Abstract
Phytochemical investigations of Cotinus coggygria Scop. wood, a medicinal and tinctorial plant used since antiquity, resulted in the
isolation and structure elucidation of the novel C-3/C-3′′ dimer of butin (3′,4′,7-trihydroxyflavanone)
and other known compounds: gallic acid and its methyl ester; catechin; profisetinidins:
fisetinidol-(4α →8)-(+)-catechin and epifisetinidol-(4β →8)-(+)-catechin; flavanonols: fustin and dihydroquercetagetin; flavanones: butin
and eriodictyol; flavonols: fisetin and quercetin; the chalcone butein and the aurone
sulfuretin. The isolated compounds were used for the development and validation of
a HPLC-method which enables the determination of these bioactive substances in C. coggygria extracts. Separation was possible on an ether-linked phenyl column material, using
as mobile phase mixtures of water, methanol, and acetonitrile with 0.02 % trifluoroacetic
acid. Sensitivity, selectivity, linearity, precision, accuracy, and repeatability
of the method were verified and assured suitability for its intended use. LC‐MS experiments
performed in positive and negative electrospray ionization mode confirmed the identity
of analytes and allowed unambiguous assignment of all peaks of interest. The analysis
of different C. coggygria samples revealed that sulfuretin (0.38–0.69 %) and fustin (0.33–0.59 %) dominated,
followed by dihydroquercetagetin (0.12–0.35 %), a rare flavanonol derivative with
a 5,6,7-trihydroxysubstituted A-ring. The new natural compound C-3/C-3′′ flavanone
dimer occurred in concentrations of 0.03–0.06 %; the two latter compounds could represent
valuable markers for the identification and quality control of C. coggygria wood.
Key words
Cotinus coggygria
- Anacardiaceae - HPLC‐DAD - LC‐MS - validation - biflavonoids
References
1 Mohan G. The atlas of medicinal plants from Romania. Bucharest; Corint 2001: 70-71
2 Huang K C. The Pharmacology of Chinese herbs, 2nd edition. Boca Raton; CRC Press
1999: 193-194
3
Westenburg H E, Kon-Joo L, Sang Kook L, Fong H H S, van Breemen R B, Pezzuto J M,
Kinghorn A D.
Activity-guided isolation of antioxidative constituents of Cotinus coggygria .
J Nat Prod.
2000;
63
1696-1698
4
Novakovic M, Vuckovic I, Janackovic P, Sokovic M, Filipovic A, Tesevic V, Milosavljevic S.
Chemical composition, antibacterial and antifungal activity of the essential oils
of Cotinus coggygria from Serbia.
J Serb Chem Soc.
2007;
72
1045-1051
5 Hegnauer R. Anacardiaceae. Chemotaxonomie der Pflanzen, Vol. 3. Basel, Stuttgart;
Birkhäuser Verlag 1964: 90-114
6
Valianou L, Stathopoulou K, Karapanagiotis I, Magiatis P, Pavlidou E, Skaltsounis A-L,
Chryssoulakis Y.
Phytochemical analysis of young fustic (Cotinus coggygria heartwood) and identification of isolated colourants in historical textiles.
Anal Bioanal Chem.
2009;
394
871-882
7
Choi J, Yoon B-J, Han Y N, Lee K-T, Ha J, Jung H-J, Park H-J.
Antirheumatoid arthritis effect of Rhus verniciflua and of the active component, sulfuretin.
Planta Med.
2003;
69
899-904
8
Choi J, Yoon B-J, Han Y N, Lee S K, Lee K-T, Park H-J.
Sulfuretin, an antinociceptive and anti-inflammatory flavonoid from Rhus verniciflua .
Nat Prod Sci.
2003;
9
97-101
9
Bezruk P I, Lyubetskaya Z A.
Antiphlogistic properties of the total flavonoids extracted from Cotinus coggygria leaves.
Pharmacol Toxicol.
1969;
32
596-598
10 Domokos J, Varga B, Verzar Petri G, Marczal G, Bakos P, Szöke E. Mouthwash containing
Cotinus coggygria Scop. extract as an active ingredient. HU Patent 29847. 1984
11 Seiberg M, Stone V I, Zhao R. Compositions containing Cotinus coggygria extract and use thereof on skin and mucosal tissues. US Patent 2006088608. 2006
12 Seiberg M, Stone V I, Zhao R. Bruning E. Compositions containing Cotinus coggygria extract and use thereof in treating hemorrhoids. US Patent 20070104806. 2007
13
Karapanagiotis I, Lakka A, Valianou L, Chryssoulakis Y.
High-performance liquid chromatographic determination of colouring matters in historical
garments from the Holy Mountain of Athos.
Microchim Acta.
2008;
160
477-483
14
Shoyama Y, Yamada Y, Nishioka I, Matsunaka H.
Depigmentation and inhibition of cell growth of B-16 melanoma cells by compounds isolated
from Paeonia suffruticosa callus.
Plant Cell Rep.
1990;
8
711-713
15
Nahrstedt A, Proksch P, Conn E E.
Dhurrin, (−)-catechin, flavonol glycosides and flavones from Chamaebatia foliolosa .
Phytochemistry.
1987;
26
1546
16
Lee J C, Lim K T, Jang Y S.
Identification of Rhus verniciflua Stokes compounds that exhibit free radical scavenging and anti-apoptotic properties.
Biochim Biophys Acta.
2002;
1570
181-191
17
Piccinelli A L, De Simone F, Passi S, Rastrelli L.
Phenolic constituents and antioxidant activity of Wendita calysina leaves (Burrito), a folk Paraguayan tea.
J Agric Food Chem.
2004;
52
5863-5868
18
Tian G, Zhang U, Zhang T, Yang F, Ito Y.
Separation of flavonoids from the seeds of Vernonia anthelmintica Willd. by high-speed counter-current chromatography.
J Chromatogr A.
2004;
1049
219-222
19
Awad H M, Boersma M G, Boeren S, van Bladeren P J, Vervoort J, Rietjens I M.
Structure-activity study on the quinone/quinone methide chemistry of flavonoids.
Chem Res Toxicol.
2001;
14
398-408
20
Moreira F P M, Voutinho V, Montanher A B P, Caro M S B, Brighente I M C, Pizzolatti M G,
Delle Monache F.
Flavonoids and triterpenes from Baccharis pseudotenuifolia – bioactivity on Artemia salina .
Quim Nova.
2003;
26
309-311
21
Jung M J, Chung H Y, Kang S S, Choi J H, Sun Bae K S, Choi J S.
Antioxidant activity from the stem bark of Albizzia julibrissin .
Arch Pharm Res.
2003;
26
458-462
22
Steynberg J P, Burger J F W, Malan J C S, Cronje A, Young D A, Ferreira D.
Natural (−)-fisetinidol-(4, 8)-(−)-epicatechin profisetinidins.
Phytochemistry.
1990;
29
275-277
23
Steynberg P J, Steynberg J P, Brandt E V, Ferreira D, Hemingway W.
Oligomeric flavanoids. Part 26. Structure and synthesis of the first profisetinidins
with epifisetinidol constituent units.
J Chem Soc [Perkin I].
1997;
1
1943-1950
24 Agrawal P K, Thakur R S, Bansal M C.
Flavonoids. Agrawal PK C-13 NMR of flavonoids. Amsterdam; Elsevier 1989: 95-182
25
Araya-Maturana R, Delgado-Castro T, Cardona W, Weiss-Lopez B E.
Use of long-range CH (n
J
C,H n > 3) heteronuclear multiple bond connectivity in the assignment of the 13C NMR
spectra of complex organic molecules.
Curr Org Chem.
2001;
5
253-263
26
Whelana T J, Gray M J, Slonecker P J, Shalliker R A, Wilson M A.
Study of the selectivity of reversed-phase columns for the separation of polycarboxylic
acids and polyphenol compounds.
J Chromatogr A.
2005;
1097
148-156
27
Karasova G, Kowalska S, Lehotay J, Buszewski B.
Mobile-phase pH influence on the retention of some benzoic acid derivatives in reversed-phase
chromatography.
J Sep Sci.
2006;
29
1074-1081
28 ICH .Harmonized tripartite guideline. Validation of analytical procedures: text
and methodology Q2 (R1). http://www.ich.org/LOB/media/MEDIA417.pdf Accessed November 3, 2009
29
Roux D G, Evelyn S R.
Condensed tannins. 4. The distribution and deposition of tannins in the heartwoods
of Acacia mollissima and Schinopsis spp.
Biochem J.
1960;
76
17-23
30
Bais H P, Walker T S, Stermitz F R, Hufbauer R A, Vivanco J M.
Enantiomeric-dependent phytotoxic and antimicrobial activity of (±)-catechin. A rhizosecreted
racemic mixture from spotted knapweed.
Plant Physiol.
2002;
128
1173-1179
31 Stevens P F. Summary of Apomorphies in/APweb/. http://www.mobot.org/MOBOT/research/APweb/ Accessed June 10, 2009
Dr. Diana S. Antal
Department of Pharmaceutical Botany Faculty of Pharmacy University of Medicine and Pharmacy of Timisoara
Piata Eftimie Murgu 2
300041 Timisoara
Romania
Phone: + 40 2 56 49 46 04
Fax: + 40 2 56 22 04 79
Email: diana.antal@umft.ro