Structural and electronic properties of Si n, Si n+, and AlSi n-1 (n=2-13) clusters: theoretical investigation based on ab initio molecular orbital theory

The geometric and electronic structures of Si(n), Si(n) (+), and AlSi(n-1) clusters (2< or =n< or =13) have been investigated using the ab initio molecular orbital theory under the density functional theory formalism. The hybrid exchange-correlation energy function (B3LYP) and a standard split-valence basis set with polarization functions [6-31G(d)] were employed for this purpose. Relative stabilities of these clusters have been analyzed based on their binding energies, second difference in energy (Delta (2)E) and fragmentation behavior. The equilibrium geometry of the neutral and charged Si(n) clusters show similar structural growth. However, significant differences have been observed in the electronic structure leading to their different stability pattern. While for neutral clusters, the Si(10) is magic, the extra stability of the Si(11) (+) cluster over the Si(10) (+) and Si(12) (+) bears evidence for the magic behavior of the Si(11) (+) cluster, which is in excellent agreement with the recent experimental observations. Similarly for AlSi(n-1) clusters, which is isoelectronic with Si(n) (+) clusters show extra stability of the AlSi(10) cluster suggesting the influence of the electronic structures for different stabilities between neutral and charged clusters. The ground state geometries of the AlSi(n-1) clusters show that the impurity Al atom prefers to substitute for the Si atom, that has the highest coordination number in the host Si(n) cluster. The fragmentation behavior of all these clusters show that while small clusters prefers to evaporate monomer, the larger ones dissociate into two stable clusters of smaller size.     

Effect of formulated ingredients on rapidly disintegrating oral tablets prepared by the crystalline transition method

The aim of this article was to determine the optimal ingredients for the rapidly disintegrating oral tablets prepared by the crystalline transition method (CT method). The effect of ingredients (diluent, active drug substance and amorphous sugar) on the characteristics of the tablets was investigated. The ingredients were compressed and the resultant tablets were stored under various conditions. The oral disintegration time of the tablet significantly depended on diluents, due to differences in the penetration of a small amount of water in the mouth and the viscous area formed inside the tablet. The oral disintegration time was 10-30 s for tablets with a tensile strength of approximately 1 MPa, when erythritol, mannitol or xylitol was used as the diluent. The increase in the tensile strength of tablets containing highly water-soluble active drug substances during storage was as large as that of tablets without active drug substances, while the increase in the tensile strength of tablets containing low water-soluble active drug substances was small. It was therefore found that highly water-soluble active drug substances were more suitable for the formulation prepared by the CT method than low water-soluble active drug substances. Irrespective of the type of amorphous sugar (amorphous sucrose, lactose or maltose) used, the porosity of tablets with 1 MPa of tensile strength was 30-40%, and their oral disintegration time was 10-20 s. The optimal ingredients for rapidly disintegrating oral tablets with reasonable tensile strength and disintegration time were therefore determined from these results.     

Aggregative growth of silicalite-1

Precursor silica nanoparticles can evolve to silicalite-1 crystals under hydrothermal conditions in the presence of tetrapropylammonium (TPA) cations. It has been proposed that in relatively dilute sols of silica, TPA, water, and ethanol, silicalite-1 growth is preceded by precursor nanoparticle evolution and then occurs by oriented aggregation. Here, we present a study of silicalite-1 crystallization in more concentrated mixtures and propose that growth follows a path similar to that taken in the dilute system. Small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), and high-resolution transmission electron microscopy (HRTEM) were used to measure nanoparticle size and to monitor zeolite nucleation and early-stage crystal development. The precursor silica nanoparticles, present in the clear sols prior to crystal formation, were characterized using two SAXS instruments, and the influence of interparticle interactions is discussed. In addition, SAXS was used to detect the onset of secondary particle formation, and HRTEM was used to characterize their structure and morphology. Cryo-TEM allowed for in situ visual observation of the nanoparticle population. Combined results are consistent with growth by aggregation of silica nanoparticles and of the larger secondary crystallites. Finally, a unique intergrowth structure that was formed during the more advanced growth stages is reported, lending additional support for the proposal of aggregative growth.     

Compressed‐gas‐induced crystallization in tert‐butyl poly(ether ether ketone)

tert‐Butyl‐substituted poly(ether ether ketone) (tBuPEEK), which does not undergo crystallization with thermal annealing, crystallizes readily when treated with compressed CO₂. The dissolved CO₂ causes a reduction in the glass‐transition temperature of the polymer–gas system and enhances the chain mobility of the macromolecules, thereby bringing about crystallization. In the presence of CO₂, crystallization is increasingly favored with increasing CO₂ pressure and treatment temperature. The melting point of tBuPEEK crystals increases linearly with the CO₂ pressure applied in the treatment, indicating an increase in the order and/or size of the crystals. The extent of crystallinity increases when small amounts of methanol or dichloromethane are used as a cosolute with CO₂. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1505–1512, 2001     

The first columnar discotic liquid crystalline anthraquinone metal complexes

In this communication we present the synthesis and characterization of the first two members of a new class of metallomesogen. The Pd and Cu complexes of 1-hydroxy-2,3,5,6,7-pentakis(dodecyloxy)anthra-9,10-quinone were prepared by reacting the respective metal(II) acetate with the ligand. Preliminary mesophase characterization by DSC and polarizing optical microscopy indicates the formation of columnar mesophases in both the complexes.     

Preparation and characterization of 1,2,3‐triazole‐cured polymers from endcapped azides and alkynes

Fourteen commercial polyols have been characterized by GPC, NMR spectroscopy, and elemental analysis. From these, eight corresponding tosylates, six nitrate esters, seven mesylates, 13 alkynes, and 14 azides have been prepared and all these derivatives have been fully characterized. Five alkyne monomers and eight azide monomers were also prepared. Twelve alkynes and 13 azides (functionality 2–4) were combined in 1,3‐dipolar cycloaddition reactions under neat conditions to prepare triazole‐cured polymers, avoiding any heavy metal catalyst. Characterization by NMR spectroscopy, elemental analysis, and gel permeation chromatography indicated triazole polymers 14 , 22 , 23 , 28 , and 30 with degrees of polymerization of 17–28 to be the best candidates for future work. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 238–256, 2008