Structural evolution in cationic micelles upon incorporation of a polar organic dopant

Micelles of cetyltrimethylammonium bromide (CTAB), when doped with increasing levels of 4-ethylphenol, show microstructural transitions from spherical micelles to elongated wormlike micelles, disks, and subsequently to globular and then to tubular vesicles. Wormlike micelles are observed at a dopant-to-CTAB molar ratio of 1:3. At higher dopant ratios (1:1), globular vesicles are observed which transition to tubular vesicles when the dopant becomes the predominant species at a ratio of 3:1. These transitions are reflected in small-angle neutron scattering analysis and, interestingly, can be directly observed through cryo-transmission electron microscopy. The para-substituted phenol is interfacially active and modulates interfacial curvature of the micelles. The observations of microstructure modifications have relevance to the synthesis of mesoporous materials using CTAB as the template.     

Shear-induced orientation of a rigid surfactant mesophase

An optically clear, crystalline, gel-like mesophase is formed by the addition of water to a micellar solution consisting of a mixture of 0.85 M anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and a 0.42 M zwitterionic surfactant phosphatidylcholine (lecithin) in isooctane. At 25 degrees C and water to AOT molar ratio of 70, the system has a columnar hexagonal microstructure with randomly oriented domains. The shear-induced orientation and subsequent relaxation of this structure were investigated by rheological characterization and small-angle neutron scattering (SANS). The rheological response implies that the domains align under shear, and remain aligned for several hours after cessation of shear. Shear-SANS confirms this picture. The sheared gel mesophase retains its alignment as the temperature is increased to 57 degrees C, indicating the potential to conduct templated polymer and polymer-ceramic composite materials synthesis in aligned systems.     

Synthesis of hydroxy-6H-benzofuro[3,2-c] [1]benzopyran-6-ones

The Micheal addition of ethyl 2-methoxy-, 2,4-dimethoxy- and 2,5-dimethoxybenzoylacetates with benzoquinone leads to ethyl 2-(rnethoxy or dimethoxy phenyl)-5-hydroxybenzofuran 3-carboxylates. Treatment of the henzofuran derivatives with anhydrous pyridine hydrochloride at 190–195° leads to hydroxy-6H-henzofuro[3,2-c] [1]benzopyran-6-ones.     

Biocatalysis in the development of functional polymer-ceramic nanocomposites

Fluorescent silica/polymer nanocomposites have been synthesized by condensing tetramethyl orthosilicate (TMOS) around fluorescent polymer strands of poly(2-naphthol). The polymer is biocatalytically synthesized via peroxidase catalyzed polymerization in micelles of the cationic surfactant, cetyltrimethylammonium bromide (CTAB). Silica condensation at the micelle-water interface results in encapsulation of the polymer. Fluorescence spectroscopy and fluorescent light microscopy provide critical evidence that the polymer luminescence properties are conferred to the composite material. The fabrication of polymer entrapped in ordered, mesoporous materials represents a viable step toward the development of functional polymer-ceramic nanocomposites.     

Structural evolution of a two-component organogel

Dry reverse micelles of AOT in isooctane spontaneously undergo a microstructural transition to an organogel upon the addition of a phenolic dopant, p-chlorophenol. This microstructural evolution has been studied through a combination of light scattering, small-angle neutron scattering (SANS), NMR, and rheology. Several equilibrium stages between the system of dry reverse micelles of AOT and a 1:1 AOT/p-chlorophenol (molar ratio) gel in isooctane have been examined. To achieve this, p-chlorophenol is added progressively to the dilute solutions of AOT in isooctane, and this concentration series is then analyzed. The dry micelles of AOT in isooctane do not undergo any detectable structural change up to a certain p-chlorophenol concentration. Upon a very small increment in the concentration of p-chlorophenol beyond this "threshold" concentration, large strandlike aggregates are observed which then evolve to the three-dimensional gel network.     

Crystallogenesis of biological macromolecules. Biological, microgravity and other physico-chemical aspects

After an historical introduction and justification of the importance of proteins (as well as other macromolecules or macromolecular assemblies of biological origin) in modern biology but also in physics, this review presents the state of the field of macromolecular crystallogenesis. The basic questions underlying the crystallization of macromolecules will be addressed and discussed in a first part. The still unsolved problems are highlighted. This section also discusses the methodological approaches that can be used. In the second part, some of the recent achievements in the field are presented. We show how physical methods have contributed to a deeper understanding of protein crystallization. Emphasis is given to the parameter microgravity, since the projects concerning crystallizations in this environment have stimulated the physico-chemical research in the field. Finally, the future perspectives are outlined.     

Efficient Non‐dissociative Activation of Dinitrogen to Ammonia over Lithium‐Promoted Ruthenium Nanoparticles at Low Pressure

There is an exciting possibility to decentralize ammonia synthesis for fertilizer production or energy storage without carbon emission from H₂ obtained from renewables at small units operated at lower pressure. However, no suitable catalyst has yet been developed. Ru catalysts are known to be promoted by heavier alkali dopants. Instead of using heavy alkali metals, Li is herein shown to give the highest rate through surface polarisation despite its poorest electron donating ability. This exceptional promotion rate makes Ru–Li catalysts suitable for ammonia synthesis, which outclasses industrial Fe counterparts by at least 195 fold. Akin to enzyme catalysis, it is for the first time shown that Ru–Li catalysts hydrogenate end‐on adsorbed N₂ stabilized by Li⁺ on Ru terrace sites to ammonia in a stepwise manner, in contrast to typical N₂ dissociation on stepped sites adopted by Ru–Cs counterparts, giving new insights in activating N₂ by metallic catalysts.     

The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl–KCl Eutectics

Molten LiCl and related eutectic electrolytes are known to permit direct electrochemical reduction of N₂ to N^3? with high efficiency. It had been proposed that this could be coupled with H₂ oxidation in an electrolytic cell to produce NH₃ at ambient pressure. Here, this proposal is tested in a LiCl–KCl–Li₃N cell and is found not to be the case, as the previous assumption of the direct electrochemical oxidation of N^3? to NH₃ is grossly over‐simplified. We find that Li₃N added to the molten electrolyte promotes the spontaneous and simultaneous chemical disproportionation of H₂ (H oxidation state 0) into H^? (H oxidation state ?1) and H⁺ in the form of NH^2?/NH₂^?/NH₃ (H oxidation state +1) in the absence of applied current, resulting in non‐Faradaic release of NH₃. It is further observed that NH^2? and NH₂^? possess their own redox chemistry. However, these spontaneous reactions allow us to propose an alternative, truly catalytic cycle. By adding LiH, rather than Li₃N, N₂ can be reduced to N^3? while stoichiometric amounts of H^? are oxidised to H₂. The H₂ can then react spontaneously with N^3? to form NH₃, regenerating H^? and closing the catalytic cycle. Initial tests show a peak NH₃ synthesis rate of 2.4×10^?8 mol cm^?2 s^?1 at a maximum current efficiency of 4.2 %. Isotopic labelling with ¹⁵N₂ confirms the resulting NH₃ is from catalytic N₂ reduction.