Antibacterial Activity of Synthetic Curcumin Derivatives: 3,5-Bis(benzylidene)-4-Piperidone (EF24) and EF24-Dimer Linked via Diethylenetriaminepentacetic Acid (EF2DTPA)

Curcumin is well known for its antimicrobial and anti-inflammatory properties. However, since systemic absorption and bioavailability of curcumin from gastrointestinal tract is considerably poor, synthetic curcuminoids are being developed as better alternatives. Two curcumin derivatives: 3,5-bis(benzylidene)-4-piperidone (EF24) and EF24-dimer linked via diethylenetriaminepentacetic acid (EF₂DTPA), were included in this study. We investigated the antibacterial activity of EF24 and EF₂DTPA against Gram-negative (Escherichia coli) and Gram-positive (Enterococcus faecalis, Staphylococcus aureus) bacteria. We also studied the effects of EF24 and EF₂DTPA on uptake and localization of pHrodo-labeled E. coli in the acidic compartments (phagolysosomes) of dendritic cells (DCs) under in vitro conditions. Our results demonstrate that treatment with EF24 and EF₂DTPA directly suppresses the bacterial growth. However, these compounds do not affect the bacterial uptake or localization in the DCs.     

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.     

Taming the Reactivity of Phosphiranium Salts: Site-Selective C-Centered Ring Opening for Direct Synthesis of Phosphinoethylamines

Advances in the field of phosphorus chemistry are documented, by revealing the synthetic utility of previously underutilized quaternary phosphiranium salts (QPrS) as three-chain-atom electrophilic building blocks. Notably, control of their challenging C-centered electrophilicity is disclosed with an expedient synthesis of tertiary β-anilino phosphines as a proof-of-concept.     

High temperature NMR approach of mixtures of rare earth and alkali fluorides: An insight into the local structure

In situ high temperature nuclear magnetic resonance in molten fluoride mixtures gives some structural picture of the complexes existing in the melt, i.e. of their nature and relative proportion. Thanks to the development of a laser heating system associated with a close crucible in boron nitride, we can describe experimentally the evolution of these complexes from the anions and the cations point of view. By ¹⁹F NMR, we have shown the existence of three kinds of fluorine atoms depending on the composition: free fluorine like in pure LiF (non-bonded), bridging fluorine in melts rich in LnF₃ in addition with terminal fluorine singly bonded to one rare earth. Data obtained by NMR spectroscopy are also combined with EXAFS measurements, again thanks to a specific development of the sample holder adapted with molten fluorides and high temperature. This study is a part of our systematic investigation of the different Alk-LnF₃ systems by NMR and EXAFS spectroscopy.     

Complexes derived from the general copper(II)/maleamic acid/N,N′,N′′-chelate reaction systems: Synthetic,reactivity, structural and spectroscopic studies

The synthetic investigation of the Cu^II/maleamate(−1) ion (HL⁻)/N,N′,N′′-chelate general reaction system has allowed access to compounds [Cu₂(HL)₂(bppy)₂](ClO₄)₂·H₂O (1·H₂O), [Cu(HL)(bppy)(ClO₄)] (2) and [Cu(HL)(terpy)(H₂O)](ClO₄) (4) (bppy = 2,6-bis(pyrazol-1-yl)pyridine, terpy = 2,2′;6′,2′′-terpyridine). In the absence of externally added hydroxides, compound [Cu₂(L′)₂(bppy)₂](ClO₄)₂ (3) was obtained from MeOH solutions; L′⁻ is the monomethyl maleate(−1) ligand which is formed in situ via the Cu^II-assisted HL⁻ → L′⁻ transformation. In the case of tptz-containing (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) reaction systems, the Cu^II-assisted hydrolysis of tptz to pyridine-2-carboxamide (L1) afforded complex [Cu(L1)₂(NO₃)₂] (5). The crystal structures of 1–5 are stabilized by intermolecular hydrogen bonding and π–π stacking interactions. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands.     

Strong antiferromagnetic coupling in doubly N,O oximato-bridged dinuclear copper(II) complexes

The use of di-2-pyridyl ketone oxime, (py)pkoH, and phenyl 2-pyridyl ketone oxime, ppkoH, in copper(II) hexafluoroacetylacetonate chemistry is reported. The reaction of CuCl₂·2H₂O with one and two equivalents of ppkoH and Na(hfac), respectively, in CH₂Cl₂ affords the dinuclear complex [Cu₂(hfac)₂(ppko)₂] (1) in excellent yield. The replacement of ppkoH by (py)pkoH gives the isostructural compound [Cu₂(hfac)₂{(py)pko}₂] (2) in good yield. The Cu^II atoms in both 1 and 2 are doubly bridged by the oximate groups of two η¹:η¹:η¹:μ₂ ppko⁻ and (py)pko⁻ ligands, respectively. The bridging Cu–(R–NO)–Cu′ units are not planar, with the torsion angles being 23.2° (1) and 20.3° (2). A bidentate chelating hfac⁻ ligand completes five-coordination at each square pyramidal metal ion. The hfac⁻-free reaction system CuCl₂·2H₂O/(py)pkoH/NEt₃ (1:2:1) gives instead the mononuclear complex [CuCl{(py)pko}{(py)pkoH}] (3) in very good yield. The Cu^II atom is coordinated by two N,N′-bidentate (py)pko⁻/(py)pkoH chelates and a monodentate chloride anion resulting in a distorted square pyramidal geometry around the metal center. Variable-temperature, solid-state dc magnetic studies were carried out on the representative dinuclear complex 1 in the 2.0–300 K range. The data indicate a very strong antiferromagnetic exchange interaction and a resulting S = 0 ground state, which is well isolated from the S = 1 excited state. The J value of −720 cm⁻¹ was derived from the fitting of the experimental data using the Hamiltonian H = −J(S₁ · S₂).     

Expedient BINOL derivative arylations

A dramatic improvement of our previous methodology based on a Suzuki–Miyaura cross-coupling to access 3,3′-disubstituted H₈-BINOLs using microwave heating is reported herein. These new conditions represent a large gain in term of atom-economy, reaction time, catalyst loading, and excess of reagents employed.     

Facile Synthesis of Bis(crown ether)benzils: Prospective Building Blocks for Metal Ion Sensors

A new facile synthetic route to benzils containing fragments of 12-crown-4, 15-crown-5, and 18-crown-6 by oxidation of corresponding stilbenes was developed. The first representative of a new family of fluorescent sensors was obtained by reaction of bis(15-crown-5)benzil with o-phenylenediamine. The latter exhibits great fluorescence enhancement upon association with K⁺ and Rb⁺ compared to Na⁺ and Cs⁺.