as solvent, diffuse reflectance spectra and X-ray powder diagram study of the inclusion of vitamin D in β-cyclodextrin and of the ternary assemblies with β-cyclodextrin, vitamin D and metal ions (e.g. Co(II), Cu(II) and Zn(II)) was carried out to determine the structure of these associations in which the molecular ratios (β-cyclodextrin:vitamin D:metal ions) were 5:1:1 or 10:1:1.