蓝莓果汁饮料原花青素的热稳定性及降解动力学模型

doi:10.3969/j.issn.1000-2006.201811013

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南京林业大学学报（自然科学版） ›› 2019, Vol. 43 ›› Issue (5): 89-95.doi: 10.3969/j.issn.1000-2006.201811013

蓝莓果汁饮料原花青素的热稳定性及降解动力学模型

夏晓雨¹(), 王凤娟¹, 符群¹, 张娜², 郭庆启¹^,³^,^*()

1.东北林业大学林学院,黑龙江哈尔滨 150040
2.哈尔滨商业大学食品工程学院,黑龙江哈尔滨 150076
3.黑龙江省森林食品资源利用重点实验室,黑龙江哈尔滨 150040

收稿日期:2018-11-06 修回日期:2019-06-30 出版日期:2019-10-08 发布日期:2019-10-08
通讯作者: 郭庆启
基金资助:
哈尔滨市科技局科技创新人才项目(2017RAQXJ012);中央高校基本科研业务费专项资金项目(2572018BA09);黑龙江省教育厅规划课题(GBC1317007)

Thermal stability and degradation kinetic model of proanthocyanidins in blueberry (Vaccinium spp.) juice beverage

XIA Xiaoyu¹(), WANG Fengjuan¹, FU Qun¹, ZHANG Na², GUO Qingqi¹^,³^,^*()

1. School of Forestry, Northeast Forestry University, Harbin 150040, China
2. College of Food Engineering,Harbin University of Commerce, Harbin 150076, China
3. Key Laboratory of Forest Food Resources Utilization of Heilongjiang Province, Harbin 150040, China

Received:2018-11-06 Revised:2019-06-30 Online:2019-10-08 Published:2019-10-08
Contact: GUO Qingqi

摘要/Abstract

摘要：

【目的】研究蓝莓果汁饮料中原花青素的热稳定性及降解动力学特征,为蓝莓果汁饮料贮藏条件的优化及保质期预测提供参考。【方法】观察不同pH蓝莓果汁饮料中原花青素含量在有氧与充氮气条件下以不同温度处理时的变化情况,判断反应级数,运用动力学方程建立蓝莓果汁饮料原花青素降解模型。【结果】有氧条件下,蓝莓果汁原花青素在pH 5.8、4.6、2.2时降解反应活化能分别为25.34、18.77、16.80 kJ/mol,半衰期为1.91~4.58 d;充氮气条件下,蓝莓果汁原花青素在pH 5.8、4.6、2.2时降解反应活化能分别为56.70、26.35、19.36 kJ/mol,半衰期为1.90~15.79 d。【结论】在有氧或充氮气条件下,随着温度的升高和pH的降低,蓝莓果汁饮料原花青素的稳定性下降,原花青素降解反应的活化能和半衰期呈明显下降趋势;充氮气处理可以提高原花青素的稳定性,降解反应均符合一级反应动力学模型。通过验证试验发现:所建立的蓝莓果汁饮料原花青素降解动力学模型与实测值拟合程度较好(决定系数R²≥60.25%)。

关键词: 蓝莓果汁, 饮料, 原花青素, 热稳定性, 降解动力学

Abstract:

【Objective】 We studied the thermal stability and degradation kinetics of proanthocyanidins in blueberry (Vaccinium spp.) juice to provide a reference for optimizing storage conditions and predicting the shelf life of blueberry juice. 【Method】 Changes in proanthocyanidins content in blueberry juice with different pH values were observed at different temperatures under aerobic or nitrogen-filled conditions and the reaction order was judged. Then, the degradation model of proanthocyanidins in blueberry juice was established using the kinetic equation. 【Result】 Under aerobic conditions, the activation energies of degradation reaction of proanthocyanidins in blueberry juice at pH 5.8, 4.6 and 2.2 were 25.34, 18.77 and 16.80 kJ/mol, respectively, and the half-life ranged from 1.91 to 4.58 days. Under nitrogen-filled conditions, the activation energies of degradation reaction of proanthocyanidins in blueberry juice at pH 5.8, 4.6 and 2.2 were 56.70, 26.35 and 19.36 kJ/mol, respectively, and the half-life ranged from 1.90 to 15.79 days. 【Conclusion】 With increase in temperature and decrease in pH value under aerobic or nitrogen-filled conditions, the stability of proanthocyanidins in blueberry juice decreased, while the activation energy and half-life of proanthocyanidins degradation reaction significantly decreased. Nitrogen-filled treatment can improve the stability of proanthocyanidins, and the degradation reactions were consistent with the first-order reaction kinetics model. Through verification experiments, it was found that the kinetic model of proanthocyanidins degradation in blueberry juice was well-fitted with the measured values (R²≥60.25%).

Key words: blueberry (Vaccinium spp.) juice, beverage, proanthocyanidin, thermal stability, degradation kinetics

中图分类号:

TS275.5
S789

夏晓雨,王凤娟,符群,等. 蓝莓果汁饮料原花青素的热稳定性及降解动力学模型[J]. 南京林业大学学报（自然科学版）, 2019, 43(5): 89-95.

XIA Xiaoyu, WANG Fengjuan, FU Qun, ZHANG Na, GUO Qingqi. Thermal stability and degradation kinetic model of proanthocyanidins in blueberry (Vaccinium spp.) juice beverage[J].Journal of Nanjing Forestry University (Natural Science Edition), 2019, 43(5): 89-95.DOI: 10.3969/j.issn.1000-2006.201811013.

图/表 6

图1

表1

有氧和充氮条件下不同pH时原花青素残留率与温度及时间的关系"

pH	贮藏时间/d storage days	有氧条件aerobic conditions				充氮条件nitrogen-filled conditions
pH	贮藏时间/d storage days	50 ℃	60 ℃	70 ℃	80 ℃	50 ℃	60 ℃	70 ℃	80 ℃
5.8	0	100	100	100	100	100	100	100	100
	1	86.60±0.13^ae	81.69±1.06^be	71.88±0.53^ce	61.79±1.06^de	88.63±1.59^ae	82.09±1.12^be	76.83±0.96^ce	69.49±0.32^de
	2	78.64±1.19^ae	67.10±1.08^be	63.12±0.80^ce	40.83±0.27^de	82.25±1.62^ae	71.40±0.96^be	64.23±0.80^ce	50.83±0.16^de
	3	68.71±0.88^ae	55.87±2.06^be	46.67±0.65^ce	29.25±0.13^de	80.01±0.18^ae	64.71±0.32^be	53.55±1.28^ce	38.08±0.15^de
	4	56.75±0.27^ae	47.60±1.19^be	36.72±0.14^ce	21.33±0.40^de	77.14±1.53^ae	58.97±1.58^be	44.93±0.94^ce	29.31±1.14^de
	5	47.86±0.66^ae	38.31±0.58^be	32.87±1.33^ce	14.43±0.15^de	73.48±1.12^ae	52.27±1.28^be	36.64±1.29^ce	23.89±0.64^de
4.6	0	100	100	100	100	100	100	100	100
	1	79.43±0.11^af	64.59±1.46^bf	48.43±0.15^cf	38.10±0.29^df	87.11±1.74^ae	76.92±0.35^bf	68.14±1.78^cf	56.54±0.70^df
	2	64.39±3.98^af	56.36±1.30^bf	39.07±2.34^cf	32.47±0.49^df	76.75±0.18^af	67.08±3.51^bf	50.22±0.70^cf	39.32±0.67^df
	3	56.29±0.73^af	48.70±2.06^bf	29.78±1.46^cf	21.60±0.15^df	64.62±2.24^af	50.10±1.47^bf	38.50±1.95^cf	29.95±1.19^df
	4	49.60±0.62^af	35.60±0.87^bf	25.29±0.87^cf	17.29±0.44^df	56.72±1.93^af	43.54±1.05^bf	30.01±0.18^cf	22.16±1.76^df
	5	41.01±1.16^af	29.48±1.19^bf	21.51±0.29^cf	11.32±0.58^df	52.85±0.53^af	38.27±0.70^bf	26.50±0.53^cf	16.83±0.35^df
2.2	0	100	100	100	100	100	100	100	100
	1	44.77±1.50^ag	30.58±1.41^bg	29.13±2.20^cg	22.70±0.78^dg	60.57±2.05^af	42.18±0.67^bg	34.21±0.67^cg	28.50±0.89^dg
	2	33.40±0.83^ag	20.92±0.08^bg	16.93±1.60^cg	13.61±0.11^dg	47.49±0.53^ag	28.17±0.31^bg	24.04±1.28^cg	18.44±1.40^dg
	3	25.75±0.50^ag	16.27±0.33^bg	11.61±0.85^cg	8.942±0.06^dg	37.01±1.87^ag	21.23±0.47^bg	18.34±0.31^cg	12.51±0.14^dg
	4	23.92±0.33^ag	12.44±0.16^bg	8.950±0.67^cg	6.563±0.23^dg	32.81±0.16^ag	17.90±0.62^bg	13.82±0.78^cg	9.557±0.62^dg
	5	19.26±1.00^ag	7.153±0.67^bg	6.554±0.33^cg	5.557±0.34^dg	29.08±0.77^ag	14.48±0.28^bg	12.58±0.15^cg	6.382±0.30^dg

表1

表2

表3

表4

蓝莓果汁饮料中原花青素在有氧和充氮条件下降解动力学模型"

pH	动力学模型kinetic model
pH	有氧条件aerobic conditions	充氮条件nitrogen-filled conditions
5.8	$t = ln c 0 - ln c 1780.41 · exp (- 3047.3 / θ)$	$t = ln c 0 - ln c 73441519.91 · exp (- 6819.9 / θ)$
4.6	$t = ln c 0 - ln c 169.66 · exp (- 2257.1 / θ)$	$t = ln c 0 - ln c 2432.32 · exp (- 3169.9 / θ)$
2.2	$t = ln c 0 - ln c 122.07 · exp (- 2020.9 / θ)$	$t = ln c 0 - ln c 255.11 · exp (- 2328.2 / θ)$

表4

表5

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pH	温度/℃ temperature	有氧条件 aerobic conditions				充氮条件 nitrogen-filled conditions
		零级反应 zero-order reaction		一级反应 first-order reaction		零级反应 zero-order reaction		一级反应 first-order reaction
		k	R²	k	R²	k	R²	k	R²
5.8	50	6.040 3	0.996 0	0.151 2	0.985 1	1.790 3	0.966 2	0.043 9	0.973 5
	60	6.459 7	0.986 7	0.185 8	0.998 2	3.645 2	0.984 5	0.109 4	0.995 0
	70	6.346 8	0.963 7	0.210 6	0.977 5	5.040 3	0.991 6	0.183 8	0.999 3
	80	6.943 5	0.942 7	0.355 8	0.997 8	5.701 6	0.950 0	0.268 6	0.994 0
4.6	50	5.078 0	0.973 9	0.158 3	0.991 7	4.064 5	0.969 0	0.130 2	0.983 4
	60	5.040 9	0.989 2	0.202 8	0.976 3	4.629 0	0.958 0	0.182 9	0.977 7
	70	3.747 3	0.959 3	0.205 8	0.989 1	4.750 0	0.935 5	0.240 4	0.981 0
	80	3.809 1	0.980 3	0.305 7	0.980 9	4.432 8	0.949 5	0.299 7	0.997 3
2.2	50	2.932 8	0.918 7	0.202 1	0.965 4	4.024 2	0.928 8	0.183 8	0.968 6
	60	2.682 3	0.966 1	0.342 5	0.977 7	3.403 2	0.898 0	0.259 3	0.970 5
	70	2.576 3	0.876 4	0.362 1	0.978 5	2.771 5	0.915 4	0.255 5	0.969 4
	80	2.003 8	0.871 0	0.354 4	0.964 6	2.752 6	0.927 6	0.365 0	0.994 6

pH	温度/℃ temper- ature	有氧条件残留率 residual rate under aerobic conditions			充氮条件残留率 residual rate under nitrogen-filled conditions
pH	温度/℃ temper- ature	预测值 predicted	实测值 measured	R²	预测值 predicted	实测值 measured	R²
5.8	4	74.30	79.14±1.43	93.88	98.52	97.80±1.29	99.27
5.8	25	52.47	57.71±0.21	90.92	91.91	87.84±0.55	95.57
4.6	4	61.22	66.69±0.99	91.80	77.05	82.40±0.39	93.51
4.6	25	41.84	43.63±1.22	95.90	55.77	61.14±1.17	91.22
2.2	4	43.68	29.35±1.19	67.19	56.51	43.74±0.14	77.40
2.2	25	25.03	15.08±1.76	60.25	35.63	25.52±0.69	71.63

蓝莓果汁饮料原花青素的热稳定性及降解动力学模型

Thermal stability and degradation kinetic model of proanthocyanidins in blueberry (Vaccinium spp.) juice beverage

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pH	温度/℃ temperature	有氧条件aerobic conditions			充氮条件nitrogen-filled conditions
pH	温度/℃ temperature	t₁_/₂/d	E_a/(kJ·mol^-1)	F_b	t₁_/₂/d	E_a/(kJ·mol^-1)	F_b
5.8	50	4.58	25.34	1 780.41	15.79	56.70	73 441 519.91
	60	3.73			6.34
	70	3.29			3.77
	80	1.95			2.58
pH	温度/℃ temperature	有氧条件aerobic conditions			充氮条件nitrogen-filled conditions
pH	温度/℃ temperature	t₁_/₂/d	E_a/(kJ·mol^-1)	F_b	t₁_/₂/d	E_a/(kJ·mol^-1)	F_b
4.6	50	4.38	18.77	169.66	5.32	26.35	2 432.32
	60	3.42			3.79
	70	3.37			2.88
	80	2.27			2.31
2.2	50	3.43	16.80	122.07	3.77	19.36	255.11
	60	2.02			2.67
	70	1.91			2.71
	80	1.96			1.90

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