New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ.     

A rapid way to synthesize Brønsted acidic ionic liquid and its application as an efficient catalyst for esterification

A novel and time-saving method to prepare a Brønsted acidic ionic liquid, 1-carboxymethyl-3-methylimidazolium hydrogen sulfate ([CMI][HSO₄]), in high yield and purity was performed under microwave irradiation. The ionic liquid showed an incomparable catalytic efficiency in the microwave-accelerated esterification of arenecarboxylic acids. Moreover, its ability of being recovered and reused many times without loss of activity has made [CMI][HSO₄] more favorable from the viewpoint of green chemistry.     

Stages of melting of graphene model in two-dimensional space

Spontaneous melting of a perfect crystalline graphene model in 2D space is studied via molecular dynamics simulation. Model containing 10⁴ atoms interacted via long-range bond-order potential (LCBOP) is heated up from 50 to 8,450 K in order to see evolution of various thermodynamic quantities, structural characteristics and occurrence of various structural defects. We find that spontaneous melting of our graphene model in 2D space exhibits a first-order behaviour of the transition from solid 2D graphene sheet into a ring-like structure 2D liquid. Occurrence and clustering of Stone–Wales defects are the first step of melting process followed by breaking of C–C bonds, occurrence/growth of various types of vacancies and multi-membered rings. Unlike that found for melting of a 2D crystal with an isotropic bonding, these defects do not occur homogeneously throughout the system, they have a tendency to aggregate into a region and liquid phase initiates/grows from this region via tearing-like or crack-propagation-like mechanism. Spontaneous melting point of our graphene model occurs at T_m = 7,750 K. The validity of classical nucleation theory and Berezinsky–Kosterlitz–Thouless–Nelson–Halperin–Young (BKTNHY) one for the spontaneous melting of our graphene model in strictly 2D space is discussed.     

Secondary Metabolites from the Fruiting Bodies of Coriolopsis aspera in Vietnam and their Bioactivities

Chemistry of Natural Compounds -     

synthesis and properties of β-brominated metal complexes of meso-triphenylcorrole

Spectral properties and chemical stability of Mn(III), Mn(IV), Fe(III), Fe(IV), and Cu(III) complexes of β-octabromotriphenylcorrole [(β-Br)₈(ms-Ph)₃Cor], synthesized from β-unsubstituted compounds by their reaction with molecular bromine, were studied. Cyclic voltammetry, electron microscopy, and X-ray spectral microanalysis were used to obtain electrochemical characteristics of metal corroles M(β-Br)₈(ms-Ph)₃Cor and gain insight into the surface texture of active catalysts on the basis of metal corroles. The electron-acceptor β-bromine substitution in the MCor macrocycle shifts the equilibrium in electron-donor solvents to lower oxidation states of the metals and also stabilizes manganese and destabilizes copper complexes in the protondonor medium HOAc-H₂SO₄. The electrocatalytic activity of the complexes in the reduction of molecular oxygen depends on the nature of the ligand and increases in the order Mn ≤ Cu ? Fe in the case of β-octabrominated macrocycles. The character of distribution of active centers on the surface of the catalysts was established for the first time.     

Effect of aspect ratio of vertically aligned copper nanowires in the presence of cellulose nanofibers on the thermal conductivity of epoxy composites

The composites comprising vertically aligned network of copper nanowires (CuNWs) in the presence of cellulose nanofibers were fabricated by using the freeze‐templating method and the effect of aspect ratio (A/R) of CuNWs on the thermal conductivity of epoxy composites was investigated. The thermal conductivity of epoxy composites increased to 0.79 W m^?1 K^?1 at 1.12 vol% of high A/R CuNWs loading, corresponding to the thermal conductivity enhancement of 365% as compared to the pure epoxy. The thermal conductivity of vertically aligned higher A/R CuNWs/epoxy, which is 38.5% and 51.9% higher than those of the lower A/R CuNWs and the randomly aligned CuNWs, respectively. The application of the epoxy composites in heat dissipation was demonstrated by the temperature changes of composites on a hot plate with the increase of heating time. These results indicate that the thermally conductive composites in this study could be applied for thermal dissipating materials in electronic devices.     

Acylated flavonoid glycosides from Barringtonia racemosa

Abstract

Using various chromatographic separations, three new acylated flavonoid glycosides, namely barringosides G–I (1–3), were isolated from the water-soluble extract of Barringtonia racemosa branches and leaves. The structure elucidation was performed by extensive analysis of the 1D and 2D NMR and HR-QTOF-MS data. Of the isolated compounds, barringoside I (3) showed moderate inhibitory effects on LPS-induced NO production in RAW264.7 cells with an IC₅₀ of 52.48?±?1.04?µM.     

Triterpene glycosides from the Vietnamese sea cucumber Holothuria edulis

Abstract

From the MeOH extract of the Vietnamese sea cucumber Holothuria edulis, eight triterpene glycosides (1–8), including one new compound namely holothurin A₅ (1), were isolated by using various chromatographic separations. Their structures were established by spectroscopic experiments including 1D, 2D NMR and HR-ESI-MS. Holothurin A₅ (1) has a hydroperoxy group at C-25. To the best of our knowledge, this is the first report of this group in triterpene saponins obtained from sea cucumbers to date. In addition, the in vitro cytotoxicity against five human cancer cell lines (HepG2, KB, LNCaP, MCF7 and SK-Mel2) of all isolated compounds was also evaluated using SRB assays.     

Photoinitiated cationic polymerisation of multifunctional systems

Different types of tridimensional polymer networks have been synthetised by photoinitiated cationic polymerisation of vinyl ether and epoxy-functionalised oligomers and polymers. The polymerisation kinetics was followed by real-time infrared (RTIR) spectroscopy, a technique that records directly conversion versus time profiles in a timescale as short as 1 s. The addition of a diacrylate monomer was shown to accelerate the ring-opening polymerisation of epoxidized polyisoprene, with formation of interpenetrating polymer networks having well contrasted properties. A dual polymer network has been generated by photocrosslinking of a polyisoprene functionalised with both epoxy and acrylate groups.