Iron porphyrin catalysed light driven C–H bond amination and alkene aziridination with organic azides

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation.

An iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.     

Water and oil signal assignment in low-moisture mozzarella as determined by time-domain NMR T2 relaxometry

A time-domain ¹H nuclear magnetic resonance relaxometry method was elaborated for the rapid microstructural characterization of mozzarella cheese. For this purpose, there is a strong need to know how the experimentally determined T₂ relaxation time distribution can be related to specific constituents in mozzarella. In this study, a detailed investigation is offered for fresh and aged low-moisture mozzarella cheese, often applied as a pizza cheese, by application of both a conventional Carr–Purcell–Meiboom–Gill (CPMG) sequence and a free-induction decay CPMG (FID-CPMG) sequence. The relaxation behavior was further elucidated by addition of deuterium oxide and by mild heat treatment of samples. The relaxation times of water protons in mozzarella were found to range from a few microseconds to some tens of milliseconds (in aged mozzarella) or to about hundred milliseconds (in fresh mozzarella). The upper limit of the T₂ distribution can even be extended to the seconds range upon releasing water protons from the mozzarella matrix using a mild heat treatment or upon addition of deuterated water. Both stimuli also provided evidence for the absorption of water into the cheese matrix. The potential release and uptake of water demonstrated that mozzarella acts as a very dynamic system during production and storage. The detected differences in the behavior of the water fraction between fresh and aged low-moisture mozzarella might be utilized to study the influence of either production and/or storage conditions on the cheese ripening process.     

Random close packing of spheres in a round cell

The paper describes the method of construction of cells containing large numbers (10⁵-10⁶) of close packed spheres, ranging in packing fractions from 0.2 to 0.60. The cells are constructed in a round form, utilizing varying surface curvature to prevent ordered packing. The properties of the cells are described by a series of distributions: (i) polar angle of contact points, (ii) maximum displacement of loose spheres, (iii) and Voronoi volumes for individual spheres. The cells of varying density appear to show the liquid-to-solid transition. All cells described here contain loose spheres. It is proposed that cells with zero loose spheres are ideal amorphous solids. Ideal amorphous solids are characterized by a number of elements, described herein.     

A facile synthesis of 5(6)‐(chloromethyl)benzimidazoles: Replacement of a sulfonic acid functionality by chlorine

Valuable new synthetic intermediates, 5(6)‐(chloromethyl)benzimidazoles, were prepared by the facile elimination of sulfur dioxide under the influence of thionyl chloride from benzimidazole‐5(6)‐methane‐sulfonic acids easily obtained from (3,4‐diaminophenyl)methanesulfonic acid with formic‐, or trifluoroacetic acid. Both reaction steps involved only acidic conditions, thus the synthesis of polysubstituted 5(6)‐(chloromethyl)benzimidazoles incorporating base‐sensitive substituents became possible.     

Molecular field theory for polar,biaxial bent-core nematics

We have studied a polar, biaxial nematic liquid crystal formed from bent-core molecules using molecular field theory. The model includes a simple Heisenberg-form dipolar intermolecular interaction in addition to the usual quadrupolar nematic interaction, and mimics a system consisting of nematogenic bent-core molecules with a large transverse dipole along the bisector of the two molecular arms. Such systems are regarded as good candidates for biaxial nematic liquid crystals. In principle, the molecular dipoles can align, thus stabilising the ordering of the minor axes. Our calculations predict that, for suitable values of the bent-core interarm angle, the biaxial nematic phase can be stabilised at higher temperatures than in the absence of the transverse dipole. In general, the transverse macroscopic polar order stabilises the biaxial nematic phase. In particular, for a large enough dipolar interaction, the Landau point in the pure biaxial nematic develops into a line of first-order polar biaxial nematic-to-isotropic phase transitions.     

Sustainability investment under cap-and-trade regulation

Carbon emission abatement is a hot topic in environmental sustainability and cap-and-trade regulation is regarded as an effective way to reduce the carbon emission. According to the real industrial practices, sustainable product implies that its production processes facilitate to reduce the carbon emission and has a positive response in market demand. In this paper, we study the sustainability investment on sustainable product with emission regulation consideration for decentralized and centralized supply chains. We first examine the order quantity of the retailer and sustainability investment of the manufacturer for the decentralized supply chain with one retailer and one manufacturer. After that, we extend our study to the centralized case where we determine the production quantity and sustainability investment for the whole supply chain. We derive the optimal order quantity (or production quantity) and sustainability investment, and find that the sustainability investment efficiency has a significant impact on the optimal solutions. Further, we conduct numerical studies and find surprisingly that the order quantity may be increasing in the wholesale price due to the effects of the sustainability and emission consideration. Moreover, we investigate the achievability of supply chain coordination by various contracts, and find that only revenue sharing contract can coordinate the supply chain whereas the buyback contract and two-part tariff contract cannot. Important insights and managerial implications are discussed.     

Effect of ionic pendent groups on a polyaniline-based electrorheological fluid

Particles of semiconducting polyaniline and a copolyaniline bearing ionic substituents were synthesized. Electrorheological (ER) fluids using these particles were compared with each other with respect to their rheological properties and dielectric spectra. In the steady shear rheological experiment conducted at 3 kV/mm (DC) at 25°C, the copolymer system showed higher stress than the polyaniline system in the whole shear rate region. This result was interpreted in terms of the conductivities of the particles and their dielectric spectra. Especially, the different behavior in the high shear rate region can be related to the electrical relaxation phenomena observed in the dielectric spectra.     

Study of diffusion and local structure of sodium-silicate liquid: the molecular dynamic simulation

A systematic analysis on sodium-silicate melt with various silica contents was carried out. The simulation revealed two diffusion mechanisms occurred in the melt: the bond-breaking and hopping between sites. The local structure was analyzed through T-simplexes. It was revealed that T-clusters have a non-spherical shape and represent the diffusion channel, in which Na atoms are dominant, but no any O atoms are located. The SiO₂-poor melt acquires a long channel. In contrast, the SiO₂-rich melt consists of unconnected short channels. The simulation also revealed the immobile and mobile regions which differ in local structure and constituent composition. We propose a new CL-function to characterizing the spatial distribution of different atom component. The spatial distribution of mobile and immobile atoms is found quite different. In particular, the immobile atoms are concentrated in high-density regions possessing very large density of immobile atoms. The spatial distribution of mobile atoms in contrast is more homogeneous.