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作为中药治疗失眠的首选药物,酸枣仁已有两千多年的临床使用历史,其道地药材产地在我国华北地区;理枣仁为近现代用药,主要分布在我国西南地区。近年来,由于二者性状特征相近,功效相似,但市场价格差异较大,从而导致理枣仁(甚至枳椇子、染色扁豆)冒充或掺伪酸枣仁的现象较为普遍,在中药材市场及临床应用中较为混乱。
As the first choice of traditional Chinese medicine for the treatment of insomnia, Ziziphi Spinosae Semen (ZSS) has a clinical history of over 2,000 years, and its authentic medicinal materials are produced in the northern region of China. In contrast, Ziziphi Mauritianae Semen (ZMS) is a modern medicine mainly distributed in the southwestern region of China. In recent years, due to the similar morphological characteristics and therapeutic effects of the two herbs, but a significant difference in market prices, it has become increasingly common for ZMS to be fraudulently labeled or adulterated as ZSS, leading to confusion in the Chinese herbal medicine market and clinical applications.
那么,二者究竟有何特点?如何准确区分酸枣仁和理枣仁呢?
What are the characteristics that distinguish ZSS from ZMS, and how can they be accurately distinguished?
酸枣仁 (Ziziphi Spinosae Semen,ZSS)为鼠李科枣属植物酸枣 Z. jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chow的干燥成熟种子,始载于《神农本草经》,位列上品,历代本草皆有收录。其味甘、酸,性平,归肝、胆、心经,具有养心补肝、宁心安神、敛汗、生津之功效。作为中药治疗失眠的首选药物,酸枣仁在治疗失眠相关的药方中使用率高达70%以上。
理枣仁 (Ziziphi Mauritianae Semen,ZMS)为酸枣仁同科同属植物滇刺枣 Z. mauritiana Lam. 的干燥成熟种子,也称“滇枣仁”、“缅枣仁”或“进口酸枣仁”等,为近现代用药,仅在《滇南本草》中有过收录。其味甘、平,归心、肝经,具有宁心安神,除烦敛汗的功效。在云南民间被作为治疗失眠的习用药材使用。
1 Pharmacopoeia Inclusion and Categorization
ZSS, also known as sour jujube seed, is the dried mature seed of the plant Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chow, which belongs to the Rhamnaceae family. It was first recorded in the classic Chinese herbal book "Shennong Bencao Jing" and was listed as a top-grade herb. It has been included in nearly all Chinese pharmacopoeias throughout history. ZSS is associated with the liver, gallbladder, and heart meridians,possess the effects of nourishing the heart and liver, calming the mind and tranquilizing the nerves, according to the theory of Traditional Chinese Medicines. As the first choice for treating insomnia in Traditional Chinese Medicines, ZSS is used in over 70% of insomnia-related prescriptions.
ZMS, also known as "Dian zao ren", "Mian zao ren", or "imported sour jujube kernel", is the dried mature seed of Ziziphi mauritiana Lam., a plant belonging to the same family and genus as ZSS, but a different species. It is a relatively modern medicinal material and has only been recorded in the "Dian Nan Ben Cao". ZMS is associated with the heart and liver meridians, and is known for its calming and sweat-reducing effects, according to TCMs. ZMS is commonly used in Yunnan folk medicine to treat insomnia.
现代药理学研究表明,酸枣仁和理枣仁均富含三萜皂苷、黄酮、生物碱和核苷类化学成分,但所含化合物的种类和含量差异明显。
2 Chemical Differences between ZSS and ZMS
It has been discovered by modern pharmacological research that both ZSS and ZMS are rich in triterpenoids, flavonoids, alkaloids, and nucleoside. However, there are also significant differences in the types and contents of these compounds between ZSS and ZMS.
2.1 三萜皂苷
酸枣仁和理枣仁所含三萜皂苷类成分差异较大,酸枣仁中皂苷类成分的种类和数量均明显多于理枣仁。研究表明,酸枣仁中总皂苷含量约为 0.09%,而理枣仁中总皂苷含量约为0.04%。其中,以酸枣仁皂苷 A为代表的达玛烷型四环三萜是酸枣仁中含量最多的一类三萜皂苷,酸枣仁皂苷 A和酸枣仁皂苷 B一般被认为酸枣仁的特征成分。而理枣仁的特征成分是白桦酯醛,理枣仁中一般检测不到酸枣仁皂苷 A,酸枣仁皂苷 B的含量也低于酸枣仁。
2.1 Triterpenoids
There is a significant difference in the triterpenoids between ZSS and ZMS. The variety and content of saponins in ZSS are significantly higher than those in ZMS. It is revealed that the total saponins in ZSS is approximately 0.09%, while that in ZMS is approximately 0.04%. Among them, dammarane-type tetracyclic triterpenoids, represented by jujuboside A (JuA), are the most abundant type of triterpenoids in ZSS. JuA and jujuboside B (JuB) are also generally considered to be the characteristic components of ZSS. The characteristic component of ZMS is betulinic aldehyde, and JuA is not detected in ZMS, while the content of JuB is lower than that in ZSS.
2.2 黄酮类化合物
酸枣仁中总黄酮含量约为 0.95%,黄酮类成分的结构类型相对丰富,但其总含量明显低于理枣仁。以芫花素C-6碳苷为骨架的斯皮诺素(spinosin)及其衍生物,为酸枣仁和理枣仁共同的特征类黄酮化合物。据文献报道,酸枣仁中斯皮诺素、6′′′-芥子酰斯皮诺素、6′′′-阿魏酰斯皮诺素等黄酮类化合物的含量均显著低于理枣仁。
2.2 Flavonoids
With more skeleton types of flavonoids in ZSS, the content of total flavonoids in ZSS is about 0.95%, which is significantly lower than that in ZMS. Spinosin and its derivatives, which have a skeleton of glycoside located at C-6 site of apigenin with a carbon atom, are common flavonoids in ZSS and ZMS. As reported in the literatures, the content of flavonoids such as spinosin, 6′′′-sinapoyl spinosin, and 6′′′-feruloyl spinosin in ZSS are all significantly lower than that in ZMS.
2.3 生物碱类化合物
酸枣仁生物碱主要包含异喹啉类生物碱、阿朴菲类生物碱和环肽类生物碱,其中,异喹啉类生物碱含量相对较高;理枣仁中的生物碱主要为环肽类生物碱。酸枣仁中木兰花碱的含量约为理枣仁的 2 倍,乌药碱、酸李碱和莲心季铵碱的含量也明显高于理枣仁。
2.3 Alkaloids
The main alkaloids in ZSS include isoquinoline alkaloids, aporphine alkaloids, and cyclic peptide alkaloids. Among them, the content of isoquinoline alkaloids is higher. In contrast, alkaloids forming as cyclic peptide alkaloids are the main alkaloids in ZMS. The content of magnoflorine in ZSS is about twice that of ZMS. The content of coclaurine, zizyphusine, and lotusine are also significantly higher in ZSS compared to ZMS, respectively.
2.4 氨基酸和核苷
酸枣仁和理枣仁均含有丰富的氨基酸。迄今,酸枣仁中已检测到 22 种氨基酸,理枣仁中已检测到 19 种氨基酸。酸枣仁中必须氨基酸的总含量约为理枣仁的 8 倍。酸枣仁中精氨酸、天冬酰胺、丝氨酸和酪氨酸等氨基酸含量较高,约占总氨基酸含量的50%,而理枣仁中精氨酸和丝氨酸含量较高。理枣仁中缬氨酸和蛋氨酸含量明显高于酸枣仁。
此外,酸枣仁中核苷的种类及含量均多于理枣仁,特别是腺苷、尿苷和腺嘌呤等核苷含量较高,占总核酸和碱基含量的 60%以上。
2.4 Amino Acids and Nucleoside
The content of amino acids in both ZSS and ZMS are rich. To date, 22 types of amino acids have been detected in ZSS and 19 types have been detected in ZMS. The total content of essential amino acids in ZSS is approximately eight times higher than those in ZMS. Arginine, asparagine, serine, and tyrosine are richer in ZSS, accounting for about 50% of the total amino acid content, while the content of arginine and serine are higher in ZMS. However, the contents of methionine and lysine in ZMS are significantly higher than those in ZSS.
In addition, the types and content of nucleosides in ZSS are higher than those in ZMS, especially adenosine, uridine, and adenine, which account for more than 60% of the total nucleic acid and base.
综上,真假酸枣仁的化学成分存在明显差异,可以通过现代检测技术快速鉴别。酸枣仁的真伪及质量的准确甄别,有助于维护市场秩序,有助于维护消费者的合法权益,有助于中药产业的健康发展。
In conclusion, there are significant chemical differences between ZSS and ZMS, which can be quickly and accurately identified by modern detection technology. It is very important and urgent to accurately distinguish the authenticity and quality of ZSS,which is crucial to maintain normal market order, safeguard the legitimate rights and interests of consumers, and ensure the healthy development of the traditional Chinese medicine industry.