基于UPLC-QTOF-MS/MS技术分析荷叶乙酸乙酯相中主要化学成分

采用超高效液相色谱-四极杆飞行时间串质谱技术分析荷叶乙酸乙酯相中的主要化学成分,根据色谱峰的精确分子质量、母离子、碎片离子、质谱裂解规律等信息,结合荷叶中已经鉴定的化合物以及相关参考文献对化合物的结构进行鉴定。从荷叶乙酸乙酯相中共鉴定出40 种化合物,包括27 种黄酮类化合物、6 种酚酸、4 种有机酸、2 种脂肪酸和1 种氨基酸。黄酮类化合物是荷叶乙酸乙酯相中的主要化学成分,主要为槲皮素糖苷、山柰酚糖苷、异鼠李素糖苷和黄酮-3-O-醇类,其次为酚酸。本研究可为荷叶资源在食品加工和功能性食品开发领域的应用提供理论基础。     

Identification of the Polyphenols in Barley and Beer by HPLC/MS and HPLC/Electrochemical Detection

Barley polyphenols were isolated using acetone/water (70/30) followed by Sephadex LH-20 chromatography. HPLC/Electrospray mass spectrometry showed the presence of proanthocyanidin dimers, trimers, tetramers, and pentamers. HPLC/electrochemical detection was used to survey the contents of these compounds in a range of barley varieties. Principal components analysis showed that the naked barley varieties Morrell, and to a lesser extent Namoi, were different from the other barley varieties. Beer polyphenol extracts were prepared using Sephadex LH-20 chromatography. A large number of proanthocyanidin dimers and trimers could be detected using HPLC/MS. HPLC/electrochemical detection was used to survey a range of beer types. Compounds detected included catechin, epicatechin, gallocatechin, epigallocatechin, a number of proanthocyanidin dimers and trimers, and a number of phenolic acids. The peaks removed by PVPP have been determined. Principal components analysis was used to identify those compounds which distinguished the beer types. The first principal component was due to prodelphinidin B3, catechin, gallocatechin and two unidentified compounds which were removed by PVPP and the second principal component was due to phenolic acids. Efforts to identify the compounds removed by PVPP have commenced.     

对国外一种新型烟熏液的初步剖析

运用GC/MS(气相色谱质谱联用法)对国外一种新型液体烟熏风味利(GLE1100)进行了初步剖析,总出色谱峰100多个,鉴定出了其中42个成分,初步剖析结果为:酚类15个;羰基化合物11个;酯类5个;酸类7个;其他化合物4个。列出了几个重要的具有明显的烟熏嗅与味的酚类化合物的质谱图。     

超高效液相色谱-三重四极杆串联质谱法定量分析云南大叶种茶酚类成分

基于超高效液相色谱-三重四极杆串联质谱联用技术,建立和验证一种高灵敏度、高特异性和高通量的靶向定量分析方法,其具有良好的线性、准确性和稳定性。该方法成功应用于4 类云南大叶种茶叶中90 个酚类成分的准确同时定量分析。结果表明,绝大部分酚类成分在未发酵茶（绿茶或普洱生茶）中含量较高,但游离酚酸、黄酮苷元和茶黄素在发酵茶（红茶或普洱熟茶）中的含量更高。偏最小二乘判别分析进一步揭示了不同类型茶叶的酚类成分差异,并筛选到系列化学标志物。     

Simultaneous Determination of 15 Phenolic Constituents of Chinese Black Rice Wine by HPLC‐MS/MS with SPE

This study established a new method for quantitative and qualitative determination of certain components in black rice wine, a traditional Chinese brewed wine. Specifically, we combined solid‐phase extraction and high‐performance liquid chromatography (HPLC) with triple quadrupole mass spectrometry (MS/MS) to determine 8 phenolic acids, 3 flavonols, and 4 anthocyanins in black rice wine. First, we clean samples with OASIS HLB cartridges and optimized extraction parameters. Next, we performed separation on a SHIM‐PACK XR‐ODS column (I.D. 3.0 mm × 75 mm, 2.2 μm particle size) with a gradient elution of 50% aqueous acetonitrile (V/V) and water, both containing 0.2% formic acid. We used multiple‐reaction monitoring scanning for quantification, with switching electrospray ion source polarity between positive and negative modes in a single chromatographic run. We detected 15 phenolic compounds properly within 38 min under optimized conditions. Limits of detection ranged from 0.008 to 0.030 mg/L, and average recoveries ranged from 60.8 to 103.1% with relative standard deviation ≤8.6%. We validated the method and found it to be sensitive and reliable for quantifying phenolic compounds in rice wine matrices.     

Flavor Components in Cognac

SUMMARY: Flavor components of a genuine cognac were identified by means of CGLC/MS. The complex extract was fractionated on a packed column preceding further separation on a capillary column. The identification of fatty acids, phenolic acids and some of the carbonyl compounds was achieved by other chromatographic methods. 81 components, of which 24 have not previously been reported in cognac and other grape brandies, were identified.     

GC-MS结合保留指数分析聚苯乙烯发泡餐盒中化学成分

采用正己烷超声提取发泡餐盒中的化学物质,经气相色谱-质谱法分析,在NIST质谱检索库检索的基础上,结合保留指数对化学物进行定性分析,再用峰面积归一法确定各个物质的含量。3 种发泡餐盒分别分离出35、39、38 种化学成分,分别确定了其中25、27、23 种物质,大都为含有苯环的有毒有害物质,相对标准偏差在2.26%～6.06%之间。本方法提高了定性分析的准确性和效率,可为发泡餐盒成分分析提供参考。     

食品中酚类成分及其与其它成分相互作用研究进展

酚类成分是植物中种类最多的重要次生代谢产物,在植物源食品中有着广泛的分布。由于其优良的抗氧化活性、护色、增加风味及潜在保健功能等,成为了食品中重要的功能性成分和常用的食品添加剂。文章就食品中酚类成分及与其他成分如蛋白质、脂类、糖类、金属离子、维生素等的作用进行综述,以期为酚类成分的应用提供参考资料。     

UHPLC-DAD-ESI-MS/MS法分析紫山药块根和茎叶中酚类物质

本文采用微波辅助法,以80%甲醇作为溶剂提取经冻干后紫山药块根和地上茎叶中的多酚类物质,提取物经超高效液相色谱分离、电喷雾串联三重四级杆质谱正和负离子方式检测分析。根据液相保留时间、紫外吸收、相对分子质量和二级碎片离子等信息,结果表明,紫山药块根和茎叶中酚类物质主要为酚酸、花色苷及黄酮类化合物。分析得到的29种酚类化合物中,5-O-咖啡酰奎宁酸、阿魏酰奎宁酸(tR:12.289)、迷迭香酸、芦丁和槲皮素为块根和茎叶共有组分,块根中另含有芥子酸、芥子酸葡萄糖苷、丁香酸衍生物、香豆酸衍生物、阿魏酸衍生物、芥子酸二葡萄糖苷和花色苷等11种酚类物质。茎叶中除5种共有组分,还含有咖啡酸、咖啡酰奎宁酸甲酯、咖啡酰莽草酸、对香豆酰奎宁酸、香豆酰奎宁酸甲酯、山奈酚-3-O-芦丁糖苷与迷迭香酸甲酯等13种酚类化合物。     

Extraction for profiling free and bound phenolic compounds in tea seed oil by deep eutectic solvents

Bound phenolic compounds have rarely been reported in vegetable oils and this may be due to little research about the extraction. Deep eutectic solvents (DESs), recently applied in the extraction of phenolic compounds as alternatives to organic solvents, were adopted in the extraction of free and bound phenolic compounds from tea seed oil in this work. First, the phenolic compounds were analyzed by ultra-high-performance liquid chromatography with quadrupole-time-of-flight and triple-quadrupole tandem mass spectrometry (UHPLC-Q-TOF-MS/MS) for characterization and UHPLC-QqQ-MS/MS for quantification and 25 phenolic compounds were found to exist in both free and bound forms. Then, DESs were screened for extraction of free and bound phenolic compounds from tea seed oil as the pretreatment for analysis and the results showed that hydrogen bond donors (HBDs) and temperature significantly affected the extraction efficiency of DESs. Finally, free phenolic compounds (83.91 µg/g) and bound phenolic compounds (25.71 µg/g), extracted by the DES with glycerol as HBD at 50 °C, were 51.0% and 93.2% higher than those extracted by methanol/water (60%, v/v), respectively. This work not only advanced the basic data of phenolic compounds in tea seed oil but also explored an efficient extraction method for scientific analysis of free and bound phenolic compounds.     

蔬菜及其制品中不同形态酚酸成分分析

采用超高效液相色谱-串联质谱法对10?种蔬菜及其制品,包括豇豆、西兰花、黄豆芽、茄子、番茄、黄瓜、菠菜、白菜、马铃薯和番茄酱中的游离型、游离酯型和结合型酚酸进行测定和分析。结果表明不同种类蔬菜酚酸含量差异较大,游离型酚酸以白菜中含量最高;游离酯型酚酸在豇豆中含量最高,其次是菠菜;结合型酚酸在菠菜中含量最高。主成分分析表明,对香豆酸是豇豆中的特征性物质,阿魏酸和异阿魏酸是菠菜区别于其他种类蔬菜的特征性组分,而芥子酸是白菜中的特征性物质。本研究可以为蔬菜中功能性成分的开发利用提供有益参考。     

Determination of phenolic and other polar compounds in flaxseed oil using liquid chromatography coupled with time-of-flight mass spectrometry

A new method based on high-performance liquid chromatography coupled with electrospray ionisation time-of-flight-mass spectrometry (HPLC–ESI–TOF (MS)) has been used to analyse phenolic compounds in flaxseed oil. Some phenolic compounds such as secoisolariciresnol, ferulic acid and its methyl ester, coumaric acid methyl ester, diphyllin, pinoresinol, matairesinol, p-hydroxybenzoic acid, vanillin and vanillic acid have been detected from flaxseed oil. The quantification of these compounds in three varieties of flaxseed oils was carried out using their commercial standards. The efficiency, rapidity and high resolution of HPLC coupled to the sensitivity, selectivity, mass accuracy and true isotopic pattern from TOF (MS) have revealed an enormous separation potential allowing the determination of a broad series of phenolic and other polar compounds present in flaxseed oil for the first time.     

UPLC-MS/MS同时测定铁皮石斛茎、叶、花中酚类组分的含量

建立超高效液相色谱-串联质谱同时、快速分析18 种酚类物质的方法,测定比较铁皮石斛茎、叶、花部位含量差异。样品用甲醇-水溶液提取,提取液中的目标化合物经Waters T3 C18柱梯度洗脱分离,电喷雾串联三重四极杆质谱仪正、负离子扫描方式多反应监测模式检测。结果表明：以18 种酚类物质标准品作为对照,在铁皮石斛样品中共检出15 种酚类组分,分别为3,5-二羟基苯甲酸、橘皮素、绿原酸、槲皮素、芦丁、对羟基苯甲酸、咖啡酸、丁香酸、香草酸、山柰酚、对香豆酸、芥子酸、阿魏酸、3-羟基肉桂酸、水杨酸。铁皮石斛不同部位多酚组分含量为花＞叶＞茎,相对于其他酚类组分,芦丁在铁皮石斛茎、叶、花中的含量均为最高。铁皮石斛不同部位主要酚类组分表现出一定的差别：铁皮石斛花中主要含有芦丁、咖啡酸、阿魏酸和对羟基苯甲酸,铁皮石斛叶中芦丁和阿魏酸的含量相对较高,而铁皮石斛茎部主要酚类组分则为芦丁、阿魏酸与香草酸。实验结果可为铁皮石斛不同部位酚类组分的利用提供一定的科学依据。     

夏枯草中16种酚类化合物含量的测定及其与抗氧化活性的相关性分析

目的:采用液相色谱-串联质谱法（LC-MS/MS）测定24批夏枯草中16种酚类化合物的含量,并采用灰色关联分析和偏最小二乘回归分析方法探讨酚类化合物与抗氧化能力的相关性。方法:夏枯草样品用80%甲醇超声提取,并基于LC-MS/MS建立夏枯草中16种酚类化合物的含量测定方法,以Waters ACQUITY UPLC BEH C₁₈（2.1 mm×100 mm,1.7 μm）色谱柱为固定相,以0.1%甲酸-乙腈为流动相在体积流量为0.4 mL/min条件下进行梯度洗脱,负离子多反应监测模式检测。以DPPH自由基清除能力、ABTS自由基清除能力和铁离子还原能力评价夏枯草的抗氧化活性。结果:16种酚类化合物在各自浓度范围内线性关系良好,相关系数r均大于0.99,精密度、重复性、稳定性和回收率良好。体外抗氧化实验证明夏枯草具有较强的清除ABTS、DPPH自由基和铁离子还原能力,灰色关联分析和偏最小二乘回归分析结果表明迷迭香酸、咖啡酸、芦丁、金丝桃苷、异槲皮苷对于抗氧化的贡献较大。结论:本研究建立了同时测定夏枯草中16种酚类化合物的LC-MS/MS方法,进一步通过相关性分析确定了夏枯草抗氧化的主要活性成分,从而为夏枯草产品的质量控制与开发利用提供科学依据。     

Evaluating the potential of phenolic profiles as discriminant features among extra virgin olive oils from Moroccan controlled designations of origin

Herewith, the potential of an approach based on the combination of the determination of phenolic compounds and the use of chemometric treatments has been evaluated to establish, for the first time, promising models to authenticate the provenance of Moroccan monovarietal olive oils produced under different geographical origin indication systems. To achieve this purpose, 136 commercial extra virgin olive oil samples from three diverse production areas (Meknès territory; the Protected Geographical Indication Ouazzane; and the Protected Designation of Origin Tyout-Chiadma) were collected over two consecutive crop seasons (2012/2013 and 2013/2014). Their phenolic fraction composition was investigated by using high performance liquid chromatography coupled to mass spectrometry (HPLC-ESI-IT MS). The results showed that geographical provenance and harvest season had a marked influence on the content of identified phenolic compounds. Principal components analysis (PCA) and linear discriminant analysis (LDA) were applied to test the potential of the determined compounds as geographical discriminant features, achieving a noticeable discrimination among the three evaluated regions. The contribution of each analyte to the statistic model has been evaluated in depth.     

超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法测定动源性食品中33种兽药残留及质谱库的建立

目的建立超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法测定动源性食品中33种兽药残留的检测方法。方法采用乙腈-水(80:20, V:V)为提取溶剂, QuEChERS方法净化,在Full MS-ddMS2正离子扫描模式下,快速对动源性食品中的目标化合物进行检测。结果在r=70000,扫描范围80~1000m/z内,33种目标化合物的线性相关系数均大于0.99,基质加标回收率范围为70.4%~97.3%,相对标准偏差(relativestandard deviation, RSD)为2.1%~6.0%(n=6)。结论建立的方法适用于动源性食品中33种兽药残留快速检测。同时,本研究建立的33种兽药高分辨质谱库,可应用于非目标化合物的定性筛查。     

Phenolic composition,antioxidant and cytoprotective effects of aqueous-methanol extract from Anneslea fragrans leaves as affected by drying methods

The present study is aimed to evaluate the effect of three different drying methods, including shade drying (SD), freeze drying (FD) and hot air dying (HAD), on the chemical components, antioxidant and cytoprotective activities of aqueous-methanol extracts from A. fragrans leaves. The total phenolic and flavonoid content were determined by spectroscopic methods, whereas the chemical profile of different extracts was determined by ultra-high-performance liquid chromatography coupled with a tandem mass spectrometry (UHPLC-MS/MS). A total of thirteen compounds were characterised and 9 phenolic compounds have been quantified. Two dihydrochalcone glycosides named confusoside and vacciniifolin were found to be the most abundant phenolic compounds in the SD extract of A. fragrans leaves, which also showed the strongest antioxidant and cytoprotective activities. The results showed that shade drying is an efficient method for preserving the chemical constituents and maintaining the antioxidant and cytoprotective activities of A. fragrans leaves.     

Changes in the volatile compounds and chemical and physical properties of Yali pear (Pyrus bertschneideri Reld) during storage

Volatiles from stored Yali pear (Pyrus bertschneideri Reld) were studied using high-resolution gas chromatography and the solid-phase microextraction (SPME) method of gas chromatography/mass spectrometry (GC/MS). The dominant components were ethyl butanoate, ethyl hexanoate, α-farnesene, hexanal, ethyl acetate, hexyl acetate, ethanol and so on. By using GC-olfactometry, it was demonstrated that the volatile compounds from SPME were responsible for the aroma of Yali pear. The levels of sugars, organic acids, and phenolic acids in Yali pear were investigated using high-performance liquid chromatography. Fructose was the dominant sugar, followed by glucose and sucrose. With increasing storage time, sucrose levels decreased, however fructose and glucose levels did not changed remarkably. There was a slight decrease in flesh firmness during storage. The general soluble solids concentration, slightly decreased after 5 months storage. Some aroma volatile components increased during storage, while others decreased, especially the esters. The organic acids and phenolic acids also changed. Yali pear flavor was affected by changes in the levels of volatile compounds, and chemical and physical properties.     

Separation and characterization of phenolic compounds in argan fruit pulp using liquid chromatography–negative electrospray ionization tandem mass spectroscopy

Liquid chromatography (LC) coupled to negative electrospray ionization (ESI) tandem mass spectrometry (MS/MS) was used for the sensitive identification of phenolic compounds in argan fruit pulp. Sixteen compounds were identified, mainly flavonoid glycosides and flavonoid aglycons.     

罗望子种皮原花青素系统的非酶褐变动力学和食品配方因素影响

本研究旨在探讨不同食品配方因素下罗望子种皮原花青素提取物(tamarind seed coat proanthocyanidins extract,TSPA)系统的非酶褐变动力学与关键酚类组分,以解析食品配方因素与热贮藏对原花青素组分的影响,推断非酶褐变的可能机理.以55％(体积分数)乙醇溶液提取所得TSPA的总酚含量...