Journal of Chromatography A, 1077 (2005) 170–180 Characterisation of proanthocyanidin aglycones and glycosides from rose hips by high-performance liquid chromatography–mass spectrometry, and their rapid quantification together with Vitamin C Juha-Pekka Salminen a,∗ , Maarit Karonen a , Ky ¨ osti Lempa b , Jaana Liimatainen a , Jari Sinkkonen a , Marjo Lukkarinen c , Kalevi Pihlaja a a Laboratory of Organic Chemistry and Chemical Biology, Department of Chemistry, University of Turku, FI-20014 Turku, Vatselankatu 2, Finland b Department of Applied Biology, University of Helsinki, FI-00014 Helsinki, Finland c Laboratory of Material Chemistry and Chemical Analysis, Department of Chemistry, University of Turku, FI-20014 Turku, Finland Received 2 February 2005; received in revised form 22 April 2005; accepted 26 April 2005 Abstract Fifteen individual proanthocyanidin aglycones and 19 glycosides, together with a complex mixture of chromatographically non-separated tetra- to octameric proanthocyanidin glycosides were detected—the non-separated glycosides being novel natural products—and characterised from dog rose hips using high-performance liquid chromatography–electrospray ionisation mass spectrometry (HPLC–ESI-MS). Along with these phenolics, a 50% aqueous ethanol extract of rose hips was found to contain high levels of Vitamin C. A simple and rapid HPLC method assisted by diode array detection for the estimation of the total concentration of proanthocyanidin aglycones and glycosides, as well as Vitamin C, in rose hip extracts was developed. © 2005 Elsevier B.V. All rights reserved. Keywords: Rose hips; Proanthocyanidins; Proanthocyanidin glycosides; Vitamin C; HPLC; ESI-MS; Rapid quantitative analysis 1. Introduction There is an increasing global interest towards develop- ing so-called functional foods or finding food additives that would be able to protect human body from diseases caused by, e.g., oxidative stress in human cells. A large number of plant derived antioxidant compounds have already been iden- tified, and the most important ones are Vitamin C, Vitamin E, several phenolic compounds and carotenoids [1–3]. How- ever, a single compound or group of compounds may not restrict the oxidative damage in a sufficient extent. Rather, a number of dietary compounds with variable antioxidative effects guarantee the best prevention against an antioxidative related disease [2]. In addition to the known antioxidants, and to widen the scope of their effects, we would need to find ∗ Corresponding author. Tel.: +358 2 333 6828; fax: +358 2 333 6700. E-mail address: j-p.salminen@utu.fi (J.-P. Salminen). a group of compounds that would be novel in its structure, highly abundant in a plant part or plant species, and possess a high antioxidant activity. Fruits of roses (Rosa L.), i.e., rose hips, are a multiple source of antioxidants, as they are rich in vitamins C and E, carotenoids and phenolic compounds such as flavonoid gly- cosides and proanthocyanidin aglycones [4–8]. Maybe for these reasons rose hips have been used, e.g., as a food source [9] and as medicine in ethnopharmacology [4,10]. In our pre- liminary high-performance liquid chromatographic (HPLC) analyses of hips of three dog rose species, i.e., Rosa dumalis, R. mollis and R. sherardii, we found high levels of unusual, very rarely reported, and even novel proanthocyanidin glyco- sides in all three species. Therefore, in this paper, we report the characterisation of these glycosides and also aglycones of proanthocyanidins (PAs, condensed tannins), from dog rose hip extracts using HPLC connected to electrospray ionisa- tion mass spectrometer (ESI-MS). Also a simple and rapid 0021-9673/$ – see front matter © 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.chroma.2005.04.073