Cyclization/hydrolysis of 1,5-enenitriles initiated by sulfonyl radicals in the aqueous phase in the presence of the I2/TBHP system.

A novel cyclization/hydrolysis of 1,5-enenitriles for the synthesis of valuable pyrrolidine-2,4-diones in the aqueous phase using I2 as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant is reported. In the presence of the I2/TBHP system, sulfonyl hydrazides produce sulfonyl radicals, which undergo radical addition, intramolecular cyclization, hydrogen abstraction, and hydrolysis to give the final products. The use of the inexpensive and environmentally friendly I2/TBHP catalytic oxidation system in the aqueous phase makes it a benign and sustainable strategy.

A microfluidic chip based ratiometric aptasensor for antibiotic detection in foods using stir bar assisted sorptive extraction and rolling circle amplification.

A ratiometric and sensitive microfluidic chip based aptasensor was developed for antibiotic detection with kanamycin (Kana) as a model analyte. A novel stir bar assisted sorptive extraction and rolling circle amplification strategy was designed to largely amplify the signal and overcome complex matrix interference in food samples. The detection mechanism was as follows: firstly, many duplex DNA probes (a single-stranded DNA as a primer hybrid with an aptamer sequence) were modified on a stir bar. In the presence of Kana, the probes on the bar could specifically capture Kana and release the primer to trigger RCA in the presence of a circular DNA template (CDT). As the reaction proceeds, the amount of CDT decreased and the number of RCA products increased. It is worth mentioning that they can be efficiently separated and detected using a microfluidic chip. The signal ratio of RCA products and CDT (IR/IC) can be employed to qualify Kana in a wide linear range from 0.8 pg mL-1 to 10 ng mL-1 with a low detection limit of 0.3 pg mL-1. This method exhibited excellent sensitivity and selectivity and can obviously reduce the matrix interference through a ratiometric strategy combined with stir bar extraction. The aptasensor was successfully tested in milk and fish samples, confirming that it can be applied for on-site quantitation of antibiotic residues in foods.

Enzyme-free fluorometric assay for chloramphenicol based on double stirring bar-assisted dual signal amplification.

An enzyme-free fluorometric assay is described that accomplishes dual signal amplification by making use of a two stirring bars. Two Y-shaped DNA probes were designed and placed on the bars. When the target (with chloramphenicol as model analyte) is added, it triggers target recycling and simultaneously catalyzes hairpin assembly (CHA). A large fraction of DNA primers is released by the analyte from the bar to the supernatant and open hairpins with G-quadruplex DNA sequence. The G-quadruplex can specifically bind thioflavin T (ThT) to emit fluorescence (with excitation/emission maxima at 445 and 485 nm) for quantification of chloramphenicol. An enzyme is not needed. ThT is added to the system as a fluorescent DNA probe. All this strongly reduces the cost for sensor construction and usage. The dual signal amplification steps occur simultaneously which reduces the detection time. The assay was successfully employed to the determination of CAP in spiked milk and fish samples within 60 min and with a 16 pM limit of detection (at S/N = 3). Graphical abstract Schematic representation of a new method for the detection of chloramphenicol by using  two stirring bars. It is based on target recycling and catalyzed hairpin assembly amplification. CAP: chloramphenicol, ThT: thioflavin T, CHA: catalyzed hairpin assembly.

A solid phase microextraction Arrow with zirconium metal-organic framework/molybdenum disulfide coating coupled with gas chromatography-mass spectrometer for the determination of polycyclic aromatic hydrocarbons in fish samples.

Solid phase microextraction (SPME) Arrows with enlarged sorption phases and Arrow-shaped tips are good alternatives to classic SPME fibers. Developing SPME Arrows with functionalized coatings has become a growing area of SPME research. In this study, a zirconium metal organic framework/molybdenum disulfide (UiO-66/MoS2) composite coating modified SPME Arrow was developed and coupled with gas chromatography-mass spectrometry for the headspace extraction and detection of 16 polycyclic aromatic hydrocarbons (PAHs). The coating preparation can be easily manipulated by the assembly strategy using silicone gels to adhere UiO-66/MoS2 powder onto the surface of the Arrows. The prepared UiO-66/MoS2 coated SPME Arrows exhibited clearly enhanced adsorption capacity (2.1-4.5 folds) and an improved degree of affinity to PAHs species when compared to commercial PDMS/CARS/DVB SPME Arrows or fibers. The improved mechanism may be due to the high specific area, hierarchical micropores and mesopores, and the largely increased and immobilized amount of UiO-66/MoS2 coating on the stainless-steel Arrow. Under optimized conditions, the SPME Arrow-based assay was successfully applied to determine PAH levels in fish samples with satisfactory recoveries of 80.2-101% and relative standard deviations (RSDs) of less than 6%. The detection limits of PAHs were between 0.11-1.40 ng kg-1. The coating showed satisfied reproducibility and repeatability (RSD <8.6%) with only 10 mL of 10% (v/v) acetone in water used as the extraction phase in an effort to be environmentally friendly. All of the results showed that the method is simple, sensitive, and robust. SPME Arrows with UiO-66/MoS2 coatings can provide new opportunities for the efficient extraction of persistent organic pollutants in food safety applications.

A multiple signal amplified colorimetric aptasensor for antibiotics measurement using DNAzyme labeled Fe-MIL-88-Pt as novel peroxidase mimic tags and CSDP target-triggered cycles.

An ultrasensitive colorimetric aptasensor was developed for antibiotics detection, with chloramphenicol (CAP) as model target, using DNAzyme labeled Fe-MIL-88-Pt as novel peroxidase mimic signal tags and target-triggered circular strand-displacement polymerization (CSDP) for signal amplification. The system consists of two components which can partially hybridize with each other: one is capture probe which was formed through immobilizing hairpin DNA containing aptamer sequence on magnetic beads (MB-cDNA), another is signal tag which was constructed through labeling single strand DNAzyme (G-quadruplex/Hemin) which can partially hybrid with cDNA on platinum nanoparticles functionalized Fe-MIL-88 (MIL-88-Pt-DNAzyme). All components of MIL-88, Pt and DNAzyme in the tag can act as peroxidase mimic to triply catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 into a blue-colored oxidized TMB (oxTMB) for the colorimetric readout. Thus distinctive signal can be observed by naked eye even in presence of 0.02 nM tags. In the presence of target and primer, cDNA loop can open to form cDNA/CAP intermediates, enabling primer to hybridize with the exposed sequences of the cDNA, which initiated target assisted CSDP recycles. Then numerous signal tags were released into supernatant to catalyze TMB for color development. There was a liner relationship between the absorbance and the concentration of CAP in the range of 0.1 pM (0.0323 pg/mL) to 1000 pM (323 pg/mL) with the detection limit of 0.03 pM (0.0097 pg/mL). The ultra-high sensitivity was ascribed to the multiplex catalytic activities from the tags and CSDP based signal amplification. Furthermore, this method can produce signals being observed by naked eye to facilitate in-situ detection and be further extended to detect other antibiotics in food just by simply replacing cDNA on the sensing system.

Enzyme- and label-free electrochemical aptasensor for kanamycin detection based on double stir bar-assisted toehold-mediated strand displacement reaction for dual-signal amplification.

It is critically important to detect antibiotic residues for monitoring food safety. In this study, an enzyme- and label-free electrochemical aptasensor for antibiotics, with kanamycin (Kana) as a typical analyte, was developed based on a double stir bar-assisted toehold-mediated strand displacement reaction (dSB-TMSDR) for dual-signal amplification. First, we modified two gold electrodes (E-1 and E-2) with different DNA probes (S1/S2 hybrid probe in E-1 and DNA fuel strand S3 in E-2). In the presence of Kana, an S1/S2 probe can be disassembled from E-1 to form an S2/Kana complex in supernatant. The S2/Kana could react with S3 on E-2 to form S2/S3 hybrid and release Kana through TMSDR. After then, the target recycling was triggered. Subsequently, the formed S2/S3 hybrid can also trigger a hybridization chain reaction (HCR). Consequently, the dual-signal amplification strategy was established, which resulted in many long dsDNA chains on E-2. The chains can associate with methylene blue (MB) as redox probes to produce a current response for the quantification of Kana. The assay exhibited high sensitivity and specificity with a detection limit at 16 fM Kana due to the dual-signal amplification. The double stir bars system can both increase phase separation and prevent leakage of DNA fuel to reduce background interference. Moreover, it allows flexible sequence design of the TMSDR probes. The assay was successfully employed to detect Kana residues in food and showed potential application value in food safety detection.

Electrochemical aptasensor for multi-antibiotics detection based on endonuclease and exonuclease assisted dual recycling amplification strategy.

An ultrasensitive electrochemical aptasensor for multiplex antibiotics detection based on endonuclease and exonuclease assisted dual recycling amplification strategy was proposed. Kanamycin and chloramphenicol were selected as candidates. Firstly, aptamers of the antibiotics were immobilized on bar A and then binding with their endonuclease labeled complementary DNA strands to construct enzyme-cleavage probes. Secondly, The nano zirconium-metal organic framework (NMOF) particles with 1,4-benzene-dicarboxylate (BDC) as linker was defined as UiO-66. And its updated version, hierarchically porous UiO-66 (HP-UIO-66) decorated with different electroactive materials as signal tags were synthesized. Then they were immobilized on bar B linked by two duplex DNA strands which can be specifically cleaved by corresponding enzyme-cleavage probes in bar A. Once targets were introduced into system, aptamers can capture them and then release enzyme-cleavage probes. In the presence of exonuclease-I, exonuclease assisted target recycling amplification was triggered and more enzyme-cleavage probes were released into solution. The probes can trigger endonuclease assisted recycles and repeatedly cleave their corresponding duplex DNA strands on bar B then released numerous signal tags into supernatant. Thus two recycling amplification was performed in the system. Finally, MB and Fc in the signal tags were detected by square wave voltammetry after removing bar A/B and the current intensities were correspondent with the concentration of KANA and CAP respectively. Under the optimum condition, the limits of detection for the KANA and CAP were 35fM and 21fM respectively with a wide linear range from 1 × 10-4 to 50nM. This dual recycling amplification detection system exhibited high sensitivities and specificity. It can be easily extended to detect other targets if changing the corresponding aptamers and has potential application values for screening of multiplex antibiotics residues in food safety.

A molybdenum disulfide/reduced graphene oxide fiber coating coupled with gas chromatography-mass spectrometry for the saponification-headspace solid-phase microextraction of polychlorinated biphenyls in food.

In this work, the molybdenum disulfide/reduced graphene oxide (MoS2/RGO) composite material was synthesized as a fiber coating to extract seven indicator polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) present in food via a saponification-headspace solid-phase microextraction assay (saponification-HS-SPME). The MoS2/RGO coating was prepared and deposited on a stainless steel wire with the help of a silicone sealant and used as an SPME fiber. The alkali solution dissolved the fat and helped in releasing the PCBs present in milk to the headspace for extraction under 100°C. Following desorption in the inlet, the targets were quantified by gas chromatography-mass spectrometry. The effects of sorbent dosage, extraction time, added salts, and stirring rate on the extraction efficiency were investigated. The new coating was able to adsorb a higher amount of analytes, which was about 1.1-2.9 times in comparison with the commercially available SPME fiber (coated with divinylbenzene/carboxen/polydimethylsiloxane). It also showed the highest adsorption capability toward PCBs, which was 1.5-2.7 times that of the prepared RGO modified fiber. Moreover, MoS2 also showed a strong affinity toward PCBs in a manner similar to its affinity for graphene. The developed method is simple and environmentally friendly as it does not require any organic solvents. Furthermore, it exhibits good sensitivity with detection limits less than 0.1ngmL-1, linearity (0.25-100ngmL-1), and reproducibility (relative standard deviation below 10% for n=3). The novel SPME fibers are inexpensive, reusable, and can be easily prepared and manipulated. In addition, the saponification-HS-SPME assay was also found to be suitable for screening persistent organic pollutants in dairy products.

Bis[4-(4-pyridyl)pyridinium] (4-carboxy-pyridine-2,6-dicarboxyl-ato-κO,N,O)(pyridine-2,4,6-tricarboxyl-ato-κO,N,O)ferrate(III) trihydrate.

In the title salt, (C(10)H(9)N(2))(2)[Fe(C(8)H(2)NO(6))(C(8)H(3)NO(6))]·3H(2)O, the Fe(III) atom is O,N,O'-chelated by dianionic and trianionic ligands in a slightly distorted octa-hedral coordination geometry. The cations and ferrate anions are linked into a layered structure; the layers are connected through the uncoordinated water mol-ecules into a hydrogen-bonded three-dimensional supra-molecular structure. One of the uncoordinated water molecules is disordered around an inversion centre and was refined with half-occupancy for each position.