香菇中不同形态甲醛的测定与分析
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摘要
香菇中同时存在游离态甲醛和结合态甲醛,建立一种可以一次性快速测定这两种形态甲醛含量的方法。根据香菇中两种形态的甲醛析出条件,实验设计了2个步骤:第一步,先通过蒸馏提取香菇中游离态甲醛;第二步,加酸后再次蒸馏,提取香菇中结合态甲醛。实验设定条件为:蒸馏时间为4 min,加10%磷酸40 mL,水浴温度为60℃,水浴时间为60 min。结论为,当甲醛浓度为0.0～10.0 mg/L时,标准曲线线性关系良好,相关系数r为0.9995,游离态甲醛检测的加标回收率为87.8%～105.9%,相对标准偏差(RSD)在3.5%～7.0%;结合态甲醛检测的加标回收率为89.5%～105.8%,相对标准偏差(RSD)在2.5%～6.7%。香菇中结合态甲醛含量占总甲醛的62.6%～71.8%,游离态甲醛和结合态甲醛在伞部的含量均高于柄部的含量。全自动定氮仪可以一次性处理香菇中不同形态的甲醛,与高效液相色谱联用,能够自动、快速、高效地完成香菇中甲醛形态的检测与分析。
In order to one-time and rapidly determine the dissociative formaldehyde and conjugate formaldehyde in Letinous edodes,the method of combining full automatic nitrogen analyzer and high performance liquid chromatography(HPLC) was established.According to the precipitation conditions with different morphology of formaldehyde in Letinous edodes,the 2 steps were set to distill with the automatic nitrogen analyzer.The first step was distilled dissociative formaldehyde and the second step was adding-acid to distill the conjugate formaldehyde.The conditions of experiment were that distilling-time 4 min,10% phosphoric acid 40 mL,water-bathing temperature 60 ℃,and water-bathing time 60 min.When formaldehyde concentration is 0.0～10.0 mg/L,the standard curve has good linear relationship,the correlation coefficient r is 0.9995.The recoveries of dissociative formaldehyde were 87.8%～105.9%,the relative standard deviation(RSD) was 3.5%～7.0%;the recovery of conjugate formaldehyde was 89.5%～105.8%,and RSD was 2.5%～6.7%.The automatic nitrogen analyzer could improve the extraction efficiency of different morphology of formaldehyde in Letinous edodes.The content of conjugate formaldehyde in Lentinus edodes accounted for 62.6%～71.8%.The contents of dissociative formaldehyde and conjugate formaldehyde in the umbrella part were higher than that in the stalk part.The method combined with high performance liquid chromatography and the automatic nitrogen analyzer was suitable for the batch detection of formaldehyde in Letinous edodes.
In order to one-time and rapidly determine the dissociative formaldehyde and conjugate formaldehyde in Letinous edodes,the method of combining full automatic nitrogen analyzer and high performance liquid chromatography(HPLC) was established.According to the precipitation conditions with different morphology of formaldehyde in Letinous edodes,the 2 steps were set to distill with the automatic nitrogen analyzer.The first step was distilled dissociative formaldehyde and the second step was adding-acid to distill the conjugate formaldehyde.The conditions of experiment were that distilling-time 4 min,10% phosphoric acid 40 mL,water-bathing temperature 60 ℃,and water-bathing time 60 min.When formaldehyde concentration is 0.0～10.0 mg/L,the standard curve has good linear relationship,the correlation coefficient r is 0.9995.The recoveries of dissociative formaldehyde were 87.8%～105.9%,the relative standard deviation(RSD) was 3.5%～7.0%;the recovery of conjugate formaldehyde was 89.5%～105.8%,and RSD was 2.5%～6.7%.The automatic nitrogen analyzer could improve the extraction efficiency of different morphology of formaldehyde in Letinous edodes.The content of conjugate formaldehyde in Lentinus edodes accounted for 62.6%～71.8%.The contents of dissociative formaldehyde and conjugate formaldehyde in the umbrella part were higher than that in the stalk part.The method combined with high performance liquid chromatography and the automatic nitrogen analyzer was suitable for the batch detection of formaldehyde in Letinous edodes.
引文
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[15]张博,石矛,马杰,等.全自动凯式定氮仪-超高效液相色谱法测定啤酒中甲醛的残留量[J].中国卫生检验杂志.2015,25(3):326-329ZHANG Bo,SHI Mao,MA Jie,et al.Determination of formaldehyde residues in beer by Kjeltec auto analyzerUPLC[J].Chin J Health Lab Technol,2015,25(3):326-329
[16]陈建华,缪恩铭,李晶,等.HPLC法测定食品用包装纸中甲醛与乙醛的含量[J].云南大学学报,2015,37(4):569-576CHEN Jian-hua,MIAO En-ming,LI Jing,et al.Determination of formaldehyde and acetaldehyde in food wrapping paper by HPLC[J].Journal of Yunnan University(Natural Sciences Edition),2015,37(4):569-576
[17]徐宝根.出口蔬菜农药残留控制实用手册[M].杭州:浙江科学技术出版社,2007XU Bao-gen.Practical book for control of residues of pesticides on the vegetable for exportation[M].Hangzhou:Zhejiang Science and Technology Press,2007
[18]中华人民共和国商务部.香菇出口标准化手册[R].2009Ministry of Commerce of P.R.C.Standardization Directory for Mushroom Exportation[R].2009
[2]张烨.香菇中甲醛的影响因素及其存在状态研究[D].重庆:西南大学,2007ZHANG Ye.Studies on influence factor and existing form of formaldehyde in Lentinulac edodes[D].Chongqing:Southwest University,2007
[3]夏苗.香菇内源性甲醛含量的消长规律及采后调控研究[D].杭州:浙江工商大学,2011XIA Miao.The growth and decline of endogenous formaldehyde in shiitake mushroom(Lentinus edodes)as well as its control research[D].Hangzhou:Zhejiang Gongshang University,2011
[4]刘华.食品中甲醛的细胞毒性及基因表达影响[J].食品与生物技术学报,2017,36(6):625-634LIU Hua.Research of cytotoxicity and gene expression by formaldehyde in the food[J].Journal of Food Science and Biotechnology,2017,36(6):625-634
[5]邱霞琴,张红琳,岳都盛,等.蒸馏-乙酰丙酮分光光度法分析香菇内源性甲醛含量变化[J].江苏农业科学,2017,45(9):141-143QIU Xia-qin,ZHANG Hong-lin,YUE Dou-sheng,et al.Determination of formaldehyde content in mushroom by distillation-acetyl acetone spectrophotometry[J].Jiangsu Agricultural Sciences,2017,45(9):141-143
[6]吴清盛,茅小燕.香菇中甲醛的提取及其乙酰丙酮分光光度法测定[J].食品与发酵科枝,2015,51(1):84-86WU Qing-sheng,MAo Xiao-yan.Extraction of formaldehyde in mushrooms and determination with acetylacetone spectrophotometric method[J].Food Ferment Technol,2015,51(1):84-86
[7]农业部.NY/T 1283-2007香菇中甲醛含量的测定[S].北京:中国农业出版社,2007Ministry of Agriculture.NY/T 1283-2007 determination of formaldehyde content in lentinula edodes[S].Beijing:China Agriculture Press,2007
[8]王丹,王宇,杨树坤.测定食品中甲醛的样品前处理方法比较[J].疾病监测与控制,2009,6:341-342WANG Dan,WANG Yu,YANG Shu-kun,et al.Comparison on the pretreatment method of formaldehyde in food[J].Journal of Disease Monitor and Control,2009,6:341-342
[9]李俊,刘永翔,王辉,等.高效液相色谱法定量测定果蔬中甲醛含量[J].食品科学,2016,37(22):218-224LI Jun,LIU Yong-xiang,WANG Hui,et al.Determination of formaldehyde in fruits and vegetables by HPLC[J].Food Science,2016,37(22):218-224
[10]ZHU Yi,PENG Zeng-qi,WANG Min,et al.Optimization of extraction procedure for formaldehyde assay in smoked meat products[J].Journal of Food Composition and Analysis,2012,28(1):1-7
[11]杨娟,秦樱瑞,曾艺涛,等.内源性甲醛,甲醛毒性及甲醛抑制物的研究进展[J].食品科学,2014,35(1):294-297YANG Juan,QIN Ying-rui,ZENG Yi-tao,et al.Progress in endogenous formaldehyde,formaldehyde toxicity and formaldehyde inhibitors[J].Food Science,2014,35(1):294-297
[12]黄文水,佘晓麒,吴丽苹,等.凯氏定氮仪-分光光度法测定鹅肠中甲醛[J].光谱实验室.2012,29(4):2607-2609HUANG Wen-shui,SHE Xiao-qi,WU Li-ping,et al.Determianatian of formaldehyde in goose sausage by Keldahl nitrogen with spectrophotometry[J].Chin J Spectrosc Lab,2012,29(4):2607-2609
[13]李冰茹,王纪华,马智宏.凯氏定氮仪联合液相色谱法测定香菇中甲醛含量[J].食品安全质量检测学报,2017,8(5):1763-1766LI Bing-ru,WANG Ji-hua,MA Zhi-hong.Determination of the formaldehyde in Lentinula edodes by automatic Kjeldahl apparatus combined with liquid chromatography[J].Journal of Food Safety and Quality Inspection,2017,8(5):1763-1766
[14]WANG Ting,GAO Xiao-ling,TONG Jia,et al.Determination of formaldehyde in beer based on cloud point extraction using 2,4-dinitrophenylhydrazine As derivative reagent[J].Food Chemistry,2012,131(4):1577-1582
[15]张博,石矛,马杰,等.全自动凯式定氮仪-超高效液相色谱法测定啤酒中甲醛的残留量[J].中国卫生检验杂志.2015,25(3):326-329ZHANG Bo,SHI Mao,MA Jie,et al.Determination of formaldehyde residues in beer by Kjeltec auto analyzerUPLC[J].Chin J Health Lab Technol,2015,25(3):326-329
[16]陈建华,缪恩铭,李晶,等.HPLC法测定食品用包装纸中甲醛与乙醛的含量[J].云南大学学报,2015,37(4):569-576CHEN Jian-hua,MIAO En-ming,LI Jing,et al.Determination of formaldehyde and acetaldehyde in food wrapping paper by HPLC[J].Journal of Yunnan University(Natural Sciences Edition),2015,37(4):569-576
[17]徐宝根.出口蔬菜农药残留控制实用手册[M].杭州:浙江科学技术出版社,2007XU Bao-gen.Practical book for control of residues of pesticides on the vegetable for exportation[M].Hangzhou:Zhejiang Science and Technology Press,2007
[18]中华人民共和国商务部.香菇出口标准化手册[R].2009Ministry of Commerce of P.R.C.Standardization Directory for Mushroom Exportation[R].2009