Fast high-performance liquid chromatography quantification of ten phenolic acids in honey using chemometric second-order calibration method

doi:10.3724/SP.J.1123.2019.09013

Abstract

Abstract:

This study aims at the determination of ten phenolic acids in honey using high-performance liquid chromatography-diode array detection (HPLC-DAD) combined with a chemometric second-order calibration method. First, the accuracy of the model was investigated by analysis of the calibration samples and validation samples. Satisfactory results were obtained; the ten phenolic acids exhibited good linearity, and the correlation coefficient (R) was in the range 0.9982-0.9999, with average recoveries of 97.6% to 101.1%, which proved that the model was stable and reliable. Second, the types and operating conditions of the SPE columns were determined by experiments using simulated honey; HLB column was selected, washed with 0.1%(v/v) formic acid aqueous solution, and eluted with methanol. Finally, the phenolic acid contents in jujube flower honey were determined under the optimum conditions for simulated honey. The recoveries of the analytes were 62.1%-93.8%, which met the requirements considering the variety of target analytes and the complexity of the honey substrate. In addition, the efficiency of the method was validated by figures of merit and statistical parameters, including sensitivity (SEN), selectivity (SEL), root-mean-square error of prediction (RMSEP), limit of detection (LOD), and limit of quantification (LOQ); the obtained results were satisfactory. This method is simple, fast, and accurate, and it can be used for the quantitative analysis of the target analytes in complex substrates.

Key words: solid phase extraction (SPE), high-performance liquid chromatography (HPLC), phenolic acids, jujube flower honey, chemometrics

ZHANG Xiaohua, LÜ Minming, ZHENG Jingjing, MU Shuting, LIU Panhua, CHEN Zheng. Fast high-performance liquid chromatography quantification of ten phenolic acids in honey using chemometric second-order calibration method[J]. Chinese Journal of Chromatography, 2020, 38(5): 572-580.

Figures/Tables 8

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No.	GA	3, 4-DA	CHA	p-HA	CA	SA	p-CA	FA	AA	CIA
GA: gallic acid; 3, 4-DA: 3, 4-dihydroxybenzoic acid; CHA: chlorogenic acid; p-HA: p-hydroxybenzoic acid; CA: caffeic acid; SA: syringic acid; p-CA: p-coumaric acid; FA: ferulic acid; AA: abscisic acid; CIA: cinnamic acid. C01-C06: calibration sample 1-calibration sample 6. V01-V05: validation sample 1-validation sample 5.
C01	0.00	0.00	4.38	0.00	4.40	0.00	0.00	5.12	0.00	5.48
C02	2.76	0.44	3.94	0.44	3.96	4.32	0.43	4.61	0.44	4.93
C03	11.04	1.74	2.63	1.76	2.64	0.86	1.72	3.07	1.76	3.29
C04	16.56	2.62	1.75	2.64	1.76	1.30	2.58	2.05	2.64	2.19
C05	22.08	3.49	0.88	3.52	0.88	1.73	3.44	1.02	3.52	1.10
C06	27.60	4.36	0.00	4.40	0.00	2.16	4.30	0.00	4.40	0.00
V01	5.52	0.87	3.50	0.88	3.52	0.43	0.86	4.10	0.88	4.38
V02	8.28	1.31	3.07	1.32	3.08	3.89	1.29	3.58	1.32	3.84
V03	13.80	2.18	2.19	2.20	2.20	3.46	2.15	2.56	2.20	2.74
V04	19.32	3.05	1.31	3.08	1.32	3.02	3.01	1.54	3.08	1.64
V05	24.84	3.92	0.44	3.96	0.44	2.59	3.87	0.51	3.96	0.55

No.	GA	3, 4-DA	CHA	p-HA	CA	SA	p-CA	FA	AA	CIA
GA: gallic acid; 3, 4-DA: 3, 4-dihydroxybenzoic acid; CHA: chlorogenic acid; p-HA: p-hydroxybenzoic acid; CA: caffeic acid; SA: syringic acid; p-CA: p-coumaric acid; FA: ferulic acid; AA: abscisic acid; CIA: cinnamic acid. C01-C06: calibration sample 1-calibration sample 6. V01-V05: validation sample 1-validation sample 5.
C01	0.00	0.00	4.38	0.00	4.40	0.00	0.00	5.12	0.00	5.48
C02	2.76	0.44	3.94	0.44	3.96	4.32	0.43	4.61	0.44	4.93
C03	11.04	1.74	2.63	1.76	2.64	0.86	1.72	3.07	1.76	3.29
C04	16.56	2.62	1.75	2.64	1.76	1.30	2.58	2.05	2.64	2.19
C05	22.08	3.49	0.88	3.52	0.88	1.73	3.44	1.02	3.52	1.10
C06	27.60	4.36	0.00	4.40	0.00	2.16	4.30	0.00	4.40	0.00
V01	5.52	0.87	3.50	0.88	3.52	0.43	0.86	4.10	0.88	4.38
V02	8.28	1.31	3.07	1.32	3.08	3.89	1.29	3.58	1.32	3.84
V03	13.80	2.18	2.19	2.20	2.20	3.46	2.15	2.56	2.20	2.74
V04	19.32	3.05	1.31	3.08	1.32	3.02	3.01	1.54	3.08	1.64
V05	24.84	3.92	0.44	3.96	0.44	2.59	3.87	0.51	3.96	0.55

No.	Analyte	Linear equation	R	Average recovery/%
y: the relative concentration values of each analyte in calibration samples; x: the nominal concentrations in calibration samples.
1	GA	y=8.43x+2.40	0.9999	99.0
2	3, 4-DA	y=10.99x+3.20	0.9993	100.6
3	CHA	y=5.77x+0.38	0.9993	99.4
4	p-HA	y=11.54x+2.30	0.9992	101.0
5	CA	y=3.93x+1.18	0.9990	98.4
6	p-CA	y=1.55x+2.15	0.9998	97.6
7	SA	y=16.68x+0.68	0.9982	101.1
8	FA	y=5.02x+0.91	0.9987	98.6
9	AA	y=8.12x+0.99	0.9998	99.4
10	CIA	y=0.14x+0.63	0.9998	99.0

No.	Analyte	Linear equation	R	Average recovery/%
y: the relative concentration values of each analyte in calibration samples; x: the nominal concentrations in calibration samples.
1	GA	y=8.43x+2.40	0.9999	99.0
2	3, 4-DA	y=10.99x+3.20	0.9993	100.6
3	CHA	y=5.77x+0.38	0.9993	99.4
4	p-HA	y=11.54x+2.30	0.9992	101.0
5	CA	y=3.93x+1.18	0.9990	98.4
6	p-CA	y=1.55x+2.15	0.9998	97.6
7	SA	y=16.68x+0.68	0.9982	101.1
8	FA	y=5.02x+0.91	0.9987	98.6
9	AA	y=8.12x+0.99	0.9998	99.4
10	CIA	y=0.14x+0.63	0.9998	99.0

Analyte	Added/ (μg/g)	HLB		PSD		MAX
Analyte	Added/ (μg/g)	Found/(μg/g)	Recovery/%	Found/(μg/g)	Recovery/%	Found/(μg/g)	Recovery/%
GA	3.45	3.53	102.2	1.92	55.7	3.52	102.1
3, 4-DA	0.55	0.46	82.8	0.37	67.3	0.43	78.2
CHA	0.55	0.50	90.6	0.47	85.5	0.01	1.8
p-HA	0.55	0.50	90.9	0.46	83.6	0.46	83.6
CA	0.86	0.61	70.9	0.61	70.9	0.62	72.1
SA	0.54	0.44	81.5	0.37	68.5	0.36	66.7
p-CA	0.84	0.54	64.3	0.53	63.1	0.52	61.9
FA	1.00	0.72	72.0	0.70	70.0	0.72	72.0
AA	0.55	0.45	82.6	0.43	78.2	0.43	78.2
CIA	0.69	0.53	76.8	0.52	75.4	0.53	76.8