Controlled Zn‐Mediated Grafting of Thin Layers of Bipodal Diazonium Salt on Gold and Carbon Substrates

A controlled, rapid, and potentiostat‐free method has been developed for grafting the diazonium salt (3,5‐bis(4‐diazophenoxy)benzoic acid tetrafluoroborate (DCOOH)) on gold and carbon substrates, based on a Zn‐mediated chemical dediazonation. The highly stable thin layer organic platforms obtained were characterized by cyclic voltammetry, AFM, impedance, XP, and Raman spectroscopies. A dediazonation mechanism based on radical formation is proposed. Finally, DCOOH was proved as a linker to an aminated electroactive probe.     

Synthesis and Applications of Silyl 2‐Methylprop‐2‐ene‐1‐sulfinates in Preparative Silylation and GC‐Derivatization Reactions of Polyols and Carbohydrates

Trimethylsilyl, triethylsilyl, tert‐butyldimethylsilyl, and triisopropylsilyl 2‐methylprop‐2‐ene‐1‐sulfinates were prepared through (CuOTf)₂?C₆H₆‐catalyzed sila‐ene reactions of the corresponding methallylsilanes with SO₂ at 50 °C. Sterically hindered, epimerizable, and base‐sensitive alcohols gave the corresponding silyl ethers in high yields and purities at room temperature and under neutral conditions. As the byproducts of the silylation reaction (SO₂+isobutylene) are volatile, the workup was simplified to solvent evaporation. The developed method can be employed for the chemo‐ and regioselective semiprotection of polyols and glycosides and for the silylation of unstable aldols. The high reactivity of the developed reagents is shown by the synthesis of sterically hindered per‐O‐tert‐butyldimethylsilyl‐α‐d ‐glucopyranose, the X‐ray crystallographic analysis of which is the first for a per‐O‐silylated hexopyranose. The per‐O‐silylation of polyols, hydroxy carboxylic acids, and carbohydrates with trimethylsilyl 2‐methylprop‐2‐ene‐1‐sulfinate was coupled with the GC analysis of nonvolatile polyhydroxy compounds both qualitatively and quantitatively.     

Locking of Turing patterns in the chlorine dioxide-iodine-malonic acid reaction with one-dimensional spatial periodic forcing

We use the photosensitive chlorine dioxide-iodine-malonic acid reaction-diffusion system to study wavenumber locking of Turing patterns with spatial periodic forcing. Wavenumber-locked stripe patterns are the typical resonant structures that labyrinthine patterns exhibit in response to one-dimensional forcing by illumination when images of stripes are projected on a working medium. Our experimental results reveal that segmented oblique, hexagonal and rectangular patterns can also be obtained. However, these two-dimensional resonant structures only develop in a relatively narrow range of forcing parameters, where the unforced stripe pattern is in close proximity to the domain of hexagonal patterns. Numerical simulations based on a model that incorporates the forcing by illumination using an additive term reproduce well the experimental observations. These findings confirm that additive one-dimensional forcing can generate a two-dimensional resonant response. However, such a response is considerably less robust than the effect of multiplicative forcing.     

Aryl–Aryl Interactions in (Aryl-Perhalogenated) 1,2-Diaryldisilanes

Three 1,2-diaryltetramethyldisilanes X₅C₆-(SiMe₂)₂-C₆X₅ with two C₆H₅, C₆F₅, or C₆Cl₅ groups were studied concerning the importance of London dispersion driven interactions between their aryl groups. They were prepared from 1,2-dichlorotetramethyldisilane by salt elimination. Their structures were determined in the solid state by X-ray diffraction and for free molecules by gas electron-diffraction. The solid-state structures of the fluorinated and chlorinated derivatives are dominated by aryl–aryl interactions. Unexpectedly, Cl₅C₆-(SiMe₂)₂-C₆Cl₅ exists exclusively as an eclipsed syn-conformer in the gas phase with strongly distorted Si-C₆Cl₅ units due to strong intramolecular interactions. In contrast, F₅C₆-(SiMe₂)₂-C₆F₅ reveals weaker interactions. The contributions to the total interaction energy were analyzed by SAPT calculations.     

Dependence of the redshifted and blueshifted photoluminescence spectra of single In(x)Ga(1-x)As/GaAs quantum dots on the applied uniaxial stress

We apply external uniaxial stress to tailor the optical properties of In(x)Ga(1-x)As/GaAs quantum dots. Unexpectedly, the emission energy of single quantum dots controllably shifts to both higher and lower energies under tensile strain. Theoretical calculations using a million atom empirical pseudopotential many-body method indicate that the shifting direction and magnitude depend on the lateral extension and more interestingly on the gallium content of the quantum dots. Our experimental results are in good agreement with the underlying theory.     

Creep prediction of a layered fiberglass plastic

The results of short-term creep tests of a layered glass fiber/polyester resin plastic in tension at angles of 90, 70, and 45° to the direction of the principal fiber orientation are presented. The applicability of the principle of time-temperature analogy for the prediction of long-term creep of the composite and its structural components is revealed. The possibility of evaluating the viscoelastic properties of the composite from the properties of structural components is shown.Presented at the 10th International Conference on the Mechanics of Composite Materials (Riga, April 20–23, 1998).Translated from Mekhanika Kompozitnykh Materialov, Vol. 34, No. 3, pp. 295–306, May–June, 1998.     

Minimal Submanifolds in Sp+3 with Constant Scalar Curvature

Let M be a compact, minimal 3-dimensional submanifold with constant scalar curvature R immersed in the standard sphere S^3+p. In codimension 1, we know from the work that has been done on Chern’s conjecture that M is isoparametric and R = 3D0, R = 3D3 or R = 3D6. In this paper we extend this result from codimension one to compact submanifolds with a flat normal bundle and give a complete classification.     

Markov Chain Analysis for One-Dimensional Asynchronous Cellular Automata

We consider the finite homogeneous Markov chain induced by a class of one-dimensional asynchronous cellular automata—automata that are allowed to change only one cell per iteration. Furthermore, we confine to totalistic automata, where transitions depend only on the number of 1s in the neighborhood of the current cell. We consider three different cases: (i) size of neighborhood equals length of the automaton; (ii) size of neighborhood two, length of automaton arbitrary; and (iii) size of neighborhood three, length of automaton arbitrary. For each case, the associated Markov chain proves to be ergodic. We derive simple-form stationary distributions, in case (i) by lumping states with respect to the number of 1s in the automaton, and in cases (ii) and (iii) by considering the number of 0–1 borders within the automaton configuration. For the three-neighborhood automaton, we analyze also the Markov chain at the boundary of the parameter domain, and the symmetry of the entropy. Finally, we show that if the local transition rule is exponential, the stationary probability is the Boltzmann distribution of the Ising model.     

Synthesis of allyl sulfones from potassium allyltrifluoroborates

Potassium allyltrifluoroborates underwent a bora-ene reaction with sulfur dioxide in the absence of Lewis acid catalysts to give sulfinyloxy-trifluoroborates, which subsequently undergo alkylation with electrophiles to produce sulfones in up to 91% yield. Benzyl halides and haloacetic acid derivatives can be used as the alkylation reagents while the Sanger reagent undergoes a S_NAr reaction with sulfinyloxy-trifluoroborates to produce the corresponding 2,4-dinitrophenylsulfone. The developed method allows the transformation of potassium allyltrifluoroborates into allyl sulfones.