Differentiation of carbohydrate gums and mixtures using fourier transform infrared spectroscopy and chemometrics

Guar gum, a nonionic galactomannan, is used as an economical thickener and stabilizer in the food industry and is often combined with xanthan, locust bean gum (LBG), or carboxymethylcellulose (CMC) to promote synergistic changes in viscosity or gelling behavior via intermolecular interactions; however, the adulteration of LBG with guar gum is a well-known industrial problem. The ability to identify the purity of gums and concentrations of individual gums in mixtures would be advantageous for quality control in the food industry. Fourier transform infrared spectroscopy (FTIR) methods are rapid and require minimum sample preparation. The objectives of this study were to evaluate the ability of FTIR techniques to (1) differentiate LBG with a variety of mannose/galactose (M/G) ratios, (2) differentiate guar, LBG, tara, and fenugreek gums, (3) differentiate pure guar gum from guar gum mixed with LBG, xanthan gum, or CMC, (4) quantify LBG, xanthan gum, and CMC in guar gum, and (5) quantify guar gum in LBG. Two FTIR methods were used: diffuse reflectance (DRIFT) on powdered gum samples added to KBr at 5%, w/w, and attenuated total reflectance (ATR) on 1%, w/w, gum solutions. Spectra were collected and then analyzed by multivariate statistical procedures (chemometrics). The DRIFT method provided better discrimination and quantitative results than the ATR method. Canonical variate analysis (CVA) of DRIFT spectra (1200-700 cm(-1)) was able to classify LBG with various M/G ratios, pure galactomannans, and pure versus mixtures of gums with 100% accuracy. Quantification of an individual gum in gum mixtures (0.5-15%, w/w) was possible using partial least-squares (PLS) analysis of DRIFT spectra with R2 > 0.93 and using this approach for quantifying guar gum added to LBG resulted in an R2 > 0.99, RMSEC = 0.29, and RMSEP = 3.31. Therefore, the DRIFT FTIR method could be a useful analytical tool for quality control of select gums and gum mixtures used in the food industry.     

柑桔黄龙病近红外光谱无损检测

为探讨快速无损检测柑桔黄龙病的可行性,应用近红外光谱技术结合机器学习方法进行研究。在4000~9000cm-1光谱范围内,采集黄龙病、缺素和健康3类叶片样本的近红外光谱。采用一阶导数、平滑和多元散色校正组合的光谱预处理方法,消除光谱的基线漂移和散射效应。分别对偏最小二乘判别模型(PLS-DA)的主成分因子数和最小二乘支持向量机(LS-SVM)的输入变量数量、核函数类型及其参数进行了优化,建立了PLS-DA和LS-SVM模型。采用预测集样本,评价模型的预测能力,经比较,采用11个主成分得分向量为输入、线性核函数和惩罚因子为2.25的LS-SVM模型预测效果最佳,模型误判率为0。结果表明采用近红外光谱技术结合最小二乘支持向量机进行柑桔黄龙病无损检测是可行的。     

Detection of sugar adulterants in apple juice using fourier transform infrared spectroscopy and chemometrics

Fourier transform infrared spectroscopy and attenuated total reflection sampling have been used to detect adulteration of single strength apple juice samples. The sample set comprised 224 authentic apple juices and 480 adulterated samples. Adulterants used included partially inverted cane syrup (PICS), beet sucrose (BS), high fructose corn syrup (HFCS), and a synthetic solution of fructose, glucose, and sucrose (FGS). Adulteration was carried out on individual apple juice samples at levels of 10, 20, 30, and 40% w/w. Spectral data were compressed by principal component analysis and analyzed using k-nearest neighbors and partial least squares regression techniques. Prediction results for the best classification models achieved an overall (authentic plus adulterated) correct classification rate of 96.5, 93.9, 92.2, and 82.4% for PICS, BS, HFCS, and FGS adulterants, respectively. This method shows promise as a rapid screening technique for the detection of a broad range of potential adulterants in apple juice.     

茶叶咖啡碱近红外光谱模型简化方法

该文以茶叶为研究对象,以近红外光谱分析技术快速检测茶叶中的咖啡碱含量为目的,采用一种小波包分析-移动窗口偏最小二乘法（WPA-MWPLS）的处理光谱数据方法,即利用小波包精细的多层分解功能扣除背景、降低噪声的影响,利用移动窗口偏最小二乘法（MWPLS）挑选与茶叶中咖啡碱相关性较大的波数区间使用偏最小二乘法建立校正模型。与只经过Savitzky–Golay预处理后直接利用PLS所建模型相比,采用小波包分析-移动窗口偏最小二乘法使得预测相关系数R由0.9170提高到了0.9625;预测均方差RESEP由0.3071下降为0.2463。该结果表明：该方法具有预处理简单、优选参数和建模变量少等特点,能在很大程度上简化建模过程、提高建模和分析速度。     

大米胶稠度近红外光谱分析数学模型的建立

胶稠度是评价大米蒸煮食用品质的重要指标之一。研究了运用近红外光谱分析技术检测大米胶稠度的测试原理，对60个样品的光谱数据用偏最小二乘法(PLS)建立了测定大米胶稠度的数学模型，其回判结果与化学分析值之间的相关系数为0.95，建模标准差为0.66；用41个样品对建立的数学模型进行了交叉验证，其检测结果与用标准化学分析方法测得结果的相关系数达0.92，预测标准差为0.78。试验证明，可以利用近红外光谱分析技术对大米胶稠度进行快速检测。     

近红外光谱快速检测马铃薯全粉还原糖

还原糖含量是评价马铃薯全粉品质的重要指标之一,该文研究基于近红外光谱技术结合最小二乘支持向量机（least squares support vector machine,LSSVM）算法的马铃薯全粉还原糖含量非线性数学模型。采用移动窗口偏最小二乘法（moving windows partial least square,MWPLS）和连续投影算法（successive projections algorithm,SPA）组合方法筛选出20个特征变量,作为LSSVM的输入向量。优化径向基函数（radial basis function,RBF）的惩罚因子和核参数,训练LSSVM校正模型。经比较,LSSVM校正模型预测结果最优,预测相关系数为0.984,预测标准差为0.223%,相对分析误差（standard deviation ratio,SDR）为5.62。结果表明：近红外光谱结合LSSVM算法提高了马铃薯全粉还原糖含量的预测精度。     

Application of multibounce attenuated total reflectance fourier transform infrared spectroscopy and chemometrics for determination of aspartame in soft drinks

Aspartame is a low-calorie sweetener commonly used in soft drinks; however, the maximum usage dose is limited by the U.S. Food and Drug Administration. Fourier transform infrared (FTIR) spectroscopy with attenuated total reflectance sampling accessory and partial least-squares regression (PLS) was used for rapid determination of aspartame in soft drinks. On the basis of spectral characterization, the highest R2 value, and lowest PRESS value, the spectral region between 1600 and 1900 cm(-1) was selected for quantitative estimation of aspartame. The potential of FTIR spectroscopy for aspartame quantification was examined and validated by the conventional HPLC method. Using the FTIR method, aspartame contents in four selected carbonated diet soft drinks were found to average from 0.43 to 0.50 mg/mL with prediction errors ranging from 2.4 to 5.7% when compared with HPLC measurements. The developed method also showed a high degree of accuracy because real samples were used for calibration, thus minimizing potential interference errors. The FTIR method developed can be suitably used for routine quality control analysis of aspartame in the beverage-manufacturing sector.     

基于变量选择的蚕茧茧层量可见-近红外光谱无损检测

以蚕茧茧层量为研究对象,研究了基于可见-近红外光谱技术的蚕茧茧层量无损检测方法。采用最小二乘支持向量机（least square-support vector machine,LS-SVM）建立可见-近红外光谱模型。采用无信息变量消除算法（uninformative variable elimination, UVE）与连续投影算法（successive projections algorithm, SPA）相结合选取光谱有效波长。结果表明,基于UVE-SPA法进行变量选择,最终将原始光谱的600个光谱变量减少到了8个（673,937,963,982,989,992,995和1 008 nm）。基于此8个变量建立的LS-SVM模型得到了预测集的确定系数（Rp2）为0.5354,误差均方根（RMSEP）为0.0373的预测结果。表明可见-近红外光谱可以用于对蚕茧的茧层量进行无损检测,同时UVE-SPA是一种有效的光谱变量选择方法。     

Dietary supplement oil classification and detection of adulteration using Fourier transform infrared spectroscopy

Fourier transform infrared spectroscopy (FT-IR) methods and common chemometric techniques [including discriminant analysis (DA), Mahalanobis distances, and Cooman plots] were used to classify various types of dietary supplement oils (DSO) and less expensive, common food oils. Rapid FT-IR methods were then developed to detect adulteration of DSO with select common food oils. Spectra of 14 types of DSO and 5 types of common food oils were collected with an FT-IR equipped with a ZnSe attenuated total reflectance cell and a mercury cadmium telluride A detector. Classification of DSO and some common food oils was achieved successfully using FT-IR and chemometrics. Select DSO were adulterated (2-20% v/v) with the common food oils that had the closest Mahalanobis distance to them in a Cooman plot based on the DA analysis, and data were also analyzed using a partial least-squares (PLS) method. The detection limit for the adulteration of DSO was 2% v/v. Standard curves to determine the adulterant concentration in DSO were also obtained using PLS with correlation coefficients of >0.9. The approach of using FT-IR in combination with chemometric analyses was successful in classifying oils and detecting adulteration of DSO.     

Classification of smoke tainted wines using mid-infrared spectroscopy and chemometrics

In this study, the suitability of mid-infrared (MIR) spectroscopy, combined with principal component analysis (PCA) and linear discriminant analysis (LDA), was evaluated as a rapid analytical technique to identify smoke tainted wines. Control (i.e., unsmoked) and smoke-affected wines (260 in total) from experimental and commercial sources were analyzed by MIR spectroscopy and chemometrics. The concentrations of guaiacol and 4-methylguaiacol were also determined using gas chromatography-mass spectrometry (GC-MS), as markers of smoke taint. LDA models correctly classified 61% of control wines and 70% of smoke-affected wines. Classification rates were found to be influenced by the extent of smoke taint (based on GC-MS and informal sensory assessment), as well as qualitative differences in wine composition due to grape variety and oak maturation. Overall, the potential application of MIR spectroscopy combined with chemometrics as a rapid analytical technique for screening smoke-affected wines was demonstrated.     

基于红外光谱技术的蜂蜜理化性质快速检测

该论文以116个蜂蜜样品为对象，考察蜂蜜理化指标间的相关性，并采用红外光谱技术结合偏最小二乘回归法建立快速定量模型，探讨模型对蜂蜜理化性质指标的定量能力，比较近、中红外光谱在定量检测中的能力，从数据层融合角度考究光谱融合对定量精度的提升。主要研究结论如下：蜂蜜的部分理化性质间具相互关联性，色差、电导率和pH两两呈正相关，pH和可滴定酸，水分与黏度之间彼此呈负相关；近红外光谱技术（near-infrared spectrum，NIR）和中红外光谱技术（mid-infrared spectrum，MIR）对果糖、葡萄糖、还原糖、果糖/葡萄糖、水分、黏度、pH和色差具有良好的定量分析能力（R²＞0.9），对电导率、蔗糖、麦芽糖和可滴定酸的精度和模型相关系数尚可接受；二者单独对淀粉酶值、脯氨酸的定量结果较差，通过数据融合后，脯氨酸精度有所提升（Rc 0.825，Rp 0.664，RMSEC 38.68，RMSEP 49.57），淀粉酶值无优化（Rc 0.799，Rp 0.695，RMSEC 2.57，RMSEP 3.02）。MIR对糖的定量分析精度略优于NIR。研究证明将近、中红外光谱用于蜂蜜部分理化指标的快速定量是可行的，数据融合对模型产生积极影响，但仍存在很多理论和算法问题需要解决。     

Discrimination of irradiated starch gels using FT-Raman spectroscopy and chemometrics

The effects of gamma-irradiation on starch gels were characterized at the molecular level by Fourier transform (FT) Raman spectroscopy. Starches from five different sources were gelatinized and irradiated at 3, 5, and 10 kGy using a Co60 gamma-irradiator. Gamma-irradiation effects on starch gels were noted by the C-H stretch (2800-3000 cm(-1)) and O-H stretch (3000-3600 cm(-1)) and bend (1600-1800 cm(-1)) regions of the FT-Raman spectra. FT-Raman molecular fingerprints obtained through spectral analyses were used for discrimination of the gels based on the extent of irradiation by means of two different pattern-recognition techniques: canonical variate analysis (CVA) and soft modeling of class analogy (SIMCA). A complete discrimination of irradiated starches was attained using a hybrid partial least-squares (PLS) and CVA model, using the spectral variations in the C-H stretch and O-H stretch and bend regions of FT-Raman spectra. Using the same spectral regions, SIMCA predicted 84% of samples correctly.     

近红外光谱技术在牛奶及乳制品分析中的应用研究

近红外光谱作为一种新型的分析检测技术,正在获得越来越广泛的应用.本文阐述了近红外光谱技术应用于农产品检测的基本原理和具体检测步骤.从建模算法、谱图预处理和检测系统结构等方面综述了国内外近红外光谱技术在牛奶及乳制品中的最新研究进展.对目前研究中存在的问题进行了分析,对以后进一步的研究进行了展望,并提出了一些建议.     

不同类型近红外模型在苹果汁检测中的应用

为了探讨近红外光谱分析中模型的稳定性和适应范围,该研究建立了4种模型（局部模型、转移的局部模型、全局模型、优化全局模型）,分别对5种鲜榨苹果汁的3种品质参数（可溶性固形物SSC、pH值、电导率）进行分析。在对苹果汁品质的分析中,SSC的预测准确度较高（r=0.93,相对预测标准差3.7%）;电导率与近红外光谱之间间接相关,其预测准确度较低（r=0.84,相对预测标准差12.7%）;pH全局模型的相关系数较高（r=0.94）,但其分辨能力较差（其局部模型的参考值标准偏差与预测标准差的比值为1.1）。采用相对预测标准差、参考值标准偏差与预测标准差的比值等参数来评价各种模型的稳定性和适应范围,通过对4种近红外模型的稳定性、适配性及准确度的比较,发现模型的适应范围对预测结果的影响很大,对不同的分析要求应该建立不同的模型,具体为：采用单一品种建立的局部模型准确度高,但稳定性较差,一般只适用于本品种样品的预测。通过在现有局部模型中加入少数几个待测品种的样本重新建立模型,可以实现模型的转移,使之适用于其它品种样品的预测。采用多个品种建立的全局模型稳定性高,其准确度较之局部模型稍有下降。通过挑选有代表性的样品来建立优化全局模型,可以在保持模型性能的同时降低建模工作量,是值得推荐的建模方法。     

近红外光谱结合化学计量学方法检测蜂蜜产地

为了实现蜂蜜产地的快速判别,应用近红外光谱结合化学计量学方法对蜂蜜产地进行了判别分析。kennard-Stone法划分训练集和预测集。光谱用一阶导数加自归一化预处理后,再用小波变换（WT）进行压缩和滤噪。结合滤波后光谱信息,分别用径向基神经网络（RBFNN）和偏最小二乘-线性判别分析（PLS-LDA）建立了苹果蜜产地和油菜蜜产地的判别模型。对不同小波基和分解尺度进行了讨论。对苹果蜜,WT-RBFNN模型和WT-PLS-LDA模型都是小波基为db1、分解尺度为2时的预测精度较好,都为96.2%。对油菜蜜：WT-RBFNN模型在小波基为db4和分解尺度为1时,预测精度较好,为85.7%;WT-PLS-LDA模型在小波基为db9、分解尺度也为1时,预测精度较好,为90.5%。研究表明：WT结合线性的PLS-LDA建模比WT结合非线性的RBFNN建模更适于蜂蜜产地判别;近红外光谱技术具有快速判别蜂蜜产地的潜力。     

Mid-infrared spectroscopy and chemometrics for the authentication of meat products.

Mid-infrared (MIR) spectroscopy is used to address certain issues connected with the authentication of beef and ox kidney and liver: is it possible to distinguish muscle from offal tissue; does the condition, cut of meat, or type of offal influence the distinction; can pure minced beef be distinguished from that adulterated with offal? Using partial least squares (PLS) and canonical variate analysis, predictive models are developed to identify MIR spectra of beef, kidney, and liver. Using modified SIMCA, the pure beef specimens are modeled as a single class; this model identifies spectra of unadulterated beef as such, with an acceptable error rate, while rejecting spectra of specimens containing 10-100% w/w kidney or liver. Finally, PLS regressions are performed to quantify the amount of added offal. The prediction errors obtained (+/-4.8 and +/-4.0% w/w, respectively, for the kidney and liver calibrations) are commensurate with the detection limits suggested by the SIMCA analysis.     

基于近红外光谱的活体植物叶片水分检测仪器

在近红外光谱区,采用超低功耗单片机MSP430及新型的光频转换芯片TSL230,研制快速无损、可现场测定植物叶片水分含量的透射式检测仪器。仪器整体由信号采集系统、单片机系统及相应的软件支撑、校正模型组成。其信号采集系统采用近红外LED光源,890 nm和980 nm的窄带干涉滤光片和光频转换芯片。光频转换芯片的使用简化了信号采集电路,减少了噪声的引入。该文介绍了该仪器的硬件设计、软件设计,对紫荆叶片水分含量的建模及预测。预测结果与水分真实值基本一致,二者相关系数为0.900。仪器具有较高的重复性、稳定性和可靠性,与其他水分测量仪相比,该仪器具有体积小、结构简单、重量轻、超低功耗、抗干扰等特点。试验结果表明本仪器可在田间现场对植物叶片水分含量进行快速无损检测。     

Authentication of organic feed by near-infrared spectroscopy combined with chemometrics: a feasibility study

Organic products tend to retail at a higher price than their conventional counterparts, which makes them susceptible to fraud. In this study we evaluate the application of near-infrared spectroscopy (NIRS) as a rapid, cost-effective method to verify the organic identity of feed for laying hens. For this purpose a total of 36 organic and 60 conventional feed samples from The Netherlands were measured by NIRS. A binary classification model (organic vs conventional feed) was developed using partial least squares discriminant analysis. Models were developed using five different data preprocessing techniques, which were externally validated by a stratified random resampling strategy using 1000 realizations. Spectral regions related to the protein and fat content were among the most important ones for the classification model. The models based on data preprocessed using direct orthogonal signal correction (DOSC), standard normal variate (SNV), and first and second derivatives provided the most successful results in terms of median sensitivity (0.91 in external validation) and median specificity (1.00 for external validation of SNV models and 0.94 for DOSC and first and second derivative models). A previously developed model, which was based on fatty acid fingerprinting of the same set of feed samples, provided a higher sensitivity (1.00). This shows that the NIRS-based approach provides a rapid and low-cost screening tool, whereas the fatty acid fingerprinting model can be used for further confirmation of the organic identity of feed samples for laying hens. These methods provide additional assurance to the administrative controls currently conducted in the organic feed sector.     

黄桃表面缺陷和可溶性固形物光谱同时在线检测

表面缺陷和可溶性固形物是评价黄桃品质的重要指标,采用可见/近红外漫透射光谱技术,探讨黄桃表面缺陷与可溶性固形物同时在线检测的可行性。在运动速度为5个/s、积分时间100 ms、光照强度1 000 W的条件下采集黄桃表面缺陷果与正常果的近红外漫透射光谱。对比分析了同一个黄桃样品损伤前后的光谱特征,建立了黄桃的最小二乘支持向相机判别模型与偏最小二乘判别模型。同时建立了黄桃可溶性固形物偏最小二乘回归模型并采用连续投影算法对模型进行优化,研究了表面缺陷果对黄桃可溶性固形物检测模型精度的影响,最终实现了黄桃表面缺陷与可溶性固形物同时在线检测。采用未参与建模的样品来评价模型的在线分选的准确性,其中表面缺陷果的正确判断率为100%,可溶性固形物分选准确率达到93%。试验结果表明:黄桃表面缺陷与可溶性固形物同时在线检测是可行的,研究可为黄桃在线分选提供技术参考和理论依据。