本文主要研究内容
作者(2019)在《基于表面增强拉曼光谱技术的茶叶中农药残留高灵敏快速检测研究》一文中研究指出:茶(Camellia sinensis L.)是世界上饮用最为广泛的非酒精饮料之一,具有多种保健功能。作为我国主要的木本经济作物,茶有助于增加农业效益及茶农收入。但茶在生产过程中会产生一定的农药残留,不仅威胁到消费者健康,也对我国茶及茶制品出口贸易造成严重影响。但现有的检测技术存在着检测效率低、检测成本高等局限性。因此,茶叶中农药残留快速检测技术的研究和开发引发了越来越多的关注。本课题开展了基于表面增强拉曼光谱(surface-enhanced Raman spectroscopy,SERS)技术的茶叶中农药残留快速检测研究,主要研究内容如下:1.基于表面增强拉曼光谱技术的茶叶中吡虫啉残留快速检测研究。本研究提出了一种利用银纳米花(silver nano flower,AgNF)对茶中的吡虫啉进行SERS快速检测的方法,首先,制备了表面高度粗糙的银纳米花作为免标记SERS基底,通过扫描电镜(SEM)、透射电镜(TEM)等手段对该基底进行表征并优化合成参数;而后将该基底与样品混合后收集SERS光谱,光谱经预处理后结合偏最小二乘法(PLS)、联合区间偏最小二乘法(Si-PLS)、反向区间偏最小二乘法(Bi-PLS)、遗传偏最小二乘法(GA-PLS)分别建立样品中吡虫啉含量的预测模型,参数优选后将预测能力最强的模型应用于茶中吡虫啉的定量预测中。实验结果表明,所合成的AgNF形貌均一,平均粒径约为780 nm;以剩余预测偏差(RPD)作为评价预测能力的指标,所建立的模型其预测能力按照PLS<Bi-PLS<Si-PLS<GA-PLS的顺序逐渐增加,最优的GA-PLS模型的测试集Rp=0.9702、RPD=4.95%;所提出的检测方法对吡虫啉的最低检测限(LOD)可达4.55×10-5μg/g且相对标准偏差(RSD)小于4.50%。该研究最终证实所提出的AgNF结合GA-PLS的SERS技术对茶中吡虫啉残留检测的思路切实可行。2.基于表面增强拉曼光谱技术的茶叶中2,4-二氯苯氧基乙酸(2,4-dichlorophenoxyacetic acid,2,4-D)残留快速检测研究。本研究首先合成了银纳米颗粒(AgNPs)作为SERS基底使2,4-D分子在其表面吸附,之后分别尝试了PLS、GA-PLS、蚁群偏最小二乘法(ACO-PLS)、竞争性自适应重加权偏最小二乘法(CARS-PLS)等化学计量学模型以实现2,4-D浓度的预测,并对所建立模型的参数进行了对比以筛选最优预测模型。实验结果表明,2,4-D与AgNPs混合后在391cm-1处产生了强SERS信号,说明2,4-D通过Cl原子与银纳米的作用成功吸附在AgNPs表面;选取RPD作为模型预测能力指标进行对比,所建立模型的预测能力按照PLS<ACO-PLS<GA-PLS<CARS-PLS的顺序递增且最优CARS-PLS的Rc=0.9939、Rp=0.9931、RPD=6.62;在此条件下对2,4-D的LOD可达2.88×10-5μg/g且RSD<5%;将该检测方法与标准规定的高效液相色谱法(HPLC)结果进行对比,统计学差异不显著。该研究结果证实SERS技术结合化学计量学模型可以成功应用于茶叶中2,4-D的快速检测。3.基于表面增强拉曼光谱技术的茶中啶虫脒快速检测研究。本研究制备了一种新型氧化石墨烯搭载金纳米星(rGO-NS)的复合SERS基底并结合化学计量学模型以实现茶中啶虫脒的SERS快速检测。利用湿化学手段使星形金纳米颗粒原位生长在氧化石墨烯表面,通多多种表征手段证实该基底材料合成成功;之后利用石墨烯结构中π-π键与芳香基团的亲和作用,将rGO-NS应用于茶叶中啶虫脒的检测;最后结合GA-PLS对样品SERS光谱进行模型建立以实现茶中啶虫脒的快速定量检测。研究结果显示,金纳米星被成功负载在氧化石墨烯上;之后将rGO-NS应用于啶虫脒的SERS检测中,所收集的SERS光谱强度与啶虫脒浓度在1.0×10-4至1.0×103μg/g具有线性关系;利用GA-PLS对光谱进行预测模型建立,训练集和预测集的均方根误差分别为0.9772和0.9757,在该条件下LOD可达2.13×10-5μg/g;实际茶叶样品加标回收结果显示回收率范围为97.06%至115.88%,RSD<5.98%。该研究表明,基于rGO-NS的SERS基底结合GA-PLS模型可以对茶叶中啶虫脒进行快速检测。4.表面增强拉曼光谱技术对茶叶中两种农药残留的同时快速检测研究。为同时检测茶叶中两种农药残留,本研究首先合成了金银核壳纳米颗粒(Au@Ag)作为SERS基底,之后利用SPE技术对实际茶叶样品进行了净化,将净化后的流出液作为检测样品并收集SERS光谱,最终结合化学计量学构建了预测模型。研究结果显示,Au@Ag颗粒大小均一粒径约为20 nm,金壳厚度约为2 nm;样品经SPE净化后,在1.0×10-4-1.0×103μg/g浓度范围内啶虫脒和2,4-D在单一及混合条件下均可以产生强SERS信号;多种模型优化后确定GA-PLS作为预测模型,对啶虫脒和2,4-D的Rp分别为0.9943和0.9923,RPD分别为6.53和6.23,说明所建立的模型具有较好的鲁棒性和稳定性;该方法对啶虫脒的检测限为2.63×10-5μg/g,对2,4-D的检测限为4.15×10-5μg/g。结果表明所建立的SERS检测手段可以实现茶叶样品中2,4-D及啶虫脒的同时检测,检测结果稳定性好灵敏度高,为复杂食品基质的多指标同时检测提供了新方法。5.基于特异性表面增强拉曼光谱技术的茶叶中啶虫脒高灵敏检测研究。研究提出了一种新型银金核壳纳米粒(Ag@Au CSNPs)的合成手段并将其应用于啶虫脒的高灵敏SERS检测中。首先,采用原位水热种子生长法成功制备了Ag@Au CSNPs,并对其表面修饰SERS信号分子4,4’-二吡啶(4,4’-dipyridyl,DP)和硫醇化的啶虫脒核酸适配体,构建了对啶虫脒具有特异性的信号探针;并且制备硫醇化的啶虫脒适配体修饰的Fe3O4@Au核壳纳米粒子(Fe3O4@Au CSNPs)作为啶虫脒捕获探针;当体系中存在啶虫脒时由于核酸适配体的特异性亲和作用,可将信号探针、捕获探针连接成三明治结构并分离富集;所得三明治结构在1290 cm-1处有较强的SERS信号并且与啶虫脒的浓度呈良好线性关系。多种表征手段证实,Ag@Au CSNPs合成成功,粒径约为48 nm且金壳厚度约7 nm;透射电镜显示核酸适配体成功的修饰在Ag@Au CSNPs及Fe3O4@Au CSNPs表面;1290 cm-1处的SERS信号进行啶虫脒定量检测,LOD为5.894×10-6μg/g,实际样品的加标回收率在96.14%到118.33%范围内,RSD值≤4.93%;与HPLC的对比结果无显著统计学差异。研究结果表明,所合成的生物传感器可以实现对啶脒的高灵敏SERS检测,为农药残留的特异性SERS检测提供了可行的方法。
Abstract
cha (Camellia sinensis L.)shi shi jie shang yin yong zui wei an fan de fei jiu jing yin liao zhi yi ,ju you duo chong bao jian gong neng 。zuo wei wo guo zhu yao de mu ben jing ji zuo wu ,cha you zhu yu zeng jia nong ye xiao yi ji cha nong shou ru 。dan cha zai sheng chan guo cheng zhong hui chan sheng yi ding de nong yao can liu ,bu jin wei xie dao xiao fei zhe jian kang ,ye dui wo guo cha ji cha zhi pin chu kou mao yi zao cheng yan chong ying xiang 。dan xian you de jian ce ji shu cun zai zhao jian ce xiao lv di 、jian ce cheng ben gao deng ju xian xing 。yin ci ,cha xie zhong nong yao can liu kuai su jian ce ji shu de yan jiu he kai fa yin fa le yue lai yue duo de guan zhu 。ben ke ti kai zhan le ji yu biao mian zeng jiang la man guang pu (surface-enhanced Raman spectroscopy,SERS)ji shu de cha xie zhong nong yao can liu kuai su jian ce yan jiu ,zhu yao yan jiu nei rong ru xia :1.ji yu biao mian zeng jiang la man guang pu ji shu de cha xie zhong bi chong lin can liu kuai su jian ce yan jiu 。ben yan jiu di chu le yi chong li yong yin na mi hua (silver nano flower,AgNF)dui cha zhong de bi chong lin jin hang SERSkuai su jian ce de fang fa ,shou xian ,zhi bei le biao mian gao du cu cao de yin na mi hua zuo wei mian biao ji SERSji de ,tong guo sao miao dian jing (SEM)、tou she dian jing (TEM)deng shou duan dui gai ji de jin hang biao zheng bing you hua ge cheng can shu ;er hou jiang gai ji de yu yang pin hun ge hou shou ji SERSguang pu ,guang pu jing yu chu li hou jie ge pian zui xiao er cheng fa (PLS)、lian ge ou jian pian zui xiao er cheng fa (Si-PLS)、fan xiang ou jian pian zui xiao er cheng fa (Bi-PLS)、wei chuan pian zui xiao er cheng fa (GA-PLS)fen bie jian li yang pin zhong bi chong lin han liang de yu ce mo xing ,can shu you shua hou jiang yu ce neng li zui jiang de mo xing ying yong yu cha zhong bi chong lin de ding liang yu ce zhong 。shi yan jie guo biao ming ,suo ge cheng de AgNFxing mao jun yi ,ping jun li jing yao wei 780 nm;yi sheng yu yu ce pian cha (RPD)zuo wei ping jia yu ce neng li de zhi biao ,suo jian li de mo xing ji yu ce neng li an zhao PLS<Bi-PLS<Si-PLS<GA-PLSde shun xu zhu jian zeng jia ,zui you de GA-PLSmo xing de ce shi ji Rp=0.9702、RPD=4.95%;suo di chu de jian ce fang fa dui bi chong lin de zui di jian ce xian (LOD)ke da 4.55×10-5μg/gju xiang dui biao zhun pian cha (RSD)xiao yu 4.50%。gai yan jiu zui zhong zheng shi suo di chu de AgNFjie ge GA-PLSde SERSji shu dui cha zhong bi chong lin can liu jian ce de sai lu qie shi ke hang 。2.ji yu biao mian zeng jiang la man guang pu ji shu de cha xie zhong 2,4-er lv ben yang ji yi suan (2,4-dichlorophenoxyacetic acid,2,4-D)can liu kuai su jian ce yan jiu 。ben yan jiu shou xian ge cheng le yin na mi ke li (AgNPs)zuo wei SERSji de shi 2,4-Dfen zi zai ji biao mian xi fu ,zhi hou fen bie chang shi le PLS、GA-PLS、yi qun pian zui xiao er cheng fa (ACO-PLS)、jing zheng xing zi kuo ying chong jia quan pian zui xiao er cheng fa (CARS-PLS)deng hua xue ji liang xue mo xing yi shi xian 2,4-Dnong du de yu ce ,bing dui suo jian li mo xing de can shu jin hang le dui bi yi shai shua zui you yu ce mo xing 。shi yan jie guo biao ming ,2,4-Dyu AgNPshun ge hou zai 391cm-1chu chan sheng le jiang SERSxin hao ,shui ming 2,4-Dtong guo Clyuan zi yu yin na mi de zuo yong cheng gong xi fu zai AgNPsbiao mian ;shua qu RPDzuo wei mo xing yu ce neng li zhi biao jin hang dui bi ,suo jian li mo xing de yu ce neng li an zhao PLS<ACO-PLS<GA-PLS<CARS-PLSde shun xu di zeng ju zui you CARS-PLSde Rc=0.9939、Rp=0.9931、RPD=6.62;zai ci tiao jian xia dui 2,4-Dde LODke da 2.88×10-5μg/gju RSD<5%;jiang gai jian ce fang fa yu biao zhun gui ding de gao xiao ye xiang se pu fa (HPLC)jie guo jin hang dui bi ,tong ji xue cha yi bu xian zhe 。gai yan jiu jie guo zheng shi SERSji shu jie ge hua xue ji liang xue mo xing ke yi cheng gong ying yong yu cha xie zhong 2,4-Dde kuai su jian ce 。3.ji yu biao mian zeng jiang la man guang pu ji shu de cha zhong ding chong mi kuai su jian ce yan jiu 。ben yan jiu zhi bei le yi chong xin xing yang hua dan mo xi da zai jin na mi xing (rGO-NS)de fu ge SERSji de bing jie ge hua xue ji liang xue mo xing yi shi xian cha zhong ding chong mi de SERSkuai su jian ce 。li yong shi hua xue shou duan shi xing xing jin na mi ke li yuan wei sheng chang zai yang hua dan mo xi biao mian ,tong duo duo chong biao zheng shou duan zheng shi gai ji de cai liao ge cheng cheng gong ;zhi hou li yong dan mo xi jie gou zhong π-πjian yu fang xiang ji tuan de qin he zuo yong ,jiang rGO-NSying yong yu cha xie zhong ding chong mi de jian ce ;zui hou jie ge GA-PLSdui yang pin SERSguang pu jin hang mo xing jian li yi shi xian cha zhong ding chong mi de kuai su ding liang jian ce 。yan jiu jie guo xian shi ,jin na mi xing bei cheng gong fu zai zai yang hua dan mo xi shang ;zhi hou jiang rGO-NSying yong yu ding chong mi de SERSjian ce zhong ,suo shou ji de SERSguang pu jiang du yu ding chong mi nong du zai 1.0×10-4zhi 1.0×103μg/gju you xian xing guan ji ;li yong GA-PLSdui guang pu jin hang yu ce mo xing jian li ,xun lian ji he yu ce ji de jun fang gen wu cha fen bie wei 0.9772he 0.9757,zai gai tiao jian xia LODke da 2.13×10-5μg/g;shi ji cha xie yang pin jia biao hui shou jie guo xian shi hui shou lv fan wei wei 97.06%zhi 115.88%,RSD<5.98%。gai yan jiu biao ming ,ji yu rGO-NSde SERSji de jie ge GA-PLSmo xing ke yi dui cha xie zhong ding chong mi jin hang kuai su jian ce 。4.biao mian zeng jiang la man guang pu ji shu dui cha xie zhong liang chong nong yao can liu de tong shi kuai su jian ce yan jiu 。wei tong shi jian ce cha xie zhong liang chong nong yao can liu ,ben yan jiu shou xian ge cheng le jin yin he ke na mi ke li (Au@Ag)zuo wei SERSji de ,zhi hou li yong SPEji shu dui shi ji cha xie yang pin jin hang le jing hua ,jiang jing hua hou de liu chu ye zuo wei jian ce yang pin bing shou ji SERSguang pu ,zui zhong jie ge hua xue ji liang xue gou jian le yu ce mo xing 。yan jiu jie guo xian shi ,Au@Agke li da xiao jun yi li jing yao wei 20 nm,jin ke hou du yao wei 2 nm;yang pin jing SPEjing hua hou ,zai 1.0×10-4-1.0×103μg/gnong du fan wei nei ding chong mi he 2,4-Dzai chan yi ji hun ge tiao jian xia jun ke yi chan sheng jiang SERSxin hao ;duo chong mo xing you hua hou que ding GA-PLSzuo wei yu ce mo xing ,dui ding chong mi he 2,4-Dde Rpfen bie wei 0.9943he 0.9923,RPDfen bie wei 6.53he 6.23,shui ming suo jian li de mo xing ju you jiao hao de lu bang xing he wen ding xing ;gai fang fa dui ding chong mi de jian ce xian wei 2.63×10-5μg/g,dui 2,4-Dde jian ce xian wei 4.15×10-5μg/g。jie guo biao ming suo jian li de SERSjian ce shou duan ke yi shi xian cha xie yang pin zhong 2,4-Dji ding chong mi de tong shi jian ce ,jian ce jie guo wen ding xing hao ling min du gao ,wei fu za shi pin ji zhi de duo zhi biao tong shi jian ce di gong le xin fang fa 。5.ji yu te yi xing biao mian zeng jiang la man guang pu ji shu de cha xie zhong ding chong mi gao ling min jian ce yan jiu 。yan jiu di chu le yi chong xin xing yin jin he ke na mi li (Ag@Au CSNPs)de ge cheng shou duan bing jiang ji ying yong yu ding chong mi de gao ling min SERSjian ce zhong 。shou xian ,cai yong yuan wei shui re chong zi sheng chang fa cheng gong zhi bei le Ag@Au CSNPs,bing dui ji biao mian xiu shi SERSxin hao fen zi 4,4’-er bi ding (4,4’-dipyridyl,DP)he liu chun hua de ding chong mi he suan kuo pei ti ,gou jian le dui ding chong mi ju you te yi xing de xin hao tan zhen ;bing ju zhi bei liu chun hua de ding chong mi kuo pei ti xiu shi de Fe3O4@Auhe ke na mi li zi (Fe3O4@Au CSNPs)zuo wei ding chong mi bu huo tan zhen ;dang ti ji zhong cun zai ding chong mi shi you yu he suan kuo pei ti de te yi xing qin he zuo yong ,ke jiang xin hao tan zhen 、bu huo tan zhen lian jie cheng san ming zhi jie gou bing fen li fu ji ;suo de san ming zhi jie gou zai 1290 cm-1chu you jiao jiang de SERSxin hao bing ju yu ding chong mi de nong du cheng liang hao xian xing guan ji 。duo chong biao zheng shou duan zheng shi ,Ag@Au CSNPsge cheng cheng gong ,li jing yao wei 48 nmju jin ke hou du yao 7 nm;tou she dian jing xian shi he suan kuo pei ti cheng gong de xiu shi zai Ag@Au CSNPsji Fe3O4@Au CSNPsbiao mian ;1290 cm-1chu de SERSxin hao jin hang ding chong mi ding liang jian ce ,LODwei 5.894×10-6μg/g,shi ji yang pin de jia biao hui shou lv zai 96.14%dao 118.33%fan wei nei ,RSDzhi ≤4.93%;yu HPLCde dui bi jie guo mo xian zhe tong ji xue cha yi 。yan jiu jie guo biao ming ,suo ge cheng de sheng wu chuan gan qi ke yi shi xian dui ding mi de gao ling min SERSjian ce ,wei nong yao can liu de te yi xing SERSjian ce di gong le ke hang de fang fa 。
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论文作者分别是来自江苏大学的,发表于刊物江苏大学2019-09-19论文,是一篇关于茶叶论文,农药残留论文,吡虫啉论文,二氯苯氧基乙酸论文,啶虫脒论文,快速定量论文,表面增强拉曼光谱技术论文,纳米传感器论文,化学计量学论文,江苏大学2019-09-19论文的文章。本文可供学术参考使用,各位学者可以免费参考阅读下载,文章观点不代表本站观点,资料来自江苏大学2019-09-19论文网站,若本站收录的文献无意侵犯了您的著作版权,请联系我们删除。
标签:茶叶论文; 农药残留论文; 吡虫啉论文; 二氯苯氧基乙酸论文; 啶虫脒论文; 快速定量论文; 表面增强拉曼光谱技术论文; 纳米传感器论文; 化学计量学论文; 江苏大学2019-09-19论文;