Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin based on SERS substrates composited of Au nanoparticles supported on twice-oxidized graphene oxide.

A surface-enhanced Raman spectroscopy (SERS) substrate consisting of Au nanoparticles supported on twice-oxidized graphene oxide (ro-GO) for the determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was prepared. The Raman shift at △v = 779, 993, and 1203 cm-1 was collected on the excitation condition of λ = 785 nm for the qualitative identification of 2,3,7,8-TCDD in milk. The peak at △v = 1203 cm-1 was selected as the characteristic peak for quantitation. The quantitation calculation was realized in the concentration range 10 to 100 ng mL-1 with a limit of detection of 3.24 ng mL-1 in milk samples. The average recoveries of 2,3,7,8-TCDD in milk were 60.6-68.6% with relative standard deviations less than 6.4%. The long-term stability of the substrates was approximately 180 days at 4 °C. Further, the SERS method for the determination of 2,3,7,8-TCDD in milk samples based on the optimized hybrid SERS substrate and corresponding pre-treatment procedure is proposed. Graphical abstract Schematic representation of surface-enhanced Raman spectroscopy (SERS) determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in milk samples by Au nanoparticles supported on twice-oxidized graphene oxide (ro-GO/AuNP) as a substrate.

[Simultaneous determination of 37 mycotoxins in grain and animal feed by impurity adsorption purification coupled with ultra-performance liquid chromatography-tandem mass spectrometry].

A rapid method based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 37 mycotoxins having various physicochemical properties in grain and animal feed samples. The 37 analytes were extracted from ground samples with acetonitrile-water-formic acid (84:15.9:0.1, v/v/v) by 20 min vibration, and purified using a commercial MLJ-1 pass-through solid-phase extraction (SPE) clean-up cartridge. The analytes were then separated on a reversed-phase BEH RP18 column by a gradient elution program with 0.1 mmol/L ammonium acetate (containing 0.1% (v/v) formic acid) aqueous solution and 0.1% (v/v) formic acid methanol solution as mobile phases. The separated analytes were detected by MS/MS in the multiple reaction monitoring (MRM) mode via ESI+/- ionization. The results showed that the purification was completed in 1 min and that the 37 analytes could be separated on the chromatographic column in 15 min. The 37 mycotoxins showed a linear relationship within their respective linear ranges, and the correlation coefficients of the matrix-matched calibration curves were greater than 0.98. The average recoveries at four spiked levels (limit of quantification (LOQ), LOQ×5, LOQ×10, LOQ×25) for all the targets except fumonisins ranged from 80% to 120%, with the relative standard deviations (RSDs) lower than 20% (n=6). The limits of quantification (LOQs) for all the analytes were between 2 and 40 µg/kg. The proposed method is simple, fast, and accurate, thus being suitable for detecting multiple mycotoxins in grain and animal feed samples.

Metal-Organic Frameworks for Food Safety.

Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

Rapid and sensitive detection of acrylamide in fried food using dispersive solid-phase extraction combined with surface-enhanced Raman spectroscopy.

A rapid, reliable, and quantitative method to determine acrylamide content in fried food based on surface-enhanced Raman spectroscopy (SERS) by re-oxidized graphene oxide/Au nanoparticle composites and dispersive solid-phase extraction has been proposed. The peak at △v = 1478 cm-1 was selected as the characteristic peak of acrylamide for quantitation. Sufficient linearity was obtained in the concentration range of 5-100 µg·kg-1 (R2 = 0.983). The limits of detection and quantification in fried food were 2 and 5 µg·kg-1, respectively. The recovery rates for acrylamide were 73.4-92.8% with coefficients of variation less than 4.2%, and the long-term stability of the substrates was approximately 180 days at 4 °C. The results of detection using the proposed method were consistent with those obtained by LC-MS/MS, while the measurement time was reduced to 9.5 min per sample. The study also demonstrates that this method can potentially be used for acrylamide detection in the field.

Phosphoproteome Analysis Reveals the Molecular Mechanisms Underlying Deoxynivalenol-Induced Intestinal Toxicity in IPEC-J2 Cells.

Deoxynivalenol (DON) is a widespread trichothecene mycotoxin that commonly contaminates cereal crops and has various toxic effects in animals and humans. DON primarily targets the gastrointestinal tract, the first barrier against ingested food contaminants. In this study, an isobaric tag for relative and absolute quantitation (iTRAQ)-based phosphoproteomic approach was employed to elucidate the molecular mechanisms underlying DON-mediated intestinal toxicity in porcine epithelial cells (IPEC-J2) exposed to 20 µM DON for 60 min. There were 4153 unique phosphopeptides, representing 389 phosphorylation sites, detected in 1821 phosphoproteins. We found that 289 phosphopeptides corresponding to 255 phosphoproteins were differentially phosphorylated in response to DON. Comprehensive Gene Ontology (GO) analysis combined with Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment revealed that, in addition to previously well-characterized mitogen-activated protein kinase (MAPK) signaling, DON exposure altered phosphatidylinositol 3-kinase/Akt (PI3K/Akt) and Janus kinase/signal transducer, and activator of transcription (JAK/STAT) pathways. These pathways are involved in a wide range of biological processes, including apoptosis, the intestinal barrier, intestinal inflammation, and the intestinal absorption of glucose. DON-induced changes are likely to contribute to the intestinal dysfunction. Overall, identification of relevant signaling pathways yielded new insights into the molecular mechanisms underlying DON-induced intestinal toxicity, and might help in the development of improved mechanism-based risk assessments in animals and humans.

Highly Sensitive Detection of Clenbuterol in Animal Urine Using Immunomagnetic Bead Treatment and Surface-Enhanced Raman Spectroscopy.

Combining surface-enhanced Raman spectroscopy (SERS) of aggregated graphene oxide/gold nanoparticle hybrids with immunomagnetic bead sample preparation method, a highly sensitive strategy to determine the clenbuterol content in animal urine was developed. Based on a linear calibration curve of the SERS characteristic peak intensity of clenbuterol at Δv = 1474 cm(-1) versus the spiked clenbuterol concentration in the range of 0.5-20 ng·mL(-1), the quantity of clenbuterol in real animal urine samples can be determined and matches well with those determined by LC-MS/MS, while the detection time is significantly reduced to 15 min/sample. The limits of detection and quantification in the urine are 0.5 ng·mL(-1) and 1 ng·mL(-1), respectively, and the recovery clenbuterol rates are 82.8-92.4% with coefficients of variation <9.4%. The day-to-day variation of the detection is less than 6.41%, and the shelving life of the SERS substrates is no less than 4 weeks. All these indicate that this proposed SERS detection protocol for clenbuterol is reproducible, reliable, and can be easily developed for the routine monitoring of the illicit use of clenbuterol in animal farming.

Highly Sensitive Detection of Melamine Using a One-Step Sample Treatment Combined with a Portable Ag Nanostructure Array SERS Sensor.

There is an urgent need for rapid and reliable methods able to detect melamine in animal feed. In this study, a quick, simple, and sensitive method for the determination of melamine content in animal feed was developed using surface-enhanced Raman spectroscopy on fabricated Ag nanorod (AgNR) array substrates with a one-step sample extraction procedure. The AgNR array substrates washed by HNO3 solvent (10-7 M) and methanol and showed the good stability within 6 months. The Raman shift at △ν = 682 cm-1 was used as the characteristic melamine peak in the calculations. Sufficient linearity was obtained in the 2-200 µg·g-1 range (R2 = 0.926). The limits of detection and quantification were 0.9 and 2 µg·g-1, respectively. The recovery rates were 89.7-93.3%, with coefficients of variation below 2.02%. The method showed good accuracy compared with the tradition GC-MS analysis. This new protocol only need 2 min to fininsh the detection which could be developed for rapid onsite screening of melamine contamination in quality control and market surveillance applications.

Development of a Efficient and Sensitive Dispersive Liquid-Liquid Microextraction Technique for Extraction and Preconcentration of 10 ß2-Agonists in Animal Urine.

Dispersive liquid-liquid microextraction (DLLME) coupled with ultra-performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) was developed for the extraction and determination of 10 ß2-agonists in animal urine. Some experimental parameters, such as the type and volume of the extraction solvent, the concentration of the dispersant, the salt concentration, the pH value of the sample solution, the extraction time and the speed of centrifugation, were investigated and optimized. Under the optimized conditions, a good enrichment factors (4.8 to 32.3) were obtained for the extraction. The enrichment factor show that the concentration rate of DLLME is significantly higher than other pretreatment methods, and the detection sensitivity has been greatly improved. The calibration curves were linear, the correlation coefficient ranged from 0.9928 to 0.9999 for the concentration range of 0.05 to 50 ng mL(-1) and 0.1 to 50 ng mL(-1), and the relative standard deviations (RSDs, n = 15, intra and inter-day precision) at a concentration of 5 ng mL(-1) were in the range of 1.8 to 14.6%. The limits of detection (LODs) for the 10 ß2-agonists, based on a signal-to-noise ratio (S/N) of 3, were in the range of 0.01 to 0.03 ng mL(-1). The proposed method was used to identify ß2-agonists in three types of animal urine (swine, cattle, sheep), and the relative recoveries from each matrix were in the range of 89.2 to 106.8%, 90.0 to 109.8% and 89.2 to 107.2%, respectively.

Detection of melamine in feed using liquid-liquid extraction treatment combined with surface-enhanced Raman scattering spectroscopy.

A rapid, selective, and sensitive method to determine the melamine content in animal feeds was developed using surface-enhanced Raman scattering spectroscopy on aggregated 55 nm Au nanoparticles with liquid-liquid extraction sample preparation. Butyl alcohol was used as the initial extraction solvent, and liquid-liquid extraction was performed twice using HCl (pH 3-4) and 6:1 (v/v) n-butyl alcohol/ethyl acetate. The intensity of the matrix-based peak at 731 cm⁻¹ was set at 100 as a basis for the feeds, and the peak at 707 cm-1 was the characteristic peak of melamine used in the calculations. Sufficient linearity was obtained in the range 2-10 µg·g⁻¹ (R²â€Š= 0.991). Limits of detection and quantification in the feeds were 0.5 and 2 µg·g⁻¹, respectively. The recovery rates were 82.5-90.2% with coefficients of variation below 4.02%. This new protocol could be easily developed for the routine monitoring of on-site feed quality and market surveillance.

Simultaneous identification and quantification of 20 ß-receptor agonists in feed using gas chromatography-tandem mass spectrometry.

"Lean meat powder" is a class of toxic chemicals that have structures similar to that of ß-adrenergic receptor agonists. At least 16 chemicals from this class have been specifically banned by the 176(th) bulletin of the Chinese Department of Agriculture on breeding animals, and methods for monitoring the illicit use of ß-agonists in animal feed are required. Herein, a method to quantify 20 ß-agonists in feed, via analyte derivatization followed by gas chromatography-tandem mass spectrometry, has been developed. The optimized method has a good linear correlation (calibration coefficient > 0.99) between the quantitative ion peak area and the concentration of ß-agonists over a large working range (0.05-1 mg/kg). The limit of detection (LOD) was 0.01 mg/kg, the recoveries for three ß-agonists spikes (0.05, 0.1, and 1 µg/g) in feed ranged from 75.6 to 102.4%, repeatability ranged from 1.2 to 9.4% for all of the compounds, and intermediate precisions were lower than 13.8%. This precise, accurate method was applied to quantify 20 ß-agonists in actual feed samples and represents an excellent complement to existing quantification methods.

[Rapid determination of melamine in pet food by surface enhanced Raman spectroscopy in combination with Ag nanoparticles].

The rapid qualitative and quantitative analysis of melamine in pet food was realized by surface-enhanced Raman spectroscopy in combination with Ag nanoparticle. In the present study, the 709 and 1 542 cm(-1) Raman shift was chosen as qualitative basis. The quantitative calculation of the concentration range between 1.0 and 10.0 mg x kg(-1) was achieved based on the intensity of 1 149 cm(-1) Raman peak which was used as a normalization standard. The limit of detection was 0.5 mg x kg(-1). The Ag nanoparticle had a strong Raman enhancement effect on melamine and the intensity was affected by the adding time of Ag nanoparticle and the vortex strength. At the same time, the intensity of SERS was affected by the extraction solvent type, and the manner of extraction. The analysis time of each sample was about 5 min. It was so quick that it was easy to realize the rapid detection of melamine in pet food compared with existing methods.

Variable levels of 37-kDa/67-kDa laminin receptor (RPSA) mRNA in ovine tissues: potential contribution to the regulatory processes of PrPSc propagation?

The 37-kDa laminin receptor precursor/67-kDa laminin receptor (LRP/LR, also known as ribosomal protein SA, RPSA) has been reported to be involved in cancer development and prion internalization. Previous studies have shown that the LRP/LR is expressed in a wide variety of tissues. In particular, expression of LRP/LR mRNA may be closely related to the degree of PrP(Sc) propagation. This study presents a detailed investigation of the LRP/LR mRNA expression levels in eleven normal ovine tissues. Using real-time quantitative PCR, the highest LRP/LR expression was found in neocortex (p < 0.05). Slightly lower levels were found in the heart and obex. Intermediate levels were seen in hippocampus, cerebellum, spleen, thalamus, mesenteric lymph node, and the lowest levels were present in liver, kidney, and lung. In general, the LRP/LR mRNA levels were much higher in neuronal tissues than in peripheral tissues. The observation that differences in LRP/LR mRNA expression levels are consistent with the corresponding variation in PrP(Sc) accumulation suggests that the 37-kDa/67-kDa laminin receptor may be involved in the regulation of PrP(Sc) propagation.

Microvalve-actuated precise control of individual droplets in microfluidic devices.

Integrated microvalves have been used to precisely and flexibly control the generation, size, composition of individual droplets and fusion of different droplets in microfluidic devices.

[Study on the method of using ICP-MS to determine microelements in the animal feed].

The method for the determination of microelements such as Cu, Zn, Fe, Mn, Cr, Cd, Pb, As and Se in the animal feed by inductively coupled plasma-mass spectrometry was developed. The operation parameters, spectrum interference, matrix effect and memorial effect were studied in detail. Under optimal condition, the detection limits of these nine elements were from 2.03 x 10(-3) to 3.17 microg x L(-1), and the linear range was over three orders with a correlation coefficient above 0.999. This method was applied directly to determine microelements in real samples involving the standard wheat powder, formular feed and pre-mix feed. The determination results of microelements in the standard wheat powder accorded with reference results. The recovery of microelements in the formular feed was from 86% to 115%, and the relative standard deviations < or = 8.2% (n = 6). The results of elements content in the pre-mix feed were identical with those determined by national standard method. This method is simple, sensitive, accurate and can perform simultaneous multi-elements determination compared with conventional method of animal feed determination. The results were satisfactory.

[Study on determination of rare earth La and Ce in feed by using ICP-MS].

An advanced method for the determination of rare earth La and Ce in animal feed by using of inductively coupled plasma mass spectrometry was studied. The operation parameters for ICP-MS was optimized, the effect of pre-mix feed matrix and formular feed matrix for La and Ce was studied by the conventional method and stepwise dilution method, and the suppression of signal intensity of La and Ce by nitric acid was examined. Under the optimum condition, the limit of determination for La and Ce were 2.62 x 10(-2) microg x kg(-1) and 6.47 x 10(-3) microg x kg(-1), respectively, the linear coefficient was 1.000 0, the dynamical linear range was of 3 order of magnitudes, and the internal standards were In(115) and Tb(159). The developed method was applied to the determination of rare earth La and Ce in pre-mix feed and formular feed, with the recovery > or = 77.8% and the relative standard deviation(RSD) < or = 8.5%, and the testing results were satisfactory.