Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides

We report a new visible-light-mediated carbonylative amidation of aryl, heteroaryl, and alkyl halides. A tandem catalytic cycle of [Ir(ppy)₂(dtb-bpy)]⁺ generates a potent iridium photoreductant through a second catalytic cycle in the presence of DIPEA, which productively engages aryl bromides, iodides, and even chlorides as well as primary, secondary, and tertiary alkyl iodides. The versatile in situ generated catalyst is compatible with aliphatic and aromatic amines, shows high functional-group tolerance, and enables the late-stage amidation of complex natural products.     

Bioactive Properties and Phenolic Compound Profiles of Turnip-Rooted,Plain-Leafed and Curly-Leafed Parsley Cultivars

Petroselinum crispum Mill., Fuss., is a culinary vegetable used as an aromatic herb that garnishes and flavours a great variety of dishes. In the present study, the chemical profiles and bioactivities of leaf samples from 25 cultivars (three types: plain- and curly-leafed and turnip-rooted) from this species were assessed. Seven phenolic compounds were identified in all the varieties, including apigenin and kaempherol derivates. Apigenin-O-pentoside-O-hexoside was the major compound in all the tested parsley types (20, 22 and 13 mg/g of extract, respectively) and responsible for its excellent antioxidant activity, also investigated in this study. Antimicrobial activities were also explored, and the results revealed a good bioactivity against specific tested pathogens, such as bacteria and fungi. In conclusion, the leaves of all the types of P. crispum are a good source of natural bioactive compounds that confer health benefits, and thus, they should be part of a balanced and diversified diet.     

Temperature dependent characteristics of La2O2S: Ln [Ln=Eu, Tb] with various Ln concentrations over 5-60 °C

This research is aimed at developing an optical sensor for remotely measuring human skin temperature in electromagnetically hostile environments, such as within a magnetic resonance imaging (MRI) scanner. In this feasibility study, various concentrations of europium-doped lanthanum oxysulphide (La₂O₂S: Eu—0.1-15 mol% (m/o)) and terbium-doped lanthanum oxysulphide (La₂O₂S: Tb—0.005-50 m/o) have been investigated in terms of crystallinity, photoluminescent (PL) spectral and decay time characteristics. For both phosphors, X-ray diffraction (XRD) has shown that as dopancy increases, the (1 0 0) and (0 0 2) reflections merge and there is a reduction in the c-axis parameter as well as the crystallite size. Photoluminescent characterisation (337 nm excitation) has also shown a dependency to dopant concentration through variance of peak intensity. Temperature dependent decay time measurements were carried out over a low temperature range 5-60 °C. Optimum brightness of these temperature dependent lines is achieved at concentrations of 1 and 10 m/o for La₂O₂S: Eu and La₂O₂S: Tb respectively. However, optimum temperature dependency is achieved at lower concentration for La₂O₂S: Eu, specifically at 0.1 m/o. In comparison to conventional phosphor temperature dependent characteristic, La₂O₂S: Tb showed an increase in decay time with respect to temperature for concentrations above 2 m/o.     

Spectrum planning and performance evaluation between heterogeneous satellite networks

A new network has been recently proposed for the provision of fixed broadband services via high altitude platform stations (HAPS) in the 48/47 GHz band. One of the critical issues of this technology is spectrum sharing with the fixed satellite service. This paper examines the effect of Earth-to-stratosphere co-channel interference produced by ground stations of HAPS network to geostationary orbit (GEO) satellite receivers and proposes an interference-to-noise (I/N) calculation model for the evaluation of the current HAPS ground stations power characteristics set by ITU-R. Analytical and simulation results for archetypal systems in realistic scenarios indicate that efficient use of the spectrum shared between heterogeneous HAPS and Fixed Satellite Networks is feasible. Certain consideration is needed prior to the HAPS network development in suburban areas for latitudes from 55° to 65°, and in rural areas for latitudes from 60° to 75°.     

Flow synthesis of tricyclic spiropiperidines as building blocks for the histrionicotoxin family of alkaloids

A domino cyclization reaction of the bis-unsaturated ketone 3 with hydroxylamine proceeds with good yield and high stereoselectivity, in a flow reactor system. The tricyclic spiropiperidine products 5 and 2 obtained are valuable building blocks for the synthesis of analogues of the histrionicotoxin alkaloids.     

Synthesis of 1,2,3-triazole linked galactopyranosides and evaluation of cholera toxin inhibition

We report the synthesis of a series of bivalent 1,2,3-triazole linked galactopyranosides as potential inhibitors of cholera toxin (CT). The inhibitory activity of the bivalent series was examined (ELISA) and the series showed low inhibitory activity (millimolar IC(50)s). Conversely, the monomeric galactotriazole analogues were strong inhibitors of cholera toxin (IC(50) = 71-75 μM).     

Stretching of polymer chains by fluctuating flow fields

We investigate polymer stretching by fluctuating flow fields via numerical solutions of the Brownian dynamics of multibead polymer chains taking into account nonlinear elasticity, hydrodynamic interactions and good solvent, excluded volume interaction effects. By varying the scaling exponent of the energy spectrum whilst keeping the same Reynolds and Deborah numbers, as well as microscale length and turnover times, we show that steeper spectra are associated with stronger stretching. We compute the probability density functions of chain length, and explain their main features by examining explicit molecular histories. We quantify the interaction between strain rate tensor structure and chain geometry as a means of understanding better the different stretching mechanisms in mild, moderate and strong polymer stretching regimes.     

Coherent structure formation in turbulent thermal superfluids

By means of numerical calculations, we show that in turbulent thermal superfluids the normal fluid induces coherent bundles of quantized line vortices in the superfluid. These filamentary structures are formed in between the normal fluid vortices, acquiring eventually comparable circulation. They are self-stretched and evolve according to self-regulating dynamics. Their spectrum mimics the normal fluid spectrum with the mutual friction force exciting the large scales and damping the small scales. Strongly interacting triads of them merge sporadically into stronger, braided vortex filaments, inducing strong fluctuations in the system's energetics. A theoretical account of the system's statistical mechanics is proposed.