Simultaneous detection of phosphatidylcholines and glycerolipids using matrix‐enhanced surface‐assisted laser desorption/ionization‐mass spectrometry with sputter‐deposited platinum film

Matrix‐assisted laser desorption/ionisation (MALDI) imaging mass spectrometry (IMS) allows for the simultaneous detection and imaging of several molecules in brain tissue. However, the detection of glycerolipids such as diacylglycerol (DAG) and triacylglycerol (TAG) in brain tissues is hindered in MALDI‐IMS because of the ion suppression effect from excessive ion yields of phosphatidylcholine (PC). In this study, we describe an approach that employs a homogeneously deposited metal nanoparticle layer (or film) for the detection of glycerolipids in rat brain tissue sections using IMS. Surface‐assisted laser desorption/ionisation IMS with sputter‐deposited Pt film (Pt‐SALDI‐IMS) for lipid analysis was performed as a solvent‐free and organic matrix‐free method. Pt‐SALDI produced a homogenous layer of nanoparticles over the surface of the rat brain tissue section. Highly selective detection of lipids was possible by MALDI‐IMS and Pt‐SALDI‐IMS; MALDI‐IMS detected the dominant ion peak of PC in the tissue section, and there were no ion peaks representing glycerolipids such as DAG and TAG. In contrast, Pt‐SALDI‐IMS allowed the detection of these glycerolipids, but not PC. Therefore, using a hybrid method combining MALDI and Pt‐SALDI (i.e., matrix‐enhanced [ME]‐Pt‐SALDI‐IMS), we achieved the simultaneous detection of PC, PE and DAG in rat brain tissue sections, and the sensitivity for the detection of these molecules was better than that of MALDI‐IMS or Pt‐SALDI alone. The present simple ME‐Pt‐SALDI approach for the simultaneous detection of PC and DAG using two matrices (sputter‐deposited Pt film and DHB matrix) would be useful in imaging analyses of biological tissue sections. Copyright © 2015 John Wiley & Sons, Ltd.     

Moderate deviations of generalized method of moments and empirical likelihood estimators

This paper studies moderate deviation behaviors of the generalized method of moments and generalized empirical likelihood estimators for generalized estimating equations, where the number of equations can be larger than the number of unknown parameters. We consider two cases for the data generating probability measure: the model assumption and local contaminations or deviations from the model assumption. For both cases, we characterize the first-order terms of the moderate deviation error probabilities of these estimators. Our moderate deviation analysis complements the existing literature of the local asymptotic analysis and misspecification analysis for estimating equations, and is useful to evaluate power and robust properties of statistical tests for estimating equations which typically involve some estimators for nuisance parameters.     

Synthesis of Pr<Superscript>3+</Superscript> doped or Tb<Superscript>3+</Superscript>–Mg codoped CaSnO<Subscript>3</Subscript> perovskite phosphor by the polymerized complex method

Pr³⁺ doped or Tb³⁺–Mg codoped CaSnO₃ phosphor powder with perovskite structure was synthesized by the polymerized complex method. Powder samples crystallized into the perovskite phase at approximately 600 °C, which is 400 °C lower than the crystallization temperature for the solid-state reaction method. Uniform-sized powders with average particle sizes of 1–2 μm were obtained after heat treatment at 1,400 °C. Although the samples heat-treated at 600 °C did not exhibit photoluminescence, white photoluminescence of Pr³⁺ doped CaSnO₃ or green photoluminescence of Tb³⁺–Mg codoped CaSnO₃ was observed from the sample heat-treated above 800 °C. The intensity of the photoluminescence increased with increase of the heat-treatment temperature and reached a maximum for heat treatment at 1,400 °C. The maximum photoluminescence intensity for the samples prepared by the polymerized complex method was larger than those prepared by solid-state reaction method, which is probably due to the homogeneous mixing of the doped rare earth ions.     

Reciprocating Motion of a Self‐Propelled Object on a Molecular Layer

The mode change of a simple autonomous motor depending on the nature of a monolayer on water is investigated. A camphor disk is floated on a molecular layer of N‐stearoyl‐p‐nitroaniline (C₁₈ANA), which gives a surface‐pressure (π)–area per molecule (A) isotherm with a local maximum and a local minimum. The nature of the camphor motion changes depending on A, and in particular, reciprocating motion is observed at a lower A while cutting out its own trajectory of motion. The characteristic motion of a camphor disk depending on A is discussed in relation to the π–A isotherm of C₁₈ANA and the influence of the molecular interaction between molecules on the driving force of motion.     

Cu(dap)2Cl] as an efficient visible-light-driven photoredox catalyst in carbon-carbon bond-forming reactions

Copper sees the light of day: [Cu(dap)(2)Cl] proved to be an excellent photoredox catalyst for atom-transfer radical addition reactions, as well as for allylation reactions (see scheme), providing an attractive alternative to commonly used iridium- and ruthenium-based catalysts.     

6‐[3‐Hydroxy‐17‐oxoestra‐1,3,5(10)‐trien‐7β‐yl]­hexane­nitrile

In the title compound, C₂₄H₃₁NO₂, ring B adopts a conformation between the boat and twisted‐boat forms. This conformation best accommodates adverse intramolecular H⋯H interactions between the H atoms of the 7β‐substituent and the two nearest ring H atoms. The tilt angle between rings A and D is 28.6 (1)°.     

Infrared diode laser spectroscopic detection of CF2 carbene produced by CO2 laser photolysis of CHCLF2

Infrared diode laser spectroscopy was applied to the detection of CF₂ carbene produced by CO₂-laser-induced dissociation of CHClF₂. Time-resolved spectra of CF₂ in several rotation-vibration states were observed. The initial concentration of CF₂ was estimated to be 5 × 10¹⁶ molecules cm⁻¹ from an analysis of the time-resolved spectra. The effect of Ar diluent on the time variation of the concentration of CF₂ is discussed.     

Synthesis of 3-methylisoguanosine,a positional isomer of pharmacologically active nucleosides from marine animals

3-Methylisoguanosine ($\text{4c}$) has been synthesized from 5-(cyanomethylamino)-1(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazole-4-carboxamide ($\text{1b}$) through the carbonitrile ($\text{2b}$).     

Host-guest recognition of calcium by crown-ether substituted phthalocyanine array on Au(111): relationship between crown moieties and gold lattice

High-resolution scanning tunneling microscopy has revealed that, of the four crown-ether moieties of 15-crown-5-ed phthalocyanine array on Au(111) surface, only two crown-ether voids at diagonal positions, where the void centers and hollows surrounded by three gold atoms match exactly, trap two Ca2+ ions.