花椒果皮中麻味物質(zhì)的研究

摘   要

花椒(Zanthoxylum bungeanum Maxim.)為蕓香科花椒屬植物，主要產(chǎn)地分布在四川、河北、河南、山東、重慶等地。花椒是藥食兩用的植物，作為我國(guó)傳統(tǒng)的調(diào)味品及中藥材有著非常悠久的歷史。因花椒具有濃郁的香氣和辛麻味，同時(shí)具有“鎮(zhèn)膻解腥”的作用，是我國(guó)常用的特色調(diào)味品之一。同時(shí)花椒作為中藥材，具有溫中止痛，抗菌殺蟲的功效，常用于治療呼吸系統(tǒng)、消化系統(tǒng)等方面的疾病，同時(shí)還具有很好的麻醉鎮(zhèn)痛等功效?；ń纷鳛槲覈?guó)傳統(tǒng)的“八大調(diào)味品”之一，辛麻味是重要的風(fēng)味特征，也是評(píng)定其品質(zhì)優(yōu)劣的指標(biāo)。然而到目前為止，國(guó)內(nèi)外尚未建立有關(guān)花椒麻味評(píng)價(jià)的標(biāo)準(zhǔn)方法，也未有可用于麻味檢測(cè)的標(biāo)準(zhǔn)樣品，這對(duì)于花椒產(chǎn)業(yè)以品質(zhì)目標(biāo)為導(dǎo)向在原料品種選育、產(chǎn)品加工工藝改良與質(zhì)量控制、商品流通分級(jí)、優(yōu)質(zhì)優(yōu)價(jià)等方面都造成了缺乏客觀依據(jù)的發(fā)展瓶頸。同時(shí)花椒的辛麻程度與其麻味物質(zhì)的化學(xué)成分和結(jié)構(gòu)關(guān)系密切，本文對(duì)花椒麻味物質(zhì)的化學(xué)基礎(chǔ)進(jìn)行研究，為麻度的測(cè)量提供單體化合物，為花椒的產(chǎn)業(yè)化、現(xiàn)代化提供化學(xué)依據(jù)。

本論文采用溶劑乙酸乙酯冷浸提取花椒果皮中的麻味物質(zhì)，減壓濃縮后得花椒麻味物質(zhì)總浸膏，運(yùn)用正相硅膠柱層析，經(jīng)過石油醚、石油醚:乙酸乙酯（1:1）、甲醇三種洗脫劑分段洗脫，得到A，B和C三個(gè)部分。A部分經(jīng)硅膠柱層析，石油醚:乙酸乙酯（0:1-1:0）梯度洗脫，結(jié)合薄層層析分析，分離得到A1、A2、A3三部分，A3部分再結(jié)合薄層層析、正相硅膠柱層析、RP-18反相硅膠柱層析、重結(jié)晶、Sephadex LH-20葡聚糖凝膠柱層析等現(xiàn)代分離手段，對(duì)其中的有效化學(xué)成分進(jìn)行系統(tǒng)的分離純化，從中共得到5個(gè)單體化合物。運(yùn)用1H-NMR、13C-NMR、DEPT等光譜手段對(duì)其中1個(gè)化合物進(jìn)行了結(jié)構(gòu)鑒定，為hydroxy lycopersene（1），該化合物為四萜化合物，同時(shí)具有多個(gè)烯鍵結(jié)構(gòu)，可能為酰胺類麻味物質(zhì)的前體，其生物活性有待進(jìn)一步的研究。該化合物為首次從該植物中分離得到。本論文豐富了花椒的化學(xué)研究，也為麻度的測(cè)量提供了供試樣品。

　　　

關(guān)鍵詞：花椒；麻味物質(zhì)；分離純化；hydroxy lycopersene

Abstract

Zanthoxylum bungeanum Maxim., a number of Rutaceae family, is widely distributed in the area of Sichuan, Hebei, Henan, Shandong and Shanxi provinces of China. As China's traditional spices and herbs，Zanthoxylum bungeanum Maxim.has a very long history. It is one of the commonly used features condiments. At the same time, Zanthoxylum bungeanum Maxim., as traditional Chinese medicine has anti-bacterial insecticidal effect, etc. They are often used in the treatment of respiratory diseases, digestive diseases, and also have the anesthesia analgesia effect. It is one of the eight traditional condiments in our country. Pungent taste is the main character as the most important indicator of quality. The standardized method of eva luating pungency has not been established at present. This situation resulted in the lack of objective basis for the Zanthoxylum bungeanum Maxim.industry. The pungency of Zanthorylum bungeanum is closely associated with the chemistry compositions and the structure relation-ship of the pungent principles. We here investigated the natural spicy taste substance, and provides the test sample for the pungent measuring.

The pericarp of Zanthoxylum bungeanum was extracted with EtOAc at room temperature. After the solvent was removed by evaporation, the EtOAc extrac was recovered. The EtOAc extract was subjected to a silica gel column and eluted with petroleum ether, petroleum ether:EtOAc (1:1) and MeOH to yield three fractions (A, B and C). Fraction A was again subjected to CC over silica gel and eluted with petroleum ether–EtOAc in a gradient manner (0:1-1:0) to to yield three fractions (A1、A2、A3).  Fraction A3 was further purified by various chromatographic methods, such as Sephadex LH-20 column, RP-18 silica gel column, silica gel column and based on TLC analysis, to afford five compound. The structure of compound 1 was elucidated by spectroscopic analysis, including 1H-NMR、13C-NMR、DEPT experiments. It were identified as hydroxy lycopersene 1. Compound 1 is a polyterpene, possessing eight double bonds, and it has been isolated from this plant for the first time. This paper enriches the chemical research of Zanthoxylum bungeanum, also provided the test sample for measuring pungent principles.  

Keywords: Zanthoxylum bungeanum Maxim.;Pungent substance; Separate and purification;  Hydroxy lycopersene

目錄

第1章 緒論 1

1.1 課題研究背景及意義 1

1.1.1 研究背景 1

1.1.2 研究意義 1

1.2 課題來源 1

1.3 課題研究?jī)?nèi)容及方法 2

1.3.1 研究?jī)?nèi)容 2

1.3.2 研究方法 2

第2章 花椒中化學(xué)成分的研究 3

2.1化學(xué)成分的研究 3

2.1.1揮發(fā)油 3

2.1.2酰胺 4

2.1.3 生物堿 5

2.1.4 香豆素 19

2.1.5 木質(zhì)素 20

2.1.6 營(yíng)養(yǎng)成分 20

2.1.7 其他成分 21

2.2 化學(xué)成分的分離分析方法研究 21

2.2.1揮發(fā)油的分離分析 21

2.2.2 酰胺類物質(zhì)的分離分析 22

2.2.3 生物堿類物質(zhì)的分離分析 24

2.2.4 木質(zhì)素的分離分析 25

2.3 花椒的藥理研究 25

2.3.1 對(duì)消化系統(tǒng)的作用 25

2.3.1.1 抗?jié)冏饔?span id="aslhatb8b" class="Apple-tab-span" style="white-space:pre;"> 25

2.3.1.2 止瀉作用 26

2.3.1.3 保肝作用 26

2.3.1.4 對(duì)腸胃推動(dòng)的抑制作用 26

2.3.3 對(duì)呼吸系統(tǒng)的作用 27

2.3.4 麻醉鎮(zhèn)痛作用 27

2.3.6 抗菌消炎作用 27

2.3.7 抗氧化作用 28

2.3.8 抗癌作用 28

2.3.8 其他作用 29

第3章 花椒果皮中麻味物質(zhì)的分離 30

3.1 引言 30

3.2 實(shí)驗(yàn)部分 30

3.2.1 儀器試劑及材料 30

3.2.1.1 實(shí)驗(yàn)儀器 30

3.2.1.2 實(shí)驗(yàn)試劑 31

3.2.1.3 實(shí)驗(yàn)材料 31

3.2.2 提取分離 31

3.2.3 實(shí)驗(yàn)結(jié)果 34

結(jié)論 35

致謝 36

參考文獻(xiàn) 37

附錄 42