Carbene-Catalyzed [4+2] Cycloaddition of Cyclobutenones and Isatins for Quick Access to Chiral Chlorine-Containing Spirocyclic δ-Lactones.

Here we report a carbene-catalyzed enantio- and diastereoselective [4+2] cycloaddition reaction of cyclobutenones with isatins for the quick and efficient synthesis of spirocyclic δ-lactones bearing a chiral chlorine. A broad range of substrates with various substitution patterns proceed smoothly in this reaction, with the spirooxindole δ-lactone products afforded in generally good to excellent yields and optical purities under mild reaction conditions.

Dissipation, residues and risk assessment of spirotetramat and its four metabolites in citrus and soil under field conditions by LC-MS/MS.

A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for the simultaneous determination of spirotetramat and its four metabolite residues in citrus, peel, pulp and soil was developed and validated by liquid chromatography with tandem mass spectrometry (LC-MS/MS). The samples were extracted with acetonitrile (1%, glacial acetic acid, v/v) and purified using primary secondary amine and octadecylsilane. The limit of detection was 0.01-0.13 mg/kg, whereas that of quantification was 0.02-0.40 mg/kg for spirotetramat and its metabolites. The average recoveries of spirotetramat, spirotetramat-enol, spirotetramat-mono-hydroxy, spirotetramat-enol-glucoside and spirotetramat-ketohydroxy in all matrices were 73.33-107.91%, 75.93-114.85%, 76.44-100.78%, 71.46-103.19% and 73.08-105.27%, respectively, with relative standard deviations < 12.32%. The dissipation dynamics of spirotetramat in citrus and soil followed first-order kinetics, with half-lives of 2.3-8.5 days in the three sampling locations. The terminal residues of spirotetramat in four matrices at the three locations were measured below the 1.0 mg/kg maximum residue limit set by China, and residues were found to be concentrated on the peel. The risk assessment of citrus was evaluated using risk quotients. The risk quotient values were found to be significantly <1, suggesting that the risk to human health was negligible when using the recommended doses of spirotetramat in citrus. These results could provide guidance for the safe and proper application of spirotetramat in citrus in China.

Determination and analysis of the dissipation and residue of cyprodinil and fludioxonil in grape and soil using a modified QuEChERS method.

A simple and accurate method coupled with a gas chromatography-nitrogen phosphorus detector was developed to detect cyprodinil and fludioxonil in grape and soil. The accuracy and precision of the method in detecting the two fungicides were evaluated by conducting intra- and inter-day recovery experiments. The limits of detection were 0.017 mg/kg for cyprodinil and 0.030 mg/kg for fludioxonil. The limits of quantitation were 0.05 mg/kg for cyprodinil and 0.10 mg/kg for fludioxonil in grape and soil. The recoveries of the fungicides in grape and soil were investigated at three spiked levels and were found to range from 85.81 to 102.94% for cyprodinil and from 92.00 to 106.86% for fludioxonil, with relative standard deviations below 7%. Field experiments were conducted in two experimental locations in China. The half-lives of cyprodinil were 9.6-20.8 days in grape and 5.8-15.6 day in soil, and the half-lives of fludioxonil were 6.2-7.2 days in grape and 6.0-12.1 days in soil. When the cyprodinil and fludioxonil 62% water-dispersible granule formulation was sprayed at a low dosage three times, terminal residues of cyprodinil and fludioxonil were below 1.0 mg/kg in grape 14 days after harvest. This work may serve as a reference to establish the maximum residue limits for cyprodinil and fludioxonil in grape and promote the proper and safe use of these two fungicides.

Direct synthesis of ultralight, elastic, high-temperature insulation N-doped TiO2 ceramic nanofibrous sponges via conjugate electrospinning.

The design of three-dimensional ceramic nanofibrous materials with high-temperature insulation and flame-retardant characteristics is of significant interest due to the effectively improved mechanical properties. However, achieving a pure ceramic monolith with ultra-low density, high elasticity and toughness remains a great challenge. Herein, a low-cost, scalable strategy to fabricate ultralight and mechanically robust N-doped TiO2 ceramic nanofibrous sponges with a continuous stratified structure by conjugate electrospinning is reported. Remarkably, the introduction of dopamine into the precursor nanofibers is engineered, which realizes the nitrogen doping to inhibit the TiO2 grain growth, endowing single nanofibers with a smoother, less defective surface. Besides, the self-polymerization process of dopamine allows the construction of bonding points between nanofibers and optimizes the distribution of inorganic micelles on polymer templates. Moreover, a rotating disk receiving device under different rotating speeds is designed to obtain N-doped TiO2 sponges with various interlamellar spacings, further affecting the maximum compressive deformation capacity. The resulting ceramic sponges, consisting of fluffy crosslinked nanofiber layers, possess low densities of 12-45 mg cm-3, which can quickly recover under a large strain of 80% and have only 9.2% plastic deformation after 100 compression cycles. In addition, the sponge also exhibits a temperature-invariant superelasticity at 25-800 °C and a low heat conductivity of 0.0285 W m-1 K-1, with an outstanding thermal insulation property, making it an ideal insulation material for high-temperature or harsh conditions.

Recent progress in TiO2-based microwave absorption materials.

It is particularly important to develop high-performance microwave absorption (MA) materials to remediate the increasingly serious electromagnetic pollution. Recently, titanium dioxide-based (TiO2-based) composites have become a research hotspot owing to their light weight and synergy loss mechanism. In this study, significant research progress in TiO2-based complex-phase microwave absorption materials is reviewed, which involves carbon components, magnetic materials, polymers and so on. First, the research background and limitations of TiO2-based composites are discussed. The design principles for microwave absorption materials are elaborated in the next section. More importantly, TiO2-based complex-phase materials with multi-loss mechanisms are analyzed and summarized in this review. Finally, the conclusions and prospectives are presented, which provide a reference for the understanding of TiO2-based MA materials.

Determination of Dinotefuran and Its Metabolites in Orange Pulp, Orange Peel, and Whole Orange Using Liquid Chromatography-Tandem Mass Spectrometry.

Determination of the polar characteristics of dinotefuran and metabolite residues in orange matrixes (orange pulp, orange peel, and whole orange) is difficult. Thus, the purpose of the present study was to develop an extraction method for the determination of dinotefuran and its metabolites in oranges by using liquid chromatography with tandem mass spectrometry (LC-MS/MS). Matrix suppression effects were observed for all analytes in the orange matrixes. The proposed method displayed satisfactory linearity (R2 ≥ 0.9856) for the target molecules. The LODs were 0.03-0.10 mg/kg, whereas LOQs were 0.08-0.40 mg/kg for dinotefuran and its metabolites. Recoveries were 79.1-98.7% with RSD values <20% for all analytes in the orange matrixes. The proposed method was used to authenticate the samples and dinotefuran residues observed in field-incurred orange matrixes. The results of the proposed method could help the Chinese government establish maximum residue limits for dinotefuran in oranges and promote the safe and proper use of dinotefuran dosages in orange trees.

V-shaped ligand 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane and manganese(II), cobalt(II) and copper(II) complexes: Synthesis, crystal structure, DNA-binding properties and antioxidant activities.

A V-shaped ligand 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane (bebt) and its transition metal complexes, [Mn(bebt)(pic)2]·CH3OH (pic=picrate) 1, [Co(bebt)2](pic)22 and [Cu(bebt)2](pic)2·2DMF 3, have been synthesized and characterized. The coordinate forms of complexes 1 and 2 are basically alike, which can be described as six-coordinated distorted octahedron. The geometric structure around Cu(II) atom can be described as distorted tetrahedral in complex 3. The DNA-binding properties of the ligand bebt and complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that bebt and complexes bind to DNA via an intercalative binding mode and the order of the binding affinity is 1<2<3