An apparent ensemble effect in the oxidative coupling of methane on hydroxyapatites with incorporated lead

The introduction of small quantities of lead into calcium hydroxyapatite catalysts produces marked increases in the selectivity to C₂₊ hydrocarbons, while the conversion of methane remains relatively constant. Small surface concentrations of lead are sufficient to achieve C₂₊ selectivities of 80 and 90%, with oxygen and nitrous oxide, respectively, in contrast with 18 and 46%, respectively, obtained in the absence of lead. Since surface concentration of lead species sufficient to stabilize pairs of methyl radicals in close proximity to each other would be expected to facilitate the formation of C₂ hydrocarbons, an ensemble effect appears to be extant.     

Microporous carbons prepared from cationic surfactant-resorcinol/formaldehyde composites

Microporous carbons have been synthesized by the carbonization of cationic surfactant-resorcinol/formaldehyde (RF) composites, which were themselves formed by electrostatic organic-organic interaction. The porous structure produced by the decomposition of the surfactant plays an important role for the gasification of the RF polymer at higher temperatures. The pore size of the carbon prepared from tetrapropylammonium bromide (TPAB)-RF, cetyltrimethylammonium bromide (C₁₆TAB)-RF and decyltrimethylammonium bromide (C₁₀TAB)-RF mixtures can be estimated as 0.53 nm from the Horvath-Kawazoe method using N₂ adsorption isotherms. Their pore size distributions were very narrow, showing that the microporous carbons derived from surfactant-RF mixture may have promise as adsorbents and membrane materials.     

Structural analysis of cellulose triacetate polymorphs by two-dimensional solid-state C-C and H-C correlation NMR spectroscopies

For the elucidation of the crystal structures of the two crystalline allomorphs of cellulose triacetate (CTA), namely CTA I and CTA II, two-dimensional (2D) solid-state through-bond ¹³C-¹³C and ¹H-¹³C correlations NMR techniques applied to the two crystalline allomorphs of CTA. As a result, the ¹³C and ¹H chemical shifts of the glucopyranose ring of CTA I and CTA II were completely assigned by the 2D NMR spectra of these allomorphs. On the 2D ¹³C-¹³C correlation spectrum of CTA II, two sets of the ¹³C-¹³C correlations from C1 to C6 were observed. This indicated that the CP/MAS ¹³C NMR spectrum of CTA II can be characterized by its overlapping of the ¹³C subspectra of two kinds of 2,3,6-triacetyl-anhydroglucopyranose units and that there are two magnetically non-equivalent sites in the unit cell of CTA II. In the case of CTA I, the numbers of respective ¹³C and ¹H shifts of CTA I agreed with the those of the glucopyranose residue in the allomorph, strongly suggesting that the asymmetric unit of CTA I is only one glucose residue. In addition, conformational differences in the exocyclic C5-C6 bonds between CTA I and CTA II were strongly suggested by the notable differences in the ¹H and ¹³C chemical shifts at the C6 sites of these allomorphs.     

Recoverable shear strain of liquid crystal‐forming concentrated hydroxypropyl cellulose solutions

The recoverable shear strain (S_R) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. S_R greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of S_R on stress and concentration. S_R increased with increasing stress for the single phase and decreased for the biphase. S_R seemed to be related to the die swell (B): S_R ∝ Bⁿ. S_R exhibited a maximum and a minimum with respect to concentration. S_R for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater S_R. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002     

Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

Polymerization of macromers

Summary The possibility of group transfer polymerization of methyl methacrylate-terminated polystyrene macromer (MA-PSt) was explored by using 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene and tris(dimethylamino)sulfonium difluorotrimethylsilicate as initiator and catalyst, respectively. The results obtained at the polymerization temperature of 0°C were undesirable. However, the oligomerization at -78°C gave almost quantitatively oligo(MA-PSt) of which the degree of polymerization was in good agreement with the mole ratio of macromer to initiator. The GPC curve of oligo(MA-PSt) was sharp and symmetrical. In addition, it was shown by the copolymerization with methyl methacrylate that the polymerizability of the macromer was markedly enhanced in the presence of methyl methacrylate comonomer.     

Prediction of the biologically active sites in eclosion hormone from the silkworm, Bombyx mori

The structure-activity relationship of eclosion hormone from the silkworm, Bombyx mori, was analyzed. First, the probable active residues in silkworm eclosion hormone and also tobacco hornworm eclosion hormone were predicted by the average distance map method. To examine the contributions of those residues to the activity of silkworm eclosion hormone, Gly-substituted mutants for those predicted residues were produced by site-directed mutagenesis and their activities were evaluated by a bioassay. Finally, Glu12, Met24 and Phe25 were estimated to be the crucial residues for the eclosion hormone activity. The possibility of the development of a blocker of an eclosion hormone receptor on the basis of the present work is also discussed.      

Structures and electronic properties of surface/edges of nanodiamond and nanographite

The structure, electronic and magnetic properties of nanodiamond and nanographite/nanographene are investigated. Detonation nanodiamond particles that are covered with amorphous graphitic composites are hydrothermally treated to remove the graphitic surface composites and to terminate the surface carbon atoms with hydrogen. The number of localized spins of dangling bonds and the hydrogen concentration increase upon the increase in the hydrothermal treatment time up to 40 h. Above 40 h, both drop discontinuously, a surface structural reconstruction was suggested. The creation of dangling bonds and an incomplete hydrogenation of the surface carbon atoms destabilize the surface, resulting in the structural reconstruction. Nanodiamond particles are thermally converted to nanographite/nanographene. A single nanographene sheet is successfully prepared by heat-treating nanodiamond particles. The edge of graphene sheet with its edge carbon atoms being hydrogen-terminated is investigated by UHV-STM/STS. Zigzag edges are found to have non-bonding π-state of edge origin, in good agreement with theoretical prediction.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.