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Planta Med
DOI: 10.1055/a-2486-9139
Original Papers

New Constituents from Zanthoxylum rhoifolium

Mauro Di Stasi
1   Dipartimento di Farmacia, Università di Pisa, Pisa, Italy
,
Valentina Parisi
2   Dipartimento di Farmacia, Università degli Studi Salerno, Fisciano (SA), Italy
,
Vanessa Hernandez
3   Departamento de Farmacognosia y Medicamentos Organicos, Universidad de los Andes, Merida, Venezuela
,
Erica Gazzillo
2   Dipartimento di Farmacia, Università degli Studi Salerno, Fisciano (SA), Italy
,
Maria Giovanna Chini
4   Dipartimento di Bioscienze e Territorio, Università degli Studi del Molise, Pesche (IS), Italy
,
Giuseppe Bifulco
2   Dipartimento di Farmacia, Università degli Studi Salerno, Fisciano (SA), Italy
,
Alessandra Braca 
1   Dipartimento di Farmacia, Università di Pisa, Pisa, Italy
,
Giuliana Donadio
2   Dipartimento di Farmacia, Università degli Studi Salerno, Fisciano (SA), Italy
,
Nunziatina De Tommasi 
2   Dipartimento di Farmacia, Università degli Studi Salerno, Fisciano (SA), Italy
› Author AffiliationsThis research was funded by the Ministero dellʼUniversità e della Ricerca (MUR)–PRIN2022-PNRR project, “P2022CKMPW, TACSI Driver: a multitasks platform to guide the Target identification, Assessment of the binding, Collection of natural products from waste, Synthesis of derivatives, and in vitro/in vivo polypharmacological profile evaluation of bioactive compounds”.
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Abstract

The phytochemical study of Zanthoxylum rhoifolium apolar and medium polarity stem bark and leaf extracts afforded 29 compounds, including three new sesquiterpenes (1 – 3) and one new α-ionone glycoside (4). All compounds were characterized by means of 1D and 2D NMR and HRESIMS data. Furthermore, a precise structural analysis was performed, employing a combined density functional theory (DFT)/NMR approach to elucidate the compounds configurations. The crude extracts were then tested against a panel of gram-positive and gram-negative bacteria by broth dilution methods to determine their minimal inhibitory concentration. In these experimental conditions, no interesting antimicrobial activity was observed.

Keywords

Zanthoxylum rhoifolium - Rutaceae - sesquiterpenes - α-ionone - DFT/NMR - antibacterial

Supporting Information

    NMR and HRESIMS spectra of compounds 1 – 4 and computed and experimental chemical shifts and MAE for each stereoisomer of compounds 1, 2, and 4 are available as Supporting Information.

  • Supporting Information


Publication History

Received: 27 June 2024

Accepted after revision: 25 November 2024

Accepted Manuscript online:
25 November 2024

Article published online:
13 January 2025

© 2024. Thieme. All rights reserved.

Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany

 

  • References

  • 1 Appelhans MS, Reichelt N, Groppo M, Paetzold C, Wen J. Phylogeny and biogeography of the pantropical genus Zanthoxylum and its closest relatives in the proto-Rutaceae group (Rutaceae). Mol Phylogenet Evol 2014; 126: 31-44
    CrossrefPubMedSearch in Google Scholar
  • 2 Cruz GL. Dicionário de plantas úteis do Brasil, 5th Ed. Rio de Janeiro: Civilização Brasileira 1995.
    PubMed
  • 3 Bertani S, Bourdy G, Landau I, Robinson JC, Esterre P, Deharo E. Evaluation of French Guiana traditional antimalarial remedies. J Ethnopharmacol 2005; 98: 45-54
    CrossrefPubMedSearch in Google Scholar
  • 4 De Lucca M, Zalles J. Flora Medicinal Boliviana. La Paz: Los Amigos del Libro Editions; 1992: 498
    Search in Google Scholar
  • 5 Grenand P, Moretti C, Jacquemin H, Prévost MF. Pharmacopées Traditionnelles en Guyane. Créoles, Palikur, Wayãpi. Paris: IRD Editions; 2004: 816
    CrossrefSearch in Google Scholar
  • 6 Jullian V, Bourdy G, Georges S, Maurel S, Sauvain M. Validation of use of a traditional antimalarial remedy from French Guiana, Zanthoxylum rhoifolium Lam. J Ethnopharmacol 2006; 106: 348-352
    CrossrefPubMedSearch in Google Scholar
  • 7 Pereira SS, Lopes LS, Marques RB, Figueiredo KA, Costa DA, Chaves MH, Almeida FR. Antinociceptive effect of Zanthoxylum rhoifolium Lam. (Rutaceae) in models of acute pain in rodents. J Ethnopharmacol 2010; 129: 227-231
    CrossrefPubMedSearch in Google Scholar
  • 8 Freitas FF, Fernandes HB, Piauilino CA, Pereira SS, Carvalho KI, Chaves MH, Soares PM, Miura LM, Leite JR, Oliveira RC, Oliveira FA. Gastroprotective activity of Zanthoxylum rhoifolium Lam. in animal models. J Ethnopharmacol 2011; 137: 700-708
    CrossrefPubMedSearch in Google Scholar
  • 9 de Abreu Gonzaga W, Weber AD, Giacomelli SR, Simionatto E, Dalcol II, Machado Dessoy EC, Morel AF. Composition and antibacterial activity of the essential oils from Zanthoxylum rhoifolium . Planta Med 2003; 69: 773-775
    Thieme ConnectPubMedSearch in Google Scholar
  • 10 Carotenuto G, Carrieri R, Tarantino P, Alfieri M, Leone A, De Tommasi N, Lahoz E. Fungistatic activity of Zanthoxylum rhoifolium Lam. bark extracts against fungal plant pathogens and investigation on mechanism of action in Botrytis cinerea . Nat Prod Res 2015; 29: 2251-2255
    CrossrefPubMedSearch in Google Scholar
  • 11 de Moura NF, Ribeiro HB, Machado ECS, Ethur EM, Zanatta N, Morel A. Benzophenanthridine alkaloids from Zanthoxylum rhoifolium . Phytochemistry 1997; 46: 1443-1446
    CrossrefPubMedSearch in Google Scholar
  • 12 de Abreu Gonzaga W, Weber AD, Giacomelli SR, Dalcol II, Hoelzel SC, Morel AF. Antibacterial alkaloids from Zanthoxylum rhoifolium . Planta Med 2003; 69: 371-374
    Thieme ConnectPubMedSearch in Google Scholar
  • 13 Arruda MSP, Fernandes JB, Vieira PC, Silva MFGF, Pirani JR. Chemistry of Zanthoxylum rhoifolium: A new secofuroquinoline alkaloid. Biochem Syst Ecol 1992; 20: 173178
    PubMedSearch in Google Scholar
  • 14 Di Stasi M, Donadio G, Bader A, De Leo M, Braca A. Two new triterpenes from Commicarpus grandiflorus (A. Rich.) Standl. aerial parts exudate. Nat Prod Res 2023; 37: 3228-3236
    CrossrefPubMedSearch in Google Scholar
  • 15 Donadio G, Chini MG, Parisi V, Mensitieri F, Malafronte N, Bifulco G, Bisio A, De Tommasi N, Bader A. Diterpenoid constituents of Psiadia punctulata and evaluation of their antimicrobial activity. J Nat Prod 2022; 85: 1667-1680
    CrossrefPubMedSearch in Google Scholar
  • 16 Caliş I, Kuruüzüm-Uz A, Lorenzetto PA, Rüedi P. (6S)-Hydroxy-3-oxo-alpha-ionol glucosides from Capparis spinosa fruits. Phytochemistry 2002; 59: 451-457
    CrossrefPubMedSearch in Google Scholar
  • 17 Pabst A, Barron D, Sémon E, Schreier P. Two diastereomeric 3-oxo-α-ionol β-d-glucosides from raspberry fruit. Phytochemistry 1992; 31: 1649-1652
    CrossrefPubMedSearch in Google Scholar
  • 18 Morikawa H, Kasai R, Otsuka H, Hirata E, Shinzato T, Aramoto M, Takeda Y. Terpenic and phenolic glycosides from leaves of Breynia officinalis HEMSL. Chem Pharm Bull 2004; 52: 1086-1090
    CrossrefPubMedSearch in Google Scholar
  • 19 Miyase T, Ueno A, Takizawa N, Kobayashi H, Oguchi H. Studies on the glycosides of Epimedium grandiflorum Morr. var. thunbergianum (Miq.) Nakai. Chem Pharm Bull 1988; 36: 2475-2484
    CrossrefPubMedSearch in Google Scholar
  • 20 Xu XH, Tan CH, Jiang SH, Zhu DY. Debilosides A–C: Three new megastigmane glucosides from Equisetum debile . Helv Chim Acta 2006; 89: 1422-1426
    CrossrefPubMedSearch in Google Scholar
  • 21 Reed MW, Moore HW. Efficient synthesis of furochromone and furocoumarin natural products (khellin, pimpinellin, isophellopterin) by thermal rearrangement of 4-furyl-4-hydroxycyclobutenones. J Org Chem 1988; 53: 4166-4171
    CrossrefPubMedSearch in Google Scholar
  • 22 Zdero C, Bohlmann F, King RM, Robinson H. Diterpene glycosides and other constituents from Argentinian Baccharis species. Phytochemistry 1986; 25: 2841-2855
    CrossrefPubMedSearch in Google Scholar
  • 23 Chen IS, Lin YC, Tsai IL, Teng CM, Ko FN, Ishikawa T, Ishii H. Coumarins and anti-platelet aggregation constituents from Zanthoxylum schinifolium . Phytochemistry 1995; 39: 1091-1097
    CrossrefPubMedSearch in Google Scholar
  • 24 Sarker SD, Armstrong JA, Waterman PG. (−)-1, 12-oxagual-10 (15)-ene: A sesquiterpene from Eriostemon fitzgeraldii . Phytochemistry 1995; 40: 1159-1162
    CrossrefPubMedSearch in Google Scholar
  • 25 Raharivelomanana P, Bianchini JP, Faure R, Cambon A, Azzaro M. Two guaiane and eudesmane-type sesquiterpenoids from Neocallitropsis pancheri . Phytochemistry 1996; 41: 243-246
    CrossrefPubMedSearch in Google Scholar
  • 26 Zdero C, Bohlmann F, Niemeyer HM. Isocedrene and guaiane derivatives from Pleocarphus revolutus . J Nat Prod 1988; 51: 509-512
    CrossrefPubMedSearch in Google Scholar
  • 27 Ohmoto T, Ikeda K, Nomura S, Shimizu M, Saito S. Studies on the sesquiterpenes from Ambrosia elatior Linne. Chem Pharm Bull 1987; 35: 2272-2279
    CrossrefPubMedSearch in Google Scholar
  • 28 Iwabuchi H, Yoshikura M, Ikawa Y, Kamisako W. Studies on the sesquiterpenoids of Panax ginseng C.A. Meyer. Isolation and structure determination of sesquiterpene alcohols, panasinsanols A and B. Chem Pharm Bull 1987; 35: 1975-1981
    CrossrefPubMedSearch in Google Scholar
  • 29 Pereira MDP, da Silva T, Lopes LMX, Krettli AU, Madureira LS, Zukerman-Schpector J. 4, 5-seco-guaiane and a nine-membered sesquiterpene lactone from Holostylis reniformis . Molecules 2012; 17: 14046-14057
    CrossrefPubMedSearch in Google Scholar
  • 30 Heymann H, Tezuka Y, Kikuchi T, Supriyatna S. Constituents of Sindora sumatrana Miq. I. Isolation and NMR spectral analysis of sesquiterpenes from the dried pods. Chem Pharm Bull 1994; 42: 138-146
    CrossrefPubMedSearch in Google Scholar
  • 31 Minnaard AJ, Wijnberg JB, de Groot A. The synthesis of (+)-hedycaryol, starting from natural (−)-guaiol. Tetrahedron 1994; 50: 4755-4764
    CrossrefPubMedSearch in Google Scholar
  • 32 Xiong J, Wang LJ, Qian J, Wang PP, Wang XJ, Ma GL, Zeng H, Li J, Hu JF. Structurally diverse sesquiterpenoids from the endangered ornamental plant Michelia shiluensis . J Nat Prod 2018; 81: 2195-2204
    CrossrefPubMedSearch in Google Scholar
  • 33 Mathela CS, Melkani AB, Pant A, Dev V, Nelson TE, Hope H, Bottini AT. A eudesmanediol from Cymbopogon distans . Phytochemistry 1989; 28: 936-938
    CrossrefPubMedSearch in Google Scholar
  • 34 Tissandié L, Gaysinski M, Brévard H, Meierhenrich UJ, Filippi JJ. Revisiting the chemistry of guaiacwood oil: Identification and formation pathways of 5, 11- and 10, 11-epoxyguaianes. J Nat Prod 2017; 80: 526-537
    CrossrefPubMedSearch in Google Scholar
  • 35 Pelter A, Ward RS, Rao EV, Sastry KV. Revised structures for pluviatilol, methyl pluviatilol and xanthoxylol: General methods for the assignment of stereochemistry to 2, 6-diaryl-3, 7-dioxabicyclo [3.3. 0] octane lignans. Tetrahedron 1976; 32: 2783-2788
    CrossrefPubMedSearch in Google Scholar
  • 36 Yang CH, Cheng MJ, Lee SJ, Yang CW, Chang HS, Chen IS. Secondary metabolites and cytotoxic activities from the stem bark of Zanthoxylum nitidum . Chem Biodivers 2009; 6: 846-857
    CrossrefPubMedSearch in Google Scholar
  • 37 Achenbach H, Benirschke M, Torrenegra R. Alkaloids and other compounds from seeds of Tabernaemontana cymosa . Phytochemistry 1997; 45: 325-335
    CrossrefPubMedSearch in Google Scholar
  • 38 Boudermine S, Parisi V, Lemoui R, Boudiar T, Chini MG, Franceschelli S, Pecoraro M, Pascale M, Bifulco G, Braca A, De Tommasi N, De Leo M. Cytotoxic sesquiterpenoids from Ammoides atlantica aerial parts. J Nat Prod 2022; 85: 647-656
    CrossrefPubMedSearch in Google Scholar
  • 39 Lauro G, Bifulco G. Elucidating the relative and absolute configuration of organic compounds by quantum mechanical approaches. European J Org Chem 2020; 2020: 3929-3941
    CrossrefPubMedSearch in Google Scholar
  • 40 Grimblat N, Zanardi MM, Sarotti AM. Agar and broth dilution methods to determine the minimal inhibitory concentration (MIC) of antimicrobial substances. Nat Protoc 2008; 3: 163-175
    CrossrefPubMedSearch in Google Scholar
  • 41 Wiegand I, Hilpert K, Hancock REW. Agar and broth dilution methods to determine the minimal inhibitory concentration (MIC) of antimicrobial substances. Nat Protoc 2008; 3: 163-175
    CrossrefPubMedSearch in Google Scholar
  • 42 Watts KS, Dalal P, Tebben AJ, Cheney DL, Shelley JC. Macrocycle conformational sampling with MacroModel. J Chem Inf Model 2014; 54: 2680-2696
    CrossrefPubMedSearch in Google Scholar
  • 43 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery jr. JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09, Revision A.02 (2009). Wallingford CT: Gaussian, Inc.; 2009
    Search in Google Scholar
  • 44 Tomasi J, Mennucci B, Cammi R. Quantum mechanical continuum solvation models. Chem Rev 2005; 105: 2999-3094
    CrossrefPubMedSearch in Google Scholar
  • 45 Sarotti AM, Pellegrinet SC. Application of the multi-standard methodology for calculating 1H NMR chemical shifts. J Org Chem 2012; 77: 6059-6065
    CrossrefPubMedSearch in Google Scholar