食品多组分添加剂及非法添加物的HPLC—HRMS广谱筛查

采用离子阱飞行时间串联质谱(LCMS-IT-TOF)技术对葡萄酒、果汁等饮料中多组分添加剂和禁用染料进行快速筛查和确证。构建了合成色素、甜味剂、禁用染料等41种化合物的精确分子质量数和多级质谱碎片离子数据库。样品经甲醇—水(体积比1;1)稀释后,以C18色谱柱(150mm×4.6mm,5μm)分离,甲醇和2mmol/L乙酸铵为流动相梯度洗脱。筛查检出限为0.005~1.000 mg/kg。在3个添加浓度下平均回收率41.2%~114.1%,相对标准偏差(RSD)为4.3%~16.4%。利用精确质量数和数据库中质谱图的检索匹配度实现快速筛查;结合保留时间、同位素丰度和多级特征碎片离子对目标化合物进行确证。该方法具有简便快速、准确、灵敏度高等优点,同时可实现无标准物质的情况下,较短时间内完成对食品中可能存在的添加剂和非法添物进行筛查检测,缩短检测时间,提高检测效率。     

UPLC-Q/Orbitrap HRMS快速测定清咽类保健食品中12种非法添加药物

建立了一种基于超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法（UPLC-Q/Orbitrap HRMS）快速筛查及定量分析清咽类保健食品中12种非法添加药物的方法。样品经乙腈超声提取,高速离心,以ZORBAX XDB-C18（50 mm×2.1 mm,1.8 μm）为色谱柱,甲醇与0.1%甲酸水溶液（含5 mmol/L乙酸铵）为流动相,梯度洗脱,质谱采集用Q Extractive高分辨质谱中正离子扫描,一级全扫描和数据依赖的二级子离子扫描（Full MS/dd-MS2）监测模式,以Full MS提取高分辨母离子色谱峰的面积定量,以保留时间、一级母离子以及dd-MS2扫描所得的二级碎片离子信息建立数据库定性筛查。12种药物在7.63 min内的得到有效分离,精确质量数偏差不大于1.48×10-6,在1.00~200.00 µg/L范围内线性关系良好（相关系数≥0.999）,测定下限为50.00~150.00 μg/kg,加标回收率在75.15%~117.65%之间,相对标准偏差（RSD）为0.89%~4.84%。该方法前处理简单、快速,分析检测准确,灵敏度高,选择性强,可用于清咽类保健食品中12种非法添加药物快速定性筛查和定量分析。     

超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法快速筛查保健品中136种非法添加降血压药物

摘要: 目的 建立一种无需标准品即可快速检测保健品中136种非法添加降血压药物的超高效液相色谱-四极杆/静电场轨道阱高分辨质谱分析方法。方法 样品经甲醇溶液适当稀释,超声处理后,经 Waters Acquity BEH C18色谱柱(100 mm×2.1 mm, 1.7 μm)分离,以0.1% (V:V)甲酸水溶液-乙腈作为流动相, 进行梯度洗脱。加热电喷雾离子源正负离子同时采集,一级母离子全扫描和数据依赖的二级子离子扫描模式检测,将采集的样品质谱信息与自建立的136种非法添加降血压药物质谱信息库通过分子离子精准质量数比对、同位素分布比对进行初筛,初筛出的阳性化合物通过二级碎片离子解析进行进一步确证。结果 该方法能够在没有标准品的情况下,在20 min内对保健食品中136种非法添加降压药物同时进行精准筛查,14种降压药物的添加回收实验表明实际样品的检出限在2.0~3.0 ?g/kg,采用本方法对市售实际样品进行检验, 1款声称具有降血脂的保健食品中有坎地沙坦酯检出。结论 该方法通量高、速度快、成本低,可用于保健食品中非法添加降血压药物的快速筛查。     

超高效液相色谱仪-四级杆/静电轨道阱高分辨质谱 法快速筛查及不同酒类中64种非法添加化合物

本研究建立了一种基于超高效液相色谱-四级杆/静电场轨道阱高分辨质谱法快速筛查和定量分析酒类样本中64种非法添加化合物的方法。样品经加热除去酒精,再加入甲醇进行超声提取并定容,经微孔滤膜过滤后上机分析。利用Thermo Hypersil GOLD C18(100 mm×2.1 mm,1.9μm)柱进行色谱分离,甲酸铵溶液和乙腈为流动相进行梯度洗脱。质谱条件采用正离子和负离子同时扫描,全扫描/数据依赖的二级扫描(Full MS/dd-MS~2)模式,以分析物的保留时间和一级母离子以及自动触发采集的二级碎片离子信息建立数据库,进行高通量筛查和定量分析,并对市售酒类样品进行筛查测定。结果表明各目标化合物在一定的质量浓度范围内线性关系良好(相关系数r~20.99),定量限为0.1～2.5mg/kg,回收率为88.3%～127.9%,相对标准偏差为0.2%～6.2%(n=6)。该方法操作简单,灵敏度高,分析时间短,结果准确可靠,适用于酒类样本中64种非法添加化合物的快速筛查和确证。     

高效液相色谱-离子阱-飞行时间质谱法快速筛查饮料中植物源性成分

采用高效液相色谱-离子阱-飞行时间质谱对饮料中生物碱、皂苷和有机酸等24种植物源性成分进行快速筛查、定性识别和准确定量。样品经高速离心,过0.22μm水系滤膜后,以C_(18)色谱柱(2.1 mm×250 mm,3.0μm)分离,乙腈-0.1%甲酸溶液为流动相进行梯度洗脱,正、负离子模式同时扫描。结果表明,24种化合物在50~750μg/L范围内呈良好的线性关系,相关系数均大于0.995。样品中各化合物的检出限(以信噪比不小于3计)为8~20μg/L。在3种添加量(70、250、700μg/L)条件下,其平均回收率为63.0%~126.6%,相对标准偏差为4.11%~14.73%。该方法利用精确质量数匹配和自建标准库检索,实现快速筛查,并使用多级特征碎片离子进行确证,具有快速、高效、准确等优点,适用于饮料中多种植物源性成分的快速筛查和测定。     

蛋及蛋制品中多药物残留快速检测技术研究

目的建立蛋及蛋制品中5类49种药物残留的QuEChERS方法并应用超高效液相色谱-四极杆-飞行时间质谱(ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry,UPLC-Q-TOFMS)高分辨质谱数据库快速定性筛查确证及参考定量。方法采用5 mL 5%甲酸乙腈溶液提取,C_(18)与PSA吸附剂净化的QuEChERS方法进行前处理,经Waters ACQUITY UPLC BEH C_(18)(2.1 mm×50 mm,1.7μm)色谱柱分离,以5 mmol/L乙酸铵溶液(含0.1%甲酸)-乙腈为流动相,梯度洗脱,Q-TOF-MS电喷雾正、负离子模式检测,通过Waters Masslynx工作站的Chromalynx XS模块建立多种药物的精确质量数和全扫描碰撞诱导解离碎片离子高分辨质谱数据库。结果 49种药物呈现良好的线性关系,相关系数均大于0.99,检出限(S/N=3)为0.2～10μg/kg,回收率结果在69.4%～121.5%之间。结论该方法简便、快速、灵敏,适用于蛋及蛋制品中多类药物残留的同时检测。     

高分辨质谱快速筛查牛乳中10种禁用兽药残留

采用超高效液相色谱—四级杆飞行时间高分辨质谱(UHPLC-QTOF MS)技术建立了生鲜牛乳中10种雌激素类和氯霉素类药物的快速筛查方法,并建立了此10种化合物的精确分子质量数和二级质谱碎片离子数据库。牛乳样品经乙腈提取,采用QuECh?ERS(Quick,Easy,Cheap,Effective,Rugged and Safe)方法净化。目标药物经Agilent ZORBAX SB C18色谱柱分离,以乙腈和水为流动相进行梯度洗脱,使用Dual AJS ESI源,在负离子模式下进行数据采集,基质匹配标准曲线法定量。结果表明,10种雌激素类和氯霉素类药物的定量下限为10～50μg/kg,在3个加标水平的平均回收率为61.2%～116.3%,相对标准偏差为2.3%～10.8%。结合精确分子质量数、保留时间、同位素丰度和二级特征碎片离子对目标化合物进行快速筛查与确证。该方法快速简便、准确、灵敏度较高,适用于牛乳中雌激素类和氯霉素类药物残留的高通量筛查与定性鉴定。     

基于高分辨质谱的化妆品中防腐剂类致敏成分高通量检测方法的建立及应用

目的基于静电场轨道阱高分辨质谱,建立化妆品中异噻唑啉酮类、甲醛释放剂、对羟基苯甲酸酯类、酸类4大类防腐剂类致敏成分的高通量检测方法,幵应用于实际样品中致敏成分的筛查与定量分析。方法利用致敏成分标准品通过高分辨质谱正负离子切换FullMS/ddMS2扫描方式分析,获得多种致敏成分的保留时间、一级母离子和二级碎片离子精确质量数,构建致敏成分筛查谱库。样品经50%甲醇水溶液超声提取后,经ZORBAX Eclipse Plus C18 (3.0 mm×100 mm, 1.8μm)色谱柱分离,采用高分辨质谱分析,利用TraceFinder软件对化妆品中致敏成分与谱库相关信息匹配,实现目标物的高通量筛查确证,筛查确认后利用一级母离子外标法迚行致敏成分的定量分析。结果筛查方法既有一级母离子精确质量数和保留时间,又有二级碎片离子信息,其筛查确证结果可靠;目标化合物在相应的质量浓度范围内线性关系良好(r~20.99),检出限为0.2～20μg/g,回收率为85.6%～109.7%,相对标准偏差为3.2%～12.8%,能够满足检测需求。结论该方法简单、准确、快速,可用于化妆品中多种致敏成分的高通量快速筛查和定量分析。     

高分辨质谱法快速筛查和定量分析改善胃肠道功能类保健食品中的22种非法添加化合物

建立一种超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法,快速筛查同时定量分析保健食品中22种非法添加化合物。该研究以市面上常见的改善胃肠道功能类保健食品（片剂和口服液基质）为研究对象,样品经甲醇涡旋振荡和超声提取;用Agilent ZORBAX Eclipse XDB-C18（2.1 mm×50 mm,1.8 μm）色谱柱分离,φ=0.1%甲酸水和甲醇梯度洗脱;质谱条件采用正离子扫描,Full MS/dd-MS2（一级全扫描/数据依赖的二级扫描）模式,以化合物的保留时间、一级母离子和自动触发采集的二级碎片离子信息建立数据库,进行高通量定性筛查,以一级母离子进行定量分析,22种化合物在6.5 min内得到有效分离,精确质量数偏差≤1.77×10-6。结果表明,各目标化合物在5 ~500 ng/mL的浓度范围内线性关系良好（r2>0.995）,定量限均为50 μg/kg,片剂回收率为82.11%~116.16%,口服液回收率为83.64%~117.21%。该方法操作简单快速,灵敏度高,结果准确,适用于片剂和口服液基质的改善胃肠道功能类保健食品中22种非法添加化合物的快速筛查和定量分析。     

超高效液相色谱-四极杆串联飞行时间高分辨质谱法筛查和确证猪肉中117种兽药残留

目的 建立117种兽药化合物的高分辨质谱一级数据库和二级谱库,建立应用超高效液相色谱-四极杆串联飞行时间高分辨质谱对猪肉中多种类兽药残留进行筛查和确证的定性分析方法。方法 均匀分散的样品经提取、净化后,通过Acquity HSS T3超高效液相色谱柱（2.1 mm×100 mm, 1.8 μm）分离,流动相梯度洗脱后进入高分辨质谱检测。在正离子模式下,通过高分辨质谱一级全扫描对样品进行分析,与数据库中的目标化合物精确质量数、保留时间进行匹配。对疑似阳性样品进一步通过二级碎片离子扫描进行确证。结果 建立的分析方法对目标化合物选择性良好,检出限在1~80 μg/kg,满足对快速筛查分析的方法学要求。结论 该方法简单、灵敏、分析速度快,适用于猪肉中117种兽药化合物的筛查和确证。     

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.     

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.     

低温带皮菜籽粕微粉的不同粒级部分的功能特性

为研究低温带皮菜籽粕微粉的不同粒级部分的功能特性,以经低温脱脂的带皮菜籽粕为原料,经微粉碎后筛分成212~425μm、150~212μm和106~150μm的3个不同粒级的微粉样品,检测这些样品的吸水性、吸油性、乳化性和乳化稳定性、蛋白质体外消化率。结果表明:1 3个不同粒级的微粉样品之间的粗纤维含量存在显著差异,表明三者的结构组成成分有一定差异。23个微粉样品的乳化活性和乳化稳定性随粒度级别的减小而显著增加(P0.01)。33个微粉样品的蛋白质体外消化率随粒度级别的减小而显著增加(P0.01)。4不同粒级带皮菜籽粕微粉样品的吸水性与吸油性受其结构组成物质不同和粒度的双重影响,与粒度的相关性不明显。     

Microbiology of food taints

Fresh and processed foods are often spoilt by the presence of undesirable flavours and odours caused by microbial action. The aim of this paper is to review the current knowledge of microbiologically induced taints that occur in a wide range of foodstuffs, including meats, poultry, fish, crustaceans, milk, dairy products, fruits, vegetables, cereals and cereal products. Examples have been chosen where the compounds responsible for the taint have been identified and sufficient data obtained to demonstrate the involvement of microorganisms. However, in some cases the full identity of the causative organism may not have been elucidated. The types of microorganisms covered by this review include bacteria, fungi, yeasts, actinomycetes and cyanobacteria. Although cyanobacteria do not in general infect foods, their presence in aqueous systems and water supplies can lead to off-flavours in aquatic organisms and processed foodstuffs. Several examples of each of these processes are discussed. Wherever possible, the likely biosynthetic pathway used by the microorganism to produce the offending compound in a foodstuff is indicated.     

Analysis for organic residues from aids to polymerization used to make plastics intended for food contact

Polymers intended for food contact use have been analysed for organic residues which could be attributed to a range of substances employed as polymerization aids (e.g. initiators and catalysts). A wide range of polymers was extracted with solvents and the extracts analysed by gas chromatography-mass spectrometry (GC-MS). The overwhelming majority of substances identified were not derived from aids to polymerization but were oligomers, additives and adventitious contaminants. However, a small number of substances were identified as initiator residues. These included tetramethylsuccinonitrile (TMSN) which was observed in two polymers and it derived from recombination of two azobisisobutyronitrile (AIBN) initiator radicals. Methyl benzoate, benzoic acid, biphenyl and phenyl benzoate were detected in one poly(methyl methacrylate) sample and in two polyvinylchlorides and they are thought to be derived from benzoyl peroxide initiator. TMSN was subsequently targeted for analysis of poly-(methyl methacrylate) plastics using proton nuclear magnetic resonance spectrometry (¹     

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

Experiments were performed to characterize the kinetics of the permeation of different medium molecular weight model permeants: bisphenol A, warfarin and anthracene, from liquid paraffin, through a surrogate potential functional barrier (25 microns-thick orientated polypropylene--OPP) into the food simulants olive oil and 3% (w/v) acetic acid. The characterization of permeation kinetics generally observed the permeation models previously reported to explain the experimental permeation results obtained for a low molecular weight group of model permeants. In general, the model permeants exhibited behaviour consistent with their relative molecular weights with respect to (a) the time taken to attain steady-state permeation into the food simulant in which they were more soluble, (b) their subsequent steady-state permeation rates, and (c) their partition between liquid paraffin and the OPP membrane.     

The development of reference materials for paralytic shellfish poisoning toxins in lyophilized mussel. I: Interlaboratory studies of methods of analysis

This paper describes the first part of a project undertaken to develop mussel reference materials for Paralytic Shellfish Poisoning (PSP) toxins. Two interlaboratory studies were undertaken to investigate the performance of the analytical methodology for several PSP toxins, in particular saxitoxin (STX) and decarbamoyl-saxitoxin (dc-STX) in lyophilized mussels, and to set criteria for the acceptance of results to be applied during the second part of the project: the certification exercise. In the first study, 18 laboratories were asked to measure STX and dc-STX in rehydrated lyophilized mussel material and to identify as many other PSP toxins as possible with a method of their choice. In the second interlaboratory study, 15 laboratories were additionally asked to determine quantitatively STX and dc-STX in rehydrated lyophilized mussel and in a saxitoxin-enriched mussel material. The first study revealed that three out of four postcolumn derivatization methods and one pre-column derivatization method sufficed in principle to determine STX and dc-STX. Most participants (13 of 18) obtained acceptable calibration curves and recoveries. Saxitoxin was hardly detected in the rehydrated lyophilized mussels and results obtained for dc-STX yielded a CV of 58% at a mass fraction of 1.86 mg/kg. Most participants (14 out of 18) identified gonyautoxin-5 (GTX-5) in a hydrolysed extract provided. The first study led to provisional criteria for linearity, recovery and separation. The second study revealed that 6 out of 15 laboratories were able to meet these criteria. Results obtained for dc-STX yielded a CV of 19% at a mass fraction of 3.49mg/kg. Results obtained for STX in the saxitoxin-enriched material yielded a CV of 19% at a mass fraction of 0.34mg/kg. Saxitoxin could not be detected in the PSP-positive material. Hydrolysis was useful to confirm the identity of GTX5 and provided indicative information about C1 and C2 toxins in the PSP-positive material. The methods used in the second interlaboratory study showed sufficiently consistent analysis results to undertake a certification exercise to assign certified values for STX and dc-STX in lyophilized mussel.     

The Ministry of Environmental Protection Issued "Feasible Technology Guidelines for Pollution Prevention and Control in Wood Pulping Process of the Paper Industry (Trial)" and Two Other Guiding Technical Documents

On December 27t＂, 2013, the Ministry of Environmenta Protection announced that, in order to implement ＂The Environmental Protection Law of the People＇ s Republic of China＂, improve the working system in environmenta protection technologies, and promote technologica advancement in pollution prevention, the Ministry of Environmental Protection sponsored the formulation of three guiding technical documents including ＂Feasible Technology Guidelines for Pollution Prevention and Contro n Wood Pulping Process of the Paper Industry （Trial）＂     

1~(st) Intelli-Tissue~ EcoEc Tissue Machine Supplied by PMP Group Successfully Put into Operation in China

正On April 29th,2014,Intelli-Tissue EcoEc tissue machine supplied by PMP Group successfully put into operation at Hebei Xuesong Paper Co.,Ltd.,this is the first such kind of paper machine of PMP Group in China.