Hard domain compression of triblock-copolymer gels by high pressure X-ray small-angle scattering

Small-angle X-ray scattering using synchrotron radiation at pressures up to 700 MPa has been performed on triblock-copolymer gels, polystyrene-rubber-polystyrene with poly(ethylene/butylene) as the rubber mid-blocks. A 2-stage pressure behaviour could be verified by comparison of the experimental data with the Tait-equation and a model of pressure screening.     

Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches

The fall colors are signs of chlorophyll breakdown, the biological process in plants that generates phyllobilins. Most of the abundant natural phyllobilins are colorless, but yellow phyllobilins (phylloxanthobilins) also occur in fall leaves. As shown here, phylloxanthobilins are unique four‐stage photoswitches. Which switching mode is turned on is controlled by the molecular environment. In polar media, phylloxanthobilins are monomeric and undergo photoreversible Z/E isomerization, similar to that observed for bilirubin. Unlike bilirubin, however, the phylloxanthobilin Z isomers photodimerize in apolar solvents by regio‐ and stereospecific thermoreversible [2+2] cycloadditions from self‐assembled hydrogen‐bonded dimers. X‐ray analysis revealed the first stereostructure of a phylloxanthobilin and its hydrogen‐bonded self‐templating architecture, helping to rationalize its exceptional photoswitch features. The chemical behavior of phylloxanthobilins will play a seminal role in identifying biological roles of phyllobilins.     

Formation of metal-anion arrays within layered perovskite hosts. Preparation of a series of new metastable transition-metal oxyhalides, (MCl)LaNb(2)O(7) (M = Cr,Mn, Fe,Co)

A new series of transition-metal oxyhalides (MCl)LaNb(2)O(7) (M = Cr, Mn, Fe, Co) have been prepared by a simple topochemical route. Layered perovskite hosts (ALaNb(2)O(7), A = Li, Na, K or Rb) were reacted with the corresponding anhydrous metal halides under mild reaction conditions (<400 degrees C). The compounds were examined by X-ray powder diffraction; the series appears to be isostructural with (CuCl)LaNb(2)O(7), and the layer spacings, with the exception of M = Co, follow the trend expected from transition-metal cationic radii. Thermal analysis with differential scanning calorimetry (DSC) shows the materials to be metastable where all four compounds decompose exothermically above 690 degrees C.     

Towards a synthetic model of the photosynthetic water oxidizing complex: [Mn3O4(O2CMe)4(bpy)2] containing the [MnIV3(mu-O)4]4+ core

The 3 MnIV title compound has been prepared and characterized by X-ray crystallography and magnetochemistry; the complex contains a [Mn(mu-O)2Mn(mu-O)2Mn]4+ core and possesses an S = 3/2 ground state.     

Spectroscopic characterization of the matrix–silane coupling agent interface in fiber-reinforced composites

The copolymerizations of anhydride-cured epoxy resin on fiberglass surfaces treated with a N-methylaminopropyltrimethoxysilane coupling agent has been investigated using Fourier-transform infrared spectroscopy. The structure of the interface of the silane and the resin in fiber-reinforced composites is composed of copolymers of the epoxy resin with the organofunctionality of the deposited silanes. The number of interfacial bonds formed depends on the amount of silane coupling agent deposited on the fiberglass and the reaction conditions. The silane induces additional esterification and increases the curing density of the epoxy matrix near the fiber surface by about 5–10% relative to the bulk resin.     

Raman spectra of poly(ethylene glycols) in solution

Raman spectra have been obtained from poly(ethylene glycol) (PEG) in the solid and molten phases and in aqueous and chloroform solutions. Several new lines are observed or resolved in the Raman spectrum of the solid state as a result of using a high-power argon-ion laser as a source. The Raman spectra of the molten polymer and the chloroform solutions are indicative of a disordered structure, since additional Raman lines appear as a result of the additional rotational isomers. The Raman spectrum of the aqueous solution shows that considerably less structural change occurs upon dissolution in water.