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.     

Determination of 6-Benzylaminopurine and Hg<Superscript>2+</Superscript> in Bean Sprouts and Drinking Mineral Water by Surface-Enhanced Raman Spectroscopy

A novel method for the determination of 6-benzyladenine (6-BA) in bean sprouts and Hg²⁺ in drinking mineral water by surface-enhanced Raman spectroscopy (SERS) was described. 6-BA exhibits obvious SERS signal by using the substrate of silver nanoparticles (AgNPs), and the presence of Hg²⁺ could cause the decrease of SERS signal of 6-BA. The effects of type of aggregation agent, type and level of pH buffer solution, amount of AgNPs, mixing time, concentration of 6-BA, and reaction time on the SERS signals were investigated. Under the optimized experimental conditions, good linear responses were obtained for 6-BA and Hg²⁺ in the concentration ranges of 10–200 μg L^?1 and 5–200 μg L^?1, respectively. By the present method, the limits of detection (LODs) for the determination of 6-BA and Hg²⁺ are 3.3 and 0.20 μg L^?1, and the recoveries of 6-BA and Hg²⁺ in spiked samples are 85.5–113.0 % and 98.2–111.5 %, respectively.     

Detection of Omethoate Residues in Peach with Surface-Enhanced Raman Spectroscopy

In this work, surface-enhanced Raman spectroscopy (SERS) was used with silver colloid substrate for rapid detection of omethoate (an organophosphate pesticide) in standard solution and peach extract. The findings demonstrated that the characteristic wavenumber of the pesticide could be precisely identified using the SERS method. The calibration curve was plotted between concentrations and Raman intensities of the target peak at 1649 cm^?1 for the peach extract and at 1647 cm^?1 for the standard solution. The coefficients of determination (R²) of 0.9829 and 0.98 were obtained for standard solution and for peach extract, respectively. The calculated limits of detection for omethoate in standard solution and in peach extracts were 0.001 mg L^?1 and 0.01 mg kg^?1, respectively. This study revealed that the proposed method could be used for the analysis of trace contaminants like omethoate in multifaceted food matrices.     

Aflatoxin M1 in raw,UHT milk and dairy products in Sicily (Italy)

A survey on 73 milk samples from different animal breeds and 24 dairy products samples from Sicily, Italy, was carried out for the presence of aflatoxin M₁ (AFM1) by LC-fluorescence detection after immunoaffinity cleanup. AFM1 was detected in 48% and 42% of the milk and dairy samples at concentration ranges between <5.0–16.0 and <5.0–18.0 ng L^?1, respectively. Within the raw milk samples, 92% had an AFM1 content below 5.0 ng L^?1, in 7% of the cases it was in the range 5.0–10.0 ng L^?1 and 1% was contaminated between 10.0 and 20.0 ng L^?1. For the dairy products, ultra-high-temperature treated (UHT) milk, milk cream and cheese, the incidence was 42%, of which 83% contained less than 5.0 ng L^?1 and 17% contained 10.0–20.0 ng L^?1 AFM1. The levels of contamination found justify continuous monitoring for public health and to reduce consumer exposure.     

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.     

Stable Lead in Milk and Derivates

Lead is a heavy metal widely distributed in soil since it is constantly produced by the radioactive decay series of uranium (²³⁸U), actinium (²³⁵U), and thorium (²³²Th). The purpose of this research was to determine lead concentrations in fresh milk and derivates of the farms located in the municipalities of Pedra and Venturosa, in the state of Pernambuco, Brazil. The concentration of lead varied from 3 to 90 µg L^?1 in fresh milk, from 20 to 1,050 µg kg^?1 in curdled cheese, and from 6 to 20 µg L^?1 in milk serum. Seven samples of fresh milk and one of curdled cheese presented concentration limits higher than those established by the Brazilian Ministry of Health.     

Total arsenic in rice milk

Rice milk and its by-products were tested for total arsenic concentration. Total arsenic concentration was determined using graphite-furnace atomic absorption spectrometry. The arsenic concentrations ranged from 2.7 ± 0.3 to 17.9 ± 0.5 µg L^?1. Rice milk and its by-products are not clearly defined as food, water or milk substitute. The US Environmental Protection Agency (EPA), the European Union (EU) and the World Health Organization (WHO) have set a level of 10 µg L^?1 for total arsenic concentrations in drinking water. The EU and the US regulatory agencies do not provide any guidelines on total arsenic concentrations in foods. This study provides us with a starting point to address this issue in the State of Mississippi, USA.     

Hollow Fiber Liquid Phase Microextraction Method Combined with High-Performance Liquid Chromatography for Simultaneous Separation and Determination of Ultra-Trace Amounts of Naproxen and Nabumetone in Cow Milk,Water, and Biological Samples

A simple and highly sensitive method based on hollow fiber liquid phase microextraction combined with high-performance liquid chromatography and fluorescence detection has been developed for simultaneous separation, preconcentration, and determination of naproxen and nabumetone from water, wastewater, milk, and biological samples. Parameters affecting the microextraction efficiency were evaluated and optimized. Under optimum conditions (extractant (14 μL of 1-undecanol), sample pH (3.0), extraction time (20 min), stirring rate (600 rpm), temperature (45 °C), potassium chloride concentration (4.0 %) and sample volume (9 mL)), the limits of detection based on (S/N?=?3) were 1.3 ng L^?1 for naproxen and 2.9 ng L^?1 for nabumetone. The intra- and inter-assay relative standard deviations for naproxen and nabumetone were in the ranges of 3.2–6.1 % and 6.5–9.5 %, respectively. The calibration curves were linear in concentration ranges of 4.0–300.0 ng L^?1 and 9.0–300.0 ng L^?1 for naproxen and nabumetone, respectively, with good coefficient of determination (r ²?>?0.999). The method was successfully applied to the determination of naproxen and nabumetone in cow milk, water, wastewater, human plasma, and urine samples.     

Development of an ELISA and Immunochromatographic Assay for Tetracycline,Oxytetracycline, and Chlortetracycline Residues in Milk and Honey Based on the Class-Specific Monoclonal Antibody

A sensitive class-specific monoclonal antibody against tetracyclines (TCs) was generated and used to develop an enzyme-linked immunosorbent assay (ELISA) and an immunochromatographic assay for TC, oxytetracycline (OTC), and chlortetracycline (CTC) detection in milk and honey samples. The dynamic range of detection for TC in ELISA was 0.26–2.00 μg L^?1 with an IC₅₀ of 0.72 μg L^?1. The IC₅₀ value of OTC and CTC was 3.2 and 6.4 μg L^?1, respectively. The recovery of TC, OTC, and CTC in milk samples was 82–102, 91–105, and 90–101 %, respectively, and 88–101, 89–101, and 89–95 % in honey samples, respectively. In the immunochromatographic assay, the cutoff values for TC, OTC, and CTC were 15, 15, and 50 μg L^?1 in milk, respectively, and 40, 40, and 40 μg L^?1 in honey, respectively. The results revealed that ELISA and the immunochromatographic assay can be applied for the rapid and sensitive detection of TC, OTC, and CTC in milk and honey samples.     

Development and Optimization of a SERS Method for On-site Determination of Nitrite in Foods and Water

A rapid, sensitive, and selective detection method of nitrite in foods and water was established by surface-enhanced Raman spectroscopy (SERS) based on the diazo reaction of nitrite with p-nitroaniline and 1-naphthylamine in acidic solution. The azo dye (4-(4-nitrophenyldiazenyl)naphthalene-1-aminium, NNA), which was derived from the diazo reaction, was determined by SERS using citrate-coated silver nanoparticles (AgNPs) as SERS substrates. The concentrations of nitrite in samples were finally calculated from the intensities of SERS signals generated by NNA in the testing solutions. By using the present method combined with a portable miniature Raman spectrometer, on-site determination of nitrite could be performed easily and efficiently. The effects of several experimental parameters on the intensity of SERS signals, such as the volume of AgNP solution and the mixing time of AgNPs and NNA, were investigated. The linear range of the method was 0.1–10.0 mg L^?1. The limits of detection (LODs) were 0.01, 0.03, and 0.05 mg L^?1 at 720, 1,459, and 1,609 cm^?1, respectively. The method was applied to the determination of nitrite in real food and water samples, with recoveries in the range of 86.9–103.4 % and relative standard deviations (RSDs) less than 9.64 %.     

Use of Multivariate Optimization to Develop Methods for Direct Copper and Lead Determination in Breast Milk by Graphite Furnace Atomic Absorption Spectrometry

A direct method for lead and copper determination in breast milk by graphite furnace atomic absorption spectrometry, using aqueous calibration, was proposed in this study. Samples were diluted with hydroximethylaminomethane 80 %?v/v, pH 8. The dilution determination for Pb and Cu was 1:1 and 1:9, respectively. Fractional factorial (2^4?1) and central composite designs were used to optimize experimental conditions (pyrolysis and atomization temperatures, pyrolysis time, and modifier) using 10 μL samples introduced into a graphite furnace. The methods allowed for copper and lead determination under optimized conditions with an aqueous calibration curve between 0 and 180 μg L^?1 for Cu and 0 and 48 μg L^?1 for Pb. The detection limits were 0.92 μg L^?1 and 6.4 μg L^?1 for Pb and Cu, respectively. Intra and inter-assay studies revealed coefficients of variation of 5.0 and 6.3 %, and 6.4 and 5.5 % for Pb and Cu, respectively. Recovery studies at three concentration levels (three consecutive days, n?=?7/day) presented results between 107 and 109 % for Pb and 102 and 103 % for Cu. Good accuracy was obtained for both metals through recoveries studies using certified reference material (infant formula NIST® 1846). The method determined lead and copper in six samples and the concentrations ranged from 2.90 to 27.9 μg L^?1 for Pb and 384 to 1,212 μg L^?1 for Cu. While copper is an essential element, lead has no nutritional function and is cumulative at low concentrations. Therefore, safe, efficient, and validated methods should be available to determine its concentration in breast milk.     

Application of surface enhanced Raman spectroscopy for analyses of restricted sulfa drugs

The presence of sulfonamide residues in muscle foods is an important concern for consumers and regulatory agencies since these residues may pose potential health risks and result in an increase of drug-resistant bacteria. Surface enhanced Raman spectroscopy (SERS) was applied to analyze three sulfa drugs including sulfamerazine, sulfamethazine and sulfamethoxazole with concentrations ranging from 10 ng mL^?1 to 5 ??g mL^?1. Partial least squares regression (PLS) and principal component analysis (PCA) were used for the spectral data analyses. The three sulfa drugs could be detected at concentration levels as low as 10 ng mL^?1. For the quantitative analyses, the R ² values of actual sulfa drug concentrations versus their concentrations predicted by the PLS models ranged from 0.8149 to 0.9009. Plotting of principal components based upon PCA showed clear, separated clusters between different sulfonamides. This study indicated potential for detection and determination of trace amounts of prohibited or restricted drugs with SERS technology.     

Development of a Raman chemical imaging detection method for authenticating skim milk powder

This research developed a Raman chemical imaging method for detecting multiple adulterants in skim milk powder. Ammonium sulfate, dicyandiamide, melamine, and urea were mixed into the milk powder as chemical adulterants in the concentration range of 0.1–5.0 %. A Raman imaging system with a 785-nm laser was used to acquire hyperspectral images in the wavenumber range of 102–2,538 cm^?1 for a 25 × 25 mm² area of each mixture. A polynomial curve-fitting method was used to correct for the fluorescence background in the Raman images. An image classification method was developed based on single-band fluorescence-free images at unique Raman peaks of the adulterants. Raman chemical images were created to visualize identification and distribution of the multiple adulterant particles in the milk powder. A linear relationship was found between adulterant pixel number and adulterant concentration, demonstrating the potential of this Raman chemical imaging method for quantitative analysis of adulterants in the milk powder.     

Occurrence of pyrrolizidine alkaloids in animal- and plant-derived food: results of a survey across Europe

Pyrrolizidine alkaloids (PAs) are secondary metabolites of plant families such as Asteraceae or Boraginaceae and are suspected to be genotoxic carcinogens. Recent investigations revealed their frequent occurrence in honey and particularly in tea. To obtain a comprehensive overview of the PA content in animal- and plant-derived food from the European market, and to provide a basis for future risk analysis, a total of 1105 samples were collected in 2014 and 2015. These comprised milk and milk products, eggs, meat and meat products, (herbal) teas, and (herbal) food supplements collected in supermarkets, retail shops, and via the internet. PAs were detected in a large proportion of plant-derived foods: 91% of the (herbal) teas and 60% of the food supplements contained at least one individual PA. All types of (herbal) teas investigated were found to contain PAs, with a mean concentration of 460 µg kg^?1 dry tea (corresponding to 6.13 µg L^?1 in [herbal] tea infusion). The highest mean concentrations were found in rooibos tea (599 µg kg^?1 dry tea, 7.99 µg L^?1 tea infusion) and the lowest in camomile tea (274 µg kg^?1 dry tea, 3.65 µg L^?1 tea infusion). Occurrence of PAs in food supplements was found to be highly variable, but in comparable ranges as for (herbal) tea. The highest concentrations were present in supplements containing plant material from known PA-producing plants. In contrast, only 2% of the animal-derived products, in particular 6% of milk samples and 1% of egg samples, contained PAs. Determined levels in milk were relatively low, ranged between 0.05 and 0.17 µg L^?1 and only trace amounts of 0.10–0.12 µg kg^?1 were found in eggs. No PAs were detected in the other animal-derived products.     

表面增强拉曼光谱法快速测定保健酒中西地那非

目的 建立金核银壳结构纳米颗粒(Au@Ag NPs)的表面增强拉曼光谱法(surface-enhanced Raman scattering, SERS)快速检测保健酒中非法添加物西地那非的分析方法。方法 制备3种纳米粒子Ag、Au、Au@Ag NPs为SERS基底, 比较3种基底的增强效果。样品前处理基于溶剂萃取法, 利用二氯甲烷对保健酒中的西地那非进行简单提取, 通过调节体系pH值, 得到最佳提取率和SERS增强效果。结果 Au@Ag NPs的SERS增强效应优于Au NPs和Ag NPs; 用0.1 mol/L氢氧化钾调节溶液pH值可有效提高二氯甲烷的提取效果, 再用0.1 mol/L稀盐酸溶解挥发后残留物, 使得西地那非在pH调节后更有利于吸附在Au@Ag NPs表面, 获得更强的SERS信号。西地那非的检出限为0.5 mg/L, 在0.5~10 mg/L浓度范围内线性关系较好, 相关系数(r2)为0.9472, 回收率为86.0%~95.8%之间, 相对标准偏差(relative standard deviation, RSD)为3.6%~5.9%。 结论 SERS技术灵敏度高、特异性强, 可用于快速检测保健酒中的西地那非, 为快速筛查大量样品提供新方法。     

Dual-Label Chemiluminescence Strategy for Multiplexed Immunoassay of 20 Fluoroquinolones, 15 β-Lactams, 15 Sulfonamides,and CAP in Milk

In this paper, a novel dual-label time-resolved chemiluminescent multiplexed immunoassay (DLTRC-MIA) based on the distinction of the kinetic characteristics of horseradish peroxidase (HRP) and alkaline phosphatase (ALP) with approximate estimation approach for simultaneous determination of 20 fluoroquinolones (FQs), 15 β-lactams, 15 sulfonamides (SAs), and chloramphenicol (CAP) in milk was developed. The strategy integrated a single-chain variable fragment–alkaline phosphatase fusion protein (scFv-ALP), a recombinant penicillin-binding protein (PBP) 2×*, a monoclonal antibody (MAb), and a polyclonal antibody (PAb) in one immunoassay and in a single well together to fulfill the simultaneous detection of 51 low-molecular weight contaminants (20 FQs, 15 β-lactams, 15 SAs, and CAP). The limits of detection for FQs, β-lactams, SAs, and CAP range from 0.29 μg L^?1 for ciprofloxacin (CIP) to 81.6 μg L^?1 for trovafloxacin (TRO), 0.27 μg L^?1 for ceftiofur (CEF) to 44.1 μg L^?1 for cephalexin (CEL), 0.089 μg L^?1 for sulfadimethoxine (SDM) to 2.7 μg L^?1 for sulfadiazine (SDZ), and 0.028 μg L^?1 for CAP, respectively. The results demonstrated that the detection limits of DLTRC-MIA meet the requirement of detection levels for 51 drug residues in milk, suitable for high-throughput screening of low-molecular weight contaminants.     

Aflatoxin M1 in fresh milk collected from local markets of Karachi,Pakistan

During 2016–2017, 156 samples of fresh milk samples were collected from local markets of Karachi, Pakistan and analysed for aflatoxin M₁ (AFM₁) contamination using ELISA technique. AFM₁ was detected in 143 (91.7%) samples, ranged from 20 to 3090 ng L^?1 with a mean level of 346.2 ng L^?1. In 125 (80.1%) samples, the AFM₁ contamination was greater than the maximum limit (ML = 50 ng L^?1) set by EU. However, in 51 (32.7%) samples, the AFM₁ level was higher than the ML of 500 ng L^?1 as assigned by the USA. Statistical analysis showed that the AFM₁ level in milk samples from summer was significantly (p < 0.05) higher than that obtained in winter. It was concluded that the AFM₁ levels in the tested samples appear to be a serious public health problem. Therefore, immediate measures should be taken and re-evaluation done for the procedures for farming, transportation, refrigeration, and storage for the control of AFM₁ level in milk samples.     

Detection and differentiation of Salmonella serotypes using surface enhanced Raman scattering (SERS) technique

This research was conducted to prove that developed silver biopolymer nanoparticle substrate for surface enhanced Raman scattering (SERS) technique could detect and differentiate three different serotypes of Salmonella. Nanoparticle was prepared by adding 100 mg of silver nitrate to a 2 % polyvinyl alcohol solution, then adding 1 % trisodium citrate to reduce silver nitrate and produce silver encapsulated biopolymer nanoparticles. Then, nanoparticle was deposited on a stainless steel plate and used as SERS substrate. Fresh cultures of Salmonella typhimurium, Salmonella enteritidis and Salmonella infantis were washed and suspended in 10 mL of sterile deionized water. Approximately 5 μl of the bacterial suspensions were placed on the substrate individually and exposed to 785 nm laser excitation. SERS spectral data were recorded between 400 and 1,800 cm^?1. SERS signals were collected from 15 different spots on the substrate for each sample. PCA model was developed to classify Salmonella serotypes. PC1 identified 92 % of the variation between the Salmonella serotypes, and PC2 identified 6 % and in total 98 % between the serotypes. Soft independent modeling of class analogies of validation set gave an average correct classification of 92 %. Comparison of the SERS spectra of Salmonella serotypes indicated that both isolates have similar cell walls and cell membrane structures which were identified by spectral regions between 520 and 1,050 cm^?1. However, major differences were detected in cellular genetic material and proteins between 1,200 and 1,700 cm^?1. SERS with silver biopolymer nanoparticle substrate could be a promising tool in pathogen detection and it would potentially be used to classify them.     

Determination of Hormones Residues in Milk by Gas Chromatography-Mass Spectrometry

The article presents the use of gas chromatography-mass spectrometry (GC-MS) technique in a method for the determination of 18 anabolic hormones from synthetic stilbenes, steroids and resorcylic acid lactones (RALs) groups in raw milk and milk powder. Sample preparation consisted of liquid-liquid extraction with diethyl ether and purification by solid phase extraction (SPE). Prior to instrumental analysis, the reaction of derivatisation with the heptafluorobutyric anhydride or N-methyl-N-trimethylsilyltrifluoroacetamide was performed. Method validation was carried out according to the required performance criteria of the Commission Decision 2002/657/EC. The apparent recovery of all analytes at 1 μg L^?1 (kg^?1) level was ranged between 70.4 and 119.4 % with the coefficients of variation values less than 30 %. The decision limits (CCα) and the detection capabilities (CCβ) were in the range of from 0.11 to 0.44 μg L^?1 (kg^?1) and from 0.19 to 0.75 μg L^?1 (kg^?1), respectively. The procedure has been accredited and successfully applied as a screening method for the presence of hormone residues in the study of commercial samples of milk.     

SERS detection of urea and ammonium sulfate adulterants in milk with coffee ring effect

In the current work, surface-enhanced Raman scattering (SERS) based on gold nanoparticles (AuNPs) and silver-coated gold nanoparticles (Au@AgNPs) with coffee ring effect was employed to simultaneously ascertain urea and ammonium sulfate (AmS) in milk. A small drop (2 µL) of milk with adulterants was dried on a gold-coated slide to examine concentrations ranging from 5, 10, 20, 40 and 80 mg/dL based on spectra ranging from 400 to 1500 cm.^?1 A uniform distribution of analytes, with enhanced Raman signals was detected in a small region (maximum 1.9 mm) of coffee ring across the centre of coffee ring pattern. Nanoparticles with core (Au) diameter of 26 nm and shell thickness (Ag) of 6.5 nm were confirmed using transmission electron microscopy (TEM) images. A strong Raman peak at 980 cm^?1 was assigned to AmS, while that at 1001 cm^?1 was ascribed to urea. With AuNPs, coefficients of determination (R²) of 0.9873 and 0.9859 were achieved for urea and AmS, respectively, while for Au@AgNPs values of 0.9827 and 0.9855 were obtained for urea and AmS, respectively. This study revealed that SERS based on coffee ring effect has the potential to be further exploited for detecting other banned and hazardous adulterants in milk and milk products.