Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Generalized Darboux transformation and parameter-dependent rogue wave solutions to a nonlinear Schrödinger system

Objectives of the paper are (1) to design two new real and complex no equilibrium point hyperchaotic systems, (2) to design synchronisation technique for the new systems using the contraction theory and (3) to validate the results by using circuit realisation. First a new no equilibrium point hyperchaotic system is developed using a 3-D generalised Lorenz system; then using the new system a new complex no equilibrium point hyperchaotic system is reported. Both the new systems have hidden chaotic attractors. Various dynamical behaviours are observed in the new systems like chaotic, periodic, quasi-periodic and hyperchaotic. Both the systems have inverse crisis route to chaos with the variation of parameter a and crisis route to chaos with the variation of parameters \(b,\ c\) and d. These phenomena along with hidden attractors in a complex hyperchaotic system are not seen in the literature. Synchronisation between the identical new hyperchaotic systems is achieved using the contraction theory. Further the synchronisation between the identical new complex hyperchaotic systems is achieved using adaptive contraction theory. The proposed synchronisation strategies are validated using the MATLAB simulation and circuit implementation results. Further, an application of the proposed system is shown by transmitting and receiving an audio signal.     

Potent Anticancer Efficacy of First-In-Class CuII and AuIII Metaled Phosphorus Dendrons with Distinct Cell Death Pathways

First-in-class Cu^II and Au^III metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of Cu^II with Au^III considerably increases the antiproliferative activity of metaled phosphorus dendrons. Very interestingly, we found that the cell death pathway is related to the nature of the metal complexed by the plain dendrons. Cu^II metaled dendrons showed a potent caspase-independent cell death pathway, whereas Au^III metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with Au^III increased the cellular lethality versus dendrons with Cu^II and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C).     

A new approach on improving the fire resistance of polyamide 11 by incorporating sulfur‐based flame retardant

In this work, a novel sulfur‐based flame retardant (SA‐M) was synthesized by the self‐assembly of melamine and sulfamic acid. The chemical structure of SA‐M was fully characterized. SA‐M, in company with Al₂O₃, was then introduced into polyamide 11 (PA 11) by melt compounding in order to improve the fire resistance of the polymer substrate. The observation by scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) indicated the well dispersion of SA‐M in PA 11 matrix. The fire performance of PA 11 composites was evaluated by limiting oxygen index (LOI), vertical burning (UL‐94), and cone calorimeter tests, respectively. The results showed that the presence of 17.5% SA‐M and 2.5% Al₂O₃ increased the LOI value from 22.4% to 30.9%, upgraded the UL‐94 rating from no rating to V‐0, significantly eliminated the melt dripping, and decreased the peak heat release rate from 1024 to 603 kW/m². The thermal behaviors were investigated by thermogravimeric analysis (TGA) and TGA‐Fourier transform infrared spectroscopy (FTIR). It was suggested that SA‐M took effects mainly in gas phase by diluting the combustible fuel, leading to the improvement of the fire resistance of PA 11.     

Biomimetic versus enzymatic high-potential electrocatalytic reduction of hydrogen peroxide on a functionalized carbon nanotube electrode

We report the non-covalent functionalization of a multi-walled carbon nanotube (MWCNT) electrode with a biomimetic model of the horseradish peroxidase (HRP) active site. By modifying the MWCNT electrode surface with imidazole-modified polypyrrole, a new biomimetic complex of HRP was synthesized on the MWCNT sidewalls via the coordination of imidazole (Im) to the metal centre of iron protoporphyrin IX, affording (Im)(PP)Fe^III. Compared to the pi-stacking of non-coordinated (PP)Fe^III on a MWCNT electrode, the (Im)(PP)Fe^III-modified MWCNT electrode exhibits higher electrocatalytic activity with an I _max = 0.52 mA cm^–2 for the reduction of H₂O₂, accompanied by a high onset potential of 0.43 V vs. Ag/AgCl. The performances of these novel surface-confined HRP mimics were compared to those of a MWCNT electrode modified by HRP. Although the enzyme electrode displays a higher electrocatalytic activity towards H₂O₂ reduction, the (Im)(PP)Fe^III-modified MWCNT electrode exhibits a markedly higher operational stability, retaining 63% of its initial activity after one month.     

Congruence preserving functions on free monoids

A function on an algebra is congruence preserving if for any congruence, it maps congruent elements to congruent elements. We show that on a free monoid generated by at least three letters, a function from the free monoid into itself is congruence preserving if and only if it is of the form \({x \mapsto w_{0}xw_{1} \cdots w_{n-1}xw_n }\) for some finite sequence of words \({w_0,\ldots ,w_n}\). We generalize this result to functions of arbitrary arity. This shows that a free monoid with at least three generators is a (noncommutative) affine complete algebra. As far as we know, it is the first (nontrivial) case of a noncommutative affine complete algebra.     

Singular Solutions to Conformal Hessian Equations

The authors show that for any e ∈]0,1[,there exists an analytic outside zero solution to a uniformly elliptic conformal Hessian equation in a ball B C R5 which belongs to C1'ε(B) \ C1'ε+(B).     

Evaluation of ion mobility in capillary electrophoresis coupled to mass spectrometry for the identification in metabolomics

Currently, feature annotation remains one of the main challenges in untargeted metabolomics. In this context, the information provided by high-resolution mass spectrometry (HRMS) in addition to accurate mass can improve the quality of metabolite annotation, and MS/MS fragmentation patterns are widely used. Accurate mass and a separation index, such as retention time or effective mobility (μ_eff), in chromatographic and electrophoretic approaches, respectively, must be used for unequivocal metabolite identification. The possibility of measuring collision cross-section (CCS) values by using ion mobility (IM) is becoming increasingly popular in metabolomic studies thanks to the new generation of IM mass spectrometers. Based on their similar separation mechanisms involving electric field and the size of the compounds, the complementarity of ^DTCCS_N2 and μ_eff needs to be evaluated. In this study, a comparison of ^DTCCS_N2 and μ_eff was achieved in the context of feature identification ability in untargeted metabolomics by capillary zone electrophoresis (CZE) coupled with HRMS. This study confirms the high correlation of ^DTCCS_N2 with the mass of the studied metabolites as well as the orthogonality between accurate mass and μ_eff, making this combination particularly interesting for the identification of several endogenous metabolites. The use of IM-MS remains of great interest for facilitating the annotation of neutral metabolites present in the electroosmotic flow (EOF) that are poorly or not separated by CZE.     

An electrochemical DNA-sensor developed with the use of methylene blue as a redox indicator for the detection of DNA damage induced by endocrine-disrupting compounds

An electrochemical biosensor capable of indirect detection of DNA damage induced by any one of the three endocrine-disrupting compounds (EDCs) – bisphenol A (BPA), 4-nonylphenol (NP) and 4-t-octylphenol (OP), has been researched and developed. The methylene blue (MB) dye was used as the redox indicator. The glassy carbon electrode (GCE) was modified by the assembled dsDNA/graphene oxide-chitosan/gold nano-particles to produce a dsDNA/GO-CS/AuNPs/GCE sensor. It was characterized with the use of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and scanning electron microscopy (SEM) techniques. The loading/release of the MB dye by the dsDNA/GO-CS/AuNPs film was investigated, and the results showed that the process was reversible. Based on this, the sensor was used to measure the difference between the loading capabilities of intact and damaged dsDNA in the films. The sensor was then successfully applied to detect DNA damage electrochemically. The differential pulse voltammetry (DPV) peak current ratio for MB, observed before and after DNA damage, increased linearly in the presence the BPA, NP or OP compounds; the treatment range was 10–60 min, and the respective damage rates were 0.0069, 0.0044 and 0.0031 min⁻¹, respectively. These results were confirmed by the binding constants: 2.09 × 10⁶ M⁻¹ (BPA-DNA), 1.28 × 10⁶ M⁻¹ (NP-DNA) and 9.33 × 10⁵ M⁻¹ (OP-DNA), all of which were obtained with the use of differential pulse stripping voltammetry (DPSV).