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In response to the need from the food industry for new analytical solutions, a fit-for-purpose quantitative 1H NMR methodology was developed to authenticate pure coffee (100% arabica or robusta) as well as predict the percentage of robusta in blends through the study of 292 roasted coffee samples in triplicate. Methanol was chosen as the extraction solvent, which led to the quantitation of 12 coffee constituents caffeine, trigonelline, 3- and 5-caffeoylquinic acid, lipids, cafestol, nicotinic acid, N-methylpyridinium, formic acid, acet