B−B Bond Nucleophilicity in a Tetraaryl μ-Hydridodiborane(4) Anion

The tetraaryl μ-hydridodiborane(4) anion [ 2 H]⁻ possesses nucleophilic B−B and B−H bonds. Treatment of K[ 2 H] with the electrophilic 9-H-9-borafluorene (HBFlu) furnishes the B₃ cluster K[ 3 ], with a triangular boron core linked through two BHB two-electron, three-center bonds and one electron-precise B−B bond, reminiscent of the prominent [B₃H₈]⁻ anion. Upon heating or prolonged stirring at room temperature, K[ 3 ] rearranges to a slightly more stable isomer K[ 3 a ]. The reaction of M[ 2 H] (M⁺=Li⁺, K⁺) with MeI or Me₃SiCl leads to equimolar amounts of 9-R-9-borafluorene and HBFlu (R=Me or Me₃Si). Thus, [ 2 H]⁻ behaves as a masked [:BFlu]⁻ nucleophile. The HBFlu by-product was used in situ to establish a tandem substitution-hydroboration reaction: a 1:1 mixture of M[ 2 H] and allyl bromide gave the 1,3-propylene-linked ditopic 9-borafluorene 5 as sole product. M[ 2 H] also participates in unprecedented [4+1] cycloadditions with dienes to furnish dialkyl diaryl spiroborates, M[R₂BFlu].     

A paper-based lateral flow assay for morphine

Morphine was used as a model analyte to examine the possibility of using cellulose, physically modified by papermaking and converting techniques, as a capillary matrix in a lateral flow type of diagnostic assay. This research was directed toward low-cost, disposable, and portable paper-based diagnostics, with the aim of addressing the analytical performance of paper as a substrate in the analysis for drugs of abuse. Antibody Fab fragments were used as sensing molecules, and gold nanoparticle detection was employed. Inkjet printing was used to pattern sensing biomolecules as detection zones on paper. To validate the usefulness of paper as a diagnostic platform, the principle of a direct sandwich assay, based on immunocomplex formation between morphine and the anti-morphine Fab fragment and detection of the formed immunocomplex by another Fab fragment, was implemented. Results were compared with that achieved by using nitrocellulose as a reference material. Possible interfering from the sample matrix on assay quality was investigated with spiked oral fluid samples. Under optimized conditions, a visually assessed limit of detection for the sandwich assay was 1 ng/mL, indicating that the paper-based test devices developed in this work can perform screening for drugs of abuse and can fulfill the requirement for a sensitive assay in diagnostically relevant ranges. Fig

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Light scattering by large Saharan dust particles: Comparison of modeling and experimental data for two samples

Light scattering by large mineral-dust particles with small-scale surface roughness is investigated by comparing model simulations with laboratory-measured scattering matrices of two distinct dust samples collected from the Sahara desert. The samples have been chosen on the basis of their large effective radii, and the simulations are based on their measured size distributions. Size parameters larger than about 30 are modeled using a modified ray-optics model RODS (Ray optics with diffuse and specular interactions), while smaller particles are simulated with a T-matrix model. RODS allows us to mimic the surface roughness of large dust particles by covering the particle surface by a thin layer of external scatterers with specific single-scattering properties. The Gaussian-random-sphere geometry is used for the shapes of large dust particles. Small particles are modeled as an axial-ratio distribution of spheroids with smooth surfaces. One of the samples consists wholly of large particles and its scattering matrix can be reproduced very well by the RODS model, except for the phase function. The incorporation of wavelength-scale roughness is, however, necessary for good fits. The other sample, consisting of both small and large particles, proves more challenging to match with simulations. The analysis indicates, however, that the difficulties arise at least partially from the small-particle contribution, while RODS results are consistent with the measurements. Further, the results imply that the agreement with measurements would improve if roughness could also be accounted for in the small-particle simulations. Overall, the RODS method seems promising for modeling the optical properties of mineral-dust particles much larger than the wavelength.     

Azacyanines of the Pyrrolopyrrole Series

The reaction of POCl₃‐activated, readily soluble diketopyrrolopyrrole (DPP) with 2‐aminoheteroaromatics to yield 1:1 and 1:2 hydrogen chelates is described. Complexation of these hydrogen chelates with boron reagents results in thermally and photochemically stable fluorescent dyes (PP–azacyanines). The 1:2 complexes in particular absorb at long wavelengths and are brightly fluorescing. The rich photophysics of the new compounds are presented. Both the pronounced vibrational fine structure of the S₀→S₁ transitions and the observed fluorescence phenomena allow detailed conclusions to be made on the correlation between molecular structure and optical properties.     

Copper‐Mediated ortho‐Nitration of (Hetero)Arenecarboxylates

Various (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho‐position in the presence of [CuNO₃(PPh₃)₂] and AgNO₂ at 50 °C. A microwave‐assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or substituted by aryl‐ or alkoxy‐groups via decarboxylative cross‐coupling.     

Numerical and analytical modelling of trapped gas in micromechanical squeeze-film dampers

Damping in air gaps of micromechanical devices that vibrate out-of-plane is studied at frequencies where the acoustic wavelength is comparable with the air gap dimensions. A FEM study with a viscoacoustic solver shows that above a certain frequency, closed damper borders can be assumed in the approximate analysis of the squeeze-film damper, regardless of the practical border conditions. Here, this closed-border (trapped gas) problem is solved analytically from the linearized Navier–Stokes equations in 1D. This results in a compact model for the mechanical impedance that accounts for damping, inertial and spring forces as well as thermal behaviour and slip border conditions. The model produces the gas resonances in the air gap when the wavelength of the acoustic wave is smaller than the gap dimensions. Due to the slip conditions, the model is valid in modeling micromechanical oscillating structures with small air gaps.