Calix(8)arene LB Superlattices: Pyroelectric Molecular Baskets

Carboxyl and amino groups have been inserted into calix(8) arene rings in order to yield two materials which, when processed as alternate layer Langmuir-Blodgett assemblies, exhibit the pyroelectric effect. Such a temperature-dependent electric polarisation arises partially from the proton transfer between the acid and amine groups. The calix(8) arene system has been selected owing to the extreme tinness, of each monolayer(~1.0 nm), the resulting high density of acid-amine pairs and the very high thermal stability exhibited by calixarenes(typically m.p.>200℃).     

Radical 4-exo cyclizations via template catalysis

The mechanism of catalytic 4-exo cyclizations without gem-dialkyl substitution was investigated by a comparison of cyclic voltammetry, EPR, and computational studies with previously published synthetic results. The most active catalyst is a super-unsaturated 13-electron titanocene(III) complex that is formed by supramolecular activation through hydrogen bonding. The template catalyst binds radicals via a two-point binding that is mandatory for the success of the 4-exo cyclization. The computational investigations revealed that formation of the observed trans-cyclobutane product is not possible from the most stable substrate radical. Instead, the most stable product is formed with the lowest energy of activation from a disfavored substrate in a Curtin-Hammett related scenario.     

Restricted photochemistry in the molecular solid state: structural changes on photoexcitation of Cu(I) phenanthroline metal-to-ligand charge transfer (MLCT) complexes by time-resolved diffraction

The excited-state structure of [Cu(I)[(1,10-phenanthroline-N,N') bis(triphenylphosphine)] cations in their crystalline [BF(4)] salt has been determined at both 180 and 90 K by single-pulse time-resolved synchrotron experiments with the modified polychromatic Laue method. The two independent molecules in the crystal show distortions on MLCT excitation that differ in magnitude and direction, a difference attributed to a pronounced difference in the molecular environment of the two complexes. As the excited states differ, the decay of the emission is biexponential with two strongly different lifetimes, the longer lifetime, assigned to the more restricted molecule, becoming more prevalent as the temperature increases. Standard deviations in the current Laue study are very much lower than those achieved in a previous monochromatic study of a Cu(I) 2,9-dimethylphenanthroline substituted complex ( J. Am. Chem. Soc. 2009 , 131 , 6566 ), but the magnitudes of the shifts on excitation are similar, indicating that lattice restrictions dominate over the steric effect of the methyl substitution. Above all, the study illustrates emphatically that molecules in solids have physical properties different from those of isolated molecules and that their properties depend on the specific molecular environment. This conclusion is relevant for the understanding of the properties of molecular solid-state devices, which are increasingly used in current technology.     

Validation of an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue

The aim of this investigation was to develop receiver and extraction fluids, and subsequently validate an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue using a Franz diffusion cell. The solubility and stability of flurbiprofen in a suitable receiver fluid, and a suitable extraction method and fluid to recover and quantitate flurbiprofen from human pharynx tissue, were investigated using high‐performance liquid chromatography (HPLC). The potential interference of human pharynx tissue in the receiver fluid was also investigated. The HPLC analytical method was successfully validated according to current guidelines. The final receiver fluid demonstrated sufficient solubility and stability, and the extraction method and fluid resulted in >95% recovery of flurbiprofen following exposure to human pharynx tissue. The lower limit of quantitation of flurbiprofen was 0.045 μg/mL in both the receiver and extraction fluids. There was no interference of the human pharynx tissue with the HPLC method. This investigation validated an analytical method for quantitating flurbiprofen, and determined a suitable receiver fluid and extraction method and fluid, which can be used to investigate the permeation and penetration of flurbiprofen through human pharynx tissue using the Franz diffusion cell method.     

Fabrication and activity of silicate nanoparticles and nanosilicate-entrapped enzymes using polyethyleneimine as a biomimetic polymer

In nature, some peptides induce precipitation of silicic acid into silica nanoparticles such as is found in marine algae called diatoms. However, polybasic polymers can act as peptide mimics; one such polymer, polyethyleneimine (PEI), has the advantage that it is stable at room temperature and is inexpensive, in comparison with synthetic peptides. We describe the fabrication and characterization of biosilicate nanoparticles formed by mimicking the peptides using PEI. Brownian motion nanoparticle tracking analysis and field emission gun scanning electron microscopy have been used for the first time to characterize nanoparticles made with tetramethyl orthosilicate (TMOS) and PEI to investigate the fundamental factors that affect particle properties. These factors include the effect of phosphate concentration, PEI molecular weight, TMOS concentration, and species of alkoxy-silane used. The properties of the particles are compared with other particles made with polymers that induce silication. Our results show that using PEI gives differences in particle size compared with previous work using other polymers that induce silication. The entrapment of enzymes during the silication process, rationale for using nonphosphate and phosphate buffers during enzyme entrapment, and the analysis of enzyme activity are also presented. Because enzymes can be entrapped during fabrication, it means that there are many future possibilities for the use of silicate nanoparticles containing enzymes, such as biosensors and biocatalytic reactors.     

Recovery of organic acids from fermentation broths

Rising concerns over the use of fossil resources have generated renewed interest in the production of commodity chemicals via fermentation. Organic acids are a particularly attractive target because their functionality enables downstream catalytic upgrading to a variety of compounds. In this article, we survey how common technical issues are addressed in the recovery schemes for several organic acids. We present results for the recovery of acetate using a new method based on amine complexation. Our reactive separation scheme produces a high-purity product, is energy efficient, and avoids the coproduction of a waste salt coproduct, all prerequisites for a large-scale production process.     

Phase and orientational ordering of low molecular weight rod molecules in a quenched liquid crystalline polymer matrix with mobile side chains

We study the phase diagram and orientational ordering of guest liquid crystalline (LC) rods immersed in a quenched host made of a liquid crystalline polymer (LCP) matrix with mobile side chains. The LCP matrix lies below the glass transition of the polymer backbone. The side chains are mobile and can align to the guest rod molecules in a plane normal to the local LCP chain contour. A field theoretic formulation for this system is proposed and the effects of the LCP matrix on LC ordering are determined numerically. We obtain simple analytical equations for the nematic/isotropic phase diagram boundaries. Our calculation show a nematic-nematic (N/N) first order transition from a guest stabilized to a guest-host stabilized region and the possibility of a reentrant transition from a guest stabilized nematic region to a host only stabilized regime separated by an isotropic phase. A detailed study of thermodynamic variables and interactions on orientational ordering and phases is carried out and the relevance of our predictions to experiments and computer simulations is presented.     

Unprecedented oxo-titanium citrate complex precipitated from aqueous citrate solutions, exhibiting a novel bilayered Ti8O10 structural core

Aqueous titanium citrate solutions were prepared from the reaction of citric acid with titanium 2-propoxide in a range of molar ratios. Solutions containing two or fewer citrates per titanium resulted in the slow crystallization of an insoluble titanium oxo-citrate complex. Single-crystal X-ray analysis identified the species as Ti(8)O(10)(citrate)(4)(H(2)O)(12).14H(2)O.3HOPr(i)(), crystallized in the tetragonal space group I4(1)/a, with a = 30.775(7) A, c = 14.528(7) A, V = 13 759(8) A(3), and Z = 8. The trianionic citrate ligands supply both carboxylate and alkoxide coordination and stabilize the structure using simultaneous chelating and bridging modes of attachment. The compound is a neutral species, exhibiting titanium in three contrasting environments. Laser Raman microscopy and (13)C CPMAS solid-state NMR data were consistent with those of the X-ray crystal structure. When exposed to air, the crystals rapidly lost water and became a powder. The dehydrated powder was noncrystalline to X-rays and insoluble, but (13)C NMR results demonstrated retention of the carboxylate linkages.     

Novel carbohydrate-appended metal complexes for potential use in molecular imaging

Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) ((99m)Tc/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L(1)), 1,3-diamino-2-propyl beta-D-xylopyranoside (L(2)), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L(3)), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L(4)), 1,3-diamino-2-propyl beta-D-galactopyranoside (L(5)), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyranoside) (L(6)), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L(7)). The Re complexes [Re(L(1)-L(7))(Br)(CO)(3)] were characterized by (1)H and (13)C 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L(2))(CO)(3)Br] and [Re(L(3))(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H(2)O established that the complexes exist as [Re(L(1)-L(7))(H(2)O)(CO)(3)]Br in aqueous conditions. Radiolabelling of L(1)-L(7) with [(99m)Tc(H(2)O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period.     

Altered mechanisms of reactions of phosphate esters bridging a dinuclear metal center

Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer.