Efficient transformation of 7,14-dihydroxy-ent-kaurenes to novel ent-abietanes having cis-fused α-methylene γ-lactones under Mitsunobu reaction conditions and their cytotoxicities

Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed.     

Three lanostane triterpenoids with antitrypanosomal activity from the fruiting body of Hexagonia tenuis

During the search for new antitrypanosomal drug leads, three new antitrypanosomal compounds, hexatenuins A–C (1–3), were isolated from the fruiting body of Hexagonia tenuis. 1 and 3 possessed an unusual malonate half-ester functional group at C-3 position, and 1 and 2 had a spirostructure in the side-chain. Their structures were elucidated using MS analyses, extensive 2D-heteronuclear NMR data interpretation. Compounds 1–3 showed in vitro antitrypanosomal activity against Trypanosoma brucei brucei with IC₅₀ values of 0.57, 8.60 and 5.62 μg/ml, respectively.     

Hyperpolarized 13C Magnetic Resonance Imaging of Fumarate Metabolism by Parahydrogen-induced Polarization: A Proof-of-Concept in vivo Study

Hyperpolarized [1-¹³C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-¹³C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-¹³C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-¹³C]fumarate at sufficient ¹³C polarization for ex vivo detection of hyperpolarized ¹³C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo ¹³C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.     

Phase-I trigger readout electronics upgrade of the ATLAS liquid-argon calorimeters

This article gives an overview of the Phase-I Upgrade of the ATLAS LAr Calorimeter Trigger Readout. The design of custom developed hardware for fast real-time data processing and transfer are presented. Performance results from the prototype boards operated in the demonstrator system, first measurements of noise behavior and responses on the test pulses to the demonstrator system are shown.     

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.     

Modeling current–voltage relationships of mixed conducting cathode materials for solid oxide fuel cells

In recent decades, high-temperature oxygen reduction reaction on mixed conducting cathodes were investigated intensively by many researchers. Computational approaches as well as electrochemical and spectroscopic studies have been made to elucidate the kinetics. Contribution of oxygen vacancy to the reaction rate was suggested in multiple reports, and plausible reaction pathways were proposed based on density functional theory (DFT) calculations. The picture of oxygen reduction reaction has become clearer in these years. However, there still is a discussion about a credible formula that represents the current–voltage relationships. Discrepancies are found among the reported data on the magnitude of the rate constant and on its dependencies on partial pressure and temperature. The difference is significant between a model electrode and a practical porous electrode. Comparison of the results suggests the existence of series reaction barriers, that is, the surface reaction and subsurface transport, which should be considered for consistent representation of the total electrode process.     

Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.     

Ti complex catalysts including thiobisphenoxy group as a ligand for olefin polymerization

Titanium complexes were prepared by the reaction of 2,2′-thiobis(6-tert-butyl-4-methylphenol) (TBP) with TiCl₄ or Ti(OPrⁱ)₄. These complexes in combination with methyalumoxane as cocatalyst are highly active towards ethylene and propene, giving polymers having high molecular weights. The polymerization activities for ethylene and propene are comparable to those of Cp₂ZrCl₂-MAO catalyst. Polypropylene obtained had extremely high molecular weight (Mw>6 million) and low regioregularity (30% of head-to-head and tail-to-tail linkages). Highly syndiotactic polystyrene was obtained with these catalysts with activity up to 27 kg polymer per g Ti and hour. Copolymerization of styrene with ethylene gave highly alternating copolymer with isotactic styrene units. These catalysts are also active toward both conjugated and nonconjugated dienes such as butadiene and 1,5-hexadiene. Polybutadiene had mainly cis-1,4-structure (98%). The structure of poly(1,5-hexadiene) is rather complicated, which is quite different from that prepared with heterogeneous TiCl₃ catalysts.     

Intermolecular vibrational spectra of C3v CXY3 Molecular Liquids, CHCl3, CHBr3, CFBr3, and CBrCl3

We report the quality anisotropic intermolecular vibrational spectra within the frequency range 0.5-800 cm(-1) of four C(3v) CXY(3) molecular liquids, CHCl(3), CHBr(3), CFBr(3), and CBrCl(3), by means of femtosecond optical-heterodyne-detected Raman-induced Kerr effect spectroscopy. The results show that the first moment of the intermolecular vibrational spectrum is proportional to the square root of the value of the surface tension divided by the liquid density. This implies that the intermolecular vibrational spectrum reflects the bulk properties of the liquids. To understand the molecular-level aspects of the intermolecular vibrational spectra of the liquids, the spectra are compared with the molecular properties such as molecular weight, rotational constants, and bimolecular interaction energy. Overall, the first moment of the spectrum moderately correlates to the inverse square roots of both the molecular weight and the fast rotational constant. Therefore, the molecular properties are responsible for the intermolecular vibrational spectrum. Plots of the first moment of the intermolecular vibrational spectrum vs the square root of the value of the simple bimolecular interaction energy divided by the molecular surface area and the molecular weight show a linear correlation in the case of the oblate symmetric top molecular liquids, CHCl(3), CHBr(3), and CFBr(3). However, CBrCl(3), which is a prolate symmetric top molecular liquid, does not show the same correlation for the oblate molecular liquids.     

Enhancement of sonochemical reaction of terephthalate ion by superposition of ultrasonic fields of various frequencies

The ultrasonic reactor with dual frequency was used and the effect of frequency on the fluorescence intensity of terephthalate ion was experimentally investigated in the frequency range from 176 to 635 kHz. The sonochemical reaction fields were visualized by using sonochemical luminescence of luminol solution. Compared with the fluorescence intensity of terephthalate ion for single frequency, the fluorescence intensity for dual frequency increased. The fluorescence intensity ratio of dual frequency to single frequency had maximum value when the frequency of transducer attached at the bottom wall was comparable in magnitude to that at the side wall. In the case of dual frequency, the sonochemical reaction fields became more extensive in the reactor and more intensive around the center of the reactor.