A Six-Coordinate Silicon Dihydride Embedded in a Porphyrin: Enhanced Hydride-Donor Properties and the Catalyst-Free Hydrosilylation of CO2

The catalyst-free hydrosilylation of CO₂ under mild conditions remains limited. Herein, we report the synthesis, characterization, and reactivity of 5,10,15,20-tetraphenylporphyrinato(dihydrido)silicon(IV) ( 1 ) as a six-coordinate silicon dihydride. The Si-H moiety of 1 reacts with polar double bonds and CO₂ in the absence of a catalyst to afford hydrosilylated products. Combining the hydrosilylation with subsequent transformation furnishes formic acid from CO₂. Computational studies indicate that the hydride-donor properties of 1 are exceptionally high for a neutral silicon hydride, and that the direct hydride transfer from silicon to carbon is a pivotal step in the hydrosilylation of CO₂ with 1 .     

Preparation and reaction of uracil substituted cyclen and cyclam: formation of tricyclic guanidinium and dihydroimidazolium salts

Di-uracil substituted cyclen derivatives were prepared by the reaction of cyclen with 6-chloro-1-methyluracil or 6-chloro-1,3-dimethyluracil. The reaction of cyclam with 6-chloro-1,3-dimethyluracil gave a similar di-uracil substituted cyclam. The 1,7-di-uracil substituted cyclen was converted to the tricyclic guanidinium salt and acylurea upon heating in DMSO in the presence of weak acid. The 1,8-di-uracil substituted cyclam gave a tricyclic dihydroimidazolium salt under the same conditions. These reactions can be explained by an intramolecular uracil ring-breaking reaction mechanism.     

Removal of fluoride from water through ion exchange by mesoporous Ti oxohydroxide

In our previous study, we found that Ti(OH)(4) exhibited fluoride ion exchange properties. In order to improve the ion exchange capacity, mesoporous Ti oxohydroxide (TiOx(OH)y) had been prepared by using dodecylamine as template. Zirconia and silica had been introduced into the mesoporous Ti oxohydroxide to enhance the ion exchange capacity. The mesoporous structure and the morphology of the mesoporous materials obtained were confirmed using XRD and SEM, respectively. A fluoride ion exchange study was done on each sample. Results showed that mesoporous Ti oxohydroxide containing zirconia exhibited the highest fluoride ion exchange capacity, as it has the smallest particle size, with high uniformity among the mesoporous materials prepared.     

Bound vortex boundary layer control with application to V/STOL airplanes

Effectiveness of the bound vortex boundary layer control is assessed with reference to airfoils modified with a leading edge rotating cylinder. Results of the test program and the numerical models suggest the following:

• The surface singularity method in conjunction with the boundary layer correction scheme is capable of predicting useful information concerning bound vortex boundary layer control. The predicted pressure distributions are in good agreement with experiment almost up to the point of complete separation from the the airfoil surface except near the trailing edge where more accurate results of the flow field would require the modelling of the separated flow region using the full Navier-Stokes equations.

• The concept of bound vortex boundary layer control appears to be quite promising. With cylinder rotation. the flow never separated completely from the upper surface. The higher rates of rotation promoted reattachment of the partially separated flow giving a significant improvement in the maximum lift and stall characteristics.     

Ruthenium-catalyzed alkoxylation of a hydrodisilane without SiSi bond cleavage

Transition metal-catalyzed synthesis of alkoxydisilanes via dehydrogenative coupling of a hydrodisilane with alcohols is reported. During the reaction, the SiSi bond is preserved effectively when [RuCl₂(p-cymene)]₂ is used as a catalyst. Various alcohols can be used in this alkoxylation.     

Near-IR Absorbing J-Aggregate of an Amphiphilic BF2-Azadipyrromethene Dye by Kinetic Cooperative Self-Assembly

A new amphiphilic BF₂-azadipyrromethene (aza-BODIPY) dye 1 has been synthesized using a Cu^I-catalyzed “click” reaction. For this dye, two self-assembly pathways that lead to different type of J-aggregates with distinct near-infrared optical properties have been discovered. The metastable off-pathway product displays a broad, structureless absorption band while the thermodynamically stable on-pathway aggregate exhibits the characteristic spectral features of a J-aggregate, that is, red-shifted intense absorption band with significantly narrowed linewidth. The morphology and structure of the aggregates were studied by atomic force microscopy, transmission and scanning electron microscopy. The aggregation processes of 1 were investigated by temperature- and concentration-dependent UV/Vis spectroscopy and evaluated by models for cooperative self-assembly.     

N-monocarbamoyl derivatives of symmetrical diamines with antiviral activity

Some new N-monocarbamoyl symmetrical diamines have been prepared by the addition of symmetrical amines to isocyanates or isothiocyanates. 2,6-Diaminopyridine (1), (1R,2R)-1,2-diaminocyclohexane [(1R,2R)-2], meso-1,2-diaminocyclohexane (meso-2), or (1R,2R)-1,2-diphenylethylenediamine (3) were used as the starting symmetrical diamine frameworks. All of the newly synthesized compounds were subjected to an evaluation of antiviral activity with herpes simplex virus (HSV)-1. N-Monocarbamoyl 2,6-diaminopyridines (5a, b) showed significant antiviral activity (EC(50)=17.0, 6.2 microg/ml) comparable to that of N-monododecanoyl 2,6-diaminopyridine (A2). As a result, compound 5a showed a better selectivity index (CC(50)/EC(50) = ca. 10.0) than that of A2.     

Synthesis and biological activities of novel furo[2,3,4-jk][2]benzazepin-4(3H)-one derivatives

A novel seven-membered lactam formation method has been established by intramolecular ring closure reaction of 4-bromo-(E)-3-[(2-alkylvinyl)carbonylamino]benzo[b]furans under Heck coupling conditions. A number of furo[2,3,4-jk][2]benzazepin-4(3H)-ones, tricyclicbenzo[b]furans, have been prepared by this method and evaluated for their leukotriene B(4) (LTB(4)) receptor and poly(ADP-ribose)polymerase-1 (PARP-1) inhibitory activities.