Table S1 RHSW and PHSW from various productive area. RHSW productive area PHSW productive area

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1 Table S1 RHSW and PHSW from various productive area RHSW productive area PHSW productive area 1 Kunming, Yunnan Province 1 Yulin, Guangxi Province 2 Changchun, Jilin Province 2 Baoding, Hebei Province 3 Tongrentang, Anhui Province 3 Guangzhou, Guangdog Province 4 Tongrentang, Beijing 4 Zhaoqing, Guangdong Province 5 Dabashan, Sichuan Province 5 Bozhou, Anhui Province 6 Bozhou, Anhui Province 6 Shaoyang, HunanProvince 7 Huoshan, Anhui Province 7 Shijiazhuang, Hebei Province 8 Yuncheng, Shanxi Province 8 Changsha, Hunan Province 9 Shantou, Guangdong Province 9 Xian Shaanxi Province 10 Zhaoqing, Guangdong Province 10 Suzhou, Jiangsu Province 11 Yulin, Guangxi Province 11 Handan, Hebei Province 12 Yulihong, Guangxi Province 12 Dabashan, Sichuan Province 13 Yancheng, jiangsu Province 13 Heyuan, Guangdong Province 14 Baoding, Hebei Province 14 Tongrentang, Beijing 15 Shijiazhuang, Hebei Province 15 Nantong, Jiangsu Province 16 Taihang, Henan Province 16 Weinan, Shaanxi Province 17 Yichang, Hubei Province 17 Dazhou, Sichuan Province 18 Xichuang, Sichuan Province 18 Guiyang,Guizhou Province 19 Leping, Guizhou Province 19 Hangzhou, Zhejiang Province 20 Liupanshui, Guizhou Province 20 Leshan, Sichuan Province 21 Wangmo, Guizhou Province 21 Fuzhou, Fujian Province 22 Zhenning,Guizhou Province 23 Qianxi,Guizhou Province 24 Qianjiang,Guizhou Province 25 Baojin, Shaanxi Province RHSW : Raw Polygonum multiflorum Thunb.; Table S2 The calibration curve range for 16 components in HSW Linearity range Component Regression equation R 2 μg/ml Gallic acid y = 92.84x ~32.75 Procyanidins B 1 y = x ~32.67 Catechin y = x ~ Gallate y = x ~71.00 Aloe-emodin glycoside y = 31.66x ~19.50 Polydatin y = 43.21x ~62.50

2 Stilbene glucoside y = 22.77x ~ Rhaponticin y = x ~35.50 Resveratrol y = 83.18x ~47.00 Emodin glycoside y = x ~ Physcion glycoside y = 108.7x ~43.00 Aloe emodin y = 46.95x ~8.88 Rhein y = 55.14x ~8.10 Emodin y = x ~ Chrysophanol y = x ~5.00 Physcion y = x ~44.00 HSW: Polygonum multiflorum Thunb. Table S3 Intra- and inter-day precision for 16 components in HSW (mean±s,n=6) Component Concentration (μg/ml) Intra-assay Inter-assay mean±s RSD% mean±s RSD% ± ± Gallic acid Procyanidins B 1 Catechin Gallate Aloe-emodin glycoside Polydatin Stilbene glucoside Rhaponticin ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±

3 ± ± Resveratrol Emodin glycosides Physcion glycosides Aloe emodin Rhein Emodin ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± Chrysophanol Physcion ± ± ± ± ± ± ± ± ± ± HSW: Polygonum multiflorum Thunb. Component Table S4 Reproducibility and stability of 16 components in HSW(mean±s,n=6) Reproducibility (μg/ml) Stability(μg/mL) mean±s RSD% mean±s RSD% Gallic acid 7.69± ± Procyanidins B ± ± Catechin 42.03± ± Gallate 2.06± ± Aloe-emodin glycoside 5.27± ± Polydatin 14.43± ± Stilbene glucoside ± ± Rhaponticin 3.27± ± Resveratrol 17.54± ±

4 Emodin glycoside ± ± Physcion glycoside 1.68± ± Aloe emodin 4.44± ± Rhein 1.98± ± Emodin 94.87± ± Chrysophanol 5.11± ± Physcion 45.08± ± HSW: Polygonum multiflorum Thunb. Table S5 Recovery of 16 components in HSW (mean±s,n=6) Component Sample (μg/ml) Added (µg/ml) Measured (µg/ml) Recovery% ± Gallic acid 3.83± ± ± Procyanidins B ± ± ± ± ± Catechin 20.90± ± ± ± Gallate 1.03± ± ± ± Aloe-emodin 2.60± ± glycosides ± ± Polydatin 7.23± ± ± ± Stilbene ± ± glucoside ± ± Rhaponticin 1.67± ± ± ± Resveratrol 8.65± ± ± Emodin 57.07± ±

5 glycosides ± ± ± Physcion 0.83± ± glycosides ± ± Aloe emodin 2.27± ± ± ± Rhein 0.99± ± ± ± Emodin 47.69± ± ± ± Chrysophanol 2.50± ± ± ± Physcion 22.97± ± ± HSW: Polygonum multiflorum Thunb. Table S6 Fingerprint similarity for 21 batches PHSW No Collection location Similarity degree No Collection location Similarity degree 1 Yulin, Guangxi Dabashan,Sichuan Baoding, Heibei Heyuan, Guangdong Guangzhou, Guangdong Tongrentang, Beijing 1 4 Zhaoqing,Guangzhou Nantong, Jiangsu Bozhou, Anhui Weinan, Shanxi Shaoyang, Hunan Dazhou, Sichuan Shijiazhuang, Heibei Guiyang, Guizhou Changsha, Hunan Hanzhou, Zhejiang Xi'an, Shanxi Leshan, Sichuan Suzhou, Jiangsu Fuzhou, Fujian Handan, Hebei 0.99

6 Table S7 Principal component analysis of 21 batches PHSW Principal component Eigenvalue Variance contribution rate / % Cumulative contribution rate / % F F F F F Table S8 Component loading matrix of 21 batches PHSW Component F 1 F 2 F 3 F 4 F 5 Gallic acid Procyanidins B Catechin Gallate Aloe-emodin glycosides Polydatin Stilbene glucoside Rhaponticin Resveratrol Emodin glycosides Physcion glycosides Aloe emodin Rhein Emodin Chrysophanol Physcion Table S9 Integrated F value of 21 batches PHSW No F 1 F 2 F 3 F 4 F 5 integrated F value

7 Table S10 Weight factor of component to the whole PHSW Component A1 A2 A3 A4 A5 Wt W % of weight Gallic acid Procyanidins B Catechin Gallate Aloe-emodin glycoside Polydatin Stilbene glucoside Rhaponticin Resveratrol Emodin glycoside Physcion glycoside Aloe emodin Rhein Emodin Chrysophanol Physcion

8 Fig.S1 HCA analysis of PHSW decoction pieces with 16 components Fig.S2 HCA analysis of PHSW decoction pieces with selected 6 representative components

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