A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II)

The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.     

Direct numerical simulation of a freely decaying turbulent interfacial flow

Whereas Large Eddy Simulation (LES) of single-phase flows is already widely used in the CFD world, even for industrial applications, LES of two-phase interfacial flows, i.e. two-phase flows where an interface separates liquid and gas phases, still remains a challenging task. The main issue is the development of subgrid scale models well suited for two-phase interfacial flows. The aim of this work is to generate a detailed data base from direct numerical simulation (DNS) of two-phase interfacial flows in order to clearly understand interactions between small turbulent scales and the interface separating the two phases. This work is a first contribution in the study of the interface/turbulence interaction in the configuration where the interface is widely deformed and where both phases are resolved by DNS. To do this, the interaction between an initially plane interface and a freely decaying homogeneous isotropic turbulence (HIT) is studied. The densities and viscosities are the same for both phases in order to focus on the effect of the surface tension coefficient. Comparisons with existing theories built on wall-bounded or free-surface turbulence are carried out. To understand energy transfers between the interfacial energy and the turbulent one, PDFs of the droplet sizes distribution are calculated. An energy budget is carried out and turbulent statistics are performed including the distance to the interface as a parameter. A spectral analysis is achieved to highlight the energy transfer between turbulent scales of different sizes. The originality of this work is the study of the interface/turbulence interactions in the case of a widely deformed interface evolving in a turbulent flow.     

Fully three-dimensional direct numerical simulation of a plunging breakerSimulation numérique directe tridimensionnelle du déferlement plongeant

The scope of this paper is to show the results obtained for simulating three-dimensional breaking waves by solving the Navier–Stokes equations in air and water. The interface tracking is achieved by a Lax–Wendroff TVD scheme (Total Variation Diminishing), which is able to handle interface reconnections. We first present the equations and the numerical methods used in this work. We then proceed to the study of a three-dimensional plunging breaking wave, using initial conditions corresponding to unstable periodic sinusoidal waves of large amplitudes. We compare the results obtained for two simulations, a longshore depth perturbation has been introduced in the solution of the flow equations in order to see the transition from a two-dimensional velocity field to a fully three-dimensional one after plunging. Breaking processes including overturning, splash-up and breaking induced vortex-like motion beneath the surface are presented and discussed. To cite this article: P. Lubin et al., C. R. Mecanique 331 (2003).     

Anion binding vs. sulfonamide deprotonation in functionalised ureas

Sulfonamide groups, commonly used as neutral hydrogen bond donors in a wide variety of anion receptors, deprotonate upon addition of certain basic anionic guests in two simple functionalised ureas.     

1,3-diindolylureas and 1,3-diindolylthioureas: anion complexation studies in solution and the solid state

1,3-Diindolylureas and thioureas have been synthesised and their anion complexation properties in solution studied. Whilst diindolylthioureas showed only moderate affinities and selectivities, diindolylureas show remarkably high affinity for dihydrogen phosphate in solution for an acyclic, neutral receptor in water/[D(6)]DMSO mixtures. These easy-to-make compounds adopt relatively planar conformations in the solid-state and are able to donate four hydrogen bonds and yet not fill the coordination sphere of carbonate or phosphate, allowing two or three receptors to bind to each anion in the solid-state.     

Interaction of mixed-donor macrocycles containing the 1,10-phenanthroline subunit with selected transition and post-transition metal ions: metal ion recognition in competitive liquid-liquid solvent extraction of Cu(II), Zn(II), Pb(II), Cd(II), Ag(I), and Hg(II)

Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L(4)) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L(7)) have been synthesized and characterized. The coordination behavior of L(4) and L(7) toward the metal ions Cu(II), Zn(II), Pb(II), Cd(II), Hg(II), and Ag(I) was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by (1)H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L(1)-L(3), L(5), L(6): all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L(4) and L(7). The complexes [Cd(NO3)2(L(5))], [Pb(L(7))](ClO4)2 x 1/2MeCN, [Pb(L(4))](ClO4)2 x MeCN, and [Cu(L(7))](ClO4)2 x 3/2MeNO2 were characterized by X-ray crystallography. The efficacy of L(1)-L(7) in competitive liquid-liquid metal ion extraction of Cu(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II) was assessed. In the absence of Hg(II), a clear extraction selectivity for Ag(I) was observed in all systems investigated.     

Acridinone-based anion receptors and sensors

The interaction of a variety of acridinone derivatives containing hydrogen-bond donor groups in the 4- and 5-positions with anions demonstrate the potential of this new scaffold in anion receptor and sensor design.     

The fast peroxyoxalate-chemiluminescence of 3-1-aza-4,10-dithia-7-oxacyclododecane as a novel fluorophore

Due to their multiple selectivities, high sensitivity, and instrumental simplicity peroxyoxalate chemiluminescence (PO-CL) reactions have been used as powerful detection systems in several separation techniques. However many of the PO-CL reactions have slow kinetics and impose extra flow elements in separation systems to obtain acceptable band resolution, overcome the peak broadening and observe the reaction in a reasonable time window at maximum emission intensity. Therefore slow chemiluminescence reactions cannot be used in constructing miniaturized separation systems. To achieve the fast and intense PO-CL reactions (suitable for miniaturized separation systems) careful selection of the fluorophore molecule and the reaction conditions is of great importance. In this work, the time-dependent light emission of the fast chemiluminescence (CL) arising from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with H₂O₂ in the presence of 3-1-aza-4,10-dithia-7-oxacyclododecane (L) as a novel fluorophore, and imidazole as catalyst, has been studied in ethyl acetate solution. To find the best time-intensity emission curves the concentration of TCPO, imidazole, hydrogen peroxide and L were optimized. The maximum CL intensity and minimum reaction time were obtained at the concentration of 0.2 M H₂O₂, 2.0×10^?3 M TCPO, 1.0×10^?3 M fluorophore and 5.0×10^?3 imidazole. Under the optimum experimental condition, the entire CL reaction is completed in less than 3 s.     

Spatio-temporal dynamics of cavitation bubble clouds in a low frequency reactor: comparison between theoretical and experimental results.

The propagation of ultrasound through a liquid induces the growth of inceptions and germs into bubbles. In a low frequency reactor, fragmentary transient bubbles emerge due to the acoustic driving. They violently collapse in one cycle and fragment into many smaller bubbles than in turn cavitate. This violent collapse is responsible for the mechanical effects of ultrasounds effects. The latter bubbles gather in a ball-shaped cloud and migrate to pressure antinodes. During their migration, their nonexplosive collapses mainly contribute to activate chemical reactions by producing OH. radicals. Mathematical modelling is performed as a new approach to predict the bubbles field. Through numerical simulation, we determinate emergence sites of mechanically active cavitation bubbles. Calculus are compared with aluminium foil degradation. The modelling of bubble migration allow us to have an insight on the privileged sites of the chemical reactions. Validation of the modelling is made through direct comparison with chemiluminescence photo. All experiments and computations are made in a 28.2 kHz sonoreactor.