Regiocontrolled intramolecular cyclizations of carboxylic acids to carbon-carbon triple bonds promoted by acid or base catalyst

We systematically investigated, for the first time, the relationship between regioselectivity and acid/base effects in the cyclization reactions between carboxylic acids and carbon-carbon triple bonds. We found novel acid- and base-promoted cyclizations to selectively give isocoumarin or pyran-2(2H)-one and phthalide or furan-2(5H)-one skeletons, respectively, and established a catalytic version of regioselective heterocyclic ring synthesis. Density functional theory calculations and application to a short route to thunberginol A were also described. [reaction: see text].     

Design of Photostable,Activatable Near‐Infrared Photoacoustic Probes Using Tautomeric Benziphthalocyanine as a Platform

Near‐infrared (NIR) imaging techniques have attracted significant attention for biological and medicinal applications due to the ability of NIR to penetrate deeply into tissues. However, there are very few stable, activatable molecular probes that can utilize NIR light in the wavelength range beyond 800 nm. Herein, we report a new activatable NIR system for photoacoustic imaging based on tautomeric benziphthalocyanines (BPcs). We found that the existence of a free hydroxyl group is crucial for NIR absorption of BPcs. Synthesized water‐soluble hydroxy BPcs exhibited high photostability and no fluorescence, which are desirable features for photoacoustic imaging. We synthesized BPcs in which the free hydroxyl group was masked by an esterase‐labile or an H₂O₂‐labile group. The photoacoustic signals of these hydroxy‐masked BPcs were increased upon NIR excitation at 880 nm in the presence of esterase or H₂O₂, respectively. These are rare examples of activatable probes utilizing NIR light at around 900 nm.     

A simple high‐performance liquid chromatography for the determination of linezolid in human plasma and saliva

Linezolid is an antimicrobial agent for the treatment of multiresistant Gram‐positive infections. A practical high‐performance liquid chromatography method was developed for the determination of linezolid in human plasma and saliva. Linezolid and an internal standard (o‐ethoxybenzamide) were extracted from plasma and saliva with ethyl acetate and analyzed on a Capcell Pak C₁₈ MG column with UV detection at 254 nm. The calibration curve was linear through the range 0.5–50 µg/mL using a 200 μL sample volume. The intra‐ and interday precisions were all <6.44% for plasma and 5.60% for saliva. The accuracies ranged from 98.8 to 110% for both matrices. The mean recoveries of linezolid were 80.8% for plasma and 79.0% for saliva. This method was used to determine the plasma and saliva concentrations of linezolid in healthy volunteers who were orally administered a 600 mg dose of linezolid. Our liquid–liquid extraction procedure is easy and requires a small volume of plasma or saliva (200 μL). This small volume can be advantageous in clinical pharmacokinetic studies, especially if children participate. Copyright © 2015 John Wiley & Sons, Ltd.     

Characteristics of voltage holding ratio and residual direct current voltage for polymer-sustained-alignment liquid crystal cells formed from mixed monomers containing biphenyl- and benzilketal-groups

Abstract

For improving process efficiency of polymer-sustained-alignment liquid crystal displays (PSA-LCDs), new photo-initiation monomers (PI-monomers), 2-methoxy-2-methacryloyl-oxy-ethoxy-2-phenylacetophenon (2-MMOEP) and 2,2-dimethacryloyl-oxy-ethoxy-2-phenylacetophenon (2,2-DMOEP), were developed and investigated image sticking characteristics. LC cells having PSA layers formed from a monomer 4,4′-dimethacryloyl-oxy-biphenyl (4,4′-DMABiph) and each PI-monomer were fabricated, and voltage holding ratio (VHR) and residual direct current voltage (V_rDC) were clarified as the image sticking characteristics. The VHR and the V_rDC were improved with the LC cells having the PSA layers formed from 4,4′-DMABiph and 2,2-DMOEP owing to large rate constant of polymerization. In contrast, the VHR and the V_rDC were deteriorated with the LC cells having the PSA layers formed from 4,4′-DMABiph and 2-MMOEP. The deterioration of the VHR and the V_rDC was derived from the increase in the concentration of radical and/or ion generated from 2-MMOEP. The results indicate that the number of polymerizable group in the PI-monomer is important, and plural number of polymerizable group in the PI-monomer leads to high VHR and low V_rDC.     

Anomalous magnetic field effects on photochemical reactions in ionic liquid under ultrahigh fields of up to 28 T

The magnetic field effects (MFEs) on photoinduced hydrogen abstraction reactions between benzophenone and thiophenol in an ionic liquid, N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl) imide (TMPA TFSI), were studied by a nanosecond laser flash photolysis technique under ultrahigh fields of up to 28 T. Extremely large and anomalous stepwise MFEs were observed for the first time. The escape yield of benzophenone ketyl radical decreased with increasing magnetic field strength (B) at 0 T相似文献   

Fabrication and characterization of high performance cathode supported small-scale SOFC for intermediate temperature operation

A high performance small-scale solid oxide fuel cell supported by a microtubular cathode was successfully developed via the extrusion of a (La_0.8Sr_0.2)_0.97MnO₃ cathode support and subsequent surface coating with a (La_0.8Sr_0.2)_0.97MnO₃–Ce_0.9Gd_0.1O_1.95 activation layer followed by Sc₂O₃-doped ZrO₂ electrolyte and NiO–Ce_0.9Gd_0.1O_1.95 anode slurries. The cell was electrochemically evaluated in a humidified hydrogen (3% H₂O) atmosphere, and exhibited a stable open circuit voltage above 1.05 V in the temperature range from 550 to 750 °C. Maximum power densities of 46.5, 163.2 and 452.8 mW cm⁻² were generated at 550, 650 and 750 °C, respectively. The results indicate the realization of a stable and high performance cathode-supported micro SOFC.     

A new interpretation of the reaction pathway of deprotonative metalation with TMP-Zn-ate/TMEDA Complex [TMEDA.Na(micro-tBu)(micro-TMP)Zn(tBu)

Density functional theory (DFT) calculations of possible reaction pathways and mechanisms for the deprotonation of benzene with Mulvey's reagent, TMEDA.Na(micro-R)(micro-TMP)Zn(R) (TMEDA=N,N,N',N'-tetramethylethylenediamine, R = alkyl, TMP = 2,2,6,6-tetramethylpiperidide) indicate that the deprotonation of benzene with Mulvey's reagent proceeds through a stepwise mechanism, not a one-step mechanism. In the first step, deprotonation involving the TMP ligand on the reagent is kinetically more favorable than that involving the alkyl ligand.