Rapid classification of perfumes by extractive electrospray ionization mass spectrometry (EESI-MS)

Extractive electrospray ionization mass spectrometry (EESI-MS) was applied to rapid fingerprinting of various perfumes for quality classification. Unique EESI-MS fingerprints of ten famous brands were obtained. This technique was shown to be applicable to rapid forgery detection on the example of an authentic and a counterfeit 'Miss Dior' fragrance by Christian Dior. We believe that the high throughput and simplicity of this sample-preparation-free method can be advantageous in the perfume industry, for instance when applied to online quality control.     

Quality control and discrimination of pericarpium citri reticulatae and pericarpium citri reticulatae viride based on high-performance liquid chromatographic fingerprints and multivariate statistical analysis

High-performance liquid chromatographic (HPLC) fingerprints of Pericarpium Citri Reticulatae (PCR) and Pericarpium Citri Reticulatae Viride (PCRV) were firstly measured for deliberately collected 39 authentic samples and 21 commercial samples. Both correlation coefficients of similarity for chromatograms and absolute peak areas of characteristic compounds were calculated for quantitative expression of the HPLC fingerprints. After principal component analysis (PCA) successfully distinguished the ‘mixed peels’ samples from authentic samples, partial least squares-linear discrimination analysis (PLS-LDA) was then effectively applied to class separation between authentic PCR and PCRV. Furthermore, the unequivocally determined compounds, hesperidin, nobiletin and tangeretin, were screened out by loadings plots of PCA and PLS-LDA. The results indicated that they could be used as chemical markers for discrimination among different groups of samples. The proposed method shows an efficient strategy for quality control of PCR and PCRV, which cannot only distinguish the ‘mixed peels’ but also discriminate authentic PCR and PCRV. This method has potential perspective for quality control of traditional Chinese medicine (TCM).     

Multicomponent analytical methodology to control phthalates, synthetic musks, fragrance allergens and preservatives in perfumes

A simple, fast, robust and reliable multicomponent analytical method applicable in control laboratories with a high throughput level has been developed to analyze commercial brands of perfumes. Contents of 52 cosmetic ingredients belonging to different chemical families can be determined in a single run. Instrumental linearity, precision of the method and recovery studies in real samples showed excellent results, so that quantification by external calibration can be effectively applied. Relevant limits of detection and quantification were obtained for all the targets considered, far below the legal requirements and amply adequate for its accurate analytical control.A survey of 70 commercial perfumes and colognes has been performed, in order to verify whether these products complied with the recent changes in European legislation: regarding the maxima allowed concentrations of the ingredients and/or ingredient labelling. All samples contained some of the target ingredients. Several samples do not comply with the regulations concerning the presence of phthalates. Musks data confirmed the trend about the replacement of nitromusks by polycyclic musks; as well as the noticeable introduction of macrocyclic musks in the perfumes composition. The prohibited musk moskene has been detected in one sample in an appreciable concentration. The average number of fragrance allergens is twelve per sample; their presence must be indicated in the list of ingredients when its concentration exceeds the 0.001%, but values higher than 1% have been found in some samples. Preservatives data show that parabens, although ubiquitous in other cosmetic products, are not widely used in perfumery. In contrast, the presence of BHT is indeed widespread. The degree of compliance with the European Regulation on the labelling has been evaluated in a subset of samples, and only about the 38% of the perfumes were properly labelled for the allergens tested.     

Electrospray ionization mass spectrometry fingerprinting of beer

After just simple degassing, dilution, pH adjustment and direct flow injection, characteristic fingerprint spectra of beer samples have been obtained by fast (few seconds) electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes. A total of 29 samples belonging to the two main beer types (lagers and ales) and several beer subtypes from USA, Europe and Brazil could be clearly divided into three groups both by simple visual inspection of their ESI(+)-MS and ESI(-)-MS fingerprints as well as by chemometric treatment of the MS data. Diagnostic ions with contrasting relative abundances in both the positive and negative ion modes allow classification of beers into three major types: P = pale (light) colored (pilsener, pale ale), D = dark colored (bock, stout, porter, mild ale) and M = malt beer. For M beers, samples of a dark and artificially sweetened caramel beer produced in Brazil and known as Malzbiers were used. ESI-MS/MS on these diagnostic beer cations and anions, most of which are characterized as arising from ionization of simple sugars, oligosaccharides, and iso-alpha-acids, yield characteristic tandem mass spectra adding a second and optional MS dimension for improved selectivity for beer characterization by fingerprinting. Direct ESI-MS or ESI-MS/MS analysis can therefore provide fast and reliable fingerprinting characterization of beers, distinguishing between types with different chemical compositions. Other unusual polar components, impurities or additives, as well as fermentation defects or degradation products, could eventually be detected, making the technique promising for beer quality control.     

The Famous Amazonian Rosewood Essential Oil: Characterization and Adulteration Monitoring by Electrospray Ionization Mass Spectrometry Fingerprinting

Direct infusion of samples via electrospray ionization mass spectrometry (ESI-MS) is shown to characterize unequivocally genuine samples of Amazonian Aniba rosaeodora Ducke (Rosewood) essential oils obtained either from the wood or leafs. The ESI-MS also distinguishes the essential oils from synthetic linalool; hence, adulteration by the synthetic oil is also clearly detected. The analysis requires no pretreatment or preseparation, and the most polar components of the essential oil are extracted with an acidified 1:1 methanol/water solution. This simple extract is then analyzed by direct infusion ESI-MS in the positive ion mode, which provides characteristic fingerprintings of the sample composition. The ESI-MS fingerprinting can be used therefore as a simple and fast (few minutes) method for authenticity and quality control of this famous Amazonian essential oil.     

Electrospray ionization mass spectrometry fingerprinting of whisky: immediate proof of origin and authenticity

Authentic samples of whisky produced in Scotland and USA and counterfeit whisky samples commercialized in Brazil have been directly submitted to electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes to assess the potential of this technique for simple and rapid quality control and proof of authenticity of whisky samples. ESI in the negative ion mode yields the most characteristic whisky fingerprinting mass spectra in just a few seconds by direct infusion of the samples, detecting the most polar or acidic components of each sample in their deprotonated anionic forms. No pre-treatment of the sample, such as extraction or derivatization or even dilution, is required. The analysis of the ESI(-)-MS data both by simple visual inspection but more particularly by chemometric data treatment enables separation of the whisky samples into three unequivocally distinct groups: Scotch, American and counterfeit whisky, whereas single malt and blended Scotch whiskies are also distinguished to some extent. As indicated by ESI-MS/MS analysis, the diagnostic anions are simple sugars, disaccharides and phenolic compounds. Direct infusion ESI-MS therefore provides immediate chemical fingerprinting of whisky samples for type, origin and quality control, as demonstrated herein for American, Scottish and counterfeit samples, whereas ESI-MS/MS analysis of diagnostic ions adds a second dimension of fingerprinting characterization when improved selectivity is desired.     

New approach on similarity analysis of chromatographic fingerprint of herbal medicine

A new approach to the construction and similarity analysis of chromatographic fingerprint for herbal medicine is presented in this paper. Samples of chuanxiong, a herbal medicine for headache, from three producing areas of China were used to evaluate the utility of this study. The samples were analyzed with high-performance liquid chromatography (HPLC) and the peak areas of the chromatograms were used to construct the fingerprints of the herbal medicines. A vector of differences was defined between the two fingerprints. The scalar mean of the difference vector was taken as a statistic and both the t-test and Bayesian hypothesis testing were implemented to provide a one-to-one comparison of the fingerprints. Compared with principal component analysis (PCA), correlation coefficient and vector cosine, the new method offers a better differentiation of the similarity or difference between the fingerprints from same sample of chuanxiong. When the new method was used in the similarity analysis of the fingerprints of chuanxiong from different production areas, a clear-cut signature was obtained that reveals the significant difference between them.     

Electrospray ionization mass spectrometry fingerprinting of propolis

Crude ethanolic extracts of propolis, a natural resin, have been directly analysed using electrospray ionization mass (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) in the negative ion mode. European, North American and African samples have been analyzed, but emphasis has been given to Brazilian propolis which displays diverse and region-dependent chemical composition. ESI-MS provides characteristic fingerprint mass spectra, with propolis samples being divided into well-defined groups directly related to their geographical origins. Chemometric multivariate analysis statistically demonstrates the reliability of the ESI-MS fingerprinting method for propolis. On-line ESI-MS/MS tandem mass spectrometry of characteristic [M - H](-) ion markers provides an additional dimension of fingerprinting selectivity, while structurally characterizing the ESI-MS marker components of propolis. By comparison with standards, eight such markers have been identified: para-coumaric acid, 3-methoxy-4-hydroxycinnamaldehyde, 2,2-dimethyl-6-carboxyethenyl-2H-1-benzopyran, 3-prenyl-4-hydroxycinnamic acid, chrysin, pinocembrin, 3,5-diprenyl-4-hydroxycinnamic acid and dicaffeoylquinic acid. The negative mode ESI-MS fingerprinting method is capable of discerning distinct composition patterns to typify, to screen the sample origin and to reveal characteristic details of the more polar and acidic chemical components of propolis samples from different regions of the world.     

Extra virgin (EV) and ordinary (ON) olive oils: distinction and detection of adulteration (EV with ON) as determined by direct infusion electrospray ionization mass spectrometry and chemometric approaches

Extra virgin (EV), the finest and most expensive among all the olive oil grades, is often adulterated by the cheapest and lowest quality ordinary (ON) olive oil. A new methodology is described herein that provides a simple, rapid, and accurate way not only to detect such type of adulteration, but also to distinguish between these olive oil grades (EV and ON). This approach is based on the application of direct infusion electrospray ionization mass spectrometry in the positive ion mode, ESI(+)‐MS, followed by the treatment of the MS data via exploratory statistical approaches, PCA (principal component analysis) and HCA (hierarchical clustering analysis). Ten distinct brands of each EV and ON olive oil, acquired at local stores, were analyzed by ESI(+)‐MS and the results from HCA and PCA clearly indicated the formation of two distinct groups related to these two categories. For the adulteration study, one brand of each olive oil grade (EV and ON) was selected. The counterfeit samples (a total of 20) were then prepared by adding assorted proportions, from 1 to 20% w/w, with increments of 1% w/w, of the ON to the EV olive oil. The PCA and HCA methodologies, applied to the ESI(+)‐MS data from the counterfeit (20) and authentic (10) EV samples, were able to readily detect adulteration, even at levels as low as 1% w/w. Copyright © 2010 John Wiley & Sons, Ltd.     

Discrimination of Chinese traditional soy sauces based on their physico-chemical properties

This work aimed to classify the categories (produced by different processes) and brands (obtained from different geographical origins) of Chinese soy sauces. Nine variables of physico-chemical properties (density, pH, dry matter, ashes, electric conductivity, amino nitrogen, salt, viscosity and total acidity) of 53 soy sauce samples were measured. The measured data was submitted to such pattern recognition as cluster analysis (CA), principal component analysis (PCA), discrimination partial least squares (DPLS), linear discrimination analysis (LDA) and K-nearest neighbor (KNN) to evaluate the data patterns and the possibility of differentiating Chinese soy sauces between different categories and brands. Two clusters corresponding to the two categories were obtained, and each cluster was divided into three subsets corresponding to three brands by the CA method. The variables for LDA and KNN were selected by the Fisher F-ratio approach. The prediction ability of all classifiers was evaluated by cross-validation. For the three supervised discrimination analyses, LDA and KNN gave 100% predications according to the sample category and brand.     

Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry

Pilocarpus microphyllus (Rutaceae), popularly known as jaborandi, is the only commercial source of an imidazole alkaloid named pilocarpine. In the present study, the variation in the profile of imidazole alkaloids in different seasons and in different parts of the P. microphyllus plant during the summer was analyzed by electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS]. The fingerprints of these extracts repeatedly presented similar ions which were mass-selected and studied by tandem mass spectrometry (ESI-MS/MS and ESI-MS/MS/MS) and high-resolution mass spectrometry, resulting in the characterization of eight imidazole alkaloids. The data from the ESI(+)-MS fingerprints were analyzed by principal component analysis (PCA), showing that pilocarpine was present mainly in the summer, whereas in the autumn mainly pilosine and winter anhydropilosine were found. Three alkaloids, reported for the first time in extracts of P. microphyllus, were found. Analysis of the distribution of alkaloids in different parts of the plant during the summer showed that, although pilocarpine was present throughout the plant, 13-nor-8(11)-dihydropilocarpine was found mainly in the stem, pilosine and anhydropilosine were present mainly in the intermediary leaves, and the three new alkaloids were mainly found in the leaflets and petioles. Based on the dissociation patterns of these alkaloids, we observed that there were three structurally related groups of alkaloids differing in their distribution in the plant tissues and responding differently to seasonal variations. These results also indicate that these three groups of alkaloids could belong to intermediate, parallel or competitive pathways for pilocarpine formation biosynthesis.     

A fast and reliable method for the quantitative determination of benzimidazoles and metabolites in milk by LC-MS/MS with on-line sample treatment

A method to detect the presence of common wheat in durum wheat flour samples was developed and tested. Flour samples, or ground wheat samples, were digested by pepsin and chymotrypsin, and the peptide mixture obtained was analyzed by LC/ESI-MS and LC/ESI-MS/MS, which led to the identification of two marker peptides. One peptide was coded only in the DD genome, and thus present only in common wheat; the second was present in all wheat samples (both common and durum), so it was used as marker of the total wheat content. The ratio of the chromatographic areas of these two peptides, as determined by LC/ESI-MS, was related to the proportion of common wheat in the sample using a calibration curve that was constructed with standards of known composition. The proportions of common wheat in samples obtained by mixing different common and durum wheat varieties were accurately determined by this method. Finally, the method was applied in a survey of several durum wheat flour brands present on the Italian market. The results of the survey revealed that contamination of durum wheat flour with common wheat is commonplace.     

Study of spectral analytical data using fingerprints and scaled similarity measurements

A new chemoinformatic model has been developed for enlarging the differences between spectra and applied to differentiation of wines according to the criteria grape origin and variety and ageing process. The model is based on generation of fingerprints from normalised spectra, using empirical parameters and a set of 120 samples. After generation of the fingerprints, similarity matrixes were built on the basis of the Tanimoto similarity index between the fingerprints of the samples. Calculation of the Tanimoto index was modified to adapt the index to the characteristics of the analytical measurements. Thus, scaling factors taking into account pattern fingerprints generated from a group of samples with common characteristics were used. In addition, a modified expression for calculating the Tanimoto index was employed. Principal-components analysis (PCA) and soft independent modelling of class analogy (SIMCA) were applied to the similarity matrixes. The results obtained are discussed as a function of the normalisation method employed, the empirical factor used in generation of the fingerprints, and selection of samples for building the pattern fingerprint, etc. Finally, results from differentiation of wines are compared with those obtained by applying PCA to the unprocessed spectra as stated by the proposed model.     

基于高光谱成像结合分光光度技术的喷墨打印墨水种类鉴别方法

在法庭科学实践中,往往需要通过对文件中字迹墨水的成分分析来精确地判定检材和样本文件的同一性。利用高光谱成像和分光光度技术结合化学计量法,提出了一种对喷墨打印墨水分类的方法。采集14台不同品牌、型号的四色喷墨打印墨水高光谱数据和色度值。计算出平均色度值后进行PCA降维处理和K-Means聚类分析,将样品初步分类。之后应用LightGBM模型、XGBoost模型和SVM模型共三种分类模型,以1:4的比例确定测试集和训练集,对聚类分析结果中每一类别的样品进行逐一鉴别。结果表明,LightGBM和XGBoost对四色样品的分类精度都能达到95%以上,SVM的分类精度为100%。提出的方法能够做到无损、准确、快速地将不同品牌乃至型号的喷墨打印墨水进行区分。     

Mass spectroscopic fingerprinting method for differentiation between Scutellaria lateriflora and the germander (Teucrium canadense and T. chamaedrys) species

Scutellaria lateriflora, commonly known as skullcap, is used as an ingredient in numerous herbal products. However, it has been occasionally adulterated/contaminated with Teucrium canadense and T. chamaedrys, commonly known as germander, which contain hepatotoxic diterpenes. Due to the morphological similarities between the two genera, analytical methodologies to distinguish authentic S. lateriflora from the Teucrium species are needed to ensure public safety. In this study, a direct-injection electrospray ionization/MS method was used to generate spectral fingerprints of extracts from 21 skullcap and germander samples at a rate of 90 s/sample. MS fingerprints were analyzed by principal component analysis. The newly developed method offers a rapid and easy way to differentiate between skullcap and germander samples.     

Geographical classification of Epimedium based on HPLC fingerprint analysis combined with multi‐ingredients quantitative analysis

A reliable and comprehensive method for identifying the origin and assessing the quality of Epimedium has been developed. The method is based on analysis of HPLC fingerprints, combined with similarity analysis, hierarchical cluster analysis (HCA), principal component analysis (PCA) and multi‐ingredient quantitative analysis. Nineteen batches of Epimedium , collected from different areas in the western regions of China, were used to establish the fingerprints and 18 peaks were selected for the analysis. Similarity analysis, HCA and PCA all classified the 19 areas into three groups. Simultaneous quantification of the five major bioactive ingredients in the Epimedium samples was also carried out to confirm the consistency of the quality tests. These methods were successfully used to identify the geographical origin of the Epimedium samples and to evaluate their quality.     

Comprehensive quality evaluation of the lateral root of Aconitum carmichaelii Debx. (Fuzi): Simultaneous determination of nine alkaloids and chemical fingerprinting coupled with chemometric analysis

Amino alcohol alkaloids are the active components in the lateral root of Aconitum carmichaelii Debx. (Fuzi), and they have a variety of pharmacological activities. However, the chemical fingerprints of the ester alkaloids reported to date were mainly obtained from high‐performance liquid chromatography coupled with ultraviolet detection, and it is difficult to obtain information about amino alcohol alkaloids in Fuzi from such chromatograms. In this paper, a comprehensive fingerprinting method was established using high‐performance liquid chromatography coupled with an evaporative light‐scattering detector for the simultaneous quantitative analysis of both the amino alcohol alkaloids and ester alkaloids. A total of 42 samples of Fuzi from four production areas were analyzed by constructing high‐performance liquid chromatography fingerprints. Then, the quantitative results of the chemical fingerprints combined with chemometrics methods were employed to reveal the factors affecting the geo‐authentic Fuzi and to determine characteristic components that can be used to identify these samples. The results indicated distinct differences in the alkaloid contents among samples from the four regions; the geographical origin may be the primary factor affecting the geo‐authentic Fuzi, and 15 major components (including songorine, neoline, and hypaconitine, which were quantitatively determined) were found to be characteristic components for the discrimination of Fuzi samples from various regions. Neoline might be a critical component for identifying geo‐authentic Fuzi. This approach is convenient, reproducible and provides a promising method for the quality evaluation of Fuzi.     

Fast and Non-Destructive Profiling of Commercial Coffee Aroma under Three Conditions (Beans,Powder, and Brews) Using GC-IMS

The flavor of coffee can be affected by the preparation parameters. In this investigation, the flavor profiles of three coffee brands under three conditions (bean, powder, and brew) were analyzed by gas chromatography—ion mobility spectrometry (GC-IMS) and the electronic nose (E-nose). The flavor results were further studied using multiple factor analysis (MFA). A total of 117 peaks were identified in all coffee samples by GC-IMS, and the principal component analysis (PCA) showed these coffee samples could be grouped and separated. A total of 37 volatile organic compounds (VOCs) were selected as biomarkers to distinguish coffee samples, including 5 aldehydes, 10 ketones, 8 alcohols, 2 acids, 4 esters, 5 furans, and 3 other compounds. The comparison between E-nose and GC-IMS data using partial least squares regression (PLSR) and MFA showed GC-IMS could present very close sample spaces. Compared with E-nose, GC–IMS could not only be used to classify coffee samples in a very short time but also provide VOC bio-markers to discriminate coffee samples.     

Study of the feasibility of distinguishing cigarettes of different brands using an Adaboost algorithm and near-infrared spectroscopy

The feasibility of utilizing an Adaboost algorithm in conjuction with near-infrared (NIR) spectroscopy to automatically distinguish cigarettes of different brands was explored. Simple linear discriminant analysis (LDA) was used as the base algorithm to train all weak classifiers in Adaboost. Both principal component analysis (PCA) and its kernel version (kernel principal component analysis, KPCA) were used for feature extraction and were also compared to each other. The influence of the training set size on the final classification model was also investigated. Using a case study, it was demonstrated that Adaboost coupled with PCA or KPCA can obviously improve the ability to discriminate between samples that cannot be separated by a single linear classifier. However, in term of the overall performance, KPCA appears preferable to PCA for feature extraction, especially when the samples used for training are relatively small. The results also indicate that more training samples should be applied, if possible, in order to fully demonstrate the superiority of Adaboost. It seems that the use of an Adaboost algorithm in conjunction with NIR spectroscopy in combination with KPCA for feature extraction comprises a promising tool for distinguishing cigarettes of different brands, especially in situations where there is an obvious overlap between the NIR spectra afforded by cigarettes of different brands.     

表面解吸常压化学电离质谱法快速判别樟树化学型

采用表面解吸常压化学电离质谱(SDAPCI-MS)技术直接对5种化学型的樟树叶粉末片剂进行分析,获得其化学指纹谱图信息.采用主成分分析(PCA)、聚类分析(CA)和反向传输人工神经网络(BP-ANN)对谱图信息进行分析,获得各化学型樟树叶粉末片剂的特征质谱信息,进而对不同化学型样品进行判别.结果表明,在正离子模式下,SDAPCI-MS能快速获取樟树的化学指纹谱图;PCA分析中的PC1,PC2和PC3贡献率分别为79.9%,12.9%和4.2%,共计97.0%.SDAPCI-MS结合CA和BP-ANN测试样本准确率均为100%,能够快速、有效地判别出樟树化学型.