3-Methoxalylchromones--versatile reagents for the regioselective synthesis of functionalized 2,4'-dihydroxybenzophenones, potential UV-filters

The reaction of 1,3-bis-silyl enol ethers with 3-methoxalylchromones affords a great variety of functionalised 2,4'-dihydroxybenzophenones. These products are formed by a domino Michael/retro-Michael/Mukaiyama-aldol reaction. The synthesized compounds are promising candidates for the synthesis of the novel UV-A/B and UV-B filters.     

Ions Can Move a Proton‐Coupled Electron‐Transfer Reaction into Tunneling Regime

The effects of charged species on proton‐coupled electron‐transfer (PCET) reaction should be of significance for understanding/application of important chemical and biological PCET systems. Such species can be found in proximity of activated complex in a PCET reaction, although they are not involved in the charge transfer process. Reported here is the first study of the above‐mentioned effects. Here, the effects of Na⁺, K⁺, Li⁺, Ca²⁺, Mg²⁺, and Me₄N⁺ observed in PCET reaction of ascorbate monoanions with hexacyanoferrate(III) ions in H₂O reveal that, in presence of ions, this over‐the‐barrier reaction entered into tunneling regime. The observations are: a) dependence of the rate constant on the cation concentration, where the rate constant is 71 (at I = 0.0023), and 821 (at 0.5M K⁺), 847 (at 1.0M Na⁺), and 438 M ^?1 s^?1 (at 0.011M Ca²⁺); b) changes of kinetic isotope effect (KIE) in the presence of ions, where k_H/k_D=4.6 (at I = 0.0023), and 3.4 (in the presence of 0.5M K⁺), 3.3 (at 1.0M Na⁺), 3.9 (at 0.001M Ca²⁺), and 3.9 (at 0.001M Mg²⁺), respectively; c) the isotope effects on Arrhenius pre‐factor where A_H/A_D=0.97 (0.15) in absence of ions, and 2.29 (0.60) (at 0.5M Na⁺), 1.77 (0.29) (at 1.0M Na⁺), 1.61 (0.25) (at 0.5M K⁺), 0.42 (0.16) (at 0.001M Ca²⁺) and 0.16 (0.19) (at 0.001M Mg²⁺); d) isotope differences in the enthalpies of activation in H₂O and in D₂O, where ΔΔH^?(D,H)=3.9 (0.4) kJ mol^?1 in the absence of cations, 1.3 (0.6) at 0.5M Na⁺, 1.8 (0.4) at 0.5M K⁺, 1.5 (0.4) at 1.0M Na⁺, 5.5 (0.9) (at 0.001M Ca²⁺), and 7.9 (2.8) (at 0.001M Mg²⁺) kJ mol^?1; e) nonlinear proton inventory in reaction. In the H₂O/dioxane 1 : 1, the observed KIE is 7.8 and 4.4 in the absence and in the presence of 0.1M K⁺, respectively, and A_H/A_D=0.14 (0.03). The changes when cations are present in the reaction are explained in terms of termolecular encounter complex consisting of redox partners, and the cation where the cation can be found in a near proximity of the reaction‐activated complex thus influencing the proton/electron double tunneling event in the PCET process. A molecule of H₂O is involved in the transition state. The resulting ‘configuration’ is more ‘rigid’ and more appropriate for efficient tunneling with Na⁺ or K⁺ (extensive tunneling observed), i.e., there is more precise organized H transfer coordinate than in the case of Ca²⁺ and Mg²⁺ (moderate tunneling observed) in the reaction.     

Nonequilibrium molecular transport photoinduced by potential energy fluctuations

The mechanism of directed substrate-parallel motion of molecules caused by photoinduced potential energy fluctuations is investigated. Unlike simplistic models (e.g., an on-off ratchet), the approach suggested implies that the necessary asymmetry of the potential energy can arise not only from the asymmetry of the substrate potential but also from an asymmetric distribution of the fluctuating charge density in the molecule. The thus induced asymmetry of the potential energy governs the direction motion and enables, under certain conditions, its reversal at some frequencies of resonant laser pulses or temperature. These inferences are exemplified by the model charge distributions in the molecule and substrate, and the charge density fluctuations which are obtained by quantum chemical calculations for the realistic molecule of a substituted phenylpyrene compound on a model substrate.     

Selective molecular sequestration with concurrent natural product functionalization and derivatization: from crude natural product extracts to a single natural product derivative in one step

A resin-bound nitroso compound sequestered a single unexpected component from crude plant seed extracts. Several plants, including Piper nigrum, Eugenia caryophyllata, and Pimenta dioica, were extracted with organic solvent in the presence of a nitroso-containing resin. The nitroso resin selectively sequestered a single compound, β-caryophyllene, via a chemo- and regioselective ene reaction. The ene product was released from the resin, and proper selection of the solid-phase linker and cleavage cocktail allowed concomitant further transformation of the primary ene product to a novel functionalized polycycle. Preliminary studies indicate that the new hydroxylamine-containing natural product derivatives have antibiotic activity.     

Editorial of the Special Issue of MCAP: S4G Stochastic Geometry,Stereology and Spatial Statistics

Methodology and Computing in Applied Probability -     

Immunocytochemical Localization of XRCC1 and γH2AX Foci Induced by Tightly Focused Femtosecond Laser Radiation in Cultured Human Cells

To assess the prospects for using intense femtosecond laser radiation in biomedicine, it is necessary to understand the mechanisms of its action on biological macromolecules, especially on the informational macromolecule—DNA. The aim of this work was to study the immunocytochemical localization of DNA repair protein foci (XRCC1 and γH2AX) induced by tightly focused femtosecond laser radiation in human cancer A549 cells. The results showed that no XRCC1 or γH2AX foci tracks were observed 30 min after cell irradiation with femtosecond pulses of 10¹¹ W∙cm⁻² peak power density. An increase in the pulse power density to 2 × 10¹¹ W∙cm⁻² led to the formation of linear tracks consisting both of XRCC1 and γH2AX protein foci localized in the places where the laser beam passed through the cell nuclei. A further increase in the pulse power density to 4 × 10¹¹ W∙cm⁻² led to the appearance of nuclei with total immunocytochemical staining for XRCC1 and γH2AX on the path of the laser beam. Thus, femtosecond laser radiation can be considered as a tool for local ionization of biological material, and this ionization will lead to similar effects obtained using ionizing radiation.     

New Raman Spectroscopic Data of the Almahata Sitta Meteorite

The archaeological site of Pintia (Padilla de Duero/Peñafiel, Valladolid), considered one of the first cities on the Iberian Peninsula, has yielded very interesting archaeological records regarding the different functional areas that involve the oppidum. Pottery, metal, and bone/skeletal remains are very well preserved, being optimal for analysis and study of the ancient food contained, such as milk-based products, animal fats, beer, and wine. The combination of Raman Microscopy (RM) with other analytical techniques such as Light Microscopy (LM) and Environmental Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy (ESEM-EDX) becomes a powerful tool to obtain information on the possible content in the ceramic receptacles from historical-archaeological heritage. It can lead to an interpretation of their specific use or functionality. In this work, a unique sample preparation was used for all techniques, which lead to a very simple procedure and documentation. The degradation and aging of natural fibers and the presence of organic matter with low crystallinity and calcium oxalate–related residuals can be studied by these combined techniques. The archaeological residuals can be separated from modern contamination coming from agriculture processes, surrounding land minerals, or fresh vegetal matter.     

Algebra Forms with $$d^{N} = 0$$ on Quantum Plane. Generalized Clifford Algebra Approach

We construct a q-analog of exterior calculus with a differential d satisfying d ^N = 0, where N ≥ 2 and q is a primitive Nth root of unity, on a noncommutative space and introduce a notion of a q-differential k-form. A noncommutative space we consider is a reduced quantum plane. Our construction of a q-analog of exterior calculus is based on a generalized Clifford algebra with four generators and on a graded q-differential algebra. We study the structure of the algebra of q-differential forms on a reduced quantum plane and show that the first order calculus induced by the differential d is a coordinate calculus. The explicit formulae for partial derivatives of this first order calculus are found.