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中国精品科技期刊2020

不同类型白茶儿茶素、香气成分与感官品质比较

王若娴, 黄翔翔, 李勤, 李娟, 谭君, 朱洺志, 王坤波

王若娴,黄翔翔,李勤,等. 不同类型白茶儿茶素、香气成分与感官品质比较[J]. 食品工业科技,2022,43(5):315−321. doi: 10.13386/j.issn1002-0306.2021090001.
引用本文: 王若娴,黄翔翔,李勤,等. 不同类型白茶儿茶素、香气成分与感官品质比较[J]. 食品工业科技,2022,43(5):315−321. doi: 10.13386/j.issn1002-0306.2021090001.
WANG Ruoxian, HUANG Xiangxiang, LI Qin, et al. Comparison of Catechins, Aroma Components and Sensory Quality of Different Types of White Tea[J]. Science and Technology of Food Industry, 2022, 43(5): 315−321. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2021090001.
Citation: WANG Ruoxian, HUANG Xiangxiang, LI Qin, et al. Comparison of Catechins, Aroma Components and Sensory Quality of Different Types of White Tea[J]. Science and Technology of Food Industry, 2022, 43(5): 315−321. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2021090001.

不同类型白茶儿茶素、香气成分与感官品质比较

基金项目: 国家重点研发计划课题(2018YFC1604403);湖南省重点研发计划项目(2020WK2017);湖南省自然科学基金(2020JJ4356);湖南省教育厅重点项目(20A241);中央引导地方科技发展区域创新体系建设项目(2020ZYQ063)。
详细信息
    作者简介:

    王若娴(1997−),女,硕士研究生,研究方向:茶叶加工与功能成分利用,E-mail:527485822@qq.com

    通讯作者:

    谭君(1980−),女,博士,副教授,研究方向:植物功能成分研究与安全性评价,E-mail:junjuntan@163.com

    朱洺志(1986−),男,博士,教授,研究方向:茶叶品质化学,E-mail:mzzhucn@hotmail.com

    王坤波(1976−),男,博士,教授,研究方向:茶叶加工与功能成分利用,E-mail:wkboo163@163.com

  • 中图分类号: TS272.7

Comparison of Catechins, Aroma Components and Sensory Quality of Different Types of White Tea

  • 摘要: 白茶是我国特有的一种微发酵茶,为探明不同类型白茶的品质差异,本研究选取了白毫银针、白牡丹、贡眉、寿眉、新工艺白茶共10个白茶样品,分别进行了高效液相色谱(HPLC)检测儿茶素、气相色谱-质谱(GC-MS)检测香气成分以及感官评价,并结合方差分析和OPLS-DA等多元统计学分析。结果表明,不同类型白茶中儿茶素含量差异较大,贡眉的总儿茶素含量最高,寿眉最低,分别为66.84和32.66 mg/g,并且所有白茶共检测到50种香气物质,主要香气组分有正己醛、(E)-2-己烯醛、苯甲醛、芳樟醇及其氧化物(I、II)等。白毫银针、白牡丹、贡眉、寿眉等4种传统工艺白茶的香气组成和含量与新工艺白茶有明显差异,其中,(E)-2-戊烯醛、2-庚酮等8种香气成分在4种传统工艺白茶中大量存在,而在新工艺白茶中未检测出。通过多组分化学计量学分析发现,白毫银针、白牡丹、贡眉与新工艺白茶的儿茶素和香气代谢物存在显著差异,而寿眉与新工艺白茶相差不大。本研究初步探明了不同类型白茶的品质差异,为白茶风味品质调控提供理论依据。
    Abstract: White tea is a unique kind of micro-fermented tea in China. In order to explore the quality differences of different types of white tea, ten samples including Baihaoyinzhen, Baimudan, Gongmei, Shoumei and New White tea were selected for high performance liquid chromatography (HPLC) detection of catechins, gas chromatography-mass spectrometry (GC-MS) detection of aroma components and sensory evaluation, combining with multivariate statistical analysis such as analysis of variance and OPLS-DA. The results showed that the content of catechins in different types of white tea varied greatly, the total catechin content of Gongmei was the highest and that of Shoumei was the lowest, which were 66.84 and 32.66 mg/g respectively, and a total of fifty aroma substances were detected in all white tea, the main aroma components consisted of hexanal, (E)-2-hexenal, benzaldehyde, linalool and its oxides (I, II). The aroma composition and content of Baihaoyinzhen, Baimudan, Gongmei and Shoumei were different from those of the New White tea. Among them, eight aroma components such as (E)-2-pentenoaldehyde and 2-heptanone existed in a large number in the four traditional white tea, but they were not detected in the New White tea. Through multi-component chemometric analysis, it was found that there were significant differences in catechins and aroma metabolites between Baihaoyinzhen, Baimudan, Gongmei and New White tea, but there was little difference between Shoumei and New White tea. This study preliminarily proved the quality differences of different types of white tea, which provided a theoretical basis for the regulation of white tea flavor quality.
  • 白茶是我国特有的一种微发酵茶,产地主要集中在福鼎、政和、建阳、松溪等地,依照芽叶采摘嫩度的不同可分为白毫银针、白牡丹、贡眉和寿眉等[1]。白毫银针以白毫密布为特点,银白隐绿有光泽;白牡丹外形呈自然花朵形,显毫心,色泽灰绿尚润;寿眉叶态较紧卷,色泽灰绿带褐;贡眉叶态卷有毫心,色泽灰绿[2]。而在白茶传统工艺萎凋后加入轻微揉捻和高温烘焙步骤,所制得的白茶称为新工艺白茶,其外形半卷,色泽暗绿带褐[3-4]。近年来,因其抗氧化、抗突变、抗癌、神经保护、减肥等健康功效[5-8],白茶消费市场正不断扩大。

    儿茶素是白茶的关键滋味物质,因加工工艺相对简单,儿茶素氧化时间较短,损失较少,含量较高[9],故对茶汤的浓度、收敛感和苦涩味有重要影响[10-11]。已有研究发现表没食子儿茶素没食子酸酯(EGCG)、表没食子儿茶素(EGC)、表儿茶素没食子酸酯(ECG)、儿茶素没食子酸酯(CG)等儿茶素与白茶“清、鲜”的滋味品质有较高的相关性,儿茶素(C)、EGCG、没食子儿茶素没食子酸酯(GCG)、CG与涩味相关密切,EGC与苦味相关密切[12-13]。白茶中儿茶素含量与白茶类型有很大的关系,杨晨[14]和陈志达等[13]的研究表明白毫银针和白牡丹的大部分儿茶素及聚合物含量相近,且与寿眉相比,EGCG、GCG、ECG、CG含量均较高,但寿眉的GC、EGC、EC含量要高于白牡丹。因此,探究不同白茶中的儿茶素含量有利于丰富白茶的基础内含成分研究。香气是决定茶叶品质的重要因素之一[15]。不同于其它茶,白茶富含新鲜茶叶固有的挥发性化合物,由高比例的醇类、醛类和酮类物质组成,主要有芳樟醇及其氧化物、己醛、(E)-2-己烯醛、(E)-香叶醇、苯乙醇、苯甲醛、β-紫罗酮和α-紫罗酮等,并且它们属于内源性生物合成挥发性化合物[16-18]。不同类型的白茶,其香气组成和含量各有不同。在不同类型白茶中,白毫银针、白牡丹的香气组成相似,都具有相对含量较高的醇类物质,而两者与寿眉相差较大,寿眉中醛类、酮类、酯类和内酯类香气成分的含量较高。白毫银针的特征性香气成分为苯乙醇、顺-茉莉酮、1-辛烯-3-醇等,白牡丹为β-雪松烯、罗汉柏烯、L-薄荷醇等,寿眉为2,4-庚二烯醛、己醛、α-雪松烯等[16-17]

    然而,目前对不同类型白茶的儿茶素、香气和感官品质缺乏系统的研究。因此,本研究通过HPLC和GC-MS对白毫银针、白牡丹、贡眉、寿眉和新工艺白茶五种类型的白茶进行儿茶素和香气成分分析,并结合感官审评,比较它们之间的品质差异,以期为白茶产品研发和风味品质机理探索提供重要的技术支撑。

    供试白茶样品(白毫银针、白牡丹、贡眉、寿眉、新工艺白茶) 均收集于福建福鼎,每个类型的白茶根据品质和等级的不同分为一级、特级(如表1);儿茶素标准品(表没食子儿茶素没食子酸酯EGCG、表儿茶素EC、表没食子儿茶素EGC、表儿茶素没食子酸酯ECG、没食子儿茶素没食子酸酯GCG、儿茶素C) 纯度99%,美国Sigma公司;甲醇、乙腈 均为色谱纯,美国TEDIA公司;己酸乙酯 纯度>99%,上海阿拉丁公司;乙醚、无水硫酸钠、磷酸二氢钾、磷酸、乙腈 均为分析纯,国药集团化学试剂有限公司。

    表  1  样本名称及编号
    Table  1.  Sample name and corresponding number
    编号样本名称
    T1一级白毫银针
    T2特级白毫银针
    T3一级白牡丹
    T4特级白牡丹
    T5一级贡眉
    T6特级贡眉
    T7一级寿眉
    T8特级寿眉
    T9一级新工艺白茶
    T10特级新工艺白茶
    下载: 导出CSV 
    | 显示表格

    LC-2010AHT高效液相色谱仪、GCMS-QP2010气-质联用仪 日本岛津公司;Rtx-5MS熔融石英毛细管柱(30.0 m×0.25 mm×0.25 μm) 美国restek公司;Welchrom C18色谱柱(250 mm×4.6 mm, 5 μm) 上海月旭科技股份有限公司。

    参照GB/T 23776-2018《茶叶感官审评方法》[19]对供试白茶样品进行感官审评分析。参评人由2名男性、3名女性专业人员组成,参评项目有外形、香气、汤色、滋味和叶底,评分标准参照此国标。

    儿茶素HPLC检测方法参照文献[20],梯度洗脱程序:0~15 min,B泵乙腈维持13%,15~25 min,13% B线性升至20% B,保持5 min后于2 min内降至13% B;流速:1.0 mL/min;进样量10 μL;检测波长278 nm;柱温30 ℃。

    样本前处理方法、香气提取方法、GC-MS检测条件参照文献[21]。香气成分定性定量分析:根据在GC-MS上的各色谱峰的质谱峰及标准谱库NIST05s.LIB进行检索比对,以匹配度大于80%为标准,对白茶香气化合物进行定性,并根据检测出的各香气组分峰面积与内标(己酸乙酯)峰面积的比值进行相对定量。

    采用IBM SPSS Statistics 19.0软件进行数据方差分析,不同组间采用比较单因素分析和最小显著差异法(LSD法)比较,P<0.05表示差异显著,P<0.01表示差异极显著。采用SIMCA 14.1软件进行PCA和OPLS-DA分析。采用TBtools软件制作热图。

    为确定不同类型白茶和同类型不同等级间白茶样品的品质差异,对所有白茶样品进行感官审评。结果由表2可知,不同类型白茶感官品质差异较大,白毫银针和白牡丹感官评分更高。外形方面,白毫银针、白牡丹和贡眉有芽头且白毫显露,而寿眉和新工艺白茶芽头较少、无毫;汤色方面,白毫银针、白牡丹和贡眉大都是黄且明亮,而寿眉和新工艺白茶是黄和橙红明亮;香气方面,白毫银针、白牡丹和贡眉清香夹有毫香,寿眉和新工艺白茶只有清香;滋味方面,白毫银针、白牡丹和贡眉呈鲜嫩醇爽、有毫味,寿眉和新工艺白茶呈浓醇较清甜;叶底方面,白毫银针、白牡丹和贡眉叶底色泽绿、匀亮、有毫心,寿眉和新工艺白茶色泽黄绿或青灰带黄,匀整度稍差。由于加工白茶的品种、鲜叶原料和加工工艺间的差异,不同类型白茶的品质存在一定差异,如单芽制成的白茶如白毫银针,滋味清甜特点明显,随原料嫩度的增加,滋味表现为浓醇的特点,此与前人研究结果一致[22]

    表  2  五种类型白茶感官审评结果
    Table  2.  Sensory evaluation results of five types of white tea
    编号外形汤色香气滋味叶底感官评分(分)
    T1芽叶瘦长、匀齐,银灰白,洁净杏黄明亮清香,尚有毫香醇爽较鲜甜嫩匀明亮,色泽嫩绿,芽头较瘦弱,较匀93.34
    T2芽头肥壮,满披白毫,银灰色,洁净浅杏黄明亮清香,毫香显清鲜醇爽芽头肥壮较明亮,色泽嫩绿97.45
    T3叶缘紧卷尚匀整,毫心稍显尚壮,叶面灰绿,
    色泽尚调和,毫针尚银白
    黄明亮尚有毫香鲜嫩醇爽,有毫味毫心尚显,叶张软嫩尚匀整,
    叶张微红尚明亮
    91.72
    T4芽叶连枝,缘垂卷匀整,毫心多肥壮,叶面灰绿,
    色泽调和,毫针银白色,叶被有白茸毛
    橙黄明亮毫香显鲜嫩醇爽,毫味足毫心多肥壮,叶张软嫩,芽叶连枝,
    叶色黄绿,叶梗叶脉微红明亮
    94.58
    T5叶态尚紧卷尚匀,色泽灰绿尚润,毫针尚银白黄明亮清纯,尚有毫香醇厚较鲜甜稍有芽尖,叶张软尚匀整,灰绿稍匀亮87.48
    T6芽叶连枝,叶态紧卷,匀整,毫尖显,
    色泽墨绿、鲜活,毫针银白色
    橙黄明亮清纯,毫香显鲜甜醇爽有芽尖,叶张软嫩,色灰绿匀亮90.48
    T7多单片茎梗,色泽灰褐,欠匀,净度稍差黄尚亮带青气浓醇色泽花杂,稍硬,欠匀,净度稍差79.71
    T8叶态较紧卷,色泽绿中带褐,尚匀,
    较洁净,稍带梗
    深黄明亮清香浓醇色泽黄绿,稍带红片,柔软,欠匀,
    较洁净,稍带梗
    83.49
    T9条索较紧结,叶张略有缩褶,呈半卷条形,
    色泽暗绿略带褐
    橙红明亮清香浓醇较鲜甜色泽青灰带黄,筋脉带红,较匀整87.65
    T10条索紧结,叶张略有缩褶,呈半卷条形,
    色泽暗绿略带褐
    橙红明亮清香浓醇清甘色泽青灰带黄,筋脉带红,较匀整89.22
    下载: 导出CSV 
    | 显示表格

    通过HPLC对五种类型白茶样品中儿茶素含量进行检测,结果如表3所示。EGCG为白茶中含量最丰富的儿茶素,其次是ECG。在五种白茶中,贡眉的总儿茶素含量最高,平均为66.84 mg/g,其次是新工艺白茶、白毫银针和白牡丹,寿眉的总儿茶素含量最低,平均为32.66 mg/g。在同类型不同等级的白茶中,儿茶素总量随等级下降而降低,其中,白毫银针、白牡丹、寿眉及新工艺白茶的两个等级间均达到显著水平(P<0.05)。特级白毫银针中EGC、C、EC、EGCG、GCG、ECG和总儿茶素的相对含量全都高于一级白毫银针。特级白牡丹茶儿茶素成分由较高水平的EGCG、GCG、ECG、C和总儿茶素组成,而EGC含量低于一级白牡丹。寿眉样品中三种酯型儿茶素含量明显较其他白茶低,与胡金祥[23]、陈志达[24]结果一致,只有GCG与新工艺白茶相近,且新工艺白茶的EC和EGC明显高于传统白茶。总之,不同类型白茶中的儿茶素组分含量差异较大,这与茶树品种、采摘标准、加工条件(如萎凋时间)等密切相关。

    表  3  五种类型白茶中六种儿茶素含量(mg/g)
    Table  3.  Contents of six catechins in five types of white tea (mg/g)
    编号六种主要儿茶素总儿茶素
    CECECGEGCGCGEGCG
    T11.57±0.110.68±0.2811.52±0.020.91±0.4012.87±0.4226.63±0.3154.18±1.54c
    T21.80±0.221.07±0.3412.56±0.041.68±0.3214.56±0.3330.49±0.5662.16±1.81b
    T31.54±0.011.42±0.228.97±0.212.45±0.2810.70±0.4225.68±0.5150.76±1.65d
    T41.77±0.041.44±0.2012.16±0.271.95±0.1114.57±0.1330.43±0.3162.32±1.06b
    T52.20±0.050.91±0.3114.16±0.081.51±0.3116.68±0.2230.71±0.2466.17±1.21a
    T62.18±0.031.06±0.0415.16±0.311.44±0.1915.47±0.2432.20±0.2167.51±1.02a
    T71.36±0.151.55±0.164.89±0.112.89±0.125.27±0.2912.98±0.3328.94±1.16f
    T82.52±0.141.81±0.216.32±0.153.30±0.236.35±0.0116.07±0.3236.37±1.06e
    T91.05±0.034.62±0.1214.58±0.314.11±0.076.10±0.2626.30±0.3056.76±1.09c
    T104.26±0.124.94±0.0911.00±0.308.67±0.137.61±0.3430.79±0.1567.27±1.13a
    注:同列不同小写字母表示差异显著(P<0.05)。
    下载: 导出CSV 
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    在五种类型白茶中共检测出50种主要的挥发性香气成分(表4),根据化合物主要官能团的不同可分为5大类,其中,醇类化合物和醛类化合物最多,均为17种,酮类化合物11种,酯类化合物4种及1种氧杂环化合物。从表4可知,五种白茶类型的挥发性成分相对总含量排序为贡眉(366.64)>白毫银针(328.87)>白牡丹(310.12)>寿眉(208.08)>新工艺白茶(101.67)。此外,同种类型不同等级间特级白茶的挥发性成分相对总含量大于一级白茶。所有白茶样品的主要挥发性香气组分为正己醛、(E)-2-己烯醛、(Z)-3-己烯醇、苯甲醛、香叶醇、苯乙醛、苯乙醇、芳樟醇及其氧化物(Ⅰ、Ⅱ)等,这些化合物与庚醛、水杨酸甲酯、苯甲醇、壬醛、1-戊烯-3-醇、正戊醇、2-正戊基呋喃和β-紫罗酮共同构成白茶鲜嫩、清醇、毫香显露香气特征的重要物质基础[25-26],此结果与CHEN等[16]、QI等[27]和LIN等[28]的研究结果相近。白毫银针和贡眉主要以正己醛、(E)-2-己烯醛、苯甲醛、芳樟醇、苯乙醇为主,寿眉主要以正己醛、(E)-2-己烯醛、芳樟醇氧化物II、芳樟醇、苯乙醛为主,白牡丹主要以正己醛、(E)-2-己烯醛、芳樟醇氧化物II、芳樟醇、芳樟醇氧化物I为主,新工艺白茶主要以芳樟醇、香叶醇、芳樟醇氧化物II、(Z)-3-己烯醇、正己醛为主。与白毫银针、白牡丹、贡眉、寿眉4种传统工艺白茶相比,新工艺白茶的香气组分差异明显。其中,(E)-2-戊烯醛、2-庚酮、2,3-辛二酮、正辛醛、(E,E)-2, 4-庚二烯醛、(E)-2-辛烯醛、(E,Z)-2, 6-壬二烯醛、(Z)-3-己烯醇苯甲酸酯8种具有花香和果香的香气成分在4种传统工艺白茶中大量存在,而在新工艺白茶未检测出。与传统工艺白茶相比,新工艺白茶中正己醛和(E)-2-己烯醛含量大大降低,说明添加了揉捻和高温干燥工艺后,新工艺白茶中部分低沸点香气物质消失,同时,由于揉捻过程中的剧烈酶促氧化作用,产生了一些新的香气物质,使传统白茶和新工艺白茶在香气上有较大差异。

    表  4  白茶香气组分及其相对含量
    Table  4.  Aroma components and relative contents of white tea samples
    编号香气物质T1T2T3T4T5T6T7T8T9T10
    醇类化合物
    M11-戊烯-3-醇0.94±0.020.91±0.062.43±0.011.00±0.072.79±0.083.06±0.010.74±0.030.68±0.050.92±0.020.63±0.08
    M2正戊醇0.57±0.030.52±0.092.52±0.080.91±0.081.08±0.072.08±0.070.28±0.030.20±0.080.45±0.030.17±0.10
    M32-戊烯醇0.20±0.090.26±0.091.04±0.090.33±0.050.71±0.040.88±0.041.22±0.070.93±0.011.01±0.050.47±0.10
    M4(Z)-3-己烯醇2.33±0.010.89±0.062.31±0.091.30±0.102.19±0.073.84±0.053.99±0.051.09±0.012.79±0.083.62±0.07
    M5(E)-2-己醇0.44±0.090.32±0.071.32±0.090.36±0.010.43±0.080.38±0.030.10±0.04n.d.0.37±0.030.22±0.02
    M6苯甲醇2.55±0.062.15±0.060.58±0.061.59±0.072.16±0.021.73±0.052.06±0.050.87±0.080.44±0.091.10±0.08
    M7芳樟醇氧化物I2.00±0.051.01±0.108.31±0.103.23±0.011.39±0.091.98±0.025.36±0.104.49±0.042.77±0.012.31±0.05
    M8芳樟醇氧化物II4.12±0.102.42±0.0826.01±0.066.59±0.043.49±0.044.85±0.107.36±0.096.83±0.085.63±0.046.78±0.03
    M9芳樟醇7.59±0.073.94±0.026.11±0.026.82±0.046.39±0.079.94±0.017.08±0.065.25±0.104.48±0.1010.59±0.08
    M10脱氢芳樟醇n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.0.85±0.060.67±0.08
    M11苯乙醇5.04±0.045.46±0.021.41±0.052.18±0.016.89±0.055.90±0.045.19±0.075.37±0.101.32±0.042.79±0.08
    M12芳樟醇氧化物Ⅲ0.20±0.050.17±0.040.69±0.070.30±0.010.21±0.080.30±0.021.36±0.011.23±0.070.27±0.060.28±0.01
    M13芳樟醇氧化物Ⅳ1.17±0.030.28±0.011.50±0.060.52±0.010.59±0.010.70±0.062.51±0.022.38±0.041.23±0.071.76±0.08
    M14α-松油醇0.23±0.030.17±0.010.29±0.040.23±0.090.34±0.040.24±0.040.35±0.100.19±0.070.15±0.030.23±0.01
    M15香叶醇2.50±0.041.18±0.026.82±0.082.47±0.022.38±0.053.14±0.012.00±0.070.98±0.092.53±0.0210.57±0.04
    M16橙花叔醇0.15±0.020.24±0.061.10±0.060.77±0.050.12±0.010.07±0.050.44±0.010.47±0.050.29±0.020.45±0.01
    M17雪松醇0.04±0.020.37±0.010.15±0.040.55±0.100.33±0.030.20±0.010.36±0.100.39±0.090.08±0.060.16±0.08
    醛类化合物
    M18戊醛2.02±0.022.31±0.041.91±0.102.93±0.082.43±0.052.67±0.061.82±0.092.35±0.020.55±0.070.52±0.08
    M19(E)-2-戊烯醛0.24±0.010.23±0.100.27±0.100.34±0.080.25±0.030.18±0.070.16±0.060.26±0.03n.d.n.d.
    M20正己醛90.75±0.06105.27±0.0351.85±0.0580.26±0.03104.14±0.02108.4±0.0210.68±0.0342.45±0.033.18±0.12.85±0.06
    M21(E)-2-己烯醛17.99±0.0220.89±0.0516.30±0.0221.71±0.0221.83±0.0918.14±0.088.31±0.0725.01±0.041.84±0.021.74±0.04
    M22庚醛2.77±0.032.97±0.011.58±0.082.14±0.082.20±0.011.75±0.021.01±0.090.56±0.090.46±0.060.37±0.04
    M23苯甲醛6.27±0.065.57±0.083.69±0.025.22±0.025.17±0.055.03±0.033.36±0.031.25±0.061.09±0.101.2±0.10
    M24正辛醛0.25±0.060.19±0.090.30±0.080.30±0.060.23±0.050.21±0.060.42±0.100.72±0.06n.d.n.d.
    M25(E,E)-2,4-庚二烯醛0.05±0.040.05±0.010.13±0.060.13±0.010.12±0.050.09±0.080.23±0.050.18±0.05n.d.n.d.
    M26苯乙醛2.02±0.061.72±0.022.71±0.023.01±0.092.25±0.081.75±0.065.92±0.065.56±0.012.97±0.072.39±0.06
    M27(E)-2-辛烯醛0.11±0.010.14±0.060.12±0.060.15±0.020.12±0.090.13±0.080.38±0.100.09±0.02n.d.n.d.
    M28壬醛2.03±0.051.67±0.011.07±0.051.80±0.031.39±0.061.41±0.062.57±0.060.61±0.060.11±0.090.19±0.02
    M29(E,Z)-2,6-壬二烯醛0.10±0.010.08±0.030.07±0.070.11±0.060.13±0.080.09±0.070.17±0.10n.d.n.d.n.d.
    M30(E)-2-壬烯醛0.11±0.030.07±0.050.08±0.090.15±0.040.14±0.030.11±0.030.23±0.040.16±0.010.06±0.060.03±0.05
    M31藏花醛0.17±0.070.14±0.020.16±0.050.13±0.070.11±0.040.14±0.050.48±0.060.30±0.010.20±0.070.19±0.09
    M32癸醛0.04±0.060.07±0.070.06±0.050.07±0.100.05±0.090.05±0.050.20±0.090.05±0.020.07±0.030.05±0.04
    M33β-环柠檬醛0.29±0.030.19±0.010.16±0.090.13±0.060.32±0.100.27±0.070.50±0.080.22±0.090.15±0.020.09±0.04
    M34柠檬醛0.05±0.070.06±0.010.42±0.020.12±0.07n.d.0.11±0.070.02±0.050.02±0.070.05±0.090.08±0.01
    酮类化合物
    M35(E)-3-戊烯-2-酮0.16±0.060.20±0.030.13±0.080.20±0.06n.d.0.06±0.010.19±0.090.17±0.020.20±0.070.19±0.07
    M362-庚酮0.79±0.010.82±0.010.70±0.010.75±0.011.01±0.030.99±0.030.36±0.07n.d.n.d.n.d.
    M372,3-辛二酮0.45±0.060.50±0.041.03±0.100.79±0.091.09±0.020.68±0.100.72±0.050.16±0.06n.d.n.d.
    M386-甲基-5-庚烯-2-酮0.31±0.060.27±0.050.82±0.020.39±0.030.43±0.030.53±0.080.49±0.090.19±0.080.22±0.010.26±0.06
    M39苯乙酮0.16±0.100.19±0.020.15±0.040.13±0.050.16±0.050.13±0.080.11±0.030.04±0.050.02±0.030.03±0.08
    M403,5-辛二烯-2-酮0.61±0.020.18±0.030.21±0.060.24±0.080.25±0.100.34±0.080.60±0.070.19±0.030.32±0.080.62±0.02
    M41顺式茉莉酮0.56±0.040.32±0.040.15±0.060.22±0.010.30±0.030.17±0.050.10±0.060.10±0.070.04±0.010.40±0.09
    M42α-紫罗酮0.05±0.020.06±0.040.47±0.030.24±0.010.07±0.020.05±0.100.62±0.040.35±0.040.19±0.020.12±0.06
    M43香叶基丙酮0.07±0.070.12±0.050.09±0.040.09±0.040.08±0.030.05±0.091.37±0.100.54±0.040.37±0.030.27±0.07
    M44β-紫罗酮0.52±0.010.32±0.040.66±0.020.69±0.090.74±0.040.62±0.014.50±0.062.01±0.011.40±0.090.99±0.04
    M45植酮0.06±0.050.32±0.031.66±0.010.98±0.040.14±0.080.08±0.021.45±0.031.10±0.040.48±0.100.37±0.09
    氧杂环化合物
    M462-正戊基呋喃1.63±0.051.55±0.021.84±0.091.87±0.052.21±0.071.87±0.031.15±0.040.09±0.090.41±0.020.57±0.03
    酯类化合物
    M47水杨酸甲酯0.88±0.020.22±0.012.97±0.020.99±0.050.66±0.101.23±0.071.16±0.040.17±0.071.34±0.102.35±0.01
    M48(Z)-3-己烯醇己酸酯n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.0.09±0.020.23±0.05
    M49(Z)-3-己烯醇苯甲酸酯n.d.0.01±0.070.04±0.080.15±0.050.07±0.010.09±0.070.12±0.080.13±0.09n.d.n.d.
    M50棕榈酸甲酯0.20±0.050.10±0.010.06±0.070.09±0.040.27±0.100.08±0.080.92±0.050.98±0.050.52±0.010.86±0.05
    注:n.d.表示未检测出该物质。
    下载: 导出CSV 
    | 显示表格

    将儿茶素组分和10个茶样的37种共有香气组分进行PCA和OPLS-DA分析,如图1所示。从图1a可看出前两个主成分累计方差贡献率为59%,五种类型白茶被明显分为两类,一类是白毫银针、贡眉和白牡丹,另一类是新工艺白茶和寿眉,说明它们之间存在代谢物的显著差异。基于PCA结果对这两类进一步OPLS-DA分析,得出图1b (R2X=0.688,R2Y=0.997,Q2=0.948)和图1c,经置换检验验证(R2=0.935,Q2=−0.848)该判别模型稳健,没有过拟合。根据VIP值>1、P值<0.05的标准,共筛选出13种化合物,它们是区分这两类的标志差异代谢物。

    图  1  多组分PCA和OPLS-DA分析
    注:a:PCA得分图;b:OPLS-DA得分图;c:S-plot得分图。
    Figure  1.  Multicomponent PCA and OPLS-DA analysis

    将13种标志差异代谢物进行热图分析,如图2所示。13种标志差异代谢物被聚类成了两大类:第一类EGC、EC、香叶基丙酮、β-紫罗酮、棕榈酸甲酯和芳樟醇氧化物Ⅳ,它们在新工艺白茶和寿眉中的相对含量明显高于白毫银针、贡眉和白牡丹;第二类正戊醇、(E)-2-己烯醛、2-正戊基呋喃、正己醛、苯乙酮、庚醛、苯甲醛,它们在白毫银针、贡眉和白牡丹中的相对含量明显高于新工艺白茶和寿眉。而这也是五种白茶被这13种代谢物划分成两类的原因。新工艺白茶中EGC和EC的相对含量明显高于其他茶,可作为新工艺白茶的特征代谢物;同理,具有花果香、青草香、紫罗兰香的香叶基丙酮、β-紫罗酮、棕榈酸甲酯、芳樟醇氧化物Ⅳ可作为寿眉的特征代谢物;具有发酵味、略有果香的正戊醇可作为白牡丹的特征代谢物;具有花果香、青草香、杏仁气味的苯乙酮、庚醛、苯甲醛可作为白毫银针的特征代谢物;具有果香、青草香的2-正戊基呋喃和正己醛可作为贡眉的特征代谢物。在其他研究中也证明了2-正戊基呋喃和正己醛是贡眉中的主要挥发性物质,苯甲醛是白毫银针的特征成分,以及β-紫罗酮是寿眉的特征香气成分[17, 29-30]

    图  2  标志差异代谢物热图分析
    Figure  2.  Heat map of marker differential metabolites

    五种白茶的儿茶素组成和含量差异明显,贡眉的总儿茶素含量最高,寿眉的总儿茶素含量最低,寿眉中酯型儿茶素含量明显较低,新工艺白茶的EC、EGC含量明显较高。五种白茶共检测出50种香气成分,主要有清香气味的正己醛和(E)-2-己烯醛、花果香气味的芳樟醇及其氧化物(Ⅰ、Ⅱ)和苯乙醇、杏仁气味的苯甲醛以及玫瑰花香、青甜气味的香叶醇等。白毫银针、白牡丹、贡眉、寿眉四种传统白茶在香气组成上差异不大,但其相对含量差异明显。而传统白茶与新工艺白茶在香气组成和相对含量上均有差异,有8种成分组成在新工艺白茶中未检出。多组分化学计量学分析表明,白毫银针、白牡丹、贡眉与新工艺白茶存在儿茶素和共有香气成分的差异。新工艺白茶的特征代谢物是EGC和EC,香叶基丙酮、β-紫罗酮、棕榈酸甲酯、芳樟醇氧化物Ⅳ是寿眉的特征代谢物,正戊醇是白牡丹的特征代谢物,苯乙酮、庚醛、苯甲醛是白毫银针的特征代谢物,2-正戊基呋喃和正己醛是贡眉的特征代谢物。总之,由不同嫩度原料、不同加工方法制成的不同类型白茶在儿茶素、香气成分和感官评价方面各有差别,未来还需加大对白茶内含成分的基理研究。

  • 图  1   多组分PCA和OPLS-DA分析

    注:a:PCA得分图;b:OPLS-DA得分图;c:S-plot得分图。

    Figure  1.   Multicomponent PCA and OPLS-DA analysis

    图  2   标志差异代谢物热图分析

    Figure  2.   Heat map of marker differential metabolites

    表  1   样本名称及编号

    Table  1   Sample name and corresponding number

    编号样本名称
    T1一级白毫银针
    T2特级白毫银针
    T3一级白牡丹
    T4特级白牡丹
    T5一级贡眉
    T6特级贡眉
    T7一级寿眉
    T8特级寿眉
    T9一级新工艺白茶
    T10特级新工艺白茶
    下载: 导出CSV

    表  2   五种类型白茶感官审评结果

    Table  2   Sensory evaluation results of five types of white tea

    编号外形汤色香气滋味叶底感官评分(分)
    T1芽叶瘦长、匀齐,银灰白,洁净杏黄明亮清香,尚有毫香醇爽较鲜甜嫩匀明亮,色泽嫩绿,芽头较瘦弱,较匀93.34
    T2芽头肥壮,满披白毫,银灰色,洁净浅杏黄明亮清香,毫香显清鲜醇爽芽头肥壮较明亮,色泽嫩绿97.45
    T3叶缘紧卷尚匀整,毫心稍显尚壮,叶面灰绿,
    色泽尚调和,毫针尚银白
    黄明亮尚有毫香鲜嫩醇爽,有毫味毫心尚显,叶张软嫩尚匀整,
    叶张微红尚明亮
    91.72
    T4芽叶连枝,缘垂卷匀整,毫心多肥壮,叶面灰绿,
    色泽调和,毫针银白色,叶被有白茸毛
    橙黄明亮毫香显鲜嫩醇爽,毫味足毫心多肥壮,叶张软嫩,芽叶连枝,
    叶色黄绿,叶梗叶脉微红明亮
    94.58
    T5叶态尚紧卷尚匀,色泽灰绿尚润,毫针尚银白黄明亮清纯,尚有毫香醇厚较鲜甜稍有芽尖,叶张软尚匀整,灰绿稍匀亮87.48
    T6芽叶连枝,叶态紧卷,匀整,毫尖显,
    色泽墨绿、鲜活,毫针银白色
    橙黄明亮清纯,毫香显鲜甜醇爽有芽尖,叶张软嫩,色灰绿匀亮90.48
    T7多单片茎梗,色泽灰褐,欠匀,净度稍差黄尚亮带青气浓醇色泽花杂,稍硬,欠匀,净度稍差79.71
    T8叶态较紧卷,色泽绿中带褐,尚匀,
    较洁净,稍带梗
    深黄明亮清香浓醇色泽黄绿,稍带红片,柔软,欠匀,
    较洁净,稍带梗
    83.49
    T9条索较紧结,叶张略有缩褶,呈半卷条形,
    色泽暗绿略带褐
    橙红明亮清香浓醇较鲜甜色泽青灰带黄,筋脉带红,较匀整87.65
    T10条索紧结,叶张略有缩褶,呈半卷条形,
    色泽暗绿略带褐
    橙红明亮清香浓醇清甘色泽青灰带黄,筋脉带红,较匀整89.22
    下载: 导出CSV

    表  3   五种类型白茶中六种儿茶素含量(mg/g)

    Table  3   Contents of six catechins in five types of white tea (mg/g)

    编号六种主要儿茶素总儿茶素
    CECECGEGCGCGEGCG
    T11.57±0.110.68±0.2811.52±0.020.91±0.4012.87±0.4226.63±0.3154.18±1.54c
    T21.80±0.221.07±0.3412.56±0.041.68±0.3214.56±0.3330.49±0.5662.16±1.81b
    T31.54±0.011.42±0.228.97±0.212.45±0.2810.70±0.4225.68±0.5150.76±1.65d
    T41.77±0.041.44±0.2012.16±0.271.95±0.1114.57±0.1330.43±0.3162.32±1.06b
    T52.20±0.050.91±0.3114.16±0.081.51±0.3116.68±0.2230.71±0.2466.17±1.21a
    T62.18±0.031.06±0.0415.16±0.311.44±0.1915.47±0.2432.20±0.2167.51±1.02a
    T71.36±0.151.55±0.164.89±0.112.89±0.125.27±0.2912.98±0.3328.94±1.16f
    T82.52±0.141.81±0.216.32±0.153.30±0.236.35±0.0116.07±0.3236.37±1.06e
    T91.05±0.034.62±0.1214.58±0.314.11±0.076.10±0.2626.30±0.3056.76±1.09c
    T104.26±0.124.94±0.0911.00±0.308.67±0.137.61±0.3430.79±0.1567.27±1.13a
    注:同列不同小写字母表示差异显著(P<0.05)。
    下载: 导出CSV

    表  4   白茶香气组分及其相对含量

    Table  4   Aroma components and relative contents of white tea samples

    编号香气物质T1T2T3T4T5T6T7T8T9T10
    醇类化合物
    M11-戊烯-3-醇0.94±0.020.91±0.062.43±0.011.00±0.072.79±0.083.06±0.010.74±0.030.68±0.050.92±0.020.63±0.08
    M2正戊醇0.57±0.030.52±0.092.52±0.080.91±0.081.08±0.072.08±0.070.28±0.030.20±0.080.45±0.030.17±0.10
    M32-戊烯醇0.20±0.090.26±0.091.04±0.090.33±0.050.71±0.040.88±0.041.22±0.070.93±0.011.01±0.050.47±0.10
    M4(Z)-3-己烯醇2.33±0.010.89±0.062.31±0.091.30±0.102.19±0.073.84±0.053.99±0.051.09±0.012.79±0.083.62±0.07
    M5(E)-2-己醇0.44±0.090.32±0.071.32±0.090.36±0.010.43±0.080.38±0.030.10±0.04n.d.0.37±0.030.22±0.02
    M6苯甲醇2.55±0.062.15±0.060.58±0.061.59±0.072.16±0.021.73±0.052.06±0.050.87±0.080.44±0.091.10±0.08
    M7芳樟醇氧化物I2.00±0.051.01±0.108.31±0.103.23±0.011.39±0.091.98±0.025.36±0.104.49±0.042.77±0.012.31±0.05
    M8芳樟醇氧化物II4.12±0.102.42±0.0826.01±0.066.59±0.043.49±0.044.85±0.107.36±0.096.83±0.085.63±0.046.78±0.03
    M9芳樟醇7.59±0.073.94±0.026.11±0.026.82±0.046.39±0.079.94±0.017.08±0.065.25±0.104.48±0.1010.59±0.08
    M10脱氢芳樟醇n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.0.85±0.060.67±0.08
    M11苯乙醇5.04±0.045.46±0.021.41±0.052.18±0.016.89±0.055.90±0.045.19±0.075.37±0.101.32±0.042.79±0.08
    M12芳樟醇氧化物Ⅲ0.20±0.050.17±0.040.69±0.070.30±0.010.21±0.080.30±0.021.36±0.011.23±0.070.27±0.060.28±0.01
    M13芳樟醇氧化物Ⅳ1.17±0.030.28±0.011.50±0.060.52±0.010.59±0.010.70±0.062.51±0.022.38±0.041.23±0.071.76±0.08
    M14α-松油醇0.23±0.030.17±0.010.29±0.040.23±0.090.34±0.040.24±0.040.35±0.100.19±0.070.15±0.030.23±0.01
    M15香叶醇2.50±0.041.18±0.026.82±0.082.47±0.022.38±0.053.14±0.012.00±0.070.98±0.092.53±0.0210.57±0.04
    M16橙花叔醇0.15±0.020.24±0.061.10±0.060.77±0.050.12±0.010.07±0.050.44±0.010.47±0.050.29±0.020.45±0.01
    M17雪松醇0.04±0.020.37±0.010.15±0.040.55±0.100.33±0.030.20±0.010.36±0.100.39±0.090.08±0.060.16±0.08
    醛类化合物
    M18戊醛2.02±0.022.31±0.041.91±0.102.93±0.082.43±0.052.67±0.061.82±0.092.35±0.020.55±0.070.52±0.08
    M19(E)-2-戊烯醛0.24±0.010.23±0.100.27±0.100.34±0.080.25±0.030.18±0.070.16±0.060.26±0.03n.d.n.d.
    M20正己醛90.75±0.06105.27±0.0351.85±0.0580.26±0.03104.14±0.02108.4±0.0210.68±0.0342.45±0.033.18±0.12.85±0.06
    M21(E)-2-己烯醛17.99±0.0220.89±0.0516.30±0.0221.71±0.0221.83±0.0918.14±0.088.31±0.0725.01±0.041.84±0.021.74±0.04
    M22庚醛2.77±0.032.97±0.011.58±0.082.14±0.082.20±0.011.75±0.021.01±0.090.56±0.090.46±0.060.37±0.04
    M23苯甲醛6.27±0.065.57±0.083.69±0.025.22±0.025.17±0.055.03±0.033.36±0.031.25±0.061.09±0.101.2±0.10
    M24正辛醛0.25±0.060.19±0.090.30±0.080.30±0.060.23±0.050.21±0.060.42±0.100.72±0.06n.d.n.d.
    M25(E,E)-2,4-庚二烯醛0.05±0.040.05±0.010.13±0.060.13±0.010.12±0.050.09±0.080.23±0.050.18±0.05n.d.n.d.
    M26苯乙醛2.02±0.061.72±0.022.71±0.023.01±0.092.25±0.081.75±0.065.92±0.065.56±0.012.97±0.072.39±0.06
    M27(E)-2-辛烯醛0.11±0.010.14±0.060.12±0.060.15±0.020.12±0.090.13±0.080.38±0.100.09±0.02n.d.n.d.
    M28壬醛2.03±0.051.67±0.011.07±0.051.80±0.031.39±0.061.41±0.062.57±0.060.61±0.060.11±0.090.19±0.02
    M29(E,Z)-2,6-壬二烯醛0.10±0.010.08±0.030.07±0.070.11±0.060.13±0.080.09±0.070.17±0.10n.d.n.d.n.d.
    M30(E)-2-壬烯醛0.11±0.030.07±0.050.08±0.090.15±0.040.14±0.030.11±0.030.23±0.040.16±0.010.06±0.060.03±0.05
    M31藏花醛0.17±0.070.14±0.020.16±0.050.13±0.070.11±0.040.14±0.050.48±0.060.30±0.010.20±0.070.19±0.09
    M32癸醛0.04±0.060.07±0.070.06±0.050.07±0.100.05±0.090.05±0.050.20±0.090.05±0.020.07±0.030.05±0.04
    M33β-环柠檬醛0.29±0.030.19±0.010.16±0.090.13±0.060.32±0.100.27±0.070.50±0.080.22±0.090.15±0.020.09±0.04
    M34柠檬醛0.05±0.070.06±0.010.42±0.020.12±0.07n.d.0.11±0.070.02±0.050.02±0.070.05±0.090.08±0.01
    酮类化合物
    M35(E)-3-戊烯-2-酮0.16±0.060.20±0.030.13±0.080.20±0.06n.d.0.06±0.010.19±0.090.17±0.020.20±0.070.19±0.07
    M362-庚酮0.79±0.010.82±0.010.70±0.010.75±0.011.01±0.030.99±0.030.36±0.07n.d.n.d.n.d.
    M372,3-辛二酮0.45±0.060.50±0.041.03±0.100.79±0.091.09±0.020.68±0.100.72±0.050.16±0.06n.d.n.d.
    M386-甲基-5-庚烯-2-酮0.31±0.060.27±0.050.82±0.020.39±0.030.43±0.030.53±0.080.49±0.090.19±0.080.22±0.010.26±0.06
    M39苯乙酮0.16±0.100.19±0.020.15±0.040.13±0.050.16±0.050.13±0.080.11±0.030.04±0.050.02±0.030.03±0.08
    M403,5-辛二烯-2-酮0.61±0.020.18±0.030.21±0.060.24±0.080.25±0.100.34±0.080.60±0.070.19±0.030.32±0.080.62±0.02
    M41顺式茉莉酮0.56±0.040.32±0.040.15±0.060.22±0.010.30±0.030.17±0.050.10±0.060.10±0.070.04±0.010.40±0.09
    M42α-紫罗酮0.05±0.020.06±0.040.47±0.030.24±0.010.07±0.020.05±0.100.62±0.040.35±0.040.19±0.020.12±0.06
    M43香叶基丙酮0.07±0.070.12±0.050.09±0.040.09±0.040.08±0.030.05±0.091.37±0.100.54±0.040.37±0.030.27±0.07
    M44β-紫罗酮0.52±0.010.32±0.040.66±0.020.69±0.090.74±0.040.62±0.014.50±0.062.01±0.011.40±0.090.99±0.04
    M45植酮0.06±0.050.32±0.031.66±0.010.98±0.040.14±0.080.08±0.021.45±0.031.10±0.040.48±0.100.37±0.09
    氧杂环化合物
    M462-正戊基呋喃1.63±0.051.55±0.021.84±0.091.87±0.052.21±0.071.87±0.031.15±0.040.09±0.090.41±0.020.57±0.03
    酯类化合物
    M47水杨酸甲酯0.88±0.020.22±0.012.97±0.020.99±0.050.66±0.101.23±0.071.16±0.040.17±0.071.34±0.102.35±0.01
    M48(Z)-3-己烯醇己酸酯n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.0.09±0.020.23±0.05
    M49(Z)-3-己烯醇苯甲酸酯n.d.0.01±0.070.04±0.080.15±0.050.07±0.010.09±0.070.12±0.080.13±0.09n.d.n.d.
    M50棕榈酸甲酯0.20±0.050.10±0.010.06±0.070.09±0.040.27±0.100.08±0.080.92±0.050.98±0.050.52±0.010.86±0.05
    注:n.d.表示未检测出该物质。
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-09-01
  • 网络出版日期:  2021-12-29
  • 刊出日期:  2022-02-28

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