New tridentate cyclometalated platinum(II) and palladium(II) complexes of N,2-diphenyl-8-quinolinamine: syntheses, crystal structures, and photophysical properties

A new tridentate cyclometalated platinum(II) complex derived from N,2-diphenyl-8-quinolinamine, which consists of two crystallographic independent molecules with two intermolecular N-H-Cl-Pt hydrogen bonds forming a dimer, exhibited a low-energy luminescence at ca. 740 nm in a 1 × 10⁻³ M dichloromethane solution and a strong emission centered at 670 nm in a solid state, but the analogous palladium(II) complex was nonemissive at room temperature.     

Isothermal differential scanning calorimetry on an exothermic phenomenon during thermal decomposition of hydromagnesite 4 MgCO3 · Mg(OH)2 · 4 H2O

An exothermic phenomenon and a simultaneous rapid evolution of a small amount of carbon dioxide at ?500°C during thermal decomposition of hydromagnesite 4 MgCO₃ · Mg(OH)₂ · 4 H₂O was studied by isothermal DSCTG in a carbon dioxide atmosphere. It was quantitatively confirmed that the exothermic phenomenon was due to crystallization of MgCO₃ from the amorphous phase and that the evolution of carbon dioxide was due to decomposition of the MgCO₃ by the heat of crystallization (?3.4 kcal mole^?1.     

Inclusion of cut and as-grown single-walled carbon nanotubes in the helical superstructure of schizophyllan and curdlan (beta-1,3-glucans)

We have found that single-chain schizophyllan and curdlan (s-SPG and s-curdlan, respectively) can dissolve as-grown and cut single-walled carbon nanotubes (ag-SWNTs and c-SWNTs, respectively) in aqueous solution. The vis-NIR spectra of the composites suggest that c-SWNTs are dissolved as a bundle, whereas ag-SWNTs exist as one or only a few pieces in the tubular hollow constructed by the helical structure inherent to these beta-1,3-glucans. EDX and CLSM measurements and TEM observation established that the distribution map of these polysaccharides overlaps well with the image of SWNTs, indicating that these two components form a composite. Very interestingly, when c-SWNTs were dissolved with the aid of s-SPG or s-curdlan in water, a clear periodical structure with inclined stripes, as detected by AFM, appeared on the fibrous composite surface. Because this periodical structure has never been recognized for the composites with other water-soluble polymers, one can regard that s-SPG or s-curdlan wraps c-SWNTs constructing a helically twined structure. High-resolution TEM observation of an ag-SWNTs/s-SPG composite gave a clearer image in that two s-SPG chains twine one ag-SWNT and the helical motif is right-handed. When this sample was subjected to the AFM measurement, the composite showed the 2-3 nm height. This height implies that one piece of ag-SWNT is included in the s-SPGs helical structure. As a summary, it has been established that beta-1,3-glucans such as s-SPG and s-curdlan not only dissolve SWNTs but also create a novel superstructure on the surface.     

Polymeric organosilicon systems. XVII. Synthesis and photochemical and conducting properties of poly[o-and m-(disilanylene)phenylene]s

Poly[o-(tetramethyldisilanylene)phenylene] ( 2a ), poly[o-(1,2-dimethyldiphenyldisilanylene)-phenylene] ( 2b ), poly[m-(tetramethyldisilanylene)phenylene] ( 2c ), and poly[m-(1,2-dimethyldiphenyldisilanylene)phenylene] ( 2d ) were prepared by the sodium condensation reaction of the corresponding 1,2-and 1,3-bis (chlorosilyl)benzenes in toluene. Irradiation of thin films of 2a-2d in air resulted in a rapid decrease of absorption maxima in the ultraviolet region. The photolysis of 2b and 2d in benzene afforded photodegradation products with low molecular weights. When thin films of 2b and 2d were doped with antimony pentafluoride vapor, films which have conductivities of semi-conductor level were obtained. © 1993 John Wiley & Sons, Inc.     

Novel phenoxyalkylamine derivatives. VII. Synthesis and pharmacological activities of 2-alkoxy-5-[(phenoxyalkylamino)alkyl]benzenesulfonamide derivatives.

To find a novel alpha-blocker with high alpha-blocking selectivity against dopamine D2-receptor affinity, we performed structural modification of the alkylene chains and the substituents on two benzene rings of 2-alkoxy-5-[(phenoxyalkylamino)alkyl]benzenesulfonamide derivatives. The modification of the alkylene chain between the amino moiety in the center of the molecule and the benzene ring (ring A) was found to be the most significant. 5-[2-[[2-(5-Fluoro-2-methoxyphenoxy)ethyl]amino]propyl]-2- methoxybenzenesulfonamide (II-4), which possesses 1-methylethyl as the alkylene chain, exhibited high alpha-blocking selectivity as well as potent alpha-blocking activity.     

Michael addition reactions of acetoacetates and malonates with acrylates in water under strongly alkaline conditions

Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions.     

Evaluation of mass transfer rate during Ziegler-Natta propylene polymerization

Mass transfer which affects the rate of propylene polymerization with titanium trichloride–triethylaluminum, has been evaluated by use of a new method developed for this heterogeneous reaction. The polymerization was carried out with the usual flask reactor equipped with a paddle stirrer; the rate of gas absorption into the polymerization slurry was proportional to stirring speed and the reciprocal of the total amount of polymers produced. It has been confirmed that the polymerization rate separated from the absorption rate is purely kinetic (propagation), and an effective physical process, such as monomer transfer through a polymer film covering the catalyst surface, no longer exists.