气相色谱-质谱检测葡萄酒中氨基甲酸乙酯预处理方法的比较研究

目的比较液液萃取法、固相萃取法和分散式固相萃取法作为预处理方法对葡萄酒中的氨基甲酸乙酯的处理效率。方法葡萄酒样品中的氨基甲酸乙酯分别用二氯甲烷进行液液萃取,用氨基甲酸乙酯专用柱进行固相萃取,用乙腈、石墨化炭黑和N-丙基乙二胺进行分散式固相萃取,再以气相色谱-质谱联用仪测定其含量。结果 3种预处理方法的平均回收率均在70%~110%之间,相对标准偏差(n=5)均小于6%。液液萃取法处理单个样品成本小于5元,富集倍数可达5倍,可用于低含量样品的预处理和进出口企业的产品合规性检测;固相萃取法操作简便,每人每工作日可处理40个样品,可用于企业的高通量检测;分散式固相萃取法成本适中、回收率最佳、综合预处理效率高,一次预处理可同时检测葡萄酒中农药残留和氨基甲酸乙酯含量,适用于葡萄酒中多种危害物质的筛查。结论三种方法各具优势,综合考虑处理效率和实验成本,分散式固相萃取法更适合葡萄酒生产企业的日常应用。该方法已用于葡萄酒中氨基甲酸乙酯的含量测定。     

热脱附-气相色谱/质谱联用分析初榨橄榄油挥发性风味成分

以橄榄油为原料,分别采用液液萃取法、顶空法、固相微萃取法、热脱附法提取橄榄油风味成分,使用气相色谱-质谱法(GC-MS)结合Massworks~(TM)质谱解析软件鉴定分析,并针对最佳提取方法进行工艺优化。结果表明,热脱附法因操作简单、重复性好、无需溶剂及样品检测非破坏性等优点,适宜橄榄油风味成分的检出。最佳萃取条件为:吸附温度40℃;吸附时间2 h;一级解吸温度180℃;一级解吸时间5 min;二级解吸温度280℃;二级解吸时间8 min;冷阱温度-30℃。橄榄油风味成分共鉴定出26种,有醇类、醛类、酯类、酮类、烃类,不同国家的初榨橄榄油挥发性组分存在差异;同一国家的初榨橄榄油挥发性组分存在差异;同一国家不同等级橄榄油挥发性组分存在差异。     

西班牙和意大利进口特级初榨橄榄油品质比较

为了系统研究我国主要进口的特级初榨橄榄油性质,比较分析了我国主要进口的8种西班牙和意大利特级初榨橄榄油的脂肪酸组成、酸值、过氧化值及微量成分含量,并对其进行了挥发性成分分析及感官评价。结果表明：西班牙特级初榨橄榄油的C18∶1（77.22%）和C23∶0（0.94%）含量平均值高于意大利样品（分别为72.46%和0.64%）,西班牙特级初榨橄榄油的酸值、过氧化值低于意大利样品;西班牙特级初榨橄榄油中含有γ-生育酚和δ-生育三烯酚,而意大利样品中未检出这两种,且西班牙特级初榨橄榄油中α-生育酚含量平均值（189.58 mg/kg）高于意大利样品（161.26 mg/kg）,角鲨烯含量平均值（6 127.83 mg/kg）远高于意大利样品（4 083.50 mg/kg）,两者甾醇含量差异很小。虽然西班牙特级初榨橄榄油的醛类含量平均值低于意大利样品,但酯类含量更高。感官评价发现,西班牙特级初榨橄榄油的果味、苦味、辣味评分皆高于意大利样品。综上,西班牙特级初榨橄榄油的酸值、过氧化值较低,α-生育酚、角鲨烯含量高于意大利样品,且感官评分较高。     

固相微萃取、液液萃取结合气相色谱-质谱法分析芝麻香型白酒中的含硫化合物

应用固相微萃取法、液液萃取法结合气相色谱-质谱联用分析手段对芝麻香型白酒中含硫化合物进行定性分析。通过配制模拟酒样对固相微萃取法、液液萃取法的前处理条件进行优化。在最优条件下对36 个芝麻香型白酒酒样中的微量成分提取分析,固相微萃取法共检出178 种挥发性成分,液液萃取法共检出239 种挥发性成分。两种方法共检出14 种含硫化合物,均采用标准品比对进行准确定性。首次在中国白酒中检测出硫代丁酸甲酯、糠基甲基硫醚、硫代呋喃甲酸甲酯、4-甲基二苯并噻吩、3-甲硫基丁醛、甲基硫代磺酸甲酯6 种含硫化合物;此外,首次在芝麻香型白酒中检出苯并噻唑和苯并噻吩。     

基于电子鼻和GC-MS的不同品牌橄榄油挥发性风味物质研究

本文旨在探讨不同品牌的橄榄油挥发性风味物质的差异,为研究鉴别不同品牌的橄榄油提供参考。方法:运用电子鼻和顶空固相微萃取-气质联用仪(HS-SPME-GC-MS)对不同品牌的橄榄油挥发性物质进行检测和分析。结果表明:电子鼻能灵敏地检测到不同品牌橄榄油气味的差异性。GC-MS在不同品牌的橄榄油中检测出76种挥发性物质,主要为烃类、醇类、醛类、酮类、酯类、酸类及其他化合物。酸类物质是除帆船牌特级初榨橄榄油外其他4种橄榄油都具有的物质,1号曼托瓦特级初榨橄榄油特有的关键挥发性化合物是癸烷、E-2-庚烯、6-乙基-2-甲基辛烷、戊醛、庚醛、辛醇和2-辛酮;2号百一牌特级初榨橄榄油特有的挥发性物质是1-癸烯和2,2,4,6,6-五甲基庚烷;3号福恩牌特级初榨橄榄油特有的化合物是1-十三烯和辛烷;4号帆船特级初榨橄榄油特有的化合物是十二烷、3,5-二甲基辛烷、D-柠檬烯和3,7-二甲基-1-辛醇;5号斯巴达(金)特级初榨橄榄油特有的化合物是(E)-2-己烯醛。不同品牌的橄榄油之间共有的关键风味化合物主要有己醛和壬醛。结论:橄榄油品牌不同,主要的挥发性成分种类及其相对含量有差异。     

初榨橄榄油挥发性风味成分的鉴定

采用顶空固相微萃取-气质联用(HS-SPME-GC/MS)分离鉴定了陇南市武都初榨橄榄油和西班牙特级初榨橄榄油中的挥发性风味成分。结果表明,在7个不同品种油橄榄的国产初榨橄榄油中共鉴定出86种化合物,主要是C6的醛和醇,以及它们相应的酯,还有一些烯烃和萜烯类化合物。其中(E)-2-己烯醛相对质量分数为7.14%~46.22%;在6个西班牙特级初榨橄榄油中共鉴定出101种化合物,其中(E)-2-己烯醛质量分数(1.76%~5.25%)低于国产初榨橄榄油,而(Z)-乙酸-3己烯酯(7.53%~13.76%)和(E)-2-十二碳烯(5.47%~34.75%)相对质量分数较高。试验结果还表明,初榨橄榄油挥发性风味成分很大程度上取决于油橄榄品种和产地。     

28份国产特级初榨橄榄油中多酚含量及其变化规律北大核心CSCD

为了对我国油橄榄产业提供基础数据支持,采用国际油橄榄理事会推荐的HPLC法检测特级初榨橄榄油中的多酚含量,分析了我国不同产地的28份市售食用特级初榨橄榄油样品的多酚含量,并对不同生产年度和不同产地单果级特级初榨橄榄油中多酚含量变化规律进行了分析。结果表明:市售国产特级初榨橄榄油中均含有较为丰富的多酚类化合物,多酚含量范围为(63.885±2.345)mg/kg~(307.325±6.865)mg/kg;特级初榨橄榄油中多酚含量受贮存时间的影响较大,同时不同产地中适合生产高多酚含量特级初榨橄榄油的品种具有差异。不同特级初榨橄榄油样品之间多酚含量波动较大,需要通过多种方法来防止油脂中多酚类化合物的降解,以保证油品的质量,并因地制宜对油橄榄品种进行优化筛选。     

六种特级初榨橄榄油挥发性香气成分的比较

为探究比较特级初榨橄榄油挥发性香气成分,采用固相微萃取(solid phase micro-extraction,SPME)结合气相色谱嗅闻质谱(gas chromatography-olfactrometry-mass spectrometry,GC-O-MS)联用、感官评价和电子鼻技术对3个国家的6种特级初榨橄榄油挥发性香气成分进行分析。结果表明,电子鼻可以明显区分不同橄榄油;GC-O-MS通过极性色谱柱(DB-Wax)和非极性色谱柱(DB-5)结合分析,鉴定得出65种挥发性香气活性化合物,包括醛类16种,醇类12种,酯类9种,酮类6种,烯烃及萜烯类8种,芳香类5种,酸类3种及6种其他类型化合物。结合文献、检测及嗅闻结果得出特级初榨橄榄油中的特征香气成分为反-2-己烯醛、己醛、反-2-壬烯醛、6-甲基-5-庚烯-2-酮和顺-3-己烯-1-醇等以醛醇为代表的小分子化合物。     

超临界色谱串联质谱法测定橄榄油中 维生素E含量的研究

目的建立运用超临界色谱串接质谱法同时测定橄榄油中4种生育酚和4种生育三烯酚含量的方法,并比较不同产地的特级初榨橄榄油中8种生育酚类化合物的含量差异。方法运用超临界色谱将橄榄油中多种生育酚和生育三烯酚分离,用三重四极杆质谱进行定性和定量分析,通过线性范围、回归系数、加标回收率等指标评价方法的准确性和可靠性。通过运用两个独立样本间的t检验的方法计算西班牙产和意大利产的特级初榨橄榄油中8种生育酚类化合物浓度的差异。结果 4种生育酚和4种生育三烯酚的浓度在0.10~100.0 mg/L范围内与峰面积呈良好线性关系,线性回归系数(r2)均大于0.99,加标回收率81.0%~108.3%之间。西班牙产和意大利产的特级初榨橄榄油中,未检出β-生育三烯酚、γ-生育三烯酚和δ-生育三烯酚;两地产橄榄油的α-生育酚、β-生育酚和δ-生育酚的含量无统计学差异(P0.05);两地产橄榄油中γ-生育酚浓度有统计学差异(P0.05)。结论运用超临界色谱串联质谱法可将橄榄油中4种生育酚和4种生育三烯酚完全分离,方法准确、可靠。意大利产和西班牙产特级初榨橄榄油中γ-生育酚含量不同,可作为鉴定原产地的依据之一。     

不同前处理方法对酱香型白酒挥发性风味成分的影响

以酱香型白酒为研究对象,采用固相微萃取（SPME）和液液萃取（LLE）对白酒样品进行前处理,并采用单因素试验优化其萃取条件,结合气相色谱-质谱联用（GC-MS）技术对其挥发性风味成分进行分析。结果表明,最适固相微萃取条件为：萃取时间45 min,萃取温度50℃,酒精度15%vol;最适液液萃取试剂为二氯甲烷;液液萃取优于固相微萃取。在最适液液萃取条件下,酱香型白酒中共检出挥发性风味成分162种,包括酯类58种,醇类37种,酸类7种,酚类4种,醛酮类25种,呋喃类4种,吡嗪类7种,其他类20种。其中酯类、醇类和酸类物质含量较丰富,分别占总含量的41.4%、11.4%和39.9%。     

Comparison of Different Extraction Methods to Determine Phenolic Compounds in Virgin Olive Oil

A comparison between different extraction methods has been performed in order to assess their effectiveness for the analysis of total phenols (liquid–liquid extraction (LLE), liquid–liquid micro extraction (LLME), and ultrasound liquid–liquid extraction (USE)) and individual phenols (LLME, USE, and solid-phase extraction (SPE)) from virgin olive oil (VOO). Statistical analysis of the analytical data obtained for the total phenol content of a VOO, showed that LLME and USE can represent a reliable alternative to the traditional procedure based on LLE that needs more amount of sample, generates more wastes, and is more time consuming. When an olive oil spiked with phenols was used to test the efficiency of LLME, USE, and SPE methods, the statistical analysis of the data obtained for each individual phenol, again proved LLME and USE methods to be the most suitable, in terms of precision and recoveries, for this purpose. The analysis of real samples (Arbequina and Picual cultivars) confirmed the results obtained for the spiked oil.     

测定菜籽油中酚类化合物样品前处理方法的比较

采用液液萃取(LLE)、固相萃取(SPE)、QuEChERS 3种不同前处理方法提取菜籽油中酚类化合物,并采用超高效液相色谱串联质谱(LC-MS/MS)进行测定,分析比较了3种不同前处理方法对菜籽油中酚类化合物提取效果的影响。结果表明:在3种不同的前处理方法中,QuEChERS前处理方法的提取效果最好,对菜籽油中7种酚类化合物的回收率最高,可达85.16%～101.78%,基质共提物含量最低,为2.04 mg/g;LLE的回收率为66.04%～101.11%,基质共提物含量最高,为6.80 mg/g;SPE的回收率最低,仅为56.98%～83.79%,基质共提物含量为2.30 mg/g。     

Determination of phenolic compounds in olive oil: New method based on liquid–liquid micro extraction and ultra high performance liquid chromatography-triple–quadrupole mass spectrometry

A novel analytical approach has been performed and evaluated for the identification and quantification of phenolic compounds (phenolic alcohols, secoiridoid derivates, lignans, flavonoids, phenolic acids and aldehydes) which can be found in both virgin olive oil (VOO) and extra virgin olive oil (EVOO). An improved liquid–liquid micro extraction (LLME) method combining with ultra high performance liquid chromatography (UHPLC) coupled to electrospray ionization source (ESI) and tandem mass spectrometry (MS/MS) in Dynamic Multiple Reaction Monitoring (DMRM) mode has been developed, reducing the amount of sample, reagents and time consumed. The proposed methodology was applied to standard solutions, and the quality control parameters obtained were compared with those achieved in spiked refined olive oil (SROO). Generally, these parameters showed lower values in SROO than in standard solutions. Matrix effect, recovery and process efficiency have been studied using SROO. The recoveries were around 90% and the process efficiency of the whole method was higher than 80% for most of the phenolic compounds studied. Examination of these parameters revealed that work straight in the olive oil matrix, which is closer to behave as a real sample, provides better results. The applicability and reliability of this methodology have been confirmed using real samples.     

Aroma and physical characteristics of cakes prepared by replacing margarine with extra virgin olive oil

The effect of margarine substitution by extra virgin olive oil on the quality of Madeira cakes was studied. Three cakes containing either extra virgin olive oil or extra virgin olive oil/margarine mixture or margarine were prepared. The use of extra virgin olive oil increased batter density and cake volume while decreased the weight loss (%) during baking. Texture profile analysis also showed that the replacement of margarine by extra virgin olive oil affected significantly hardness and cohesiveness of the cakes. Headspace solid phase microextraction was applied in order to analyze the aroma of the three cakes. The addition of extra virgin olive oil produced a wide range of volatile compounds, which were analyzed by gas chromatography/mass spectrometry and were originated either from extra virgin olive oil or were produced during the baking process. Hedonic sensory tests were also conducted revealing that the cake prepared with extra virgin olive oil/margarine mixture was highly appreciated by the consumers as it got scores similar to control.     

橄榄木酚素及其生物活性研究进展

橄榄木酚素包括松脂醇和1-乙酰氧基松脂醇,是存在于橄榄油中的主要酚类化合物。橄榄木酚素是构成特级初榨橄榄油内源性抗氧化体系的重要脂质伴随物之一。对橄榄木酚素的生物合成与代谢途径,含量、分布及稳定性,吸收代谢,体外抗氧化活性,生物活性进行了综述,提出橄榄木酚素研究存在的问题,并对今后的研究方向进行了展望,以期为橄榄油提质制取和木酚素相关健康产品研发提供理论指导。     

Has the use of talc an effect on yield and extra virgin olive oil quality?

The maximization of both extraction yield and extra virgin olive oil quality during olive processing are the main objectives of the olive oil industry. As regards extraction yield, it can be improved by both acting on time/temperature of malaxation and using physical coadjuvants. It is well known that, generally, increasing temperature of malaxation gives an increase in oil extraction yield due to a reduction in oily phase viscosity; however, high malaxation temperature can compromise the nutritional and health values of extra virgin olive oil, leading to undesirable effects such as accelerated oxidative process and loss of volatile compounds responsible for oil flavor and fragrance. The addition of physical coadjuvants in olive oil processing during the malaxation phase, not excluded by EC regulations owing to its exclusively physical action, is well known to promote the breakdown of oil/water emulsions and consequently make oil extraction easier, thus increasing the yield. Among physical coadjuvants, micronized natural talc is used for olive oil processing above all for Spanish and Italian olive cultivars. The quality of extra virgin olive oil depends on numerous variables such as olive cultivar, ripeness degree and quality, machines utilized for processing, oil storage conditions, etc. However, the coadjuvants utilized in olive processing can also influence virgin olive oil characteristics. The literature highlights an increase in oil yield by micronized natural talc addition during olive processing, whereas no clear trend was observed as regards the chemical, nutritional and sensory characteristics of extra virgin olive oil. Although an increase in oil stability was reported, no effect of talc was found on the evolution of virgin olive oil quality indices during storage. © 2016 Society of Chemical Industry     

两种前处理方法分析竹醋液挥发性成分的比较

为探明用于熏液的竹醋液挥发性成分,分别采用吹扫捕集-热脱附法(purge and trap-thermal desorption,P＆T-TD)和液液分配萃取(liquid-liquid extraction,LLE)法对竹醋液中挥发性成分进行富集,以气相色谱-质谱联用法(gas chromatography-mass spectrometry,GC-MS)进行定性检测,用面积归一化法确定各组分的相对含量。结果表明：两种方法共鉴定竹醋液挥发性成分--酸类、酚类、酮类、酯类、醛类等化合物共50种,其中P＆T-TD-GC-MS鉴定出28种、LLE-GC-MS鉴定出29种,相对含量在2%以上的主要成分为乙酸甲酯、丙酸甲酯、乙酸、1-羟基-2-丁酮、环戊酮、糠醛、苯酚、甲基环戊烯醇酮和2,6-二甲氧基苯酚。两种方法获得的竹醋液挥发性成分差异较大,具有一定的互补性,相结合应用两种方法能够较全面地检测出竹醋液的挥发性成分。