腌制食品中敌敌畏和敌百虫检测的前处理方法研究

采用超高效液相色谱-串联质谱法(UPLC-MS/MS),对腌制食品中敌敌畏和敌百虫的前处理方法进行研究。方法 样品用含0.1%甲酸的乙腈溶液超声提取后,分别经分散固相萃取(d-SPE)或凝胶渗透色谱(GPC)净化;采用BEH C₁₈色谱分离柱,以乙腈-0.1%甲酸水溶液梯度洗脱,正离子多反应监测模式测定,外标法定量。结果 敌敌畏和敌百虫在一定浓度范围内呈良好线性,r均＞0.999。d-SPE净化方法对敌敌畏和敌百虫的检出限均为1.0 μg/kg,定量限为2.0 μg/kg;而GPC净化方法的检出限和定量限分别为0.5和1.0 μg/kg。以空白样品(选取火腿和腊肉为代表性基质)进行2、10、20和40 μg/kg水平的加标回收试验,d-SPE和GPC两种净化方法对敌敌畏和敌百虫的平均回收率均分别在81.7%～104.2%之间和72.4%～89.8%之间,RSD均＜7.8%。采用d-SPE和GPC两种净化方法对阳性样品的测定结果无明显差异。结论 本方法快速、准确、灵敏度高,适用于火腿和腊肉等腌制食品中非法添加敌敌畏和敌百虫的监测。对采集的8份火腿、腊肉和咸鱼干样品进行检测,1份火腿样品检出痕量敌敌畏。     

固相萃取结合超高效液相色谱-质谱法测定畜禽肉及肉制品中肾上腺素和多巴胺的残留量

建立畜禽肉及肉制品中2 种儿茶酚胺类化合物（肾上腺素和多巴胺）的超高效液相色谱-质谱联用检测方法。样品采用10 mmol/L磷酸二氢钾溶液提取,WCX固相萃取柱净化,Waters Acquity BEH C18柱分离,采用电喷雾离子源,正离子多反应模式监测,基质匹配内标法定量。结果表明：肾上腺素和多巴胺在0.5～50 ng/mL范围内,相关系数（R2）均大于0.996;在畜肉中的检出限和定量限分别为0.39～0.40 μg/kg和1.00 μg/kg,在禽肉中的检出限和定量限分别为0.36～0.37 μg/kg和0.98 μg/kg,在肉制品中的检出限和定量限分别为0.38 μg/kg和0.96～0.97 μg/kg;加标量为1～10 μg/kg时,方法回收率为83.7%～111.2%,相对标准偏差为1.28%～5.76%。该方法具有灵敏度高、定量准确等优点,适用于畜禽肉及肉制品中残留儿茶酚胺类化合物含量的测定。     

UPLC-MS/MS结合新型固相萃取技术快速确证猪肉中17种β-受体阻断剂

目的 建立新型固相萃取技术结合超高效液相色谱串联质谱测定猪肉中17种β-受体阻断剂的测定方法。方法 猪肉样品经酶解,乙腈沉淀蛋白并萃取后,经Oasis PRiME HLB固相萃取柱通过式净化。以甲醇和0.1%甲酸水为流动相梯度洗脱,采用迪马Endeavorsil C18色谱柱分离,ESI源正离子模式进行多反应监测(MRM),内标法定量。结果 17种β-受体阻断剂的线性范围在0.2～20 μg/L,相关系数(r)＞0.999,检出限(LOD)为0.05～0.07 μg/kg,定量限(LOQ)为0.15～0.2 μg/kg。3个加标水平下(0.2、0.4、2 μg/kg)的回收率为84.97%～123.40%,RSD为0.41%～13.94%。结论 本方法灵敏、快速、准确,可用于猪肉中β-受体阻断剂的定性、定量检测。     

高效液相色谱-串联质谱测定猪肉中万古霉素、去甲万古霉素和替考拉宁

建立猪肉样品中万古霉素、去甲万古霉素和替考拉宁的高效液相色谱-串联质谱测定方法,采用选择反应监测方式,外标法定量。猪肉样品经0.1%甲酸-乙腈（85∶15,V/V）溶液提取,正己烷脱脂后,万古霉素和去甲万古霉素经阳离子交换柱净化、替考拉宁经C18固相萃取柱净化,以乙腈-0.1%甲酸为流动相梯度洗脱,经C18柱分离、质谱进行测定。添加量为10、20 μg/kg和50 μg/kg时,方法回收率范围为75.3%～83.3%,相对标准偏差小于9%。猪肉中万古霉素、去甲万古霉素的检出限、定量限分别为2 μg/kg和4 μg/kg,替考拉宁的检出限、定量限分别为4 μg/kg和8 μg/kg。该方法适用于猪肉样品中万古霉素、去甲万古霉素和替考拉宁的定性、定量检测。     

液质法测定水产品中敌百虫、敌敌畏、甲胺磷

采用超高效液相色谱-串联质谱法测定水产品中敌百虫、敌敌畏、甲胺磷的的含量。试样经0.1%甲酸-乙酸乙酯超声萃取,HC-C18固相萃取柱净化后,UPLC BEH C18色谱柱分离,选择离子监测(SIM),定量离子对(m/z):258.7/127.0(敌百虫)、221.0/127.1(敌敌畏)、142.1/94.1(甲胺磷);定性离子对(m/z):258.7/109.0(敌百虫)、221.0/109.1(敌敌畏)、221.0/112.0(甲胺磷)。结果表明:敌百虫、敌敌畏、甲胺磷加标回收率在90.6%~106.0%之间,相对标准偏差不大于8.8%;以信噪比RSN=3计算,方法检出限均为1.5μg/kg,方法定量限均为5.0μg/kg。     

超高效液相色谱-四极杆/飞行时间质谱检测猪肉和牛肉中30 种食源性兴奋剂类药物残留

建立猪肉和牛肉中30 种食源性兴奋剂的超高效液相色谱-四极杆/飞行时间质谱的快速筛查和确证方法。样品经37 ℃酶解16 h,体积分数1.0%甲酸-乙腈溶液提取后,经PRiME-HLB通过式固相萃取小柱净化,用Waters XBridge BEH C18柱分离,在飞行时间质谱模式和数据依赖扫描串联质谱模式对目标物进行检测,通过一次数据采集,可同时完成化合物的定性筛查和确证。结果表明：30 种食源性兴奋剂的精确质量数偏差小于5.0×10－6,在0.5～100.0 ng/mL范围内线性良好,相关系数大于0.998 0。检出限范围为0.1～2.0 μg/kg;定量限范围为0.2～4.0 μg/kg。方法回收率范围为77.99%～109.2%,相对标准偏差为0.29%～9.68%（n=6）。该方法有效提高了食源性兴奋剂检测的效率和准确度,具有较强的实用价值。     

高效液相色谱-串联质谱法测定蜂王浆中 红霉素及其代谢物

目的 建立蜂王浆中红霉素A、红霉素A烯醇醚、脱水红霉素A和N-脱甲基红霉素A的高效液相色谱-串联质谱检测方法。方法 以pH 6.0磷酸盐缓冲液为提取剂, 经HLB小柱净化富集后, 采用高效液相色谱-串联质谱仪分析。采用Agilent Polaris C18色谱柱(100 mm×2.0 mm, 5 μm), 以甲醇和0.1%甲酸为流动相, 质谱模式为电喷雾正离子监测。结果 该方法前处理简单, 线性范围为2.0~100 μg/L, 相关系数在0.99以上, 四种化合物的检出限和定量限分别为0.5 μg/kg和5.0 μg/kg。方法采用内标法定量, 回收率范围为70.0~118.1%, 相对标准偏差小于10%。结论 方法回收率稳定且重现性较好, 能够满足日常检测工作的需要。     

液相质谱法同时检测猪肉中氯霉素和地塞米松

建立一种利用高效液相色谱-串联质谱法同时检测猪肉中氯霉素和地塞米松药物残留的方法。猪肉样品中的药物残留经乙酸乙酯提取后,经氮气吹干,残渣溶解后过Silica柱,洗脱液经氮气吹干,用初始流动相溶解定容。用Shim-pack GIST C18色谱柱(150 mm×2.1 mm,5μm)分离,以纯水-甲醇为流动相进行梯度洗脱,质谱采用多反应监测模式,氯霉素以内标法定量,地塞米松以外标法定量。在5 min内完成了两种目标化合物的分离分析。氯霉素和地塞米松在0.2μg/kg～40μg/kg范围内线性关系良好,相关系数r2分别为0.999 9和0.999 7。氯霉素添加水平在1、2.5、5μg/kg时,回收率在90.54%～101.73%之间;地塞米松添加量在0.5、2.5、5μg/kg时,回收率在83.82%～87.5%之间;批内标准偏差和批间标准偏差均小于10%(n=5),方法定量限均小于0.15μg/kg。     

高效液相色谱-荧光法测定腊肉中的苯并芘残留

建立高效液相色谱-荧光法检测腊肉中苯并芘的分析方法.以市售的腊肉作为供试样品,样品经皂化,正己烷超声提取后,用Waters X BridgeTMC18柱分离,甲醇和水(90:10,v/v)为流动相,流速为1.0mL/min,荧光检测器激发波长为365 nm,检测波长为410nm,外标法峰面积定量.结果表明:苯并芘在0.002 ～ 0.5 μg/mL范围内呈现良好的线性关系,相关系数0.9999,在1～ 10 μg/kg添加水平时,加标回收率为85.14％～91.01％,相对标准偏差为1.96％～5.37％(n=6);方法的检出限和定量限分别为0.15和0.5 μg/kg.该方法测定腊肉中的苯并芘方便,快捷,准确可靠,易推广使用.     

超高效液相色谱-串联质谱法测定鸡肉和猪肉中利尿剂残留量

目的:建立测定鸡肉和猪肉中违禁添加物呋塞米、螺内酯和布美他尼含量的超高效液相色谱-串联质谱法。方法:样品用乙酸乙酯提取后,经C₁₈粉净化。色谱柱为Hypersil GOLD C₁₈（1.9 μm,2.1 mm×50 mm）,流动相为乙腈和0.1%甲酸水,梯度洗脱,流速为0.4 mL/min,柱温为40℃。采用电喷雾正负离子同时扫描,多反应监测模式（MRM）进行质谱检测。结果:3种利尿剂在1.0~500.0 μg/L浓度范围内线性关系良好（r>0.996）;平均加标回收率67.3%~111.6%,方法检出限均为0.5 μg/kg,定量限均为1.0 μg/kg。结论:该方法简便、准确,可作为鸡肉和猪肉中利尿剂快速检测的方法。     

Reliable identification of grapevine rootstock varieties using RAPD PCR on woody samples

Since grapevine ( Vitis spp .) rootstock material is being traded increasingly as disbudded woody material a lack of distinctive morphological features on such material necessitates an alternative and reliable means of identification. Methods described here were developed for rapid and efficient extraction of DNA from woody samples rich in phenolic compounds and polysaccharides, and for subsequent identification of varieties by RAPD PCR. Using these methods, and with the application of only one selected RAPD primer, we were able to differentiate sixteen rootstock varieties, including the seven varieties most commonly used in Germany. Problems commonly encountered with reproducibility of RAPD patterns were avoided by choosing primers with a dinucleotide sequence and a high G/C content that allowed a rather high annealing temperature of 45°C. Methods described here should also be useful for other horticultural crops, especially those with woody tissues rich in phenolic compounds and polysaccharides.     

An internet compendium of analytical methods and spectroscopic information for monomers and additives used in food packaging plastics

An internet website (http://cpf.jrc.it/smt/) has been produced as a means of dissemination of methods of analysis and supporting spectroscopic information on monomers and additives used for food contact materials (principally packaging). The site which is aimed primarily at assisting food control laboratories in the European Union contains analytical information on monomers, starting substances and additives used in the manufacture of plastics materials. A searchable index is provided giving PM and CAS numbers for each of 255 substances. For each substance a data sheet gives regulatory information, chemical structures, physico-chemical information and background information on the use of the substance in particular plastics, and the food packaging applications. For monomers and starting substances (155 compounds) the infra-red and mass spectra are provided, and for additives (100 compounds); additionally proton NMR are available for about 50% of the entries. Where analytical methods have been developed for determining these substances as residual amounts in plastics or as trace amounts in food simulants these methods are also on the website. All information is provided in portable document file (PDF) format which means that high quality copies can be readily printed, using freely available Adobe Acrobat Reader software. The website will in future be maintained and up-dated by the European Commission's Joint Research Centre (JRC) as new substances are authorized for use by the European Commission (DG-ENTR formerly DGIII). Where analytical laboratories (food control or other) require reference substances these can be obtained free-ofcharge from a reference collection housed at the JRC and maintained in conjunction with this website compendium.     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

European priorities for research to support legislation in the area of food contact materials and articles

A strong science base is required to underpin the planning and decision-making process involved in determining future European community legislation on materials and articles in contact with food. Significant progress has been made in the past 5 years in European funded work in this area, with many developments contributing to a much better understanding of the migration process, and better and simpler approaches to food control. In this paper this progress is reviewed against previously identified work-areas (identified in 1994) and conclusions are reached about future requirements for R&D to support legislation on food contact materials and articles over the next 5 or so years.     

Textural Properties of Cold-set Gels Induced from Heat-denatured Whey Protein Isolates

A 9% whey protein (WP) isolate solution at pH 7.0 was heat-denatured at 80°C for 30 min. Size-exclusion HPLC showed that native WP formed soluble aggregates after heat-treatment. Additions of CaCl2 (10–40 mM), NaCl (50–400 mM) or glucono-delta-lactone (GDL, 0.4–2.0%, w/v) or hydrolysis by a protease from Bacillus licheniformis caused gelation of the denatured solution at 45°C. Textural parameters, hardness, adhesiveness, and cohesiveness of the gels so formed changed markedly with concentration of added salts or pH by added GDL. Maximum gel hardness occurred at 200 mM NaCl or pH 4.7. Increasing CaCl2 concentration continuously increased gel hardness. Generally, GDL-induced gels were harder than salt-induced gels, and much harder than the protease-induced gel.     

Aroma characterization of various apricot varieties using headspace–solid phase microextraction combined with gas chromatography–mass spectrometry and gas chromatography–olfactometry

The characterization of the aromatic profile of several apricot cultivars with molecular tracers in order to obtain objective data concerning the aromatic quality of this fruit was undertaken using headspace–solid phase microextraction (HS–SPME). Six apricot cultivars were selected according to their organoleptic characteristics: Iranien, Orangered, Goldrich, Hargrand, Rouge du Roussillon and A4025. The aromatic intensity of these varieties measured by HS–SPME–Olfactometry were defined and classified according to the presence and the intensity of grassy, fruity and apricot like notes. In the six varieties, 23 common volatile compounds were identified by HS–SPME–GC–MS. Finally, 10 compounds, ethyl acetate, hexyl acetate, limonene, β-cyclocitral, γ-decalactone, 6-methyl-5-hepten-2-one, linalool, β-ionone, menthone and (E)-hexen-2-al were recognized by HS–SPME–GC–O as responsible of the aromatic notes involved in apricot aroma and considered as molecular tracers of apricot aromatic quality which could be utilized to discriminate apricot varieties.     

Tests of potential functional barriers for laminated multilayer food packages. Part I: Low molecular weight permeants

The advent of the functional barrier concept in food packaging has brought with it a requirement for fast tests of permeation through potential barrier materials. In such tests it would be convenient for both foodstuffs and materials below the functional barrier (sub-barrier materials) to be represented by standard simulants. By means of inverse gas chromatography, liquid paraffin spiked with appropriate permeants was considered as a potential simulant of sub-barrier materials based on polypropylene (PP) or similar polyolefins. Experiments were performed to characterize the kinetics of the permeation of low molecular weight model permeants (octene, toluene and isopropanol) from liquid paraffin, through a surrogate potential functional barrier (25 μm-thick oriented PP) into the food simulants olive oil and 3% (w/v) acetic acid. These permeation results were interpreted in terms of three permeation kinetic models regarding the solubility of a particular model permeant in the post-barrier medium (i.e. the food simulant). The results obtained justify the development and evaluation of liquid sub-barrier simulants that would allow flexible yet rigorous testing of new laminated multilayer packaging materials.     

Occurrence of bisphenol-F-diglycidyl ether (BFDGE) in fish canned in oil

The levels of bisphenol-F-diglycidyl ether (BFDGE) were quantified as part of a European survey on the migration of residues of epoxy resins into oil from canned fish. The contents of BFDGE in cans, lids and fish collected from all 15 Member States of the European Union and Switzerland were analysed in 382 samples. Cans and lids were separately extracted with acetonitrile. The extraction from fish was carried out with hexane followed by re-extraction with acetonitrile. The analysis was performed by reverse phase HPL C with fluorescence detection. BFDGE could be detected in 12% of the fish, 24% of the cans and 18% of the lids. Only 3% of the fish contained BFDGE in concentrations considerably above 1mg/kg. In addition to the presented data, a comparison was made with the levels of BADGE (bisphenol-A-diglycidyl ether)analysed in the same products in the context of a previous study.     

Contribution of European research to risk analysis

The European Commission's, Quality of Life Research Programme, Key Action 1—Health, Food & Nutrition is mission-oriented and aims, amongst other things, at providing a healthy, safe and high-quality food supply leading to reinforced consumer confidence in the safety of European food. Its objectives also include the enhancing of the competitiveness of the European food supply. Key Action 1 is currently supporting a number of different types of European collaborative projects in the area of risk analysis. The objectives of these projects range from the development and validation of prevention strategies including the reduction of consumers risks; development and validation of new modelling approaches; harmonization of risk assessment principles, methodologies, and terminology; standardization of methods and systems used for the safety evaluation of transgenic food; providing of tools for the evaluation of human viral contamination of shellfish and quality control; new methodologies for assessing the potential of unintended effects of genetically modified (genetically modified) foods; development of a risk assessment model for Cryptosporidium parvum related to the food and water industries; to the development of a communication platform for genetically modified organism, producers, retailers, regulatory authorities and consumer groups to improve safety assessment procedures, risk management strategies and risk communication; development and validation of new methods for safety testing of transgenic food; evaluation of the safety and efficacy of iron supplementation in pregnant women; evaluation of the potential cancer-preventing activity of pro- and pre-biotic ('synbiotic') combinations in human volunteers. An overview of these projects is presented here.     

Influence des ions sur le pouvoir hydratant de l'ure e: e tude sur peau de porc ex vivo

This study deals with the influence of ions (NaCl and MgSO4) in a W/O emulsion containing 10% urea. Moisturization kinetics are assessed by corneometry on pig skin ex vivo. The formula's influence on urea penetration is measured by infrared spectrometry with an ATR device and the stripping method. Corneometry and spectroscopy were chosen to record simultaneously the hydratation levels and urea localization into superficial cell layers. Urea crystallization after evaporation of emulsions and aqueous solutions is described. Results show that urea does not hydrate nor penetrate when applied to the skin through an aqueous gel. In a W/O emulsion, sodium chloride increases the ability of urea to moisturize without improving penetration. In vitro urea crystallization is disturbed by sodium chloride or magnesium sulphate for solutions and emulsions. This stabilization by ions is correlated with good moisturization values. The stabilization of urea in the solute state provided by ions increases its water epidermal binding capacity without enhancing penetration.