Research Progress on Flavor Characteristics of Strong Fragrance Spices and Their Effects on Flavor Formation of Meat Products
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摘要: 浓香型天然香辛料以浓香为香气特征,具有芳香性和刺激性,呈香组分以芳香化合物为主,典型代表为八角、桂皮、小茴香、丁香等。国内外广泛使用上述浓香型天然香辛料,尤其是在酱卤肉制品和发酵肉制品中。然而,目前对于天然香辛料赋香呈味机制的研究仍不够深入和系统。本文在查阅近年来国内外相关研究基础上,以典型的浓香型天然香辛料为代表,系统综述了浓香型天然香辛料的风味分析方法、风味特征及其关键风味成分。同时讨论了其对肉制品风味形成的影响:香辛料风味成分可以通过直接迁移进食物中对酱卤肉制品的风味产生影响,也可以通过抑制脂肪氧化和抗杂菌作用等方式改善发酵肉制品的风味。在此基础上,本文进一步总结了浓香型天然香辛料的赋香呈味机制,即香辛料中风味成分直接迁入食品中赋香;香辛料组分与食品基质发生生香反应;抑制风味前体物氧化进程;抑制致腐菌生长,改善不良风味的形成。通过对浓香型天然香辛料风味特征及赋香呈味机制总结,有利于科研工作者深入发掘浓香型天然香辛料调控食品风味形成机理,同时为食品企业,尤其是肉制品生产企业进一步合理开发、利用天然香辛料提供参考。Abstract: Strong-aroma natural spices are characterized by their strong aroma, possessing aromatic and irritating properties, with the main components being aromatic compounds. Typical representatives include star anise, cinnamon, fennel, and cloves. The aforementioned strong-aroma natural spices are widely used both domestically and internationally, especially in soy sauce stewed meat products and fermented meat products. Nonetheless, current research on the aroma-imparting and flavor-presenting mechanisms of natural spices remains insufficiently in-depth and systematic. This paper bases on a review of relevant domestic and international research in recent years, systematically summarizes the flavor analysis methods, flavor characteristics, and key flavor components of typical strong-aroma natural spices. It concurrently discusses their impact on the flavor formation of meat products: spice flavor components can influence the flavor of soy sauce stewed meat products by directly migrating into the food or by improving the flavor of fermented meat products through inhibiting fat oxidation and anti-bacterial effects. Building on this, the paper further elucidates the aroma-imparting and flavor-presenting mechanisms of strong-aroma natural spices, encompassing direct migration of flavor components into food for aroma enhancement, aroma-generating reactions between spice components and food matrices, inhibition of flavor precursor oxidation processes, and suppression of spoilage bacteria growth to ameliorate undesirable flavor formation. The summary of the flavor characteristics and aroma-imparting mechanisms of strong-aroma natural spices facilitates researchers in delving into the mechanisms by which these spices regulates food flavor formation and provides a reference for food enterprises, particularly meat product manufacturers, in further rational development and utilization of natural spices.
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Keywords:
- strongly aromatic spices /
- meat products /
- flavor /
- characteristic /
- mechanism
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天然香辛料是一类可直接食用的植物种子、花蕾、叶茎、根块、果实或整体植株等天然性产品的总称[1]。目前,世界上已知的天然香辛料多达500种,被国际标准化组织确认并列入标准的达110种,其中适宜我国种植且被列入国家标准(GB/T 12729.1-2008香辛料和调味品)的品种有68种[2]。我国作为全球香辛料的主要生产种植和出口国,除了拥有丰富的天然香料资源外[3],在天然香辛料加工和应用方面也有着悠久的历史,我国将天然香辛料分为三大种类(GB/T 21725-2017),即浓香型天然香辛料、辛辣型天然香辛料和淡香型天然香辛料:浓香型天然香辛料以浓香为香气特征,呈味组分多为芳香化合物;辛辣型天然香辛料以辛、辣味等强刺激性气味为主要呈味特征,呈味成分多为硫或酰胺类化合物[1]。
常用的浓香型香辛料主要有八角茴香、丁香、百里香、桂皮、小茴香等,此外还有一些不常用的香辛料,如莳萝、甜罗勒等。浓香型香辛料多用于肉制品加工,不仅可以在赋予肉制品特色香气的同时抑制异味的产生,还能发挥抑菌、防腐和抗氧化的作用[4],例如百里香中的百里酚、桂皮中的桂皮醛都具有调味潜力,而丁香中的丁香酚更是与抗菌和抑菌活性有关[5]。在酱卤肉制品和发酵肉制品的加工中,上述作用尤为重要,在酱卤肉制品中香辛料可以赋予其不同的特征风味;而在发酵肉制品中添加香辛料不仅可以去除原料肉中的不良气味,还可以使某些有益菌更好的生长。因此,浓香型天然香辛料对肉制品的风味的形成和品质调控具有重要意义。然而,浓香型天然香辛料赋味机制及其对肉制品风味形成的影响研究鲜有报道。本文综述了浓香型香辛料风味成分及其赋味特征和机制,以及对肉制品风味形成的影响,以期为天然香辛料的进一步合理化开发利用提供参考。
1. 浓香型天然香辛料风味成分
1.1 风味成分分析方法
1.1.1 挥发性香气成分分析方法
浓香型天然香辛料是肉制品加工中起重要作用的香辛料,特征是具有芳香性和刺激性。相较于滋味成分,浓香型天然香辛料中的挥发性香气成分对于肉制品风味形成或调控起到十分重要的作用,因此对于浓香型天然香辛料中的挥发性香气成份的检测是重中之重。
目前,固相微萃取-气相色谱-质谱联用法是分析香辛料香气成分的常用方法,固相微萃取(solid-phase micro-extraction,SPME)已成为食品分析中常用的分析标度萃取方法。它利用固定相和样品基质之间的化合物吸附系数进行选择性萃取。在固相微萃取中,萃取温度和时间对于香气成分的影响较大,萃取温度较低不利于香辛料中挥发性成分的释放,而萃取时间达到某一特定值时,萃取时间的延长对萃取效果影响并不显著[6]。
SPME是一种相对简单、快速的样品前处理方法,对样品操作的要求较低[7]。而气相色谱-嗅觉法是一种常用的表征气味活性和特征影响化合物的仪器技术,可以对香辛料中香气成分进行分离与粗鉴定,但是气相色谱-嗅觉法/质谱法在复杂基质中测定气味剂时,可能存在芳香区化合物共洗脱的问题,这给气味剂的鉴定带来困难。多维气相色谱通常能够解决香气峰的共洗脱问题,将目标区域从一维色谱柱转移到具有不同分离机制的二维色谱柱,从而达到进一步分离的目的[8]。香气活力值(odour active values,OAV)是指香气成分的浓度与该成分阈值的比值,是评判香气强度和影响因素的重要指标,若OAV>1,则表示该成分对香辛料香气起着较为显著的作用;若OAV<1,则相反。周天姣等[9]研究显示,丁香中丁香酚的OAV值为93367~466833,是丁香特征香气形成的关键成分;刘慧勤等[10]利用顶空固相微萃取结合气相色谱-质谱联用的方法对三种不同方式提取的八角籽油香气成分进行了分析,根据OAV值的大小,可以推测出反式茴香脑、芳樟醇、草蒿脑、桉叶油醇这四种物质对八角籽油的总体香气起主导作用。
另一方面,由一系列电化学传感器组成的电子鼻和电子舌也被广泛应用于风味分析,以避免感官评价过程中主观因素的影响[11]。电子舌与电子鼻已经成为测定香气与味感物质的重要工具。李霞等[12]通过S曲线和OAV法统计分析了多种物质的香气强度,发现两种同种香韵的香气物质混合后一般表现为协同或加成作用,如愈创木酚与丁香酚(图1)。利用S型曲线法分析香气阈值等相互作用,再利用U模型构建香气强度预测模型的分析方法,对于指导香气成分的混合使用具有着重要意义。
近年来,浓香型天然香辛料的应用愈发广泛,不仅在提高风味,还在抑菌防腐等方面有着重要作用,而对于其挥发性香气成分的分析仍然还是以固相微萃取-气相色谱-质谱法为主。目前已有将顶空取样与固相微萃取相结合的方法,但总体还是具有一定局限性。
1.1.2 非挥发性成分分析方法
对于香辛料中非挥发性风味物质,例如核苷酸、氨基酸与有机酸等目前分析方法已经比较成熟。游离氨基酸含量与动植物、食品的香气、风味等品质相关[13],氨基酸分析法、高效液相色谱法、液相色谱-串联质谱法等都是十分常用的分析检测方法[14],而超临界流体色谱法也正在发展成为氨基酸分离的首选技术[15]。核苷酸与有机酸可利用高效液相色谱法测定,Kong等[16]采用高效液相色谱法分离,再采用外标法进行定量分析有机酸;呈味核苷酸的测定也普遍利用高效液相色谱法,黄艳等[17]建立了一种超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法测定核苷酸含量的分析方法,可为核苷酸的分析提供新的技术支持。
1.2 风味成分
1.2.1 挥发性风味成分
浓香型天然香辛料的挥发性成分种类繁多,且在不同的香辛料里组成和含量差异明显。这些挥发性成分不仅赋予了食品特有的香气和滋味,同时也提高了食品的品质与价值。浓香型天然香辛料关键挥发性风味成分种类很多,例如茴香脑、丁香酚、百里香酚、甲基丁香酚、桂皮醛、豆蔻醚等。下面列举几种代表性挥发性风味成分具体介绍。
1.2.1.1 茴香脑
茴香脑有种甜润的茴香香气,其分子式为C10H12O,相对分子量为148.21,已知在茴香油、八角茴香油和小茴香油等精油中以天然产物形式存在,其中大多数皆为反式体[18]。八角茴香属木兰科常绿芳香树种,其果实是一种有特殊气味的星形果实,具有挥发性的八角茴香精油就是从八角茴香果实中提取出的物质。八角茴香精油由苯丙素、单萜化合物、倍半萜化合物、氧合单萜化合物和含氧倍半萜化合物组成[19],其中反式茴香脑占总成分的85%~90%[20]。因此,茴香脑可以作为八角茴香典型的挥发性风味成分。茴香脑抑菌活性很强早已被相关研究证实[21], 而其特殊的风味,Toshio等[22]研究发现与其结构特征中的甲氧基和甲基苯基团密切相关。如果用氢原子取代甲氧基或甲基将导致衍生物的特征气味丧失,并产生具有类似脂肪气味的化合物;郑燕菲等[23]通过水蒸气蒸馏法和气相色谱-质谱(Gas Chromatography-Mass Spectrometry,GC-MS)联用技术,对八角茴香壳和籽中挥发油的化学成分进行提取和分析,发现在八角茴香壳和籽挥发油中,茴香脑均是化学组分中含量最高的一种,分别占组分的68.51%和75.24%;屈云萍等[24]对新货和陈货八角茴香提取挥发油进行研究发现,新货挥发油有着更高的提取得率,外观色泽更淡,且挥发油组分中反式茴香脑的含量较高。因此,工业生产中使用新货提取八角茴香油更为合理;熊耀坤等[25]对比八角茴香干燥前后挥发油成分发现,干燥前后八角茴香中挥发油的化学成分及含量发生了显著变化,干品中双戊烯含量相比鲜品降低,茴香脑相比鲜品中含量增高,由此推测干品中的部分茴香脑由鲜品中的双戊烯转化而来。该发现深化了对八角茴香的干燥加工过程的认识,对于八角茴香中挥发油成份的合理利用具有指导意义。
1.2.1.2 丁香酚
丁香酚,外观为液体,具有强烈的辛香香气[18]。丁香是一种干燥花蕾,桃金娘科植物,是我国重要的香料之一[26],隶属浓香型天然香辛料。研究发现丁香风味浓郁,具有诸多的药理成分,同时具有镇静、抗菌消炎和抗氧化的作用[27−28]。作为一种属于药食同源植物,丁香的主要药效成分是丁香挥发油[29]。而丁香酚是丁香挥发油的主要活性成分,占总提取物成分的50%以上[30]。姜薇等[31]研究表明,丁香中挥发性成分气味浓烈,呈辛辣味,同时对酱卤牛肉的甜味呈现有着突出贡献。李霞等[12]利用S型曲线法测定了天然产物中部分香气物质的阈值,并通过U模型构建香气强度预测模型,为丁香酚/乙酸等不同比例混合后的香气强度与加成或掩盖效果做出了准确预测。
1.2.1.3 百里香酚
百里香酚又名麝香草酚,天然存在于百里香精油中,其分子式为C10H14O[17]。百里香是唇形科百里香属的一种开花植物,原产于南欧,如今它被作为一种药用植物广泛应用于食品和医药行业[32]。百里香整株具有浓郁的、芳香的麝香气味,它的命名也源自于此。百里香精油主要成分为百里香酚、芳樟醇等多种化合物。虽然不同种百里香挥发油成分种类和含量存在明显差异,但百里香酚的相对质量分数最高(32.86%~79.04%)[33],被认为是百里香主要的挥发性风味成分。百里香酚在欧盟和美国已被列入食品添加剂公认安全名单,由于其对多种食源性致病菌和果蔬腐烂菌具有抑制作用,故已作为一种天然抗菌剂应用于食品保鲜[34]。陈丽艳等[35]采用GC-MS技术鉴定百里香挥发油的成分,并使用琼脂扩散法研究其对大肠杆菌及金黄色葡萄球菌生物活性的影响。实验结果表明,百里香酚是百里香精油中主要成分,且具有较好的抑菌活性。
1.2.1.4 其他挥发性风味成分
龙蒿、小茴香、桂皮、豆蔻等也是非常重要的浓香型天然香辛料,这些香辛料大多气味浓郁,但是挥发性风味成分却不尽相同。龙蒿是菊科蒿属的植物,新疆龙蒿的嫩叶有花椒的麻辣味[36],其主要挥发性风味成分是甲基丁香酚、甲基胡椒酚等物质。小茴香是非常重要的浓香型天然香辛料,主要挥发性成分是茴香脑、葑酮和爱草脑等[37],其中反式茴香脑与茴香脑可以通过异构作用相互转化。对于小茴香的研究,Viuda-Martos等[38]发现茴香脑是小茴香中最重要的香气成分,但是Napoli等[39]研究发现在小茴香香气中草蒿脑的作用可能强于茴香脑的作用。张艳等[40]使用三种溶剂提取桂皮精油,通过GC-MS对提取出的成分进行分析,发现桂皮醛是桂皮精油的主要成分。肉豆蔻中肉豆蔻醚和桧烯等是它的主要风味成分[41],采用超临界二氧化碳流体萃取提取豆蔻成分,能够提取出许多诸如长链脂肪烃等物质,这些物质是传统水蒸气提取法无法提取的[42],对豆蔻的完整成分分析有重要作用。浓香型香辛料种类多,范围广,且挥发性风味成分具体含量会随着品种和产地的不同而产生一定差异。常见浓香型天然香辛料及其典型挥发性风味成分见表1。
表 1 常见浓香型天然香辛料及其典型挥发性风味成分Table 1. Fragrant natural spices and their typical volatile flavor components浓香型香辛料 典型挥发性风味成分及其化学结构 典型挥发性风味成分含量 香辛料风味特征 丁香[43]
丁香酚75.0%~88.0% 气芳香浓烈,味辛辣、有麻舌感 八角茴香[44]
茴香脑80.0%~90.0% 气芳香,味辛、甜 小茴香[45]
反式茴香脑65.0%~78.0% 味辛,性温 牛至[46−47]
香芹酚12.9%~83.6% 风味相对强烈浓郁,有辛辣感 龙蒿[48]
3,7-二甲基-1,3,7-辛三烯35.0%~42.0% 气味比较柔和 百里香[49−50]
百里香酚37.5%~43.9% 气味芳香浓郁,味道辛香 阴香[51−52]
龙脑38.6%~47.2% 味辛、微甘 芹菜籽[53−54]
柠檬烯44.6%~58.4% 香气浓郁,清新,有木质香 多香果[55−56]
甲基丁香酚55.5%~67.4% 味辛、性温,具多种芳香气味 芫荽[57]
芳樟醇69.6%左右 辛,温 葛缕子[58]
D-柠檬烯47.2%~60.0% 味辛,性温,具有独特的薄荷香味 桂皮[40]
肉桂醛79.8%~81.5% 性辛甘,同时带有一点甜味 甜罗勒[59]
芳樟醇23.9%~50.0% 略带薄荷味,但稍甜,有点辣味 1.2.2 非挥发性风味(滋味)成分
风味包括香味和滋味,是评价肉制品重要的感官特性[60]。浓香型天然香辛料中主要含有挥发性物质,但是其中某些的非挥发性物质也有着不可忽视的作用,通常表现在滋味形成方面。由于挥发性风味物质发挥着主体性作用,以及味觉阈值的影响存在,对于非挥发性风味物质的感觉可能会存在一些偏差或分辨不清的现象。同辛辣味香辛料相同[61],浓香型天然香辛料中也存在着核苷酸、氨基酸等风味物质,它们可以作为风味物质或是风味前体物质;Duan等[62]对于18种浓香型香辛料的研究表明,氨基酸中的谷氨酸、丙氨酸、甘氨酸和天冬氨酸是决定食物味觉的主要因素[63],排名前五的氨基酸分别是天冬氨酸、谷氨酸、丝氨酸、丙氨酸、甘氨酸,而八角茴香中总游离氨基酸含量为1.20 g/kg。这也与王震等[64]的报道相似。根据Phat等[65]的研究,5′-鸟苷酸(5'-Guanylic acid,5′-GMP)和5'-肌苷酸(5’-inosinicacid,5′-IMP)之间的协同作用可被认为是鲜味产生的原因,5′-IMP可以与其他成分结合,在炖煮过程中改善鲜味。5′-GMP提供了一种肉味,并可作为比味精更强的增味剂[66]。小豆蔻中核苷酸含量最低,而八角茴香和丁香中含量较高。一些有机酸及其钠盐具有鲜味,如琥珀酸钠和二钠盐,可以作为增味剂添加到食品中[67]。在Duan等[62]关于18种浓香型天然香辛料中,八角茴香中有机酸含量最低,而百里香中有机酸含量则最高。综上所述,浓香型天然香辛料中非特征风味物质氨基酸等对于风味的呈现也有着重要作用,尽管这些成分没有发挥主体作用,但是对于风味的调控,风味物质之间的相互作用仍然发挥着不可或缺的作用,同时因为含量较低,而某些风味物质味觉阈值可能较高而难以分辨。这些非特征性风味物质也需要进行进一步研究。
2. 浓香型天然香辛料对肉制品风味形成的影响
肉制品的风味与原料和加工处理过程密切相关。肉类中发生的变化包括糖和核糖核苷酸的降解,肽和氨基酸的热解,美拉德反应,脂质氧化,硫胺素和脂肪的降解以及微生物代谢等[68],这些变化赋予了肉制品独特的风味。目前已经有研究表明,浓香型天然香辛料的添加对于肉类中的变化过程有影响。如百里香具有较高的磷酸酶活性,可以对5'-核糖核苷酸的稳定性产生影响[69];紫外光谱分析表明,微量添加葛缕子种子精油显著降低了美拉德褐变[70];丁香、百里香、桂皮等香料的液体提取物的添加显著抑制猪肉中的脂质氧化过程[71]。因此,香辛料可通过影响肉制品中酶促反应或氧化进程以实现改善肉制品风味的目的。
2.1 挥发性风味的影响
2.1.1 香辛料挥发性风味对酱卤肉制品的影响
酱卤肉作为我国具有代表性的传统肉制品之一,是以鲜(冻)畜禽肉和可食副产品放在加有食盐、酱油(或不加)、香辛料的水中,经预煮、浸泡、烧煮、酱制(或卤制)等工艺加工而成的酱卤类肉制品[72]。常见的加工工序是先将原料肉进行预煮,而后施用香辛料和调味料一起加水煮制,重用黄酱和香辛料是其一大特色[73]。在加工过程合理使用香辛料可以让酱卤肉获得不同的特征风味。目前,很多浓香型天然香辛料,如八角茴香、丁香、桂皮等已经广泛应用于酱卤肉生产中。对于浓香型香辛料对于酱卤肉风味影响深入研究,目前已经有了一定的成果。
姜薇等[31]通过电子舌和超高效液相色谱-串联质谱技术系统研究了酱卤肉加工中常用的香辛料品类对酱卤牛肉的赋味效应(图2),结果发现桂皮、八角、丁香对甜味贡献突出,小茴香对鲜味具有增益作用。此方法对于酱卤肉行业的标准化具有一定的借鉴意义,有利于香辛料的科学复配与风味调控,避免香辛料利用率不足造成资源浪费和加工成本提高。孙灵霞[74]通过研究八角茴香对卤鸡肉挥发性风味形成的作用机制,发现添加八角茴香的实验组对照空白组,主体风味物质中增加了反式茴香脑。此发现说明八角茴香中固有特征风味物质的释放和迁移改变了卤鸡的挥发性成分组成和比例,对卤鸡肉的挥发性风味影响较大。Sun等[75]通过GC-MS分析,八角茴香的加入,与对照组相比,醛类挥发物的峰面积和百分比组成增加,而美拉德反应衍生挥发物包括一些含硫化合物、羰基化合物和杂环化合物等的峰面积和百分比组成减少。这个结果表明了相较于生产过程中的美拉德反应,香辛料特征风味对于酱卤肉制品的影响可能更具决定性。桂皮对于卤鸡腿肉挥发性风味成分影响早有研究,刘欣等[76]发现添加桂皮的鸡肉相比空白对照新增了苯丙醛、桂皮醛、甲氧基桂皮醛、香叶基丙酮、吡啶等9种物质,鸡肉样品中新增的挥发性风味物质除吡啶外均属于桂皮的直接引入。张洁[77]对单一香辛料提取液卤制和复合卤制过程中主效成分变化进行研究,发现桂皮醛和丁香酚附着速度在卤制前15 min较快,这一点与β-山椒素恰恰相反。
传统酱卤肉制品制作过程,对于香辛料的用法用量并不明确或多凭经验,因此推动酱卤肉走向更大市场的过程,必然伴随着卤制标准化的研究。林柔汐[78]研究了卤鸭制品卤制过程香辛料主要成分的迁移规律,结果发现闷煮时间对浓香型桂皮的特征性风味成分桂皮醛的迁移无显著影响。Qin等[79]采用三角感官试验和GC-MS法对重复使用的传统肉汤中挥发性成分进行研究,发现茴香脑作为八角茴香含量最高的特征香气化合物,对肉汤和炖肉制品的风味影响主要是通过风味成分的迁移引入。添加八角茴香的肉汤重复使用3次后,其挥发性化合物包括茴香脑在内的含量显著下降。由此建议在重复使用2次后再添加40%~50%的八角茴香,在重复使用3次后再添加20%~30%的八角茴香。此研究对于卤水重复使用中的风味变化研究有一定指导意义,有利于具有稳定感官特性的酱卤肉制品的生产。传统酱卤肉制品生产时,浓香型香辛料的选择与搭配、香辛料和其它辅料的准确添加量、老汤重复使用中风味物质的变化,对于探究传统酱卤肉制品调味呈味规律、确保产品稳定的感官特性、改进酱卤肉制品加工工艺、促进传统酱卤肉制品的工业标准化生产都具有重要的参考价值[80]。
综上,香辛料对酱卤肉制品风味的影响主要来自香辛料风味成分的直接迁移引入,且酱卤肉制品的风味受到其中香辛料风味成分含量变化的影响较大。
2.1.2 香辛料挥发性风味对发酵肉制品的影响
发酵肉制品在我国有着十分悠长的历史,其独特的风味和口感使其在众多美食中脱颖而出。在发酵肉制品加工中,香辛料的添加除了可以有效去除原料肉中的不良气味,赋予产品独特的风味外,更重要的作用是使某些有益菌更好地生长,更有利于有益菌的竞争作用。发酵香肠作为其中重要的一部分,其品质与香辛料、微生物因素、脂肪氧化等原因密切相关[81−82]。丁香作为一种重要的浓香型香辛料,在发酵肉制品加工中应用十分广泛,其特征性风味物质丁香酚是一种具有抗菌作用的天然芳香成分。在Jia等[83]的研究中,丁香香料对于干发酵羊肠中生物胺的合成具有显著抑制作用,从而提高发酵制品风味。张慧芸等[84]在丁香研究中发现,其能抑制肉糜产品中的脂肪氧化,延缓脂肪腐败劣变带来的不良风味。脂质氧化是肌肉食物酸败和风味变质的主要原因[85],而发酵肉制品加工制作时间较长,在加工过程中脂肪极易氧化,因此添加丁香香料抑制脂肪氧化对于保证发酵肉制品风味质量有着重要意义。为了鉴定出发酵香肠中风味物质,Marco等[86]用同时蒸馏萃取法测定其中的挥发性风味物质,包括了醛、酮、醇、酯、呋喃等。香辛料通常用作加工肉制品中的增味剂[87],具有生物活性的丁香酚等风味物质对肉制品风味的提升有着积极意义,此外丁香水杨酸甲酯、甲基正戊基酮等风味物质也是影响发酵香肠风味重要物质[88]。同时丁香对发酵肉制品中有害微生物有着抑制作用,抑制有害微生物产生有害物质影响食品风味以及损害人体健康,可作为加工食品的防腐剂。Ravishankar等[89]通过研究含有香芹酚和桂皮醛的果胶基苹果、胡萝卜和芙蓉食用膜对火腿和腊肠上单核细胞增生李斯特菌的灭活效果表明,在一般情况下,香芹酚制备的膜比桂皮醛制备的膜对单核细胞增生乳杆菌具有更好的抗菌活性,从而延缓脂质氧化,维持发酵肉制品良好风味。总的来说,浓香型天然香辛料在发酵肉制品主要通过抑制脂肪氧化和抗杂菌作用两条途径确保了发酵质量,从而有效的改善了发酵肉制品的风味,保证了其食品质量和市场价值。
2.2 非挥发性成分的影响
浓香型天然香辛料中除了含有挥发性风味物质外,还含有大量的非挥发性风味物质,例如核苷酸、氨基酸与有机酸等。这些非挥发性风味物质对于肉制品风味的影响也不可小觑。浓香型香辛料中非挥发性风味物质可以通过以下3种途径改善肉制品的风味:a.风味成分本身具有特定的滋味;b.对肉制品原有滋味的增强或对异味的掩盖;c.通过对微生物生长的影响改变肉制品的风味[90]。例如:小茴香中具有天冬氨酸、谷氨酸、苏氨酸、丝氨酸、脯氨酸等17种氨基酸,其中含量最高为谷氨酸[91],而谷氨酸是一种鲜味物质[92]。桂皮中多为酚类和多酚类化合物,对香肠的一次氧化和二次氧化产物会产生较好的抑制作用,从而减少脂质氧化产生的异味[93];八角、丁香等香辛料中含有生物碱类物质,而生物碱类是天然药物中六种主要的抗氧化剂之一[94],同样有助于抑制脂质氧化对风味的影响。丁香中Mn2+含量很高,添加到香肠中可以促进产酸,从而提高发酵质量,产生独特的发酵风味[95]。
3. 浓香型天然香辛料赋香呈味特征及机制
3.1 赋香呈味特征
浓香型香辛料中的挥发性风味成分是赋予食品风味的主要因素。Diaz-Maroto等[96]研究发现,一些浓香型香辛料如百里香中的有机酸能够赋予食品细腻淡雅的香气。此外,不同的香辛料赋味特征不尽相同,八角茴香和丁香对于肉制品甜味和香气有着较大的贡献作用,小茴香对于鲜味增益效果明显,白芷、草果和香叶等则对于形成苦味有着明显作用[31]。香辛料中的氨基酸类、多肽类等物质对于食品的赋味作用十分明显,其中鲜味氨基酸是重要的鲜味剂[97],如甘氨酸、谷氨酸等。香辛料中谷氨酸的味觉活性值远高于其他游离氨基酸,能够赋予食品极高的鲜味特性[98]。Raza等[99]对酵母抽提物的挥发性成分进行研究,发现了半胱氨酸具有赋予食品肉味,同时延缓鲜味的作用。相关研究还发现香辛料中的一些核苷酸同样会对食品产生鲜味作用[65]。
3.2 赋香呈味机制
尽管浓香型香辛料已经广泛用于改善肉制品的风味,但是对其赋香/味机制的相关研究仍然较少。因此研究香辛料对肉制品的赋香/味机制,对于改善肉制品的风味,保证肉制品标准化生产的风味质量具有指导意义。鲁松涛等[100]在研究丁香对卤制鸡肉风味物质形成的影响时发现,添加丁香卤制后鸡肉挥发性成分中新增了丁香酚、芳樟醇等7种风味物质,其中一部分是丁香中固有挥发性成分的直接引入,另一部分是鸡肉中脂肪氧化的产物。在他另一篇关于道口烧鸡风味与品质形成机理的文章中,也指出了单种香辛料对鸡肉风味的影响主要源于香辛料中直接引入的物质,以及引入成分与鸡肉成分发生反应所产生的物质[101]。林柔汐[78]对卤鸭的研究中同样表明多种香辛料挥发性主效成分都发生了一定程度的从卤水到肉制品上的迁移。除此之外,在肉制品加工过程中,脂质被脂肪酶水解,产生游离脂肪酸等风味前体,然后进一步氧化形成挥发性风味化合物[102],而许多植物化学提取物富含酚类化合物,已被证明具有很强的自由基清除和金属离子结合特性,因此在肉制品中发挥抗氧化活性[103],可能对肉制品的风味产生影响。 Huang等[104]研究发现,丁香提取物能显著抑制猪肉馅料贮藏过程中蛋白质和脂肪的氧化,从而抑制了馅料发生酸败产生异味。孙灵霞[74]在研究八角茴香对卤鸡肉挥发性风味及风味前体物的影响后得出结论,八角茴香在卤鸡肉制品中的赋香/味机制在煮制前后期有较大的区别,蒸煮前期主要是通过抑制游离脂肪酸的氧化降解来实现,在煮制后期除了抑制游离脂肪酸氧化外,主要是通过八角茴香中固有的挥发性物质如茴香脑的释放和迁移而实现赋香/味效果。除此之外,香辛料对李斯特菌属、假单胞菌属等腐败菌均具有一定抗菌活性[105],而这些致腐杂菌往往会导致肉的风味缺陷[106]。由此可见,浓香型香辛料的赋香/味机制主要概括为四种:a.香辛料的风味成分直接迁移引入食品中;b.引入的风味成分与食品基质成分发生的反应;c.抑制加工和贮藏过程中的氧化进程;d.抑制致腐菌的生长,改善不良风味的形成。在肉制品加工中,四种赋香/味机制协同作用从而影响肉制品的整体风味,但是起主要作用的赋香/味机制可能会随着加工阶段和加工对象的不同而有所差异。
4. 结论
本文以典型的浓香型天然香辛料为研究对象,从分析方法出发,系统综述了香辛料中的典型挥发性风味成分与非挥发性风味成分,及其对肉制品风味形成的影响,最后总结探讨了浓香型天然香辛料的赋香/味特征和机制等。浓香型天然香辛料在肉制品风味调控中发挥着重要的作用,其不仅能够改善食品风味,还能在抑菌防腐方面发挥作用。对浓香型天然香辛料的深入研究,不仅能了解浓香型天然香辛料对于肉制品的风味影响以及风味调控机理,更有利于肉类加工企业改善肉制品加工工艺,推动肉制品标准化生产。然而,目前对于浓香型天然香辛料风味成分的作用机理以及与肉制品自身风味成分之间的相互影响研究相对较少,未来可以在此方面进一步研究,从而最大程度的实现对风味成分的利用,并为肉类加工企业的生产提供理论指导。
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表 1 常见浓香型天然香辛料及其典型挥发性风味成分
Table 1 Fragrant natural spices and their typical volatile flavor components
浓香型香辛料 典型挥发性风味成分及其化学结构 典型挥发性风味成分含量 香辛料风味特征 丁香[43]
丁香酚75.0%~88.0% 气芳香浓烈,味辛辣、有麻舌感 八角茴香[44]
茴香脑80.0%~90.0% 气芳香,味辛、甜 小茴香[45]
反式茴香脑65.0%~78.0% 味辛,性温 牛至[46−47]
香芹酚12.9%~83.6% 风味相对强烈浓郁,有辛辣感 龙蒿[48]
3,7-二甲基-1,3,7-辛三烯35.0%~42.0% 气味比较柔和 百里香[49−50]
百里香酚37.5%~43.9% 气味芳香浓郁,味道辛香 阴香[51−52]
龙脑38.6%~47.2% 味辛、微甘 芹菜籽[53−54]
柠檬烯44.6%~58.4% 香气浓郁,清新,有木质香 多香果[55−56]
甲基丁香酚55.5%~67.4% 味辛、性温,具多种芳香气味 芫荽[57]
芳樟醇69.6%左右 辛,温 葛缕子[58]
D-柠檬烯47.2%~60.0% 味辛,性温,具有独特的薄荷香味 桂皮[40]
肉桂醛79.8%~81.5% 性辛甘,同时带有一点甜味 甜罗勒[59]
芳樟醇23.9%~50.0% 略带薄荷味,但稍甜,有点辣味 -
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