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中国精品科技期刊2020

杜仲籽精炼油的氧化稳定性及货架期预测

王小媛 牛涵 马宝晨 纵伟

王小媛,牛涵,马宝晨,等. 杜仲籽精炼油的氧化稳定性及货架期预测[J]. 食品工业科技,2021,42(14):310−319. doi:  10.13386/j.issn1002-0306.2020110267
引用本文: 王小媛,牛涵,马宝晨,等. 杜仲籽精炼油的氧化稳定性及货架期预测[J]. 食品工业科技,2021,42(14):310−319. doi:  10.13386/j.issn1002-0306.2020110267
WANG Xiaoyuan, NIU Han, MA Baochen, et al. Oxidation Stability and Shelf Life Prediction of Refined Eucommia ulmoides Seed Oil[J]. Science and Technology of Food Industry, 2021, 42(14): 310−319. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020110267
Citation: WANG Xiaoyuan, NIU Han, MA Baochen, et al. Oxidation Stability and Shelf Life Prediction of Refined Eucommia ulmoides Seed Oil[J]. Science and Technology of Food Industry, 2021, 42(14): 310−319. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020110267

杜仲籽精炼油的氧化稳定性及货架期预测

doi: 10.13386/j.issn1002-0306.2020110267
基金项目: “十三五”国家重点研发计划项目(2017YFD060130205);河南省科技攻关项目(212102110345)
详细信息
    作者简介:

    王小媛(1986−),女,博士,副教授,研究方向:果蔬加工及安全控制,E-mail:wang459381@163.com

    通讯作者:

    纵伟(1965−),男,博士,教授,研究方向:果蔬深加工,E-mail:weizong1965@126.com

  • 中图分类号: TS225.1

Oxidation Stability and Shelf Life Prediction of Refined Eucommia ulmoides Seed Oil

  • 摘要: 本文以杜仲籽毛油为原料,经过精炼后以过氧化值、酸价和脂肪酸含量为评判指标,采用Schaal烘箱法探究了5种抗氧化剂在不同浓度和温度下对杜仲籽精炼油氧化稳定性的影响,建立了杜仲籽精炼油货架期模型,预测其货架期。结果表明,添加丁基羟基茴香醚(butyl hydroxyanisole,BHA)、叔丁基对苯二酚(tert-butyl hydroquinone,TBHQ)、维生素E(vitamin E,VE)、鼠尾草酸(carnosic acid,CA)和L-抗坏血酸棕榈酸酯(L-ascorbyl palmitate,L-AP)的抗氧化效果从大到小依次为TBHQ>CA>L-AP>BHA>VE,CA、TBHQ、VE、BHA、L-AP的最佳添加量分别为0.05%、0.02%、0.01%、0.02%、0.02%;随着储藏温度的升高和储藏时间的延长,过氧化值和酸价升高,氧化速度加快,饱和脂肪酸和单不饱和脂肪酸含量增加,不饱和脂肪酸含量减少;杜仲籽精炼油的氧化符合一级氧化动力学反应,通过构建的杜仲籽精炼油货架期模型,预测出在25、40、50和60 ℃的温度下,杜仲籽精炼油的货架期分别为10.70、8.76、7.74和6.89 d,添加抗氧化剂能延缓不饱和脂肪酸的氧化,其中TBHQ的抗氧化效果最好,添加0.02% TBHQ的杜仲籽精炼油的货架期可以延长至41.41、19.71、12.48和8.13 d,说明添加抗氧化剂可以有效延长杜仲籽精炼油的货架期。
  • 图  1  抗氧化剂浓度对杜仲籽精炼油过氧化值和酸价的影响

    Figure  1.  Effects of antioxidant concentration on peroxide value and acid value of refined Eucommia ulmoides seed oil

    注:a. CA;b. TBHQ;c. VE;d. BHA;e. L-AP。

    图  2  温度对添加不同抗氧化剂样品过氧化值和酸价的影响

    Figure  2.  Effects of temperature on peroxide value and acid value of samples with different antioxidants

    注:a. 空白;b. CA;c. TBHQ;d. VE;e. BHA;f. L-AP。

    图  3  杜仲籽精炼油过氧化值变化的Arrhenius曲线

    Figure  3.  Arrhenius curve of changes in peroxide value of refined Eucommia ulmoides seed oil

    注:a. 空白;b. CA;c. TBHQ;d. VE;e. BHA;f. L-AP。

    表  1  初始杜仲籽精炼油脂肪酸组成

    Table  1.   Initial fatty acid composition of refined Eucommia ulmoides seed oil

    脂肪酸含量(%)
    棕榈酸C16:05.69
    硬脂酸C18:02.30
    油酸C18:1n9c15.67
    亚油酸C18:2n6c10.93
    α-亚麻酸C18:3n363.01
    ∑PUFA73.94
    ∑UFA89.61
    ∑SFA7.99
    注:∑PUFA表示多不饱和脂肪酸(polyunsaturated fatty acid,PUFA)之和;∑UFA表示不饱和脂肪酸(unsaturated fatty acid,UFA)之和;∑SFA表示饱和脂肪酸(saturated fatty acid,SFA)之和;表2同。
    下载: 导出CSV

    表  2  温度对不同杜仲籽精炼油样品脂肪酸含量的影响

    Table  2.   Effects of temperature on fatty acid content of different refined Eucommia ulmoides seed oil samples

    样品温度(℃)天数(d)棕榈酸
    C16:0 (%)
    硬脂酸
    C18:0 (%)
    油酸
    C18:1n9c (%)
    亚油酸
    C18:2n6c (%)
    α-亚麻酸
    C18:3n3 (%)
    ∑PUFA
    (%)
    ∑UFA
    (%)
    ∑SFA
    (%)
    空白4055.672.3115.6410.7361.7272.4588.097.98
    105.702.3215.6510.7061.5172.2187.868.02
    155.732.3415.6610.6460.5371.1786.838.07
    205.782.3515.6910.6360.3670.9986.688.13
    255.802.3815.7010.6359.5470.1785.878.18
    5055.702.3415.6610.7261.5372.2587.918.04
    105.722.3415.6710.6861.4472.1287.798.06
    155.742.3515.6810.6560.7071.3587.038.09
    205.802.3715.7310.6159.2069.8185.548.17
    255.802.3715.7510.4356.4066.8382.588.19
    6055.732.3515.8110.6861.3572.0387.848.08
    105.752.3415.7410.5761.3871.9587.698.09
    155.802.3515.6910.5358.5569.0884.778.15
    206.002.4015.7210.5054.3764.8780.598.40
    256.062.4115.7910.0852.6662.7478.538.47
    CA4055.612.3115.6210.8462.2373.0788.697.92
    105.642.3115.6610.7662.0072.7688.427.95
    155.672.3215.6810.6961.0171.7087.387.99
    205.662.3415.8010.6660.9671.6287.428.00
    255.702.3916.0110.6060.7771.3787.388.09
    5055.622.3115.7210.6861.8072.4888.207.93
    105.632.3215.7410.6461.6872.3288.067.95
    155.752.3615.7810.6561.6172.2688.048.11
    205.802.3915.7810.6260.6271.2487.028.19
    255.742.3615.8210.5859.2569.8385.658.10
    6055.682.3315.7610.7261.6872.4088.168.01
    105.732.3615.8610.6961.5372.2288.088.09
    155.722.3516.0310.6461.1871.8287.858.07
    205.732.3516.1510.5959.7370.3286.478.08
    255.942.3816.1710.5859.1969.7785.548.32
    TBHQ4055.622.3215.6410.9162.6573.5689.207.94
    105.632.3115.7010.8262.3973.2188.917.94
    155.642.3515.7310.8061.9572.7588.487.99
    205.662.3415.7610.7261.3272.0487.808.00
    255.662.3716.0510.6861.1371.8187.868.03
    5055.632.3215.6810.7462.2873.0288.707.95
    105.642.3215.7410.6962.0072.6988.437.96
    155.752.3615.7410.6661.7772.4388.178.11
    205.762.3715.7810.6361.2971.9287.708.13
    255.772.3615.8110.6160.0870.6986.978.13
    6055.662.3315.7110.7362.1572.8888.597.99
    105.692.3215.8410.7261.7472.4688.308.01
    155.682.3416.0310.6761.3472.0188.048.02
    205.712.3516.0510.6260.7071.3287.378.06
    255.792.3616.1510.5360.2570.6786.938.15
    VE4055.642.3015.1310.6661.7072.3687.497.94
    105.692.3015.2010.6561.4872.1387.337.99
    155.652.3015.1310.6260.5071.1286.257.95
    205.742.3415.4010.6160.2570.8686.268.08
    256.032.4616.0110.6059.4270.0286.038.23
    5055.652.3015.1510.6761.4872.1587.307.95
    105.692.3115.2510.7061.1671.8687.118.00
    155.702.3315.3610.6260.3670.9886.348.03
    205.832.4115.6010.6159.1369.7485.348.24
    255.872.4215.7110.5156.0066.5182.108.29
    6055.712.3215.3510.7861.9272.7088.058.03
    105.792.3615.5110.6561.2771.9287.438.15
    155.682.3215.6610.5158.4668.9784.638.00
    205.862.3415.8310.6154.0764.6880.518.20
    256.182.3818.289.9452.3562.2980.578.56
    BHA4055.672.3115.6610.7761.7872.5588.217.98
    105.722.3315.7110.7861.6072.3888.098.05
    155.722.3516.0910.6960.9471.6387.728.07
    205.742.3415.8010.6260.5771.1986.998.08
    255.772.3716.0110.6260.2070.8286.838.14
    5055.702.3515.7310.7761.5972.3688.098.05
    105.712.3515.7510.7161.5072.2187.968.06
    155.752.3615.8110.6861.0271.7087.518.11
    205.802.3815.8210.6359.9970.6286.448.18
    255.852.4015.8510.6256.7467.3683.218.25
    6055.692.3415.8010.6961.4572.1487.948.03
    105.742.3615.8710.6561.4072.0587.928.10
    155.792.3616.0710.6060.9871.5887.658.15
    205.812.3616.1110.5555.7766.3282.438.17
    255.932.3716.3510.0953.7963.8880.238.30
    L-AP4055.612.3115.6410.8762.4673.3388.977.92
    105.632.3115.6510.7462.1072.8488.497.94
    155.672.3315.7010.7261.6472.3688.068.00
    205.672.3415.7910.6461.0471.6887.478.01
    255.682.3816.0410.6460.8071.4487.488.06
    5055.632.3215.6910.7261.9972.7188.407.95
    105.642.3215.7310.6761.8072.4788.207.96
    155.752.3515.7710.6461.5672.2087.978.10
    205.792.3615.8010.6360.5871.2187.018.15
    255.802.4016.0710.6058.7269.3285.398.20
    6055.682.3415.8210.7061.5172.2188.038.02
    105.742.3515.8510.7061.4672.1688.018.09
    155.742.3416.0210.6261.0871.7087.728.08
    205.772.3616.0410.5858.8269.4085.448.13
    256.052.4116.3610.3856.6567.0383.398.46
    下载: 导出CSV

    表  3  添加不同抗氧化剂的杜仲籽精炼油过氧化值回归方程

    Table  3.   Peroxide value regression equation of refined Eucommia ulmoides seed oil with different antioxidants

    样品温度(℃)零级反应回归方程零级反应回归系数一级反应回归方程一级反应回归系数
    空白40$y = 0.1057x - 0.2500$0.9211$y = 0.1021{e^{0.142x}}$0.9643
    50$y = 0.2015x - 0.5240$0.8847$y = 0.1483{e^{0.1556x}}$0.9090
    60$y = 0.4397x - 1.4514$0.8432$y = 0.1854{e^{0.1805x}}$0.8862
    CA40$y = 0.0555x - 0.1869$0.8019$y = 0.0573{e^{0.1273x}}$0.9722
    50$y = 0.0996x - 0.2321$0.9251$y = 0.0989{e^{0.1408x}}$0.9688
    60$y = 0.2218x - 0.7751$0.8356$y = 0.1213{e^{0.1638x}}$0.9536
    TBHQ40$y = 0.0095x + 0.0327$0.8077$y = 0.062{e^{0.0594x}}$0.9002
    50$y = 0.0544x - 0.1771$0.8109$y = 0.0586{e^{0.1263x}}$0.9765
    60$y = 0.0907x - 0.2830$0.8808$y = 0.0749{e^{0.1436x}}$0.9922
    VE40$y = 0.1089x - 0.2422$0.8879$y = 0.1183{e^{0.1365x}}$0.9407
    50$y = 0.2118x - 0.5215$0.8792$y = 0.1613{e^{0.1543x}}$0.8824
    60$y = 0.4891x - 1.7433$0.8295$y = 0.1836{e^{0.1832x}}$0.8799
    BHA40$y = 0.0985x - 0.2563$0.9081$y = 0.0911{e^{0.1425x}}$0.9786
    50$y = 0.2014x - 0.6487$0.8568$y = 0.1224{e^{0.1609x}}$0.9523
    60$y = 0.4786x - 1.9352$0.8129$y = 0.1408{e^{0.1922x}}$0.9465
    L-AP40$y = 0.0303x - 0.0677$0.8096$y = 0.056{e^{0.1036x}}$0.9483
    50$y = 0.1202x - 0.4528$0.8291$y = 0.0713{e^{0.1554x}}$0.9969
    60$y = 0.2631x - 0.9201$0.8408$y = 0.1307{e^{0.1694x}}$0.9456
    下载: 导出CSV

    表  4  添加不同抗氧化剂的杜仲籽精炼油不同储藏温度下过氧化值的变化速率常数

    Table  4.   Change rate constants of peroxide value of refined Eucommia ulmoides seed oil with different antioxidants at different storage temperatures

    样品储藏温度(K)过氧化值起始值(A0变化速率常数(K)
    空白313.150.07300.1420
    323.150.07300.1556
    333.150.07300.1805
    CA313.150.07300.1273
    323.150.07300.1408
    333.150.07300.1638
    TBHQ313.150.07300.0594
    323.150.07300.1095
    333.150.07300.1436
    VE313.150.07300.1365
    323.150.07300.1543
    333.150.07300.1832
    BHA313.150.07300.1425
    323.150.07300.1609
    333.150.07300.1922
    L-AP313.150.07300.1036
    323.150.07300.1554
    333.150.07300.1864
    下载: 导出CSV

    表  5  杜仲籽精炼油的氧化动力学模型及货架期模型

    Table  5.   Oxidation kinetics model and shelf life model of refined Eucommia ulmoides seed oil

    抗氧化剂氧化反应动力学模型货架期模型
    空白对照$k = 7.56 \times \exp \left( { - \dfrac{ {1247.9} }{T} } \right)$${A_e} = {A_0}\exp \left[ {7.56 \times {t_e} \times \exp \left( { - \dfrac{ {1247.9} }{T} } \right)} \right]$
    CA$k = 8.32 \times \exp \left( { - \dfrac{ {1311.9} }{T} } \right)$${A_e} = {A_0}\exp \left[ {8.32 \times {t_e} \times \exp \left( { - \dfrac{ {1311.9} }{T} } \right)} \right]$
    TBHQ$k = 160331.69 \times \exp \left( { - \dfrac{ {4621.5} }{T} } \right)$${A_e} = {A_0}\exp \left[ {160331.69 \times {t_e} \times \exp \left( { - \dfrac{ {4621.5} }{T} } \right)} \right]$
    VE$k = 18.01 \times \exp \left( { - \dfrac{ {1531.8} }{T} } \right)$${A_e} = {A_0}\exp \left[ {18.01 \times {t_e} \times \exp \left( { - \dfrac{ {1531.8} }{T} } \right)} \right]$
    BHA$k = 20.36 \times \exp \left( { - \dfrac{ {1557.2} }{T} } \right)$${A_e} = {A_0}\exp \left[ {20.36 \times {t_e} \times \exp \left( { - \dfrac{ {1557.2} }{T} } \right)} \right]$
    L-AP$k = 1968.64 \times \exp \left( { - \dfrac{ {3074.9} }{T} } \right)$${A_e} = {A_0}\exp \left[ {1968.64 \times {t_e} \times \exp \left( { - \dfrac{ {3074.9} }{T} } \right)} \right]$
    其中,te表示储藏时间,d;Ae表示t=e时的过氧化值,g/100 g;A0表示杜仲籽精炼油起始过氧化值,g/100 g。
    下载: 导出CSV

    表  6  不同温度下杜仲籽精炼油的货架期及实际储藏期

    Table  6.   Shelf life and actual storage life of refined Eucommia ulmoides seed oil at different temperatures

    样品储藏温度(℃)货架期模型预测值(d)油脂货架期实测值(d)
    空白408.7610
    507.745
    606.895
    CA409.7615
    508.5810
    607.595
    TBHQ4019.7125
    5012.4815
    608.1310
    VE409.105
    507.825
    606.795
    BHA408.7310
    507.495
    606.485
    L-AP4011.5020
    508.4810
    606.385
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-11-30
  • 网络出版日期:  2021-06-07
  • 刊出日期:  2021-07-07

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