Fluorescent Imprinted Nanoparticles for Sensing of Chlorogenic Acid in Coffee Extracts.

Green coffee beans are particularly rich in chlorogenic acids (CGAs), and their identification and quantification are usually performed by HPLC, coupled with mass spectrometry (LC-MS). Although there are a few examples of molecularly imprinted polymers (MIPs) for chlorogenic acid (5-CQA) recognition present in the literature, none of them are based on optical fluorescence, which is very interesting given its great sensitivity. In the present manuscript, fluorescent polymeric imprinted nanoparticles were synthetized following the non-covalent approach using hydrogenated 5-O-caffeoylquinic acid (H-5-CQA) as the template. The capability of the polymer to bind 5-CQA was evaluated by HPLC and fluorescence. A real sample of coffee extract was also analyzed to verify the selectivity of the polymer. Polymer fMIP01, containing 4-vinylpyridine and a naphtalimide derivative as monomers, showed a good response to the fluorescence quenching in the range 39 µM-80 mM. In the real sample, fMIP01 was able to selectively bind 5-CQA, while caffeine was not recognized. To demonstrate this, there is a promising system that can be exploited in the design of an optical sensor for 5-CQA detection. Polymer fMIP01 was immobilized by physical entrapment on a functionalized glass surface, showing a quenching of fluorescence with an increase of the CGA concentration between 156 µM and 40 mM.

Distribution of p-coumaroylquinic acids in commercial Coffea spp. of different geographical origin and in other wild coffee species.

Quantitative analyses of mono-p-coumaroylquinic acids (pCoQAs) and total chlorogenic acids (CGAs) in green coffee commercial lots of C. arabica, C. canephora and C. liberica from different geographical origins and eight wild Coffea species were carried out. Among the commercial lots, pCoQAs average content of C. arabica (0.67 mg/g) is higher than that of C. canephora (0.40 mg/g) being C. liberica intermediate (0.58 mg/g). As far as the analyzed wild Coffea species is concerned, C. pseudozanguebariae is characterized by the lower pCoQAs content (0.12 mg/g) whereas C. sessiliflora is by far the richest source of pCoQAs (2.18 mg/g). Effect of the roasting process on the mono-p-coumaroylquinic acids profile was evaluated for the economically exploited species C. arabica and C. canephora. For the first time distribution of mono-p-coumaroylquinic acid isomers in wild coffee species by fast and accurate UHPLC-DAD analyses using authentic standards previously synthetized, is reported.

Aqueous extracts of walnut (Juglans regia L.) leaves: quantitative analyses of hydroxycinnamic and chlorogenic acids.

Identification of both hydroxycinnamic and chlorogenic acids present in aqueous extracts of walnut leaves (Juglans regia L.) were carried out by using, for the first time, standard compounds not commercially available for qualitative identification. In particular, in addition to caffeic, ferulic, p-coumaric and sinapic acids, cis and trans mono-caffeoylquinic, dicaffeoylquinic, mono-feruloylquinic and cis and trans mono-p-coumaroylquinic acid isomers were detected and quantified by Ultra High Pressure Liquid Chromatography and the seasonal variations of these secondary metabolites were investigated.