Improving the flame retardancy of polyamide 6 by incorporating hexachlorocyclotriphosphazene modified MWNT

A nitrogen‐, phosphorus‐ and chlorine‐containing flame retardant, hexachlorocyclotriphosphazene (HCTP), has been covalently grafted onto the surface of multi‐wall carbon nanotubes (MWNT) to obtain MWNT‐HCTP. Polyamide 6 (PA6)/MWNT composites were then prepared via melt compounding. The flammability of PA6/MWNT composite was characterized by cone calorimetry, limiting oxygen index (LOI) and UL‐94 tests. The results showed that peak heat release rate of samples containing 3 wt% MWNT‐HCTP was only 460 kW/m², which decreased by 35.2% compared with that of a neat PA6 sample. The LOI value was increased from 22.7% to 26.5%, and UL‐94 test performance was also significantly improved by the presence of MWNT‐HCTP. Scanning electron microscope (SEM) and optical microscope analysis showed that modified MWNT had a better dispersion and compatibility in PA6 than unmodified MWNT. The composition of residue chars and volatile products was investigated by SEM/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric‐FTIR, respectively. It was proposed that grafted HCTP was mainly functioned in the condensed phase, where P, N can synergistically promote char formation and Cl element can catch free radicals to terminate the chain reaction during combustion of the PA6 composite. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterisation of Taxlllaids A–G; Natural Products from Xenorhabdus indica

Six new lipodepsipeptides and an additional linear derivative named taxlllaids A–G ( 1 – 7 ) have been identified in the entomopathogenic bacterium Xenorhabdus indica. The structures of the main compounds have been solved by detailed NMR spectroscopic analysis and the structures of minor derivatives were elucidated by a combination of labelling experiments and detailed MS experiments. The absolute configuration of the taxlllaids was deduced by using the advanced Marfey method and analysis of the biosynthesis gene cluster showing the presence of epimerisation domains, which was subsequently proved to be correct by solid‐phase peptide synthesis of all taxlllaids. The exchange of a single amino acid in the adenylation domain was shown to be responsible for substrate promiscuity of the third A domain, resulting in the incorporation of leucine, phenylalanine or tyrosine. Bioactivity testing revealed the taxlllaids to be weakly active against Plasmodium falciparum and against a number of eukaryotic cell lines.     

Investigation of monoterpenes complexation with hydroxypropyl-β-cyclodextrin

In this study, we investigated the inclusion complexation of 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) and eight monoterpenes (eucalyptol, geraniol, limonene, linalool, α-pinene, β-pinene, pulegone, and thymol) in aqueous solution and solid state. The formation constants (K _f) of inclusion complexes were determined using fluorescence spectroscopy and static headspace gas chromatography. The results indicated the formation of 1:1 inclusion complexes between HP-β-CD and all studied guests. A linear relationship was found between K _f values and the hydrophobic character of the monoterpenes expressed as logP. Solid complexes were prepared by the freeze-drying method in a 1:1 (HP-β-CD:monoterpene) molar ratio. Physicochemical characterization of solid inclusion complexes was carried out using Fourier transform infrared spectroscopy and differential scanning calorimetry. Finally, the encapsulation efficiency (EE%) of HP-β-CD was determined using HPLC analysis. Noticeable difference in the EE% was observed between monoterpene hydrocarbons and oxygenated monoterpenes. These results suggested that complexation with HP-β-CD could be a promising strategy to enlarge the application of monoterpenes in cosmetic, pharmaceutical and food industries.     

Tuning the Reactivity of a Heterogeneous Catalyst using N-Heterocyclic Carbene Ligands for C−H Activation Reactions

We report the dramatic impact of the addition of N-heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C−H activation reactions. Using a simple and robust method, we prepared a series of new air-stable catalysts starting from commercially available Ru on carbon (Ru/C) and differently substituted NHCs. Associated with C−H deuteration processes, depending on Ru/C-NHC ratios, the chemical outcome can be controlled to a large extent. Indeed, tuning the reactivity of the Ru catalyst with NHC enabled: 1) increased chemoselectivity and the regioselectivity for the deuteration of alcohols in organic media; 2) the synthesis of fragile pharmaceutically relevant deuterated heterocycles (azine, purine) that are otherwise completely reduced using unmodified commercial catalysts; 3) the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely the selective C-1 deuteration of aldehydes.     

UV-Induced 1,3,4-Oxadiazole Formation from 5-Substituted Tetrazoles and Carboxylic Acids in Flow

A range of 1,3,4-oxadiazoles have been synthesized using a UV-B activated flow approach starting from carboxylic acids and 5-substituted tetrazoles. The application of UV light represents an attractive alternative to the traditional thermolytic approach and has demonstrated comparable efficiency and versatility, with a diverse substrate scope, including the incorporation of highly substituted amino acids.     

Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N-Heterocycles and Reaction Mechanism Insights

Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D₂ or T₂ gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC-MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T₂ gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT-based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters.     

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Sensitivity‐Enhanced 13C‐NMR Spectroscopy for Monitoring Multisite Phosphorylation at Physiological Temperature and pH

Abundant phosphorylation events control the activity of nuclear proteins involved in gene regulation and DNA repair. These occur mostly on disordered regions of proteins, which often contain multiple phosphosites. Comprehensive and quantitative monitoring of phosphorylation reactions is theoretically achievable at a residue‐specific level using ¹H‐¹⁵N NMR spectroscopy, but is often limited by low signal‐to‐noise at pH>7 and T>293 K. We have developed an improved ¹³Cα‐¹³CO correlation NMR experiment that works equally at any pH or temperature, that is, also under conditions at which kinases are active. This allows us to obtain atomic‐resolution information in physiological conditions down to 25 μm . We demonstrate the potential of this approach by monitoring phosphorylation reactions, in the presence of purified kinases or in cell extracts, on a range of previously problematic targets, namely Mdm2, BRCA2, and Oct4.     

Recent developments in heterocyclic systems with a Si–M′–Ge or Ge–M′–Ge linkage (M′ = Fe,Ru, or Co)

The present review describes recent work on the synthesis, spectroscopic analysis, and investigation of the chemical behaviors of new polynuclear heterocyclic complexes 1–7 having M–M′–M catenation. Various CO substitution, cleavage, expansion, and adducts decomposition reactions are described.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.