Abstract
Six protoalkaloids in the fruits of 34 Chinese local loose-skin mandarins and 25 sweet oranges were detected simultaneously by strong cation exchange-high performance liquid chromatography with an ultraviolet detector (SCX-HPLC-UV). Linear regression analysis showed satisfactory linearity for all the analytes with the correlation coefficients (R2) higher than 0.9998. The satisfactory recoveries of the six protoalkaloids in pulps at two spiked levels ranged from 82.8 to 93.4% (RSDs, 1.5–6.1%) and those of synephrine in peels ranged from 89.3 to 91.9% (RSDs, 4.8–5.3%). The limits of quantification (LOQs) were 0.2 mg kg−1. The proposed method was used to determinate the protoalkaloids in loose-skin mandarins and sweet oranges to evaluate its feasibility and accuracy. The major alkaloid in the tested samples was synephrine, and the predominant alkaloid was N-methyltyramine, followed by octopamine. The variations in alkaloid components and contents were both largely the same for the tested varieties, verifying that alkaloids in plants are genetically controlled.
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References
Andrade AS, Schmitt GC, Rossato LG, Russowsky D, Limberger RP (2009) Gas chromatographic method for analysis of p-synephrine in Citrus aurantium L. products. Chromatographia 69:S225
Avula B, Khan IA (2004) Separation and determination of ephedrine enantiomers and synephrine by high performance capillary electrophoresis in dietary supplements. Chromatographia 59:71
Bader M, Lang T, Lang R, Hofmann T (2017) Synephrine as a specific marker for orange consumption. J Agric Food Chem 65(23):4853–4858
Chen G, Zhang LY, Zhao JQ (2002) Determination of hesperidin and synephrine in Pericarpium Citri Reticulatae by capillary electrophoresis with electrochemical detection. Anal Bioanal Chem 373(3):169–173
Francis PS, Brown AJ, Bellomarino SA, Taylor AM, Slezak T, Barnett NW (2009) Selectivity and potential interference from phenolic compounds in chemiluminescence methods for the determination of synephrine. Luminescence 24:90–95
Fugh-Berman A, Myers A (2004) Citrus aurantium, an ingredient of dietary supplements marketed for weight loss: current status of clinical and basic research. Exp Biol Med 229:698–704
Gay ML, Niemann RA, Musser SA (2006) An isotopically labeled internal standard liquid chromatography-tandem mass spectrometry method for determination of ephedrine alkaloids and synephrine in dietary supplements. J Agric Food Chem 54:285–291
Hashimoto K, Yasuda T, Ohsawa K (1992) Determination of synephrine from Chinese medicinal drugs originating from citrus species by ion-pair high-performance liquid-chromatography. J Chromatogr 623(2):386–389
Kusu F, Li XD, Takamura K (1992) Determination of synephrine and N-methyltyramine in Citrus aurantium by high-performance liquid chromatography with electrochemical detector. Chem Pharm Bull 40(12):3284–3286
Li XR, Ma ZJ, Lin S, Gu XZ, Mao SJ (2004) Determination of synephrine and N-methyltyramine in Pericarpium Citri Reticulatae viride by HPLC. China J Chin Mater Med 29(6):537
Marchei E, Pichini S, Pacifici R (2006) A rapid and simple procedure for the determination of synephrine in dietary supplements by gas chromatography-mass spectrometry. J Pharm Biomed Anal 41(4):1468–1472
Nelson BC, Putzbach K, Sharpless KE, Sander LC (2007) Mass spectrometric determination of the predominant adrenergic protoalkaloids in bitter orange (Citrus aurantium). J Agric Food Chem 55:9769–9775
Niemann RA, Gay ML (2003) Determination of ephedrine alkaloids and synephrine in dietary supplements by column-switching cation exchange high-performance liquid chromatography with scanning-wavelength ultraviolet and fluorescence detection. J Agric Food Chem 51(19):5630–5638
Pellati F, Benvenuti S, Melegari M (2005) Enantioselective LC (2005) analysis of synephrine in natural products on a protein-based chiral stationary phase. J Pharmaceut Biomed 37:839
Roman MC, Betz JM, Hildreth J (2007) Determination of synephrine in bitter orange raw materials, extracts, and dietary supplements by liquid chromatography with ultraviolet detection: single-laboratory validation. J AOAC Int 90(1):68–81
Sakai Y, Kotani A, Umemura T, Mori Y, Kusu F, Yamamoto K, Hakamata H (2016) Electrochemical determination of synephrine by hydrophilic interaction liquid chromatography using a zwitterionic monolith column. Electroanalysis 28:1947–1950
Santana J, Sharpless KE, Nelson BC (2008) Determination of para-synephrine and meta-synephrine positional isomers in bitter orange-containing dietary supplements by LC/UV and LC/MS/MS. Food Chem 109:675–682
Servillo L, Castaldo D, Giovane A, Casale R, D'Onofrio N, Cautela D, Balestrieri ML (2017) Tyramine pathways in citrus plant defense: glycoconjugates of tyramine and its N-methylated derivatives. J Agric Food Chem 65:892–899
Shawky E (2014) Determination of synephrine and octopamine in bitter orange peel by HPTLC with densitometry. J Chromatogr Sci 52:899–904
Tang F, Tao L, Luo XB, Ding L, Guo ML, Nie LH, Yao SZ (2006) Determination of octopamine, synephrine and tyramine in citrus herbs by ionic liquid improved 'green' chromatography. J Chromatogr A 1125:182–188
Xia DX, Zhao XY, Chen XZ, Tan ZR, Xie WB (1994) Quantitative analysis of synephrine in Zhishi injection by RP-HPLC. China J Chin Mater Med 19(7):419
Yi YN, Cheng XM, Liu LA, Hu GY, Wang ZT, Deng YD, Huang KL, Cai GX, Wang CH (2012) Simultaneous determination of synephrine, arecoline, and norisoboldine in Chinese patent medicine Si-Mo-Tang oral liquid preparation by strong cation exchange high performance liquid chromatography. Pharm Biol 50(7):832–838
Funding
This work was supported financially by China Agriculture Research System (No. CARS-26), Fundamental Research Fund for the Central Universities (No. XDJK2017B034), and National Risk Assessment Program for Agricultural Products Quality and Safety (No. GJFP2018004).
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Yaohai Zhang declares that he has no conflict of interest. Bining Jiao declares that he has no conflict of interest.
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Zhang, Y., Jiao, B. Simultaneous Determination of Six Protoalkaloids in Chinese Local Varieties of Loose-Skin Mandarins and Sweet Oranges by Strong Cation Exchange-High Performance Liquid Chromatography. Food Anal. Methods 12, 677–686 (2019). https://doi.org/10.1007/s12161-018-1401-0
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DOI: https://doi.org/10.1007/s12161-018-1401-0