Nearly Degenerate Isomers of C(BH)2: Cumulene,Carbene, or Carbone?

The ground electronic state of C(BH)₂ exhibits both a linear minimum and a peculiar angle‐deformation isomer with a central B‐C‐B angle near 90°. Definitive computations on these species and the intervening transition state have been executed by means of coupled‐cluster theory including single and double excitations (CCSD), perturbative triples (CCSD(T)), and full triples with perturbative quadruples (CCSDT(Q)), in concert with series of correlation‐consistent basis sets (cc‐pVXZ, X=D, T, Q, 5, 6; cc‐pCVXZ, X=T, Q). Final energies were pinpointed by focal‐point analyses (FPA) targeting the complete basis‐set limit of CCSDT(Q) theory with auxiliary core correlation, relativistic, and non‐Born–Oppenheimer corrections. Isomerization of the linear species to the bent form has a minuscule FPA reaction energy of 0.02 kcal mol^?1 and a corresponding barrier of only 1.89 kcal mol^?1. Quantum tunneling computations reveal interconversion of the two isomers on a timescale much less than 1 s even at 0 K. Highly accurate CCSD(T)/cc‐pVTZ and composite c～CCSDT(Q)/cc‐pCVQZ anharmonic vibrational frequencies confirm matrix‐isolation infrared bands previously assigned to linear C(BH)₂ and provide excellent predictions for the heretofore unobserved bent isomer. Chemical bonding in the C(BH)₂ species was exhaustively investigated by the atoms‐in‐molecules (AIM) approach, molecular orbital plots, various population analyses, local mode vibrations and force constants, unified reaction valley analysis (URVA), and other methods. Linear C(BH)₂ is a cumulene, whereas bent C(BH)₂ is best characterized as a carbene with little carbone character. Weak B–B attraction is clearly present in the unusual bent isomer, but its strength is insufficient to form a CB₂ ring with a genuine boron–boron bond and attendant AIM bond path.     

Equilibrium Cationic Polymerization of Tetrahydrofuran in Benzene

Abstract

The equilibrium cationic polymerization of tetrahydrofuran in benzene is investigated in the 15 to 50°C range. Polymerizations are initiated with triethyloxonium hexafluorophos-phate (Et₃O⁺PF₅ ^?) and performed using high vacuum techniques. It is shown that, at a given temperature, the equilibrium monomer concentration varies linearly with polymer concentration. Values of ΔG_lc, the free-energy change upon the polymerization of 1 mole of liquid monomer to 1 base-mole of liquid amorphous polymer of infinite chain length, is deduced from these results. Values of ΔG_lc, obtained are in good agreement with those found in the literature for the equilibrium polymerization of tetrahydrofuran in bulk, However, there is a large discrepancy between these values of     

Electrochemical study of the corrosion inhibition ability of “smart” coatings applied on AA2024

Smart epoxy coatings modified with different additives were applied on AA2024. The following three different systems were studied: a reference consisting of an epoxy coating containing chromate active pigments and two “smart” coatings modified with containers loaded with corrosion inhibitor—layered double hydroxides filled with mercaptobenzothiazole and tubular halloysites (HS) filled with 8-hydroxyquinoline. The thickness of the coatings was determined by scanning electron microscopy. The barrier properties and the average corrosion resistance were assessed by electrochemical impedance spectroscopy (EIS). The long-term corrosion repair ability of the various coatings was confirmed by EIS measurements carried for a period of 3 weeks in scratched samples. The ability of the smart additives to inhibit corrosion over defects with different sizes and geometry was studied at the microscale by using localized impedance spectroscopy (LEIS) and the scanning vibrating electrode technique. The results demonstrate that the additives provide effective corrosion inhibition on defects of various sizes. Moreover, the LEIS measurements give some important highlights concerning the mechanisms and kinetics of inhibition of each system.     

Superior performance of liposomes over enzymatic amplification in a high-throughput assay for myoglobin in human serum

Myoglobin is one of several cardiac markers which become elevated in the blood following an acute myocardial infarction and can aid in the diagnosis of a heart attack. Here, a sandwich immunoassay for myoglobin was developed, including a thorough optimization of fluorescent dye-encapsulating liposomes versus enzymatic amplification (alkaline phosphatase and horseradish peroxidase) at each step. The optimized microtiter plate-based assay was capable of detecting as low as 11.3 pg/mL myoglobin and was successfully applied for the quantification of myoglobin in human serum. In comparison to enzymatic approaches, the liposomes demonstrated lower limits of detection, significantly reduced limits of quantification, improved signal discrimination through substantial signal enhancement, and reduced assay time. Liposomes were stable and functional at ambient temperatures for over 400 days. Finally, ease of use was greater due to lack of reliance on additional reagents, non-time-based signal enhancement, and excellent photostability. Optimal conditions identified for enzymatic approaches can also be used for liposome amplification, which makes substitution of these liposomes into existing assays straightforward. Thus, the extensive studies carried out here suggest that liposomes may be incorporated into formats currently utilizing enzymatic enhanced fluorescence with a potential for increased performance on various levels.

Clarifying some remaining questions in the anomaly puzzle

We discuss several points that may help to clarify some questions that remain about the anomaly puzzle in supersymmetric theories. In particular, we consider a general N=1\mathcal{N}=1 supersymmetric Yang–Mills theory. The anomaly puzzle concerns the question of whether there is a consistent way in the quantized theory to put the R-current and the stress tensor in a single supermultiplet called the supercurrent, even though in the classical theory they are in the same supermultiplet. It was proposed that the classically conserved supercurrent bifurcates into two supercurrents having different anomalies in the quantum regime. The most interesting result we obtain is an explicit expression for the lowest component of one of the two supercurrents in 4-dimensional spacetime, namely the supercurrent that has the energy-momentum tensor as one of its components. This expression for the lowest component is an energy-dependent linear combination of two chiral currents, which itself does not correspond to a classically conserved chiral current. The lowest component of the other supercurrent, namely, the R-current, satisfies the Adler–Bardeen theorem. The lowest component of the first supercurrent has an anomaly, which we show is consistent with the anomaly of the trace of the energy-momentum tensor. Therefore, we conclude that there is no consistent way to construct a single supercurrent multiplet that contains the R-current and the stress tensor in the straightforward way originally proposed. We also discuss and try to clarify some technical points in the derivations of the two supercurrents in the literature. These latter points concern the significance of infrared contributions to the NSVZ β-function and the role of the equations of motion in deriving the two supercurrents.     

Observation of two-neutrino double-beta decay in 136Xe with the EXO-200 detector

We report the observation of two-neutrino double-beta decay in (136)Xe with T(1/2) = 2.11 ± 0.04(stat) ± 0.21(syst) × 10(21) yr. This second-order process, predicted by the standard model, has been observed for several nuclei but not for (136)Xe. The observed decay rate provides new input to matrix element calculations and to the search for the more interesting neutrinoless double-beta decay, the most sensitive probe for the existence of Majorana particles and the measurement of the neutrino mass scale.     

Toward mechanistic understanding of nuclear reprocessing chemistries by quantifying lanthanide solvent extraction kinetics via microfluidics with constant interfacial area and rapid mixing

The closing of the nuclear fuel cycle is an unsolved problem of great importance. Separating radionuclides produced in a nuclear reactor is useful both for the storage of nuclear waste and for recycling of nuclear fuel. These separations can be performed by designing appropriate chelation chemistries and liquid-liquid extraction schemes, such as in the TALSPEAK process (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes). However, there are no approved methods for the industrial scale reprocessing of civilian nuclear fuel in the United States. One bottleneck in the design of next-generation solvent extraction-based nuclear fuel reprocessing schemes is a lack of interfacial mass transfer rate constants obtained under well-controlled conditions for lanthanide and actinide ligand complexes; such rate constants are a prerequisite for mechanistic understanding of the extraction chemistries involved and are of great assistance in the design of new chemistries. In addition, rate constants obtained under conditions of known interfacial area have immediate, practical utility in models required for the scaling-up of laboratory-scale demonstrations to industrial-scale solutions. Existing experimental techniques for determining these rate constants suffer from two key drawbacks: either slow mixing or unknown interfacial area. The volume of waste produced by traditional methods is an additional, practical concern in experiments involving radioactive elements, both from disposal cost and experimenter safety standpoints. In this paper, we test a plug-based microfluidic system that uses flowing plugs (droplets) in microfluidic channels to determine absolute interfacial mass transfer rate constants under conditions of both rapid mixing and controlled interfacial area. We utilize this system to determine, for the first time, the rate constants for interfacial transfer of all lanthanides, minus promethium, plus yttrium, under TALSPEAK process conditions, as a first step toward testing the molecular mechanism of this separation process.     

Electron transfer between colloidal ZnO nanocrystals

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.     

Influence of the inverse sheath on divertor plasma performance in tokamak edge plasma simulations

Recently, it was shown that strong electron thermionic emission from material walls could result in the formation of an “inverse sheath,” which prevents the flow of cold ions to the wall.^[1–3] Such regimes look very favourably from the point of view of plasma–material interactions at the edge of magnetic fusion devices, where the problem of the erosion of plasma-facing components under ion irradiation is one of the key issues for the development of future magnetic fusion reactors. However, it is not clear whether such regimes are compatible with edge plasma parameters and heat removal requirements in fusion reactors. To address the issue of practicality of the “inverse sheath” regime for edge tokamak plasma conditions, we perform a set of numerical simulations with 2D edge plasma transport code UEDGE^[4] for a DIII-D-like geometry and magnetic configuration. To describe both “standard” and “inverse sheath” conditions within the framework of the UEDGE code (which does not consider the sheath region per se), at the material surfaces, we apply effective boundary conditions that emulate both “standard” and “inverse sheath” regimes. We demonstrate that, for the same input parameters, spatial distributions of edge plasma parameters corresponding to detached divertor and “inverse sheath” regimes are similar, with only a few minor differences. We discuss the compatibility of “inverse sheath” regimes with core plasma parameters.     

Synthesis and In Vitro Characterization of Selective Cannabinoid CB2 Receptor Agonists: Biological Evaluation against Neuroblastoma Cancer Cells

1,8-naphthyridine-3-carboxamide structures were previously identified as a promising scaffold from which to obtain CB2R agonists with anticancer and anti-inflammatory activity. This work describes the synthesis and functional characterization of new 1,8-naphthyridin-2(1H)-one-3-carboxamides with high affinity and selectivity for CB2R. The new compounds were able to pharmacologically modulate the cAMP response without modulating CB2R-dependent β-arrestin2 recruitment. These structures were also evaluated for their anti-cancer activity against SH-SY5Y and SK-N-BE cells. They were able to reduce the cell viability of both neuroblastoma cancer cell lines with micromolar potency (IC₅₀ of FG158a = 11.8 μM and FG160a = 13.2 μM in SH-SY5Y cells) by a CB2R-mediated mechanism. Finally, in SH-SY5Y cells one of the newly synthesized compounds, FG158a, was able to modulate ERK1/2 expression by a CB2R-mediated effect, thus suggesting that this signaling pathway might be involved in its potential anti-cancer effect.