Determination of vitamin C and preservatives in beverages by conventional capillary electrophoresis and microchip electrophoresis with capacitively coupled contactless conductivity detection

The separation and detection of commonly used preservatives (benzoate, sorbate) and vitamin C by both conventional CE and microchip electrophoresis with capacitively coupled contactless conductivity detection is presented. The separation was optimized by adjusting the pH-value of the buffer and the use of hydroxypropyl-beta-CD (HP-beta-CD) and CTAB as additives. For conventional CE, optimal separation conditions were achieved in a histidine/tartrate buffer at pH 6.5, containing 0.025% HP-beta-CD and 0.1 mM CTAB. LOD ranged from 0.5 to 3 mg/L (S/N = 3) and the RSDs for migration time and peak area were less than 0.1 and 2%, respectively. A considerable reduction of analysis time can be accomplished by using microchip electrophoresis without significant loss in sensitivity under optimal separation conditions. A histidine/tartrate buffer at pH 6.5, incorporating 0.06% HP-beta-CD and 0.25 mM CTAB, gave detection limits ranging between 3 and 10 mg/L and satisfactory reproducibilities of < or =0.4% for the migration time and < or =3.5% for the peak area. The methods developed are useful for the quantitative determination of food additives in real samples such as soft drinks and vitamin C tablets.     

Repeated migration of additives from a polymeric article in food simulants

The migration of three additives from polypropylene samples into a series of five liquid food simulants was investigated at 60 °C in a repeated migration regime. This regime was simulated by 20 migration periods each of 8 h and using initially additive free food simulants. Between these migration periods the bare samples were stored in an air conditioned room at around 23 °C for 16 h at working days and for 64 h during weekends. An asymptotic decrease of the additive level in the food simulants in the successive migration periods, from a maximum values towards zero, was observed when the additives easily solve in the food simulants. In contrast when the additives solve poorly in the food simulants this additive level decrease is almost linear and shows a slow decrease rate. In the first case the leaching/migration of the additives is controlled mainly by their diffusion in the matrix of the polymer. In the latter case this process is controlled mainly by the partitioning of the additives between the polymer and food simulants. Two approaches were used to model theoretically these results.In the first approach the mass transport equation was solved by using as input parameters overestimated diffusion and partitioning coefficients as estimated for polypropylene homopolymer, the used food simulants and the three additives according to the recommendations of a practical guidance document in support of migration modelling as stipulated in the Regulation (EU) 10/2011. As expected the results of these calculations overestimate the vast majority of the migration levels determined experimentally. However there are also situations in which this approach leads to underestimations of the real migration levels.In the second approach numerical fitting was applied with the same equation and using the diffusion and partition coefficients as adjustable parameters to obtain a best-fit between experimental and calculated results. It was found that the so obtained “realistic” diffusion coefficients are all lower than the overestimated ones mentioned above. Moreover these “realistic” coefficients depend not only on the nature of the additive but also on the nature of the food simulant in contact with the polymer. This suggests that interaction of food simulants with the polypropylene occurs, which changes the properties of the polymer and thus the mobility of the additive molecules in its matrix. For the “realistic” partition coefficients it was found that they all are higher than the conservative ones mentioned above. Using these “realistic” parameters a good fit between calculated and experimental migration results was found.     

Multi-Residue Analysis of Chemical Additives in Edible Vegetable Oils Using QuEChERS Extraction Method Followed by Supercritical Fluid Chromatography

Since the quality and safety of food highly depend on its preservation and protection, the use of food packaging materials increases the risk of chemical contamination of the packaged food by migration. Herein, we focused on antioxidants, photoinitiators, UV absorbers and plasticizers which are extensive additives used in food packaging materials. In the present study, a rapid, simple, green and reliable method was developed and validated for the determination of twelve chemical additives in edible vegetable oils using SFC together with a modified QuEChERS procedure. Under the optimum conditions, twelve additives were separated within 10 min, and the consumption of the organic solvent was significantly reduced, which improved the environmentally friendliness. The performance of the developed method was evaluated. Good linearity (r > 0.999) was obtained in the range of 0.20–20.0 µg/mL and 0.50–20.0 µg/mL, respectively. The limits of detection and limits of quantification of the twelve additives in vegetable oils were 0.05–0.15 µg/mL and 0.15–0.50 µg/mL, respectively. Recoveries of all the chemical additives for the spiked samples were between 60.9% and 106.4%, with relative standard deviations (RSD) lower than 9.9%. The results demonstrated that the proposed method was efficient, reliable and robust for the routine analysis of additives in edible vegetable oils and can be an alternative to the multi-residue analysis of chemical additives for other packaged foods.     

FTIR investigation of the specific migration of additives from rigid poly(vinyl chloride)

Commercial sunflower oil was epoxidized and used as organic costabiliser for rigid poly (vinyl chloride) (PVC) containing zinc and calcium stearates as primary stabilisers and stearic acid as lubricant. For applications in the packaging of foodstuffs, migration testing must be realised. For that purpose, two food simulants were used (sunflower oil and 15% (v/v) aqueous ethanol). The test conditions were 12 days at 40 °C. Circular samples of rigid PVC were immersed in a well known volume of food simulant. A circular sample and 10 ml of food simulant were taken off every day to be analysed. The specific migrations of the additives were investigated by using Fourier transform infrared spectroscopy.The direct analysis of the food simulants was difficult because overlapping of the bands of the additives. However, the analysis of PVC films obtained by dissolution of the circular samples in tetrahydrofuran and evaporation of the solvent was more conclusive. The specific migrations of the metal carboxylates and epoxidized sunflower oil were evidenced.     

顶空气相色谱法测定食品添加剂中15种有机溶剂残留量

建立了顶空气相色谱法同时测定食品添加剂中甲苯、甲醇、正己烷等15种有机溶剂残留量的分析方法。选择N,N-二甲基甲酰胺对不同食品添加剂中的有机溶剂进行提取,将样液转移至顶空瓶中密封,顶空进样测定。对提取溶剂、提取方式、平衡时间和平衡温度等进行了优化。结果表明,15种有机溶剂分离良好,各残留溶剂在相应浓度范围内呈良好的线性关系,相关系数不小于0.999 8,定量下限为10.0 mg/kg(三氯甲烷和吡啶为20.0 mg/kg),回收率为90.6%~109.1%,相对标准偏差为0.1%~7.2%。该方法灵敏度高,重现性好,适用于食品添加剂中甲苯、甲醇、正己烷等15种残留溶剂的检测分析。     

Determination of Dihydroxybenzenes in Plastic Food Packaging Materials and in Food Simulating Liquids Using Capillary Electrophoresis

A capillary electrophoresis method has been developed to determine 1,2-dihydroxybenzene and 1,3-dihydroxybenzene in the food simulants distilled water, 3% acetic acid, 15% ethanol, and olive oil. Both substances, used as monomers and additives to make food packaging plastics, could be analyzed within 15 min. The 1,4-dihydroxybenzene isomer was unretained and eluted with the electroosmotic flow, and so the CE method can give only a semi-quantitative estimate of this isomer if it is present as a migrant. The analytical recovery for the 1,2- and 1,3-isomers from spiked simulants was good at 87% to 98% except for 1,2-dihydroxybenzene which could only be recovered to the extent of 58% from olive oil. Calibration graphs were linear and the limit of detection for each substance was 0.6 mg/kg, which is well below migration limits for these substances. It is concluded that CE offers a rapid and reliable analysis for the control of migration from plastics intended for food contact which employ 1,2-dihydroxybenzene or 1,3-dihydroxybenzene during manufacture, and offers a screening method for 1,4-dihydroxybenzene migration.     

常见食品中邻苯二甲酸酯类增塑剂含量及食品包装材料中邻苯二甲酸酯类增塑剂迁移量的测定

采用气相色谱-质谱联用(GC-MS)方法并结合液液萃取及基质分散固相萃取的样品处理方式,建立了测定饮料、牛奶、白酒3类食品中16种邻苯二甲酸酯类增塑剂的分析方法。研究结果表明16种邻苯二甲酸酯类增塑剂的检出限(LOD, S/N=3)范围为0.005~0.025 mg/L;峰面积的相对标准偏差(RSD)均小于2%。饮料、牛奶、白酒3种样品的加标回收率范围普遍在60%~110%。所建方法简便、灵敏、准确,可满足饮料、牛奶和白酒中痕量邻苯二甲酸酯类增塑剂的测定需要。此外,将该方法应用于食品包装材料中邻苯二甲酸酯类增塑剂的迁移研究,以异辛烷为油脂食品模拟物,测定了保鲜膜与保鲜袋中16种邻苯二甲酸酯类增塑剂的迁移量。结果显示保鲜膜存在显著的邻苯二甲酸酯类增塑剂迁移现象。     

高效液相色谱法同时测定食品中的8种添加剂

建立高效液相色谱法同时测定食品中的安赛蜜、苯甲酸、山梨酸、苋菜红、脱氢乙酸、胭脂红、日落黄、诱惑红8种添加剂。样品采用Agilent zorbax sb–C_(18)色谱柱梯度洗脱,紫外检测器检测,外标法定量分析。结果表明,8种添加剂的质量浓度在0.5~20μg/m L范围内与其色谱峰面积线性关系良好,相关系数均大于0.999,方法检出限为0.06~0.18 mg/kg。样品的加标回收率为91.3%~101.1%,测定结果的相对偏差为0.47%~1.35%(n=6)。该方法操作简单,灵敏度高,结果准确可靠,适用于食品添加剂的常规分析。     

高效液相色谱法同时测定蜜饯中的16种食品添加剂

建立了同时检测蜜饯中16种食品添加剂(安赛蜜、糖精钠、苯甲酸、山梨酸、脱氢乙酸、新红、诱惑红、柠檬黄、苋菜红、胭脂红、日落黄、亮蓝、赤藓红、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯)含量的高效液相色谱法.选用Athena C18-wp色谱柱(4.6 mm×250 mm,5 μm),以0.02mol/L乙酸铵...     

Identification and quantification of (polymeric) hindered-amine light stabilizers in polymers using pyrolysis-gas chromatography-mass spectrometry and liquid chromatography-ultraviolet absorbance detection-evaporative light scattering detection

Direct analysis of polymers containing polymeric hindered amine light stabilizers (HALS) by using pyrolysis coupled to GC-MS is applied successfully for fast and straightforward identification of these HALS additives. Each of the HALS additives shows different pyrolysis gas chromatograms containing characteristic pyrolysis products. As a result, HALS additives with very similar chemical structures, e.g. Chimassorb 944 and Chimassorb 2020, can be distinguished. A HPLC method with both ultraviolet (UV) and evaporative light scattering detection (ELSD) is developed to quantify the various HALS additives in extracts of polymers. The critical factor of the HPLC method is the use of a basic amine, like n-hexylamine, as a solvent additive to facilitate the elution of HALS additives. The various HALS additives can be distinguished according to retention time and peak shape and by using different detection methods. The suitability of the developed methods is demonstrated by the analytical performance of the HPLC method and the identification and determination of the actual content of HALS additives in polyolefines using pyrolysis GC-MS and HPLC. The HPLC method can also be used for the determination of the specific migration of HALS additives from food contact materials.     

Analytical screening of polyadipates and other plasticisers in poly(vinyl chloride) gasket seals and in fatty food by gas chromatography-mass spectrometry

Fourteen poly(vinyl chloride) (PVC) gasket seals and 15 samples of pesto, tomatoes sauces, olive oil and olives in oil were analysed for the additives and plasticisers. The systematic screening of the representative samples revealed that epoxidised soybean oil (ESBO) was the principal plasticiser in eight gaskets and the concentrations of the substance ranged from 15% to 42%. Diisodecyl phthalate (DIDP) as main plasticiser was revealed in three samples and the amount ranged from 37 to 41%. Polyadipate was added in four samples at 16-46%. The concentration of ESBO exceeded 60 mg kg(-1) in three food samples with extreme at 281.9 mg kg(-1) and average 61.3 mg kg(-1). Di-(2-ethylhexyl) phthalate (DEHP) was detected in six food samples and it ranged from 2.5 to 8.7 mg kg(-1). The concentration of DEHP exceeded SML (3 mg kg(-1)) in five cases. The concentration of total polyadipate (PA) was 16.3 mg kg(-1) in average. All eight positive food samples for total PA showed the concentrations below SML (30 mg kg(-1)), which are specified for the fraction of polyadipates lower than 1000 Da. The migration rate of polyadipate in the food ranged from 1 to 7%. At such low transfer rate the polyadipates could be promising plasticisers for PVC gasket seals used in food industry.     

A comprehensive NMR methodology to assess the composition of biobased and biodegradable polymers in contact with food

A nuclear magnetic resonance (NMR) methodology was assessed regarding the identification and quantification of additives in three types of polylactide (PLA) intended as food contact materials. Additives were identified using the LNE/NMR database which clusters NMR datasets on more than 130 substances authorized by European Regulation No. 10/2011. Of the 12 additives spiked in the three types of PLA pellets, 10 were rapidly identified by the database and correlated with spectral comparison. The levels of the 12 additives were estimated using quantitative NMR combined with graphical computation. A comparison with chromatographic methods tended to prove the sensitivity of NMR by demonstrating an analytical difference of less than 15%. Our results therefore demonstrated the efficiency of the proposed NMR methodology for rapid assessment of the composition of PLA.     

毛细管区带电泳法同时测定饮料中16种食品添加剂

建立了毛细管区带电泳法测定饮料中酸性红92、专利蓝V、荧光素二钠、酸性红1、靛蓝胭脂红、亮黑、丽春红6R、日落黄、苋菜红、柠檬黄等10种人工合成色素和苯甲酸、山梨酸、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯等6种防腐剂的分析方法。考察了缓冲溶液种类、浓度、pH值及运行电压、温度等对分离的影响,确定最佳电泳条件为: 未涂层弹性石英毛细管柱(46 cm×50 μm),缓冲溶液为70 mmol/L硼酸(pH=9.5)(含体积分数为4%的乙腈),检测波长220 nm,电泳电压30 kV,进样时间5 s,电泳温度25 ℃。该法用于测定市售饮料样品得到满意结果: 在1～250 mg/L范围内线性关系良好,相关系数不小于0.9938,回收率在95.8%与108.7%之间。该法简便、准确,能够满足食品添加剂的常规检测要求。     

Simultaneous determination of methyl tert.-butyl ether and its degradation products,other gasoline oxygenates and benzene,toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.     

Simultaneous quantification of five proteins and seven additives in dairy products with a heart‐cutting two‐dimensional liquid chromatography method

A heart‐cutting two‐dimensional high‐performance liquid chromatography method was developed to simultaneously quantify five major proteins and seven food additives (maltol, ethyl maltol, vanillin, ethyl vanillin, benzoic acid, sorbic acid, and saccharin sodium) in milk and milk powders. In this two‐dimensional system, a Venusil XBP‐C4 column was selected in the first dimension for protein separation, and a Hypersil ODS‐2 C18 column was employed in the second dimension for additive separation; a two‐position, six‐port switching valve was used to transfer the targets (additives) from the first dimension to the second dimension. Method validation consisted of selectivity, response function, linearity, precision, sensitivity, and recovery. In addition, a conventional one‐dimensional high‐performance liquid chromatography method was also tested for comparison. The two‐dimensional method resulted in significantly improved recovery of the food additives compared to the conventional method (90.6–105.4% and 65.5–86.5%, respectively). Furthermore, this novel method has a simple one‐step sample preparation procedure, which shortens the analysis time, resulting in more efficient analysis and less solvent usage.     

Separation of fluorescein dyes by capillary electrophoresis using β-cyclodextrin

Summary A capillary electrophoresis method for the separation and determination of five synthetic dyes used in pharmaceutical preparations, cosmetics and as food additives is described. The dyes, fluorescein, dichlorofluorescein, Rose Bengal erythrosine and eosine are well separated in less than 12 min using an electrolyte of 50 mM phosphate buffer (pH 7.5), 10 mM β-cyclodextrin and 5% (v/v) methanol. A linear relationship between concentration and peak area for each dye was obtained in the concentration range 0.3–500 μg mL⁻¹, with a correlation coefficient greater than 0.999. Intra- and inter-day precision of about 0.2–2.6% RSD (n=11) and 4.9–9.7% RSD (n=30), respectively, were obtained. The method has been used for determining the purity of fluorescein and erythrosine in practical samples.     

Determination of benzophenones in a cosmetic matrix by supercritical fluid extraction and capillary electrophoresis

Benzophenones are common additives in commercial sunscreen products. These UV absorbers were extracted by supercritical fluid extraction (SFE), and then analyzed by capillary zone electrophoresis (CZE) and high-performance liquid chromatography. This study was applied to identify the contents of benzophenones in cosmetic matrix, and simultaneously, to investigate the behavior of migration in CZE. Adding non-ionic surfactant (Tween 20) to optimize the separation in the CZE operation improves resolution. In SFE, we chose carbon dioxide with 2.5% modifier of 10% aqueous phosphoric acid-MeOH (1:1) as the supercritical fluid. Real recoveries of up to 92% with relative standard deviations of less than 4.0% were achieved. These analytical techniques were also applied to assay benzophenones for ten commercial sunscreen cosmetics. We found benzophenone 3 was the most commonly used sunscreen additive in Taiwan.     

Analytical protocol to study the food safety of (multiple-)recycled high-density polyethylene (HDPE) and polypropylene (PP) crates: Influence of recycling on the migration and formation of degradation products

An analytical protocol was set up and successfully applied to study the food safety of recycled HDPE and PP crates. A worst-case scenario was applied that focused not only on overall migration and specific migration of accepted starting materials but also on migratable degradation products of polymers and additives that may be formed during mechanical recycling.The analytical protocol was set up to cover a wide variety of possible migrants. Identification and semi-quantification were possible for almost all migrants that increased significantly with increasing mechanical recycling steps for both the HDPE and PP crates.It was concluded that the analytical protocol was suitable to study the influence of (multiple) recycling on the food safety of plastic materials. The protocol can be applied to other plastic food contact materials and provides valuable information on the food safety of the recycling process and the resulting recycled food contact materials in addition to challenge testing.     

Improved repeatability and matrix-assisted desorption/ionization - time of flight mass spectrometry compatibility in capillary isoelectric focusing

Low repeatability of migration time, peak area, and linearity (pI vs. mobilization time) is a problem often encountered in capillary IEF (cIEF) and is mainly caused by protein precipitation and protein-wall interactions. In order to study the influence of these phenomena, the effect of different classes of additives on repeatability of migration time, peak area and linearity of a mixture of seven model proteins has been investigated. Moreover, the influence of these additives on protein signal suppression in MALDI-TOF MS has been studied. The optimal ampholyte blend (stabilizes pH gradient) to be used depends on the selected UV detection wavelength. All tested ampholyte blends show a significant and comparable signal suppression in MS. The best detergent (to prevent precipitation and wall interaction) should be determined for each sample individually, but generally polyethylene oxide and zwitterionic detergents show good repeatability for migration time (RSD <4.5%) and peak area (majority <10%). The RSD of R(2) is <1.3% for the hydrophilic protein mixture. However, these components cause severe signal suppression in MS. Therefore glucoside detergents should preferably be used for MS coupling. Viscosity-increasing agents (for hydrodynamic wall coating and to minimize diffusion) in particular cellulose derivatives, give good repeatability for migration times (RSD <4.5% at lower concentrations), peak area (except for high concentration methylcellulose and hydroxyethylcellulose all within 7.5%), and correlation (pI vs. migration time), but severe signal suppression is observed in MALDI-TOF MS. Overall, cIEF repeatability and linearity can significantly be improved by adding the appropriate components. However, when the system is coupled to a MALDI-TOF MS, compromises have to be made between high repeatability and linearity on one hand and MS signal intensity on the other.     

Solution-phase synthesis of branched DNA hybrids via H-phosphonate dimers

A method for the solution-phase synthesis of branched oligonucleotides with tetrahedral or pseudo-octahedral geometry is described that involves the coupling of 3'-H-phosphonates of protected dinucleoside phosphates and organic core molecules. The dimer building blocks are produced by a synthesis that requires no chromatographic purification and that produces the dimer H-phosphonates in up to 44% yield in less than three days of laboratory work. A total of seven different branched hybrids were prepared, including a new hybrid of the sequence (CG)(4)TBA, where TBA stands for tetrakis(p-hydroxybiphenyl)adamantane that assembles into a material from micromolar aqueous solution upon addition of MgCl(2).