Pd‐PEPPSI‐IPent: An Active,Sterically Demanding Cross‐Coupling Catalyst and Its Application in the Synthesis of Tetra‐Ortho‐Substituted Biaryls

Incredible Bulk : A series of N‐heterocyclic carbene catalysts (see picture) were prepared and evaluated in the Suzuki–Miyaura reaction. A variety of sterically encumbered tetra‐ortho‐substituted biaryl products were formed from unreactive aryl chlorides using the isopentyl‐substituted catalyst at temperatures ranging from 65 °C to room temperature. The cyclopentyl‐substituted catalyst was virtually inactive, demonstrating that “flexible bulk” is essential to promote these transformations.

     

Determination of trace level chemical warfare agents in water and slurry samples using hollow fibre-protected liquid-phase microextraction followed by gas chromatography-mass spectrometry

A simple and solvent-minimised sample preparation technique based on hollow fibre-protected liquid-phase microextraction was investigated for the gas chromatography/mass spectrometric analysis of chemical warfare agents in water and slurry samples. The chemical warfare agents included four nerve agents and a blister agent. Parameters such as extraction solvent, salt concentration, stirring speed and extraction time were optimised using spiked deionised water samples. The technique provided a linear range of two orders of magnitude, good repeatability (RSDs < 10%, n = 6), good linearity (r2 >or= 0.995) and limits of detection (LODs) in the range of 0.02-0.09 microg l(-1) (S/N = 3) under full scan mode. The optimised technique was also applied to more complex slurry samples and similar precision (RSD < 15%, n = 3) and limits of detection (0.02-0.2 microgl(-1), S/N = 3) were obtained.     

Combined effect of the perpendicular magnetic field and dilute charged impurity on the electronic phase of bilayer AA-stacked hydrogenated graphene

We address the electronic phase engineering in the impurity-infected functionalized bilayer graphene with hydrogen atoms (H-BLG) subjected to a uniform Zeeman magnetic field, employing the tight-binding model, the Green's function technique, and the Born approximation. In particular, the key point of the present work is focused on the electronic density of states (DOS) in the vicinity of the Fermi energy. By exploiting the perturbative picture, we figure out that how the interaction and/or competition between host electrons, guest electrons, and the magnetic field potential can lead to the phase transition in H-BLG. Furthermore, different configurations of hydrogenation, namely reduced table-like and reduced chair-like, are also considered when impurities are the same and/or different. A comprehensive information on the various configurations provides the semimetallic and gapless semiconducting behaviors for unfunctionalized bilayer graphene and H-BLGs, respectively. Further numerical calculations propose a semimetal-to-metal and gapless semiconductor-to-semimetal phase transition, respectively, when only turning on the magnetic field. Interestingly, the results indicate that the impurity doping alone affects the systems as well, leading to semimetal-to-metal and no phase transition in the pristine system and hydrogenated ones, respectively. However, the combined effect of charged impurity and magnetic field shows that the pristine bilayer graphene is not influenced much as the functionalized ones and phase back transitions appear. Tuning of the electronic phase of H-BLG by using both types of electronic and magnetic perturbations play a decisive role in optical responses.     

光纤光热干涉气体检测技术研究进展

本文阐述光纤光热干涉气体检测的基本原理,从光纤光热相位调制的产生、动态过程、探测方法以及响应时间等方面出发,综述本研究组在光纤光热干涉气体检测方面的最新工作进展.光纤光热干涉技术具有灵敏度高、动态范围大、测量不受散射及其他损耗影响等优势,能够实现小型化、多点复用、组网及远程监测,在环境、医疗、安防等领域具有重要的应用.     

High‐mobility pentacene OTFT with TaLaO gate dielectric passivated by fluorine plasma

Pentacene thin‐film transistor with high‐κ TaLaO as gate dielectric has been fabricated and shows a carrier mobility of 0.73 cm²/V s, much higher than that based on pure La₂O₃ (0.43 cm²/V s) due to the smoother surface of the TaLaO film and thus larger pentacene islands grown on it in the initial stage. Moreover, among various times for fluorine‐plasma treatment on the TaLaO gate dielectric, 100 seconds result in the highest carrier mobility of 1.12 cm²/V s due to (1) smoothest oxide surface achieved by fluorine passivation of oxide traps, as measured by AFM and supported by smallest sub‐threshold swing and lowest low‐frequency noise; (2) the largest pentacene grains grown on the smoothest oxide surface, as demonstrated by AFM.

     

The Development of Bulky Palladium NHC Complexes for the Most-Challenging Cross-Coupling Reactions

Palladium‐catalyzed cross‐coupling reactions enable organic chemists to form C? C bonds in targeted positions and under mild conditions. Although phosphine ligands have been intensively researched, in the search for even better cross‐coupling catalysts attention has recently turned to the use of N‐heterocyclic carbene (NHC) ligands, which form a strong bond to the palladium center. PEPPSI (pyridine‐enhanced precatalyst preparation, stabilization, and initiation) palladium precatalysts with bulky NHC ligands have established themselves as successful alternatives to palladium phosphine complexes. This Review shows the success of these species in Suzuki–Miyaura, Negishi, and Stille–Migita cross‐couplings as well as in amination and sulfination reactions.     

Single-turn helix-coil strands stabilized by metal···metal and π-π interactions of the alkynylplatinum(II) terpyridyl moieties in meta-phenylene ethynylene foldamers

Dinuclear alkynylplatinum(II) terpyridyl complexes with oligomeric bridge consisting of five repeating meta-phenylene ethynylene (mPE) units have been found to exhibit a strong tendency to fold back onto themselves to form short helical strands through the stabilization of Pt···Pt and π-π interactions. The steric bulk of the terpyridine ligands and the length of the oligomeric bridge have been found to affect the extent of the intramolecular Pt···Pt interaction that governs the stabilization of the short helical strand in solution. Their folding properties via Pt···Pt and π-π stacking interactions have been studied by (1)H NMR, 2D ROESY NMR, electronic absorption, and emission spectroscopies.     

Fast electro-optical mode in photo-aligned reflective deformed helix ferroelectric liquid crystal cells

The electro-optical behavior of deformed helix ferroelectric liquid crystal in reflective mode is described in this paper. The electrically controlled reflectance has been measured at subkilohertz driving voltage frequency for different polarizations of the incident light and compared quite successfully with the simulation results.