溫 超,王紫夢(mèng),石星波*,鄧放明*
(湖南農(nóng)業(yè)大學(xué)食品科技學(xué)院,食品科學(xué)與生物技術(shù)湖南省重點(diǎn)實(shí)驗(yàn)室,湖南 長(zhǎng)沙 4101 28)
食品中丙烯酰胺與5-羥甲基糠醛的研究進(jìn)展
溫超,王紫夢(mèng),石星波*,鄧放明*
(湖南農(nóng)業(yè)大學(xué)食品科技學(xué)院,食品科學(xué)與生物技術(shù)湖南省重點(diǎn)實(shí)驗(yàn)室,湖南 長(zhǎng)沙 4101 28)
食品熱加工過(guò)程生成的丙烯酰胺與5-羥甲基糠醛嚴(yán)重影響人們的身體健康。研究這兩種物質(zhì)的毒性、形成機(jī)理以及抑制方法,有助于合理控制熱加工工藝,改善熱加工食品的安全性,開(kāi)發(fā)新的抑制方法。本文評(píng)述了丙烯酰胺與5-羥甲基糠醛的毒性、形成機(jī)理、檢測(cè)及抑制方法,總結(jié)了目前抑制方法存在的問(wèn)題,提出未來(lái)將朝著能同時(shí)抑制多種潛在毒性的美拉德反應(yīng)產(chǎn)物的可能途徑發(fā)展。
丙烯酰胺;5-羥甲基糠醛;毒性;美拉德反應(yīng);抑制
自從2002年瑞典國(guó)家食品管理局(Swedish National Food Administration,SNFA)首次提出丙烯酰胺廣泛存在于熱加工食品中后[1-2],熱加工食品的安全性引起了世界范圍內(nèi)科研工作者的高度重視,而食品的熱處理又是現(xiàn)代食品工藝中不可或缺的一道加工工序。食品在熱加工過(guò)程中常常伴隨著美拉德反應(yīng)的發(fā)生,進(jìn)而生成諸如丙烯酰胺(分子結(jié)構(gòu)如圖1A)、5-羥甲基糠醛(5-hydroxymethylfurfural,HMF)(分子結(jié)構(gòu)如圖1B)等[3]有毒有害的物質(zhì),其中丙烯酰胺被國(guó)際癌癥研究機(jī)構(gòu)(International Agency for Research on Cancer,IARC)劃分為“2類致癌物”,同時(shí)HMF是一種能誘導(dǎo)細(xì)胞和基因突變的毒素,具有潛在的致癌性[4]。然而我們?nèi)粘K攀车氖称?,比如,面包?-6]、干制品[7]、薯?xiàng)l等存在大量的丙烯酰胺和HMF,對(duì)消費(fèi)者的身體健康帶來(lái)了一定的威脅。
圖1 丙烯酰胺(A)與5-羥甲基糠醛(B)分子結(jié)構(gòu)式Fig.1 Molecular structures of acrylamide (A) and HMF (B)
近年來(lái),科研工作者們展開(kāi)不少有關(guān)食品熱加工中丙烯酰胺形成的抑制研究。雖然開(kāi)發(fā)了一些控制食品中丙烯酰胺含量的有效方法,但是如何有效的控制HMF含量的報(bào)道甚少。只考慮抑制丙烯酰胺形成的方法顯然不能徹底的解決食品的安全隱患。與此同時(shí),不少課題組綜述了丙烯酰胺的毒性、檢測(cè)方法、生成機(jī)理、抑制手段等[8-10],為開(kāi)展抑制丙烯酰胺的工作提供了便捷的文獻(xiàn)資料。所以,同時(shí)綜述有關(guān)丙烯酰胺與HMF的工作,將有助于科研工作者開(kāi)發(fā)同時(shí)抑制丙烯酰胺和HMF形成的方法。
本文就近年來(lái)國(guó)內(nèi)外科研者對(duì)丙烯酰胺和HMF的毒性、生成機(jī)理、檢測(cè)方法及抑制手段等有關(guān)研究進(jìn)行了綜述。旨在為同時(shí)抑制或控制食品熱加工中丙烯酰胺和HMF的形成提供一定的理論依據(jù),促進(jìn)更為科學(xué)合理的工藝和技術(shù)的開(kāi)發(fā),提高消費(fèi)者的飲食健康。
丙烯酰胺和HMF主要存在于高溫油炸烘烤的食品中,其中,面包中丙烯酰胺平均含量136 μg/kg,HMF含量11.8~87.7 mg/kg;谷物早餐中丙烯酰胺平均含量156 μg/kg,HMF含量為6.9~240.5 mg/kg;另外咖啡中丙烯酰胺平均含量253 μg/kg,HMF含量為100~1 900 mg/kg[11]。然而,世界衛(wèi)生組織(World Health Organization,WHO)推薦飲用水中丙烯酰胺最大限量不高于0.5 μg/L,比常見(jiàn)食品中丙烯酰胺含量低幾百倍[12],嚴(yán)重影響到消費(fèi)者身體健康。綜述丙烯酰胺和HMF的毒性具有重要的意義。
1.1丙烯酰胺的毒性
1.1.1致癌性
自從開(kāi)展丙烯酰胺的毒理學(xué)研究以來(lái),丙烯酰胺對(duì)人體是否具有致癌作用一直是科研工作者們爭(zhēng)議的話題??蒲泄ぷ髡甙l(fā)現(xiàn)丙烯酰胺能誘導(dǎo)老鼠的肺、胃、乳腺、甲狀腺等多個(gè)器官長(zhǎng)出惡性腫瘤,體現(xiàn)為丙烯酰胺具有致癌性[13-14]。但是,不少的課題組認(rèn)為動(dòng)物實(shí)驗(yàn)難以直接證明食品中丙烯酰胺的攝入量在人體內(nèi)能起到致癌作用[15-18]。2012年,Lipworth等[15]研究發(fā)現(xiàn)食品中丙烯酰胺攝入量未能增加患癌癥的風(fēng)險(xiǎn),并提出從當(dāng)前流行病學(xué)角度來(lái)看,丙烯酰胺與惡性腫瘤形成之間不存在直接聯(lián)系。
1.1.2遺傳毒性
丙烯酰胺的遺傳毒性在細(xì)菌、動(dòng)物細(xì)胞、人體淋巴細(xì)胞等體系已得到評(píng)估[18-19],表現(xiàn)為能使染色體斷裂、減緩細(xì)胞分裂等特點(diǎn)[20-21]。研究發(fā)現(xiàn)丙烯酰胺主要由以下兩種方式來(lái)表達(dá)其遺傳毒性,一種方式是通過(guò)新陳代謝而轉(zhuǎn)變?yōu)槟苷T導(dǎo)基因中HPRT位點(diǎn)突變的環(huán)氧丙酰胺;另一種方式是作為Michael受體,與DNA中的硫醇、羥基、氨基結(jié)合形成復(fù)合物[22]。
1.1.3神經(jīng)毒性
眾所周知,丙烯酰胺對(duì)人體具有神經(jīng)毒性[23]。對(duì)長(zhǎng)期暴露于丙烯酰胺環(huán)境的工作人員進(jìn)行健康調(diào)查的報(bào)告顯示,丙烯酰胺能導(dǎo)致小腦功能障礙和神經(jīng)系統(tǒng)混亂[24]。有文獻(xiàn)報(bào)道暴露于以平均每日30 μg/kg劑量(以體質(zhì)量計(jì))的丙烯酰胺中,可致人體周圍神經(jīng)病變[25]。但是其神經(jīng)毒性作用機(jī)理還缺乏令人信服的科學(xué)依據(jù),還需要進(jìn)一步的研究[26]。
1.1.4生殖毒性
在已報(bào)告的動(dòng)物實(shí)驗(yàn)中,丙烯酰胺主要通過(guò)干擾交配,誘發(fā)胚胎細(xì)胞核和雄性動(dòng)物的精子異常等途徑影響生殖功能的正常運(yùn)行,導(dǎo)致生育率下降[27]。Titenko-Holland等[28]發(fā)現(xiàn)雄性老鼠連續(xù)5 d攝入50 mg/kg劑量的丙烯酰胺,會(huì)導(dǎo)致精子數(shù)量銳減,形態(tài)明顯異常。然而目前還沒(méi)有得到作為丙烯酰胺給人體生殖功能帶來(lái)不良影響的證據(jù)[17,27]。
1.2HMF的毒性
通常認(rèn)為,HMF是一種弱致癌性的細(xì)胞毒素,在高濃度下,可傷害眼睛、呼吸道、皮膚和黏膜[11]。事實(shí)上,從多個(gè)HMF毒理學(xué)的動(dòng)物實(shí)驗(yàn)中得出的結(jié)論互相矛盾,一些研究表明HMF不具有遺傳毒性和致癌性[29],而Anese等[4]研究發(fā)現(xiàn)HMF能在老鼠體內(nèi)誘發(fā)基因突變,導(dǎo)致老鼠患結(jié)腸癌和肝癌。其實(shí),5-HMF本身沒(méi)有毒性,主要是因?yàn)槠淠茉隗w內(nèi)和體外分別形成磺酸氧甲基糠醛(sulfoxymethylfurfural,SMF)和5-氯甲基糠醛(5-chloromethylfurfural,5-CMF),而這些物質(zhì)具有較強(qiáng)致癌性和基因毒性[28,30]。
2.1丙烯酰胺的形成機(jī)理
2.1.1天冬酰胺途徑
天冬酰胺途徑是指由天冬酰胺與含羰基化合物(還原糖)通過(guò)美拉德反應(yīng)而形成丙烯酰胺,是食品中丙烯酰胺形成的最重要途徑[1,31]。天冬酰胺途徑發(fā)生在美拉德反應(yīng)初期階段,由天冬酰胺與含羥基化合物(還原糖)通過(guò)脫水縮合形成極不穩(wěn)定的席夫堿后,再分別以兩種不同的方式形成丙烯酰胺。一種方式是通過(guò)分子的內(nèi)環(huán)化形成唑烷酮,接著脫羧為偶氮甲堿葉拉德內(nèi)翁鹽,再經(jīng)過(guò)質(zhì)子轉(zhuǎn)移生成中性胺去羥基Amadori化合物,進(jìn)而生成丙烯酰胺[32-33]。另一種方式是席夫堿在分子重排后形成Amadori化合物,Amadori化合物在高溫條件下直接分解生成丙烯酰胺或者通過(guò)形 成3-氨基丙烯胺,再脫氨生成丙烯酰胺[34]。在此途徑中,單獨(dú)加熱的天冬酰胺可以直接脫羧基和脫氨基形成丙烯酰胺,但是丙烯酰胺形成量極低,而在羰基化合物存在的條件下才能形成大量的丙烯酰胺[1,31]。并且Zyzak[35]和Stadler[2]等通過(guò)標(biāo)記同位素實(shí)驗(yàn)證明天冬酰胺是丙烯酰胺形成的主要來(lái)源,為丙烯酰胺的形成提供了結(jié)構(gòu)框架。對(duì)于此途徑的研究,科研工作者通常借用天冬酰胺和葡萄糖的反應(yīng)作為研究模型。2012年,G?kmen等[3]發(fā)現(xiàn)加熱天冬酰胺與HMF反應(yīng)模型也能形成大量的丙烯酰胺。
2.1.2非天冬酰胺途徑
在食品加工中天冬酰胺途徑并不是形成丙烯酰胺的唯一途徑,一些研究表明在缺乏天冬酰胺的條件下也能生成大量的丙烯酰胺,這些途徑統(tǒng)稱為非天冬酰胺途徑[36-38]。研究發(fā)現(xiàn),丙烯醛和丙烯酸是非天冬酰胺途徑能順利進(jìn)行的重要物質(zhì),它們的化學(xué)結(jié)構(gòu)與丙烯酰胺的極其相似,被公認(rèn)為是形成丙烯酰胺的關(guān)鍵中間產(chǎn)物[38]。Ehling等[39]研究發(fā)現(xiàn)油脂類物質(zhì)在高溫條件下通過(guò)水解、氧化等反應(yīng)生成三碳化合物丙烯酸,丙烯酸再與氨基化合物作用形成丙烯酰胺。Vattem等[40]指出單糖在加熱過(guò)程中能分解生成許多小分子物質(zhì)(如甲醛、乙醛),這些物質(zhì)在適合條件下可以重新形成丙烯酸,進(jìn)而形成丙烯酰胺。
2.2HMF的形成機(jī)理
通常認(rèn)為,HMF由碳水化合物經(jīng)加熱分解形成,其實(shí)氨基酸、氨基酸-糖類混合物、維生素、多不飽和脂肪酸和類胡蘿卜素在加熱的過(guò)程中也能形成少量的HMF[27,41]。鑒于碳水化合物是形成HMF的主要反應(yīng)物,科研工作者常以果糖、葡萄糖、蔗糖等碳水化合物作為反應(yīng)物來(lái)研究HMF 形成的機(jī)理,并發(fā)現(xiàn)在低pH值條件下,葡萄糖或者果糖在高溫中經(jīng)過(guò)烯醇化和脫水作用形成了3-脫氧己糖酮,3-脫氧己糖酮進(jìn)一步脫水、分子環(huán)化生成HMF[42-44]。而加熱有金屬離子存在的碳水化合物會(huì)使HMF的形成途徑發(fā)生改變,金屬離子能與碳水化合物結(jié)合形成高活性的果糖陽(yáng)離子,并且這種陽(yáng)離子比3-脫氧己糖酮更能有效地分解形成HMF[45-46]。
在富含天冬酰胺和葡萄糖的食品中,葡萄糖能與天冬酰胺反應(yīng)形成丙烯酰胺,也能通過(guò)加熱分解而形成HMF,是形成丙烯酰胺及HMF的共同反應(yīng)物。同時(shí),美拉德反應(yīng)所形成的HMF作為反應(yīng)物與天冬酰胺反應(yīng)也能生成丙烯酰胺。所以,在食品體系中,有必要同時(shí)考慮這兩種物質(zhì)的形成機(jī)理及相互影響機(jī)制。
3.1抗氧化劑
一般認(rèn)為,抗氧化劑能有效地避免食品原料中的還原糖被氧化,進(jìn)而起到抑制丙烯酰胺的作用。然而,研究發(fā)現(xiàn)由于抗氧化劑在結(jié)構(gòu)和特性上具有多樣性,不同的抗氧化劑在美拉德反應(yīng)過(guò)程中參與不同的反應(yīng)途徑,進(jìn)而造成了抗氧化劑對(duì)丙烯酰胺的形成具有不一致的影響效果,有的甚至能起到促進(jìn)作用。比如,Kotsiou等[47]研究發(fā)現(xiàn)沒(méi)食子酸和阿魏酸能使丙烯酰胺的含量分別減少70%和50%。而B(niǎo)iedermann等[48]發(fā)現(xiàn)在馬鈴薯模型中添加抗壞血酸及其衍生物對(duì)丙烯酰胺的形成幾乎沒(méi)有影響。類似的結(jié)果在餅干、土豆模型中同樣被發(fā)現(xiàn)[49-50]。但是,添加綠原酸于高溫條件下的葡萄糖-天冬酰胺模型中,發(fā)現(xiàn)丙烯酰胺的含量明顯增加了[51]。其實(shí),相同類型的抗氧化劑對(duì)丙烯酰胺形成的影響效果也不一致。有研究發(fā)現(xiàn)隸屬于酚酸化合物的咖啡酸和沒(méi)食子酸在兩個(gè)不同模型的實(shí)驗(yàn)中的結(jié)果完全相反,這2 種酚酸化合物在乳液模型中對(duì)丙烯酰胺形成表現(xiàn)為抑制作用,而在天冬酰胺-葡萄糖模型中表現(xiàn)為促進(jìn)作用[47,52]。
3.2植物提取物
植物提取物一般會(huì)存在大量的酚類、生物黃酮、無(wú)機(jī)鹽等化合物,對(duì)丙烯酰胺的形成具有潛在的抑制作用。Oral等[53]發(fā)現(xiàn)植物提取物(橄欖、橘子、石榴皮)在甘氨酸-葡萄糖模型中對(duì)丙烯酰胺形成的抑制率達(dá)到30%~85%,而在餅干中能使丙烯酰胺的含量減少10%~19%。Cheng Kawing等[54]研究發(fā)現(xiàn)蘋果提取物能夠非常有效的抑制丙烯酰胺的形成,藍(lán)莓、山竹果、龍眼提取物抑制丙烯酰胺的效果并不明顯,而紅龍果提取物能顯著地增加丙烯酰胺的含量。而Acar等[55]發(fā)現(xiàn)葡萄籽提取物的添加對(duì)面包中丙烯酰胺形成沒(méi)有任何影響。起不到抑制效果的植物提取物有可能是因?yàn)槠涮崛∥锂?dāng)中含有相當(dāng)一部分還原糖所致。
3.3含硫化合物
由于含巰基官能團(tuán)的氨基酸和硫醇在加熱條件下能與丙烯酰胺直接反應(yīng)形成復(fù)合物或者通過(guò)消除巰基官能團(tuán)形成脫氫丙氨酸后,再與丙烯酰胺發(fā)生加成反應(yīng),從而起到抑制丙烯酰胺形成的效果[56]。比如,在丙烯酰胺溶液中分別添加谷胱甘肽、半胱氨酸、N-乙酰-半胱氨酸、芐硫醇,加熱一段時(shí)間后發(fā)現(xiàn)大量的丙烯酰胺消失了,而且發(fā)現(xiàn)谷胱甘肽的消除率最高[57-58]。將?;撬崽砑拥酵炼蛊吞於0?葡萄糖模型中,研究結(jié)果表明?;撬嵩趦煞N反應(yīng)模型中都能大量地降低丙烯酰胺的含量,并發(fā)現(xiàn)在天冬酰胺-葡萄糖模型中丙烯酰胺的抑制率隨?;撬釢舛鹊脑黾佣龃螅谟驼ㄍ炼蛊袥](méi)有得到體現(xiàn)[59]。然而含巰基化合物的添加對(duì)產(chǎn)品的風(fēng)味造成一定副作用,所以不宜大量的使用。
3.4天冬酰胺酶
天冬酰胺酶是將食品原料中形成丙烯酰胺的前體物天冬酰胺水解為天冬氨酸,因此能起到抑制丙烯酰胺形成的作用。Pedreschi等[60-61]分別把土豆條和土豆片浸泡在天冬酰胺酶溶液中,在相同的油炸條件加工后發(fā)現(xiàn)在薯?xiàng)l中丙烯酰胺的含量下降了30%,而薯片中只減少了15%。同時(shí),原料的結(jié)構(gòu)和成分也會(huì)影響到天冬酰胺酶抑制丙烯酰胺形成的效率。有研究發(fā)現(xiàn)天冬酰胺酶在美拉德反應(yīng)模型中能使丙烯酰胺的含量減少85%~90%[62-63],在食物中丙烯酰胺的抑制率為27%~70%[64]。另外,2011年,Anese等[65]發(fā)現(xiàn)對(duì)于烘焙產(chǎn)品而言,水分含量較高的原料能增強(qiáng)天冬酰胺酶對(duì)丙烯酰胺形成的抑制作用,而脂肪的存在降低了天冬酰胺酶的活性,相對(duì)于無(wú)脂肪存在的實(shí)驗(yàn),表現(xiàn)為促進(jìn)了丙烯酰胺的形成,并指出丙烯酰胺的減少量隨著脂肪濃度的增加而逐漸變小。
3.5氨基酸
一些實(shí)驗(yàn)已證明丙氨酸、賴氨酸、甘氨酸、谷氨酸、半胱氨酸都能有效的抑制丙烯酰胺的形成[66-67]。除了以上氨基酸以外,Lopez-Lopez等[68]從研究一系列氨基酸在橄欖汁加工過(guò)程中對(duì)丙烯酰胺形成的影響中,發(fā)現(xiàn)脯氨酸、肌氨酸、鳥(niǎo)氨酸和γ-氨基丁酸也能抑制丙烯酰胺的形成,并且抑制率達(dá)50%~75%。這可能是因?yàn)檫@些游離氨基酸在美拉德反應(yīng)中與天冬酰胺形成了一定的競(jìng)爭(zhēng)作用或者與丙烯酰胺發(fā)生共價(jià)結(jié)合反應(yīng),從而降低了產(chǎn)品中丙烯酰胺的含量[26]。
3.6金屬離子
同種金屬離子在不同的反應(yīng)模型或者食品中對(duì)丙烯酰胺的抑制效果不一。Yuan Yuan等[69]研究了NaCl在天冬酰胺-葡萄糖模型和天冬酰胺-果糖模型中對(duì)丙烯酰胺的影響,發(fā)現(xiàn)NaCl在天冬酰胺-葡萄糖模型中對(duì)丙烯酰胺的抑制率為14.78%,而在天冬酰胺-果糖模型中抑制率達(dá)到24.58%。2013年,Kalita等[70]發(fā)現(xiàn)硫酸釩在油炸馬鈴薯薯?xiàng)l和葡萄糖-天冬酰胺模型中都具有抑制丙烯酰胺形成的作用,并且浸泡于0.1 mmol/L釩離子溶液的薯?xiàng)l中丙烯酰胺抑制率為92.5%,而在模型中釩離子濃度為6 mmol/L時(shí)抑制率最大,達(dá)到97.6%。
不同價(jià)態(tài)金屬離子在同種反應(yīng)模型或者食品中對(duì)丙烯酰胺的抑制效果也不一樣。G?kmen等[71]向葡萄糖-天冬酰胺模型添加NaCl、CaCl2、MgCl2、FeCl3,發(fā)現(xiàn)這些物質(zhì)都能大量的降低丙烯酰胺含量,并且指出一價(jià)金屬離子抑制效果比二價(jià)金屬離子抑制效果差。
與金屬離子結(jié)合的陰根離子不同,同樣會(huì)對(duì)丙烯酰胺的形成造成不一樣的影響效果。Kukurova等[72]在谷物模型中研究了無(wú)機(jī)鹽對(duì)丙烯酰胺形成的影響,比如,酸性焦磷酸鈉、磷酸二氫鈉抑制率為75%,碳酸氫鈉和碳酸氫鉀抑制率為30%。NaCl和氯化鉀的抑制率為40%~45%。A?ar等[73]研究了氯化鈣和乳酸鈣對(duì)丙烯酰胺形成的影響,結(jié)果發(fā)現(xiàn)在質(zhì)量分?jǐn)?shù)為1%的時(shí)候抑制率最大,分別為81%和53%。而向面團(tuán)餅干中添加質(zhì)量分?jǐn)?shù)0.2%丙酸鈣后,促進(jìn)90%的丙烯酰胺形成。
研究還發(fā)現(xiàn)金屬離子對(duì)丙烯酰胺形成的影響,既有抑制作用,又有促進(jìn)作用,還有隨離子濃度增加先抑制后促進(jìn)的效應(yīng)。Casado等[74]發(fā)現(xiàn)在堿性橄欖油模型中添加50 mmol/L的氯化鈣后,丙烯酰胺含量增加了24%。而在天冬酰胺-葡萄糖模型中氯化鈣表現(xiàn)為抑制作用。2013年,Tan等[75]在生產(chǎn)棕櫚糖中的研究發(fā)現(xiàn)Ca2+對(duì)丙烯酰胺的形成具有抑制作用,但是,在Ca2+質(zhì)量濃度為0~20 mg/L時(shí)丙烯酰胺含量隨著Ca2+質(zhì)量濃度的升高而減少,而在質(zhì)量濃度為20~80 mg/L時(shí)丙烯酰胺含量隨著Ca2+質(zhì)量濃度的升高而增加。
3.7微生物發(fā)酵
有些微生物能發(fā)酵天冬酰胺和碳水化合物,進(jìn)而降低了食品原料中天冬酰胺和碳水化合物的含量,并且能形成一些可以抑制丙烯酰胺的化合物,因此能降低產(chǎn)品中丙烯酰胺的含量。Baardseth等[76]發(fā)現(xiàn)用乳酸菌分別發(fā)酵未熱燙和已熱燙的馬鈴薯?xiàng)l,在油炸后,發(fā)酵前未熱燙處理的馬鈴薯?xiàng)l中丙烯酰胺含量減少了48%~71%,而發(fā)酵前已熱燙的馬鈴薯?xiàng)l中丙烯酰胺含量降低了79%~94%,并指出可能是原料的糖類被乳酸菌發(fā)酵轉(zhuǎn)變?yōu)槿樗?,從而既減少了原料中反應(yīng)物的含量,同時(shí)又降低了pH值的緣故。也有科研工作者[77]發(fā)現(xiàn)酵母菌發(fā)酵能顯著降低產(chǎn)品中丙烯酰胺的含量,而且在面包中發(fā)酵時(shí)間越長(zhǎng)丙烯酰胺的含量越少,但是這樣會(huì)促進(jìn)一種有毒物質(zhì):3-氯甘油(3-monochloropropanediol,3-MCPD)的形成。所以,利用微生物發(fā)酵策略來(lái)抑制丙烯酰胺形成的同時(shí)需要考慮是否會(huì)形成新的有毒有害物質(zhì)。
眾所周知,HMF的含量隨著溫度和加熱時(shí)間的增加而增加[71]。因此,選用不同的加熱方式,進(jìn)而選擇適當(dāng)?shù)臏囟群蜁r(shí)間就能有效減少HMF的形成[78]。Akkarachaneeyakorn等[79]在麥芽中發(fā)現(xiàn)相對(duì)于傳統(tǒng)的加工方式,采取微波加熱的方式明顯降低了HMF的形成,而且不影響產(chǎn)品的顏色。Felke等[80]運(yùn)用了射頻加熱方式的巴氏消毒后,發(fā)現(xiàn)番茄醬中HMF的含量特別低,同時(shí)提高了其營(yíng)養(yǎng)品質(zhì)。在生產(chǎn)果汁過(guò)程中,用超高壓均質(zhì)的方式代替常規(guī)巴氏滅菌法同樣能顯著地減少HMF的含量,并且能導(dǎo)致微生物數(shù)量的減少[81]。另外,在模型和面包產(chǎn)品中,用非還原糖和多元醇代替葡萄糖、果糖等還原糖后能顯著減少產(chǎn)品中HMF[82-83]。在葡萄糖-蘋果酸的溶液中添加較高濃度(10 mmol/L)的天冬酰胺能明顯抑制蘋果醋中HMF的形成[84]。真空處理的方式也是減少HMF含量的有效方法,但是利用真空處理除去HMF的同時(shí)也減少了所需的風(fēng)味物質(zhì),并且極大地依賴于食品原料中的成分和含水量[85]。
由于美拉德反應(yīng)所形成的丙烯酰胺和HMF來(lái)自不同反應(yīng)途徑,并且HMF是生成丙烯酰胺的可能前體物,因此,添加抑制劑能抑制丙烯酰胺或者HMF形成,但有可能會(huì)促進(jìn)HMF或者丙烯酰胺的生成。以添加金屬離子為例,F(xiàn)iore等[45]發(fā)現(xiàn)雖然NaCl能有效地抑制丙烯酰胺,但是也能非常顯著地促進(jìn)HMF的生成,其促進(jìn)率達(dá)75%。寄希望于同時(shí)抑制丙烯酰胺和HMF的形成的方法還需要進(jìn)一步的研究。
目前,檢測(cè)丙烯酰胺和HMF的常規(guī)方法主要有高效液相色譜法、氣相色譜法、氣相色譜-質(zhì)譜聯(lián)用法、液相色譜-質(zhì)譜聯(lián)用法[86]。但是其檢測(cè)成本高、設(shè)備要求精密、操作較為復(fù)雜,并且常規(guī)方法難以對(duì)痕跡含量的樣品進(jìn)行快速準(zhǔn)確檢測(cè)[8]。Sun Qing等[87]以親水性印跡膜作為仿生抗體,利用此仿生抗體對(duì)丙烯酰胺的高結(jié)合力和特異性,開(kāi)發(fā)出檢測(cè)丙烯酰胺的仿生酶聯(lián)免疫吸附測(cè)定法,此法的最低檢測(cè)質(zhì)量濃度達(dá)到(85.0±4.2) μg/L,提高了檢測(cè)的準(zhǔn)確性。同時(shí),Rizelio[88]和Zhou Xun[89]等分別發(fā)現(xiàn)膠束電動(dòng)毛細(xì)管色譜法也能快速檢測(cè)低含量HMF和丙烯酰胺。除了以上檢測(cè)方法以外,微乳液電動(dòng)色譜法[90]、基體分散固相萃取法[91]、固相微萃取-氣相質(zhì)譜法[92]、毛細(xì)管電泳質(zhì)譜法[93]、電化學(xué)生物傳感器法[94]等新方法也被用來(lái)檢測(cè)丙烯酰胺含量。近年來(lái),生化檢測(cè)分析領(lǐng)域已廣泛引用量子點(diǎn)技術(shù),為開(kāi)發(fā)檢測(cè)丙烯酰胺的新方法提供了新思路。2014年,Hu Qinqin等[95]用N-丙烯酰氧基琥珀酰亞胺修飾量子點(diǎn),以不同濃度丙烯酰胺來(lái)調(diào)節(jié)量子點(diǎn)間的距離,從而避免量子點(diǎn)的自淬滅。根據(jù)量子點(diǎn)發(fā)射不同熒光強(qiáng)度來(lái)考量丙烯酰胺的濃度,開(kāi)發(fā)了一種新穎的丙烯酰胺檢測(cè)方法,且在質(zhì)量濃度為3.5×10-5~3.5 g/L范圍內(nèi)線性關(guān)系良好。
綜上所述,本文對(duì)丙烯酰胺與HMF的毒性、形成機(jī)理、檢測(cè)及抑制方法進(jìn)行了全面綜述。丙烯酰胺和HMF的形成機(jī)理已基本得到公認(rèn),快速準(zhǔn)確的檢測(cè)方法也已成熟,但是丙烯酰胺和HMF對(duì)人體的毒性劑量還未明確。同時(shí),雖然有大量的研究報(bào)道了分別抑制丙烯酰胺和HMF的方法,并為食品的熱處理工藝提供了一定的理論基礎(chǔ)。然而,同時(shí)抑制丙烯酰胺與HMF的方法甚少,還需要進(jìn)一步研究開(kāi)發(fā)。
最近,Akillioglu等[96]用酵母發(fā)酵來(lái)抑制速溶咖啡中的丙烯酰胺和HMF的形成,結(jié)果表明混合了面包酵母和蔗糖的速溶咖啡在30 ℃發(fā)酵48 h后,HMF和丙烯酰胺含量以不同的速率呈指數(shù)下降,因?yàn)樵诎l(fā)酵過(guò)程中HMF能轉(zhuǎn)換為酒精,而丙烯酰胺被酵母菌所降解。NaCl微膠囊同時(shí)抑制這兩種物質(zhì)的方法也被報(bào)道,F(xiàn)iore等[45]研究膠囊NaCl對(duì)HMF的影響,發(fā)現(xiàn)NaCl溶液質(zhì)量濃度在0~0.65 g/100 mL之間,HMF增加了75%,而膠囊NaCl能降低HMF 18%~61%,這是因?yàn)槟z囊NaCl提高了蔗糖水解的溫度,抑制了蔗糖的水解和果糖離子的形成。這些方法的開(kāi)發(fā)為同時(shí)抑制丙烯酰胺與HMF的形成提供了思路,期待科研工作者在這兩個(gè)方面做出更好的工作。除此之外,美拉德反應(yīng)生成的其他有毒有害的物質(zhì)將陸續(xù)被發(fā)現(xiàn),這需要科研工作者們及時(shí)開(kāi)發(fā)能抑制多種有毒有害物質(zhì)的方法。
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A Review of Acrylamide and 5-Hydroxymethylfurfural in Foods
WEN Chao, WANG Zimeng, SHI Xingbo*, DENG Fangming*
(Hunan Provincial Key Laboratory of Food Science and Biotechnology, College of Food Science and Technology,Hunan Agricultural University, Changsha 410128, China)
Acrylamide and 5-hydroxymethylfurfural formed in thermal treatment of foods have serious harmful impacts on consumers' health. Thorough research on their toxicity a nd formation mechanism, and approaches to detecting and inhibiting them can contribute to rational utilizati on of heat treatment processes, improving the safety of thermally processed foods,and exploiting new methods for inhibiting their formation. In this review, the toxicity, formation mechanisms, and inhibitory methods of acrylamide and 5-hydroxymethylfurfural are documented. The existing problems involved in the inhibition methods are summarized. In the future, the development of inhibition methods should be focused on simultaneously inhibiting multiple Maillard reaction products with potential toxicity.
acrylamide; 5-hydroxymethylfurfural; toxicity; Maillard reaction; inhibition
TS201.6
A
1002-6630(2015)13-0257-08
10.7506/spkx1002-6630-201513048
2015-01-21
國(guó)家自然科學(xué)基金青年科學(xué)基金項(xiàng)目(31301484);湖南省自然科學(xué)基金青年項(xiàng)目(2015JJ3082);湖南農(nóng)業(yè)大學(xué)青年科學(xué)基金項(xiàng)目(12YJ09;14QN11)
溫超(1989—),男,碩士研究生,研究方向?yàn)槭称芳庸み^(guò)程中有毒有害物質(zhì)的分析。E-mail:270631806@qq.com
石星波(1984—),男,講師,博士,研究方向?yàn)槭称芳庸み^(guò)程中有毒有害物質(zhì)的分析。E-mail:shixingbo123@aliyun.com鄧放明(1962—),男,教授,博士,研究方向?yàn)楣呤称芳庸ぜ暗~加工與綜合利用。E-mail:fmdenghnau@sina.com