Article(id=1256183364516700361, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1256183358493679805, articleNumber=null, orderNo=null, doi=10.13193/j.issn.1673-7717.2025.12.013, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=null, receivedDateStr=null, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1777427052859, onlineDateStr=2026-04-29, pubDate=1765296000000, pubDateStr=2025-12-10, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1777427052859, onlineIssueDateStr=2026-04-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1777427052858, creator=13701087609, updateTime=1777427052858, updator=13701087609, issue=Issue{id=1256183358493679805, tenantId=1146029695717560320, journalId=1255847919539208197, year='2025', volume='43', issue='12', pageStart='1', pageEnd='258', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1777427051344, creator=13701087609, updateTime=1777427760067, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1256186331126969089, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1256183358493679805, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1256186331126969090, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1256183358493679805, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=79, endPage=86, ext={EN=ArticleExt(id=1256183367779868896, articleId=1256183364516700361, tenantId=1146029695717560320, journalId=1255847919539208197, language=EN, title=Influence of Different Preparation and Processing Methods on Oil Components in Dihuang(Rehmanniae Radix)and Correlation between Properties and Effects, columnId=1256183361521967297, journalTitle=Chinese Archives of Traditional Chinese Medicine, columnName=Target on National Project, runingTitle=null, highlight=null, articleAbstract=
Objective

To investigate the effects of preparation and processing methods on the contents of oil components in Dihuang(Rehmanniae Radix)and clarify the correlation between oil components with medicinal properties,in order to provide guidance for processing research and clinical application.

Methods

The extraction of volatile oil refers to the volatile oil determination method A in the 2020 edition of Chinese Pharmacopoeia,and the Soxhlet method was used to extract fatty oil.Gas Chromatography Mass Spectrometry(GC-MS)was used to identify the oil components and their relative contents.Thermographic analysis was used to clarify the characteristics of the influence of different preparation and processing methods on oil components.Combined with literature review,the correlation of processing,preparation,components and properties was discussed.

Results

The oil components weremainly fatty acids.The order of the extraction rate of fatty oil was fresh Dihuang(Rehmanniae Radix)>raw Dihuang(Rehmanniae Radix)>steaming with wine≈stewing with wine>steaming and exposing nine times with Sharen(Amomi Fructus)>steaming without ingredients,and the order of the volatile oil extraction rate was stewing with wine>steaming with wine>steaming and exposing nine times with Sharen(Amomi Fructus)>raw Dihuang(Rehmanniae Radix)≈steaming without ingredients>fresh Dihuang(Rehmanniae Radix).The heatmap analysis of fatty oil and volatile oil showed that Shudihuang(Rehmanniae Radix Praeparata)stewing with wine and that steaming and exposing nine times with Sharen(Amomi Fructus)were clustered one category.

Conclusion

The changes and adjustments of the types and relative contents of oil componentswere important material basis for the differences in medicinal property of Dihuang(Rehmanniae Radix)processed products.Adding wine,Sharen(Amomi Fructus)or increasing steaming and exposing times were helpful in reducing the cold nature of Dihuang(Rehmanniae Radix),and the greasy nature of Shudihuang(Rehmanniae Radix Praeparata),and enhance thewarming-reinforcing effect.The volatile oil components in different products of Dihuang(Rehmanniae Radix)were the material basis of their“Qiwei”.

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目的

考察不同炮制方法和工艺对地黄中油类成分的影响,明晰方法、工艺和所含成分与制品的药性的关联性,为地黄炮制研究和临床应用提供指导。

方法

挥发油提取参照2020年版《中华人民共和国药典》中挥发油测定法甲法提取,索氏法提取脂肪油,气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometry,GC-MS)鉴定油类成分及其相对含量,热图分析明晰不同制方法和工艺对油类成分影响的特点,结合文献学探讨制法、工艺-成分-性效关联性。

结果

地黄不同炮制品中油成分主要是脂肪酸类;脂肪油提取率为鲜地黄>生地黄>酒蒸≈酒炖>九制>清蒸,挥发油提取率为酒炖>酒蒸>九制>生地黄≈清蒸>鲜地黄。脂肪油和挥发油热图均显示酒炖和九制熟地黄聚为一类。

结论

油类成分种类和相对含量改变和调整,是熟地黄药性和功能主治差异的重要物质基础;加入辅料酒、砂仁和增加蒸晒次数有助于降低地黄的寒滑之性和熟地黄的滋腻之性,增强熟地黄温补作用;挥发油成分是熟地黄“气微”的物质基础。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
李红伟(1979-),男,河南长葛人,副教授,硕士研究生导师,博士,研究方向:中药炮制机理及饮片标准化。E-mail:
冯卫生(1960-),男,河南林州人,教授,博士研究生导师,博士,研究方向:中药药效物质基础研究及新药开发。E-mail:
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李宁(1998-),女,山东潍坊人,硕士在读,研究方向:中药炮制机理及饮片标准化。

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李宁(1998-),女,山东潍坊人,硕士在读,研究方向:中药炮制机理及饮片标准化。

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序号tR/(min)成分分子式鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
15.468草蒿脑C10H12O0.05-0.310.190.070.69
25.781壬酸甲酯C10H20O20.030.020.10---
36.334正十四烷C14H300.020.03----
46.0393-甲基-5-丙基壬烷C13H28-0.01----
56.5094,6-二甲基十二烷C14H300.160.14-0.162.800.45
66.3346-乙基-3-草酸正丁酯C18H34O4--0.06---
76.5042,7,10-三甲基十二烷C15H32--0.27---
86.670茴香脑C10H12O0.040.050.450.04--
97.153癸酸甲酯C11H22O20.300.500.370.360.280.23
107.977肉桂酸甲酯C10H10O2---0.04--
118.189正十二烷C12H26-----0.09
128.9902,6,10-三甲基十四烷C17H360.020.070.790.041.130.60
138.9352,6-双(1,1-二甲基乙基)-2,5-环己烯-1,4-二酮C14H20O2--0.63---
149.239正十七烷C17H360.040.04----
159.289正十六烷C16H340.170.130.590.260.320.67
169.678肉豆蔻醚C11H12O30.04-----
179.740月桂酸甲酯C13H26O20.400.410.360.580.350.33
189.8602,6,11,15-四甲基十六烷C20H420.050.070.18---
1910.8375,9-二甲基-三环[6.3.0.0(1,5)]十一碳-2-烯-4-酮C13H18O---0.09--
2010.8413,3,4,6-四甲基-2,3-2H-苯并呋喃-2-酮C12H14O2-0.07----
2111.200正十三烷酸甲酯C14H28O20.01-----
2211.6242,6,10-三甲基十五烷C18H38--0.06-0.05-
2311.6282,6,11-三甲基十二烷C15H32----0.03-
2412.40212-甲基十三烷酸甲酯C15H30O2--0.110.050.050.10
2512.7932,6,10,14-四甲基十五烷C19H400.01-0.05---
2613.249肉豆蔻酸甲酯C15H30O25.991.331.062.511.871.71
2713.7192,6,10,15-四甲基十七烷C21H440.13-0.30-0.310.38
2813.783正二十一烷C21H440.040.01----
2914.174正十一烷基环己烷C17H34--0.02---
3014.584正十四烷酸C14H28O20.06-----
3115.280顺-5-月桂烯酸甲酯C13H24O20.100.13----
3215.505正十八烷C18H380.020.02----
3315.708(9Z)-9-油酸甲酯C19H36O20.130.09-0.21--
3416.0121,2-环氧十六烷C16H32O0.01-----
3516.404正十五烷酸甲酯C16H32O20.680.510.520.760.841.39
3616.7252-甲基二十六烷C27H560.01-----
3716.937植酮C18H36O0.020.01----
3817.779植醇C20H40O-0.01---0.24
3917.807顺-9-棕榈油酸C16H30O2-0.03----
4017.817棕榈醛C16H30O0.02-----
4119.05117-炔-十八酸甲酯C19H34O20.020.01-0.03-0.26
4219.06414-甲基十五烷酸甲酯C17H34O2---0.05--
4319.708顺-7-十六碳烯酸甲酯C17H32O2--0.520.02-2.55
4419.850(9Z)-9-棕榈油酸甲酯C17H32O21.070.540.221.121.93-
4520.7633,5-双(1,1-二甲基乙基)-4-羟基-苯丙酸甲酯C18H28O3--1.47--0.76
4622.296棕榈酸甲酯C17H34O222.7623.777.5825.30 23.4521.34
4723.0292,6,10,14-四甲基十六烷C20H420.040.03-0.02--
4824.520月桂醛二甲缩醛C14H30O20.030.05----
4925.418棕榈酸C16H32O2-0.19-0.06--
5025.566(9Z,12Z)-9,12-亚油酸C18H32O20.14--0.03--
5125.795(9Z,12Z)-9,12-亚麻酰氯C18H31ClO0.160.11-0.13--
5226.317顺-10-十七碳烯酸甲酯C18H34O20.130.07----
5326.7812-己基-环丙烷辛酸甲酯C18H34O20.030.01-0.120.05-
5427.843正十五烷醛C15H30O--0.200.050.080.12
5527.983硬脂烷醛C18H36O0.03-----
5628.011,2-环氧十八烷C18H36O-0.01----
5728.556正十七烷酸甲酯C18H36O20.350.25-0.380.330.31
5828.55715-甲基十六烷酸甲酯C18H36O2--0.12---
5932.674(3Z)-3-十七碳烯-5-炔C17H30---0.03--
6038.766(9Z,12Z)-9,12-亚油酸甲酯C19H34O243.2639.994.7126.36 26.5929.32
6139.203(9Z,12Z,15Z)-9,12,15-亚麻酸甲酯C19H32O22.805.951.054.996.096.52
6239.834(9E)-9-油酸甲酯C19H36O28.8510.752.0615.458.78-
6340.170(11 E)-11-油酸甲酯C19H36O22.390.833.844.831.6114.13
6440.548(9Z)-9-油酸甲酯C19H36O20.040.02----
6538.6863,8-二甲基十一烷C13H28--0.09---
6638.9122-甲基二十四烷C25H52---0.02--
6740.486硬脂酸甲酯C19H38O22.733.381.713.472.002.38
6844.411(11 Z)-11-油酸C18H34O20.030.14----
6946.63棕榈酰胺C16H33NO-0.04----
7047.0081,1-二甲氧基十八烷C20H42O20.07-----
7147.2331-三十七烷醇C37H76O-0.01----
7247.486顺-9-反-11-油酸甲酯C19H34O20.09-----
7347.786顺-10-十九烯酸甲酯C20H38O20.020.03----
7447.984顺9,10-环丙基十九烷酸甲酯C20H38O20.02-----
7548.368乙酸二十烷酯C22H44O20.060.010.35-0.750.38
76
77
49.05649.063(7Z,12Z)-7,12-十八碳二烯酸甲酯花生四烯酸甲酯C19H34O2C21H34O20.03------0.16----
7849.215正十九烷酸甲酯C20H40O20.070.07-0.06--
7949.782(5Z,8Z,11 Z,14Z,17Z)-5,8,11,14,17-二十碳五烯酸甲酯C21H32O20.04--0.25--
8050.737(6Z,9Z,12Z)-6,9,12-十八碳三烯酸甲酯C19H32O20.01-----
8151.243顺-6,9-反-11-十八碳三烯酸甲酯C19H32O20.010.01-0.04--
8251.253顺-9-反-11,13-十八碳三烯酸甲酯C19H32O20.020.01----
8351.692顺-11,14-二十碳二烯酸甲酯C21H38O20.170.24-0.16--
8451.696(9Z,12Z)-9,12-亚麻醇C18H34O----0.11-
8552.184顺-11-二十碳烯酸甲酯C21H40O20.240.42-0.50--
86
87
52.47353.469顺-13-二十碳烯酸正二十烷酸甲酯C20H38O2C21H42O2-0.760.03------0.89-0.64
8853.47018-甲基-十九烷酸甲酯C21H42O2---0.92--
8954.103(9Z)-9-油酸酰胺C18H35NO0.01-----
9054.259(9Z,12Z)-9,12-十八碳二烯酸丁酯C22H40O2-0.01----
9154.591顺-11-十八碳烯酸C18H34O2-0.01---
9256.526正二十七烷C27H560.020.02--2.650.23
9356.925乙酸二十二烷酯C24H48O20.03-----
9457.015(9Z)-8-甲基-9-十四碳烯酸甲酯C15H28O2---0.11--
95
96
57.57160.014正二十一烷酸甲酯顺-13,16-二十碳二烯酸甲酯C22H44O2C23H42O20.16-0.230.03--0.17-0.14---
9760.229芥酸C22H42O2---0.10--
9860.273(13Z)-13-芥酸甲酯C23H44O20.040.41----
9960.44正二十一烷C21H440.030.20--1.08-
10060.484正二十五烷C25H520.02-----
10161.453山嵛酸甲酯C23H46O20.410.65-1.012.150.98
10264.20011-(1-乙基丙基)-二十一烷C26H54-0.02----
10365.160正二十三烷酸甲酯C24H48O20.230.30-0.28--
10466.0602,2-二甲基-3-(3,7,16,20-四甲基-3,7,11,15,19-二十碳戊烯基)-环氧乙烷C29H48O-0.18----
10568.741正二十四烷酸甲酯C25H50O20.471.040.451.483.161.24
10669.704(13Z)-13-芥酸酰胺C22H43NO0.220.580.59---
10769.714(9Z)-9-油酸酰胺C18H35NO---0.06--
10870.399(1 E,6E,10E,14E,18E,22E)-2,6,10,15,19,23-六甲基-1,6,10,14,18,22-二十碳六烯-3-醇C30H50O0.03-8.762.81--
10971.0992,3-环氧角鲨烯C30H50O---0.04--
11071.150角鲨烯C30H500.100.13----
11171.582正二十八烷酸甲酯C29H58O20.520.8542.96-3.292.87
11272.356正二十五烷酸甲酯C26H52O2-0.15-0.11--
11373.175β-谷甾醇C29H50O--2.90---
11473.459正二十二烷二酸二甲酯C24H46O4-0.02----
11576.950蜡酸甲酯C27H54O20.591.99-1.380.12-
), ArticleFig(id=1256183526320365696, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1256183364516700361, language=CN, label=表1, caption=

各样品脂肪油成分及相对含量(n=3)

, figureFileSmall=null, figureFileBig=null, tableContent=
序号tR/(min)成分分子式鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
15.468草蒿脑C10H12O0.05-0.310.190.070.69
25.781壬酸甲酯C10H20O20.030.020.10---
36.334正十四烷C14H300.020.03----
46.0393-甲基-5-丙基壬烷C13H28-0.01----
56.5094,6-二甲基十二烷C14H300.160.14-0.162.800.45
66.3346-乙基-3-草酸正丁酯C18H34O4--0.06---
76.5042,7,10-三甲基十二烷C15H32--0.27---
86.670茴香脑C10H12O0.040.050.450.04--
97.153癸酸甲酯C11H22O20.300.500.370.360.280.23
107.977肉桂酸甲酯C10H10O2---0.04--
118.189正十二烷C12H26-----0.09
128.9902,6,10-三甲基十四烷C17H360.020.070.790.041.130.60
138.9352,6-双(1,1-二甲基乙基)-2,5-环己烯-1,4-二酮C14H20O2--0.63---
149.239正十七烷C17H360.040.04----
159.289正十六烷C16H340.170.130.590.260.320.67
169.678肉豆蔻醚C11H12O30.04-----
179.740月桂酸甲酯C13H26O20.400.410.360.580.350.33
189.8602,6,11,15-四甲基十六烷C20H420.050.070.18---
1910.8375,9-二甲基-三环[6.3.0.0(1,5)]十一碳-2-烯-4-酮C13H18O---0.09--
2010.8413,3,4,6-四甲基-2,3-2H-苯并呋喃-2-酮C12H14O2-0.07----
2111.200正十三烷酸甲酯C14H28O20.01-----
2211.6242,6,10-三甲基十五烷C18H38--0.06-0.05-
2311.6282,6,11-三甲基十二烷C15H32----0.03-
2412.40212-甲基十三烷酸甲酯C15H30O2--0.110.050.050.10
2512.7932,6,10,14-四甲基十五烷C19H400.01-0.05---
2613.249肉豆蔻酸甲酯C15H30O25.991.331.062.511.871.71
2713.7192,6,10,15-四甲基十七烷C21H440.13-0.30-0.310.38
2813.783正二十一烷C21H440.040.01----
2914.174正十一烷基环己烷C17H34--0.02---
3014.584正十四烷酸C14H28O20.06-----
3115.280顺-5-月桂烯酸甲酯C13H24O20.100.13----
3215.505正十八烷C18H380.020.02----
3315.708(9Z)-9-油酸甲酯C19H36O20.130.09-0.21--
3416.0121,2-环氧十六烷C16H32O0.01-----
3516.404正十五烷酸甲酯C16H32O20.680.510.520.760.841.39
3616.7252-甲基二十六烷C27H560.01-----
3716.937植酮C18H36O0.020.01----
3817.779植醇C20H40O-0.01---0.24
3917.807顺-9-棕榈油酸C16H30O2-0.03----
4017.817棕榈醛C16H30O0.02-----
4119.05117-炔-十八酸甲酯C19H34O20.020.01-0.03-0.26
4219.06414-甲基十五烷酸甲酯C17H34O2---0.05--
4319.708顺-7-十六碳烯酸甲酯C17H32O2--0.520.02-2.55
4419.850(9Z)-9-棕榈油酸甲酯C17H32O21.070.540.221.121.93-
4520.7633,5-双(1,1-二甲基乙基)-4-羟基-苯丙酸甲酯C18H28O3--1.47--0.76
4622.296棕榈酸甲酯C17H34O222.7623.777.5825.30 23.4521.34
4723.0292,6,10,14-四甲基十六烷C20H420.040.03-0.02--
4824.520月桂醛二甲缩醛C14H30O20.030.05----
4925.418棕榈酸C16H32O2-0.19-0.06--
5025.566(9Z,12Z)-9,12-亚油酸C18H32O20.14--0.03--
5125.795(9Z,12Z)-9,12-亚麻酰氯C18H31ClO0.160.11-0.13--
5226.317顺-10-十七碳烯酸甲酯C18H34O20.130.07----
5326.7812-己基-环丙烷辛酸甲酯C18H34O20.030.01-0.120.05-
5427.843正十五烷醛C15H30O--0.200.050.080.12
5527.983硬脂烷醛C18H36O0.03-----
5628.011,2-环氧十八烷C18H36O-0.01----
5728.556正十七烷酸甲酯C18H36O20.350.25-0.380.330.31
5828.55715-甲基十六烷酸甲酯C18H36O2--0.12---
5932.674(3Z)-3-十七碳烯-5-炔C17H30---0.03--
6038.766(9Z,12Z)-9,12-亚油酸甲酯C19H34O243.2639.994.7126.36 26.5929.32
6139.203(9Z,12Z,15Z)-9,12,15-亚麻酸甲酯C19H32O22.805.951.054.996.096.52
6239.834(9E)-9-油酸甲酯C19H36O28.8510.752.0615.458.78-
6340.170(11 E)-11-油酸甲酯C19H36O22.390.833.844.831.6114.13
6440.548(9Z)-9-油酸甲酯C19H36O20.040.02----
6538.6863,8-二甲基十一烷C13H28--0.09---
6638.9122-甲基二十四烷C25H52---0.02--
6740.486硬脂酸甲酯C19H38O22.733.381.713.472.002.38
6844.411(11 Z)-11-油酸C18H34O20.030.14----
6946.63棕榈酰胺C16H33NO-0.04----
7047.0081,1-二甲氧基十八烷C20H42O20.07-----
7147.2331-三十七烷醇C37H76O-0.01----
7247.486顺-9-反-11-油酸甲酯C19H34O20.09-----
7347.786顺-10-十九烯酸甲酯C20H38O20.020.03----
7447.984顺9,10-环丙基十九烷酸甲酯C20H38O20.02-----
7548.368乙酸二十烷酯C22H44O20.060.010.35-0.750.38
76
77
49.05649.063(7Z,12Z)-7,12-十八碳二烯酸甲酯花生四烯酸甲酯C19H34O2C21H34O20.03------0.16----
7849.215正十九烷酸甲酯C20H40O20.070.07-0.06--
7949.782(5Z,8Z,11 Z,14Z,17Z)-5,8,11,14,17-二十碳五烯酸甲酯C21H32O20.04--0.25--
8050.737(6Z,9Z,12Z)-6,9,12-十八碳三烯酸甲酯C19H32O20.01-----
8151.243顺-6,9-反-11-十八碳三烯酸甲酯C19H32O20.010.01-0.04--
8251.253顺-9-反-11,13-十八碳三烯酸甲酯C19H32O20.020.01----
8351.692顺-11,14-二十碳二烯酸甲酯C21H38O20.170.24-0.16--
8451.696(9Z,12Z)-9,12-亚麻醇C18H34O----0.11-
8552.184顺-11-二十碳烯酸甲酯C21H40O20.240.42-0.50--
86
87
52.47353.469顺-13-二十碳烯酸正二十烷酸甲酯C20H38O2C21H42O2-0.760.03------0.89-0.64
8853.47018-甲基-十九烷酸甲酯C21H42O2---0.92--
8954.103(9Z)-9-油酸酰胺C18H35NO0.01-----
9054.259(9Z,12Z)-9,12-十八碳二烯酸丁酯C22H40O2-0.01----
9154.591顺-11-十八碳烯酸C18H34O2-0.01---
9256.526正二十七烷C27H560.020.02--2.650.23
9356.925乙酸二十二烷酯C24H48O20.03-----
9457.015(9Z)-8-甲基-9-十四碳烯酸甲酯C15H28O2---0.11--
95
96
57.57160.014正二十一烷酸甲酯顺-13,16-二十碳二烯酸甲酯C22H44O2C23H42O20.16-0.230.03--0.17-0.14---
9760.229芥酸C22H42O2---0.10--
9860.273(13Z)-13-芥酸甲酯C23H44O20.040.41----
9960.44正二十一烷C21H440.030.20--1.08-
10060.484正二十五烷C25H520.02-----
10161.453山嵛酸甲酯C23H46O20.410.65-1.012.150.98
10264.20011-(1-乙基丙基)-二十一烷C26H54-0.02----
10365.160正二十三烷酸甲酯C24H48O20.230.30-0.28--
10466.0602,2-二甲基-3-(3,7,16,20-四甲基-3,7,11,15,19-二十碳戊烯基)-环氧乙烷C29H48O-0.18----
10568.741正二十四烷酸甲酯C25H50O20.471.040.451.483.161.24
10669.704(13Z)-13-芥酸酰胺C22H43NO0.220.580.59---
10769.714(9Z)-9-油酸酰胺C18H35NO---0.06--
10870.399(1 E,6E,10E,14E,18E,22E)-2,6,10,15,19,23-六甲基-1,6,10,14,18,22-二十碳六烯-3-醇C30H50O0.03-8.762.81--
10971.0992,3-环氧角鲨烯C30H50O---0.04--
11071.150角鲨烯C30H500.100.13----
11171.582正二十八烷酸甲酯C29H58O20.520.8542.96-3.292.87
11272.356正二十五烷酸甲酯C26H52O2-0.15-0.11--
11373.175β-谷甾醇C29H50O--2.90---
11473.459正二十二烷二酸二甲酯C24H46O4-0.02----
11576.950蜡酸甲酯C27H54O20.591.99-1.380.12-
), ArticleFig(id=1256183527121477771, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1256183364516700361, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
序号tR/(min)成分分子式鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
12.179正十四烷C14H30---0.01--
22.2792,6,10-三甲基十五烷C18H38---0.02--
32.3204-甲基十二烷C13H28---0.01--
42.3954,6-二甲基十二烷C14H30---0.02--
52.437正十六烷C16H340.14-0.030.230.040.02
62.475正十八烷C18H38---0.01--
72.5255-丁基壬烷C13H28---0.01--
82.7402-异丙基-5-甲基-1-庚醇C11H24O0.02-----
92.8552,2,6-三甲基环己酮C9H16O0.01-0.01---
102.956异丙基十四烷基醚C17H36O---0.02--
113.165正十七烷C17H36---0.03--
123.1952-甲基二十八烷C29H600.01-----
133.198正十九烷C19H40---0.02--
143.265正二十烷C20H420.18-0.020.300.01-
153.365正二十一烷C21H44---0.05--
163.375β-环柠檬醛C10H16O0.04-----
173.595壬基十四烷基醚C23H48O---0.01--
183.986乙酸异龙脑酯C12H20O2-----0.02
194.279α-二氢萜品醇C10H20O---0.09--
204.3306-甲基-1,2,3,5,8,8a-六氢萘C11H160.02-----
214.525藏花烷C20H42---0.02--
225.426正二十九烷C29H60---0.04--
235.526月桂酸乙酯C14H28O2---0.080.04-
245.530二十二烷酸乙酯C24H48O2--0.01---
255.534十一烷酸乙酯C13H26O2-0.01----
265.627顺式茴香脑C10H12O0.050.05----
275.69511-(1-乙基丙基)-二十一烷C26H54---0.02--
285.705顺式香叶基丙酮C13H22O0.020.010.01---
295.820正二十四烷C24H500.01-0.010.02--
305.8953-(1,5-二甲基己-4-烯基)-2,2-二甲基-环五烷-3-烯-1-醇C15H26O-----0.01
315.8972-甲基十二烷C13H28---0.01--
326.0706-甲基-6-(5-甲基呋喃-2-基)庚烷-2-酮C13H20O20.030.010.02---
336.2453-[[(呋喃-2-甲基)氨基]甲基]-4a-羟基-5-甲氧基-5-十氢萘并[2,3-b]呋喃-2-酮C21H31NO5-----0.02
347.105肉豆蔻酸甲酯C15H30O2-0.030.04---
357.270植酮C18H36O---0.030.01-
367.2752-十五烷酮C15H30O--0.02---
377.290丁香酚甲醚C11H14O2-0.01----
387.37513-甲基-十四醛C15H30O---0.02--
397.376十四烷醛C14H28O--0.01---
407.570肉豆蔻酸乙酯C16H32O2-0.070.030.570.270.12
418.079蓝桉醇C15H26O-----0.03
428.475十五烷酸甲酯C16H32O2-0.010.01---
439.060十五烷酸乙酯C17H34O2--0.010.090.050.03
449.480(9Z)-9-十五碳烯酸乙酯C17H32O2---0.030.02-
459.992二十二烷C22H46---0.14--
4610.315棕榈酸甲酯C17H34O20.160.561.020.190.080.16
4710.945(9Z)-9-棕榈油酸甲酯C17H32O2-0.010.05---
4811.210棕榈酸乙酯C18H36O2-0.520.71 10.274.712.23
4911.631正癸酸C10H20O20.540.090.120.170.100.05
5011.800(9E)-9-棕榈油酸乙酯C18H34O2--0.030.410.200.08
5111.835(9E)-9-棕榈油酸甲酯C17H32O2-0.02----
5212.375(5E)-1,5-十二碳二烯C12H22--0.02---
5312.3802-甲基二十四烷C25H52---0.13--
5412.8212,4-二叔丁基苯酚C14H22O---0.12--
5513.824十七烷酸乙酯C19H38O2---0.060.03-
5614.245法尼基丙酮C18H30O-0.110.310.160.060.12
5715.155正二十一烷C21H44---0.11--
5815.680硬脂酸甲酯C19H38O2-0.050.08---
5916.153(9E)-9-油酸甲酯C19H36O20.160.531.150.130.050.11
6016.415(11 E)-11-油酸甲酯C19H36O2-0.040.11---
6116.670硬脂酸乙酯C20H40O2-0.040.050.780.390.13
6217.150(9Z)-9-油酸乙酯C20H38O2--0.64--1.30
6317.200(9E)-9-油酸乙酯C20H38O2-0.42-8.783.83-
6417.355月桂酸C12H24O20.590.180.57--0.62
6517.485(9Z,12Z)-9,12-亚油酸甲酯C19H34O20.120.421.020.290.120.17
6618.610(9Z,12Z)-9,12-亚油酸乙酯C20H36O2-0.370.684.411.910.97
6719.675(9Z,12Z,15Z)-9,12,15-亚麻酸甲酯C19H32O2-0.110.30-0.03-
6820.925(9Z,12Z,15Z)-9,12,15-亚麻酸乙酯C20H34O2-0.910.201.990.820.36
6921.375(9E)-9-油酸C18H34O21.650.60-2.60-
7021.820(9Z)-9-油酸C18H34O227.062.330.810.196.72-
7122.335(13Z)-13芥酸C22H42O2-0.14----
7222.500(9Z)-9-十六碳烯醛C16H30O1.68-----
7322.910(13Z)-13-油酸C18H34O2-0.41----
7422.940(10Z)-10-十七碳烯酸C17H32O2-0.400.39---
7523.350(11 Z)-11-油酸C18H34O2-1.11--1.171.32
7624.875肉豆蔻酸C14H28O22.000.873.512.910.923.28
7728.000(9Z,12Z)-9,12-亚油酸C18H32O241.9552.363.923.74 48.0745.79
7828.160正十五烷酸C15H30O2-2.167.422.460.030.04
7929.135(6Z)-6-油酸C18H34O2--0.110.44-0.78
8029.1452-羟基环十五烷酮C15H28O2-0.860.70---
8129.171(9Z)-9-十八碳烯醛C18H34O0.08-----
8229.438(9E,12E)-9,12-亚油酸C18H32O2-3.04----
8332.080棕榈酸C16H32O212.2114.3571.11 57.86 12.8428.43
8433.550(9E)-9-棕榈油酸C16H30O20.12-----
8533.555(9Z)-9-棕榈油酸C16H30O2-0.212.911.510.711.45
8634.105(11 Z)-11-棕榈油酸C16H30O2----0.03-
8735.025α-亚麻酸C18H30O23.129.640.87-8.8312.01
8835.620(8Z,11 Z,14Z)-8,11,14-二十碳三烯酸C20H34O2-1.59----
8936.810十七烷酸C17H34O2--0.35-0.03-
9036.752硬脂酸C18H36O2---0.120.20-
9136.545(9E,12E)-9,12-亚油酸甲酯C19H34O2-1.03---0.11
), ArticleFig(id=1256183528375574681, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1256183364516700361, language=CN, label=表2, caption=

各样品水蒸气蒸馏提取挥发油成分及相对含量(n=3)

, figureFileSmall=null, figureFileBig=null, tableContent=
序号tR/(min)成分分子式鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
12.179正十四烷C14H30---0.01--
22.2792,6,10-三甲基十五烷C18H38---0.02--
32.3204-甲基十二烷C13H28---0.01--
42.3954,6-二甲基十二烷C14H30---0.02--
52.437正十六烷C16H340.14-0.030.230.040.02
62.475正十八烷C18H38---0.01--
72.5255-丁基壬烷C13H28---0.01--
82.7402-异丙基-5-甲基-1-庚醇C11H24O0.02-----
92.8552,2,6-三甲基环己酮C9H16O0.01-0.01---
102.956异丙基十四烷基醚C17H36O---0.02--
113.165正十七烷C17H36---0.03--
123.1952-甲基二十八烷C29H600.01-----
133.198正十九烷C19H40---0.02--
143.265正二十烷C20H420.18-0.020.300.01-
153.365正二十一烷C21H44---0.05--
163.375β-环柠檬醛C10H16O0.04-----
173.595壬基十四烷基醚C23H48O---0.01--
183.986乙酸异龙脑酯C12H20O2-----0.02
194.279α-二氢萜品醇C10H20O---0.09--
204.3306-甲基-1,2,3,5,8,8a-六氢萘C11H160.02-----
214.525藏花烷C20H42---0.02--
225.426正二十九烷C29H60---0.04--
235.526月桂酸乙酯C14H28O2---0.080.04-
245.530二十二烷酸乙酯C24H48O2--0.01---
255.534十一烷酸乙酯C13H26O2-0.01----
265.627顺式茴香脑C10H12O0.050.05----
275.69511-(1-乙基丙基)-二十一烷C26H54---0.02--
285.705顺式香叶基丙酮C13H22O0.020.010.01---
295.820正二十四烷C24H500.01-0.010.02--
305.8953-(1,5-二甲基己-4-烯基)-2,2-二甲基-环五烷-3-烯-1-醇C15H26O-----0.01
315.8972-甲基十二烷C13H28---0.01--
326.0706-甲基-6-(5-甲基呋喃-2-基)庚烷-2-酮C13H20O20.030.010.02---
336.2453-[[(呋喃-2-甲基)氨基]甲基]-4a-羟基-5-甲氧基-5-十氢萘并[2,3-b]呋喃-2-酮C21H31NO5-----0.02
347.105肉豆蔻酸甲酯C15H30O2-0.030.04---
357.270植酮C18H36O---0.030.01-
367.2752-十五烷酮C15H30O--0.02---
377.290丁香酚甲醚C11H14O2-0.01----
387.37513-甲基-十四醛C15H30O---0.02--
397.376十四烷醛C14H28O--0.01---
407.570肉豆蔻酸乙酯C16H32O2-0.070.030.570.270.12
418.079蓝桉醇C15H26O-----0.03
428.475十五烷酸甲酯C16H32O2-0.010.01---
439.060十五烷酸乙酯C17H34O2--0.010.090.050.03
449.480(9Z)-9-十五碳烯酸乙酯C17H32O2---0.030.02-
459.992二十二烷C22H46---0.14--
4610.315棕榈酸甲酯C17H34O20.160.561.020.190.080.16
4710.945(9Z)-9-棕榈油酸甲酯C17H32O2-0.010.05---
4811.210棕榈酸乙酯C18H36O2-0.520.71 10.274.712.23
4911.631正癸酸C10H20O20.540.090.120.170.100.05
5011.800(9E)-9-棕榈油酸乙酯C18H34O2--0.030.410.200.08
5111.835(9E)-9-棕榈油酸甲酯C17H32O2-0.02----
5212.375(5E)-1,5-十二碳二烯C12H22--0.02---
5312.3802-甲基二十四烷C25H52---0.13--
5412.8212,4-二叔丁基苯酚C14H22O---0.12--
5513.824十七烷酸乙酯C19H38O2---0.060.03-
5614.245法尼基丙酮C18H30O-0.110.310.160.060.12
5715.155正二十一烷C21H44---0.11--
5815.680硬脂酸甲酯C19H38O2-0.050.08---
5916.153(9E)-9-油酸甲酯C19H36O20.160.531.150.130.050.11
6016.415(11 E)-11-油酸甲酯C19H36O2-0.040.11---
6116.670硬脂酸乙酯C20H40O2-0.040.050.780.390.13
6217.150(9Z)-9-油酸乙酯C20H38O2--0.64--1.30
6317.200(9E)-9-油酸乙酯C20H38O2-0.42-8.783.83-
6417.355月桂酸C12H24O20.590.180.57--0.62
6517.485(9Z,12Z)-9,12-亚油酸甲酯C19H34O20.120.421.020.290.120.17
6618.610(9Z,12Z)-9,12-亚油酸乙酯C20H36O2-0.370.684.411.910.97
6719.675(9Z,12Z,15Z)-9,12,15-亚麻酸甲酯C19H32O2-0.110.30-0.03-
6820.925(9Z,12Z,15Z)-9,12,15-亚麻酸乙酯C20H34O2-0.910.201.990.820.36
6921.375(9E)-9-油酸C18H34O21.650.60-2.60-
7021.820(9Z)-9-油酸C18H34O227.062.330.810.196.72-
7122.335(13Z)-13芥酸C22H42O2-0.14----
7222.500(9Z)-9-十六碳烯醛C16H30O1.68-----
7322.910(13Z)-13-油酸C18H34O2-0.41----
7422.940(10Z)-10-十七碳烯酸C17H32O2-0.400.39---
7523.350(11 Z)-11-油酸C18H34O2-1.11--1.171.32
7624.875肉豆蔻酸C14H28O22.000.873.512.910.923.28
7728.000(9Z,12Z)-9,12-亚油酸C18H32O241.9552.363.923.74 48.0745.79
7828.160正十五烷酸C15H30O2-2.167.422.460.030.04
7929.135(6Z)-6-油酸C18H34O2--0.110.44-0.78
8029.1452-羟基环十五烷酮C15H28O2-0.860.70---
8129.171(9Z)-9-十八碳烯醛C18H34O0.08-----
8229.438(9E,12E)-9,12-亚油酸C18H32O2-3.04----
8332.080棕榈酸C16H32O212.2114.3571.11 57.86 12.8428.43
8433.550(9E)-9-棕榈油酸C16H30O20.12-----
8533.555(9Z)-9-棕榈油酸C16H30O2-0.212.911.510.711.45
8634.105(11 Z)-11-棕榈油酸C16H30O2----0.03-
8735.025α-亚麻酸C18H30O23.129.640.87-8.8312.01
8835.620(8Z,11 Z,14Z)-8,11,14-二十碳三烯酸C20H34O2-1.59----
8936.810十七烷酸C17H34O2--0.35-0.03-
9036.752硬脂酸C18H36O2---0.120.20-
9136.545(9E,12E)-9,12-亚油酸甲酯C19H34O2-1.03---0.11
), ArticleFig(id=1256183529759695010, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1256183364516700361, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
指标油类鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
提取率脂肪油0.470±0.0300.360±0.0100.026±0.0040.043±0.0050.043±0.0020.041±0.001
挥发油0.008±0.0030.010±0.0010.010±0.0010.019±0.0060.025±0.0030.017±0.009
不饱和脂肪酸脂肪油22(59.63)22(59.75)6(12.40)16(54.36)5(45.00)5(52.78)
挥发油7(74.18)21(75.69)15(13.19)11(21.92)15(75.11)12(64.45)
饱和脂肪酸脂肪油22(36.66)20(35.68)13(55.75)19(39.05)16(39.72)13(33.90)
挥发油5(15.50)13(18.94)15(85.04)12(75.56)13(19.69)10(35.09)
烷烃脂肪油17(0.86)14(0.80)9(2.35)5(0.50)8(8.37)6(2.42)
挥发油4(0.34)-3(0.06)18(1.18)2(0.05)1(0.02)
挥发油3(0.06)4(0.99)6(1.07)2(0.19)2(0.07)2(0.14)
其他脂肪油12(0.75)11(1.24)8(15.31)10(3.48)3(0.26)4(1.81)
挥发油6(1.89)2(0.06)2(0.03)6(0.28)  -3(0.06)
), ArticleFig(id=1256183530481115306, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1256183364516700361, language=CN, label=表3, caption=

地黄不同炮制品脂肪油、挥发油提取率及种类、相对含量比较

, figureFileSmall=null, figureFileBig=null, tableContent=
指标油类鲜地黄生地黄熟地黄
清蒸酒蒸酒炖九制
提取率脂肪油0.470±0.0300.360±0.0100.026±0.0040.043±0.0050.043±0.0020.041±0.001
挥发油0.008±0.0030.010±0.0010.010±0.0010.019±0.0060.025±0.0030.017±0.009
不饱和脂肪酸脂肪油22(59.63)22(59.75)6(12.40)16(54.36)5(45.00)5(52.78)
挥发油7(74.18)21(75.69)15(13.19)11(21.92)15(75.11)12(64.45)
饱和脂肪酸脂肪油22(36.66)20(35.68)13(55.75)19(39.05)16(39.72)13(33.90)
挥发油5(15.50)13(18.94)15(85.04)12(75.56)13(19.69)10(35.09)
烷烃脂肪油17(0.86)14(0.80)9(2.35)5(0.50)8(8.37)6(2.42)
挥发油4(0.34)-3(0.06)18(1.18)2(0.05)1(0.02)
挥发油3(0.06)4(0.99)6(1.07)2(0.19)2(0.07)2(0.14)
其他脂肪油12(0.75)11(1.24)8(15.31)10(3.48)3(0.26)4(1.81)
挥发油6(1.89)2(0.06)2(0.03)6(0.28)  -3(0.06)
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不同制法和工艺对地黄中油类成分影响及性效关联性研究
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李宁 1 , 李红伟 1, 2, 3 , 张玉梅 1 , 张壹明 1 , 刘梦云 1 , 康乐 1 , 曹彦刚 1 , 李凯 1, 2, 3 , 朱建光 1 , 冯卫生 1
中华中医药学刊 | 国家项目点击 2025,43(12): 79-86
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中华中医药学刊 | 国家项目点击 2025, 43(12): 79-86
不同制法和工艺对地黄中油类成分影响及性效关联性研究
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李宁1, 李红伟1, 2, 3 , 张玉梅1, 张壹明1, 刘梦云1, 康乐1, 曹彦刚1, 李凯1, 2, 3, 朱建光1, 冯卫生1
作者信息
  • 1.河南中医药大学药学院,河南 郑州 450046
  • 2.豫药全产业链研发河南省协同创新中心,河南 郑州 450046
  • 3.河南省中药特色炮制技术工程研究中心,河南 郑州 450046
  • 李宁(1998-),女,山东潍坊人,硕士在读,研究方向:中药炮制机理及饮片标准化。

通讯作者:

李红伟(1979-),男,河南长葛人,副教授,硕士研究生导师,博士,研究方向:中药炮制机理及饮片标准化。E-mail:
冯卫生(1960-),男,河南林州人,教授,博士研究生导师,博士,研究方向:中药药效物质基础研究及新药开发。E-mail:
Influence of Different Preparation and Processing Methods on Oil Components in Dihuang(Rehmanniae Radix)and Correlation between Properties and Effects
Ning LI1, Hongwei LI1, 2, 3 , Yumei ZHANG1, Yiming ZHANG1, Mengyun LIU1, Le KANG1, Yangang CAO1, Kai LI1, 2, 3, Jianguang ZHU1, Weisheng FEGN1
Affiliations
  • 1.School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,Henan,China
  • 2.Collaborative Innovation Center of Research and Development on theWhole Industry Chain of Yu-Yao,Zhengzhou 450046,Henan,China
  • 3.Henan Research Center for Special Processing Technology of Chinese Medicine,Zhengzhou 450046,Henan,China
出版时间: 2025-12-10 doi: 10.13193/j.issn.1673-7717.2025.12.013
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目的

考察不同炮制方法和工艺对地黄中油类成分的影响,明晰方法、工艺和所含成分与制品的药性的关联性,为地黄炮制研究和临床应用提供指导。

方法

挥发油提取参照2020年版《中华人民共和国药典》中挥发油测定法甲法提取,索氏法提取脂肪油,气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometry,GC-MS)鉴定油类成分及其相对含量,热图分析明晰不同制方法和工艺对油类成分影响的特点,结合文献学探讨制法、工艺-成分-性效关联性。

结果

地黄不同炮制品中油成分主要是脂肪酸类;脂肪油提取率为鲜地黄>生地黄>酒蒸≈酒炖>九制>清蒸,挥发油提取率为酒炖>酒蒸>九制>生地黄≈清蒸>鲜地黄。脂肪油和挥发油热图均显示酒炖和九制熟地黄聚为一类。

结论

油类成分种类和相对含量改变和调整,是熟地黄药性和功能主治差异的重要物质基础;加入辅料酒、砂仁和增加蒸晒次数有助于降低地黄的寒滑之性和熟地黄的滋腻之性,增强熟地黄温补作用;挥发油成分是熟地黄“气微”的物质基础。

熟地黄  /  炮制  /  脂肪油  /  挥发油  /  GC-MS
Objective

To investigate the effects of preparation and processing methods on the contents of oil components in Dihuang(Rehmanniae Radix)and clarify the correlation between oil components with medicinal properties,in order to provide guidance for processing research and clinical application.

Methods

The extraction of volatile oil refers to the volatile oil determination method A in the 2020 edition of Chinese Pharmacopoeia,and the Soxhlet method was used to extract fatty oil.Gas Chromatography Mass Spectrometry(GC-MS)was used to identify the oil components and their relative contents.Thermographic analysis was used to clarify the characteristics of the influence of different preparation and processing methods on oil components.Combined with literature review,the correlation of processing,preparation,components and properties was discussed.

Results

The oil components weremainly fatty acids.The order of the extraction rate of fatty oil was fresh Dihuang(Rehmanniae Radix)>raw Dihuang(Rehmanniae Radix)>steaming with wine≈stewing with wine>steaming and exposing nine times with Sharen(Amomi Fructus)>steaming without ingredients,and the order of the volatile oil extraction rate was stewing with wine>steaming with wine>steaming and exposing nine times with Sharen(Amomi Fructus)>raw Dihuang(Rehmanniae Radix)≈steaming without ingredients>fresh Dihuang(Rehmanniae Radix).The heatmap analysis of fatty oil and volatile oil showed that Shudihuang(Rehmanniae Radix Praeparata)stewing with wine and that steaming and exposing nine times with Sharen(Amomi Fructus)were clustered one category.

Conclusion

The changes and adjustments of the types and relative contents of oil componentswere important material basis for the differences in medicinal property of Dihuang(Rehmanniae Radix)processed products.Adding wine,Sharen(Amomi Fructus)or increasing steaming and exposing times were helpful in reducing the cold nature of Dihuang(Rehmanniae Radix),and the greasy nature of Shudihuang(Rehmanniae Radix Praeparata),and enhance thewarming-reinforcing effect.The volatile oil components in different products of Dihuang(Rehmanniae Radix)were the material basis of their“Qiwei”.

Dihuang(Rehmanniae Radix)  /  processing  /  fatty oil  /  volatile oil  /  GC-MS
李宁, 李红伟, 张玉梅, 张壹明, 刘梦云, 康乐, 曹彦刚, 李凯, 朱建光, 冯卫生. 不同制法和工艺对地黄中油类成分影响及性效关联性研究. 中华中医药学刊, 2025 , 43 (12) : 79 -86 . DOI: 10.13193/j.issn.1673-7717.2025.12.013
Ning LI, Hongwei LI, Yumei ZHANG, Yiming ZHANG, Mengyun LIU, Le KANG, Yangang CAO, Kai LI, Jianguang ZHU, Weisheng FEGN. Influence of Different Preparation and Processing Methods on Oil Components in Dihuang(Rehmanniae Radix)and Correlation between Properties and Effects[J]. Chinese Archives of Traditional Chinese Medicine, 2025 , 43 (12) : 79 -86 . DOI: 10.13193/j.issn.1673-7717.2025.12.013
地黄为玄参科植物地黄Rehmannia glutinosa Libosch.的新鲜或干燥块根,始载于《神农本草经》,被列为上品,因其功效显著而作为对症之要药—君药。《中华人民共和国药典》2020年版收载地黄3种炮制品—鲜地黄、生地黄和熟地黄,三者药性和功能主治迥异[1]。现有研究表明无论从化学成分的含量,还是从种类来说三者都具有明显差别[2-3]
地黄及其炮制品中化学成分的研究,先前多集中于环烯醚萜、苯乙醇苷、酚酸、糖类等,而油类成分的研究相对较少[4-7]。倪慕云等最早研究发现地黄及其炮制品中含有脂肪酸类成分[8-10],陈旭等从鲜地黄中分离得到十七烷酸甲酯等油类成分[11],李孟等对鲜地黄、生地黄和熟地黄中脂肪油类成分的种类和相对含量进行分析,明确三者之间的差异[12]。挥发油成分最早发现于干地黄中,并初步进行了定性鉴别[13]。目前,地黄不同制品中油类成分研究亟待解决两方面的科学问题:一是熟地黄炮制品存在多种炮制方法和工艺,不同炮制方法和工艺对其油类成分的影响和变化规律并不明确;二是地黄各炮制品中油类成分的变化与其药性和功能主治的关联性未得到科学的阐释。因此,本研究基于气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometry,GC-MS)和聚类热图分析,全面和系统性对地黄3种炮制品中油类成分(脂肪油和挥发油)进行定量和定性分析,明晰制法和工艺对油类成分的影响,探讨制法和工艺-油类成分-药性-功能主治的关联性,从油类成分角度阐明地黄不同制品的性效关联性,以及熟地黄炮制方法和工艺的科学内涵。
GC-2010Uira型气相色谱-质谱仪(日本岛津公司);色谱柱为HP-FFAP(30 mm×0.25 mm×0.25μm)。7890/7000B型三重串联四极杆GC-MS仪(美国Agilent公司);色谱柱为HP-5(30 mm×0.25 mm×0.1μm)。LGJ-10D型冷冻干燥机(北京四环科学仪器厂有限公司);SHSL型电热套(上海树立仪器仪表有限公司);114B摇摆式粉碎机(瑞安市永历制药机械有限公司);HH-6数显恒温水浴锅(上海力辰邦西仪器科技有限公司);N-1100旋转蒸发仪(日本东京理化器械株式会社);HWL-125型电热恒温干燥箱(天津市莱玻特瑞仪器设备有限公司)。
石油醚(批号20230515)及甲醇(批号20230212),天津市富宇精细化工有限公司;正己烷(批号2020091801),山东禹王和天下新材料有限公司;无水硫酸钠(批号S112268),阿拉丁试剂有限公司;氢氧化钾(批号20140601),天津市致远化学试剂有限公司;三氟化硼甲醇络合物(批号C10006531),上海麦克林生化科技有限公司;黄酒(批号20211013A),绍兴柯桥第三酒厂。
鲜地黄、生地黄产自河南焦作,砂仁产自广东阳春,经河南中医药大学药学院董诚明教授鉴定为玄参科地黄属植物地黄R.glutinosa Libosch.的新鲜块根与干燥块根以及姜科植物阳春砂Amomum villosum Lour.的干燥成熟果实。
鲜地黄:取鲜地黄原药材,除去杂质,洗净,切厚片,冷冻干燥[12]
生地黄:取鲜地黄药材,置于烘箱中75℃干燥,取出,稍闷,放凉,干燥,即得[12]
九制熟地黄:取生地黄,参照《河南省中药饮片炮制规范》2022版方法制备:加入黄酒和砂仁蒸制九次,晾至外皮黏液稍干时,切厚片,干燥。(100 kg生地黄用黄酒50 kg、砂仁粉0.9 kg)
清蒸熟地黄:取生地黄,蒸制12 h,闷12 h后,上下翻动1次,如此反复蒸闷2次,70℃干燥,取出,放凉[14]
酒蒸熟地黄:取生地黄,加入黄酒。蒸制12 h,闷12 h后,上下翻动1次,如此反复蒸闷2次,70℃干燥,取出,放凉。(100 kg生地黄用黄酒40 kg)[14]
酒炖熟地黄:取生地黄,加入黄酒拌匀,闷润至酒吸尽,在陶瓷罐里隔水,连续炖制48 h后,70℃干燥,取出,放凉(100 kg生地黄用黄酒40 kg)[14]
挥发油提取参照2020年版《中华人民共和国药典》中挥发油测定法甲法,分别取100.00 g地黄不同炮制品,粉碎,加10倍量蒸馏水,保持微沸提取8 h,收集挥发油,无水硫酸钠脱水干燥即得[15]
脂肪油提取,分别取地黄不同炮制品20.0 g,粉碎,加入200 mL石油醚索氏回流提取8 h,减压干燥即得。所得脂肪油进一步进行甲酯化反应,得到脂肪油供试品[15]
计算得率为y=a/b×100%,其中y为脂肪油或挥发油得率,a为各制品脂肪油或挥发油质量,b为各炮制品质量。
脂肪油:HP-5型石英毛细管柱(30 mm×0.25 mm,0.1μm);高纯氦气(99.999%),1.0 mL·min-1;进样口温度为240℃;进样量为1.0μL;2∶1分流;升温程序为80℃保持2 min,按10℃·min-1升温至155℃并保持35 min,再按10℃·min-1升温至190℃并保持2 min,然后再以2℃·min-1升温至230℃并保持10min;气化室温度为280℃;接口温度为240℃。离子源为电子轰击源,温度为230℃,电子能量为70 eV;扫描范围为质荷比(m·z-1)30~600;溶剂延迟时间为4.5 min,接口温度为240℃。
挥发油:HP-FFAP型石英毛细管柱(30 mm×0.25 mm×0.25μm),高纯氦气(99.999%),流速:1.0 mL·min-1,进样口温度:250℃。进样量:1.0μL,分流比:40∶1。升温程序:初始温度80℃并保持0.5 min,以30℃·min-1的速度升温至165℃并保持1 min,再以4℃·min-1的速度升温至175℃并保持5 min,再以3℃·min-1的速度升温至190℃并保持5 min,再以4℃·min-1的速度升温至210℃并保持8 min,然后再以4℃·min-1升温至220℃并保持2 min。离子源为电子轰击源,温度为200℃,电子能量为70 eV;扫描范围为质荷比35~1000 m·z-1;溶剂延迟时间为2 min,接口温度为220℃。
运用GC-MS分析鲜地黄与生地黄及炮制品的挥发油、脂肪油成分,得到的总离子流图在NIST11、NIST17质谱数据库(匹配度为90%以上)中检索,并查阅文献进行定性分析,采用峰面积归一化法计算各挥发性成分的相对含量。统计学方法采用TBtools v1.120软件绘制热图。
鲜地黄脂肪油、挥发油总离子流图见图1图2,成分种类及相对含量检测结果见表1表2。生地黄不同炮制品中的脂肪油和挥发油类成分主要是脂肪酸类,其次是萜类、芳香族类、醇、醛和酮等。
脂肪油提取率为鲜地黄>生地黄>酒蒸≈酒炖>九制>清蒸,表明鲜地黄→生地黄→熟地黄,脂肪油提取率、检出成分种类和鉴定成分种类均逐渐降低或减少;熟地黄不同炮制工艺中,加辅料酒炮制熟地黄脂肪油提取率高于清蒸炮制。脂肪油所含不饱和脂肪酸的相对含量大小顺序为生地黄>鲜地黄>酒蒸>九制>酒炖>清蒸。见表1表3
挥发油提取率为酒炖>酒蒸>九制>生地黄≈清蒸>鲜地黄,酒炖由于密闭性相对较好,其挥发油提取率最高,表明酒炖炮制利于挥发性成分的保留;九制熟地黄挥发油提取率相对清蒸熟地黄高,可能与添加富含挥发油的砂仁有关,因九制熟地黄挥发油中检测出砂仁挥发油中成分—乙酸异龙脑酯和蓝桉醇[16]。挥发油成分以脂肪酸为主,其中所提取不饱和脂肪酸的相对含量大小顺序为鲜地黄>生地黄>酒炖>九制>酒蒸>清蒸。见表2表3
为探究不同炮制品中油类全成分的差异,采用聚类热图分析。以鉴定出化合物峰面积为变量,采用样品间连接平方欧式测度的方法进行聚类分析,并绘制聚类热图,见插页ⅩⅩⅧ图3,图中每一行代表一个化合物,每一列代表一个样品,暖色调红色代表峰面积较大,冷色调蓝色代表峰面积较小[17]。由插页ⅩⅩⅧ图3可知,各样品聚类热图红色部分为其独有成分,即各炮制品间的特异性物质。脂肪油聚类热图(插页ⅩⅩⅧ图3A)中生地黄和鲜熟地黄聚为一类,酒炖和九制熟地黄聚为一类,表明以上炮制品中脂肪油类成分相似度较高。挥发油聚类热图(插页ⅩⅩⅧ图3B)中酒炖和九制熟地黄聚为一类。
《中华人民共和国药典》2020年版载“气微”为鲜地黄、生地黄和熟地黄三者的共性,通过本研究表明,三者制品所含的挥发油类共有成分包括棕榈酸及其甲酯、(9Z,12Z)-9,12-亚油酸及其甲酯、肉豆蔻酸,以上共有成分总相对含量均超过56.00%以上,说明共有成分不仅是三者共性“气微”的重要物质基础,也是三者药性和功能主治共性的重要物质基础。现有文献研究可知,肉豆蔻酸及其甲酯无气味,棕榈酸及其甲酯具有脂肪味,而(9Z,12Z)-9,12-亚油酸微弱的脂肪味,其余成分的含量和气味多无气味或脂肪味,进一步说明不同制品“气微”的科学性。
鲜地黄味甘、苦,性寒,炮制加工成生地黄,寒性和苦味减弱;生地黄加工成熟地黄,苦味消失,寒转微温,功能由清转补。从油类成分角度阐释,油类具有润肠通便或致泻等作用,其主要成分为长链脂肪酸类。熟地黄,鲜地黄和生地黄中含一定量的长链脂肪酸类成分,如棕榈酸、(9Z,12Z)-9,12-亚油酸和肉豆蔻酸等[18]。中医认为生地黄之寒,往往致大瘕之泻,不可不慎用也。《本草新编》载:“久则脾胃太凉,必至泄泻”。本研究结果表明,鲜地黄→生地黄→熟地黄炮制后,脂肪油提取率显著降低,以及调整脂肪油成分的种类和相对含量,从而减少或消除鲜地黄和生地黄的苦寒滑肠致泻不良反应,增强熟地黄的温补作用。
目前,熟地黄炮制并无统一、规范的炮制方法和工艺,究其重要原因中医药学者忌惮其滋腻之性,并以“相恶为制”为制则,通过添加黄酒、砂仁辅料,以及增加蒸晒次数等法来降低其滋腻之性,如《本草害利》载:“盖熟地性泥,得之香窜砂仁,合和五脏冲和之气,归宿丹田,故用好酒入砂仁末在内,拌蒸晾九蒸九晾乃止,入药为良。”[1419-22]李娴等研究表明,在熟地黄不同炮制品中,以清蒸熟地黄的滋腻之性最强,加入辅料酒、砂仁,以及蒸晒次数有助于降低滋腻之性[14]。现代研究表明,挥发油多属辛“能行能散”,兴奋胃肠蠕动,排除胃肠积气呆滞,消除胸腹痞满之效[23]。本研究结果表明,相对于清蒸熟地黄,加入辅料酒、砂仁,以及蒸晒次数能提高熟地黄中脂肪油和挥发油的提取率及二者不饱和脂肪酸的相对含量,这可能是熟地黄“相恶炮制”降低滋腻之性的原因之一。脂肪油和挥发油热图均显示酒炖和九制熟地黄聚为一类,清蒸熟地黄明显区别于地黄其他炮制品,进一步表明加入辅料酒、砂仁以及增加蒸晒次数是熟地黄“相恶为制”降腻的炮制机制。
同时,九制熟地黄挥发性成分中含有相对其他制品的独有成分:乙酸异龙脑酯和蓝桉醇,二者是砂仁中原有挥发性成分,因此,二者可以作为砂仁降低熟地黄滋腻之性的重要标志性成分[24-25]
综上所述,本研究明晰了地黄不同制品“气微”的物质基础;降低脂肪油提取率,有利于降低鲜地黄和生地黄的寒滑之性,增强熟地黄的温补性能;加入辅料酒、砂仁,以及增加蒸晒次数有利于挥发油提取率升高,是降低熟地黄滋腻之性的原因之一;确立了九制熟地黄的标志性成分,为加辅料酒和砂仁炮制降低熟地黄滋腻之性下一步研究提供思路和研究方向。
  • 国家自然科学基金面上项目(82474099)
  • 河南省科技攻关项目(232102311214; 242102310542)
  • 河南省科技研发计划联合基金(优势学科培育类)项目(232301420073)
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doi: 10.13193/j.issn.1673-7717.2025.12.013
  • 首发时间:2026-04-29
  • 出版时间:2025-12-10
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国家自然科学基金面上项目(82474099)
河南省科技攻关项目(232102311214; 242102310542)
河南省科技研发计划联合基金(优势学科培育类)项目(232301420073)
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    1.河南中医药大学药学院,河南 郑州 450046
    2.豫药全产业链研发河南省协同创新中心,河南 郑州 450046
    3.河南省中药特色炮制技术工程研究中心,河南 郑州 450046

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李红伟(1979-),男,河南长葛人,副教授,硕士研究生导师,博士,研究方向:中药炮制机理及饮片标准化。E-mail:
冯卫生(1960-),男,河南林州人,教授,博士研究生导师,博士,研究方向:中药药效物质基础研究及新药开发。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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