Origin of enhanced crystal growth kinetics near Tg probed with indomethacin polymorphs

Using three crystal polymorphs of indomethacin (IMC), we tested two interpretations of the enhanced crystal growth kinetics near the glass transition temperature Tg. This enhancement refers to the stronger temperature dependence of liquid viscosity eta than crystal growth rate (corrected for thermodynamic driving force). This enhancement is attributed in the first interpretation to an increase of the number of preferred interfacial growth sites with decreasing temperature and, in the second interpretation, to the breakdown of the Stokes-Einstein relation in deeply supercooled liquids. We measured the growth rates of the IMC polymorphs (alpha, gamma, and delta) from Tg + 9 K (Tg = 314 K) to near the respective melting points. From Tg + 19 K to Tg + 69 K, the growth rates of the polymorphs changed by 10(4) fold but displayed the same temperature dependence (eta-0.78) after corrections for thermodynamic driving forces. These results argue for a liquid-state origin of the enhanced growth kinetics. Below ca. Tg + 19 K, delta IMC continued to grow in the same spherulite morphology but alpha and gamma IMC grew in different, fiberlike morphologies and, if measured consistently, at faster rates. We conclude that the liquid dynamics of IMC controls its crystal growth kinetics over a wide range of temperatures but changes of growth morphologies near Tg also lead to apparent acceleration of growth of certain polymorphs. This work also extended a previous study of D-sorbitol to lower temperatures to enable a broader analysis of crystal growth kinetics of organic molecules near Tg.     

Selective extraction and purification of endohedral metallofullerene from carbon soot

A preferential extraction of endohedral metallofullerenes (EMFs) from carbon soot through the use of reduction in the extraction process and a convenient isolation of endohedral metallofullerene anions (EMFs(-)) and empty fullerenes utilizing their difference in solubility are accomplished. EMFs are easily isolated by one-stage high-performance liquid chromatography after chemical oxidation of the extracted endohedral EMFs(-).     

Electrowetting of aligned carbon nanotube films

Electrowetting is one approach to reducing the interfacial tension between a solid and a liquid. In this method, an electrical potential is applied across the solid/liquid interface which modifies the wetting properties of the liquid on the solid without changing the composition of the solid and liquid phases. Electrowetting of aligned carbon nanotube (CNT) films is investigated by the sessile drop method by dispensing deionized (DI) water or 0.03 M NaCl droplets (contacted by Au wire) onto aligned CNT films assembled on a copper substrate. The results demonstrate that electrowetting can greatly reduce the hydrophobicity of the aligned CNTs; the contact angle saturation for DI water and 0.03 M NaCl droplets occurs at 98 and 50 degrees , respectively. The combined effects of the geometrical roughness and the electrical potential on the contact angle are briefly discussed and modeled. Such a strategy may be invoked to controllably reduce the interfacial tension between carbon nanotubes (CNTs) and polymer precursors when infiltrating the monomers into the prealigned nanotube films.     

On relations between weak approximation properties and their inheritances to subspaces

It is shown that for the separable dual X^∗ of a Banach space X, if X^∗ has the weak approximation property, then X^∗ has the metric weak approximation property. We introduce the properties W^∗D and MW^∗D for Banach spaces. Suppose that M is a closed subspace of a Banach space X such that M^⊥ is complemented in the dual space X^∗, where for all m∈M}. Then it is shown that if a Banach space X has the weak approximation property and W^∗D (respectively, metric weak approximation property and MW^∗D), then M has the weak approximation property (respectively, bounded weak approximation property).     

Efficient electrocatalyst utilization: electrochemical deposition of Pt nanoparticles using nafion membrane as a template

We deposit Pt particles electrochemically on an electrode covered with a Nafion membrane. Platinum ions travel through the hydrophilic channels of the membrane, and platinum deposits are formed at the place where the channels make contact with the planar electrode. This procedure deposits the catalyst only at the end of the hydrophilic channels that cross the membrane; no catalyst is placed under the hydrophobic domains, where it would not be in contact with the electrolyte. By performing a series of cyclic voltammograms with this system, we show that deposition of the platinum through the membrane achieves better platinum utilization than deposition of platinum on the naked electrode followed by the placement of the membrane on top.     

Study of molecular behavior in a water nanocluster: size and temperature effect

Temperature and size effects on the behavior of nanoscale water molecule clusters are investigated by molecular dynamics simulations. The flexible three-centered (F3C) water potential is used to model the inter- and intramolecular interactions of the water molecule. The differences between the structural properties for the surface region and those for the interior region of the cluster are also investigated. It is found that as the temperature rises, the average number of hydrogen bonds per water molecule decreases, but the ratio of surface water molecules increases. After comparing the water densities in interior regions and the average number of hydrogen bonds in those regions, we find there is no apparent size effect on water molecules in the interior region, whereas the size of the water cluster has a significant influence on the behavior of water molecules at the surface region.     

Kinetics of receptor directed assembly of multisegment nanowires

We demonstrate the receptor directed end-to-end assembly of multisegment Au/Ni/Au nanowires under agitation in ethanol. The gold end-segments were functionalized with biotin-terminated thiol thereby restricting aggregation to end-to-end attachment via an avidin linkage. On mixing biotin-terminated nanowires with avidin-terminated nanowires, the average chain length is shown to increase linearly with time. The rate constant was independent of the nanowire concentration. Kinetic Monte Carlo simulations were used to model the self-assembly process, and we show that the directed end-to-end assembly of nanowires is similar to the polycondensation of linear polymers.     

Rapid separation of strychnine and brucine on a dynamically modified poly(dimethylsiloxane) microchip followed by electrochemical detection

A method has been developed for rapidly separating and detecting strychnine and brucine using a poly(dimethysiloxane) (PDMS) microchip and electrochemical (EC) detection. PDMS microchannels dynamically modified by Brij35 are shown to be more efficient than native ones. The two analytes are well separated within 90 s in 70 mmol/L acetate buffer (pH 5.5) containing 0.01% (v/v) Brij35. Detection limits were found to be 1.0 μmol/L for strychnine and 0.2 μmol/L for brucine at S/N=3. The method was used to determine trace strychnine and brucine in rat serum, and the results obtained correlate well with those obtained via high-performance liquid chromatography (HPLC).      

Silicon hydride clusters Si5Hn (n = 3-12) and their anions: structures, thermochemistry, and electron affinities

The molecular structures, electron affinities, and dissociation energies of the Si(5)H(n)/Si(5)H(n)(-) (n = 3-12) species have been calculated by means of three density functional theory (DFT) methods. The basis set used in this work is of double-zeta plus polarization quality with additional diffuse s- and p-type functions, denoted DZP++. The geometries are fully optimized with each DFT method independently. Three different types of the neutral-anion energy separations presented in this work are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). The first Si-H dissociation energies for neutral Si(5)H(n) and its anion have also been reported.     

Study of asymmetric wavenumber shift of the Fermi doublet ν1 − 2ν2 in the Raman spectrum of liquid carbon disulfide

The Raman spectra of liquid carbon disulfide (CS₂) diluted with benzene (C₆H₆) have been measured. By changing the CS₂, the concentration, we found an asymmetric wavenumber shift phenomenon. With decreasing concentration of CS₂, the position of the ν₁ (655 cm⁻¹) band remains practically unchanged, and the 2ν₂ (796 cm⁻¹) band shifts toward higher wavenumbers. To interpret this asymmetric wavenumber shift phenomenon of the Fermi doublet ν₁ − 2ν₂ in the Raman spectra satisfactorily, we propose a modified Bertran model. The values of the Fermi resonance (FR) parameters of CS₂ at different concentrations were calculated using the Bertran equations. In addition, we found the fundamental ν₂, which should be independent of the FR interaction, shifted to higher wavenumbers as the concentration decreased. This shift was probably driven by the tuning of the FR. Copyright © 2009 John Wiley & Sons, Ltd.