葡萄酒和软木塞中2,4,6-三氯苯甲醚检测方法的研究进展

本文介绍了葡萄酒和软木塞中2,4,6-三氯苯甲醚（2,4,6-trichloroanisole,TCA）的来源及影响,分析了2,4,6-三氯苯甲醚的检测难点,总结了目前检测2,4,6-三氯苯甲醚方法的总体趋势及现状。按照前处理方法的原理分类,介绍了前处理方法的定义、特点,并概述和讨论了前处理方法在萃取葡萄酒和软木塞中2,4,6-三氯苯甲醚中的应用;根据仪器检测方法的不同特点,总结和讨论了仪器检测方法在分析检测葡萄酒和软木塞中2,4,6-三氯苯甲醚的应用。前处理方法和仪器检测方法相结合,达到了浓缩和检测葡萄酒和软木塞中2,4,6-三氯苯甲醚的目的。     

超声波辅助-顶空固相微萃取-气相色谱法测定软木塞中痕量2,4,6-三氯苯甲醚

通过对软木塞样品提取过程的优化,建立了超声波法辅助顶空固相微萃取-气相色谱仪检测软木塞中痕量2,4,6-三氯苯甲醚(TCA)的方法。试验结果表明,该方法的线性范围0.5 ng/L~80.0 ng/L,R2为0.999 8,线性关系良好。方法检出限为0.2 ng/g,方法定量限为0.5 ng/g,精密度(RSD)在1.35%~5.47%之间,加标回收率为81.5%~97.8%。该方法操作简便、快速、易操作、准确度高、重现性好,适用于普通实验室对软木塞中痕量2,4,6-三氯苯甲醚残留的检测。     

顶空固相微萃取联合气相色谱-质谱检测葡萄酒中2,4,6-三氯苯甲醚

利用响应面法优化采用顶空固相微萃取联合气相色谱-质谱技术检测葡萄酒中2,4,6-三氯苯甲醚（2,4,6-trichloroanisole,TCA）。对萃取头进行了选择,并优化固相微萃取参数：样品体积、萃取温度、平衡时间和萃取时间等对TCA萃取效果的影响。结果表明,用聚二甲基硅氧烷/二乙烯基苯（65 μm）萃取头进行TCA萃取的最佳条件：样品9.8 mL、2 g NaCl、33 ℃平衡10 min、萃取90 min进行气相色谱-质谱分析,以TCA-d5为内标物进行定量。该方法的相关系数R2为0.999 9,重复性的相对标准偏差为1.03%,加标回收率范围在95.7%～106.1%之间,检出限和定量限分别为0.3 ng/L和1 ng/L。检测7 种市售葡萄酒产品的TCA含量在0～7.6 ng/L之间,干白葡萄酒中TCA含量低于干红葡萄酒。该方法操作简单、可靠,适用于葡萄酒中TCA的测定。     

气相色谱电子捕获技术分析检测葡萄酒及软木塞中TCA的研究进展

软木塞污染影响葡萄酒感官质量已成为葡萄酒行业最为关注的问题之一,主要原因在于软木塞中存在2,4,6-三氯苯甲醚(TCA).介绍了利用气相色谱电子捕获技术(GC-ECD)检测葡萄酒及软木塞中TCA的研究进展,同时对GC-ECD的工作原理及应用进行了阐述,为有效分析检测和控制葡萄酒及软木塞中的TCA含量提供参考.     

超声波辅助-顶空固相微萃取-气相色谱法测定葡萄酒中痕量2,4,6-三氯苯甲醚

建立了超声波-顶空固相微萃取-气相色谱检测葡萄酒中的痕量木塞污染物——2,4,6-三氯苯甲醚（TCA）的方法。试验结果表明,该方法有良好的线性关系,相关系数为0.999 89,方法定量限为0.5 ng/L,相对标准偏差RSD在1.98%～5.32%之间,加标回收率为89.0%～103.2%。该方法操作简便、快速、准确度高、重现性好,适用于普通实验室对葡萄酒中痕量TCA残留的检测。     

山药酒中甾醇含量测定及清除DPPH自由基活性研究

采用固相微萃取（SPME）结合气相色谱-质谱联用（GC-MS）仪测定葡萄酒用软木塞中2,4,6-三氯苯甲醚的迁移量,对整个过程引入的不确定度进行分析评定。依据CNAS-GL006：2019《化学分析中不确定度的评估指南》和JJF 1059.1—2012《测量不确定度评定与表示》,构建了不确定度评定的数学模型,分析了不确定度来源,并对各分量加以量化和合成。评定结果表明,其不确定度主要来源于标准溶液系列配制过程,其次是内标物质添加过程;当木塞中2,4,6-三氯苯甲醚迁移量为2.04 ng/L时,其扩展不确定度为0.26 ng/L（k=2）。     

顶空-固相微萃取/气相色谱串联质谱法测定葡萄酒中多种氯酚及氯代茴香醚

样品中氯酚经乙酰化生成乙酰氯酚后,通过优化萃取头、离子强度、温度、时间等固相微萃取条件后,建立顶空-固相微萃取-气相色谱串联质谱法同时测定测定葡萄酒中的3种氯酚2,4,6-三氯酚(TCP)、2,3,4,6-四氯酚(TeCP)、五氯酚(PCP)以及两种氯代茴香醚2,4,6-三氯苯甲醚(TCA)、五氯苯甲醚(PCA)含量的方法。结果表明：该方法检出限为0.1ng/L,回收率为86.0%～105.9%,相对标准偏差小于16.5%。该方法前处理简单、高效、检测灵敏度高,可应用于进出口葡萄酒中木塞污染物的监控。     

红葡萄酒中2,4,6-三氯苯甲醚(TCA)感官阈值的研究

2,4,6-三氯苯甲醚(TCA)是葡萄酒软木塞常见污染物之一,在酒中的含量极低(ng/L级别),但特殊的霉味会使消费者产生排斥.国外已对其进行了深入的仪器与感官分析研究,国内还未开展针对TCA的感官分析研究.本实验主要目的是测算多大浓度TCA污染的葡萄酒会使消费者产生排斥反应,通过成对比较及三点比较的检验方法,测定消费者排斥阈(CRT)及消费者觉察阈(DT),5%显著性结果分别为64ng/L和2ng/L,且两者间未呈现显著相关性.对比国外相关文献发现,国内外消费者察觉阈值比较接近,TCA的感官敏感性无较大差异;而国内消费者在对葡萄酒的喜好性评价中,相比国外消费者更不易受TCA的影响.     

不同软木塞中2,4,6-三氯苯甲醚迁移量的检测和评价分析

本文在建立了稳定的2,4,6-三氯苯甲醚(TCA)检测方法基础上,对不同类别的软木塞进行了TCA迁移量的检测,并对检测结果进行分析评价。结果表明,DIAM塞为TCA"零污染",天然塞和微颗粒塞次之,风险程度较低;1+1塞有较高的检出率,但TCA迁移量均在2 ng/L以下的可控范围内;而聚合塞不仅检出率高、合格率低,而且TCA检出值范围较宽,最大值达5.76 ng/L,对葡萄酒的污染风险程度最高。该研究为酿酒师木塞的选用提供数据支撑和指导作用。     

葡萄酒中2,4,6-三氯苯甲醚(TCA)检测新技术的研究进展

2,4,6-三氯苯甲醚(TCA)是危害葡萄酒感官品质的一种物质,通常来自于葡萄酒封装所用的软木塞,也可能来自葡萄原料或酿酒过程中的污染,它的存在使葡萄酒产生不良气味和口感。简介了最近十几年来检测葡萄酒中TCA的新方法和新仪器,包括葡萄酒中TCA的萃取技术和检测技术。并对这些新技术的特点、原理及应用优势进行了阐述。目的是为对葡萄酒中的TCA做到精确、低检出限和高灵敏性的定性及定量测定提供参考,从而对葡萄酒中的TCA进行准确的监测,最终提高葡萄酒的品质。     

Absorption of chloroanisoles from wine by corks and by other materials

Sixty 750 mL bottles of a white wine were each spiked with deuterium-labelled 2,4,6-trichloroanisole (d₅ TCA) and then sealed with a variety of wine corks. Thirty months later, approximately half of the d_5-TCA had been absorbed by each of the corks, regardless of supplier, bleaching treatment or whether the corks were natural or agglomerate. In addition to the added labelled TCA, every one of these corks also contained endogenous (i.e. unlabelled) TCA. Fifteen of the corks, mostly agglomerates, imparted some of their endogenous TCA into the wines. There was no direct relationship between the amount of endogenous TCA in the corks and that found in wines. The high variability in the distribution of endogenous TCA between wine and cork contrasts with the relatively uniform distribution of the d₅-_-TCA. This contrasting behaviour distinguishes between wines tainted prior to closure and wine tainted by corks. Natural bark corks in wine bottles can also absorb 2,3,4,6-tetrachloroanisole (TeCA) and pentachloro-anisole (PCA) from bottled wine. Bottle storage of commercial wines that had become tainted with TeCA and PCA during production resulted in the corks absorbing most of these two compounds, so that the wines were no longer tainted to a significant extent. Soaking whole corks in wine spiked with chloroanisoles, under conditions typically employed in the wine industry to test batches of corks for possible taint, resulted in most of the TCA in the wine being absorbed by the corks. Thus, if five corks are being soaked in wine in order to test for taint, four sound corks could reabsorb TCA that had leached into the surrounding wine from a single contaminated cork, reducing the concentration of TCA to a point where it escapes detection. Soaking corks singly rather than in groups of five will therefore be a more sensitive method of screening batches of corks for taint than soaking them in groups of five. Plastic materials such as the lids of glass containers used to store wine samples were also able to absorb chloroanisoles via both direct liquid contact and the vapour phase. Wine cask bladders and polyethylene film were particularly effective in removing TCA from wine.     

黄酒中9 种生物胺的高效液相色谱分析法

建立一种检测黄酒中生物胺的反相高效液相色谱法。用三氯乙酸提取黄酒中生物胺,丹磺酰氯作为衍生化试剂,1,7-二氨基庚烷作为内标定量。色谱条件为：Waters XBridge C18色谱柱（4.5 mm×250 mm,3.8 μm）作为分离柱,乙腈和水作为流动相进行梯度洗脱,流速1 mL/min,紫外检测波长254 nm。结果表明,9 种生物胺（盐酸吡哆胺、色胺、腐胺、尸胺、β-苯乙胺、组胺、酪胺、精胺和亚精胺）在40 min内能被很好分离。在1～50 mg/L质量浓度范围内,各种生物胺呈现良好的线性相关性（R2＞0.999）。各生物胺加标回收率为79.54%～89.55%,相对标准偏差为3.14%～6.35%,该法各组分检出限（RSN=3）为0.002～0.009 mg/L。应用柱前衍生化高效液相色谱-紫外检测法,实现了黄酒中生物胺的准确检测。     

The analysis of 2,4,6-trichloroanisole and other chloroanisoles in tainted wines and corks

A new method has been developed for the analysis, by gas chromatography/mass spectrometry, of 2,4,6-trichloroanisole (TCA) and other chloroanisoles in cork-tainted wines, using a polydeuterated form of TCA as an internal standard. In a survey of wines presented at a wine assessment course, 4.8% (i.e. 18 bottles out of 374) were assessed by at least 20% of the participants as being affected by cork taint. TCA was present in each of these 18 wines at a concentration close to, or above the sensory detection threshold. All cases of taint seen by the participants could therefore be attributed, at least in part, to the presence of TCA, and this in turn could be attributed to the cork, since variation in apparent taint between bottles of the same wine was observed in every case. TCA was also found in the corks from the wines. Randomly selected bottles of wines considered to be affected by a high proportion of cork taint, and the corks from those bottles, were also analysed. There was considerable variation in the distribution of TCA and other chloroanisoles between wine and cork. In many cases, chloroanisoles were found only in the cork. TCA in corks was accompanied by varying amounts of 2,4– or 2,6-dichloroanisoles, 2,3,4,6-tetrachloroanisole and pentachloroanisole, indicating more than one origin for chloroanisoles in corks. No chloroanisoles, other than those derived by methylation of products formed by non-enzymatic chlorination of phenol, were detected in any of the samples.     

Effect of wine style on the perception of 2,4,6-trichloroanisole,a compound related to cork taint in wine

2,4,6-Trichloroanisole (TCA) is a fungal metabolite that can contaminate cork stoppers and wines producing a very unpleasant mouldy odour (cork taint). Sensory control is very widely used for the detection of possible TCA presence in corks and wine, but the correct identification of TCA, especially at low concentrations, can be difficult. The aim of this study was to show how wine styles can affect the ability of the same panel to perceive TCA. For this purpose, a panel was selected, according to the panelists’ sensitivity to the TCA stimulus. The triangle test, a sensory difference test, was carried out by the panel with both white and red wines, using samples both free from TCA and spiked with known quantities of this contaminant. The results showed that the panelists identified the difference caused by the added TCA at different significance levels, depending on the wine style, so TCA detection was influenced by wine style for the selected panel.     

崇明老白酒酿造贮存过程中氨基甲酸乙酯变化及检测方法优化

优化氨基甲酸乙酯（ethyl carbamate,EC）的气相色谱-质谱联用检测方法,跟踪崇明老白酒在酿造、加工及贮存过程中EC含量的变化,为控制米酒中EC的产生提供依据。样品前处理的最佳参数为：加入内标物EC后,调节pH值至9.0,分别加入3 次10 mL二氯甲烷作为直接萃取剂。在检测范围5～400 μg/L内呈良好线性关系,相关系数大于0.999,检出限为2 μg/L,定量限为5 μg/L。当添加水平分别为0.1、0.2、0.3 μg时,平均回收率为90.0%～97.5%,相对标准偏差为1.040%～2.778%。老白酒酿造过程中EC含量的增长缓慢,在煎酒灭菌后增长快速;常温条件下贮存样品的EC增长速率明显高于4 ℃条件下贮存样品,老白酒在室温条件下贮存1 a后EC含量为99.2 μg/L,低于蒸馏酒、清酒的最高限量。高温和长时间贮存会促进EC的产生,在老白酒生产流通环节中有必要优化灭菌条件,改善贮存条件。     

葡萄酒及软木塞中TCA的检测分析方法研究现状及应用前景

软木塞污染已经成为葡萄酒行业最为严重的问题之一,而导致软木塞和葡萄酒污染的最主要物质之一就是TCA。本文主要介绍葡萄酒和软木塞中TCA 的检测方法和萃取浓缩方法,同时也对TCA 检测的应用前景和发展趋势进行了展望。     

高效液相色谱-串联质谱检测保健酒中非法添加物艾地那非

目的：采用高效液相色谱-串联质谱（high performance liquid chromatography-tandem mass spectrometry,HPLC-MS/MS）法,建立保健酒中非法添加物艾地那非的检测方法。方法：使用Agilent RRDH Eclipse-plus C18色谱柱（2.1 mm×100 mm,1.8 μm）,以0.1%甲酸-乙腈溶液为流动相A、0.1%乙酸-20 mmol/L乙酸铵溶液为流动相B进行梯度洗脱。通过HPLC-MS/MS系统中全扫描模式对艾地那非进行定性分析,多反应监测模式对艾地那非进行定量分析。结果：该方法线性r2大于0.99,精密度相对标准偏差小于3%,不同质量浓度样品平均回收率为97.31%～100.66%,检出限为0.6 ng/mL,定量限为1.6 ng/mL。结论：此方法测定准确、灵敏度高、分离度高,可用于保健酒中非法添加物艾地那非的筛选和检测。     

Migration of 2,4,6-trichloroanisole from cork stoppers to wine

The migration of 2,4,6-trichloroanisole (TCA) from cork stoppers to wine is studied under different experimental conditions. Corks that were either naturally contaminated or spiked with a TCA solution were immersed in an ethanol–water mixture (12% v/v) for 6 days or were used as a closure for bottled wines over periods of 1, 4 and 8 months. The TCA content was determined after the stated periods using headspace solid-phase microextraction and gas chromatography electron capture detection. Three different spiking procedures were tested: the injection of a TCA solution into the cork, the immersion of the cork in a TCA in hexane solution, and cutting off a thin slab to inject different quantities of a TCA solution into it before rejoining the two parts. Only the first of these procedures was subsequently used as the immersion technique failed to retain sufficient quantities of TCA and the slab technique retained too much. Corks spiked with 120 ng TCA gave 8% migration after 6 days for corks used in the immersion experiments and less than 1% migration for corked bottles kept for 1 month. When the contact time was 4 and 8 months, migration was 4 and 8% respectively for corks spiked with 1 g TCA. It was concluded that the contact surface, temperature and time all favour TCA migration. Under the same conditions, wine bottled with naturally contaminated cork stoppers showed TCA concentrations which varied depending on the characteristics of every individual cork stopper.