基于连续投影算法的油菜蜜近红外光谱真伪鉴别的研究

采用连续投影算法(successive project algorithm,SPA)对177个不同产地油菜蜜样本的近红外光谱做波长选择,然后以33个特征变量作线性识别分析(LDA)。同时,也采用了主成分分析(PCA)对变量进行压缩。比较了二次识别分析(QDA)和簇类独立软模式分类法(SIMCA)的鉴别结果。SPA-LDA模型预测集的鉴别准确率为97.7%,而PCA-LDA、全谱的SIMCA和SPA-QDA预测集的正确率分别为93.2%、95.4%和90.9%;上述四种方法ROC曲线下的面积分别为0.964、0.912、0.948和0.933。SPA-LDA性能比其他三种方法要好。该方法准确、可靠,为蜂蜜真实性的现场快速检测提供了一种新方法。     

Rapid classification of virgin and recycled EPS containers by Fourier transform infrared spectroscopy and chemometrics

ABSTRACT

A rapid and sensitive method for classification of virgin and recycled expanded polystyrene (EPS) food containers was developed using Fourier transform infrared spectroscopy (FTIR) and chemometrics. This method includes preparing a transparent film by dissolution, examining by FTIR and developing classification models. The degradation of EPS containers occurring during the recycling process was reflected by the carbonyl region of the infrared spectrum which was used as variables for multivariate data analysis. PCA was used to reduce the data dimension and view the sample similarities. Soft independent modelling of class analogy (SIMCA), partial least squares-discrimination analysis (PLS-DA) and linear discrimination analysis (LDA) were applied to construct three classification models. The best discrimination results were obtained by an LDA model, with all samples correctly classified. PLS-DA and SIMCA could not classify the recycled EPS samples with low levels of adulteration. When applying this method to commercially available EPS containers, about 45% of samples were shown to contain recycled polystyrene resins. It is concluded that the carbonyl region of the infrared spectra coupled with chemometrics could be a powerful tool for the classification of virgin and recycled EPS food containers.     

Multivariate Classification of UHT Milk as to the Presence of Lactose Using Benchtop and Portable NIR Spectrometers

Lactose hydrolyzed milk was developed in the 1970s to serve individuals with lactose intolerance. This demand for lactose-free products by lactose-intolerant consumers has created a market segment for this food whose quality control has to be guaranteed. In order to assess milk samples for lactose content, this work proposes an analytical methodology to classify regular and lactose-free ultra high temperature (UHT) milks using multivariate classification methods and NIR spectra obtained in FT-NIR and ultra-compact NIR spectrometers, aiming at field analysis. For this, 71 samples were purchased; 41 were lactose-free UHT milk and 30 regular UHT milk. Diffuse transflectance spectra were obtained by FT-NIR (833 to 2500 nm, 4 cm^?1 of resolution and mean of 16 scans), and by ultra-compact NIR (908 to 1676 nm, with 12.5 nm of resolution and mean of 50 scans). The classification models were obtained by PLS-DA and LDA techniques with robust variables selection by SPA and GA, evaluating different spectral pre-processing (MSC, SNV, and derivatives). The three models developed (PLS-DA, GA-LDA, and SPA-LDA) with benchtop equipment spectra correctly classified all samples with sensitivity and specificity of 100%. For the portable equipment spectra, PLS-DA and GA-LDA models obtained sensitivity and specificity of 100%. The SPA-LDA model, however, presented sensitivity and specificity of 80 and 100%, respectively. These results indicate that methodologies using NIR equipment, especially the ultra-compact NIR, with multivariate classification techniques are feasible in discrimination between regular and lactose-free milk in the field, thus enabling a quick and precise analysis.     

基于气相色谱-质谱技术与多元统计分析对不同栗香特征绿茶判别分析

采用气相色谱-质谱联用技术结合多元统计分析主成分分析（principal component analysis,PCA）、偏最小二乘法-判别分析（partial least squares-discriminant analysis,PLS-DA）和系统聚类分析（hierarchical cluster analysis,HCA）对18?个不同栗香特征的绿茶开展研究。结果表明,PCA、PLS-DA和HCA均可直观地对3?种不同栗香特征的绿茶进行有效区分;PLS-DA中,18?个栗香茶样基于其香气特征实现良好分离,其中R2Y＝0.843、Q2＝0.694,说明该模型对3?种栗香特征绿茶具有良好的稳定性和较好的预测能力;HCA中,3种栗香绿茶在聚类距离12处被清晰地分成3?类,其中板栗香型和嫩栗香型距离更接近,聚类效果和感官辨识基本一致。此外,基于变量投影重要性大于1,筛选出了38?种区分不同栗香特征的重要挥发性组分。     

Analysis of metabolic markers of tea origin by UHPLC and high resolution mass spectrometry

Tea is an infusion made from the dried leaves of Camellia sinensis L. and is the second most consumed beverage in the world. It has been shown that factors such as fermentation methods, cultivar, geographical origin and season can affect the biochemical composition of tea. In this study, the biochemical composition of green, oolong and black commercial tea samples from around the world was studied using a non-targeted method utilising reversed phase ultra high pressure liquid chromatography (UHPLC) and high resolution mass spectrometry. Principal component analysis of green, oolong and black tea extracts clearly showed that fermented tea can be resolved from non-fermented tea. When the non-targeted data were combined with the supervised multivariate technique, partial least squares discriminant analysis, the method was able to clearly distinguish ‘country of origin’ within green tea and to a lesser extent within a black tea sample set, plus provide indicative marker ions for the country of origin. Many of the significant components detected in this study are unknowns, emphasising the importance of un-biased non-targeted analytical techniques. This study highlights the potential efficacy of non-targeted UHPLC–mass spectrometry when combined with multivariate statistics to differentiate fermented from non-fermented tea and provide potential indicators of provenance of tea samples for further examination.     

Detecting bunch withering disorder in date fruit by near infrared spectroscopy

This study introduces the application of near infrared spectroscopy (NIRs) to detect bunch withering disorder in date fruit (cv. Mazafati). The samples included intact as well as infected date fruits at different stages of ripening. Chemometric evaluation of the data was performed by soft independent modeling of class analogy (SIMCA), partial least squares discriminant analysis (PLS-DA), and principal components analysis combined with artificial neural networks (PCA–ANN). The PLS-DA algorithm was able to provide models with the best classification performance, followed by SIMCA and then PCA–ANN. The maturity stage of samples influenced the performance of the classification methods. The classification accuracy for the late harvested samples was better than those harvested at normal time and the combined data set in all classification analyses. The total accuracies of 82%, 93% and 86%, respectively for normal, late and combined data sets demonstrate that NIRs with PLS-DA has a strong potential to detect the bunch withering disorder in date fruit.     

电子舌在工夫红茶甜纯滋味特征评价中的应用

为了更客观、快速、准确地评价工夫红茶的甜纯滋味特征,首先以专家人工感官审评为依据,根据茶汤滋味特点将工夫红茶分为甜纯、纯正、欠纯3?组。然后采用电子舌分析并结合多元统计分析手段综合评价茶汤滋味,并建立甜纯滋味判别方程。最后,对验证集中的工夫红茶开展电子舌分析进行验证。结果表明：基于电子舌响应的主成分分析、偏最小二乘判别分析揭示电子舌可有效区分滋味甜纯或非甜（纯正、欠纯）工夫红茶,且影响甜纯滋味识别的关键电子舌传感器为SWS甜味传感器（P＜0.001,单因素方差分析）。基于二元逻辑回归构建甜纯滋味判别预测方程,且整体预测准确率达93.8%。此外,验证集茶样的电子舌分析结果进一步证实电子舌用于评判工夫红茶甜纯滋味的有效性。综上,本研究采用电子舌技术实现了对工夫红茶甜纯滋味特征的快速、准确判别评价,为后续茶叶滋味特征成分的研究提供理论依据,亦可为茶汤滋味的客观、智能评价提供依据。     

Confirmation of brand identity in foods by near infrared transflectance spectroscopy using classification and class-modelling chemometric techniques — The example of a Belgian beer

Food and beverage processors require tools to monitor conformance of finished goods to their defined specification; regulatory authorities need appropriate methods for detecting retail fraud. In this report, samples (n = 275) of Belgian and other European beers were collected and analysed using near infrared transflectance spectroscopy; three class-modelling techniques (soft independent modelling of class analogy, SIMCA; potential functions techniques, POTFUN; and unequal dispersed classes, UNEQ) were employed to characterise beer types (firstly Trappist and then Rochefort) while a classification method (partial least squares discriminant analysis, PLS-DA) was applied to discriminate between two final beer classes: Rochefort 8° and Rochefort 10°. The class-models and the classification rules developed were validated by means of an external prediction set. A discussion on the appropriate use of these chemometric approaches is included. Modelling of Trappist beers met with limited success while model efficiencies for Rochefort samples were highest for SIMCA and UNEQ applications i.e. 81.4% and 84.5% respectively. The classification of beers as Rochefort 8? or Rochefort 10? was possible with an average correct classification rate of 93.4%.     

Classification of longan fruit bruising using visible spectroscopy

This research showed the potential of using visible spectroscopy for classification of non-bruised and bruised longan fruits. The visible spectra of bruised and non-bruised longan fruits were acquired from 400 to 700 nm with 10 nm resolution by the spectrophotometer. The principal component analysis (PCA), Partial Least Square Discriminant Analysis (PLS-DA) and Soft Independent Modeling of Class Analogy (SIMCA) were used to develop classification models. The Partial Least Square Discriminant Analogy (PLS-DA) showed better classification accuracy than SIMCA with 100% correctness. The result was found to be helpful for the application in the industry for on-line and portable application.     

基于HS-SPME-GC-MS和PLS-DA分析不同季节早白尖红茶挥发性风味物质

采集四川省筠连县春、夏、秋三季共15份早白尖红茶样品，采用顶空固相萃取-气相色谱-质谱技术对红茶样品的香气成分进行测定，运用偏最小二乘-判别分析（partial least square-discriminant analysis，PLS-DA）建立不同季节茶叶判别模型，绘制层次聚类的树状热图确定关键香气成分在不同季节样品中的分布规律。结果表明，春季样品醇类（113.05 μg/g）和酯类物质（34.92 μg/g）含量明显高于夏秋两季样品，而醛类物质（23.85 μg/g）明显低于夏秋两季样品，且所建PLS-DA模型可将春和夏秋两季样品明显区分。进一步分析后的分层聚类的树状热图显示，苯乙醛、橙花醇和香叶醇是春季样品区别于其它两季茶样的特征香气化合物，在此基础上可通过芳樟醇、芳樟醇氧化物Ⅰ和Ⅱ对夏、秋两季样品进行进一步区分。该研究为解析不同季节早白尖红茶香气物质提供基础研究数据，也为进一步探究筠连早白尖红茶关键香气形成机制奠定基础。     

Identification of Possible Milk Adulteration Using Physicochemical Data and Multivariate Analysis

Milk is one the most widely consumed foods in the world, with an average annual production of 723 million tons in the second half of the past decade. However, to increase milk’s profitability, some actors in the dairy chain may adulterate it, altering its chemical composition, and reducing the nutritional value of this food. The quality of milk is therefore assessed through chemical and physical analyses such as total dry matter, total Kjeldahl nitrogen, ash, acidity, fat, reducing sugars, depression of freezing point, and relative density. In this work, we have used Principal Components Analysis (PCA) and supervised methods (PLS-DA, SIMCA, kNN, and SVM-DA) to explore physicochemical data from milk and to classify and discriminate between samples that were compliant or not to the parameters set in the Brazilian Regulation for the Inspection of Animal Products and other national regulations. Classification results regarding specificity and selectivity for PLS-DA, SIMCA, kNN, and SVM-DA for noncompliant samples in the test group were, respectively, the following: 91, 88; 100, 97; 78, 67; 78, and 71%.     

Multivariate analysis of NMR fingerprint of the unsaponifiable fraction of virgin olive oils for authentication purposes

A new approach to the geographical characterisation of virgin olive oils (VOOs) based on the ¹H NMR fingerprint of the unsaponifiable matter is presented. The ¹H NMR spectra of the unsaponifiable fraction of virgin olive oils from Spain, Italy, Greece, Tunisia, Turkey, and Syria were analysed by several pattern recognition techniques (LDA, PLS-DA, SIMCA, and CART). PLS-DA (PLS-1 approach) obtained the best classification results for all classes. Moreover, ¹H NMR spectra of the bulk oil, and its corresponding unsaponifiable fraction, as well as the subfractions of the unsaponifiable fraction (alcohol, sterol, hydrocarbon, and tocopherol fractions) were studied in the search for the markers that multivariate techniques revealed to be related to the geographical origin of olive oils. Additionally, a preliminary study regarding ¹H NMR data of the bulk oil and the corresponding unsaponifiable fraction of VOOs suggested that these spectral data contained complementary information for the geographical characterisation of VOOs.     

Instrumental and multivariate statistical analyses for the characterisation of the geographical origin of Apulian virgin olive oils

In this paper, virgin olive oils (VOOs) coming from three different geographic origins of Apulia, were analysed for free acidity, peroxide value, spectrophotometric indexes, chlorophyll content, sterol, fatty acid, and triacylglycerol compositions. In order to predict the geographical origin of VOOs, different multivariate approaches were applied. By performing principal component analysis (PCA) a modest natural grouping of the VOOs was observed on the basis of their origin, and consequently three supervised techniques, i.e., general discriminant analysis (GDA), partial least squares-discriminant analysis (PLS-DA) and soft independent modelling of class analogy (SIMCA) were used and the results were compared. In particular, the best prediction ability was produced by applying GDA (average prediction ability of 82.5%), even if interesting results were obtained also by applying the other two classification techniques, i.e., 77.2% and 75.5% for PLS-DA and SIMCA, respectively.     

斯里兰卡红碎茶与滇红碎茶主要香气成分比较分析

目的 比较分析斯里兰卡红碎茶与滇红碎茶香气成分及含量的差异性,探明区分两地红碎茶差异的主要香气成分。方法 采用GC-MS法测定斯里兰卡红碎茶及滇红碎茶样品的香气成分,通过主成分分析法比较斯里兰卡红碎茶与滇红碎茶香气成分特征差异性,根据第一主成分贡献值大小,筛选出决定区分两地红碎茶差异的主要香气成分。结果 两地红碎茶样品共分析到香气化合物40种,以醛类、酮类、酯类、醇类为主,香气成分及含量相近,但略有差异。其中反-2-己烯醛、苯乙醇、香叶醇、壬醛香气成分滇红碎茶明显高于斯里兰卡红碎茶（高出80%以上）,分别高出110.00%、108.73%、93.64%、84.91%,二氢猕猴桃内酯、吲哚香气成分滇红碎茶明显低于斯里兰卡红碎茶（50%以上）,分别低至56.19%、52.38%。其中烯类香气成分滇红碎茶比斯里兰卡红碎茶高出最为明显,高出53.53%,吲哚类香气成分滇红碎茶比斯里兰卡红碎茶低出最为明显,低出52.48%。两类红碎茶中,水杨酸甲酯占比最高,在斯里兰卡红碎茶中最高可达26.60%,在滇红碎茶中最高可达29.79%。斯里兰卡红碎茶和滇红碎茶中,酯类和醇类含量最高,酯类在斯里兰卡红碎茶中最高可达34.38%,在滇红碎茶中最高可达35.69%,醇类在斯里兰卡红碎茶中最高可达32.48%,在滇红碎茶中最高可达34.84%。各香气成分中二氢猕猴桃内酯（C15）、反-戊酸-2-己烯酯（C29）最能代表斯里兰卡红碎茶香气特征,a-萜品醇（C30）、橙花醇（C40）最能代表滇红碎茶香气成分特征。结论 对香气成分进行分析,可明显区分斯里兰卡红碎茶与滇红碎茶特征。     

Comparison of the antioxidant capacity and the antimicrobial activity of black and green tea

Tea is a common beverage. The green tea is preferentially recommended for its strong antioxidant properties and also for its antimicrobial activity. The antioxidant capacities of 30 samples (black and green tea) were determined by the chemiluminescent Trolox equivalent antioxidant capacity (TEAC) determination. The average value of TEAC of the non-fermented (green tea) and semi-fermented tea samples was 1.43 mM and the average value of TEAC of the fermented teas (black tea) samples was 1.43 mM. All samples were stored in freezer (?20 °C) and the TEAC determination was repeated after a year. The average values of TEAC of non-fermented and semi-fermented tea samples were twofold lower in comparison to fermented tea samples and only 20% of average value of TEAC of the fresh tea infusion. The parallel determinations of minimal inhibitory concentration (MIC) on gram-positive and gram-negative bacterial strains (Enterococcus faecalis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli) were done. Also the MIC was possible to determine after a year. The assumed prevailing antioxidant and antimicrobial activities of non-fermented tea infusions were not confirmed as well as the dominant antioxidant and antimicrobial properties of specific type of tea infusion.     

绿茶矿质元素特征分析及产地判别研究

本实验采用湿法消解结合ICP-AES法对来自不同产地的28种绿茶中的K、Ca、Mg、Fe、Zn、Cu等9种元素进行了分析测定,结合主成分分析及聚类分析模式识别方法进行茶叶产地的分类。结果表明,采用该方法对不同产地绿茶能够良好地区分,聚类效果明显。本法简便、准确,对茶叶产地判别以及标准化工作具有重要意义。     

Authenticity green coffee bean species and geographical origin using near-infrared spectroscopy combined with chemometrics

To prevent the adulteration of agricultural resources and provide a solution to enhance the green coffee bean supply chain, authentication using the near-infrared spectroscopy (NIRS) technique was investigated. Partial least square with discrimination analysis (PLS-DA) models combined with various preprocessing methods were built from NIR spectra of 153 Vietnamese green coffee samples. The model combined with the standard normal variate and the first order of derivative yielded excellent performance in predicting coffee species with the error cross-validation of 0.0261. PLS-DA model of mean centre and first-order derivative spectra also yielded good performance in verifying geographical indication of green coffee with the error of 0.0656. By contrast, the predicting abilities of post-harvest methods were poor. The overall results showed a high potential of the NIRS in online authentication practices.     

Total content and speciation of aluminium in tea leaves and tea infusions

A total of 29 tea samples of different origin, 13 green tea samples, 13 black tea samples, two semi-fermented and one white tea, imported to the Czech Republic, were collected and analysed for total content of aluminium (Al) in tea leaves and tea infusions, as well as for Al compounds in these infusions. The total content of metals in tea leaves differs according to the type of tea (green or black) and is probably influenced by many factors, e.g., soil properties. The HPLC/IC speciation of Al in tea infusions was performed for all samples. The addition of Al³⁺ to the tea infusion proved that Al³⁺, Al(Y)²⁺ and Al(X)¹⁺ species can be determined in tea infusions. Increased extraction time did not show any affect on Al speciation, neither did the addition of sugar. After the addition of lemon juice, the speciation changed in one sample of black tea and five samples of green tea. These findings suggest that lemon juice as an additive can significantly influence Al speciation in tea infusions.     

超高效液相色谱-三重四极杆串联质谱法定量分析云南大叶种茶酚类成分

基于超高效液相色谱-三重四极杆串联质谱联用技术,建立和验证一种高灵敏度、高特异性和高通量的靶向定量分析方法,其具有良好的线性、准确性和稳定性。该方法成功应用于4 类云南大叶种茶叶中90 个酚类成分的准确同时定量分析。结果表明,绝大部分酚类成分在未发酵茶（绿茶或普洱生茶）中含量较高,但游离酚酸、黄酮苷元和茶黄素在发酵茶（红茶或普洱熟茶）中的含量更高。偏最小二乘判别分析进一步揭示了不同类型茶叶的酚类成分差异,并筛选到系列化学标志物。     

Influence of starter cultures on the antioxidant activity of kombucha beverage

This paper investigates the influence of starter cultures, obtained from kombucha isolates, on the antioxidant activity of kombucha beverages. Three starter cultures were used as follows: (1) mixed culture of acetic bacteria and Zygosaccharomyces sp. (SC1); (2) mixed culture of acetic bacteria and Saccharomyces cerevisiae (SC2); as well as (3) native local kombucha. The starter cultures were added to black and green tea sweetened with 7% of sucrose. Fermentation was carried out at 28 °C for 10 days. Antioxidant activity to hydroxyl and DPPH radicals was monitored. Kombucha beverage on black tea has shown the highest antioxidant activity to both types of radicals with starter SC1, while the green tea beverage has shown the highest activity with native kombucha. The main reason for the different antioxidant activities, beside tea composition, was ascribed to differing production of both vitamin C and total organic acids in the investigated systems.