富DHA藻油及其在水包油型乳液中的氧化行为分析

doi:10.7506/spkx1002-6630-20241205-037

食品科学 ›› 2025, Vol. 46 ›› Issue (13): 41-41.doi: 10.7506/spkx1002-6630-20241205-037

• 食品化学 • 上一篇

富DHA藻油及其在水包油型乳液中的氧化行为分析

张泽楠，刘君，黄雪艳，朱雪晴，金帅祥，杨瑞楠，马祥，孙聪，毕艳兰

（1.河南工业大学粮油食品学院，河南郑州 450001；2.河南工业大学小麦和玉米深加工国家工程研究中心，河南郑州 450001；3.中粮工科（西安）国际工程有限公司，陕西西安 710082；4.河南工业大学国际教育学院，河南郑州 450001）

发布日期:2025-06-13
基金资助:
国家自然科学基金青年科学基金项目（31110419）；河南省国际合作培育项目（232102520013）；河南工业大学学生学术及科技创新培育项目（GJXY202408）

Oxidation Behavior of Docosahexaenoic Acid-Enriched Algal Oil and Its Oil-in-Water Emulsion

ZHANG Zenan, LIU Jun, HUANG Xueyan, ZHU Xueqing, JIN Shuaixiang, YANG Ruinan, MA Xiang, SUN Cong, BI Yanlan

(1. College of Food Science and Engineering, Henan University of Technology, Zhengzhou 450001, China; 2. National Engineering Research Center of Wheat and Corn Further Processing, Henan University of Technology, Zhengzhou 450001, China; 3. COFCO Engineering (Xi’an) International Engineering Co. Ltd., Xi’an 710082, China; 4. School of International Education, Henan University of Technology, Zhengzhou 450001, China)

Published:2025-06-13

摘要/Abstract

摘要： 以3%的富二十二碳六烯酸（docosahexaenoic acid，DHA）藻油为油相、1%的Tween 60为乳化剂和96%水相，应用高压微射流法制得低内相水包油型藻油乳液，研究常温密闭储存条件下富DHA藻油及其在乳液体系中的氧化行为。实验通过过氧化值（peroxide value，PV）和硫代巴比妥酸（thiobarbituric acid reactive substances，TBARS）值反映藻油的初级和次级氧化产物水平，应用气相色谱（gas chromatography，GC）、核磁共振氢谱（1H nuclear magnetic resonance，1H NMR）和顶空固相微萃取-GC-质谱（mass spectrometry，MS）法分析各脂肪酸损耗及氧化产物分子组成及变化。结果表明：乳液体系藻油的PV、TBARS值及脂肪酸损耗均高于纯藻油体系，藻油在低内相乳液中的氧化速率更快。在1H NMR谱图中观测到藻油DHA端位单氢过氧化物（DHA-terminal monohydroperoxide，DHA-TMHP）和内位单氢过氧化物（DHA-inner monohydroperoxide，DHA-IMHP）共振信号，内位氢过氧化物中含有一定比例的环化氢过氧化物，次级裂解产生非挥发性α,β-含氧烯醛；定量分析共轭二烯类氧化产物（DHA-conjugated diene，DHA-CD）、氢过氧化物（DHA-OOH）和非挥发性醛类氧化产物（DHA-non-volatile aldehyde oxidation products，DHA-NAD），含量水平为DHA-CD＞DHA-OOH＞DHA-NAD，反映了DHA产生较高水平的中间氧化产物；比较乳液及纯藻油体系DHA-TMHP与DHA-IMHP相对比例，发现乳液体系中DHA-TMHP比例显著高于纯藻油体系，说明乳液体系利于端位DHA-OOH的生成路径；DHA-NAD在氧化初级阶段即产生，含量水平为饱和醛＞(E,Z)-2,4-二烯醛＞α,β-含氧烯醛＞(E)-2-烯醛。GC-MS的结果显示，DHA藻油乳液在储藏开始即产生挥发性次级氧化产物（volatile secondary oxidation products，VSOPs）。乳液和纯藻油VSOPs的主要成分包括烯醛、烯酮类和烯醇，相对水平为醛类＞酮类＞醇类。其中，(E,E)-2,4-庚二烯醛、1-辛烯-3-醇、3,5-辛二烯-2-酮、2,4-壬二烯醛、2-戊烯基呋喃、1-戊烯-3-醇、庚烷、1-壬烯和辛醛为主要VSOPs贡献物质，推测由DHA-IMHP发生α、β裂解产生。

关键词: 二十二碳六烯酸-藻油；氢过氧化物；挥发性氧化产物；核磁共振氢谱；气相色谱-质谱法

Abstract: In this study, low-internal-phase oil-in-water (O/W) emulsion consisting of 3% algal oil rich in docosahexaenoic acid (DHA) as the oil phase, 1% Tween-60 as the emulsifier and 96% water phase was prepared using high-pressure micro-fluidization. The oxidation behavior of DHA-rich algae oil and its emulsion system at ambient temperature under sealed conditions was investigated. The levels of primary and secondary oxidation products in algae oil were determined by measuring peroxide value (PV) and thiobarbituric acid reactive substances (TBARS) value. Gas chromatography (GC), 1H nuclear magnetic resonance (1H NMR) spectroscopy, and headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) were employed to analyze the loss of fatty acids and changes in the composition of oxidation products. Results indicated that the PV, TBARS value, and fatty acid loss of the emulsion system were higher than those of algae oil, suggesting a faster oxidation rate of DHA-algae oil in the low-internal-phase emulsion. In the 1H NMR spectra, resonance signals of terminal monohydroperoxide (DHA-TMHP) and inner monohydroperoxide (DHA-IMHP) were observed, with the inner hydroperoxides containing cyclic hydroperoxides and intermediate oxidation products, which produced α,β-unsaturated oxygenated aldehydes by secondary cleavage. The content of conjugated diene (CD) was the highest, followed by hydroperoxides (OOH), and the content of non-volatile aldehyde oxidation products (NAD) was the lowest, reflecting the generation of high levels of intermediate oxidation products from DHA. In addition, it was found that the proportion of DHA-TMHP in the emulsion system was significantly higher than that in algae oil, indicating that the emulsion system favors the formation pathway of DHA-TMHP. DHA-NAD were generated at the initial oxidation stage, the content of DHA-NAD declining in the order: saturated aldehydes > (E,Z)-2,4-dienals > oxygenated α,β-unsaturated aldehydes > (E)-2-enals. GC-MS showed that volatile secondary oxidation products (VSOPs) were produced in the emulsion from the beginning of storage. The major components of VSOPs in both the emulsion and algae oil included enal, enone and enol, the relative levels of volatile compounds decreasing in the order: aldehydes > ketones > alcohols. (E,E)-2,4-heptadienal, 1-octen-3-ol, 3,5-octadien-2-one, 2,4-nonadienal, 2-pentenylfuran, 1-penten-3-ol, heptane, 1-nonene, and octanal were the major contributors to VSOPs, probably generated through the α and β cleavage of DHA-IMHP.

Key words: docosahexaenoic acid algae oil; hydrogen peroxide; volatile oxidation products; 1H nuclear magnetic resonance; gas chromatography-mass spectrometry

中图分类号:

TS221

张泽楠，刘君，黄雪艳，朱雪晴，金帅祥，杨瑞楠，马祥，孙聪，毕艳兰. 富DHA藻油及其在水包油型乳液中的氧化行为分析[J]. 食品科学, 2025, 46(13): 41-41.

ZHANG Zenan, LIU Jun, HUANG Xueyan, ZHU Xueqing, JIN Shuaixiang, YANG Ruinan, MA Xiang, SUN Cong, BI Yanlan. Oxidation Behavior of Docosahexaenoic Acid-Enriched Algal Oil and Its Oil-in-Water Emulsion[J]. FOOD SCIENCE, 2025, 46(13): 41-41.

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富DHA藻油及其在水包油型乳液中的氧化行为分析

Oxidation Behavior of Docosahexaenoic Acid-Enriched Algal Oil and Its Oil-in-Water Emulsion

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