Sun Xue-Hao, Chen Jia-Xuan, Yin Jia-Xin, Han Xiao, Dou Zhi-Ying, Li Zheng, Kang Li-Ping, Yu He-Shui
College of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine Tianjin 301617, China.
School of Chinese Materia Medica, Tianjin University of Traditional Chinese Medicine Tianjin 301617, China.
Zhongguo Zhong Yao Za Zhi. 2025 Jul;50(14):3909-3917. doi: 10.19540/j.cnki.cjcmm.20250321.302.
The study investigated the intrinsic changes in material basis of Angelicae Sinensis Radix during wine processing by headspace-gas chromatography-ion mobility spectrometry(HS-GC-IMS), headspace-solid phase microextraction-gas chromatography-mass spectrometry(HS-SPME-GC-MS), and ultra-high performance liquid chromatography-quadrupole-orbitrap mass spectrometry(UPLC-Q-Orbitrap-MS) combined with chemometrics. HS-GC-IMS fingerprints of Angelicae Sinensis Radix before and after wine processing were established to analyze the variation trends of volatile components and characterize volatile small-molecule substances before and after processing. Principal component analysis(PCA) and orthogonal partial least squares-discriminant analysis(OPLS-DA) were employed for differentiation and difference analysis. A total of 89 volatile components in Angelicae Sinensis Radix were identified by HS-GC-IMS, including 14 unsaturated hydrocarbons, 16 aldehydes, 13 ketones, 9 alcohols, 16 esters, 6 organic acids, and 15 other compounds. HS-SPME-GC-MS detected 118 volatile components, comprising 42 unsaturated hydrocarbons, 11 aromatic compounds, 30 alcohols, 8 alkanes, 6 organic acids, 4 ketones, 7 aldehydes, 5 esters, and 5 other volatile compounds. UPLC-Q-Orbitrap-MS identified 76 non-volatile compounds. PCA revealed distinct clusters of raw and wine-processed Angelicae Sinensis Radix samples across the three detection methods. Both PCA and OPLS-DA effectively discriminated between the two groups, and 145 compounds(VIP>1) were identified as critical markers for evaluating processing quality, including 4-methyl-3-penten-2-one, ethyl 2-methylpentanoate, and 2,4-dimethyl-1,3-dioxolane detected by HS-GC-IMS, angelic acid, β-pinene, and germacrene B detected by HS-SPME-GC-MS, and L-tryptophan, licoricone, and angenomalin detected by UPLC-Q-Orbitrap-MS. In conclusion, the integration of the three detection methods with chemometrics elucidates the differences in the chemical material basis between raw and wine-processed Angelicae Sinensis Radix, providing a scientific foundation for understanding the processing mechanisms and clinical applications of wine-processed Angelicae Sinensis Radix.
本研究采用顶空-气相色谱-离子迁移谱(HS-GC-IMS)、顶空-固相微萃取-气相色谱-质谱(HS-SPME-GC-MS)和超高效液相色谱-四极杆-轨道阱质谱(UPLC-Q-Orbitrap-MS)结合化学计量学方法,研究了当归酒制过程中物质基础的内在变化。建立了当归酒制前后的HS-GC-IMS指纹图谱,以分析挥发性成分的变化趋势,并表征酒制前后的挥发性小分子物质。采用主成分分析(PCA)和正交偏最小二乘法判别分析(OPLS-DA)进行区分和差异分析。通过HS-GC-IMS共鉴定出当归中的89种挥发性成分,包括14种不饱和烃、16种醛、13种酮、9种醇、16种酯、6种有机酸和15种其他化合物。HS-SPME-GC-MS检测到118种挥发性成分,包括42种不饱和烃、11种芳香化合物、30种醇、8种烷烃、6种有机酸、4种酮、7种醛、5种酯和5种其他挥发性化合物。UPLC-Q-Orbitrap-MS鉴定出76种非挥发性化合物。PCA显示,在三种检测方法中,生当归和酒制当归样品明显聚类。PCA和OPLS-DA均能有效区分两组样品,共鉴定出145种化合物(VIP>1)作为评价炮制质量的关键标志物,包括HS-GC-IMS检测到的4-甲基-3-戊烯-2-酮、2-甲基戊酸乙酯和2,4-二甲基-1,3-二氧戊环,HS-SPME-GC-MS检测到的当归酸、β-蒎烯和吉马烯B,以及UPLC-Q-Orbitrap-MS检测到的L-色氨酸、甘草素和当归新醇。总之,三种检测方法与化学计量学的结合阐明了生当归和酒制当归化学物质基础的差异,为理解酒制当归的炮制机制和临床应用提供了科学依据。