Microwave spectra of isotopic pyrazoles and molecular structure of pyrazole

Microwave spectra of the complete set of monosubstituted isotopic pyrazoles have been investigated and the complete r_s structure of pyrazole determined. The deuterated and ¹⁵N species of pyrazole were prepared, while the ¹³C species were examined in natural abundance. The spectrum of the parent compound was remeasured yielding rotational and centrifugal distortion constants.The mutual position of the hydrogen atoms and the direction of the dipole moment in the pyrazole principal axis system has been unambiguously established.The ¹⁴N quadrupole hyperfine structure was resolved and the quadrupole coupling constants derived by Blackman et al. [8] were confirmed.An estimated r_z structure is compared to crystal structures derived by X-ray and neutron diffraction showing the N-H bond in the crystal to be prolonged. But, otherwise no significant differences seem to develop when bringing the molecule from its isolated state into the crystal with its strong hydrogen bonds.     

Radioisotope in Wissenschaft und Technik

Zusammenfassung Es werden einige Beispiele für die Anwendung der Tracer-methode angeführt, die nicht so allgemein bekannt sind wie ihre Ausnutzung für Probleme der Biologie oder der reinen Chemic.     

Functionalized carbo- and heterocycles via Pt-catalyzed asymmetric alkoxycyclization of 1,6-enynes

This paper describes the asymmetric version of highly atom-economical alkoxycyclization of 1,6-enynes, using a combination of silver salts with the Pt(II)/(R)-Ph-BINEPINE system.     

Nonconservative earthquake model of self-organized criticality on a random graph

We numerically investigate the Olami-Feder-Christensen model on a quenched random graph. Contrary to the case of annealed random neighbors, we find that the quenched model exhibits self-organized criticality deep within the nonconservative regime. The probability distribution for avalanche size obeys finite size scaling, with universal critical exponents. In addition, a power law relation between the size and the duration of an avalanche exists. We propose that this may represent the correct mean-field limit of the model rather than the annealed random neighbor version.     

Exponential Decay of Correlations for Strongly Coupled Toom Probabilistic Cellular Automata

We investigate the low-noise regime of a large class of probabilistic cellular automata, including the North-East-Center model of Toom. They are defined as stochastic perturbations of cellular automata belonging to the category of monotonic binary tessellations and possessing a property of erosion. We prove, for a set of initial conditions, exponential convergence of the induced processes toward an extremal invariant measure with a highly predominant spin value. We also show that this invariant measure presents exponential decay of correlations in space and in time and is therefore strongly mixing.     

Thin-layer chromatography of green leaves extracts: Zinc migrates into pheophytin on TLC silica plates with fluorescence indicator (F254)

JPC – Journal of Planar Chromatography – Modern TLC -     

Asymmetric Brønsted Base Catalyzed and Directed [3+2] Cycloaddition of 2‐Acyl Cycloheptatrienes with Azomethine Ylides

Conjugated cyclic trienes have the potential for different types of cycloaddition reactions. In the present work, we will, in a novel asymmetric cycloaddition reaction, demonstrate that the organocatalytic reaction of 2‐acyl cycloheptatrienes with azomethine ylides proceeds as a [3+2] cycloaddition, which is in contrast to the Lewis acid‐catalyzed reaction, in which a [3+6] cycloaddition takes place. In the presence of a chiral organosuperbase, 2‐acyl cycloheptatrienes react in a highly enantioselective manner in the [3+2] cycloaddition with azomethine ylides, providing the 1,3‐dipolar cycloaddition product in high yields and up to 99 % ee. It is also shown that the diene formed by the reaction can undergo stereoselective dihydroxylation, bromination, and cycloaddition reactions. Finally, based on experimental observations, some mechanistic considerations are discussed.     

Enzyme-linked immunosensor based on super paramagnetic nanobeads for easy and rapid detection of okadaic acid

Okadaic acid (OA), a lipophilic phycotoxin highly toxic to humans is produced by toxigenic dinoflagellates. The need to develop high performing methods for OA analysis able to improve the traditional ones is evident. In this work, competitive indirect enzyme-linked electrochemical immunosensor based on super paramagnetic nanobeads has been developed for the detection of OA. Streptavidin-coated magnetic beads were used as support to immobilize the biotinylated OA. Preliminary, colorimetric tests were performed in order to optimize different experimental parameters. Electrochemical detection was carried out by differential pulse voltammetry (DPV). The limit of detection (LOD) (0.38 μg L⁻¹), the mid point value (IC₅₀) (3.15 μg L⁻¹) and the time needed (60 min) for analysis of a real sample validated the developed electrochemical immunosensor as a promising tool for routine use. The matrix effect and the recovery rate were also assessed, showing an excellent percentage of recovery.     

Electron Transfer in the Cs⊂{Mn4Fe4} Cubic Switch: A Soluble Molecular Model of the MnFe Prussian‐Blue Analogues

A mixed‐valence {Mn^II₃Mn^IIIFe^II₂Fe^III₂} cyanide‐bridged molecular cube hosting a caesium cation, Cs?{Mn₄Fe₄}, was synthesized and structurally characterized by X‐ray diffraction. Cyclic‐voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable electrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin‐state change near room temperature, which could be ascribed to a metal‐to‐metal electron transfer converting the {Fe^II?CN?Mn^III} pair into a {Fe^III?CN?Mn^II} pair. This feature was only previously observed in the polymeric MnFe Prussian‐blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials.