One-pot synthesis of stable NIR tetracene diimides via double cross-coupling

Tetracene tetracarboxylic diimides have been synthesized based on direct double ring extension of electron-deficient naphthalene diimides involving metallacyclopentadienes. Atomic structure and electronic transitions responsible for their NIR absorption spectra are investigated with quantum-chemical calculations. In light of their unique structure and admirable photophysical and electronic properties, this new molecular skeleton is promising candidate for n-type semiconductors.     

Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays

The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)₃]²⁺, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L^?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches.     

A random telegraph signal of Mittag-Leffler type

A general method is presented to explicitly compute autocovariance functions for non-Poisson dichotomous noise based on renewal theory. The method is specialized to a random telegraph signal of Mittag-Leffler type. Analytical predictions are compared to Monte Carlo simulations. Non-Poisson dichotomous noise is non-stationary and standard spectral methods fail to describe it properly as they assume stationarity.     

Incorporation of smooth spherical bodies in the Lattice Boltzmann method

A method to simulate bodies suspended in a Lattice Boltzmann solvent is proposed. It is based on a generalized reaction force that enforces no-slip boundary conditions at the fluid–body interface as the limiting case of an iterative procedure. A smooth version of the Heaviside function allows to treat spherical particles of arbitrary size and produces smooth hydrodynamic forces as particles move in the continuum. Numerical tests demonstrate the accuracy of the method in reproducing the hydrodynamic field around a single particle and the fluid-mediated forces between pairs of particles. The drag force experienced by a particle moving in a straight channel and at various Reynolds numbers is studied as a non-trivial testcase.     

Experimental and theoretical analysis of bias ionization by?α-particles in a nitrogen laser

Nitrogen laser performance with TE configuration and wedge electrodes is analyzed with background ionization in the laser discharge channel by α particles at a low exposition rate. With the bias ionization, the laser power presents two peaks as a function of gas pressure, with one at the normal low pressure, without bias ionization, and the other at high pressure generated by bias ionization. A simple theoretical model has been developed in a trial to understand this behavior. This model was first tested in later results for a TE configuration nitrogen laser, with flat electrodes, without and with bias ionization. It has been observed that due to the competition between electrode shielding by positively charged α particles and bulk ionization by impact, the laser energy is suppressed with pressure below 50 Torr and enhanced above it.     

Novel stereocontrolled addition of allylmetal reagents to alpha-imino esters: efficient synthesis of chiral tetrahydroquinoline derivatives

To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives.     

High-performance liquid chromatographic/tandem mass spectrometric identification of the phototransformation products of tebuconazole on titanium dioxide

Tebuconazole is a widely used fungicide. The formation of by-products on irradiated titanium dioxide as a photocatalyst was evaluated. Several species derived from tebuconazole degradation were identified and characterized by HPLC/MS(n). A pattern of reactions accounting for the observed intermediates is proposed. Different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds), leading to a wide range of intermediate compounds. All these molecules are more hydrophylic than tebuconazole. The main steps involved are (1) the hydroxylation of the molecule with the formation of three species having [M + H](+) 324; the hydroxylation occurs on the C-1 carbon and on the aromatic ring in the two ortho-positions; (2) the cleavage of a C--C bond with the release of the tert-butyl moiety and the formation of a species having m/z 250; analogously to step 1, also on this species a further hydroxylation reaction occurs; (3) through the loss of the triazole moiety with the formation of a structure with m/z 257.