Palladium-catalysed Heck reaction on 1,2-dien-1-ols: a stereoselective synthesis of α-arylated α,β-unsaturated aldehydes

A new methodology for preparing α-arylated α,β-unsaturated aldehydes is reported. The starting materials are all commercially available alkyn-1-ols (1a-c) that have been easily isomerised to the corresponding allenes (2a-c). The key step is the Heck coupling of the 1,2-dien-1-ols with a series of iodo- and bromoarene. The products have been synthesised in good yields, and the reactions were carried out under very mild conditions.     

Looking for a synergic effect between NHCs and chiral P-ligands

The issue of the added value of NHCs in asymmetric catalysis with respect to trusted chiral P-ligands was addressed: considering a prototypical asymmetric allylic alkylation reaction as a model, the association of a priori inhibiting and achiral NHCs with modular P-ligand resulted in enhancement of er up to 508% and increased rates.     

Platinum(II)-coordinated phosphinous acid-catalyzed alkylidenecyclopropanation of bicyclic alkenes with terminal alkynes

New Pt(eta2-acetato){[(R)(Ph)PO]2H} complexes 3 prepared from PtCl2(CH3CN)2 and secondary phosphine oxides (SPOs) catalyzed the [2+1] cycloaddition of phenylethyne (5a) with norbornene derivatives 4 to afford benzylidenecyclopropanes.     

Effect of biotic and abiotic stresses on volatile emission of Achillea collina Becker ex Rchb

This study describes the application of headspace solid-phase microextraction (HS-SPME)–gas chromatography/mass spectrometry (GC/MS) to characterise the volatile fingerprint changes of Achillea collina, induced by aphids' infestation, mechanical damage and jasmonic acid (JA) treatment. The volatile organic compound profiles of A. collina, Prunus persica and Pisum sativum infested by Myzus persicae were also compared. Several changes were observed between control, infested, mechanically damaged and JA-treated plants, and new inducible volatile organic compounds (IVOCs) were emitted in response to biotic or abiotic stresses. Some of these were in common for all stresses and other compounds were in common only for two types of stress. Conversely some IVOCs were emitted only in response to the specific stimuli. The results suggested that there were species-specific and common IVOCs emitted by A. collina, P. persica and P. sativum in response to M. persicae infestation. In conclusion, HS-SPME–GC/MS seems to be a reliable analytical approach to study in vivo plant reaction to external stimuli.     

Metal Coordination Sphere Deformation Induced Highly Stokes-Shifted,Ultra Broadband Emission in 2D Hybrid Lead-Bromide Perovskites and Investigation of Its Origin

Published studies of layered (2D) (100)-oriented hybrid lead-bromide perovskites evidence a correlation between increased inter-octahedral (Pb-Br-Pb) distortions and the appearance of broadband white light emission. However, the impact of distortions within their constituent [PbBr₆]⁴⁻ octahedra has yet to be assessed. Herein, we report two new (100)-oriented 2D Pb-Br perovskites, whose structures display unusually high intra-octahedral distortions, whilst retaining minimal inter-octahedral distortions. Using a combination of temperature-dependent, power-dependent and time-resolved photoluminescence spectroscopic measurements, we show that increased intra-octahedral distortion induces exciton localization processes and leads to formation of multiple photoinduced emissive colour centres. Ultimately, this leads to highly Stokes-shifted, ultrabroad white light emission at room temperature.     

Almost Exponential Maps and Integrability Results for a Class of Horizontally Regular Vector Fields

We consider a family ${\mathcal{H}}:= \{X_1, \dots, X_m\}$ of C ¹ vector fields in ? ⁿ and we discuss the associated ${\mathcal{H}}$ -orbits. Namely, we assume that our vector fields belong to a horizontal regularity class and we require that a suitable s-involutivity assumption holds. Then we show that any ${\mathcal{H}}$ -orbit ${\mathcal{O}}$ is a C ¹ immersed submanifold and it is an integral submanifold of the distribution generated by the family of all commutators up to length s. Our main tool is a class of almost exponential maps of which we discuss carefully some precise first order expansions.     

Local {W^{2,m(\cdot)}_{loc}}regularity for p(.)-Laplace equations

We study ${W^{2,m(\cdot)}_{loc}}$ regularity for local weak solutions of p(·)-Laplace equations where ${p\in C^1(\Omega) \cap C(\overline{\Omega})}$ and ${\min_{x\in \overline{\Omega}} p(x) > 1}$ .     

Synthesis of tetrasubstituted 4,4'-biimidazoles

Highly substituted 4,4'-biimidazoles were synthesized, in good to excellent yields, through a multicomponent imidazole ring synthesis by using imidazol-4-yl-ethane-1,2-diones as starting materials. The obtained compounds were preliminarily tested as chromogenic and fluorescent sensors for heavy metals.     

Analysis of explosive and other organic residues by laser induced breakdown spectroscopy

With the aim of realizing a compact instrument for detection of energetic materials at trace levels, laser induced breakdown spectroscopy was applied on residues from nine explosives in air surroundings. Different potentially interfering organic materials were also analyzed. The residues were not uniformly distributed on an aluminum support and single-shot discrimination was attempted. For a single residue type, large shot-to-shot fluctuations of the line intensity ratios characteristic for organic samples were observed, which made material classification difficult. It was found that both atomic and molecular emission intensities, as well as their ratios, are strongly affected by an amount of the ablated support material, which mainly determines the plasma temperature. With respect to the spectra from the clean support, emission intensities of atomic oxygen and nitrogen are always reduced in the presence of an organic material, even if its molecules contain these elements. This was attributed to chemical reactions in a plasma containing carbon or its fragments. Hydrogen atomic emission depends strongly on the local humidity above the sampled point and its line intensity shows shot to shot variations up to 50%, also on a homogeneous sample. It is argued that shock waves generated by previous spatially and/or temporally close laser pulses blow away a relatively heavy water aerosol, which later diffuses slowly back towards the sampled point. C₂ and CN exhibit a peak emission behavior with atomic Al emission, and their variable ratio indicates an existence of different formation or removal mechanisms from the plasma, depending on the plasma parameters and on the composition of the organic residue. On the basis of these observations, an attempt is made to establish a suitable procedure for data analysis and to determine the optimal experimental conditions, which would allow for discrimination of explosives from other, potentially interfering, residues.