ICP-MS/MS analysis and evaluation of inorganic nutrient elements in different parts of Tetrastigma hemsleyanum Diels et Gilg

doi:10.3969/j.issn.1004-1524.20240174

Acta Agriculturae Zhejiangensis ›› 2024, Vol. 36 ›› Issue (9): 2122-2131.DOI: 10.3969/j.issn.1004-1524.20240174

• Quality and Safety of Agricultural Products • Previous Articles Next Articles

ICP-MS/MS analysis and evaluation of inorganic nutrient elements in different parts of Tetrastigma hemsleyanum Diels et Gilg

ZHU Sibei¹^,²(), NIE Jing²^,³, ZHANG Jinjun⁴, LI Chunlin²^,³, ZHANG Yongzhi²^,³, WANG Ping¹, TAO Yi¹^,^*(), YUAN Yuwei²^,³^,^*()

1. College of Pharmacy, Zhejiang University of Technology, Hangzhou 310014, China
2. Institute of Agro-Products Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China
3. Key Laboratory of Information Traceability for Agricultural Products, Ministry of Agriculture and Rural Affairs, Hangzhou 310021, China
4. Zhejiang Wuyi Huimei Traditional Chinese Medicine Co. Ltd., Wuyi 321200, Zhejiang, China

Received:2024-03-01 Online:2024-09-25 Published:2024-09-30

Abstract

Abstract:

To establish a method for the simultaneous determination of 12 inorganic nutrient elements (Na, Mg, Al, P, S, K, Ca, Fe, Ni, Cu, Zn, Se) in Tetrastigma hemsleyanum Diels et Gilg (T. hemsleyanum) by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS), and to explore the content distribution of these 12 inorganic nutrient elements in different parts (stem and leaf, tuberous root, fibrous root). The method for simultaneous analysis of 12 nutrient elements in T. hemsleyanum was established by ICP-MS/MS in the form of multiple reaction gases (O₂, H₂, NH₃) under the mode of single rod and series four rod, and the contents of inorganic nutrient elements in different parts of T. hemsleyanum were determined, and the differences of inorganic nutrient elements in different parts of medicinal materials were compared by one-way analysis of variance (ANOVA). Partial least squares-discriminant analysis (PLS-DA) was used to construct identification models for different parts. The results showed that the linearity, detection limit, precision, repeatability and stability test results of ICP-MS/MS method were good, and the recoveries ranged from 90.66% to 108.50%. There were significant differences in contents of inorganic nutrient elements in different parts of T. hemsleyanum, and the contents of inorganic nutrients in root were significantly higher than those in aboveground. Ca, Al, K and Na were the main difference elements among the three parts of T. hemsleyanum. In this study, the rapid analysis and determination of T. hemsleyanum inorganic elements was established, and the contents of inorganic elements in tuberous root, fibrous root, stem and leaf were effectively identified, which provided technical basis for quality control, origin tracing and germplasm resource evaluation of T. hemsleyanum.

Key words: Tetrastigma hemsleyanum Diels et Gilg, inorganic element, inductively coupled plasma tandem mass spectrometry, partial least squares discriminant analysis

CLC Number:

S567.239

ZHU Sibei, NIE Jing, ZHANG Jinjun, LI Chunlin, ZHANG Yongzhi, WANG Ping, TAO Yi, YUAN Yuwei. ICP-MS/MS analysis and evaluation of inorganic nutrient elements in different parts of Tetrastigma hemsleyanum Diels et Gilg[J]. Acta Agriculturae Zhejiangensis, 2024, 36(9): 2122-2131.

Figures/Tables 8

Table 1 The background equivalent concentration of each element under different analysis models

元素 Elements	潜在干扰离子 Potentially interfering ions	背景等效浓度 Background equivalent concentration/(μg·L^-1)
		SQ模式SQ model			MS/MS模式MS/MS model
		No gas	He	HEHe	H₂	O₂	NH₃
²³Na		16.255	15.850	14.985	18.220	17.335	18.280
²⁴Mg	¹² $C 2 +$	1.454	1.461	1.385	1.833	1.746	1.725
²⁷Al		1.984	1.173	1.842	3.579	4.179	3.909
³¹P	³⁰Si¹H⁺、¹⁴N¹H¹⁶O⁺、¹⁴N¹⁷O⁺、¹⁵H¹⁶O⁺、¹²C¹⁹F⁺	24.230	6.929	2.437	67.860	0.955	3.817
³²S	¹⁶O¹⁶O⁺、¹⁶O¹H¹⁵N⁺、¹⁸O¹⁴N⁺、¹H³¹P⁺、¹²C³⁰Ne⁺、¹³C¹⁹F⁺	4 046	2 109	849.8	2 004	4.985	4 104
³⁹K	³⁸Ar¹H⁺	51.010	16.800	49.760	19.410	25.260	24.580
⁴⁴Ca	¹²C¹⁶ $O 2 +$ 、¹⁴ $N 216$ O、²⁸Si¹⁶O	21.210	18.240	19.990	19.860	19.720	26.190
⁵⁶Fe	⁴⁰Ar¹⁶O⁺、⁴⁰Ca¹⁶O⁺、³⁷Cl¹⁷O⁺、¹¹²Sn²⁺、⁴⁰Ar¹⁵N¹H⁺、	86.090	1.341	1.357	1.223	1.593	4.499
	³⁸Ar¹⁸O⁺、³⁸Ar¹⁷O¹H⁺、³⁷Cl¹⁸O¹H⁺
⁵⁸Ni	⁵⁸Fe、⁴⁰Ar¹⁸O⁺、⁴⁰Ca¹⁸O⁺、⁴²Ca¹⁶O⁺、¹¹⁶Sn²⁺、	0.091	0.203	0.176	0.094	0.136
	⁴⁰Ar¹⁷O¹H⁺、⁴⁰Ca¹⁷O¹H⁺	0.471
⁶³Cu	⁴⁷Ti¹⁶O⁺、⁴⁶Ca¹⁶O¹H⁺、³⁶Ar¹²C¹⁴N¹H⁺、¹⁴N¹²C³⁷Cl⁺、	0.113	0.087	0.166	0.504	0.140	0.223
	¹⁶O¹²C³⁵Cl⁺
⁶⁶Zn	⁵⁰Ti¹⁶O⁺	1.045	0.893	1.200	0.930	1.239	1.643
⁷⁸Se	⁷⁸Kr、⁴⁰Ar³⁸Ar⁺、³⁸Ar⁴⁰Ca²⁺	5.520	0.130	0.015	0.012	0.016	0.026

Table 1 The background equivalent concentration of each element under different analysis models

元素 Elements	潜在干扰离子 Potentially interfering ions	背景等效浓度 Background equivalent concentration/(μg·L^-1)
		SQ模式SQ model			MS/MS模式MS/MS model
		No gas	He	HEHe	H₂	O₂	NH₃
²³Na		16.255	15.850	14.985	18.220	17.335	18.280
²⁴Mg	¹² $C 2 +$	1.454	1.461	1.385	1.833	1.746	1.725
²⁷Al		1.984	1.173	1.842	3.579	4.179	3.909
³¹P	³⁰Si¹H⁺、¹⁴N¹H¹⁶O⁺、¹⁴N¹⁷O⁺、¹⁵H¹⁶O⁺、¹²C¹⁹F⁺	24.230	6.929	2.437	67.860	0.955	3.817
³²S	¹⁶O¹⁶O⁺、¹⁶O¹H¹⁵N⁺、¹⁸O¹⁴N⁺、¹H³¹P⁺、¹²C³⁰Ne⁺、¹³C¹⁹F⁺	4 046	2 109	849.8	2 004	4.985	4 104
³⁹K	³⁸Ar¹H⁺	51.010	16.800	49.760	19.410	25.260	24.580
⁴⁴Ca	¹²C¹⁶ $O 2 +$ 、¹⁴ $N 216$ O、²⁸Si¹⁶O	21.210	18.240	19.990	19.860	19.720	26.190
⁵⁶Fe	⁴⁰Ar¹⁶O⁺、⁴⁰Ca¹⁶O⁺、³⁷Cl¹⁷O⁺、¹¹²Sn²⁺、⁴⁰Ar¹⁵N¹H⁺、	86.090	1.341	1.357	1.223	1.593	4.499
	³⁸Ar¹⁸O⁺、³⁸Ar¹⁷O¹H⁺、³⁷Cl¹⁸O¹H⁺
⁵⁸Ni	⁵⁸Fe、⁴⁰Ar¹⁸O⁺、⁴⁰Ca¹⁸O⁺、⁴²Ca¹⁶O⁺、¹¹⁶Sn²⁺、	0.091	0.203	0.176	0.094	0.136
	⁴⁰Ar¹⁷O¹H⁺、⁴⁰Ca¹⁷O¹H⁺	0.471
⁶³Cu	⁴⁷Ti¹⁶O⁺、⁴⁶Ca¹⁶O¹H⁺、³⁶Ar¹²C¹⁴N¹H⁺、¹⁴N¹²C³⁷Cl⁺、	0.113	0.087	0.166	0.504	0.140	0.223
	¹⁶O¹²C³⁵Cl⁺
⁶⁶Zn	⁵⁰Ti¹⁶O⁺	1.045	0.893	1.200	0.930	1.239	1.643
⁷⁸Se	⁷⁸Kr、⁴⁰Ar³⁸Ar⁺、³⁸Ar⁴⁰Ca²⁺	5.520	0.130	0.015	0.012	0.016	0.026

Fig.1 Schematic diagram of eliminating interference by ICP-MS/MS analysis of inorganic nutrient elements

Table 2 Spike recovery rate of 12 inorganic nutrient elements in Tetrastigma hemsleyanum Diels et Gilg

元素 Element	本底浓度 Background concentration/(mg·L^-1)	加标浓度 Standard concentration/ (mg·L^-1)	测定浓度 Determination of concentration/(mg·L^-1)	回收率 Recovery rate/%
²³Na	801.53	320.00	1 069.72	95.38
²⁴Mg	7 992.18	3 200.00	11 797.68	105.41
²⁷Al	343.40	120.00	445.70	96.18
³¹P	6 716.63	2 000.00	8 577.16	98.40
³²S	3 269.77	1 200.00	4 767.90	106.67
³⁹K	19 586.21	8 000.00	26 979.31	97.80
⁴⁴Ca	15 464.21	6 000.00	19 782.68	108.50
⁵⁶Fe	542.66	200.00	731.52	98.50
⁵⁸Ni	3.74	1.00	4.30	90.66
⁶³Cu	9.27	4.00	13.69	103.20
⁶⁶Zn	41.07	16.00	61.64	100.80
⁷⁸Se	0.05	0.02	0.07	101.25

Table 3 Contents of inorganic nutrient elements in different parts of Tetrastigma hemsleyanum Diels et Gilg (n=10)

元素 Elements	茎叶 Stem and leaf	块根 Tuberous root	须根 Fibrous root
²³Na	2 766.2±1 638.3 a	259.7±91.2 b	406.1±33.1 b
²⁴Mg	4 277.9±1 886.7 a	2 035.9±527.2 b	4 313.9±1 500.1 a
²⁷Al	1 776.8±827.5 b	1 153.9±640.5 b	6 738.2±3 219.9 a
³¹P	3 587.2±1 069.3 b	2 269.5±809.1 c	5 098.7±2 177.2 a
³²S	2 614.9±970.7 b	1 522.6±304.6 c	3 971.8±974.3 a
³⁹K	20 994.4±8 032.2 a	9 098.9±2 338.7 b	17 426.9±4 551.4 a
⁴⁴Ca	17 087.1±4 953.9 a	5 635.6±1 866.7 b	13 256.5±2 629.5 a
⁵⁶Fe	430.5±204.7 b	280.3±143.5 c	2 331.0±1 613.3 a
⁵⁸Ni	1.31±0.4 b	0.7±0.3 b	10.5±5.5 a
⁶³Cu	11.7±3.0 b	5.8±1.7 b	52.4±21.5 a
⁶⁶Zn	114.4±43.9 b	110.5±36.7 b	406.5±115.9 a
⁷⁸Se^*	133.5±102.3 b	55.0±32.4 b	300.0±143.3 a

Table 4 PLS-DA discriminant analysis results of stem and leaf, tuberou root and fibrous root of Tetrastigma hemsleyanum Diels et Gilg

数据集 Data set	部位 Part	数量 Number	测试结果Test result			判别准确率 Discriminant accuracy/%	总体准确率 Overall accuracy/%
数据集 Data set	部位 Part	数量 Number	茎叶 Stem and leaf	块根 Tuberous root	须根 Fibrous root	判别准确率 Discriminant accuracy/%	总体准确率 Overall accuracy/%
训练集	茎叶Stem and leaf	8	7	1	0	87.5	91.67
Training set	块根Tuberous root	8	0	8	0	100
	须根Fibrous root	8	1	0	7	87.5
验证集	茎叶Stem and leaf	2	2	0	0	100	100
Validation set	块根Tuberous root	2	0	2	0	100
	须根Fibrous root	2	0	0	2	100

Fig.2 PLS-DA model score diagram of stem and leaf, tuberous root and fibrous root of Tetrastigma hemsleyanum Diels et Gilg

Fig.3 Permutation test plot of PLS-DA model for stem and leaf, tuberous root and fibrous root of Tetrastigma hemsleyanum Diels et Gilg (n=200) R2 was the model interpretation rate, Q2 was the model prediction ability.

Fig.4 Variable importance in the projection (VIP) of inorganic nutrient elements in stem and leaf, tuberous root and fibrous root of Tetrastigma hemsleyanum Diels et Gilg

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ICP-MS/MS analysis and evaluation of inorganic nutrient elements in different parts of Tetrastigma hemsleyanum Diels et Gilg

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