Simultaneous determination of boscalid and fludioxonil in grape and soil under field conditions by gas chromatography/tandem triple quadrupole mass spectrometry

A gas chromatography–tandem mass spectrometry method was developed and validated to simultaneously determine boscalid and fludioxonil in grape and soil samples. These samples were extracted with 10 mL of acetonitrile and purified using a mixed primary secondary amine/octadecylsilane sorbent. The method showed good linearity (R² > 0.99) in the calibration range 0.005–2 μg/mL for both pesticides. The limits of detection and quantification for the two analytes in grape and soil were 0.006 and 0.02 mg/kg, respectively. Fungicide recoveries in grape and soil were 81.18–92.11% for boscalid and 82.73–97.67% for fludioxonil with relative standard deviations of 1.31–10.31%. The established method was successfully applied to the residual analysis of boscalid and fludioxonil in real grape and soil samples. The terminal residue concentrations of boscalid and fludioxonil in grape samples collected from Anhui and Guizhou were <5 mg/kg (the maximum residue limit set by China) 7 days after the last application and 1 mg/kg (the maximum residue limit set by USA) 14 days after the last application. These results could provide guidance for the proper and safe use of boscalid and fludioxonil in grape and help the Chinese government to establish an MRL for fludioxonil in grape.     

Double Orthogonal Click Reactions for the Development of Antimicrobial Peptide Nanotubes

A new class of amphipathic cyclic peptides, which assemble in bacteria membranes to form polymeric supramolecular nanotubes giving them antimicrobial properties, is described. The method is based on the use of two orthogonal clickable transformations to incorporate different hydrophobic or hydrophilic moieties in a simple, regioselective, and divergent manner. The resulting cationic amphipathic cyclic peptides described in this article exhibit strong antimicrobial properties with a broad therapeutic window. Our studies suggest that the active form is the nanotube resulted from the parallel stacking of the cyclic peptide precursors. Several techniques, CD, FTIR, fluorescence, and STEM, among others, confirm the nanotube formation.     

Approximant crystals of icosahedral Mg–(Ga,Al)–Zn alloys

The zero field cooled (ZFC) and field cooled (FC) low-field magnetic moment m of a dense frozen ferrofluid containing Fe₅₅Co₄₅ particles of size 4.6nm in hexane exhibits irreversibility at temperatures T?T _b≈ 30?K. FC in μ ₀ H ≤ 1?T gives rise to shifted minor hysteresis loops below T _b. At T _c≈ 10?K, sharp peaks of m ^ZFC and of the ac susceptibility χ ′, a kink of the thermoremanent magnetic moment m ^TRM, a sizeable reduction of the coercive field H _c, and the appearance of a spontaneous moment m ^SFM indicate a phase transition with near mean-field critical behaviour of both m ^SFM and χ ′ . These features are explained within a core-shell model of nanoparticles, whose strongly disordered shells gradually become blocked below T _b, while their soft ferromagnetic cores couple dipolarly and become superferromagnetic (SFM) below T _c.     

A CSP and tabulation-based adaptive chemistry model

We demonstrate the feasibility of a new strategy for the construction of an adaptive chemistry model that is based on an explicit integrator stabilized by an approximation of the Computational Singular Perturbation (CSP)-slow-manifold projector. We examine the effectiveness and accuracy of this technique first using a model problem with variable stiffness. We assess the effect of using an approximation of the CSP-slow-manifold by either reusing the CSP vectors calculated in previous steps or from a pre-built tabulation. We find that while accuracy is preserved, the associated CPU cost was reduced substantially by this method. We used two ignition simulations – hydrogen–air and heptane–air mixtures – to demonstrate the feasibility of using the new method to handle realistic kinetic mechanisms. We test the effect of utilizing an approximation of the CSP-slow-manifold and find that its use preserves the order of the explicit integrator, produces no degradation in accuracy, and results in a scheme that is competitive with traditional implicit integration. Further analysis on the performance data demonstrates that the tabulation of the CSP-slow-manifold provides an increasing level of efficiency as the size of the mechanism increases. From the software engineering perspective, all the machinery developed is Common Component Architecture compliant, giving the software a distinct advantage in the ease of maintainability and flexibility in its utilization. Extension of this algorithm is underway to implement an automated tabulation of the CSP-slow-manifold for a detailed chemical kinetic system either off-line, or on-line with a reactive flow simulation code.     

Solving stochastic convex feasibility problems in hilbert spaces

In a stochastic convex feasibility problem connected with a complete probability space (Ω,A,μ) and a family of closed convex sets (C_ω)_ωεΩ in a real Hilbert space H, one wants to find a point that belongs to C_ω for μ almost all ω ε Ω. We present a projection based method where the variable relaxation parameter is defined by a geometrical condition, leading to an iteration sequence that is always weakly convergent to a μ almost common point. We then give a general condition assuring norm convergence of this equation to that μ almost common point     

Convergence of mann iteration processes for nonexpansive operators in equi-connected metric spaces

The paper deals with various conditions implying the convergence of a Mann type iteration process constructed for a non-expansive operator in an equi-connected space (i. e. metric space equipped with a connecting function; so the iterates are taken along certain curves). Coefficients of the iterates do not have to be separated from 0 or 1. 1].     

Quadratic decomposition of symmetric semi-classical polynomial sequences of even class: an example from the case s = 2

In the present work, we deal with the quadratic decomposition of symmetric semi-classical polynomial sequences of even class. An example from class 2 is settled. We give an integral representation of the considered symmetric form.     

Difluorocarbene-Induced Ring-Opening Difluoromethylation-Halogenation of Cyclic (Thio)Ethers with TMSCF2X (X=Br,Cl)**

The ring-opening difluoromethylation-halogenation of cyclic (thio)ethers is reported through a simple strategy relying on carbon-chalcogen bond activation with difluorocarbene. The reaction proceeds through in situ protonation of the previously little-known difluoromethylene oxonium or sulfonium ylide intermediate followed by ring-opening with halide ion to afford halogenated acyclic difluoromethyl (thio)ethers that can then be employed for further elaboration. TMSCF₂X (X=Br, Cl) are unique reagents to achieve this synthetic purpose, which serve as both the difluorocarbene source and the halide ion source.     

Gaussian unitary ensembles with two jump discontinuities,PDEs, and the coupled Painlevé II and IV systems

We consider the Hankel determinant generated by the Gaussian weight with two jump discontinuities. Utilizing the results of Min and Chen [Math. Methods Appl Sci. 2019;42:301‐321] where a second‐order partial differential equation (PDE) was deduced for the log derivative of the Hankel determinant by using the ladder operators adapted to orthogonal polynomials, we derive the coupled Painlevé IV system which was established in Wu and Xu [arXiv: 2002.11240v2] by a study of the Riemann‐Hilbert problem for orthogonal polynomials. Under double scaling, we show that, as , the log derivative of the Hankel determinant in the scaled variables tends to the Hamiltonian of a coupled Painlevé II system and it satisfies a second‐order PDE. In addition, we obtain the asymptotics for the recurrence coefficients of orthogonal polynomials, which are connected with the solutions of the coupled Painlevé II system.