Structure and thermal stability of Langmuir-Blodgett films of barium arachidate

The structures of multilayer Langmuir-Blodgett films of barium arachidate before and after heat treatment have been investigated using both atomic force microscopy (AFM) and grazing incidence synchrotron X-ray diffraction (GIXD). AFM gave information on surface morphology at molecular resolution while GIXD provided quantitative details of the lattice structures of the films with their crystal symmetries and lattice constants. As-prepared films contained three coexisting structures: two triclinic structures with the molecularchains tilted by about 20degrees from the film normal and with 3 x 1 or 2 x 2 super-lattice features arising from height modulation of the molecules in the films; a rectangular structure with molecules perpendicular to the film surface. Of these, the 3 x 1 structure is dominant with a loose correlation between the bilayers. In the film plane both superstructures are commensurate with the local structures, having different oblique symmetries. The lattice constants for the 3 x 1 structure are a(s) = 3a = 13.86 Angstrom, b(s) = b = 4.31 Angstrom and gamma(s) = gamma = 82.7degrees; for the 2 x 2 structure a(s) = 2a = 16.54 Angstrom, b(s) = 2b = 9.67 Angstrom, gamma(s) = gamma = 88degrees. For the rectangular structure the lattice constants are a = 7.39 Angstrom, b = 4.96 Angstrom and gamma = 90degrees. After annealing, the 2 x 2 and rectangular structures were not observed, while the 3 x 1 structure had developed over the entire film. For the annealed films the correlation length in the film plane is about twice that in the unheated films, and in the out-of-plane direction covers two bilayers. The above lattice parameters, determined by GIXD, differed significantly from the values obtained by AFM, due possibly to distortion of the films by the scanning action of the AFM tip. (C) 2004 Published by Elsevier B.V.

The problem of purity in evaluating surfactant performance

Labeled surfactants have impurities in the form of un-reacted molecules or distributed products which is a constraint in evaluating its performance. This short review deals with the purity issue of surfactants and is divided into two parts. The first part deals with the methods of purification employed for obtaining a surface chemically pure surfactant for evaluation. In the second part the use of surface chemically impure surfactant in application areas of formulations is presented to highlight the impending impact on reproducibility of results.

Why H Atom Prefers the On-Top Site and Alkali Metals Favor the Middle Hollow Site on the Basal Plane of Graphite

In this work, the different adsorption properties of H and alkali metal atoms on the basal plane of graphite are studied and compared using a density functional method on the same model chemistry level. The results show that H prefers the on-top site while alkali metals favor the middle hollow site of graphite basal plane due to the unique electronic structures of H, alkali metals, and graphite. H has a higher electronegativity than carbon, preferring to form a covalent bond with C atoms, whereas alkaline metals have lower electronegativity, tending to adsorb on the highest electrostatic potential sites. During adsorption, there are more charges transferred from alkali metal to graphite than from H to graphite.

Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2](2+) (Chart 1). By contrast, Stern-Volmer analysis of intermolecular quenching of [ZnL2](2+) by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.

The design of planar gradient coils. Part ll: A weighted superposition method

In this work a superposition technique for designing gradient coils for the purpose of magnetic resonance imaging is outlined, which uses an optimized weight function superimposed upon an initial winding similar to that obtained from the target field method to generate the final wire winding. This work builds on the preliminary work performed in Part I on designing planar insertable gradient coils for high resolution imaging. The proposed superposition method for designing gradient coils results in coil patterns with relatively low inductances and the gradient coils can be used as inserts into existing magnetic resonance imaging hardware. The new scheme has the capacity to obtain images faster with more detail due to the deliver of greater magnetic held gradients. The proposed method for designing gradient coils is compared with a variant of the state-of-the-art target field method for planar gradient coils designs, and it is shown that the weighted superposition approach outperforms the well-known the classical method.

Effect of osmolytes on the interaction of flavin adenine dinucleotide with muscle glycogen phosphorylase b

The effect of three osmolytes, trimethylamine N-oxide (TMAO), betaine and proline, on the interaction of muscle glycogen phosphorylase b with allosteric inhibitor FAD has been examined. In the absence of osmolyte, the interaction is described by a single intrinsic dissociation constant (17.8 muM) for two equivalent and independent binding sites on the dimeric enzyme. However, the addition of osmolytes gives rise to sigmoidal dependencies of fractional enzyme-site saturation upon free inhibitor concentration. The source of this cooperativity has been shown by difference sedimentation velocity to be an osmolyte-mediated isomerization of phosphorylase b to a smaller dimeric state with decreased affinity for FAD. These results thus have substantiated a previous inference that the tendency for osmolyte-enhanced self-association of dimeric glycogen phosphorylase b in the presence of AMP was being countered by the corresponding effect of molecular crowding on an isomerization of dimer to a smaller, nonassociating state. (C) 2004 Elsevier Ltd. Inc. All rights reserved.

Synthesis of gadolinium-labeled shell-crosslinked nanoparticles for magnetic resonance imaging applications

Shell-crosslinked knedel-like nanoparticles (SCKs; knedel is a Polish term for dumplings) were derivatized with gadolinium Shell chelates and studied as robust magnetic-resonance-imaging-active structures with hydrodynamic diameters of 40 +/- 3 nm. SCKs possessing an amphiphilic core-shell morphology were produced from the aqueous assembly of diblock copolymers of poly(acrylic acid) (PAA) and poly(methyl acrylate) (PMA), PAA(52)-b-PMA(128), and subsequent covalent crosslinking by amidation upon reaction with 2,2'-(ethylenedioxy)bis(ethylamine) throughout the shell layer. The properties of these materials, including non-toxicity towards mammalian cells, non-immunogenicity within mice, and capability for polyvalent targeting, make them ideal candidates for utilization within biological systems. The synthesis of SCKs derivatized with Gd-III and designed for potential use as a unique nanometer-scale contrast agent for MRI applications is described herein. Utilization of an amino-functionalized diethylenetriaminepentaacetic acid-Gd analogue allowed for direct covalent conjugation throughout the hydrophilic shell layer of the SCKs and served to increase the rotational correlation lifetime of the Gd. In addition, the highly hydrated nature of the shell layer in which the Gd was located allowed for rapid water exchange; thus, the resulting material demonstrated large ionic relaxivities (39 s(-1) mM(-1)) in an applied magnetic field of 0.47 T at 40 degrees C and, as a result of the large loading capacity of the material, also demonstrated high molecular relaxivities (20 000 s(-1) mM(-1)).

Organic-inorganic poly(methyl methacrylate) hybrids with confined polyhedral oligosilsesquioxane macromonomers

We herein report the synthesis of organic-inorganic hybrid poly(methyl methacrylate) containing 1 polyhedral oligosilsesquioxanes. Octakis(3-hydroxypropyldimethylsiloxy)octasilsesquioxane (OHPS) was synthesized from octakis(hydridodimethylsiloxy)octasilsesquioxane [Si8O12(OSiMe2H)(8), Q(8)M(8)(H)] following literature procedures. Octakis(tnethacryloxypropyldimethylsiloxy) octasilsesquioxane (OMPS) was synthesized via the reaction of methacryloyl chloride or methacrylic acid anhydride with OHPS, with the latter giving improved purity. Polymerization of OMPS with methyl inethacrylate using a dibenzoylperoxide initiator gave a highly cross-linked polymer. Characterization of the polymer was performed using Fourier transform IR spectroscopy, Si-29 NMR, differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, and transmission electron microscopy with energy-dispersive X-ray analysis. The polymer was found to be largely homogeneous. Increasing the OMPS concentration in the polymer gave increased decomposition and glass transition temperatures.

Quantitative fluorescence excitation spectra of synthetic eumelanin

Previously reported excitation spectra for eumelanin are sparse and inconsistent. Moreover, these studies have failed to account for probe beam attenuation and emission reabsorption within the samples, making them qualitative at best. We report for the first time quantitative excitation spectra for synthetic eumelanin, acquired for a range of solution concentrations and emission wavelengths. Our data indicate that probe beam attenuation and emission reabsorption significantly affect the spectra even in low-concentration eumelanin solutions and that previously published data do not reflect the true excitation profile. We apply a correction procedure (previously applied to emission spectra) to account for these effects. Application of this procedure reconstructs the expected relationship of signal intensity with concentration, and the normalized spectra show a similarity in form to the absorption profiles. These spectra reveal valuable information regarding the photophysics and photochemistry of eumelanin. Most notably, an excitation peak at 365 urn (3.40 eV), whose position is independent of emission wavelength, is possibly attributable to a 5,6-dihydroxyindole-2-carboxylic acid (DHICA) component singly linked to a polymeric structure.

Surface morphology dependent photoluminescence from colloidal silicon nanocrystals

Monodisperse 1-2 nm silicon nanocrystals are synthesized in reverse micelles and have their surfaces capped with either allylamine or 1-heptene to produce either hydrophilic or hydrophobic silicon nanocrystals. Optical characterization (absorption, PL, and time-resolved PL) is performed on colloidal solutions with the two types of surface-capped silicon nanocrystals with identical size distributions. Direct evidence is obtained for the modification of the optical properties of silicon nanocrystals by the surface-capping molecule. The two different surface-capped silicon nanocrystals show remarkably different optical properties.

Energy transfer dynamics of nanocrystal-polymer composites

Steady-state and time-resolved photoluminescence spectroscopy are used to examine the photoluminescent properties of nanocrystal-polymer composites consisting of colloidal PbS nanocrystals blended with poly(2-methoxy-5(2-ethylhexyloxy)-p-phenylene vinylene). Quenching of the emission from the conjugated polymer due to the PbS nanocrystals is observed along with band edge emission from the ligand capped PbS nanocrystals. A decrease in the photoluminescence lifetime of MEH-PPV is also observed in the thin film nanocrystal-polymer composite materials. Photoluminescence excitation spectroscopy of the PbS nanocrystal emission from the composite shows features attributed to MEH-PPV providing evidence of a Forster transfer process.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Microstructure of MmM(5)/Mg multi-layer films prepared by magnetron sputtering

Microstructure of MmNi(3.5)(CoAlMn)(1.5)/Mg (here Mm denotes La-rich mischmetal) multi-layer hydrogen storage thin films prepared by direct current magnetron sputtering was investigated by cross-sectional transmission electron microscopy (XTEM). It was shown that the MMM5 layers are composed of two regions: an amorphous region with a thickness of similar to 4nm at the bottom of the layers and a randomly orientated nanocrystallite region on the top of the amorphous region and the Mg layers consist of typical columnar crystallite with their [001] direction nearly parallel to the growth direction. The mechanism for the formation of the above microstructure characteristics in the multi-layer thin films has been proposed. Based on the microstructure feature of the multi-layer films, mechanism for the apparent improvement of hydrogen absorption/desorption kinetics was discussed. (c) 2005 Elsevier B.V. All rights reserved.

Scaling laws for the critical rupture thickness or common thin films

Despite decades of experimental and theoretical investigation on thin films, considerable uncertainty exists in the prediction of their critical rupture thickness. According to the spontaneous rupture mechanism, common thin films become unstable when capillary waves. at the interfaces begin to grow. In a horizontal film with symmetry at the midplane. unstable waves from adjacent interfaces grow towards the center of the film. As the film drains and becomes thinner, unstable waves osculate and cause the film to rupture, Uncertainty sterns from a number of sources including the theories used to predict film drainage and corrugation growth dynamics. In the early studies, (lie linear stability of small amplitude waves was investigated in the Context of the quasi-static approximation in which the dynamics of wave growth and film thinning are separated. The zeroth order wave growth equation of Vrij predicts faster wave growth rates than the first order equation derived by Sharma and Ruckenstein. It has been demonstrated in an accompanying paper that film drainage rates and times measured by numerous investigations are bounded by the predictions of the Reynolds equation and the more recent theory of Manev, Tsekov, and Radoev. Solutions to combinations of these equations yield simple scaling laws which should bound the critical rupture thickness of foam and emulsion films, In this paper, critical thickness measurements reported in the literature are compared to predictions from the bounding scaling equations and it is shown that the retarded Hamaker constants derived from approximate Lifshitz theory underestimate the critical thickness of foam and emulsion films, The non-retarded Hamaker constant more adequately bounds the critical thickness measurements over the entire range of film radii reported in the literature. This result reinforces observations made by other independent researchers that interfacial interactions in flexible liquid films are not adequately represented by the retarded Hamaker constant obtained from Lifshitz theory and that the interactions become significant at much greater separations than previously thought. (c) 2005 Elsevier B.V. All rights reserved.