碳-4植物糖超标蜂蜜样品的多维分析

本文从124份市面蜂蜜样品中筛选出21份C-4植物糖超标蜂蜜样品,应用元素分析-同位素质谱联用技术（EA-IRMS）、液相色谱-同位素质谱联用技术（LC-IRMS）、液相色谱测定蜂蜜还原糖含量等检测方法,对C-4植物糖超标蜂蜜样品进行多维分析。结果表明：C-4植物糖超标样品在市面上仍占有一定比例,本批次检出超标率为16.94%,且存在少量严重超标样品,最高达到82.35%。C-4植物糖超标蜂蜜样品大致可归纳为以下三类：一是源于生产操作不规范的轻微超标型,该类样品的碳-4植物糖含量为7~10%之间,△δ13CF-G、△δ13Cmax跟真实蜂蜜要求相差不远;二是人为掺入碳-4植物源淀粉转化产物型,该类样品寡糖含量较高,△δ13Cmax较大。三是人为掺入碳-4植物源果葡糖浆型,该类样品本身不含寡糖,δ13CF、δ13CG完成丧失碳-3植物特征。     

δ~(13)C_H值小于δ~(13)C_P值的蜂蜜样品的综合鉴评

为加强蜂蜜真实性监测,从124份市面蜂蜜样品中筛选出51份δ13CH值(蜂蜜的δ13C值)小于δ13CP值(蜂蜜中蛋白质的δ13C值)的蜂蜜样品,采用元素分析-同位素质谱联用技术(EA-IRMS)、液相色谱-同位素质谱联用技术(LC-IRMS)以及液相色谱测定蜂蜜还原糖含量等多种检测手段,通过检测这些蜂蜜样品的系列稳定碳同位素比值、还原糖和蔗糖含量,对δ13CH值小于δ13CP值的蜂蜜样品进行了综合分析。结果表明:51份源于δ13CH值小于δ13CP值无法检测碳-4植物糖的样品,δ13CH值皆小于-23.5‰,2份样品还原糖含量低于60 g/100g,1份样品蔗糖含量超标,含量为7 g/100g,目前常规检测方法难以有效鉴评δ13CH值小于δ13CP值蜂蜜样品的真实性。将δ13CP-H(δ13CP-δ13CH)、Δδ13CF-G(δ13CF-δ13CG)、Δδ13Cmax(各类糖组分δ13C值的最大差值)以及寡糖检出等指标纳入综合鉴评,发现51份蜂蜜样品中的47份存在掺假掺杂嫌疑,所占比率高达92.16%,掺假掺杂主要以添加碳-3植物源转化产物为主,掺假原料可能是多类物质的复配组合。     

液相色谱质谱技术在食品掺假中的应用

食品欺诈是食品安全风险防控领域中的重要方面, 其中食品掺假作为食品欺诈的一种类型, 因其掺假物的种类性质、方式等不同往往可能带来或者引入食品安全问题。针对全球性食品掺假行为, 本文综述了近年来液相色谱-质谱联用技术用于解决肉制品、牛奶、食用植物油、蜂蜜4类食品掺假问题, 总结了该4类食品的主要掺假行为, 其中肉制品掺假分为地理来源改变、肉种类替代、添加剂非法使用、过敏原引入、病死畜禽肉; 乳制品掺假主要有奶源产地改变、不同动物奶、添加富氮化合物、添加剂违规; 植物油掺假主要有油种类混合、掺入不可食用油、植物油产地改变、添加工业染料; 蜂蜜常见的掺假方式有蜂蜜产地、植物源、添加糖浆。对液相色谱-质谱鉴别食品真伪的前处理方法(液液萃取、固相萃取)也进行了总结, 以期为液相色谱-质谱联用技术在食品真实性技术鉴别应用提供有益参考。     

蜂蜜品种识别和掺假鉴别的研究进展

蜂蜜作为一种天然甜味剂,不仅营养价值高,而且还具备医疗功效,从而受到消费者青睐。市场上蜂蜜质量问题频繁发生,如混淆植物源和地理源,向蜂蜜中掺杂糖浆等。蜂蜜来源识别和掺假鉴别是中国乃至世界蜂业亟需解决的问题。因此,主要介绍仪器分析法在蜂蜜掺假、品种识别、产地鉴别方面研究进展,并对所有方法进行客观评价分析。对蜂蜜掺假和溯源从联合多种技术(掺假:碳同位素检测技术与色谱技术、光谱技术联合;溯源:其他技术和DNA技术联用)、化学计量学引入、构建蜂蜜数据库3个方面提出建议和展望。     

同位素比率质谱技术对蜂蜜掺假的鉴别

本文扩展了同位素比率质谱联用技术的应用,完善了液相色谱联用同位素比率质谱（LC-IRMS）测定蜂蜜中多种糖组分δ13C值的方法。通过对3种糖浆、3种掺糖蜜和纯正蜂蜜测定结果和图谱的多重比较,发现单纯的使用元素分析联用同位素比率质谱(HT-IRMS)进行测定,无法完全鉴别出掺糖蜜,但是结合LC-IRMS的测定结果则能有效的对以上3种方式的掺假进行鉴别。对6种特制蜂蜜进行测定并判定,判定结论与实际制样情况相符。该技术手段丰富了鉴别掺假蜂蜜的方法,具有较强的应用价值。     

碳同位素比率法检测分析市售蜂蜜碳-4糖浆的 掺假情况

目的优化稳定碳同位素比率法,分析蜂蜜市场质量状况。方法蜂蜜用水混匀后,利用钨酸钠溶液和硫酸溶液沉淀蛋白,多次洗涤后冷冻干燥获得蜜蛋白,利用同位素质谱仪同时检测蜜蛋白和蜂蜜δ~(13)C值,用两点标准漂移校准进行数据处理分析,测得碳-4植物糖浆含量。结果对来自19个省的137批样品进行检测,有15批蜂蜜不符合我国蜂蜜产品行业标准的真实性要求,检出碳-4植物糖浆掺假情况,不合格率10.95%。结论检测方法优化后,检测时间缩短,蛋白提取成功率提高。通过对实际样品的分析,发现目前市售蜂蜜质量不容乐观。     

基于稳定氢氧同位素技术的花生油掺假检测技术研究

建立了高温裂解/元素分析-稳定同位素比值质谱联用技术（TC/EA-IRMS）测定油脂稳定氢氧同位素比值（δ2H和δ18O）的方法,并根据氢氧同位素特征开展花生油掺假检测技术研究。对28个花生样品、5个大豆样品和6个油菜籽样品榨油后测定δ2H值和δ18O值,结果发现三种油的δ2H值分布范围分别为-231.50‰~-213.69‰、-183.11‰~-169.53‰和-192.17‰~-175.82‰;δ18O值分布范围为14.06‰~16.77‰、19.77‰~20.98‰和24.31‰~27.45‰;其中花生油的δ2H值与大豆油和菜籽油存在显著性差异（p＜0.01）,模拟实验表明根据氢氧同位素特征可检测花生油中掺入大豆油或菜籽油。通过对氢氧同位素比值的二维分布对比,可以更为全面的评价和鉴别花生油的掺杂掺假情况,为花生油的掺假鉴别提供了研究基础和技术支持。     

气相色谱-稳定同位素质谱分析酱香型白酒中乙醇的稳定碳同位素比值

应用气相色谱-稳定同位素质谱分析技术,建立了酱香型白酒中乙醇稳定碳同位素比值的分析方法,并对产自贵州省茅台镇某酒厂的33份不同批次酱香型白酒样品、30份其他白酒样品和2份工业酒精进行了分析。方法专属性、精确度和准确度符合分析要求。33份贵州省茅台镇某酒厂生产的酱香型白酒样品中乙醇的稳定碳同位素比值分布在-19.53‰至-19.11‰之间,样品间的标准偏差小于方法精度,经单样本t检验与其他白酒间呈现显著性差异。以单一粮食品种为主要发酵原料的酱香型白酒中乙醇的稳定碳同位素比值能反映其原料特征。研究结果表明,稳定碳同位素比值分析技术在白酒真伪和掺假鉴别中具有应用潜力。     

固态法五粮浓香型白酒掺杂己酸乙酯的鉴别研究

采用气相色谱-高温氧化-同位素比值质谱联用技术(GC-C-IRMS),以国内市场上广泛存在的针对己酸乙酯掺假的白酒为研究对象,对5种不同等级(优级、一级)、不同年份(2009年、2018年和2019年)的固态法浓香型原酒和市面上最主要的3种关于己酸乙酯掺假的白酒进行了己酸乙酯碳同位素组成测试,结果显示固态法浓香型原酒中...     

基于HPLC-ELSD和偏最小二乘判别分析法的蜂蜜掺假鉴别

为了实现蜂蜜掺假的简便、快速识别,应用高效液相色谱技术和化学计量学手段建立了一种蜂蜜掺假检测的新方法。该研究收集了中国不同品种、不同地域的典型天然蜂蜜样品,根据目前市场上常见的蜂蜜掺假手段、掺假物质及相对含量情况模拟制备系列掺假蜂蜜样品,利用HPLC-ELSD对样品中糖类物质进行分离测定,并采用PLS-DA统计学方法进行蜂蜜掺假识别研究。研究结果表明:掺入质量分数10%以上果葡糖浆和麦芽糖浆的掺假蜂蜜样品均能利用本方法予以鉴别,其校正集的正确判别率达到92.5%,验证集的正确判别率为100%。     

SPME-GC-MS analysis of volatile organic compounds in honey from Basilicata. Evidence for the presence of pollutants from anthropogenic activities

Solid‐phase microextraction gas chromatography‐mass spectrometry analysis of nineteen samples of honey from Basilicata (southern Italy) showed the presence of some flavour components never described before in honey. Furthermore, some phenyl‐substituted hydrocarbons were detected. These compounds may be derived from the wastewater treatment plant in the area. Furthermore, in honey collected near an oil extraction plant, hydrocarbons were found; these may be derived from such plants present in the area.     

UPLC-Q-Exactive四极杆-静电场轨道阱高分辨质谱联用鉴别掺假蜂蜜

为对掺假蜂蜜识别提供新思路和新方法,本研究应用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱联用的方法鉴定4种未掺假蜂蜜及2种掺假蜂蜜中肽类物质的组成和结构,并探讨未掺假蜂蜜和掺假蜂蜜多肽的差异。以20%的三氯乙酸溶液沉淀蜂蜜蛋白,所得蜂蜜蛋白以胰蛋白酶酶解,然后通过C₁₈固相萃取柱净化酶解肽段。采用0.1%甲酸和乙腈作为流动相进行梯度洗脱,以高分辨质谱(Q-Exactive)的Full MS/ddMS2模式对胰蛋白酶酶解后的蜂蜜多肽进行鉴定,MaxQuant软件分析质谱结果,分析所得肽段在Uniprot上进行Blast序列对比。结果显示,4种未掺假蜂蜜中均存在来自蜂王浆主要蛋白(MRJPs)的多肽,2种掺假蜂蜜中未检测出MRJPs,且4种未掺假蜂蜜中所鉴定出的多肽80%以上来自于蜜蜂(Apis cerana cerana、Apis cerana、Apis mellifera)。通过比对6种蜂蜜酶解肽段序列发现,肽段EYILVLSNK在4种未掺假蜂蜜中均有检测到,在2种掺假蜂蜜中未检出。因此,来自于Apis mellifera的MRJP1酶解产生的肽段EYILVLSNK或可作为辨别真伪蜂蜜的潜在肽段。     

Study on distribution pattern of stable carbon isotope ratio of Chinese honeys by isotope ratio mass spectrometry

The δ ¹³C values of 26 varieties of Chinese pure single‐flower honeys, 323 census samples of six varieties of single‐flower honeys and one multi‐flower honey as well as 20 888 commercial honey samples from 135 honey‐related enterprises in 25 provinces of China were analysed by stable carbon isotope ratio mass spectrometry between 1998 and 2004. It was found that the δ ¹³C values of different Chinese honeys fell within the ranges of values proposed by JW White. This shows that White's theory of the stable carbon isotope ratio of honeys is applicable to Chinese honeys and further demonstrates that the theory is universal to honeys from all over the world. The study also confirmed that the δ ¹³C values of honeys do not bear much relation to the environment in which the honey plants are grown, e.g. geographical area, water and soil, climate, etc., but do vary slightly with the honey plant species. Copyright © 2005 Society of Chemical Industry     

Comprehensive screening of veterinary drugs in honey by ultra-high-performance liquid chromatography coupled to mass spectrometry

In the context of multi-residue screening in honey, a complete methodology was developed for 200 veterinary drugs comprising a sample preparation step and an ultra-high-performance liquid chromatography (UHPLC) coupled to time-of-flight (TOF) mass spectrometry analysis. In addition, specific analytical strategies were developed for two compounds, streptomycin and chloramphenicol, using UHPLC and tandem mass spectrometry (MS/MS). Methodologies were then applied to real honey samples obtained from the Swiss market.     

高效液相色谱-离子阱-飞行时间质谱法定性分析蜂蜜中的黄酮类未知物

目的 建立高效液相色谱-离子阱-飞行时间串联质谱法(high performance liquid chromatography-ion trap-time of flight tandem mass spectrometry, HPLC-MS-IT-TOF)定性分析蜂蜜中的未知黄酮类物质的分析方法。方法 通过查阅相关资料, 推断该未知物可能是黄酮类物质, 用质谱检测可知与其他干扰物质是否分离。在确定干扰物质与未知黄酮进行分离后, 可以得到未知黄酮类物质的分子离子峰和三级质谱碎片, 根据碎片离子, 推导出了裂解途径, 并使用分子式软件预测了未知黄酮类物质的分子式。结果 综合实验结果, 最后定性了蜂蜜中的未知黄酮类物质为“短叶松素”, 其分子式为C15H12O5。用超高效液相色谱-串联质谱(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)将黄酮类未知物质与短叶松素标准品的保留时间、离子对m/z 271.06＞253.10和m/z 271.06＞191.00及离子比率进行比对, 确证定性结果是准确的。结论 本实验为蜂蜜中黄酮类未知物定性提供了一个有效的思路和方法。     

Erythromycin residue in honey from the Southern Marmara region of Turkey

Honey samples, collected from the Southern Marmara region of Turkey, were analysed for erythromycin residues by liquid chromatography–mass spectrometry using electrospray ionization in the positive ion mode (LC–ESI–MS). Fifty samples, comprising chestnut, pine, linden and multi-flower honeys, were collected directly from hives and analyzed. The limit of detection and quantification were 6 and 20 ng g^?1, respectively, and recovery ranged from 85 to 89%. Four of the honey samples (8%) were found to be contaminated with erythromycin residues at concentrations ranging from 50 to 1776 ng g^?1. An erythromycin-fortified cake feeding assay was also performed in a defined hive to test the transfer of erythromycin residue to the honey matrix. In this test hive, the residue level in the honey, 3 months after dosing, was approximately 28 ng g^?1.     

Occurrence of naphthalene in honey consumed in Turkey as determined by high-pressure liquid chromatography

This study is the first report on an investigation of the naphthalene concentration in samples of contaminated honey consumed in Turkey. Naphthalene was detected using high-performance liquid chromatography with a diode array detector at 220 nm. In one suspected contaminated specimen, the presence of naphthalene was confirmed by gas chromatography with mass spectrometry (GC-MS) at a concentration of 1.13 microg/kg. The limit of detection was 0.023 microg/g and the limit of quantification was 0.078 microg/g with signal-to-noise ratios of 3 and 10, respectively. A total of 100 samples of commercially available honey obtained from markets (53 samples) and street bazaars (47 samples) were analyzed. Mean naphthalene recovery from honey known to be contaminated with 1 microg/g was 80.4% (SD = 4.84%, n = 7).     

Analysis of imidocarb in livestock and seafood products using LC-MS/MS

A simple method using high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was investigated for the detection of the antiprotozoal drug imidocarb in 10 livestock and seafood products. Liquid chromatographic separation employed a TSK VMpak-25 column with ammonium acetate-acetonitrile as a mobile phase. Mass spectral acquisition was performed in the ESI positive-ion mode. Imidocarb was extracted from all samples using liquid extraction with acetonitrile under basic conditions. For samples other than honey, fat-soluble impurities were removed by acetonitrile-hexane partitioning. The salting-out technique was used for extraction from honey in order to improve the separation of the organic solvent and water added to the honey sample. The limit of quantitation was 0.005 μg/g (expressed as concentration in samples). The recoveries from all samples were 76-109%, and the repeatability and reproducibility were also satisfactory.     

Volatile norisoprenoids as markers of botanical origin of Sardinian strawberry-tree (Arbutus unedo L.) honey: Characterisation of aroma compounds by dynamic headspace extraction and gas chromatography–mass spectrometry

In order to characterize and authenticate the aromatic profile of strawberry-tree (Arbutus unedo L.) honey, a dynamic headspace (DHS) extraction, followed by gas chromatography–mass spectrometry (GC–MS) analysis, was performed on 10 Sardinian strawberry-tree (Arbutus unedo L.) honey samples. A total of 28 aroma compounds were identified, but only norisoprenoid compounds such as α-isophorone, β-isophorone and 4-oxoisophorone, were recognized as specific floral origin markers of the strawberry-tree honey. The α-isophorone/β-isophorone ratio varied from 4 to 8, whereas the α-isophorone/4-oxoisophorone ratio was found to range from 11 to 20. The DHS extraction method was proposed as a valid alternative to pollen analysis for floral source detection, especially for products like strawberry-tree honey, characterized by a low pollen content.     

Pyrrolizidine alkaloids in floral honeys of tropical Ghana: a health risk assessment

ABSTRACT

There is a vast amount of information about the nutritional and medicinal properties of honey as a result of its numerous benefits. However, honeys have been found to be contaminated with hepatotoxic and carcinogenic pyrrolizidine alkaloids (PAs) on account of bees foraging on PA-containing plants. This study deals with the analysis of PAs in tropical honeys emanating from different agro-ecological zones of Ghana in order to assess its potential health risk. PAs of 48 honey samples were analysed using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The results show that a total of 85% of the honeys from various agro-ecological zones were PA positive including all honeys from supermarkets. The highest concentration of PAs was 2639 μg kg^?1, while the average PA concentration of the samples was 283 μg kg^?1. The study also found Chromolaena odorata pollens in majority of the honeys, thus indicating the plant as major source of PA contamination of honeys in the tropical regions.