Boron- versus Nitrogen-Centered Nucleophilic Reactivity of (Cyano)hydroboryl Anions: Synthesis of Cyano(hydro)organoboranes and 2-Aza-1,4-diborabutatrienes

Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes.     

A semiclassical adiabatic calculation of state densities for molecules exhibiting torsion: application to hydrogen peroxide and its isotopomers

A practical computational method is discussed for obtaining the rotational–vibrational molecular state densities of molecules with large amplitude torsional degrees of freedom (DoFs). This method goes beyond the traditional harmonic oscillator/rigid rotor or separable hindered rotor approximations in that it includes coupling between the torsion, the remaining vibrational modes, and the overall rotation. The method is based on the vibrationally adiabatic approximation whereby the torsional motion is assumed to be slow compared to the remaining vibrational DoFs although the nonseparability may be large. The torsional coordinate therefore parameterizes the rotational constants and the effective vibrational potential. A semiclassical method is then introduced to calculate the total state density in which the torsion is treated classically while the remaining coordinates are treated quantum mechanically. The method is also formulated for reactive problems in which the density of states is parameterized by a second large amplitude degree of freedom, the reaction coordinate. The performance of the method is assessed using the dissociation reaction of the hydrogen peroxide molecule and its isotopomers. It is found that the method performs well based on numerical tests. The torsional nonseparability is found to yield errors of factors of 2–3 in the statistical rate coefficient when compared with results of traditional separable models.     

Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties

The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes₂)(PiPr₃)₂] and trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂].     

Antibacterial Activity of Pharmaceutical-Grade Rose Bengal: An Application of a Synthetic Dye in Antibacterial Therapies

Rose bengal has been used in the diagnosis of ophthalmic disorders and liver function, and has been studied for the treatment of solid tumor cancers. To date, the antibacterial activity of rose bengal has been sporadically reported; however, these data have been generated with a commercial grade of rose bengal, which contains major uncontrolled impurities generated by the manufacturing process (80–95% dye content). A high-purity form of rose bengal formulation (HP-RBf, >99.5% dye content) kills a battery of Gram-positive bacteria, including drug-resistant strains at low concentrations (0.01–3.13 μg/mL) under fluorescent, LED, and natural light in a few minutes. Significantly, HP-RBf effectively eradicates Gram-positive bacterial biofilms. The frequency that Gram-positive bacteria spontaneously developed resistance to HP-RB is extremely low (less than 1 × 10⁻¹³). Toxicity data obtained through our research programs indicate that HP-RB is feasible as an anti-infective drug for the treatment of skin and soft tissue infections (SSTIs) involving multidrug-resistant (MDR) microbial invasion of the skin, and for eradicating biofilms. This article summarizes the antibacterial activity of pharmaceutical-grade rose bengal, HP-RB, against Gram-positive bacteria, its cytotoxicity against skin cells under illumination conditions, and mechanistic insights into rose bengal’s bactericidal activity under dark conditions.     

Untersuchungen zur heteroepitaktischen Abscheidung von GaP auf GaAs aus der Sn-Lösung

The used liquid-phase epitaxy apparates are described and the experimental conditions of growth on GaP and Ga(AsP) onto GaAs-substrates are reported. The influence of growing conditions (temperature, cooling rate, composition of melt) on the quality of interface and on the inlusion of solvent are discussed. The consequence of varying degrees of substrat-misorientation on the surface morphology has been studied.     

N.M.R. Spectra of the Fuchs0Nes: Structure of Naphthofuchsone

Following the initial synthesis of the fuchsones¹I, (α, η -diphenyl-1,4-benzoquinone methides), numerous substituted members of this series have been described by workers interested in triphenylmethane dyes. The fuchsones have been synthesized by the sulfuric acid condensation of benzilic acid and appropriate phenol¹, by dehydration of 4-hydroxytriphenylcarbinol², by oxidation 4-hydroxytri-phenylmethane and by photochemically induced reactions benzophenones with 2,6-dialkylphenols⁴.     

Loop Groups and Twin Buildings

In these notes we describe some buildings related to complex Kac–Moody groups. First we describe the spherical building of SL_n() (i.e. the projective geometry PG(ⁿ)) and its Veronese representation. Next we recall the construction of the affine building associated to a discrete valuation on the rational function field (z). Then we describe the same building in terms of complex Laurent polynomials, and introduce the Veronese representation, which is an equivariant embedding of the building into an affine Kac–Moody algebra. Next, we introduce topological twin buildings. These buildings can be used for a proof which is a variant of the proof by Quillen and Mitchell, of Bott periodicity which uses only topological geometry. At the end we indicate very briefly that the whole process works also for affine real almost split Kac–Moody groups.Supported by a Heisenberg fellowship by the Deutsche Forschungsgemeinschaft.