Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

On the Frequency of Zeros of Solutions of Second Order Linear Differential Equations

We consider the equation \(\rm f^{\prime\prime}+{A}(z){f}=0\) with linearly independent solutions f₁,₂, where A(z) is a transcendental entire function of finite order. Conditions are given on A(z) which ensure that max{λ(f₁),λ(f₂)} = ∞, where λ(g) denotes the exponent of convergence of the zeros of g. We show as a special case of a further result that if P(z) is a non-constant, real, even polynomial with positive leading coefficient then every non-trivial solution of \(\rm f^{\prime\prime}+{e}^P{f}=0\) satisfies λ(f) = ∞. Finally we consider the particular equation \(\rm f^{\prime\prime}+({e}^Z-K){f}=0\) where K is a constant, which is of interest in that, depending on K, either every solution has λ(f) = ∞ or there exist two independent solutions f₁, f₂ each with λ(f_i) ≤ 1.     

Effect of time on the interfacial and foaming properties of beta-lactoglobulin/acacia gum electrostatic complexes and coacervates at pH 4.2

The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on the air/water interfacial properties of the beta-lactoglobulin/acacia gum electrostatic complexes can be understood by their reorganization at the interface to form a coacervate phase that is more fluid/viscous at t approximately 0 h vs rigid/elastic at t = 24 h.     

Structure (x-ray analysis) of Manicoline B,a mixture of two diastereoisomers of a new alkaloid from dulacia guianensis (olacaceae)

Manicoline B, isolated from the root bark of $\text{Dulacia guianensis}$ (Olacaceae), was shown by X-ray analysis to be an equimolecular mixture of two diastereoisomers of a new alkaloid and to have structure (3).     

Interfacial microgels formed by oppositely charged polyelectrolytes and surfactants. Part 2. Influence of surfactant chain length and surfactant/polymer ratio

The adsorption and complexation of polystyrene sulfonate (a highly charged anionic polyelectrolyte) and a series of cationic surfactants, alkyltrimethylammonium bromide, CnTAB, n = 8-16, at the air-water interface has been studied by combining surface tension and ellipsometry measurements. We find that increasing the chain length of the surfactant from 8 to 10 carbons leads to a sharp increase in adsorption of PSS/CnTAB complexes. When the surfactant tail length is further increased to 12 and 14 carbons, surface adsorption becomes less favored than macroscopic phase separation, resulting in a partial surface depletion. Furthermore, we find that when surface tensions are plotted against surfactant/monomer molar concentration ratio, all data collapse to a single curve. This result shows that the surfactant-polymer molar ratio, s/p, is a key parameter for tuning the surface activity of the complexes formed.     

The mixed ionocovalent bonding in small insulating clusters

We report a selfconsistent tight binding calculation of the electronic and structural properties of small insulating clusters (up to 12 atoms): these include alkaline-earth oxides (MgO and CaO) and NaCl clusters. Interatomic distance contractions are found in most cases, as in small metallic clusters. In addition, new effects take place in some of the compounds; these are a reduction of the ionic charge and, for the first time, the prediction of a dimerization of the interatomic distances. The microscopic processes responsible for their occurence and size dependence are dicussed with analytical arguments. It is shown that for these small clusters the equilibrium configuration and the electronic structure are fixed by a competition between covalent and electrostatic interactions, especially in the oxides.     

Particle-stabilized emulsions comprised of solid droplets

We kinetically stabilize oil-in-water emulsions comprising paraffin crystals by adsorbing solid particles (silica) of colloidal size at the oil/water interface. We obtain a set of emulsions that are quiescently stable for a long period of time (months), while the same emulsions are destabilized after only a few hours in the presence of surfactant molecules alone. The emulsions are submitted to a shear stress in order to probe their stability under flow conditions. Partial coalescence and gelation occur when the shear is applied for a sufficiently long period of time. The experiments reveal the existence of a critical droplet mass fraction, phi*, that defines a sharp transition between slow and fast gelation. The process of gelation is rather slow for phi < phi*, occurring at the scale of hours, and becomes almost instantaneous above phi*.