CN111474267A - Corn flavor quality evaluation method based on quantitative detection of flavor substances - Google Patents
Corn flavor quality evaluation method based on quantitative detection of flavor substances Download PDFInfo
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Abstract
一种基于风味物质定量检测的玉米风味品质评估方法,采用顶空固相微萃取‑气相色谱‑质谱联用方法测定玉米籽粒中的挥发性成分,并进行定性定量检测,利用相对风味活度值法确定玉米的特征风味化合物,得到玉米的特征风味化合物与原生态风味品质指标的多重回归线性方程,建立玉米原生态风味评估模型;将待评估玉米籽粒的特征风味化合物的定量结果代入所述多重回归线性方程中,计算得到玉米原生态风味的预估值,评估玉米的风味品质。本发明具有风味评估数据量化的特点,具有结果客观、判别准确度高的优点,适用于玉米选育过程中的品种筛选,为玉米原生态风味鉴评结果由主观感受型向数据定量型转变提供技术支持。A corn flavor quality evaluation method based on the quantitative detection of flavor substances, adopts headspace solid-phase microextraction-gas chromatography-mass spectrometry method to determine volatile components in corn kernels, and performs qualitative and quantitative detection, using relative flavor activity value The characteristic flavor compounds of corn were determined by the method, the multiple regression linear equations between the characteristic flavor compounds of corn and the original ecological flavor quality indexes were obtained, and the evaluation model of corn original ecological flavor was established; the quantitative results of the characteristic flavor compounds of the corn kernels to be evaluated were substituted into the multiple regression equations In the regression linear equation, the estimated value of the original ecological flavor of corn was calculated to evaluate the flavor quality of corn. The invention has the characteristics of flavor evaluation data quantification, has the advantages of objective results and high discrimination accuracy, is suitable for variety screening in the process of maize breeding, and provides for the transformation of the original ecological flavor evaluation results of maize from subjective perception type to data quantitative type. Technical Support.
Description
技术领域technical field
本发明属于作物风味品质判别领域,具体涉及一种基于风味物质定量检测的玉米风味品质评估方法。The invention belongs to the field of crop flavor quality discrimination, in particular to a corn flavor quality evaluation method based on quantitative detection of flavor substances.
背景技术Background technique
原生态风味是玉米的重要品质之一,挥发性风味物质的构成和含量是鲜食玉米呈香的关键,随着社会的发展和人民生活水平的提高,玉米的风味品质越来越被重视。The original ecological flavor is one of the important qualities of corn. The composition and content of volatile flavor substances are the key to the aroma of fresh corn. With the development of society and the improvement of people's living standards, the flavor quality of corn has been paid more and more attention.
糯玉米(Zea mays L.certain Kulesh)是玉米属的一个亚种,是因玉米九号染色体wx基因发生隐形突变导致胚乳中直链淀粉极端降低甚至缺失而产生的。鲜食糯玉米含有丰富的淀粉、脂肪、氨基酸、微量元素和矿物质,具有较高的营养价值。蒸煮后籽粒透明,色泽晶莹,皮薄渣少,软粘细腻,适口性好,具有黏、糯、香、滑、嫩等特点,深受消费者青睐。Waxy maize (Zea mays L.certain Kulesh) is a subspecies of the genus Maize, which is produced by a recessive mutation of the wx gene of maize chromosome 9, resulting in extreme reduction or even deletion of amylose in the endosperm. Fresh waxy corn is rich in starch, fat, amino acids, trace elements and minerals, and has high nutritional value. After cooking, the grains are transparent, the color is crystal clear, the skin is thin and the residue is less, the soft and sticky is delicate, and the palatability is good.
目前,对鲜食糯玉米风味物质的定量检测方法中,对风味物质的定量检测偏重于乳熟期的糯玉米,未考虑不同生长期中糯玉米的原生态风味差别;且,由于糯玉米风味品质很难量化,缺乏客观判别标准等原因,在长期的糯玉米选育过程中,逐渐使得糯玉米丢失了原本的“糯玉米味”。At present, among the quantitative detection methods for flavor substances in fresh waxy corn, the quantitative detection of flavor substances focuses on the waxy corn in the milk-ripening stage, and does not consider the difference in the original ecological flavor of waxy corn in different growth stages; The quality is difficult to quantify, and there is a lack of objective criteria. During the long-term breeding process of waxy corn, the waxy corn gradually lost its original "waxy corn flavor".
根据玉米的特征性风味物质进行原生态风味品质进行量化评估的方法尚未见报道。There is no report on the quantitative assessment of the original flavor quality based on the characteristic flavor substances of corn.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种基于风味物质定量检测的玉米风味品质评估方法,结合相对风味活度值法,建立玉米的特征风味化合物与原生态风味品质指标的多重回归线性方程,确定建立玉米原生态风味品质的分析方法,具有数据量化,结果客观,判别准确度高的优点,适用于玉米选育过程中的品种筛选,为玉米原生态风味鉴评结果由主观感受型向数据定量型转变提供技术支持。The object of the present invention is to provide a corn flavor quality evaluation method based on quantitative detection of flavor substances, and to establish a multiple regression linear equation between the characteristic flavor compounds of corn and the original ecological flavor quality index in combination with the relative flavor activity value method, and to determine the establishment of the original corn flavor quality index. The analysis method of ecological flavor quality has the advantages of data quantification, objective results, and high discrimination accuracy. It is suitable for cultivar screening in the process of corn breeding, and provides for the transformation of corn original ecological flavor evaluation results from subjective perception type to data quantitative type. Technical Support.
为了达到上述目的,本发明提供如下技术方案:In order to achieve the above object, the present invention provides the following technical solutions:
一种基于风味物质定量检测的玉米风味品质评估方法,包括以下步骤:A corn flavor quality assessment method based on quantitative detection of flavor substances, comprising the following steps:
1)检测1) Detection
取玉米样品,以顶空固相微萃取-气相色谱-质谱联用方法测定玉米籽粒中的挥发性成分;Taking corn samples, the volatile components in corn kernels were determined by headspace solid-phase microextraction-gas chromatography-mass spectrometry;
2)定性定量分析2) Qualitative and quantitative analysis
将检测出所得挥发性成分的检测数据通过NIST08质谱数据库比对,进行定性分析,选取匹配度在85%以上的若干挥发性成分分别进行定量分析,分别计算所选取的每种挥发性成分的相对百分含量;The detection data of the obtained volatile components were compared through the NIST08 mass spectrometry database, and qualitative analysis was carried out. Several volatile components with a matching degree of more than 85% were selected for quantitative analysis, and the relative ratio of each selected volatile component was calculated separately. percentage content;
3)数据处理3) Data processing
针对测定的玉米品系选取对总体风味贡献最大的组分,利用定量分析结果,计算出所选取的每种挥发性成分的相对风味活度值ROAV,其中,某挥发性成分i的相对风味活度值ROAVi的计算公式为:Select the components that contribute the most to the overall flavor for the measured corn strains, and use the results of quantitative analysis to calculate the relative flavor activity value ROAV of each volatile component selected. Among them, the relative flavor activity value of a volatile component i The formula for calculating ROAV i is:
式中,Ci为某挥发性成分i的相对百分含量,Ti为该挥发性成分相对应的察觉阈值;Cstan为对总体风味贡献最大的组分的相对百分含量,Tstan为对总体风味贡献最大的组分相对应的察觉阈值,100为对样品总体风味贡献最大的组分的相对风味活度值;In the formula, C i is the relative percentage content of a volatile component i, T i is the corresponding detection threshold of the volatile component; C stan is the relative percentage content of the component that contributes the most to the overall flavor, and T stan is The detection threshold corresponding to the component that contributes the most to the overall flavor, 100 is the relative flavor activity value of the component that contributes the most to the overall flavor of the sample;
根据挥发性成分的ROAV选出玉米的若干特征风味化合物,使用数据处理软件进行主成分分析,得到特征风味化合物相关矩阵的特征值、特征向量和主成分载荷矩阵,进一步得到玉米的特征性化合物与原生态风味品质指标的多重线性回归方程;According to the ROAV of volatile components, several characteristic flavor compounds of corn were selected, and data processing software was used to perform principal component analysis to obtain the eigenvalues, eigenvectors and principal component loading matrix of the correlation matrix of characteristic flavor compounds, and further obtain the characteristic compounds of corn and The multiple linear regression equation of the original ecological flavor quality index;
4)风味评估4) Flavor Evaluation
对待评估玉米籽粒采用顶空固相微萃取-气相色谱-质谱联用方法进行检测,获得每种特征风味化合物的定量分析结果;The corn kernels to be evaluated were detected by headspace solid-phase microextraction-gas chromatography-mass spectrometry, and the quantitative analysis results of each characteristic flavor compound were obtained;
将得到的特征风味化合物的定量分析结果代入步骤3)的多重回归线性方程中,计算得到预估值;根据预估值的高低判断待测玉米的原生态风味品质。Substitute the obtained quantitative analysis results of characteristic flavor compounds into the multiple regression linear equation of step 3), and calculate the estimated value; judge the original ecological flavor quality of the corn to be tested according to the level of the estimated value.
优选地,步骤1)中,测定的玉米为不同生长期的玉米籽粒。Preferably, in step 1), the measured corn is corn kernels in different growth stages.
进一步,步骤1)中,所述玉米为选自籽粒形成期、水泡期、灌浆期、乳熟前期、乳熟期、蜡熟期或/和完熟期的玉米。Further, in step 1), the corn is selected from the grain formation stage, the blister stage, the grain filling stage, the early stage of milk maturity, the milk maturity stage, the wax maturity stage or/and the full maturity stage.
优选地,步骤1)中,顶空固相微萃取-气相色谱-质谱联用方法中,固相微萃取条件为:固相萃取头平衡时间15min,萃取温度50℃,萃取时间30min,解吸附时间5min。Preferably, in step 1), in the headspace solid-phase micro-extraction-gas chromatography-mass spectrometry method, the solid-phase micro-extraction conditions are: solid-phase extraction head equilibration time 15min, extraction temperature 50 ℃, extraction time 30min, desorption time Time 5min.
又,步骤1)中,顶空固相微萃取-气相色谱-质谱联用方法中,色谱条件:升温程序:柱初温40℃,保持5min,以5℃/min升至220℃,不保持;而后以20℃/min升至250℃,保持2.5min;进样口温度260℃;载气(He)流量1.0m L/min。In addition, in step 1), in the headspace solid-phase microextraction-gas chromatography-mass spectrometry method, the chromatographic conditions: heating program: the initial temperature of the column is 40 ° C, maintained for 5 min, and raised to 220 ° C at 5 ° C/min, without maintaining ; Then rise to 250°C at 20°C/min and hold for 2.5min; the inlet temperature is 260°C; the carrier gas (He) flow rate is 1.0 mL/min.
优选地,步骤1)中,顶空固相微萃取-气相色谱-质谱联用方法中,质谱条件:离子源温度230℃;电离方式EI;电子能量70eV;质量范围m/z 20~400。Preferably, in step 1), in the headspace solid phase microextraction-gas chromatography-mass spectrometry method, mass spectrometry conditions: ion source temperature 230°C; ionization mode EI; electron energy 70eV; mass range m/z 20-400.
又,步骤2)中,通过内标法测定所选取的每种挥发性成分的含量。Also, in step 2), the content of each selected volatile component is determined by the internal standard method.
进一步,步骤3)中,选出ROAV>1的挥发性成分作为糯玉米的特征风味化合物。Further, in step 3), volatile components with ROAV>1 are selected as characteristic flavor compounds of waxy corn.
又,所述步骤3)中选出的特征风味化合物为:(E)-2-壬烯醛、1-辛烯-3-酮、己醛、(E,Z)-2,6-壬二烯醛、(Z)-4-庚烯醛、正辛醛、二甲基硫醚、(E,E)-2,4-壬二烯醛、(E,E)-2,4-癸二烯醛、1-辛烯-3-醇、(E,E)-2,6-壬二烯醛、2-正戊基呋喃、2-庚烯醛、1-壬醇、壬醛、正己醇、乙醛、庚醛、(E)-2-辛烯醛和3-羟基-2-丁酮。In addition, the characteristic flavor compounds selected in the step 3) are: (E)-2-nonenal, 1-octen-3-one, hexanal, (E,Z)-2,6-nonenal Alkenal, (Z)-4-heptenal, n-octylaldehyde, dimethyl sulfide, (E,E)-2,4-nonadienal, (E,E)-2,4-decanedi Alkenal, 1-octen-3-ol, (E,E)-2,6-nonadienal, 2-n-pentylfuran, 2-heptenal, 1-nonanol, nonanal, n-hexanol , acetaldehyde, heptanal, (E)-2-octenal and 3-hydroxy-2-butanone.
优选地,步骤1)中,所述的玉米样品为糯玉米,步骤3)中选取的对总体风味贡献最大的组分为1-辛烯-3-酮。Preferably, in step 1), the corn sample is waxy corn, and the component selected in step 3) that contributes the most to the overall flavor is 1-octen-3-one.
本发明顶空固相微萃取-气相色谱-质谱联用(SPME-GC-MS)方法对玉米进行检测,将检测出的挥发性成分通过NIST08质谱数据库比对进行定性分析,选取与NIST08质谱数据库中匹配度85%以上者,而后去除由萃取头带来的硅化物杂峰,使得定性定量结果更准确,再根据峰面积归一化法计算各挥发性化合物的相对百分含量。The headspace solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method of the present invention is used to detect corn, and the detected volatile components are compared with the NIST08 mass spectrometry database for qualitative analysis, and the selected volatile components are compared with the NIST08 mass spectrometry database. If the matching degree is more than 85%, then remove the silicide impurity peak brought by the extraction head to make the qualitative and quantitative results more accurate, and then calculate the relative percentage content of each volatile compound according to the peak area normalization method.
经过研究发现,玉米的原生态风味是由各挥发性化合物的察觉阈值与其在风味体系中的含量共同决定的,一些烷烃类化合物相对百分含量较高,但因其察觉阈值较大,而对原生态风味品质的影响较小,几乎可以忽略;本发明结合挥发性成分的含量及察觉阈值对玉米的原生态风味进行考量,可以明确各挥发性化合物对糯玉米风味的贡献程度,评估结果更科学更准确。After research, it was found that the original flavor of corn is determined by the detection threshold of each volatile compound and its content in the flavor system. Some alkane compounds have relatively high relative percentages, but because of their large detection threshold, they are not suitable for The influence of the original ecological flavor quality is small and can almost be ignored; the present invention considers the original ecological flavor of corn in combination with the content of volatile components and the detection threshold, and can clarify the contribution degree of each volatile compound to the flavor of waxy corn, and the evaluation result is better. Science is more accurate.
本发明利用相对风味活度值法,将对总体风味贡献最大的组分的相对风味活度值ROAVstan设为100,计算挥发性成分的ROAV值,选出关键特征风味化合物,所选择的特征风味化合物的ROAV值越大,则该组样品总体风味贡献越大,再通过主成分分析,进一步确定特征风味化合物与原生态风味指标的多重回归线性方程,可以结合多个多重回归线性方程的预估结果进行评估,若预估值为负值,则风味淡薄,若预估值介于0~10之间,则风味适宜,若预估值>10,则风味饱满,且风味品质随预估值的增加而增加。The invention uses the relative flavor activity value method, sets the relative flavor activity value ROAV stan of the component that contributes the most to the overall flavor as 100, calculates the ROAV value of the volatile components, selects key characteristic flavor compounds, and the selected characteristic The larger the ROAV value of the flavor compounds, the greater the overall flavor contribution of the group of samples, and then through the principal component analysis, the multiple regression linear equations between the characteristic flavor compounds and the original ecological flavor indicators can be further determined, which can be combined with the predictions of multiple multiple regression linear equations. If the estimated value is negative, the flavor is weak; if the estimated value is between 0 and 10, the flavor is appropriate; if the estimated value is greater than 10, the flavor is full, and the flavor quality varies with the estimated value. increases as the value increases.
本发明中,选择不同生长期的玉米籽粒进行检测,可以明确不同生长期玉米关键性风味物质,建立全生长周期的玉米风味品质的多重线性回归方程,可预估不同生长期的玉米的原生态风味品质。In the present invention, corn kernels in different growth periods are selected for detection, the key flavor substances of corn in different growth periods can be clarified, the multiple linear regression equation of the flavor quality of corn in the whole growth period can be established, and the original ecology of corn in different growth periods can be estimated. Flavor quality.
与现有技术相比,本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
本发明结合挥发性化合物的风味察觉阈值,利用相对风味活度值法计算出各挥发性化合物的相对风味活度值,可以明确各挥发性化合物对糯玉米风味的贡献程度,选出关键特征风味化合物,提高评估玉米的原生态风味的准确度。In the present invention, the relative flavor activity value of each volatile compound is calculated by using the relative flavor activity value method in combination with the flavor detection threshold of volatile compounds, so that the contribution degree of each volatile compound to the flavor of waxy corn can be determined, and the key characteristic flavor can be selected. Compounds that improve the accuracy of assessing the native flavor of maize.
本发明对提取的主成分建立多重线性回归方程,建立了玉米的特征风味化合物与原生态风味品质指标的多重回归线性方程,将待评估玉米的特征风味化合物的定量结果代入多重回归线性方程中,计算得到玉米原生态风味的预估值,据预估值的高低判定待测玉米的风味品质;根据主成分数量,可以计算得到多个预估值,多个预估值相加可得到综合预估值,使得数据量化,结果客观可靠。The invention establishes a multiple linear regression equation for the extracted principal components, establishes a multiple regression linear equation between the characteristic flavor compounds of corn and the original ecological flavor quality index, and substitutes the quantitative results of the characteristic flavor compounds of the corn to be evaluated into the multiple regression linear equation, Calculate the estimated value of the original ecological flavor of corn, and determine the flavor quality of the corn to be tested according to the level of the estimated value. Valuation makes the data quantified and the results objective and reliable.
本发明中,对糯玉米选定了20种特征性风味物质,其ROAV值均大于1,对糯玉米整体风味起重要作用,可涵盖不同生长期糯玉米的风味特征,其中4个主成分对原生态风味品质指标的累积贡献率达90.37%,可以充分代表20个指标的综合信息。In the present invention, 20 kinds of characteristic flavor substances are selected for waxy corn, and their ROAV values are all greater than 1, which play an important role in the overall flavor of waxy corn, and can cover the flavor characteristics of waxy corn in different growth periods. The cumulative contribution rate of the original ecological flavor quality indicators reached 90.37%, which can fully represent the comprehensive information of 20 indicators.
本发明为玉米原生态风味品质测评提供技术支持,该方法具有操作简便,数据量化,结果客观,判别准确度高的优点,为玉米选育过程中风味品质判别提供有效的技术支持。The invention provides technical support for the evaluation of the flavor quality of the original ecology of corn. The method has the advantages of simple operation, data quantification, objective results and high discrimination accuracy, and provides effective technical support for the discrimination of the flavor quality in the process of corn breeding.
附图说明Description of drawings
图1为本发明实施例中沪紫黑糯1号乳熟期糯玉米挥发性成分的离子流图。Fig. 1 is the ion current diagram of the volatile components of the waxy corn in the milk-maturing stage of Huzi Hei Nuo No. 1 in the embodiment of the present invention.
图2为本发明实施例中的主成分分析碎石图。FIG. 2 is a principal component analysis gravel diagram in an embodiment of the present invention.
图3为本发明实施例中的主成分分析组件图。FIG. 3 is a component diagram of principal component analysis in an embodiment of the present invention.
具体实施方式Detailed ways
以下结合具体实施例对本发明作进一步说明。The present invention will be further described below in conjunction with specific embodiments.
试验样品:沪紫黑糯1号,申科糯602,糯玉米种子均由上海市农业科学院提供。Test samples: Huzihei Nuo 1, Shenke Nuo 602, and waxy corn seeds were all provided by Shanghai Academy of Agricultural Sciences.
仪器:Tri Plus AS全自动顶空固相微萃取自动进样器,美国Thermo Fisher公司;50/30μm(DVB/CAR/PDMS)萃取纤维头,美国Supelco公司;6890N-5973N型气相色谱-质谱仪,美国Agilent公司;数据分析软件为IBM SPSS Statistics 23.0。Instrument: Tri Plus AS automatic headspace solid-phase microextraction autosampler, Thermo Fisher, USA; 50/30 μm (DVB/CAR/PDMS) extraction fiber head, Supelco, USA; 6890N-5973N gas chromatography-mass spectrometer , Agilent, USA; data analysis software is IBM SPSS Statistics 23.0.
实施例Example
1、检测1. Detection
沪紫黑糯1号糯玉米授粉后分别套袋标记,自授粉后8天起,取4个平行,每间隔4天取一次玉米样品,直至糯玉米成熟(授粉后36天),即分别取籽粒形成期、水泡期、灌浆期、乳熟前期、乳熟期、蜡熟期及完熟期的糯玉米籽粒,制作每一个玉米样的待测样品,将糯玉米样品分别置于组织研磨仪中60Hz/s条件下磨样60s,精确称取5g(±0.01g)糯玉米匀浆于20ml进样瓶中,并于采后24h内完成SPME-GC-MS检测,获得挥发性成分的离子流图,参见图1,横坐标表示出峰时间,纵坐标表示各物质的响应强度,检测条件如下:After pollination, the waxy corn of Huzihei Nuo No. 1 was bagged and marked. From 8 days after pollination, 4 parallel samples were taken, and corn samples were taken every 4 days until the waxy corn was mature (36 days after pollination). Waxy corn kernels in the grain formation stage, blister stage, grain filling stage, early milk maturity stage, milk maturity stage, wax maturity stage and full maturity stage were prepared for each corn sample to be tested, and the waxy corn samples were placed in the tissue grinder respectively. Grind the sample for 60s under the condition of 60Hz/s, accurately weigh 5g (±0.01g) of waxy corn homogenate into a 20ml injection bottle, and complete the SPME-GC-MS detection within 24h after sampling to obtain the ion current of volatile components. Figure, see Figure 1, the abscissa represents the peak time, the ordinate represents the response intensity of each substance, the detection conditions are as follows:
固相微萃取条件:固相萃取头平衡时间15min,萃取温度50℃,萃取时间30min,解吸附时间5min;Solid phase microextraction conditions: solid phase extraction head equilibration time 15min, extraction temperature 50℃, extraction time 30min, desorption time 5min;
色谱条件:DB-WAX毛细管柱(30m×0.25mm,0.25μm);不分流模式进样;升温程序:柱初温40℃,保持5min,以5℃/min升至220℃,不保持;而后以20℃/min升至250℃,保持2.5min;进样口温度260℃;载气(He)流量1.0m L/min;Chromatographic conditions: DB-WAX capillary column (30m×0.25mm, 0.25μm); injection in splitless mode; temperature program: initial column temperature 40°C, hold for 5min, rise to 220°C at 5°C/min, no hold; then Rise to 250°C at 20°C/min, hold for 2.5min; inlet temperature 260°C; carrier gas (He) flow rate 1.0 mL/min;
质谱条件:离子源温度230℃;电离方式EI;电子能量70eV;质量范围m/z 20~400。Mass spectrometry conditions: ion source temperature 230°C; ionization mode EI; electron energy 70eV; mass range m/z 20-400.
2、定性定量分析2. Qualitative and quantitative analysis
将检测出的挥发性成分的离子流图通过NIST08质谱数据库比对进行定性分析,选取质谱数据匹配度85%以上的若干挥发性成分,再通过面积归一化法计算所选取的挥发性成分的相对百分含量。The ion chromatograms of the detected volatile components were qualitatively analyzed by comparing the NIST08 mass spectrometry database, and a number of volatile components with a matching degree of more than 85% of the mass spectral data were selected, and then the area normalization method was used to calculate the selected volatile components. relative percentage.
在7个生长期的沪紫黑糯1号糯玉米籽粒中共检出121种挥发性成分,醛、酮、醇类化合物是糯玉米籽粒最主要的风味物质,其种类及相对百分含量在各生长期均存在明显差异;醚类、酮类物质在籽粒形成期相对百分含量最高,醛类、醇类物质在水泡期相对百分含量最高,杂环类物质在籽粒灌浆期相对百分含量最高,烃类、其他类物质在乳熟前期相对百分含量最高,酯类物质在蜡熟期相对百分含量最高,酸类物质在成熟期相对百分含量最高;籽粒灌浆期糯玉米挥发性组分较复杂,随着籽粒生长发育,烃类、酯类、酸类、杂环类化合物种类呈先增加后降低的趋势,醇类、醛类、酮类、醚类化合物种类逐渐减少。A total of 121 volatile components were detected in the waxy corn kernels of Huzihei Nuo No. 1 in 7 growing periods. Aldehyde, ketone and alcohol compounds were the most important flavor substances in waxy corn kernels. There were obvious differences in the growth stages; the relative percentages of ethers and ketones were the highest in the grain formation stage, the relative percentages of aldehydes and alcohols were the highest in the blister stage, and the relative percentages of heterocyclic substances in the grain filling stage. The highest relative percentage of hydrocarbons and other substances in the early stage of milk maturity, the highest relative percentage of ester substances in the wax maturity stage, and the highest relative percentage of acid substances in the mature stage. The composition is more complex. With the growth and development of grains, the types of hydrocarbons, esters, acids, and heterocyclic compounds increased first and then decreased, and the types of alcohols, aldehydes, ketones, and ethers gradually decreased.
利用相对风味活度值法确定不同生长期鲜食糯玉米特征性风味化合物并进行差异分析,7个生长期糯玉米籽粒中各有11种、7种、13种、8种、7种、8种、7种挥发性风味成分ROAV大于1,是影响沪紫黑糯1号糯玉米风味的关键物质,其中(E)-2-壬烯醛、1-辛烯-3-酮、正辛醛、己醛和1-辛烯-3-醇是整个生长期糯玉米籽粒共有的主体风味物质;2-正戊基呋喃、壬醛、庚醛、2-庚烯醛、乙醛、正己醇等物质对沪紫黑糯1号糯玉米总体风味具有重要的修饰作用。The relative flavor activity value method was used to determine the characteristic flavor compounds of fresh waxy maize in different growth periods and analyze the differences. There were 11, 7, 13, 8, 7, and 8 in the waxy maize grains of 7 growth periods. There are 7 kinds of volatile flavor components ROAV greater than 1, which are the key substances affecting the flavor of Huzihei Nuo No. 1 waxy corn. Among them, (E)-2-nonenal, 1-octen-3-one, n-octaldehyde , hexanal and 1-octen-3-ol are the main flavor substances shared by waxy corn grains in the whole growing period; 2-n-pentylfuran, nonanal, heptanal, 2-heptenal, acetaldehyde, n-hexanol, etc. The substances have an important modification effect on the overall flavor of Huzihei Nuo 1 waxy maize.
3、数据分析3. Data analysis
针对测定的糯玉米选取对总体风味贡献最大的组分为1-辛烯-3-酮,设定其ROAVstan为100,利用定量分析结果,计算出所选取的每种挥发性成分的相对风味活度值ROAV,其中,某挥发性成分i的相对风味活度值ROAVi的计算公式为:1-octen-3-one was selected as the component that contributed the most to the overall flavor of the measured waxy corn, and its ROAVstan was set to 100. Using the quantitative analysis results, the relative flavor activity of each selected volatile component was calculated. value ROAV, where the formula for calculating the relative flavor activity value ROAV i of a volatile component i is:
式中,Ci为某挥发性成分i的相对百分含量,Ti为该挥发性成分相对应的察觉阈值;Cstan为1-辛烯-3-酮的相对百分含量,Tstan为对1-辛烯-3-酮的察觉阈值,100为1-辛烯-3-酮的相对风味活度值。In the formula, C i is the relative percentage content of a volatile component i, T i is the detection threshold corresponding to the volatile component; C stan is the relative percentage content of 1-octen-3-one, and T stan is The detection threshold for 1-octen-3-one, 100 is the relative flavor activity value of 1-octen-3-one.
某挥发性成分的ROAV值越大,则该成分的总体风味贡献越大,按照挥发性成分的ROAV值大于1的条件,选出了糯玉米的20种特征风味化合物,包括化合物1到化合物20所示的化合物,所述化合物1为(E)-2-壬烯醛,化合物2为1-辛烯-3-酮,化合物3为己醛,化合物4为(E,Z)-2,6-壬二烯醛,化合物5为(Z)-4-庚烯醛,化合物6为正辛醛,化合物7为二甲基硫醚,化合物8为(E,E)-2,4-壬二烯醛,化合物9为(E,E)-2,4-癸二烯醛,化合物10为1-辛烯-3-醇,化合物11为(E,E)-2,6-壬二烯醛,化合物12为2-正戊基呋喃,化合物13为2-庚烯醛,化合物14为1-壬醇,化合物15为壬醛,化合物16为正己醇,化合物17为乙醛,化合物18为庚醛,化合物19为(E)-2-辛烯醛,化合物20为3-羟基-2-丁酮。The larger the ROAV value of a volatile component, the greater the overall flavor contribution of the component. According to the condition that the ROAV value of the volatile component is greater than 1, 20 characteristic flavor compounds of waxy corn were selected, including compounds 1 to 20. The compound shown, the compound 1 is (E)-2-nonenal, the compound 2 is 1-octen-3-one, the compound 3 is hexanal, the compound 4 is (E, Z)-2,6 -Nonadienal, compound 5 is (Z)-4-heptenal, compound 6 is n-octylaldehyde, compound 7 is dimethyl sulfide,
使用使用SPSS 23.0软件进行主成分分析,得到主成分分析碎石图及组件图,参见图2-3,碎石图以特征值为纵轴,成分为横轴,前面陡峭的部分特征值大,包含的信息多,后面平坦的部分特征值小,包含的信息也小;根据分析结果得到特征风味化合物化合物1到化合物20相关矩阵的特征值、特征向量和主成分载荷矩阵,4个主成分对原生态风味品质的累积贡献率达90.37%,可以充分代表20个指标的综合信息,进一步得到玉米的特征性化合物与原生态风味品质指标的4个多重线性回归方程,建立风味评估模型,所述4个多重回归线性方程如下:Use SPSS 23.0 software to carry out principal component analysis to obtain the principal component analysis gravel diagram and component diagram, see Figure 2-3, the gravel diagram takes the eigenvalue as the vertical axis and the component as the horizontal axis. It contains a lot of information, and the eigenvalues of the flat part in the back are small, and the information contained is also small; according to the analysis results, the eigenvalues, eigenvectors and principal component loading matrix of the correlation matrix of the characteristic flavor compounds compounds 1 to 20 are obtained, and four principal component pairs are obtained. The cumulative contribution rate of the original ecological flavor quality is 90.37%, which can fully represent the comprehensive information of 20 indicators, and further obtain four multiple linear regression equations between the characteristic compounds of corn and the original ecological flavor quality indicators, and establish a flavor evaluation model. The four multiple regression linear equations are as follows:
F1=-0.856X1+0.901X2+0.084X3-0.803X4-0.794X5+0.779X6+0.42X7+0.387X8+0.377X9+0.971X10+0.658X11-0.254X12-0.094X13+0.843X14+0.628X15+0.476X16-0.451X17-0.862X18+0.593X19-0.393X20;F1=-0.856X 1 +0.901X 2 +0.084X 3 -0.803X 4 -0.794X 5 +0.779X 6 +0.42X 7 +0.387X 8 +0.377X 9 +0.971X 10 +0.658X 11 -0.254X 12 -0.094X 13 +0.843X 14 +0.628X 15 +0.476X 16 -0.451X 17 -0.862X 18 +0.593X 19 -0.393X 20 ;
F2=0.402X1+0.123X2+0.742X3+0.114X4-0.22X5+0.389X6-0.88X7+0.553X8-0.92X9-0.153X10-0.056X11-0.024X12+0.81X13-0.043X14+0.557X15-0.102X16-0.436X17-0.439X18+0.601X19-0.293X20;F2=0.402X 1 +0.123X 2 +0.742X 3 +0.114X 4 -0.22X 5 +0.389X 6 -0.88X 7 +0.553X 8 -0.92X 9 -0.153X 10 -0.056X 11 -0.024X 12 + 0.81X 13 -0.043X 14 +0.557X 15 -0.102X 16 -0.436X 17 -0.439X 18 +0.601X 19 -0.293X 20 ;
F3=0.282X1-0.092X2-0.655X3+0.377X4+0.531X5+0.208X6+0.194X7+0.622X8+0.095X9-0.121X10+0.305X11+0.389X12+0.439X13+0.502X14-0.314X15+0.814X16+0.666X17+0.154X18+0.524X19-0.381X20;F3=0.282X 1 -0.092X 2 -0.655X 3 +0.377X 4 +0.531X 5 +0.208X 6 +0.194X 7 +0.622X 8 +0.095X 9 -0.121X 10 +0.305X 11 +0.389X 12 + 0.439X 13 +0.502X 14 -0.314X 15 +0.814X 16 +0.666X 17 +0.154X 18 +0.524X 19 -0.381X 20 ;
F4=-0.112X1+0.135X2+0061X3-0.002X4-0.336X6+0.104X7+0.393X8+0.036X9+0.092X10+0.059X11+0.754X12+0.22X13+0.042X14-0.193X15-0.284X16-0.26X17-0.2X18+0.092X19+0.539X20。F4 = -0.112X 1 +0.135X 2 +0061X 3 -0.002X 4 -0.336X 6 +0.104X 7 +0.393X 8 +0.036X 9 +0.092X 10 +0.059X 11 +0.754X 12 +0.22X 13 + 0.042X 14 -0.193X 15 -0.284X 16 -0.26X 17 -0.2X 18 +0.092X 19 +0.539X 20 .
其中,F1、F2、F3、F4为四个预估值,所述X1到X20为化合物1到化合物20的定量结果,所述定量结果为相对百分含量,将F1、F2、F3、F4四个预估值相加即得到综合预估值。Among them, F1, F2, F3, F4 are four estimated values, and the X 1 to X 20 are the quantitative results of compounds 1 to 20, and the quantitative results are relative percentages. F1, F2, F3, The four estimated values of F4 are added together to obtain the comprehensive estimated value.
4、风味评估4. Flavor assessment
利用SPME-GC-MS测定待评估的两个品种糯玉米沪紫黑糯1号、申科糯602,分别于七个生长期测定糯玉米样品的定量结果,将测定的定量结果代入上述多重回归线性方程中,根据预估值的高低判定待测玉米的原生态风味品质,结果见表1,其中,FH1、FH2、FH3、FH4、FH5、FH6及FH7分别代表沪紫黑糯1号的籽粒形成期、水泡期、灌浆期、乳熟前期、乳熟期、蜡熟期及完熟期样品,FK1、FK2、FK3、FK4、FK5、FK6及FK7分别代表沪紫黑糯1号的籽粒形成期、水泡期、灌浆期、乳熟前期、乳熟期、蜡熟期及完熟期样品,每样品3个重复。The two waxy corn varieties to be evaluated, Huzihei Nuo 1 and Shenke Nuo 602, were determined by SPME-GC-MS, and the quantitative results of the waxy corn samples were determined in seven growth periods respectively, and the quantitative results were substituted into the above multiple regression line In the property equation, the original ecological flavor quality of the corn to be tested is determined according to the estimated value. The results are shown in Table 1. Among them, FH1, FH2, FH3, FH4, FH5, FH6 and FH7 represent the grains of Huzihei Nuo 1, respectively. Formation stage, blister stage, grain filling stage, early milk maturity stage, milk maturity stage, wax maturity stage and full maturity stage samples, FK1, FK2, FK3, FK4, FK5, FK6 and FK7 represent the grain formation stage of Huzihei Nuo 1, respectively , blister stage, filling stage, early milk maturity, milk maturity, wax maturity and full maturity samples, each sample was replicated 3 times.
表1Table 1
通过以上结果可知,糯玉米不同生长期原生态风味差异明显,沪紫黑糯1号糯玉米水泡期原生态风味预估值最高,其次为乳熟期,完熟期原生态风味最为淡薄;申科糯602乳熟期原生态风味预估值最高,其次为灌浆期,完熟期原生态风味预估值最低,食用品质低,实现了糯玉米原生态风味评估的数据定量评估。From the above results, it can be seen that the original ecological flavor of waxy corn has obvious differences in different growth periods. The estimated value of the original ecological flavor of the waxy corn No. 1 in the blister period is the highest, followed by the milk ripening period, and the original ecological flavor in the mature period is the weakest; Shenke The estimated value of the original ecological flavor of waxy 602 was the highest at the milk-maturing stage, followed by the filling stage, and the predicted value of the original ecological flavor at the full-ripening stage was the lowest, and the edible quality was low.
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