表面增强拉曼散射技术对白酒中克百威残留的定性检测

建立表面增强拉曼散射（surface enhanced Raman scattering,SERS）技术对白酒中的克百威残留进行定性检测方法。制备金溶胶（Au nanoparticles,Au NPS）和不同Ag壳厚度的银包金纳米粒子（Au@Ag NPS）,通过探测分子罗丹明B（R6G）比较Au NPS和不同Ag壳厚度Au@Ag NPS的SERS增强效果;碱性条件下,向克百威分子引入标记物2,6-二氯醌-4-氯亚胺,再与增强效果较好的NPS按比例混合进行拉曼测试,讨论SERS信号采集条件,并对拉曼谱峰进行比较和归属,计算克百威在Au@Ag NPS增强基底上的增强因子。结果表明：克百威、标记物和Au@Ag NPS的比例为1∶0.225∶7,约7 nm Ag壳厚度Au@Ag NPS效果最好,克百威的检测下限为1×10－16 mol/L,Au@Ag NPS增强因子为2×108,用此方法检测3 种市售白酒中均含有微量的克百威,方法快速、简便、结果可靠。     

表面增强拉曼光谱法筛查保健酒中那非类药物

目的:利用表面增强拉曼光谱(SERS)技术快速非靶向筛查保健酒中非法添加那非类药物。方法:制备合适的那非类药物胶体金SERS基底,基底与78种那非类药物混合后进行SERS分析,建立谱图筛查数据库,以匹配度是否高于70%作为评判是否疑似添加那非类药物的依据。最后考察方法的灵敏度和特异性。结果:那非类药物胶体金SERS基底最佳制备方式为98.3 mL超纯水中加入1.0 mL 1%氯金酸和0.7 mL 1%柠檬酸三钠;最低检出质量浓度分别为西地那非0.05 mg/L、他达那非0.5 mg/L、硫代西地那非0.05 mg/L、乙酰伐地那非0.1 mg/L;对模拟样品进行检测,其定性结果与高效液相色谱—质谱法测量结果一致。结论:理论上,该方法可非靶向筛查出保健酒中非法添加的那非类药物。     

树枝状表面增强拉曼散射基底制备及孔雀石绿痕量检测

在表面活性剂十二烷基甲基溴化哌啶(N-methyl-N-dodecylpiperidinium bromide,C12PDB)溶液中以抗坏血酸为还原剂还原氯金酸(HAuCl_4),可快速合成具有树枝状结构的金纳米粒子(gold nanoparticles,Au NPs)。透射电子显微镜结果显示得到的树枝状Au NPs具有各向异性生长的均匀对称结构,大小为3.5～4μm。此树枝状Au NPs具有优异的拉曼活性,作为表面增强拉曼光谱(surface-enhanced Raman spectroscopy,SERS)基底检测罗丹明6G(rhodamine 6G,R6G)表现出了较高的灵敏度和良好的检测重复性,可测得R6G溶液最低浓度为3×10~(-9) mol/L,计算得增强因子约为105,其检测线性范围为3×10~(-9)～3×10~(-7) mol/L,10~(-6) mol/L R6G的10次重复检测结果中各特征峰强度的相对标准偏差均低于10%。以树枝状Au NPs作为SERS基底对溶液中孔雀石绿的检出限为1×10~(-8) mol/L,并可用于鲫鱼肉中孔雀石绿的快速检测,样品加标回收率为81.6%～102.1%。     

Au@Ag NPs表面增强拉曼快速测定奶粉中的三聚氰胺

建立表面增强拉曼光谱快速检测奶粉中三聚氰胺的方法。基于溶剂萃取法,利用乙腈对奶粉中的三聚氰胺进行提取,制备银包金溶胶(Au@Ag NPs)作为增强基底,并优化增强基底的条件来获得最佳拉曼信号。用乙腈提取三聚氰胺,将5mol/L NaCl和1mol/L NaOH的混合溶液作为凝聚剂,使Au@Ag NPs与三聚氰胺分子紧密结合后检测,可获得响应最强的表面增强拉曼(surface-enhanced raman spectroscopy,SERS)信号。三聚氰胺在奶粉中的的检出限为0.008 5 mg/kg,回收率在71.07%～91.15%,相对标准偏差(n=6)在1.52%～4.22%。该方法可用于奶粉中三聚氰胺的快速检测。     

基于Fe3O4@MIL-100(Fe)@Ag NPs的三唑磷SERS检测方法

针对在农产品中简便、快速地检测农药三唑磷残留问题，建立基于磁纳米、金属有机框架和Ag纳米颗粒(Ag NPs)的核-壳-卫星纳米结构表面增强拉曼光谱(surface-enhanced Raman scattering,SERS)基底，并应用在有机磷农药三唑磷的灵敏检测。通过低温循环自组装法和银镜循环制备了由MIL-100(Fe)包覆的Fe₃O₄，并在表面原位负载Ag NPs组成的核-壳-卫星纳米结构的Fe₃O₄@MIL-100(Fe)@Ag NPs基底。对苹果中的三唑磷残留进行SERS传感，三唑磷特征峰强度对数值与质量浓度对数值的线性检测范围为0.05～10 mg/L，线性方程为Y=0.573 8X+2.804(R²=0.980)，检出限低至11.9μg/L。在加标量为2、5、10 mg/L时，该方法的回收率为90.07%～103.27%。表明制备的SERS基底在食品农残中的检测领域具有巨大潜力。     

基于D152树脂吸附蛋白质结合SERS测定鱼肉中的鸟嘌呤含量

基于大孔树脂除杂与表面增强拉曼光谱的灵敏实时性,建立一种鱼肉中鸟嘌呤含量的快速检测方法。以D152树脂为填料,柱内直径1 cm,柱高20 cm,蛋白吸附率在83%～92%之间,鸟嘌呤滤除率大于95%。经单因素试验筛选和正交试验优化得出,上样流速为3 mL/min,洗脱液pH值为4.0以及洗脱流速为0.5 mL/min。基于银包金纳米颗粒（silver-coated gold nanoparticles,Au@Ag NPs）为表面增强基底,鸟嘌呤质量浓度在0.001～100 mg/L范围,鸟嘌呤质量浓度与拉曼强度呈线性关系,R2为0.969 9,检出限为0.1 mg/L。整个检测过程只需10 min,且无需复杂的样品处理。结果表明,D152树脂作为填料的层析柱能有效去除鱼肉中蛋白质等杂质的干扰,以Au@Ag NPs为基底的表面增强拉曼光谱技术的方法能够灵敏、快速的检测鱼肉中痕量嘌呤,检出限低于现有的高效液相色谱法,为开发设计水产品中嘌呤的快速检测方法提供研究基础。     

基于表面增强拉曼光谱快速检测苹果汁中亚胺硫磷

利用种子生长法合成出不同大小(35～91nm,金核19nm;66～127nm,金核43nm)的金核银壳纳米粒子(Au-Ag NPs),对其形貌和光学特性进行表征,并将其作为表面增强拉曼散射(SERS)基底,探究不同粒径和金银比例对亚胺硫磷检测的影响。试验结果显示:42nm Au-Ag NPs(金核19nm)和78nm Au-Ag NPs(金核43nm)对亚胺硫磷标准溶液具有最佳的SERS增强效果,最低检出浓度可低至0.05mg/L。但Au-Ag NPs基底应用于苹果汁中亚胺硫磷的SERS快速检测效果存在较大差异,以42,78nm Au-Ag NPs作为增强基底时,苹果汁中的亚胺硫磷最低检出浓度分别为5.0,0.5 mg/L。研究表明通过筛选出合适的粒径及金银比例的Au-Ag NPs有望实现对果汁中亚胺硫磷的现场快速检测。     

基于单质碘诱导银包金核壳纳米颗粒形变的过氧化氢和葡萄糖检测方法研究

目的 建立基于单质碘（I2）诱导银包金核壳纳米颗粒(Au@Ag NPs)形变的比色传感器检测过氧化氢(hydrogen peroxide，H2O2)和葡萄糖的方法。方法 在钼酸铵的催化下，H2O2氧化碘化钾产生I2诱导Au@Ag NPs形成Au-AgI异质结，其溶液的颜色由橙色变为蓝紫色，从而实现H2O2的比色法检测；基于葡萄糖氧化酶(glucose oxidase，GOx)催化葡萄糖氧化生成H2O2来间接测定葡萄糖的含量。结果 0.8×10-3 mol/L碘化钾、0.8×10-3 mol/L钼酸铵、pH 4、反应时间40 min为最佳检测条件；H2O2和葡萄糖浓度线性范围分别为30~200 μmol/L和150~300 μmol/L。以饮料为实际样品，通过标准加入法测定葡萄糖的含量，加标样品的回收率范围在96%~103%。结论 该方法操作简单、检测快速，可用于饮料样品中葡萄糖的可视化检测，并具有较高的准确度。 关键词:单质碘；银包金核壳纳米颗粒；过氧化氢；葡萄糖；高灵敏检测     

基于表面增强拉曼光谱的养殖水中硝基呋喃类抗生素残留检测

建立基于表面增强拉曼光谱(SERS)技术的便携式拉曼光谱仪,用于水产品流通过程养殖水中硝基呋喃类抗生素的快速测定。参照经典方法制备了Ag、Au纳米粒子,通过优化促凝剂、调节体系pH、选择纳米溶剂及其用量、考查吸附等待时间得到最佳SERS增强效果。结果表明,养殖水中4种硝基呋喃类抗生素呋喃妥因、呋喃西林、呋喃唑酮、呋喃它酮的检测限分别为1、0.1、5、0.1 μg/mL。所建立的快检方法灵敏度、特异性≥95%、假阴性率和假阳性率≤5%,均符合食药监科便函[2016]83号《食品快速检测方法评价技术规范》的要求,可应用于水体中硝基呋喃类抗生素的残留检测。     

利用重组酶聚合酶扩增和表面增强拉曼散射快速检测大肠杆菌耐药基因mcr-1

目的 利用重组酶聚合酶扩增(recombinase polymerase amplification,RPA)方法和表面增强拉曼散射(surface enhanced Raman scattering, SERS)技术建立一种大肠杆菌(Escherichia coli, E. coli)耐药基因mcr-1的快速检测方法。方法 首先,通过RPA特异性扩增大肠杆菌耐药基因mcr-1的保守序列。然后,以金纳米粒子(gold nanoparticles, Au NPs)作为SERS增强基底,利用便携式拉曼光谱仪采集样品的SERS光谱。最后,利用样品的特征SERS信号,实现大肠杆菌耐药基因mcr-1的快速、灵敏检测。结果 样品位于505.5和840.9 cm^-1拉曼位移处的SERS信号强度与其浓度的对数值之间具有良好的线性相关关系, r²分别为0.9827和0.9636。该方法的最低检测限为3.2×10^-4 pg/μL,检测时间约为30min。结论 本研究建立的RPA结合SERS方法检测耐药基因灵敏度高、用时短,为细菌耐药基因的快...     

Rapid detection of multiple organophosphorus pesticides (triazophos and parathion-methyl) residues in peach by SERS based on core-shell bimetallic Au@Ag NPs

In this study, a surface-enhanced Raman scattering (SERS) approach based on silver-coated gold nanoparticles (Au@Ag NPs) was established for rapid detection of multiple organophosphorus pesticides (triazophos and methyl-parathion) in peach fruit. The Raman enhancement of Au@Ag NPs for detecting organophosphorus pesticides was stronger than those of single Ag and Au NPs. It was revealed that core size of Au NPs was a critical parameter affecting the enhancement of Raman signals by joining two plasma resonance absorptions. The Au@Ag NPs with 26 nm Au core size and 6 nm Ag shell thickness showed significant Raman enhancement, especially by the creation of hot spots through NPs aggregation induced by connection between Au@Ag NPs and target molecules. The detection limits of triazophos and methyl-parathion in peach were 0.001 mg/kg. Good recovery (93.36 to 123.6 %) and high selectivity of the SERS activity allowed excellent precision for the detection of the triazophos and methyl-parathion in peach. Compared to earlier studies, the current approach was rapid, inexpensive and simple without lengthy sample pre-treatment. This study revealed that the proposed method could be employed for the analysis of trace contaminants such as triazophos and methyl-parathion in many food matrices.     

SERS Detection of Insecticide Amitraz Residue in Milk Based on Au@Ag Core-Shell Nanoparticles

A simple, rapid, and environmentally friendly surface-enhanced Raman scattering (SERS) method was developed for the determination of trace amitraz in milk with the use of silver-coated gold nanoparticles (Au@Ag NPs) as enhancing reagent. The normal Raman and SERS spectra of amitraz were analyzed, and the peaks were assigned by density functional theory. The morphology of Au@Ag NPs was characterized and confirmed by transmission electron microscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The SERS effects of Au@Ag NPs were investigated, including the types of solvents for dissolving amitraz, the volume ratio of the Au@Ag NPs and amitraz, and the concentration of aggregating agent (NaCl) for aggregate Au@Ag NPs. Results show that ethanol exerts the least interference on the SERS spectrum of amitraz and is more environmentally sound than methanol. The strongest SERS signal appeared when the volume ratio of Au@Ag NPs and amitraz was 2:1. Moreover, the strongest SERS signals appeared when the concentration of NaCl was 0.025 mol L^?1 because of appropriate aggregation. Under the optimum conditions, the concentration of amitraz presents a good linear relationship with Raman intensity (723 cm^?1) with a linear range of 9.77 × 10^?4~2.93 × 10^?2 g L^?1. The detected recoveries of amitraz in milk were between 81.7 and 100.5% with a relative standard deviation (RSD) of 2.61~5.51%.     

Rapid Analysis of Multiple Sudan Dyes in Chili Flakes Using Surface-Enhanced Raman Spectroscopy Coupled with Au–Ag Core-Shell Nanospheres

Sudan dyes are often illegally added as colorants into a variety of foodstuffs and have been tied to many food safety issues. In this study, surface-enhanced Raman spectroscopy (SERS) coupled with Au–Ag core-shell nanospheres (Au@Ag) was applied to analyze standard solutions of Sudan I–IV and Sudan dyes in chili flakes. With the use of 90 ± 5 nm Au@Ag (Au seed 20 ± 2 nm) as SERS substrate, the lowest detectible concentrations for Sudan I and II were 0.10 mg/L, for Sudan III was 0.08 mg/L, and for Sudan IV was 0.2 mg/L. The use of principal component analysis (PCA) could successfully classify different Sudan dyes based upon the SERS spectra of their standard solutions. For chili flakes, the use of acetonitrile as extraction solvent led to an overall higher sensitivity for analysis of Sudan dyes with SERS method compared to that of methanol, ethanol, and n-hexane. The lowest detectible concentrations for Sudan I–III in chili flakes were 1 mg/kg and for Sudan IV was 2 mg/kg, which were about ten times as much as that for their standard solutions due to the interference of non-target compounds from sample matrices. Partial least squares (PLS) models developed for quantitative analyses showed relatively high linear correlation between the actual and predicted amounts of Sudan dyes in chili flakes (R ² _cv = 0.869–0.959). The results showed great potential of applying Au@Ag as SERS substrate for qualitative and quantitative analysis of Sudan I–IV with simplified sample preparation method.     

QuEChERS-表面增强拉曼光谱法测定花生中黄曲霉毒素B1

目的 建立基于QuEChERS净化和表面增强拉曼光谱法(surface-enhanced Raman spectroscopy,SERS)测定花生中黄曲霉毒素B1(aflatoxin B1,AFB1)的分析方法.方法 以纳米银(nano silver,AgNPs)作为SERS活性基底,结合QuEChERS样品预处理技术...     

SLE结合GC-MS法测定葡萄酒中氨基甲酸乙酯

建立了固液萃取（SLE）结合气相色谱-质谱联用（GC-MS）法测定葡萄酒中氨基甲酸乙酯（EC）含量的检测方法。以硅藻土为吸附剂,二氯甲烷为萃取溶剂,对葡萄酒中氨基甲酸乙酯进行萃取。结果表明,二氯甲烷用量为70 mL,酒样中乙醇体积分数低于12%,萃取效果最佳。EC在200～1 600 μg/L范围内线性关系良好（R2=0.997 9）。加标回收率为91.30%～99.90%,相对标准偏差（RSD）为1.26%～1.98%,方法的精密度RSD值为1.61%～3.06%。表明该方法准确度高、重现性和精密度良好,适合用于葡萄酒样品中EC含量的检测。