Determination of acrylamide in coffee and coffee products by GC-MS using an improved SPE clean-up

An improved gas chromatography-mass spectrometry (GC-MS) method to determine acrylamide (AA) in coffee and coffee products was developed. The method was based on two main purification steps: the first with ethanol and Carrez solutions in order to precipitate polysaccharides and proteins, respectively; and the second with a layered solid-phase extraction (SPE) column which proved to be efficient in the elimination of the main chromatographic interferences. The method is applicable to a wide range of coffee products. Twenty-six samples of different coffee products were analysed. The levels of AA were in the range 11.4-36.2 µg l^-1 for 'espresso coffee' and 200.8-229.4 µg l^-1 for coffee blends with cereals. The results indicate that the presence of cereals significantly increased the levels of AA.     

甘氨酸与丙烯酞胺高温反应产物的细胞毒性

丙烯酰胺是食品加热过程中生成的一种具有潜在致癌性的有毒化合物,前期研究表明甘氨酸对丙烯酰胺的生成具有抑制作用。为了探明此方法的安全性,将丙烯酰胺/甘氨酸模拟体系在高温下发生反应的产物与丙烯酰胺的细胞毒性进行初步评价,应用倒置显微镜对细胞形态学观察、台盼蓝排斥实验检测细胞存活率,结果一致表明对于神经母细胞瘤细胞(SH-SY5Y),在低于100g/mL的浓度范围内,反应产物的毒性作用明显小于丙烯酰胺。     

Dietary acrylamide exposure among Finnish adults and children: the potential effect of reduction measures

A deterministic exposure assessment using the Nusser method that adjusts for within-subject variation and for nuisance effects among Finnish children and adults was carried out. The food consumption data covered 2038 adults (25–74 years old) and 1514 children of 1, 3 and 6 years of age, with the data on foods’ acrylamide content obtained from published Finnish studies. We found that acrylamide exposure was highest among the 3-year-old children (median?=?1.01?µg?kg^?1?bw^?day^?1, 97.5th percentile?=?1.95?µg?kg^?1?bw^?day^?1) and lowest among 65–74-year-old women (median?=?0.31?µg?kg^?1?bw^?day^?1, 97.5th percentile?=?0.69?µg?kg^?1?bw^?day^?1). Among adults, the most important source of acrylamide exposure was coffee, followed by casseroles rich in starch, then rye bread. Among children, the most important sources were casseroles rich in starch and then biscuits and, finally, chips and other fried potatoes. Replacing lightly roasted coffee with dark-roasted, swapping sweet wheat buns for biscuits, and decreasing the acrylamide content of starch-based casseroles and rye bread by 50% would result in a 50% decrease in acrylamide exposure in adults. Among children, substituting boiled potatoes for chips and other friend potatoes and replacing biscuits with sweet wheat buns while lowering the acrylamide content of starch-based casseroles by 50% would lead to acrylamide exposure that is only half of the original exposure. In conclusions, dietary modifications could have a large impact in decreasing acrylamide exposure.     

Acrylamide concentrations in potato crisps in Europe from 2002 to 2011

A dataset of manufacturers’ measurements of acrylamide levels in 40,455 samples of fresh sliced potato crisps from 20 European countries for years 2002 to 2011 was compiled. This dataset is by far the largest ever compiled relating to acrylamide levels in potato crisps. Analysis of variance was applied to the data and showed a clear, significant downward trend for mean levels of acrylamide, from 763 ± 91.1 ng g^?1 (parts per billion) in 2002 to 358 ± 2.5 ng g^?1 in 2011; this was a decrease of 53% ± 13.5%. The yearly 95th quantile values were also subject to a clear downward trend. The effect of seasonality arising from the influence of potato storage on acrylamide levels was evident, with acrylamide in the first 6 months of the year being significantly higher than in the second 6 months. The proportion of samples containing acrylamide at a level above the indicative value of 1000 ng g^?1 for potato crisps introduced by the European Commission in 2011 fell from 23.8% in 2002 to 3.2% in 2011. Nevertheless, even in 2011, a small proportion of samples still contained high levels of acrylamide, with 0.2% exceeding 2000 ng g^?1.     

液相色谱-串联质谱法测定黑糖中丙烯酰胺和天冬酰胺

目的建立了一种同时检测食糖产品中丙烯酰胺和天冬酰胺的液相色谱-串联质谱(HPLC-MS/MS)方法。方法食糖产品样品不需要经过衍生,经纯水直接提取净化后就可测定,且方法检出限较低。采用含有5mM/L乙酸铵、0.1%的甲酸水(A)和乙腈(B)作为流动相进行梯度洗脱,质谱采用多反应监测模式(MRM)对定性和定量离子进行监测。结果丙烯酰胺和天冬酰胺在0.1mg/L、0.2 mg/L、0.5 mg/L三个添加浓度上回收率范围为93.5%～108.0%,相对标准偏差1.4%~5.4%;方法检出限为0.005 mg/L~0.01 mg/L。结论本方法前处理操作快速简单,可重复性好,满足国内外对食糖产品中丙烯酰胺和天冬酰胺的快速、准确的检测要求,适合大量样品的准确定量和定性分析。     

中式油炸食品中丙烯酰胺测定及降低方法初探

研究高效液相色谱法分析测定中式油炸食品中丙烯酰胺方法。样品预处理条件:油炸样品粉碎后用0.1%甲酸水溶液(料液比1:5)进行三次重复提取,提取液经高速离心、冷冻、C_(18)固相萃取小柱纯化,最后采用高效液相色谱仪进行测定。测定色谱条件:流动相为甲醇—0.02 mol/L乙酸胺溶液(5:95,v/v)、流速为0.9 ml/min、进样量为20μl、保留时间约4.887 min,检测器为紫外检测器,波长为210 nm、柱温25℃±0.5℃;试验结果表明,丙烯酰胺色谱图峰面积与其浓度在0.5～5.0μg/mL范围内呈良好线性关系,其最低检出限为10 ng/mL,回收率为94.5%～106.5%,相对标准偏差3.2%～4.5%;该法回收率高、精密度好,重复性好。利用该法测定几类市售中式油炸食品和自制油炸食品中丙烯酰胺含量,结果表明,市售中式油炸食品丙烯酰胺检出率为100%,仅含量水平有较大差异;试验也表明,通过优化工艺技术条件和配方如调节pH值或添加抗氧化剂等可降低油炸食品中丙烯酰胺含量。     

乞租色谮一质谮联用法测定纺织品中丙烯酰胺

以水等极性溶剂提取纺织品中丙烯酰胺,提取液经溴化衍生后,用乙酸乙酯溶剂萃取2,3-二溴丙酰胺（2,3-DBPA）,衍生物,采用气相色谱一质谱联用（GC-MS）分析检测,选择特征离子进行定性,外标法进行定量。该方法在O～0．2mg／kg线性范围内,相关系数户为0．9996,检出限为3,ug／kg,加标回收率在8＇7．5％～102．1％,相对标准偏差为1．98％～4．1l％。     

UPLC-MS/MS法测定茶叶中丙烯酰胺

采用超高效液相色谱串联三重四极杆质谱（UPLC-MS/MS）法测定绿茶、红茶和乌龙茶中丙烯酰胺含量。样品2.0 g经正己烷去脂和乙腈提取,MCX固相萃取柱净化,采用Waters BEH-C18色谱柱分离,以0.1%的甲酸水溶液和乙腈溶液为流动相进行梯度洗脱;质谱条件采用电喷雾离子源（ESI）和多反应监测模式（MRM）,同位素内标法定量。结果表明,丙烯酰胺的质量浓度为5.0～160.0 μg/L时,线性关系良好,相关系数（R2）＞0.999,且精密度实验结果的相对标准偏差（RSD）为1.73%,定量限为1.5 μg/kg,加标回收率为88.0%～96.8%。说明该方法精密度及准确度良好,能满足茶叶中丙烯酰胺含量检测的要求。     

Acrylamide levels in potato crisps in Europe from 2002 to 2016

ABSTRACT

European manufacturers’ data on acrylamide in potato crisps from 2002 to 2016 were analysed. A previous study showed a 53% reduction in mean acrylamide levels from 763 ng g^?1 in 2002 to 358 ng g^?1 in 2011. Analysis of data from the longer period showed that since 2011 there has been a levelling off, with the mean level for 2016 being 412 ng g^?1 (still a 46% reduction from 2002), suggesting that the most effective acrylamide reduction measures had been devised and implemented by 2011. There were similar trends in the 90^th and 95^th quantile values, with the 90^th quantile values being below 1000 ng g^?1 (the European Commission’s current ‘Indicative Value’ for acrylamide in potato crisps) since 2010. The proportion of samples with acrylamide above 2000 ng g^?1 fell from 4.8% in 2002 to 0.6% in 2016. Acrylamide levels showed marked seasonal variability, being highest in the first half of the year when potatoes were being used from storage, and lowest from July to September when potatoes were being harvested. Acrylamide levels were higher in thicker types of crisp in the early years of the study, but this difference disappeared in the later years, suggesting that manufacturers had acted to reduce acrylamide formation in these products. Higher values for acrylamide were recorded in north and east Europe than in the south and west up to 2013. Levels in the north and east declined in recent years, but remained higher in the north than in the other regions. The manufacturers’ data were compared with a much smaller dataset provided by the European Food Safety Authority (EFSA). Levels of acrylamide in the EFSA dataset were consistently higher than in the manufacturers’ data, possibly due to uneven sampling through the year and the seasonality of acrylamide levels.     

贵州主要发酵豆制品加工中丙烯酰胺形成动态

以水豆豉、黑豆豉、豆瓣酱及腐乳等贵州主要发酵豆制品为试材,采用高效液相色谱-串联质谱（HPLC-MS/MS）方法,测定其各生产阶段的丙烯酰胺含量。结果表明,在发酵前的热处理环节中,均无丙烯酰胺形成;但发酵开始,随着发酵过程的延伸,丙烯酰胺的含量呈上升趋势。到发酵结束时,黑豆豉、水豆豉、豆瓣酱及腐乳样品中丙烯酰胺含量分别达（15 040±191） μg/kg、（16 496±204）μg/kg、（16 821±45） μg/kg及（5 655±24） μg/kg,表明低温发酵的豆制品体系中会形成大量丙烯酰胺,存在一定食用安全风险。     

高效液相色谱法测定油炸鸡腿中丙烯酰胺的含量

利用高效液相色谱检测方法测定富含蛋白质的油炸鸡腿中丙烯酰胺的含量。以市售的油炸鸡腿作为供试样品,以纯水为提取剂,超声波提取,以CarrezⅠ和CarrezⅡ溶液进行净化。色谱条件为:XBridgeTMC18色谱柱(250×4.6μm,5μm),以甲醇和水(10∶90,v∶v)作为流动相,流速为0.8mL/min,紫外检测波长在210nm处进行检测。结果表明,该方法标准曲线线性关系良好,线性范围为0.2~2.5μg/mL,相关系数R2=0.9992,出峰时间为4.438min,最低检出限为0.002μg/mL,回收率为76%~90%,相对标准偏差(RSD)为0.42%。该方法测定油炸鸡腿中的丙烯酰胺方便、快捷、准确可靠、易推广使用。      

Development of extruded snacks using soy,sorghum, millet and rice blend – A response surface methodology approach

Response surface methodology (RSM) based on a five‐level‐three‐factor central composite rotatable design (CCRD) was employed for optimisation of formulation for production of a soy‐fortified millet‐based extruded snack. Effects of amount of ingredients such as ragi (40–50%), sorghum (10–20%) and soy (5–15%) on the physical properties like bulk density, expansion ratio, water absorption index and water solubility index of snacks were investigated. Significant regression models that explained the effects of different percentages of ragi, sorghum and soy on all response variables were determined. The coefficients of determination, R², of all the response variables were higher than 0.90. Based on the given criteria for optimisation, the basic formulation for production of millet‐based extruded snack with desired sensory quality was obtained by incorporating with 42.03% ragi, 14.95% sorghum, 12.97% soy and 30% rice.     

HPLC-MS/MS法定量测定方便面中的丙烯酰胺

开发了方便面中的丙烯酰胺的测定方法。试样以C3-丙烯酰胺为内标,经水溶液振荡提取,采用HPLC-MS/MS方法,以多选择反应监测（MRM）模式测定目标化合物。方法的检出限和定量限分别为10、30μg/kg,回收率为71·5%～119·5%,RSD为7·1%～8·1%。本方法定量准确、可靠,适用于测定方便面中的丙烯酰胺。      

食品中丙烯酰胺分析的样品前处理技术

近年来,关于食品中丙烯酰胺危害食品安全的问题倍受关注,在检测过程中,样品的前处理技术直接影响检测的效率和准确率。综述了近年来食品中丙烯酰胺分析的样品前处理技术,对加速溶剂萃取和固相微萃取等新技术进行了评述,并对食品中丙烯酰胺分析的前处理技术的发展方向进行了讨论。     

Determination of acrylamide content of food products in Korea

Acrylamide (AA) contents of commercial market‐purchased foods and of traditional home‐cooked Korean foods were investigated. The effect of cooking method on AA amount in potatoes was also studied. AA contents of roasted barley and corn ranged from 116 to 449 µg kg^?1 and of chips ranged from 12 to 3241 µg kg^?1, representing a very high variation in AA contents among tested samples. Lower levels of AA were found in wheat flour chips compared to potato chips. AA contents of ramen noodles were below 37 µg kg^?1, whether they contained potato starch or not. The AA contents of Korean home‐cooked oil fried foods increased in the following order: yakwa < whole deep‐fried sea tangle < ground and deep‐fried lotus root < ground and pan‐fried lotus root < French fries < ground and pan‐fried potato. Lotus root and garlic also had the potential to produce AA during cooking. Pre‐treatment such as grinding, boiling, freezing and thawing increased the AA formation in oil‐fried potato. Temperature was more influential than time on AA formation during deep‐oil frying. Removing water‐soluble fractions reduced AA content of cooked potatoes. Copyright © 2006 Society of Chemical Industry     

Determination of neotame in beverages,cakes and preserved fruits by column-switching high-performance liquid chromatography

A column-switching HPLC method for the determination of neotame in beverages, cakes and preserved fruits was developed. After pre-treatment using a Waters Oasis HLB cartridge, the sample solution was separated on two C₁₈ columns using a column-switching technique with a six-port valve. UV detection was performed at 210 nm. The effects of eluent composition and eluate volume on the retention and elution of neotame on SPE cartridge were investigated. The method is simple, rapid, sensitive and has good reproducibility. RSD was lower than 5% (n = 5). The calibration curve of neotame was in the range 5–100 µg/ml with good linearity (r ² = 0.999). Because neotame was concentrated 10 times from an original sample to a sample solution by solid-phase extraction (SPE), the limit of quantification (LOQ) of the method was 0.5 mg/kg. The recovery yields of neotame spiked in foods was >92% with a coefficient of variation <3.2%. The proposed column-switching HPLC method can be successfully used to determine neotame in routine inspection work.     

焙炒对米茶中丙烯酰胺和晚期糖基化终产物的影响

研究焙炒温度、时间、加水量和浸润时间对米茶加工过程中丙烯酰胺(Acrylamide,AA)和晚期糖基化终产物(Advanced glycation end products,AGEs)的影响。结果表明,随着焙炒温度升高和时间的增加,AA和AGEs含量增加,但是当温度高于200℃时AA含量会呈现降低趋势;随加水量增加和浸润时间延长,AGEs含量显著性减少(p<0.05),米茶中的AA含量先降低,在加水量超过10%,浸润时间超过10 min之后升高。在190℃,加水量10%(w/w),浸润10 min,焙炒35 min最适加工条件下AA和AGEs含量分别为141μg/kg和360 AU/g,低于同类产品,正常食用对人体安全。      

加压毛细管电色谱法测定不同烹饪方式食品中丙烯酰胺含量

目的 建立加压毛细管电色谱法检测食品中丙烯酰胺含量的分析方法,并依据所建立的方法研究不同烹饪方式下食品中丙烯酰胺含量变化的规律。方法 样品经1.0 mol/L NaCl溶液提取后,以乙腈-15 mmol/L pH 4.7磷酸钾缓冲液（15:85,V:V）为流动相,在电压强度＋2 kV条件下,外标法峰面积定量。结果 丙烯酰胺标准溶液在0.05~5.00 μg/mL浓度范围内线性良好,相关系数r2为0.9991,检出限为0.3 μg/g,定量限为1.5 μg/g,加标回收率达到96.3%～98.6%。通过研究发现蒸、煮2种方式对丙烯酰胺含量的影响较小,而炸和烤对淀粉质及肉类食品中的丙烯酰胺含量影响较大。结论 此法可以准确、快速的测定不同烹饪方式食品中的丙烯酰胺含量。     

固相萃取-高效液相色谱法检测油炸薯条中丙烯酰胺

目的 建立了一种采用固相萃取-高效液相色谱(SPE-HPLC)测定油炸薯条中丙烯酰胺的方法.方法 样品用2.0 mol/L氯化钠溶液进行提取,使用Styre Screen H2P固相萃取柱(200 mg/3 ml)净化,然后用Sapphire C18反相色谱柱进行分析,流动相为甲醇/水(5∶95),流速为1.0 ml/min,检测波长为200 nm.结果 在1.0 ～ 10.0 μg/g的添加水平范围内,样品中丙烯酰胺的平均回收率为66.2％ ～80.9％,相对标准偏差为1.6％ ～2.1％,最低检测限和最低定量限分别为0.025和0.080 μg/g.结论 该方法操作简单、快速、准确,可用于油炸薯条中丙烯酰胺的快速测定.