Use of Sorbent-Based Vacuum Extraction for Determination of Volatile Phenols in Beer

A novel method based on vacuum-assisted sorbent extraction (VASE) used with gas chromatography-mass spectrometry (GC-MS) for isolation of volatile phenols was described. The method is based on extraction of analytes into sorbent traps (sorbent pen) filled with Tenax in a vacuum system—vials with traps from which air was evaluated. The method was applied for extraction of volatile phenols from aqueous matrix and smoked beer was used as a food example. Methyl-, dimethyl-, and trimethylphenols, along with 4-ethylphenol, 4-methylguaiacol, 4-ethylguaiacol, 4-propylguaiacol, and eugenol, were used in method development. Optimal extraction parameters were elaborated. For the analysis of volatile phenols in beer matrix, the method was characterized with satisfactory linearity (r²?≥?0.99) in a range of 0.005–0.5 mg/L. Limits of detection (LODs) for analyzed compounds ranged from 0.0006 to 0.018 mg/L and repeatability for majority of compounds was <?5% for a single trap extraction. The detected volatile phenols in beer samples ranged from 0.003 to 0.672 mg/L.     

Development of Rapid and Label-Free Fluorescence Sensing of Tetracyclines in Milk Based on Poly(Adenine) DNA-Templated Au Nanoclusters

In this work, a rapid and label-free fluorescent sensing method has been established for tetracycline (TC) detection by using poly(adenine) (poly A) DNA-templated Au nanoclusters (AuNCs) as fluorescence indicator. The obtained AuNCs exhibited excellent fluorescence intensity and good stability. In the presence of tetracycline, the fluorescence intensity of AuNCs was obviously reduced due to the interactions between the tetracycline and the poly A DNA-templated AuNCs. Under the optimum conditions, the strategy permitted sensitive detection of tetracycline in a linear range from 0.1 to 60 μM and with a limit of detection of 20 nM. In addition, the sensor was successfully applied to determinate the tetracycline content in milk samples. More importantly, it could be easily performed within 10 min at room temperature. Thus, it could provide a rapid, convenient, label-free, and high-sensitive fluorescent platform for tetracycline detection.     

Rapid In Situ SERS Analysis of Pesticide Residues on Plant Surfaces Based on Micelle Extraction of Targets and Stabilization of Ag Nanoparticle Aggregates

A structure of polyurethane micelle/Ag nanoparticle (Ag NP) cluster was fabricated as surface-enhanced Raman scattering (SERS) substrate for in situ extracting organic compounds on the surface of different matrixes, in which polyurethane micelles acted as the host material to capture target molecules and stabilize nanoparticle cluster. This method provided stable aqueous suspensions of Ag NP cluster due to the amphiphilic properties of polyurethane. We demonstrated SERS-based in situ detection of pesticides on vegetables and fruit skin, by simply dropping polyurethane micelle/Ag NPs substrate on the sample surface where the target molecules could be detected without a previous elution and extracting. The obtained results showed that this polyurethane micelle/Ag NP cluster substrate had excellent SERS performance for pesticide molecules with ideal stability and reproducibility. With further optimization, the limit of detection of 0.03 μg/mL acetamiprid, 0.08 μg/mL phosmet, and 0.002 μg/mL thiabendazole was obtained, respectively.     

Evaluation of Phthalic Acid Esters in Fish Samples Using Gas Chromatography Tandem Mass Spectrometry with Simplified QuEChERS Technique

Phthalic acid esters (PAEs) have become an important food safety concern due to their lipophilic properties and propensity to accumulate in adipose tissue in edible fish. In this study, a simple, sensitive, and accurate analytical method was successfully established for simultaneous determination of 19 PAEs in fish samples using gas chromatography coupled with tandem mass spectrometry (GC–MS/MS). A simplified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedure was applied for sample preparation, and the Plackett-Burman factorial design was utilized for optimizing extraction parameters. The calibration curves were linear in the range 0.01–0.5 mg/kg for all of the analyzed PAEs, and the limits of quantification (LOQs) were 0.05–20 μg/kg which are much lower than those in previous reports. The average spiked recoveries ranged from 71.2 to 116.3%, with relative standard deviations (RSDs) of 3.9 to 16.2% (n?=?6). Finally, the method was applied to analyze 60 real fish samples taken from Shanghai Municipality, China, and the diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), and bis(2-ethoxyethyl)phthalate (DEHP) were found in almost all fish samples tested in this study. The present study demonstrated that the established method was suitable for market surveillance of 19 PAE residues in fish samples.     

Simultaneous Determination of TBH<Subscript>2</Subscript>Q and BHA Antioxidants in Food Samples Using Eosin Y Film Modified Electrode

A glassy carbon electrode (GCE) was modified with eosin Y that was electrodeposited on GCE via continuous cycling between ??1.6 and 1.5 V (vs Ag/AgCl). This electrode was characterized by scanning electron microscopy and electrochemical impedance spectra. The resulting electrode exhibited excellent electrocatalytic activity toward the oxidation of butylated hydroxyanisole (BHA) and tert-butyl hydroquinone (TBH₂Q); in addition, the oxidation products of BHA and TBH₂Q were found to be the same, which was studied by CV and in situ FT-IR spectroelectrochemistry. Under the optimized condition, the oxidation peak currents were linear to BHA/TBH₂Q in the range from 0.10 to 7.00 μg mL^?1 with the detection limits of 0.01 μg mL^?1 (S/N?=?3) for BHA and 0.015 μg mL^?1 (S/N?=?3) for TBH₂Q, respectively. Moreover, the reproducibility and repeatability of the electrode were determined. The proposed method was successfully applied in the simultaneous determination of BHA and TBH₂Q in several edible oil samples, and satisfactory results when compared with those obtained using high-performance liquid chromatography.     

Reproducible Molecularly Imprinted QCM Sensor for Accurate,Stable, and Sensitive Detection of Enrofloxacin Residue in Animal-Derived Foods

This study describes the development of a novel reproducible molecularly imprinted quartz crystal microbalance (QCM) sensor for the accurate and sensitive analysis of the residue of enrofloxacin (ENRO) in animal-derived foods. This proposed sensor was easily fabricated by directly immobilizing molecularly imprinted polymer (MIP) of ENRO on the surface of a QCM Au chip, which combined the advantages of selective recognition from the MIP with the high sensitivity and portability of a QCM sensor. The parameters in the fabrication and measurement process were optimized and discussed in detail. It was verified that the MIP-modified QCM Au chip performed favorably for the detection of ENRO residue in common animal-derived food products and demonstrated acceptable accuracy (recovery: pure milk 77.2–84.2%, egg 77.3–85.6%, chicken muscle 73.5–89.1%, pork 74.7–85.8%), precision (relative standard deviation (RSD, n = 3), pure milk 2.9–8.0%, egg 2.9–6.4%, chicken muscle 3.4–6.8%, pork 2.2–4.7%), and sensitivity (limit of detection, pure milk 0.31 μg L^?1, egg 0.44 μg kg^?1, chicken muscle 0.54 μg kg^?1, pork 0.57 μg kg^?1). The MIP-modified QCM Au chip for sensing ENRO was portable, could be stored for an extended period of time, and reused for more than 30 analysis cycles with a response attenuation of 7.8%. These results have demonstrated that the proposed MIP QCM sensor presents an accurate, sensitive, rapid, and low-cost methodology for ENRO residue detection in animal foods. This research is very promising for the development of novel effective devices applied to the detection of various contaminants in the field of food safety.     

Volatile Constituents of Jambolan (<Emphasis Type="Italic">Syzygium cumini</Emphasis> L.) Fruits at Three Maturation Stages and Optimization of HS-SPME GC-MS Method Using a Central Composite Design

The volatile compounds of jambolan (Syzygium cumini L.) fruit were determined at three different maturity stages (unripe, half-ripe, and ripe) by headspace solid-phase microextraction (HS-SPME)–gas chromatography-mass spectrometry (GC-MS) technique using five different fibers (Fused silica PDMS/DVB, DVB/CAR/PDMS, PEG, Stable flex PDMS/DVB, and PDMS). The optimal extraction conditions were evaluated using different variables such as adsorption temperature (minimum 25 °C, maximum 55 °C), salt quantity (minimum 0, maximum 30.0%), and extraction time (min 10, max 30 min). The major classes of compounds identified were ester, terpene, alcohol, aldehyde, and carboxylic acid. Ninety volatile compounds with characteristics aroma attributes were identified, and the primary compounds linked with development of characteristics aroma of ripe jambolan fruit pulp were trans-β-ocimene, β-ocimene, caryophyllene, humulene, D-α-pinene, L-β-pinene, β-pinene, D-limonene, α-terpineol, neo-allo-ocimene, 2-hexenal (E), δ-cadinene, 3-hexen-1-ol, (Z) β-linalool, terpinolene, eremophilene, valencene, 1-hexanol, longipinene, γ-terpinene, γ-muurolene, endo-borneol, o-cymene, nonanal, terpinen-4-ol, β-terpineol, α-muurolene, fenchol, α-fenchene, β-thujene, benzaldehyde, (E)-2-hexenal, β-cadinene, and decanal.     

A Novel Fluorescent Probe for Detecting Hydrogen Sulfide in Wine

Hydrogen sulfide (H₂S) has recently been recognized as the third endogenous gaseous signaling molecule besides NO and CO. At the same time, H₂S is responsible for an important proportion of faulty wines with potentially large economic losses. Thus, the H₂S in wine not only contributes negatively to wine aroma but also faces a problem of food safety. So an efficient and practical sensor to detect H₂S in wine was needed. A new fluorescent probe 4-methyl-2-oxo-2H-chromen-7-yl-thiophene-2-carboxylate (probe 1) was designed and synthesized for detection of H₂S. Addition of H₂S caused the fluorescence intensity of probe 1 increased and fluorescence saturation was reached in 15 min. The fluorescence of probe 1 was found turn-on under UV light at 365 nm. This noticeable change of probe 1 indicates that probe 1 could be employed as a visible detection agent for H₂S. H₂S can be detected quantitatively in the concentration range 0–20 μM, and the detection limit on fluorescence response of the probe was 18 nM. Moreover, probe 1 can be conveniently used as a signal tool to determine the H₂S levels in wine.     

Chemometric Analysis of <Superscript>1</Superscript>H NMR Fingerprints of <Emphasis Type="Italic">Coffea arabica</Emphasis> Green Bean Extracts Cultivated under Different Planting Densities

High planting density has been used to increase coffee production but there are few studies related to the variations it provokes in metabolite compositions. The use of ¹H NMR data associated with chemometric techniques allows the determination of metabolic fingerprints and verification of metabolic changes when coffee is subjected to high planting densities. The aim of this work is to investigate ¹H NMR spectral data of green bean extracts of Coffea arabica cv. IAPAR 59 grown in a square pattern at two planting densities, 6000 and 10,000 plants ha^?1. Thirty extracts were obtained using a simplex centroid design with four solvents (ethanol, acetone, dichloromethane, and hexane). The lyophilized extracts were dissolved in DMSO-d₆ to obtain the ¹H NMR spectra. The spectral data were analyzed with principal component (PCA) and cluster analyses (CA). Significant differences between ethanolic and non-ethanolic extracts were found by PCA. Only the ethanolic mean spectrum showed characteristic chemical shifts of sugars and trigonelline. Acetone extracts were separated by cluster analysis.