CN115677816B - 一种新的呋甾皂苷单体及其制备方法 - Google Patents
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
本发明公开了一种新的呋甾皂苷单体即(25R)‑26‑O‑β‑D‑吡喃葡萄糖基‑5α‑呋甾‑3β,22α,26‑三醇‑3‑O‑β‑D‑吡喃葡萄糖基‑(1→2)‑[β‑D‑吡喃葡萄糖基‑(1→3)]‑[6‑乙酰基]‑β‑D‑吡喃葡萄糖基‑(1→4)‑β‑D‑吡喃半乳糖苷及其制备方法。将新鲜的薤用水提取、提取液经大孔吸附树脂吸附,乙醇溶液洗脱,得到薤总甾体皂苷后利用硅胶柱层析、ODS柱层析,制备型高效液相色谱分离纯化,得到新呋甾皂苷单体,其纯度大于98.0%。本发明获得的新甾体皂苷单体可用于中药材薤白或农产品新鲜薤的质量控制。
Description
技术领域
本发明属于天然药物化学研究领域,涉及一种从薤中提取分离得到的新的呋甾皂苷单体及其制备方法。
背景技术
薤(Allium Chinense G.Don)为百合科葱属植物,又名藠头、苦藠、薤白头、野蒜等,可以大量种植,广泛分布于我国的中部以及东部地区,如河南、安徽、山东、江西、广东等地。薤是中药材薤白的基源植物之一,是药食同源植物。薤具有温补、理气宽胸、还阳散结的功效。其最初记载于《神农本草经》:“薤,味辛温,主治金创,创败,轻身,不饥,耐老,生平泽”。
薤中含甾体皂苷类化合物、挥发油、含氮化合物、脂肪酸类化合物和多糖类化合物等化学成分,其中,甾体皂苷是薤中最主要的活性成分之一,包括螺甾类皂苷和呋甾类皂苷两大类。它是一类由甾体皂苷元与糖基组成的皂苷类化合物。根据皂苷元基本骨架可将其分为螺甾烷醇类、异螺甾烷醇类、呋甾烷醇类和变形螺甾烷醇类,其皂苷元主要有5种,分别是吉托皂苷元(gitogenin)、提果皂苷元(tigogenin)、拉克索皂苷元(laxogenin)、撒尔沙皂苷元(sarsapogenin)、菝葜皂苷元(smilagenin)。糖基中主要有葡萄糖、半乳糖、木糖、阿拉伯糖等。
薤的水提取物或醇提取物以及甾体皂苷单体化合物常用于抑制血小板聚集、抗氧化、抑菌、抑制动脉粥样硬化、抗肿瘤、抗抑郁、降血脂、保护心肌细胞、提高免疫力等。
发明内容
本发明提供了从薤中提取分离得到的一种新的呋甾型甾体皂苷单体化合物及其制备方法。
本发明的具体技术内容如下:
以薤的鳞茎为原料,用水提取,离心,提取液利用大孔吸附树脂进行吸附,有机溶剂的水溶液进行洗脱,洗脱液TLC检测,收集含甾体皂苷部分,此部分洗脱液减压回收溶剂,干燥,得到薤总甾体皂苷。取薤总甾体皂苷进行硅胶柱层析、ODS柱层析以及制备型高效液相色谱分离纯化后,最终得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷(简称化合物1)。
所述薤的提取方法为:取新鲜的薤的鳞茎水洗干净,用破壁机搅碎,加水浸提或搅拌提取,或取干燥的薤的鳞茎粉碎,加水浸提或乙醇回流提取,离心,合并提取液,水提取液直接过大孔吸附树脂柱进行吸附,乙醇提取液回收乙醇至无醇味加水稀释后再过大孔吸附树脂柱进行吸附,有机溶剂水溶液进行洗脱,洗脱液减压回收溶剂得薤总甾体皂苷。洗脱用有机溶剂为甲醇或者乙醇或丙酮。
所述的大孔吸附树脂选自AB-8、D101、D4020和HP-20的一种或它们的两种或两种以上的混合树脂。
所述的有机溶剂的水溶液是体积百分比浓度大于或等于20%的水溶液。
所述的薤提取液经大孔吸附树脂吸附后,用体积百分比浓度大于20%的有机溶剂水溶液进行洗脱得到薤总甾体皂苷,其中含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷。
取薤总甾体皂苷以乙酸乙酯-乙醇-水(11:1:0.1~1:9:1)为洗脱剂进行硅胶柱层析梯度洗脱,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分A。将组分A以流动相二氯甲烷-甲醇-水(11:1:0.1-20:7.5:1)再次进行硅胶柱层析梯度洗脱,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分B。将组分B以流动相丙酮-水(1.5:1)进行ODS柱层析分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C。最后将组分C以乙腈-水(87:13)为流动相利用制备型高效液相色谱进行分离纯化,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷单体。
所述的薤可以是新鲜的薤,也可以是将薤蒸透或置沸水中烫透后晒干的干燥薤,最好是利用新鲜的薤,且最好使用鳞茎。也可以使用薤全草或其地上部分。
本发明利用NMR及MS等手段对分得的化合物1的化学结构进行了鉴定,鉴定过程及数据具体如下。
化合物1为白色无定形粉末,对E试剂(体积比为4:1的1%对二甲氨基苯甲醛乙醇溶液和浓盐酸)显粉红色,提示该化合物为呋甾皂苷类化合物。HR-ESI-MS给出分子离子峰为m/z1269.6111[M+H-H2O]+,提示化合物1的分子量为1269.6110,分子式为C59H98O30。
从化合物1的13C-NMR谱中,可以看到59个碳信号,其中包括27个皂苷元碳信号和32个与糖相关的碳信号。结合DEPT 90°和DEPT 135°谱可知,皂苷元中有4个伯碳信号δC16.87(C-18)、δC12.42(C-19)、δC16.59(C-21)、δC17.59(C-27);11个仲碳信号,其中连氧碳信号为δC75.53(C-26);9个叔碳信号,其中连氧碳信号δC77.62(C-3)、δC81.26(C-16);3个季碳信号δC35.94(C-10)、δC41.23(C-13)、δC110.76(C-22)。δC110.76为呋甾皂苷元C-22位的特征吸收信号。低场区出现5个糖的端基碳信号δC102.82、δC105.45、δC104.79、δC104.68、δC105.29,提示化合物1中可能存在5个糖。δC171.35处羰基碳信号和δC21.25(CH3)碳信号以及1H-NMR谱中δH1.923氢信号的出现,提示分子中可能存在一个乙酰基,高场端C-18(δC16.87)碳信号与C-19(δC12.42)碳信号相比处于低场,提示分子中存在5-α-H。
在1H-NMR谱中,低场区有5个糖的端基质子信号:δH4.683(1H,d,J=7.8Hz)、δH4.955(1H,d,J=7.8Hz)、δH5.520(1H,d,J=7.2Hz)、δH5.154(1H,d,J=7.8Hz)、δH4.687(1H,d,J=7.8Hz),进一步确定分子中可能有5分子糖,由J值可知,糖均为β-D构型。在高场区出现皂苷元上4个甲基氢信号:δH0.745(Me-18)、δH0.539(Me-19)、δH1.187(Me-21)、δH0.898(Me-27)。
在HMBC谱中,Me-18(δH0.745)分别与δC40.34,δC41.23,δC56.50,δC64.0有远程相关,结合HSQC谱,可以将这些碳信号分别归属为C-12,C-13,C-14,C-17;Me-19(δH0.539)分别与δC37.32,δC44.79,δC54.56,δC35.94有远程相关,结合HSQC谱,可以将这些碳信号分别归属为C-1,C-5,C-9,C-10;Me-21(δH1.187)分别与δC64.05,δC40.82,δC110.76有远程相关,结合HSQC谱,可以将这些碳信号分别归属为C-17、C-20和C-22;Me-27(δH0.898)分别与δC28.46,δC34.56,δC75.53有远程相关,结合HSQC谱,可以将这些碳信号分别归属为C-24、C-25和C-26。通过HMBC谱可知,半乳糖的端基质子(δH4.683)与母核C-3(δC77.62)存在远程相关,因此推测该糖连接在皂苷元母核C-3位,内侧葡萄糖的端基质子δH4.955与半乳糖C-4'(δC80.73)存在远程相关,推测其连接方式为1→4。C-6"上的氢信号δH5.058与C-5"(δC75.93)以及乙酰基的羰基δC171.35存在远程相关,推测乙酰基连接在C-6"位。外侧2个葡萄糖端基质子δH5.520,δH5.154分别与内测葡萄糖C-2"(δC81.18)和C-3"(δC88.42)存在远程相关,推测两分子葡萄糖与内侧葡萄糖的连接方式分别为1→2和1→3。另一个葡萄糖的端基质子δH4.687与母核C-26(δC75.53)存在远程相关,因此推测该糖连接在皂苷元C-26位。
化合物1的C-26位质子信号(δHa3.964、δHb3.895)的Δab=δHa-δHb≤0.48,提示25位的构型为R构型(Δab≤0.48为R构型,Δab≥0.57为S构型)。
综上所述,最终确认化合物1为(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷。(25R)-26-O-β-D-glucopyranosyl-5α-furostane-3β,22α,26-triol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-[6-acetyl]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside。经文献检索,确认其为新化合物。化合物1的HMBC、1H-1H COSY见图1,13C-NMR数据见表1。
表1化合物1的13C-NMR(150MHz)和1H-NMR(600MHz)数据(δ/ppm,C5D5N)
检测化合物1纯度的HPLC色谱条件如下:色谱柱:Agilent Eclipse XAmide(4.6ⅹ250mm,5μm),流动相:乙腈-水(87:13),流速:1L/min,柱温:30℃,进样量:20μL,ELSD检测器,漂移管温度80℃,撞击器状态:关闭,载气压力:0.45Mpa,雾化器流速:2.1L/min,放大倍数:1.0倍。
本发明获得的新的呋甾皂苷单体可用于中药材薤白的质量控制,也可以用于含有薤的保健食品或药物组合物及其他产品的质量控制。
附图说明
图1.化合物1的质谱图
图2.化合物1的1H-NMR图
图3.化合物1的13C-NMR图
图4.化合物1的DEPT 90°、DEPT 135°图
图5.化合物1的1H-1H COSY图
图6.化合物1的HMBC图
图7.化合物1的HSQC图
具体实施方式
以下对本发明的优选实施例进行说明。应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
取新鲜的薤的鳞茎10Kg,洗净,利用破壁机搅碎,破壁时间为5min,破壁后加8倍水搅拌提取三次,提取时间均为15分钟,离心,合并提取液,过D101大孔吸附树脂吸附,80%的乙醇洗脱,洗脱液减压浓缩,干燥,得到薤总甾体皂苷58g。
取薤总甾体皂苷以乙酸乙酯-乙醇-水(11:1:0.1-1:9:1)为流动相进行硅胶柱层析梯度洗脱,TLC检测,合并含化合物1组分,得组分C。将组分C以二氯甲烷-甲醇-水(11:1:0.1-20:7.5:1)为流动相进行硅胶柱层析梯度洗脱分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-1。将组分C-1以流动相丙酮-水(1.5:1)进行ODS柱层析分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-2。最后将组分C-2以乙腈-水(87:13)为流动相利用制备型高效液相色谱进行分离纯化,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷单体41mg。
分离得到的(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷(化合物1)用HPLC-ELSD法检测,其纯度为98.5%。
实施例2
取干燥薤1Kg粉碎,85%乙醇回流提取三次,乙醇用量分别为干燥薤重量的10、8、6倍(重量体积比),提取时间分别为为90、60、45分钟,离心,合并提取液,减压回收乙醇至无醇味,加20升水稀释,过AB-8大孔吸附树脂吸附,90%的甲醇溶液洗脱,洗脱液减压回收溶剂,干燥,得到薤总甾体皂苷部分45g。
取薤总甾体皂苷以乙酸乙酯-乙醇-水(11:1:0.1-1:9:1)为流动相进行硅胶柱层析梯度洗脱,TLC检测,合并含化合物1组分,得组分C。将组分C以二氯甲烷-甲醇-水(11:1:0.1-20:7.5:1)为流动相进行硅胶柱层析梯度洗脱,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-1。将组分C-1以流动相丙酮-水(1.6:1)进行ODS柱层析分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-2。最后将组分C-2以乙腈-水(87:13)为流动相利用制备型高效液相色谱进行分离,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷单体57mg。经HPLC-ELSD检测,其纯度为99.2%
实施例3
取新鲜的薤的全草10Kg,洗净,利用破壁机搅碎,破壁时间为5min,破壁后加10倍水搅拌提取三次,提取时间均为20分钟,离心,合并提取液,过D4020大孔吸附树脂吸附,80%的乙醇洗脱,洗脱液减压浓缩,干燥,得到薤总甾体皂苷62g。
取薤总甾体皂苷以乙酸乙酯-乙醇-水(11:1:0.1-1:9:1)为流动相进行硅胶柱层析梯度洗脱,经TLC分析,合并含化合物1组分,得组分C。将组分C以二氯甲烷-甲醇-水(11:1:0.1-20:7.5:1)为流动相进行硅胶柱层析,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-1。将组分C-1以流动相丙酮-水(1.4:1)进行ODS柱层析分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-2。最后将组分C-2以乙腈-水(87:13)为流动相利用制备型高效液相色谱进行分离,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷单体42mg。经HPLC-ELSD检测,其纯度为97.9%
实施例4
取新鲜的薤地上部分10Kg,洗净,利用破壁机搅碎,破壁时间为8min,破壁后加10倍水搅拌提取三次,提取时间均为15分钟,离心,合并提取液,过HP-20大孔吸附树脂吸附,80%的丙酮洗脱,洗脱液减压浓缩,干燥,得到薤总甾体皂苷66g。
取薤总甾体皂苷以乙酸乙酯-乙醇-水(11:1:0.1-1:9:1)为流动相进行硅胶柱层析梯度洗脱,经TLC分析,合并含化合物1组分,得组分C。将组分C以二氯甲烷-甲醇-水(11:1:0.1-20:7.5:1)为流动相进行硅胶柱层析,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-1。将组分C-1以流动相丙酮-水(1.8:1)进行ODS柱层析分离,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷的组分C-2。最后将组分C-2以乙腈-水(86:14)为流动相利用制备型高效液相色谱进行分离,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷单体50mg。经HPLC-ELSD检测,其纯度为95.3%
前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种呋甾皂苷单体的制备方法,其特征在于以薤为原料,用水提取,提取液经大孔吸附树脂吸附,有机溶剂洗脱,减压回收洗脱液,干燥,得到含有(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷在内的薤总甾体皂苷,取薤总甾体皂苷进行硅胶柱层析、ODS柱层析,制备型高效液相色谱分离纯化,得到(25R)-26-O-β-D-吡喃葡萄糖基-5α-呋甾-3β,22α,26-三醇-3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃葡萄糖基-(1→3)]-[6-乙酰基]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷;所述的大孔吸附树脂选自AB-8、D101、D4042或HP-20中的一种或它们中的两种或两种以上的混合树脂;所述洗脱剂为体积比浓度为20-100%的有机溶剂的水溶液,所述有机溶剂选自乙醇、甲醇、丙酮或它们中的两种或两种以上混合溶剂;所述的硅胶柱层析洗脱剂为乙酸乙酯-乙醇-水混合溶剂,体积比为11:1:0.1~1:9:1或二氯甲烷-甲醇-水混合溶剂,体积比为11:1:0.1-20:7.5:1;所述的ODS柱层析洗脱剂为丙酮-水混合溶剂,体积比为1.5:1;所述的制备型高效液相色谱流动相是乙腈-水混合溶剂,体积比为87:13;所述的薤是新鲜的薤的鳞茎。
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