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水产品中氧化三甲胺、三甲胺、二甲胺检测方法及鱿鱼丝中甲醛控制研究
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摘要
鱿鱼丝是一种广受欢迎的休闲食品,它含有丰富的氧化三甲胺(TMAO)。TMAO可以通过一定的途径分解产生等摩尔的甲醛和二甲胺(DMA),而甲醛是有毒物质,会影响鱿鱼丝的食用安全性。由于现有的水产品中甲醛含量的测定方法只能测定游离和可逆结合的甲醛,不能真实反映水产品中甲醛含量,而二甲胺与甲醛等摩尔产生,其含量可以间接反映水产品中甲醛的真实含量。此外,三甲胺(TMA)也是氧化三甲胺降解产物之一,具有腐败气味,且它和二甲胺都是致癌物亚硝基胺的前体物质。因此,检测水产品中TMAO、TMA、DMA含量对评价鱿鱼、鱿鱼丝等海产品的质量品质具有重要意义。
     基于上述原因,本论文建立了离子色谱法同时测定水产品中TMAO、TMA、DMA的方法,试验中确定了该方法的各参数,并比较了离子色谱方法与传统分光光度法测定TMAO、TMA、DMA的指标。在新方法的基础上研究了亚硫酸氢钠在鱿鱼丝加工及贮藏过程中对甲醛、TMAO、TMA、DMA的消长规律,并从美拉德反应方面对鱿鱼丝加工及贮藏过程中甲醛产生的可能机理进行了研究。本文研究的结论:
     1.建立了同时测定水产品中TMAO、TMA、DMA的非抑制型离子色谱法。色谱条件是:流动相为3.0 mmol/L的甲磺酸溶液;流速为0.8 mL/min;进样量为25μL;柱温为30℃;电导池温度为35℃;DMA、TMA、TMAO保留时间分别为11.89、14.37、15.31 min。该方法测定TMAO、TMA、DMA检出限分别为0.10、0.06、0.06mg/L,回收率在93.8%~104.1%,相对标准偏差在0.54%~3.53%。
     2.对离子色谱法与分光光度法测定水产品中TMAO、TMA、DMA进行比较,发现两种方法测定结果相近,但是离子色谱法同时测定TMAO、TMA、DMA大大缩短分析时间、具有更高的灵敏度及操作简单等优点。
     3.研究了亚硫酸氢钠在鱿鱼丝加工初期作为浸泡液及贮藏中作为吸附剂对甲醛控制的影响。鱿鱼原料经亚硫酸氢钠溶液浸泡处理后,在最终的鱿鱼丝中处理组的TMAO含量比对照组少三分之一,但是甲醛含量比对照组多。亚硫酸氢钠在鱿鱼丝贮藏过程中应用的结果表明各处理组中甲醛含量总体变化趋势随贮藏天数都是下降的,TMAO含量也呈下降趋势,而TMA和DMA含量变化是逐渐增加的。
     4.通过TMAO-乳糖反应模拟试验,发现美拉德反应也是甲醛产生的一条途径。对鱿鱼丝贮藏前后相关指标变化进行比较,结果表明鱿鱼丝在贮藏中甲醛的产生与乳糖和TMAO发生的美拉德反应有关。通过对四种鱿鱼丝在其加工及贮藏中相关指标变化分析比较,结果更进一步表明鱿鱼丝在加工及贮藏过程中甲醛的增加与美拉德反应有一定的关系,因此可以通过控制美拉德反应来达到控制甲醛的目的。
Shredded squid as a popular snack food is rich in trimethylamine-n-oxide (TMAO). TMAO can be decomposed to equimolar formaldehyde and dimethylamine (DMA) by certain ways, but the presence of formaldehyde would affect the quality of shredded squid. Up to the present, methods for the determination of formaldehyde only include free and reversible parts, which can not be a true reflection of the formaldehyde content in aquatic products. The amounts of DMA and formaldehyde are produced equally, so the amount of DMA can indirectly reflect the real content of formaldehyde. In addition, trimethylamine (TMA) with the smell of corruption is also one of the degradation products of trimethylamine oxide, and TMA and DMA are precursors of carcinogenic N-nitroso amine. Therefore, the detection of TMAO, TMA and DMA content in the aquatic products do great significance toward evaluating quality of shredded squid, squid and other seafood.
     In view of these situations, an ion chromatography method for determination of TMAO, TMA and DMA in the aquatic products was established. Parameters of this method were discussed. Then some differences of ion chromatography and regular method of spectrophometer had been compared. Based on this new approach, the influence of NaHSO3 toward the changes of formaldehyde, TMAO, TMA and DMA were studied during the process and storage stage of squid. Finally, maillard reaction as a possible production way of formaldehyde during the process and storage stage of squid was studied.
     The main results obtained in this study were as follows.
     1. An ion chromatography method with non-suppressed conductivity detection was developed for the simultaneous determination of DMA, TMA and TMAO in aquatic products. The analysis conditions were: mobile phase: 3.0 mmol/L methanesulfonic acid; flow rate: 0.8ml/min; injection volume: 25μL; Column temperature: 30℃; conductivity cell temperature: 35℃. The retention times of DMA、TMA and TMAO were 11.89, 14.37 and 15.31 min, respectively. Detection limits of DMA, TMA and TMAO were 0.06, 0.06 and 0.10 mg/L, respectively. Recoveries were between 93.8% and 104.1%. The relative standard deviations (RSD) were between 0.54% and 3.53%
     2. The methods between ion chromatography and spectrophotometer for determination of TMAO, TMA and DMA in samples were compared and found their results were similar, but the method of ion chromatography for simultaneous determination of TMAO, TMA and DMA significantly shorten the analysis time, had a higher sensitivity and a simple pre-treatment of samples.
     3. NaHSO3 as an immersion solution applied in earlier processing and an adsorbent applied in storage of shredded squid for controlling the formaldehyde content of squid product were studies. After application in processing, the content of TMAO in treated group reduced third than control group in the final product but the quantity of formaldehyde were gererated more than the control group. The result of NaHSO3 applied in storage showed that the content of formaldehyde in all treated groups was dropped as a whole and the content of TMAO also had a declined trend during the storage, while the amounts of DMA and TMA were increasing.
     4. TMAO-lactose in vitro was operated and found that formaldehyde can be generated by Maillard reaction. The changes of related substances in shredded squid were compared before and after storage, the results showed that the generated formaldehyde in the storage of shredded squid was related to the maillard reaction between lactose and TMAO. The changes of related substances in four kinds of shredded squid were also compared during the processing and storage, the results further indicated that the increasing amount of formaidehyde in the processing and storage was related to maillard reaction. Therefore, the methods for controlling the Maillard reaction are the way to control formaldehyde.
引文
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