应用电子鼻判别西湖龙井茶香气品质

根据电子鼻工作原理与西湖龙井茶香气特征,探索利用电子鼻判别西湖龙井茶等级的方法。该研究提出顶空瓶内茶水直接混合的香气制备法,增强电子鼻响应信号、减少人为冲泡误差;合理选择电子鼻顶空进样及信号采集参数,提高香气指纹图谱信噪比;采用不同等级茶样循环交叉排列采集,增加传感器的适应性,剔除仪器系统误差;经校正集与预测集的样本划分,提高模型建立的可靠判别样本集。利用软独立建模分类法（SIMCA）建立不同等级西湖龙井茶判别模型,等级分类正确率高达95%以上,实现了西湖龙井茶的智能分等分级。     

Comparison of metal oxide-based electronic nose and mass spectrometry-based electronic nose for the prediction of red wine spoilage

Taints caused by Brettanomyces sp. spoilage are of concern to winemakers and consumers. Typically the taints are described as "barnyard", "sweaty saddle", and "Band-aid" when present in red wine at concentrations of several hundred micrograms per liter or more. The two main components of the taint are 4-ethylphenol (4EP) and 4-ethylguaiacol (4EG), which are metabolites produced by Brettanomyces yeasts. There is a need for a rapid instrumental method to quantify these compounds in wines. In this paper are compared two techniques, the metal oxide sensor-based electronic nose (MOS-Enose) and the mass spectrometry-based electronic nose (MS-Enose). Gas chromatography-mass spectrometry (GC-MS) was used for quantification and prediction purposes. Following ethanol removal, the limits of detection of a MOS-Enose were determined as 44 microg L(-1) for 4EP and 91 microg L(-1) for 4EG, using the SY/gCT sensor. These values are significantly lower than the reported human sensory thresholds. Partial least-squares (PLS) regression of electronic nose signals against known levels of 4EP and 4EG in 46 Australian red wines showed that the MOS-Enose was unable to identify "brett" spoilage reliably because of the response of the gas sensors to intersample variation in volatile compounds other than ethylphenols. Conversely, the MS-Enose was capable of reliably estimating concentrations of 4EP higher than 20 microg L(-1). Correlations (r2) of 0.97 and 0.98 were obtained between estimates of 4EP and 4EG concentrations with the concentrations determined by conventional GC-MS. It is concluded that, following ethanol removal, existing metal oxide sensors are sufficiently sensitive to detect brett taints in wine but lack the selectivity needed to perform this task when the aroma volatile background varies.     

Analysis of eight capsaicinoids in peppers and pepper-containing foods by high-performance liquid chromatography and liquid chromatography-mass spectrometry

Diverse procedures have been reported for the isolation and analysis of secondary metabolites called capsaicinoids, pungent compounds in the fruit of the Capsicum (Solanaceae) plant. To further improve the usefulness of high-performance liquid chromatography (HPLC), studies were carried out on the analysis of extracts containing up to eight of the following capsaicinoids: capsaicin, dihydrocapsaicin, homocapsaicin-I, homocapsaicin-II, homodihydrocapsaicin-I, homodihydrocapsaicin-II, nonivamide, and nordihydrocapsaicin. HPLC was optimized by defining effects on retention times of (a) the composition of the mobile phase (acetonitrile/0.5% formic acid in H2O), (b) the length of the Inertsil column, and (c) the capacity values (k) of the column packing. Identification was based on retention times and mass spectra of individual peaks. Quantification was based on the UV response at 280 nm in HPLC and recoveries from spiked samples. The method (limit of detection of approximately 15-30 ng) was successfully used to quantify capsaicinoid levels of parts of the pepper fruit (pericarp, placenta, seeds, and in the top, middle, and base parts of whole peppers) in 17 species of peppers and in 23 pepper-containing foods. The results demonstrate the usefulness of the method for the analysis of capsaicinoids ranging from approximately 0.5 to 3600 microg of capsaicin equiv/g of product. The water content of 12 fresh peppers ranged from 80.8 to 92.7%. The described freeze-drying, extraction, and analysis methods should be useful for assessing the distribution of capsaicinoids in the foods and in defining the roles of these biologically active compounds in the plant, the diet, and medicine.     

电子鼻在牦牛肉和牛肉猪肉识别中的应用

为了探索电子鼻对肉类掺假识别的可行性,利用电子鼻对牦牛肉、牛肉和猪肉样品进行了分析。通过对所获得的数据进行主成分分析（principal component analysis,PCA）、判别因子分析（discriminant factor analysis,DFA）和偏最小二乘回归分析（partial least-squares analysis,PLS）。结果表明：几种肉类在电子鼻传感器上有不同的特征性响应图谱,电子鼻能够有效识别猪、牛肉;同时电子鼻能够识别不同部位的牦牛肉和普通牛肉;但不能识别不同部位的猪肉。在牛肉馅中掺入不同比例的猪肉馅时,电子鼻也能进行识别。采用偏最小二乘回归分析对数据进行处理,电子鼻响应信号和猪肉馅掺入比例之间有很好的相关性（决定系数R2为0.9762）,PLS模型预测误差在1.27%～7.00%之间。试验证明电子鼻可用于肉类的识别。     

Difference in folate content of green and red sweet peppers (Capsicum annuum) determined by liquid chromatography-mass spectrometry

Folic acid (pteroylmonoglutamic acid) is used in enriched foods; however, very little folic acid occurs naturally in fruits and vegetables. For the U.S. Department of Agriculture's National Food and Nutrient Analysis Program, a number of fruits and vegetables have been assayed for endogenous folates, by a liquid chromatography-mass spectrometry method, to evaluate the accuracy of existing data for total folate determined by standard microbiological analysis. Folate in red and green sweet peppers (Capsicum annuum) differed notably (70.2 and 20.7 microg/100 g, respectively) and exceeded existing values determined by microbiological assay (18 and 11 microg/100 g, respectively). 5-Methyltetrahydrofolate was the predominant vitamer, but a significant amount of 5-formyltetrahydrolfolate and some 10-formylfolate were present. These findings may assist in making dietary recommendations or developing research diets related to folate. The data from this study have been used to update the folate values in release 19 of the USDA Nutrient Database for Standard Reference.     

基于电子鼻的番茄成熟度及贮藏时间评价的研究

该文探讨了采用电子鼻系统对不同成熟度的番茄进行评价和对不同成熟度番茄在贮藏期间气味变化的电子鼻检测进行了研究。在按颜色进行成熟度区分时,从主成分分析(PCA)和线性判别式分析(LDA)中可以得到,电子鼻可以较好地区分半熟期和成熟期、完熟期的番茄,但成熟期、完熟期的番茄有部分区域发生重叠。按坚实度指标对番茄成熟度进行重新评价后,分析显示电子鼻可以区分坚实度的差异,当采用PCA方法分析时,电子鼻可以100%地区分不同成熟度的番茄。对不同成熟度番茄在贮藏期间电子鼻检测的研究表明:成熟期的番茄在贮藏1～6d、7～11d、14～17d之间可以较好地进行区分;完熟期的番茄采用LDA法在1～5d、6～11d、14～17d之间可以较好地进行区分。     

基于热裂解和电子鼻的土壤全氮检测方法及特征优化

土壤氮是作物生长发育所必需的营养元素,也是衡量土壤肥力特征的重要指标.为快捷准确测定土壤全氮含量,该研究提出了一种基于热裂解和电子鼻的土壤全氮含量检测方法.采用10种不同类型的气体传感器构建传感器阵列,并对其进行了不同浓度甲烷、氯乙烯和氨气等标准气体的响应测试试验.使用马弗炉裂解土壤样本得到裂解气体,采用气体传感器阵列...     

Flavor characterization of ripened cod roe by gas chromatography, sensory analysis, and electronic nose

Characterization of the flavors of ripened roe products is of importance to establish a basis for a standardized product. Flavor profiles of commercially processed ripened roe from Iceland and Norway were studied by sensory analysis, gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS), and an electronic nose to characterize the headspace of ripened roe. Sensory analysis showed that ripened roe odor and flavor in combination with caviar flavor and whey/caramel-like odor give the overall positive effect of the complex characteristic roe flavor. Analysis of volatiles by GC-MS and electronic nose confirmed the presence of aroma compounds contributing to the typical ripening and spoilage flavors detected by the sensory analysis. Methional, 1-octen-3-ol, and 2,6-nonadienal were the most important compounds contributing to ripened roe odor. Spoilage flavors were partly contributed by 3-methyl-1-butanol and 3-methylbutanal, which can be measured by the electronic nose and are suggested as quality indicators for objectively assessing the ripening of roe. Principal component analysis of the overall data showed that GC-O correlated well with sensory evaluation and the electronic nose measurements.     

Early detection of fungal growth in bakery products by use of an electronic nose based on mass spectrometry

This paper presents the design, optimization, and evaluation of a mass spectrometry-based electronic nose (MS e-nose) for early detection of unwanted fungal growth in bakery products. Seven fungal species (Aspergillus flavus, Aspergillus niger, Eurotium amstelodami, Eurotium herbariorum, Eurotium rubrum, Eurotium repens, and Penicillium corylophillum) were isolated from bakery products and used for the study. Two sampling headspace techniques were tested: static headspace (SH) and solid-phase microextraction (SPME). Cross-validated models based on principal component analysis (PCA), coupled to discriminant function analysis (DFA) and fuzzy ARTMAP, were used as data treatment. When attempting to discriminate between inoculated and blank control vials or between genera or species of in vitro growing cultures, sampling based on SPME showed better results than those based on static headspace. The SPME-MS-based e-nose was able to predict fungal growth with 88% success after 24 h of inoculation and 98% success after 48 h when changes were monitored in the headspace of fungal cultures growing on bakery product analogues. Prediction of the right fungal genus reached 78% and 88% after 24 and 96 h, respectively.     

Characterization of volatile compounds in chilled cod (Gadus morhua) fillets by gas chromatography and detection of quality indicators by an electronic nose

Volatile compounds in cod fillets packed in Styrofoam boxes were analyzed during chilled storage (0.5 degrees C) by gas chromatography (GC)-mass spectrometry and GC-olfactometry to screen potential quality indicators present in concentrations high enough for detection by an electronic nose. Photobacterium phosphoreum dominated the spoilage bacteria on day 12 when the fillets were rejected by sensory analysis. Ketones, mainly 3-hydroxy-2-butanone, were detected in the highest level (33%) at sensory rejection, followed by amines (TMA) (29%), alcohols (15%), acids (4%), aldehydes (3%), and a low level of esters (<1%). The electronic nose's CO sensor showed an increasing response with storage time coinciding with the production of ethanol and 2-methyl-1-propanol that were produced early in the storage, followed by the production of 3-methyl-1-butanol, 3-methyl-butanal, 2,3-butandiol, and ethyl acetate. Lipid-derived aldehydes, like hexanal and decanal, were detected in similar levels throughout the storage time and contributed to the overall sweet odors of cod fillets in combination with other carbonyls (3-hydroxy-2-butanone, acetaldehyde, 2-butanone, 3-pentanone, and 6-methyl-5-heptene-2-one).     

Effect of emulsion characteristics on the release of aroma as detected by sensory evaluation,static headspace gas chromatography,and electronic nose

The effects of emulsion structure and composition of the matrix on the release of linalool (nonpolar) and diacetyl (polar) were studied using sensory evaluation, static headspace gas chromatography, and an electronic nose. The matrices used were water, rapeseed oil, and eight oil-in-water emulsions differing in oil volume fraction (0.05/0.5), emulsifier type (sucrose stearate/modified potato starch), and homogenization pressure (100/300 bar). Fat content strongly affected the release of linalool, but it was not as critical a factor in the release of the more polar compound, diacetyl. A slight effect of the emulsifier type on the release of aromas was observed with sensory and gas chromatographic methods. The reduced droplet size, resulting from higher homogenization pressure, enhanced the release of linalool but had no effect on diacetyl. Sensory and gas chromatographic methods detected aroma changes quite similarly. The electronic nose was capable of detecting only the effect of fat on linalool.     

Relationship among antioxidant activity, vasodilation capacity, and phenolic content of red wines

The relationship among antioxidant activity, based on the electron-spin resonance determination of the reduction of Fremy's radical, vasodilation activity, and phenolic content was investigated in 16 red wines. The wines were selected to provide a range of origins, grape varieties, and vinification methods. Sensitive and selective HPLC methods were used for the analysis of the major phenolics in red wine: free and conjugated myricetin, quercetin, kaempferol, and isorhamnetin; (+)-catechin, (-)-epicatechin, gallic acid, p-coumaric acid, caffeic acid, caftaric acid, trans-resveratrol, cis-resveratrol, and trans-resveratrol glucoside. Total anthocyanins were measured using a colorimetric assay. The total phenolic content of the wines was determined according to the Folin-Ciocalteu colorimetric assay and also by the cumulative measurements obtained by HPLC. The 16 wines exhibited a wide range in the values of all parameters investigated. However, the total phenol contents, measured both by HPLC and colorimetrically, correlated very strongly with the antioxidant activity and vasodilation activity. In addition, the antioxidant activity was associated with gallic acid, total resveratrol, and total catechin. In contrast, only the total anthocyanins were correlated with vasodilation activity. The results demonstrate that the different phenolic profiles of wines can produce varying antioxidant and vasodilatant activities, which opens up the possibility that some red wines may provide enhanced health benefits for the consumer.     

Characterization of Citrus unshiu (C. unshiu Marcov. forma Miyagawa-wase) blossom aroma by solid-phase microextraction in conjunction with an electronic nose

The volatile composition of the headspace from Citrus unshiu Marcov. forma Miyagawa-wase blossom was investigated. The volatile constituents were absorbed by a solid-phase microextraction (SPME) fiber and directly transferred to a GC-MS. Volatile compositional changes of C. unshiu blossom prepared via different drying methods (shade, microwave, and freeze-drying methods) were also determined. A total of 96 volatile constituents were confirmed in the headspace from these samples. Monoterpene hydrocarbons were prominent in the headspace volatiles of C. unshiu blossom: fresh, 84.1%; shade-dried, 60.0%; microwave-dried, 88.4%; and freeze-dried, 29.9%. p-Cymene (23.3%) was the most abundant component in the headspace of fresh C. unshiu blossom; gamma-terpinene was the most abundant in shade- and microwave-dried samples (26.8 and 31.2%, respectively) and beta-caryophyllene (10.5%) in freeze-dried sample. By using an electronic nose consisting of six metal oxide sensors, principal component analysis of the volatile compounds showed a clear aroma discrimination of the fresh and all dried blossom samples.     

Prediction of Penicillium expansum spoilage and patulin concentration in apples used for apple juice production by electronic nose analysis

Classification models for Penicillium expansum spoilage of apples and prediction models for patulin concentration in apples usable for apple juice production were made on the basis of electronic nose (e-nose) analysis correlated to HPLC quantification of patulin. A total of 15 Golden Delicious and 4 Jonagold apples were surface sterilized and divided into three groups per variety. The Golden Delicious group consisted of five apples each. Group 1 was untreated control, group 2 was surface inoculated with P. expansum, and group 3 was inoculated in the core with P. expansum. The apples were incubated at 25 degrees C for 10 days. E-nose analysis was performed daily. At day 10 the Golden Delicious apples were individually processed for apple juice production. During apple juice production the mash and juice were analyzed by e-nose, and samples were taken for patulin analysis by HPLC. The volatile metabolite profile was obtained by collection of volatile metabolites, on tubes containing Tenax TA, overnight between the 9th and 10th days of incubation and subsequent analysis of the collected compounds by GC-MS. Prediction models using partial least-squares, with high correlation, for prediction of patulin concentration in shredded apples as well as apple juice were successfully created. It was also shown that it is possible to classify P. expansum spoilage in apples correctly on the basis of soft independent modeling of class analogy classification of e-nose analysis data. To the authors' knowledge this is the first report of a regression model between e-nose data and mycotoxin content in which actual concentrations are reported. This implies that it is possible to predict mycotoxin production and concentration by e-nose analysis.     

Behavior of methamidophos residues in peppers, cucumbers, and cherry tomatoes grown in a greenhouse: evaluation by decline curves.

Residue levels of methamidophos were determined in peppers, cucumbers, and cherry tomatoes grown in commercial greenhouses, up to 6 weeks after being sprayed with Monitor (methamidophos 60%). Mathematically defined decline curves were established by determining optimal relationships between methamidophos residues and time, using different models. Model functions that best fit experimental data were 1st-order function for cucumber, 1.5th-order function for pepper, and 1st-order root function for tomato. However, in all cases, the 1st-order function was legitimized statistically. Half-life times determined from the optimal functions were 8.68 days (cucumber), 13.28 days (pepper), and 2.77 days (tomato), whereas half-life times determined from the 1st-order reaction function were 8.68 days (cucumber), 17.04 days (pepper), and 7.47 days (tomato). In this work, some experiments to determine residue levels of methamidophos in these vegetables after multiple applications were also carried out. The unexpected high residue levels found in all cases after five successive applications seem to indicate that methamidophos presents certain long-term accumulative effects in the three studied vegetables.     

Characterization of Fuji apples from different harvest dates and storage conditions from measurements of volatiles by gas chromatography and electronic nose

Volatile compounds in Fuji apples harvested at two different maturities were measured at harvest and after 5 and 7 months of cold storage (1 degrees C) in four different atmospheres. When the samples were characterized by both chromatographic measurements of volatiles and responses of an electronic nose, the analyses showed a clear separation between fruits from different storage conditions (a normal cold atmosphere and three controlled atmospheres). During poststorage, the apples were left to ripen for 1, 5, and 10 days at 20 degrees C before analytical measurements were done involving headspace-gas chromatography methods and electronic nose type quartz crystal microbalances. Electronic nose responses registered by seven different sensors were used to classify the apples using principal component analysis. It was possible to identify the samples from different storage periods, days of shelf life, and harvest dates, but it was not possible to differentiate the fruits corresponding to different cold storage atmospheres.     

Dissipation of pyrethroid residues in peppers,zucchinis, and green beans exposed to field treatments in greenhouses: evaluation by decline curves

Dissipation of seven pyrethroid insecticides under field conditions was evaluated on green beans, zucchinis, and peppers grown in experimental greenhouses (Almería, Spain). Pyrethroid residues were determined by high performance liquid chromatography using continuous on-line post-elution photoirradiation with fluorescence detection after dichloromethane extraction and cleanup on florisil phase cartridges. Mathematically defined decline curves were established by determining optimal relationships between pyrethroid residues and time. Different models were used to find these curves. The 1st-order model achieved the best adjustment to the experimental data in 42.9% of cases. The RF (root function) 1st-order model was the best in 33.3% of times. Each of the 1.5th- and 2nd-order models provided the best adjustment in a 9.5% of the cases. Finally, the RF 1.5th-order model was the most appropriate in only 4.8% of cases. Half-life times for these three vegetables were estimated from the optimal models. The preharvest intervals for the residues in these three vegetables was obtained, taking into account the maximum residue levels established by the existing legislation. They were all lower than the ones specified by the makers of commercial formulates, which ensures a safe enough consumption.