Liu Hong-Yu, Xue Bian-Xia, Li Chun, Ou Ze-Min, Wang Zhi-Min, Yi Hong, Liu Xiao-Qian
National Engineering Laboratory of Quality Control Technology of Chinese Materia Medica, Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences Beijing 100700, China.
Zhongguo Zhong Yao Za Zhi. 2024 Aug;49(16):4477-4487. doi: 10.19540/j.cnki.cjcmm.20240509.201.
Aurantii Fructus Immaturus(AFI) is a traditional Chinese herbal medicine with multiple origins from Citrus aurantium and its legally cultivated variants. With advancements in agricultural biotechnology, many new cultivated varieties have sprung up,leading to an abundance of AFI adulterants and chaos in the herbal medicine markets. This study developed a specific identification method for AFI and its closely related adulterants by examining the appearance trait, content of extract, and multiple ingredients,involving indicators such as the ratio of pulp capsule to cross section diameter(Pc/Cs ratio), the content of extract, and the profile of 11 ingredients. The research finds that:(1) Pc/Cs ratio can conveniently identify adulterants such as Poncirus trifoliata, Ju, and Babagan from the genuine AFI.(2) The extract content can be used to identify adulterants originated from C. wilsonii with C. aurantium.(3) The contents of synephrine in all the samples were in accordance with the Chinese Pharmacopoeia except for the adulterants from P. trifoliata, C. wilsonii, C. aurantium 'Changshanhuyou' and orah mandarins. The synephrine content was high as 1. 40% in some C. sinensis varieties. The mass fraction of hesperidin was over 10. 00% in C. sinensis, while it was below 2. 50% in C. aurantium. C. aurantium contained high levels of naringin(3. 96%-15. 21%) and neo-hesperidin(9. 38%-21. 93%).(4) The compositions of adulterants from P. trifoliata and C. wilsonii were more similar to that of C. aurantium 'Daidai', but with significantly lower neo-hesperidin content(0. 03%-0. 14%) than that in C. aurantium, and they lacked hesperetin and tangeretin. C. maxima(originating from C. maxima) showed closer composition to Choucheng and hybrid originated from Citrus aurantium × Poncirus trifoliata, but had higher hesperidin content(3. 13%) than that in C. aurantium. Ju was closely related to C. sinensis and neither contained naringin nor neo-hesperidin. Hesperidins in Babagan and orah mandarins were similar to that in C. sinensis, with none containing rhoifolin. These quality indicators in combination can accurately distinguish between C. sinensis, C. aurantium, and their closely related adulterants(P. trifoliata, C. wilsonii, C. maxima, orah mandarins and C. reticulata), which are expected to provide a systematic method for quality control of AFI.
枳实是一种传统的中药材，其来源多样，包括酸橙及其合法栽培变种。随着农业生物技术的发展，许多新的栽培品种涌现出来，导致枳实掺假品大量出现，中药材市场混乱。本研究通过考察外观性状、提取物含量和多种成分，建立了一种枳实及其近缘掺假品的特异性鉴别方法，涉及果肉胶囊与横截面直径之比（Pc/Cs比）、提取物含量和11种成分的图谱等指标。研究发现：（1）Pc/Cs比可方便地从正品枳实中鉴别出枳壳、橘和八布柑等掺假品。（2）提取物含量可用于鉴别起源于香橙的掺假品与酸橙。（3）除了来自枳壳、香橙、“常山胡柚”和奥兰多橘的掺假品外，所有样品中的辛弗林含量均符合《中国药典》规定。一些甜橙品种中的辛弗林含量高达1.40%。甜橙中橙皮苷的质量分数超过10.00%，而酸橙中则低于2.50%。酸橙中柚皮苷（3.96%-15.21%）和新橙皮苷（9.38%-21.93%）含量较高。（4）枳壳和香橙的掺假品组成与代代酸橙更为相似，但新橙皮苷含量（0.03%-0.14%）明显低于酸橙，且不含橙皮素和川陈皮素。柚（源自柚）的组成与丑橙和酸橙×枳壳杂交种更为接近，但橙皮苷含量（3.13%）高于酸橙。橘与甜橙关系密切，既不含柚皮苷也不含新橙皮苷。八布柑和奥兰多橘中的橙皮苷与甜橙中的相似，均不含异鼠李素橙皮苷。这些质量指标相结合，可准确区分甜橙、酸橙及其近缘掺假品（枳壳、香橙、柚、奥兰多橘和橘），有望为枳实的质量控制提供一种系统方法。
