基于中红外光谱快速检测干红葡萄酒中的多糖类物质

    Rapid identification of polysaccharides in Xinjiang dry red wines based on Fourier Transform Infrared1 spectroscopy

    • 摘要: 为了通过衰减全反射-傅里叶变换红外光谱仪(attenuated total reflectance-fourier transform infrared, ATR-FTIR)结合化学计量学方法,开发干红葡萄酒中多糖类物质的快速无损检测方法。试验以新疆产区100款干红葡萄酒为试材,利用醇沉法提取葡萄酒多糖,经真空冷冻干燥得到多糖粉末,再用三氟乙酸将多糖分解成单糖,通过高效液相色谱(high performance liquid chromatography-photodiode array detection, HPLC-PDA)定量分析单糖,酒样中不同类别多糖含量依据各自特征结构的单糖浓度按照一定的摩尔比例进行计算,包括总可溶性多糖(total soluble polysaccharides, TSP)、甘露糖蛋白(mannoprotein, MP)、富含阿拉伯糖-半乳糖的多糖(arabinogalactan-rich polysaccharide, PRAG)、鼠李半乳糖醛酸聚糖II型(rhamnogalacturonan II, RG-II)、高半乳糖醛酸聚糖(homogalacturonan, HG)和葡聚糖(glucan, GL))。葡萄酒的中红外光谱信息通过ATR-FTIR采集,采用标准正态变换(standard normal variate, SNV)和多元散射校正(multiplicative scatter correction, MSC)等方法进行光谱预处理,随后利用竞争性自适应重加权算法(competitve adaptive reweighted sampling, CARS)进行波段筛选,最后结合偏最小二乘回归(partial least squares regression, PLSR)和反向传播神经网络(backpropagation neural network, BPNN)两种建模方法,建模和预测以及评价指标用1900 900 cm−1波段的光谱特征信息拟合HPLC-PDA测得的几种多糖类物质的含量。结果表明,供试酒样之间不同类别多糖含量差异较大,其中TSP含量为(859.41±293.65) mg/L,MP为(208.08±78.42) mg/L,PRAG 为(418.30±140.00) mg/L,RG-II为(113.17±55.11 )mg/L,GL为(95.46±62.10 )mg/L,HG为(24.41±55.86) mg/L。采用1900~900 cm−1筛选出的的特征信息拟合供试酒样中的几种多糖含量,利用线性与非线性校正方法建模,结果表明,ATR-FTIR模型对葡萄酒中几类多糖的含量均具备良好的预测能力。其中,PLSR模型的预测性能优于BPNN,多糖(TSP、MP、PRAG、RG-Ⅱ和GL)的特征波段和含量之间的PLSR模型训练集决定系数(Rc2)分别为0.98、0.96、0.92、0.99、0.98,预测集决定系数(Rp2)分别为0.85、0.92、0.83、0.83、0.84,训练集相对分析误差(RPDc)分别为6.50、5.31、3.62、9.10、7.86,预测集相对分析误差(RPDP)分别为2.68、3.99、2.44、2.52、2.37。该研究开发的ATR-FTIR检测干红葡萄酒多糖类物质的方法,利用多糖特征波段1900 ~900 cm−1的光谱信息,可对TSP、MP、PRAG、RG-Ⅱ和GL几种多糖含量进行准确预测,具有快速无损检测干红葡萄酒中多糖类物质的应用潜力。

       

      Abstract: The purpose of this study was to develop a rapid non-destructive method for the detection of polysaccharides in dry red wine by attenuating total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) combined with chemometric methods.In the experiment, 100 dry red wines from Xinjiang production area were used as test materials, wine polysaccharides were extracted by alcohol precipitation method, polysaccharide powder was obtained by vacuum freeze-drying, and then the polysaccharides were decomposed into monosaccharides with trifluoroacetic acid, and the monosaccharides were quantitatively analyzed by high performance liquid chromatography (HPLC-PDA), and the content of different types of polysaccharides in the wine samples was calculated according to the monosaccharide concentration of their respective characteristic structures according to a certain molar ratio, including total soluble polysaccharides (TSP), mannosan protein (MP), arabinose-galactose-rich polysaccharides (PRAG), rhamnogalacturonic acid glycan type II (RG-II), homogalacturonized glycan (HG), and dextran (GL).The mid-infrared spectral information of wine was collected by ATR-FTIR, and the spectral preprocessing was carried out by standard normal transform (SNV) and multivariate scattering correction (MSC) methods, followed by the competitive adaptive reweighting algorithm (CARS) for band screening, and finally combined with two modeling methods, partial least squares regression (PLSR) and backpropagation neural network (BPNN), modeling, prediction, and evaluation indicators were fitted with spectral characteristic information in the 1900~900 cm−1 band to determine the content of several polysaccharide substances measured by HPLC-PDA. The results indicate that the polysaccharide content of different categories varied greatly between the test liquor samples, with TSP content of (859.41±293.65) mg/L, MP (208.08±78.42) mg/L, PRAG (418.30±140.00) mg/L, RG-II (113.17±55.11) mg/L, GL (95.46±62.10) mg/L, and HG (24.41±55.86) mg/L. The characteristic information screened from 1900~900 cm−1 was used to fit the content of several polysaccharides in the test wine samples, modeling by using the linear and nonlinear correction methods, the results showed that the ATR-FTIR model has good predictive power for the content of several classes of polysaccharides in wine.among, The PLSR model showed a better prediction performance than the BPNN, The coefficient of determination (Rc2) of the PLSR model between the characteristic bands and content of polysaccharides (TSP, MP, PRAG, RG-II, and GL) was 0.98,0.96,0.92,0.99,0.98, respectively, The coefficient of determination (Rp2) is 0.85, 0.92, 0.83, 0.83, 0.84, respectively, The relative analysis error (RPDc) in the training set is 6.50, 5.31, 3.62, 9.10, and 7.86, respectively, The relative analysis error (RPDP) of the prediction set was 2.68, 3.99, 2.44, 2.52, and 2.37, respectively. The ATR-FTIR method developed in this study for the detection of polysaccharides in dry red wine can accurately predict the content of polysaccharides in TSP, MP, PRAG, RG-II and GL by using the spectral information of the polysaccharide characteristic band of 1900 ~900 cm−1, which has the application potential of rapid and nondestructive detection of polysaccharides in dry red wine.

       

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