高效液相色谱-高分辨飞行时间质谱联用技术筛选中国和俄罗斯人参中的差异成分

摘 要：目的 建立高效液相色谱-高分辨飞行时间质谱联用技术筛选中国和俄 罗斯人参中人参皂苷差异化合物的分析方法。方法 采用高效液相色谱-高分辨飞行时间质谱联用技术(High-Performance Liquid Chromatography Tandem Triple-Time-of-Flight Mass Spectrometry/Mass Spectrometry,HPLC-Triple-TOF MS/MS)技术对来源于中国和俄罗斯的48例人参样品进行测定,通过高分辨飞行时间质谱分析(Triple-Time-of-Flight Mass Spectrometry/Mass Spectrometry, Triple-TOF MS/MS),对48例样品的特征峰质谱信息进行提取,通过得到的一级质谱精确质荷比和二级质谱碎片信息,结合软件数据库进行成分鉴别后,采用主成分分析(Principal Component Analysis,PCA)和正交偏最小二乘法-判别分析 (Partial Least Squares Discriminant Analysis,PLS-DA)对得到的数据进行处理,筛选差异组分。结果 经上述方法进行处理和分析后,中国和俄罗斯人参样品间的组分得到明显区分,初步筛选并鉴定出了中国和俄罗斯人参间14种差异显著的人参皂苷类化学成分。结论 本研究成功建立了基于高效液相色谱-高分辨飞行时间质谱联用技术鉴别中国和俄罗斯人参的分析方法,建立的方法准确、可靠, 可用于中国和俄罗斯人参的产地鉴别和溯源。     

The effect of dietary polyphenols on intestinal absorption of glucose and fructose: Relation with obesity and type 2 diabetes

Polyphenols are a group of substances present in plant-based foods such as apples and in plant-based beverages such as red wine. This review shows that polyphenols interfere with intestinal sugar transporters, modulating their function and altering glucose and fructose absorption. Inhibition of intestinal glucose and fructose absorption contributes to the effect of polyphenols in reducing postprandial glycemia, altering the apparent glycemic index of foods and decreasing body mass index. The possible implication of these findings on type 2 diabetes and obesity is a matter of growing interest, as shown by the rise on publications on this subject.

Abbreviations: BBM: Brush Border Membrane; BLM: Basolateral Membrane; BMI: Body Mass Index; ECg: Epicatechin Gallate; EC: Epicatechin; EGC: Epigallocatechin; EGCg: Epigallocatechin Gallate; GLUT2: Facilitative Glucose Transporter 2; GLUT5: Facilitative Glucose Transporter 5; HFCS: High-Fructose Corn Syrup; HPLC/MS: High performance Liquid Chromatography/Mass Spectrometry; HOMA-IR: Homeostatic Model Assessment; IFD: International Diabetes Federation; LPH: Lactase Phloridzin Hydrolase; MAPK: Mitogen Activated Protein Kinase; MetS: Metabolic Syndrome; NHS I e II: Nurses’ Health Study I and II; PK: Protein Kinase; SGLT-1: Sodium-Glucose Co-Transporter; T2D: Type 2 Diabetes     

Helping to authenticate sparkling drinks with 13C/12C of CO2 by gas chromatography-isotope ratio mass spectrometry

We applied direct injections of headspace gas into a Gas Chromatography – Combustion – Isotope Ratio Mass Spectrometry (GC-C-IRMS) system to measure ¹³C/¹²C isotopic ratio of carbon dioxide from the headspace of several sparkling and soft-drinks. This straightforward technique, which consists in an automated analysis of the headspace sample with no prior purification steps, improves the determination of δ¹³C values of CO₂ gas as a food probe authenticity. However, for an ultimate test, combination with other isotopic data is required.     

The sensory evaluation of 2,4,6‐trichloroanisole in wines

This work proposes a sensory method to verify the ‘cork taint’ defect in food and beverages. This off‐flavour has considerable economic impact in wine but occasionally can occur in other food and beverages. In wine, 2,4,6‐trichloroanisole (TCA) is generally considered to be the main compound responsible for this taint. It is an easily recognized compound because of its low sensorial threshold, and it is described as a mouldy and damp cardboard odour. This sensory method, developed in wine, consists of specific panel training to recognize TCA in a series of olfactory tests. The effectiveness of the panel was tested with contaminated wines in which the TCA content had been previously determined by Solid Phase Microextraction‐Gas Chromatography Mass Spectrometry (SPME‐GC/MS) analysis. This sensory method is useful to train a panel able to recognize the ‘cork taint’ defect in different situations (legal appraisals or quality assurance systems). The use of a reliable sensory assay can reduce the number of chemical analyses and the proposed method can be applied to other beverages such as beer. Copyright © 2015 The Institute of Brewing & Distilling     

UPLC-MS/MS分析牛肉红朱橘成熟果实多酚类化合物积累特征

为探索贵州地方柑橘品种-牛肉红朱橘（NRH）多酚类化合物组成特征,以朱红橘（ZHJ）和红香柚（HXY）为对照,利用超高效液相质谱串联质谱技术（UPLC-MS/MS）和代谢组学方法,分析三个种质成熟果实积累特征。结果表明:共检测到493种物质,其中类黄酮（163种）最多,其次是酚酸（71种）。聚类热图、火山图、差异代谢物筛选、维恩图和KEGG功能注释等分析结果均表明,三个柑橘种质多酚类化合物种类和相对含量呈现种质特异性,遗传背景相似的NRH与ZHJ代谢物种类和相对含量更为接近,筛选到的差异代谢物较少;两者与HXY代谢物种类和相对含量差异较大,说明代谢物种类与种质类型间存在密切联系。本研究有助于了解地方柑橘种质多酚类化合物积累特征,为后期开发利用提供参考。     

类胡萝卜素纯化及分析技术最新研究进展

类胡萝卜素是一类重要的天然色素的总称,随着现代分析检测技术的快速发展,发现了越来越多的类胡萝卜素。通过对类胡萝卜素的分析检测技术如液相色谱法、质谱法等以及前处理纯化方法如膜分离技术、高速逆流色谱技术等进行总结,以期为今后进一步研究类胡萝卜素的结构及性质提供方便。     

气相色谱-电子轰击源质谱测定海产品中多溴联苯(醚)

海产品中多溴联苯残留现在已经成为新的食品安全危害因子,但是针对海产品中多溴联苯检测方法的研究还不多。针对海产品基质的特殊性,研究建立了样品的加速溶剂萃取仪(ASE)提取、多层硅胶层析柱净化前处理方法,采用定性离子和外标定量法建立了气相色谱-电子轰击源质谱(GC-EI/MS)法检测海产品中多溴联苯(PBBs)和多溴联苯醚(PBDEs)的定性和定量方法。所建立的十三种多溴联苯和多溴联苯醚GC-EI/MS方法的线性范围在10～200ng/mL,检出限在0.44～6.0ng/mL之间,具有较宽的线性范围和很高的灵敏度。通过添加回收实验表明,方法回收率在59.7%～97.2%之间,相对标准偏差(RSD)在1.0%～13.7%之间。     

反相高效液相色谱电喷雾质谱法鉴定葡萄籽低聚原花青素

建立了采用LCESIMS对葡萄籽提取物中的多种低聚原花青素进行分析鉴定的方法。原花青素用体积分数60%乙醇水溶液从葡萄籽中提取并用聚酰胺柱层析精制后,以乙腈1%醋酸水溶液为流动相在ZORBAXSBC18柱上进行梯度洗脱分离,在电喷雾电离负离子模式下采用选择离子监测模式(SIM)将几种低聚体进行了选择性的分离。结果所检葡萄籽提取物中共含有(+)儿茶素、(-)表儿茶素和(-)表儿茶素没食子酸酯3种单体、8种非酯型和4种没食子酸酯型共12种二聚体及4种非酯型三聚体等。建立的方法可以较好地解决葡萄籽中各种低聚原花青素的定性检测,了解提取物中原花青素的成分。同时文中还对原花青素二聚体的质谱碎裂途径进行了讨论。     

酿造酱油与酸水解植物蛋白调味液特征挥发性组分对比分析

应用顶空固相微萃取——气质联用技术和内标物定量方法,对酿造酱油和酸水解植物蛋白调味液中挥发性成分进行分析,筛选二者的特征挥发性组分并进行比较。发现二者的特征挥发性组分存在明显差异,主要表现在酿造酱油中特征组分以醇类、酚类、酸酯类以及呋喃类和吡咯类杂环小分子化合物为主,而酸水解植物蛋白调味液中特征组分则以吡嗪类杂环小分子化合物为主。上述研究结果为进一步开展酱油风味分析评价工作及建立基于挥发性风味组分的酿造酱油和非酿造酱油鉴别检验方法打下了较好的基础。     

蔗渣磨木木素(MWL)热解过程的初步研究

本文采用热失重、热解气相色谱质谱联用等分析方法,分析了蔗渣磨木木素的热化学特性,同时对蔗渣磨木木素快速热解过程进行了初步研究.蔗渣磨木木素在隋性气体氛围下,热化学裂解形成大量含苯环的木素基本结构单元衍生物,部分进一步降解成小分子化合物.其热化学降解特征表现为自由基反应模式.     

Physicochemical characterisation of gulupa (Passiflora edulis Sims. fo edulis) fruit from Colombia during the ripening

Gulupa (Passiflora edulis Sims. fo edulis) is a tropical fruit native to America. This study was undertaken to characterize the physicochemical properties of this fruit in three maturity stages. In all stages, the pH, °Brix, texture, and titratable acidity were determined. pH value and solid soluble content increased during ripening and titratable acidity decreased during this process; in contrast, texture values did not show significance variance. It was confirmed the presence of cyanidin-3-O-??-D-glucopyranoside as major anthocyanin. The changes on colour were followed by tristimulus colorimetry using image analysis, a very useful new approach for the measurement of non-homogeneous colours. By using PCA (Principal Component Analysis), clusters of data corresponding to each stage could be defined. Additionally, the volatile composition was followed by HS-SPME (Headspace-Solid Phase Microextraction) and GC/MS (Gas Chromatography/Mass Spectrometry) analyses. The results showed an increase in the amount of volatile during fruit ripening, with aliphatic esters as major constituents.     

大豆皂苷化学结构及分析方法的研究进展

大豆皂苷是豆科植物特别是大豆的主要活性成分之一,目前已经应用到食品、化妆品及药品各个领域。目前根据其苷元结构类型,以C-21,C-22及C-29的官能团不同,把大豆皂苷归纳为三类,分别为A型、B型及Sg-6型。为了便于分析和归纳,本文把大豆皂苷细分为大豆皂苷A、B、DDMP、E、H、I、J等。因大豆皂苷应用广泛,分离检测手段也越来越多。根据大豆皂苷定量定性原则为基础,将分析型检测手段分为两种,一种是分离型检测型的定量手段:如包括薄层色谱(Thin Layer Chromatography)、高效液相(HighPerformanceLiquidChromatography)、超高压液相(UltraPerformanceLiquidChromatography)、气相(Gas Chromatography);另一种是基于不进行分离的定性分析的检测方法:核磁共振技术(NuclearMagneticResonance)、高速逆流色谱(High-speed Countercurrent Chromatography)、质谱(Mass Spectrometry)、代谢组学指纹图谱、免疫方法分析组成。值得注意的是质谱联用技术既是重要的定性手段也是常用的定量手段。本文对大豆皂苷的化学结构、检测分析方法进行了综述研究,并对其未来的应用做出了探讨。     

ALKALOID COMPOSITION OF LUPINUS CAMPESTRIS FROM MEXICO

The content of quinolizidine alkaloids (QA) in Lupinus campestris, Fabaceae family, was analyzed by Gas Chromatography‐Mass Spectrometry (GC‐MS), Samples of various organs of Lupinus campestris collected at different monthly stages of the growing plant, were subjected to extraction in a Merck Extrelut column. The quinolizidine alkaloid patterns of stems, leaves, flowers, pods and seeds were assessed and then identified and quantified by GC. Alkaloid structures were identified according to their mass fragmentation patterns, in combination with their indicative Kovats retention index. Alkaloids found in several developmental stages of the plant were mainly: aphyllidine, 5, 6‐dehydrolupanine, aphylline, dehydro‐oxosparteine, lupanine, α‐isolupanine, hydroxyaphylline and hydroxyaphyllidine, plus two alkaloids that ‐were not identified. During the third month the relative abundance of total alkaloids were highest. The main alkaloids found in seeds were hydroxyaphylline and hydroxyaphyllidine.     

蜂毒肽的分离纯化及结构鉴定

目的 对蜂毒肽进行分离纯化,并进行结构鉴定。方法 以意大利蜜蜂蜂毒为原料,经溶解、超声、浸提、过滤等,并制备C18液相色谱柱,对一次纯化采用的流动相、洗脱程序进行优化,对二次纯化时进样量、进样浓度进行选择,冻干后得到高纯度蜂毒肽。利用基质辅助激光解析电离飞行时间质谱法(matrix-assisted laser desorption/ionization time-of-flight mass spectrometry,MALDI-TOF MS)和液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry, LC-MS/MS)进行分子量测定等定性研究,利用傅里叶变换红外光谱(Fourier transform infrared spectroscopy,FT-IR)进行二级结构表征,尝试利用低场核磁共振(nuclear magnetic resonance, NMR)技术对其氢谱定性解析,基于高效液相色谱法(high performance liquid chromatography, HPLC)的面积归一化法测定蜂毒肽纯度。结果...     

Characterisation of alkylphenols in pistachio (Pistacia vera L.) kernels

Pistachio kernels were extracted with n-hexane and the oil obtained was saponified with methanolic KOH. The extracted unsaponifiable matter was fractionated on Thin Layer Chromatography (TLC) plates. The band with R_f = 0.47, analysed by Gas Chromatography–Mass Spectrometry (GC–MS), showed the presence of long-chain alkylphenols: this is the first time that alkylphenols are reported in pistachio kernels. To elucidate the structures, Nuclear Magnetic Resonance (NMR) and GC–MS analyses (on the trimethylsilyl derivatives) were used. Sixteen different 3-alkylphenols (cardanols) with a saturated, monounsaturated and diunsaturated chain were detected. A reaction with dimethyl disulphide was successfully used to determine the double bond position in the monounsaturated compounds. Three phenols were new natural compounds. The most abundant cardanols were 3-(8-pentadecenyl)-phenol, 3-(10-pentadecenyl)-phenol, 3-pentadecyl-phenol and 3-(10-eptadecenyl)-phenol. Total amount of cardanols in the oils (mean of five samples) was roughly evaluated as 440 ± 95 mg kg⁻¹.     

Structural characterization of 132-hydroxy-(132-S)-phaeophytin-a from leaves and stems of Amaranthus tricolor isolated by high-speed countercurrent chromatography

Amaranthus tricolor (Amaranthaceae) is a popular vegetable in China. Separation of lipophilic extracts of the aerial parts of A. tricolor by means of preparative ‘High-speed Countercurrent Chromatography’ (HSCCC) led to the isolation of two chlorophyll breakdown products which were characterized as 13²-hydroxy-(13²-S)-phaeophytin-a (1) and chlorophyll b methoxylactone (2).The structure of 1 was established using a combination of 1D- and 2D-NMR spectroscopic and mass spectrometric techniques. Component 2 was identified by means of ESI-MS/MS analysis.Industrial relevanceChlorophylls and their degradation products are natural pigments of interesting bioactivities. For industry, recovery of these pigments from waste materials of fruit and vegetable processings could be a promising by-product line. Here we present the isolation of a pure chlorophyll breakdown product which is in principle suited as a nutraceutical ingredient. Large-scale isolation procedures using countercurrent chromatography techniques for chlorophyll related pigments are currently under development.     

SYNTHESIS AND CHARACTERISATION OF DIMERS OF CATECHIN AND EPICATECHIN

A method of synthesis of ‘dimers’ of catechin and epicatechin is described which gives 50% yields of the pure substances. The structures of the products are confirmed by nuclear magnetic resonance using ¹H and ¹³C resonances and by mass spectrometry. Mass spectrometry using laser impact with (+) ions allows a rapid distinction to be made between the ‘dimers’ derived from catechin or epicatechin.     

Antioxidant activity of an anatolian herbal tea—Origanum minutiflorum: isolation and characterization of its secondary metabolites

Origanum species are significant aromatic and medicinal plants used in food and pharmaceutical industries. Isolation of bioactive compounds was executed on n-butanol extract to yield the compounds responsible for the activities. Tricosan-1-ol (1), (8E,16E)-tetracosa-8,16-diene-1,24-diol (2), azepan-2-one (3), 3,4-dihydroxybenzoic acid (4), apigenin (5), eriodictyol (6), globoidnan-A (7), luteolin (8), rosmarinic acid (9), apigenin-7-O-glucuronide (10), and vicenin-2 (11) were isolated by chromatographic methods (column chromatography and semi-preparative High Performance Liquid Chromatography (HPLC) and structures were elucidated on the basis of spectroscopic techniques including 1D/2D nuclear magnetic resonance (NMR) and Liquid chromatography/Time-of-flight/Mass spectrometry (LC-TOF/MS). The isolated compounds and extracts were applied for antioxidant assays including 1,1-diphenyl-2-picrylhydrazyl (DPPH^?) scavenging, 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS^?+) scavenging, reducing power, and cuprac techniques. 3,4-Dihydroxy benzoic acid (4), eriodictyol (6), luteolin (8), and rosmarinic acid (9) revealed the considerable antioxidant activities.     

固相微萃取--气质色谱法测定玫瑰香葡萄酒中的香气成分

用固相微萃取蜒气质色谱法测定了玫瑰香葡萄酒中的挥发性香气物质,检出12个醇类化合物、16个酯类化合物、9个萜类化合物及少量醛类化合物,及其赋予的香气特征.