Analysis of early lipid oxidation in smoked, comminuted pork or poultry sausages with spices

Dynamic headspace/gas chromatography-mass spectrometry (GC-MS), front-face fluorescence spectroscopy, and a gas-sensor array technique (electronic nose) have previously detected lipid oxidation in pork back fat or mechanically recovered poultry meat earlier than or at the same time as a sensory panel. The present study was focused on measurement of early lipid oxidation in a more complicated product (freeze-stored, smoked sausages with spices). During the storage time, formation of components contributing to rancid odor and flavor (e.g., hexanal and 1-penten-3-ol) could be monitored with dynamic headspace/GC-MS. The GC-MS data also showed a decrease in 2-furancarboxaldehyde, which could indicate loss of Maillard type components often associated with acidic or meat odor and flavor. The fluorescence spectra were difficult to interpret, probably due to the simultaneous influence from increasing levels of lipid oxidation products and loss of fluorescent Maillard or spice components. The gas-sensor array responses were dominated by signals from, e.g., spice and smoke compounds.     

冷鲜肉辐照异味和脂肪氧化控制技术的研究

以猪肉为原料,通过单因素试验、正交试验、感官及电子鼻试验研究辐照剂量、TBHQ浓度和包装中氧气含量对冷鲜肉辐照异味和脂肪氧化作用的影响,确定最佳辐照工艺。结果表明,在处理条件为辐照剂量24kGy,TBHQ油溶液浓度1g/L,真空包装时,辐照冷鲜肉产生的异味达到不可察觉程度,并能较好地抑制脂肪氧化。电子鼻试验表明,通过最优控制方法,辐照后的冷鲜肉与未处理的冷鲜肉气味相似度达到9103%。     

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.     

基于电子鼻的鱼露香气品质识别

为了识别鱼露的品质,并为缩短发酵周期的工艺优选提供理论依据.利用电子鼻对7种鱼露样品的挥发性气味进行了分析,并与项空-气质联用( GC-MS)和感官分析结果进行比较.结果表明:鱼露香气成分复杂,工艺改良对气味影响很大,电子鼻18个金属传感器能很好地将不同样品的气味进行识别.以传统发酵原汁鱼露为标样,电子鼻分析结果表明,加曲改良工艺的4号样品与标样香气最为接近,相似系数达87.8％,该结果与GC-MS数据和感官分析结果一致,可为鱼露速酿工艺的优选提供参考.     

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.     

基于Hilbert-Huang变换的生物触电电流检测模型

为了检测触电时刻剩余电流中生物体触电支路电流信号的难题,应用Hilbert-Huang变换方法,确定了生物触电时剩余电流的固有模态函数中相关系数最大的IMF分量的局部幅值达34.02 m A,且与原信号相关性系数达到0.99,同时剩余电流与触电电流暂态过程频谱特性具有相似变化规律。以此为基础,应用生物电流信号高频IMF分量幅值的突变特征,作为触电故障时刻确定判据,建立生物触电故障时刻判定方法,实际数据的仿真处理正确率为94.17%;筛选剩余电流分解的相关性较高的有限个数的低频固有模态IMF分量,应用逐步多元线性回归方法,提出基于剩余电流固有模态分量的生物触电支路电流幅值检测方法,仿真试验结果的平均相对误差值5.46%,具有良好的适应性和实用性,为研发基于生物体触电电流而动作的剩余电流保护装置提供参考。     

山核桃氧化过程中品质指标变化的电子鼻快速检测

为了研究山核桃氧化过程中的品质变化规律,试验采用电子鼻获取不同氧化阶段的山核桃的挥发性氧化产物信息,运用主成分分析(principal component analysis,PCA)、线性判别分析(linear discriminant analysis,LDA)、聚类分析(cluster analysis,CA)及理化指标分析区分不同氧化阶段的山核桃样品品质变化,并通过主成分回归法(principle component regression,PCR)建立过氧化值、酸价、茴香胺值、总过氧化值的预测模型。结果表明:随着氧化时间的延长,过氧化值、酸价、茴香胺值、总过氧化值等指标显著(P0.05)增加,电子鼻传感器的响应强度逐渐增大。通过PCA、CA、LDA及理化指标分析均能较好地区分不同氧化阶段的山核桃的氧化程度。采用主成分回归法(PCR)建立过氧化值、酸价、茴香胺值、总过氧化值等理化指标的预测模型,决定系数(R2)分别为0.968、0.975、0.985、0.980。结果证明不同氧化阶段的山核桃的过氧化值,酸价,茴香胺值和总过氧化值的PCR模型验证的相对误差小于16%,预测效果较好。研究结果为山核桃氧化过程中的快速检测提供技术参考。     

HS-SPME/GC-MS和电子感官技术分析毛霉型豆豉发酵过程中风味品质

为了对毛霉型豆豉发酵过程中风味进行综合评价,本试验采用顶空固相微萃取/气相色谱-质谱法(HS-SPME/GC-MS)结合电子鼻、电子舌对其发酵过程进行研究。结果表明,毛霉型豆豉不同发酵时期的11个样品共鉴定出68种挥发性风味成分,其中包括酯类18种、醛类7种、酸类3种、醇类26种、酮类4种、其他类10种。挥发性风味成分的种类由前发酵的15种上升至豆豉发酵成熟时(35~42 d)的31种,含量由前发酵1.69 μg·g^-1上升至发酵终点44.20 μg·g^-1,呈递增趋势,至发酵成熟期稳定,与电子鼻测定结果一致。电子舌测定结果显示,后发酵35 d时,成品的涩味、苦味及苦味回味降到适宜程度,鲜味和丰富性较高,而此时的挥发性风味成分种类丰富、含量高、香味浓郁、丰富性好,滋味和气味俱佳。因此,HS-SPME/GC-MS结合电子感官技术对毛霉型豆豉产品品质的判别具有可行性,可为生产条件的优化提供理论依据。     

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。     

电子鼻技术在棉花早期棉铃虫虫害检测中的应用

为了更好地获取棉花虫害信息,该文使用电子鼻和气质联用技术对受到不同数量棉铃虫早期危害的棉花进行检测。基于气质联用技术获得了棉花挥发物的成分和含量,基于电子鼻响应曲线提取了稳定值、面积值、平均微分值、小波能量值和多项式拟合曲线参数值5种特征值,筛选出3种较优单特征:稳定值、平均微分值和面积值,之后基于多特征分别使用多层感知神经网络、径向基函数神经网络和极限学习机3种神经网络方法进行分类分析。最后采用支持向量机回归分别基于3种较优单特征及多特征对危害棉花的棉铃虫数量进行回归预测。结果表明:多特征的分类效果优于单特征,基于多特征“稳定值和平均微分值”和极限学习机分类效果最好,训练集和测试集的分类正确率均达到100%。多特征的预测能力优于单特征,基于多特征“面积值和平均微分值”的回归模型预测效果最佳,训练集回归模型的决定系数(R^2)和均方根误差(RMSE)分别为0.9940和0.0860,测试集回归模型的R^2和RMSE分别为0.9230和0.3709,电子鼻对棉花早期棉铃虫虫害具有较好的区分和预测能力,电子鼻在棉花早期棉铃虫虫害中的检测具有一定的应用潜力。     

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.     

Inhibition of lipid oxidation in pork bundles processing by superheated steam frying

The effect of superheated steam treatment on the oxidative stability of lipids in packaged Zousoon (pork bundles) was investigated. The aroma quality of Zousoon samples was evaluated by sensory analysis and chromatographic analysis of volatiles. Results of this study indicated that oxidation of lipids occurred in pan-fried Zousoon after prolonged storage. Significant amounts of highly volatile compounds such as formaldehyde, acetaldehyde, acetone, and hexanal in Zousoon were identified by a modified method of cysteamine derivatization followed by gas chromatography-mass spectrometry (GC-MS) analysis. Superheated steam was found to be effective in suppressing lipid oxidation in canned Zousoon as compared with Zousoon fried by the conventional method in a frying pan. The superheated steam-fried samples had relatively low thiobarbituric acid reactive substance (TBARS) and peroxide (POV) values before and after storage, whereas samples prepared by pan frying had relatively high TBARS and POV values before and after storage. Superheated steam-fried Zousoon had superior lipid stability to that prepared by the conventional pan-frying method.     

Characterization of Royal Gala apple aroma using electronic nose technology-potential maturity indicator

Changes in aroma of apple harvested at four different maturities were measured at harvest and after short-term storage using electronic aroma sensors ("electronic nose") and classical headspace/gas chromatography methods. Stored fruits were also evaluated by a trained sensory panel. Compared with headspace/gas chromatography, the electronic nose was found to be more sensitive ( approximately 40 times) in terms of sample size. The sampling procedure for the electronic nose was much less complex. Using discriminant function analysis, both methods classified the apples tested into groups according to harvest date. After storage, the groupings were more diffuse. Results from sensory testing showed partial separation along the first linear discriminant but did not classify the apple into distinct groups. Important differences between treatments were found for "overall flavor", "acid flavor" intensity, "crispness", "cider/fermented aroma", "vegetative aroma", and "canned pear aroma".     

Formation of cholesterol oxidation products in marinated foods during heating

The objectives of this study were to develop a gas chromatography-mass spectrometry (GC-MS) method to analyze the contents of cholesterol oxidation products (COPs) in marinated eggs, pork, and juice and to compare the effect of heating time and soy sauce or sugar on the formation of COPs. By using a silica cartridge for purification and GC-MS with selected ion monitoring for detection, seven COPs, including 7alpha-hydroxycholesterol, 7beta-hydroxycholesterol, 5,6alpha-epoxycholesterol, 5,6beta-epoxycholesterol, 5alpha-cholestane-3beta, 5,6beta-triol, 5-cholesten-3beta-25-diol, and 7-ketocholesterol, as well as internal standard 5alpha-cholestane, were resolved within 16 min by using a HP-5MS capillary column. During marinating, the levels of most COPs followed an increasing trend with increasing heating time. However, a higher amount of COPs was generated for ground pork as compared to eggs. The incorporation of soy sauce or sugar (1 and 10%) was effective in inhibiting COPs formation, with the latter being more pronounced than the former in both marinated eggs and pork.     

抗氧化剂对辐照猪肉理化和感官品质的影响

为减少猪肉辐照灭菌后产生的异味和脂肪氧化,研究了叔丁基对苯二酚、虾青素、维生素E、茶多酚4种抗氧化剂对辐照猪肉理化和感官品质的影响。采用2 g/L抗氧化剂浸泡处理,透氧包装,辐照剂量2.6 kGy,冷藏10 d。分析测定辐照猪肉感官品质、过氧化值、硫代巴比妥酸反应物、挥发性物质、抗氧化剂对羟自由基清除能力,筛选出适合猪肉辐照的高效抗氧化剂。结果表明：叔丁基对苯二酚在储藏期可以很好地减轻辐照异味并抑制脂肪氧化,效果优于虾青素、维生素E、茶多酚。叔丁基对苯二酚和维生素E可以有效地降低脂肪辐照后产生的挥发性物质含量。叔丁基对苯二酚（0.5 g/L）对羟自由基的清除率为52.5%,高于其他抗氧化剂,可抑制猪肉辐照过程中羟自由基参与的反应。     

Comparison of mass spectrometry-based electronic nose and solid phase microextraction gas chromatography-mass spectrometry technique to assess infant formula oxidation

Two headspace techniques based on mass spectrometry detection (MS), electronic nose, and solid phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GC/MS) were evaluated for their ability to differentiate various infant formula powders based on changes of their volatiles upon storage. The electronic nose gave unresolved MS fingerprints of the samples gas phases that were further submitted to principal component analysis (PCA). Such direct MS recording combined to multivariate treatment enabled a rapid differentiation of the infant formulas over a 4 week storage test. Although MS-based electronic nose advantages are its easy-to-use aspect and its meaningful data interpretation obtained with a high throughput (100 samples per 24 h), its greatest disadvantage is that the present compounds could not be identified and quantified. For these reasons, a SPME-GC/MS measurement was also investigated. This technique allowed the identification of saturated aldehydes as the main volatiles present in the headspace of infant milk powders. An isotope dilution assay was further developed to quantitate hexanal as a potential indicator of infant milk powder oxidation. Thus, hexanal content was found to vary from roughly 500 and 3500 microg/kg for relatively non-oxidized and oxidized infant formulas, respectively.     

Application of an electronic nose to predict total volatile bases in capelin (Mallotus villosus) for fishmeal production

An electronic nose was used as a rapid technique to monitor changes in the headspace gas above capelin (Mallotus villosus) during storage at 0 and 5 degrees C. At both temperatures, refrigeration was compared with an ice/seawater cooling system. At 5 degrees C, the effect of added 0.2% acetic acid was also tested. Electronic nose measurements were compared to measurements of total volatile bases (TVB), gas chromatography of volatile compounds, and sensory analysis. TVB analysis indicated less spoilage in seawater/ice systems than in refrigeration, but the other measurements indicated more spoilage in the seawater system compared to refrigeration. The possibility of using only a few sensors in the electronic nose to predict TVB was studied using partial least squares regression and a saturated generalized linear model. The results reported herein indicate that rapid electronic nose measurements, which require no sample preparation, can be used to predict the TVB value of the raw material stored under different conditions.     

Authentication of animal fats using direct analysis in real time (DART) ionization-mass spectrometry and chemometric tools

A combination of direct analysis in real time (DART) ionization coupled to time-of-flight mass spectrometry (TOFMS) and chemometrics was used for animal fat (lard and beef tallow) authentication. This novel instrumentation was employed for rapid profiling of triacylglycerols (TAGs) and polar compounds present in fat samples and their mixtures. Additionally, fat isolated from pork, beef, and pork/beef admixtures was analyzed. Mass spectral records were processed by principal component analysis (PCA) and stepwise linear discriminant analysis (LDA). DART-TOFMS profiles of TAGs were found to be more suitable for the purpose of discrimination among the examined fat types as compared to profiles of polar compounds. The LDA model developed using TAG data enabled not only reliable classification of samples representing neat fats but also detection of admixed lard and tallow at adulteration levels of 5 and 10% (w/w), respectively. The presented approach was also successfully applied to minced meat prepared from pork and beef with comparable fat content. Using the DART-TOFMS TAG profiles of fat isolated from meat mixtures, detection of 10% pork added to beef and vice versa was possible.     

包装形式对辐照冷却猪肉糜脂肪氧化的影响

本文研究了不同包装形式结合抗氧化剂对辐照冷却猪肉糜(猪五花肉)中脂肪氧化的抑制作用。添加抗氧化剂的冷却猪肉糜分别采取真空包装、无氧包装(N2+CO2)和气调有氧包装(O2+CO2+N2),然后经3kGy低剂量辐照,在4℃±1℃贮藏20d。分别在辐照的第0、5、10、15和20d对冷却猪肉糜脂肪氧化指标TBARS值、过氧化值进行测量。结果表明:添加抗氧化剂并结合真空包装能显著降低辐照猪肉糜中的脂肪氧化。因此在降低辐照及贮藏过程中冷却肉的脂肪氧化方面,真空包装要优于有氧包装。