Tetramic acids and indole derivatives from amino acid β-keto esters. Fine-tuning the conditions of the key Cu-catalyzed reaction

1,3,5-Trisubstituted tetramic acids and 2,3-disubstituted indole derivatives were prepared from β-keto esters derived from amino acids by their reaction with iodophenyl-2-trifluoroacetylamine under Cu-catalysis. Both heterocyclic systems were generated from the same starting materials by choice of the appropriate reaction conditions.     

Molecular insight into the interaction mechanisms of amino‐2H‐imidazole derivatives with BACE1 protease: A QM/MM and QTAIM study

In this study, we described quantitatively the interactions between two new amino‐2H‐imidazole inhibitors ((R)‐1t and (S)‐1m) and BACE1 using a hybrid quantum mechanics‐molecular mechanical (QM/MM) method together with a quantum theory of atoms In Molecules (QTAIM) analysis. Our computational calculations revealed that the binding affinity of these compounds is mostly related to the amino‐2H‐imidazole core, which interact tightly with the aspartate dyad of the active site. The interactions were stronger when the inhibitors presented a bulky substituent with a hydrogen bond acceptor motif pointing toward Trp76, such as the 3,5‐dimethyl‐4‐methoxyphenyl group of compound (S)‐1m. Furthermore, the QTAIM analysis revealed that many hydrophobic interactions complement cooperatively the hydrogen bond which is not present when compound (R)‐1t is bound to the enzyme. The combined QM/MM‐QTAIM analysis allows identifying the interactions that account for the activity difference between compounds, even at a nanomolar range.     

Coordination interactions in the crystalline lattice of alkaline ions with the polyoxometalate [V12B18O60H6]10− ligand

In the present work, the synthesis and structural characterization of two new polyoxovanadoborate (BVO) frameworks, based on the [V₁₂B₁₈O₆₀H₆]^10? polyanion, are reported, K(H₃O)(enH₂)₄[V₁₂B₁₈O₆₀H₆]·9.60H₂O (1) and Li₈(NH₄)₂[V₁₂B₁₈O₆₀H₆]·8.02H₂O (2). Both compounds are obtained in a mixed valence ratio of 10V^IV/2V^V. Framework 1 is characterized by potassium ions coordinated by the BVO cluster and ethylenediammonium and hydronium ions as charge-compensating agents. In framework 2, the BVO clusters are coordinating lithium ions and the charge is compensated by ammonium ions. Using the SHAPE 2.1 program, it was possible to calculate the best geometry for the existing lithium and potassium ions. For 2, the lithium ions are five-coordinate, best described by a square pyramid (SPY-5), while the coordination sphere around the potassium ions in 1 are six-coordinate. For 1, the coordination sphere of the existing potassium ions in the framework can be described as trigonal prism (TPR-6). Calculations were also done for a previously reported cluster [Na₁₀[(H₂O)V₁₂B₁₈O₆₀H₆]·18H₂O] (3), in which the sodium ions are six-coordinate but in two different geometries, these being octahedral and TPR-6. The influence of the interactions of the alkali ions with the [V₁₂B₁₈O₆₀H₆]^10? polyanion, on the vanadate and borate absorption bands observed in the infrared spectra, is discussed.     

Daily doses of biologically active UV radiation retrieved from commonly available parameters

A multiple linear correlation is done between atmospheric transmissivity for four biologically active radiation daily doses (UVB, erythemal, DNA and plant damage) T, and three parameters (daily sunshine fraction σ, cosine of the daily minimum solar zenith angle μ_min and daily total ozone column Ω). T is defined as the ratio of a daily dose to its extra‐atmospheric value. The data used are spectral UV measurements (390–400 nm at 0.5 nm step) recorded along year 2000 and over 8 months of year 2001 at Briançon Station (Alps, 1300 m above sea level) that forms part of the French UV network. The coefficients obtained from year 2000 correlation permit to retrieve daily doses for year 2001 with an average error running from 3 to 9% for monthly mean values and from 2 to 4.5% for 3‐monthly mean values, depending on daily dose type. The retrieval of yearly mean value gives an error between 4 and 7.5%. Retrieving the daily dose of a given day, where σ≥ 0.2, introduces error running from 16 to 32% depending on daily dose. An attempt to retrieve the yearly mean UVB daily dose for a northern France site, from the previous coefficients, gives encouraging results.     

Computational NMR coupling constants: Shifting and scaling factors for evaluating 1JCH

Optimized shifting and/or scaling factors for calculating one‐bond carbon–hydrogen spin–spin coupling constants have been determined for 35 combinations of representative functionals (PBE, B3LYP, B3P86, B97‐2 and M06‐L) and basis sets (TZVP, HIII‐su3, EPR‐III, aug‐cc‐pVTZ‐J, ccJ‐pVDZ, ccJ‐pVTZ, ccJ‐pVQZ, pcJ‐2 and pcJ‐3) using 68 organic molecular systems with 88 ¹J_CH couplings including different types of hybridized carbon atoms. Density functional theory assessment for the determination of ¹J_CH coupling constants is examined, comparing the computed and experimental values. The use of shifting constants for obtaining the calculated coupling improves substantially the results, and most models become qualitatively similar. Thus, for the whole set of couplings and for all approaches excluding those using the M06 functional, the root‐mean‐square deviations lie between 4.7 and 16.4 Hz and are reduced to 4–6.5 Hz when shifting constants are considered. Alternatively, when a specific rovibrational contribution of 5 Hz is subtracted from the experimental values, good results are obtained with PBE, B3P86 and B97‐2 functionals in combination with HIII‐su3, aug‐cc‐pVTZ‐J and pcJ‐2 basis sets. Copyright © 2013 John Wiley & Sons, Ltd.     

Tetrathiafulvalene‐Based Mixed‐Valence Acceptor–Donor–Acceptor Triads: A Joint Theoretical and Experimental Approach

This work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)‐based acceptor–donor–acceptor triads (BQ–TTF–BQ and BTCNQ–TTF—BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano‐p‐quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum‐chemical calculations. Emphasis is placed on the mixed‐valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ–TTF–BQ and BTCNQ–TTF–BTCNQ triads in their radical anion states behave as class‐II mixed‐valence compounds with significant electronic communication between the acceptor moieties. Density functional theory calculations (BLYP35/cc‐pVTZ), taking into account the solvent effects, predict charge‐localised species (BQ ^{. ?}–TTF–BQ and BTCNQ ^{. ?}–TTF–BTCNQ) as the most stable structures for the radical anion states of both triads. A stronger localisation is found both experimentally and theoretically for the BTCNQ–TTF–BTCNQ anion, in accordance with the more electron‐withdrawing character of the BTCNQ acceptor. CASSCF/CASPT2 calculations suggest that the low‐energy, broad absorption bands observed experimentally for the BQ–TTF–BQ and BTCNQ–TTF–BTCNQ radical anions are associated with the intervalence charge transfer (IV‐CT) electronic transition and two nearby donor‐to‐acceptor CT excitations. The study highlights the molecular efficiency of the electron‐donor TTF unit as a molecular wire connecting two acceptor redox centres.     

Scale Inhibitor and Dispersant Based on Poly(Acrylic Acid) Obtained by Redox‐Initiated Polymerization

Low molar mass poly(acrylic acid) (PAA) is generally obtained by free radical polymerization of acrylic acid (AA) in aqueous solution, using thermal initiators and some chain transfer agent. However, under such conditions it is rather difficult to efficiently produce molar masses as low as those required for obtaining an effective dispersant. In this work, the semibatch polymerization of AA at 45 °C is considered, using potassium persulfate (KPS) and sodium metabisulfite (KPS/NaMBS), or alternatively KPS and sodium hypophosphite (KPS/NaHP) as redox initiators to produce PAA of controlled low molar masses. These initiation systems allow the production of PAA with M_n as low as 2.0 kDa, relatively narrow molar mass distribution (1.5 < M_w/M_n < 3.0), and low branching degree. Most of the investigated polymerizations reach almost complete conversions (>95%); and it is verified that both reductants, NaMBS and NaHP, also behave as chain transfer agents. Finally, the investigated process with redox couples allowed the production of PAA with acceptable dispersant and antiscaling properties.     

General Design Concepts for CAPodes as Ionologic Devices

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy-efficient and nature-inspired next-generation computing devices. Here, we disclose the generalized concept for bias-direction-adjustable n- and p-CAPodes based on selective ion sieving. Controllable-unidirectional ion flux is realized by blocking electrolyte ions from entering sub-nanometer pores. The resulting CAPodes exhibit charge-storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations (‘OR’, ‘AND’). This work demonstrates CAPodes as a generalized concept to achieve p-n and n-p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion-based diodes in ionologic architectures.     

Di‐μ‐hydroxo‐bis{(aceto­nitrile)dibenzyl(6‐methyl‐2‐pyridylmethyl)amine‐κ2N,N]copper(II)} bis(perchlorate)

The title compound corresponds to a copper(II) dimer, [Cu₂(OH)₂(C₂H₃N)₂(C₂₁H₂₂N₂)₂](ClO₄)₂, where the metal centres are μ₂‐bridged by hydroxo groups. The coordination of each copper(II) centre is a slightly distorted square‐based pyramid, with two N atoms from dibenzyl(6‐methyl‐2‐pyridylmethyl)amine (BiBzMePMA) and two hydroxo O atoms occupying the basal positions, and the aceto­nitrile N atom at the apical position. The dimer is centrosymmetric, with a crystallographic inversion centre midway between the two Cu atoms [Cu⋯Cu = 2.9522 (9) Å]     

Isomer yield ratios and cross sections for110(4.9 h)In/110(69 min)In and108(58 min) In/108(39.6 min)In produced by alpha reactions on silver

This paper reports the determination of absolute excitation functions and cross section ratios for the production of 110(4.9 h)/110(69 min) In and^{108(58 min)/108(39.6 min)}In in reactions of -particles with natural silver. Target stack foils of silver were bombarded with the 55.0 MeV -particle, beam available at the Buenos Aires synchrocyclotron. The -spectrometry was used for the identification and for the determination of the absolute activity of^{110(4.9 h)}In and^{110(69 min)}In from¹⁰⁷Ag/, n/ and¹⁰⁹Ag/, 3n/ reactions and of^{108(58 min)}In and^{108(39.6 min)}In from¹⁰⁷Ag/, 3n/ and¹⁰⁹Ag/, 5n/ reactions by means of Ge intrinsic detector.This work has been sponsored by the Subsecretaria de Ciencia y Tecnología Argentina.