Fuzzy nanoassembly of polyelectrolyte and layered clay multicomposite toward a reliable gas barrier

Flexible and transparent gas-diffusion barriers have played an important role in recent years. The present study describes a flexible barrier film with a tailored architecture of cationic polyelectrolytes and clay/polymer nanoassemblies. Highly oriented and well-aligned barrier films were achieved by the consecutive absorption of flexible cationic polymer and anionic montmorillonite platelets. The experimental results showed that the layer-by-layer deposition of oppositely charged thin films containing self-assembled poly(vinyl alcohol) and montmorillonites improved their gas barrier characteristics based on the Ca degradation test, enhancing their optical transparency. This nanostructure, fabricated using a solution process, is useful in many applications, for example, flexible and moisture-free organic electronics. This simple and fast method is suitable for the mass coating of large surface areas, as required in industry.     

An unprecedented iron-catalyzed cross-coupling of primary and secondary alkyl Grignard reagents with non-activated aryl chlorides

The use of N-heterocyclic carbene ligands in the iron-catalyzed cross-coupling of alkyl Grignards has allowed, for the first time, coupling of non-activated, electron rich aryl chlorides. Surprisingly, the tetrahydrate of FeCl₂ was found to be a better pre-catalyst than anhydrous FeCl₂. Primary Grignard reagents coupled in excellent yields while secondary Grignard reagents coupled in modest yields. The use of acyclic secondary Grignard reagents resulted in the formation of isomers in addition to the desired product. These isomeric products were formed via reversible β-hydrogen elimination, indicating that the cross-coupling proceeds through an ionic pathway.     

Engineering de novo membrane-mediated protein-protein communication networks

Mechanical properties of biological membranes are known to regulate membrane protein function. Despite this, current models of protein communication typically feature only direct protein-protein or protein-small molecule interactions. Here we show for the first time that, by harnessing nanoscale mechanical energy within biological membranes, it is possible to promote controlled communication between proteins. By coupling lipid-protein modules and matching their response to the mechanical properties of the membrane, we have shown that the action of phospholipase A(2) on acyl-based phospholipids triggers the opening of the mechanosensitive channel, MscL, by generating membrane asymmetry. Our findings confirm that the global physical properties of biological membranes can act as information pathways between proteins, a novel mechanism of membrane-mediated protein-protein communication that has important implications for (i) the underlying structure of signaling pathways, (ii) our understanding of in vivo communication networks, and (iii) the generation of building blocks for artificial protein networks.     

Combustion chemistry of enols: possible ethenol precursors in flames

Before the recent discovery that enols are intermediates in many flames, they appeared in no combustion models. Furthermore, little is known about enols' flame chemistry. Enol formation in low-pressure flames takes place in the preheat zone, and its precursors are most likely fuel species or the early products of fuel decomposition. The OH + ethene reaction has been shown to dominate ethenol production in ethene flames although this reaction has appeared insufficient to describe ethenol formation in all hydrocarbon oxidation systems. In this work, the mole fraction profiles of ethenol in several representative low-pressure flames are correlated with those of possible precursor species as a means for judging likely formation pathways in flames. These correlations and modeling suggest that the reaction of OH with ethene is in fact the dominant source of ethenol in many hydrocarbon flames, and that addition-elimination reactions of OH with other alkenes are also likely to be responsible for enol formation in flames. On this basis, enols are predicted to be minor intermediates in most flames and should be most prevalent in olefinic flames where reactions of the fuel with OH can produce enols directly.     

Optical spectroscopy of graphene: From the far infrared to the ultraviolet

The unique electronic structure of graphene leads to several distinctive optical properties. In this brief review, we outline the current understanding of two general aspects of optical response of graphene: optical absorption and light emission. We show that optical absorption in graphene is dominated by intraband transitions at low photon energies (in the far-infrared spectral range) and by interband transitions at higher energies (from mid-infrared to ultraviolet). We discuss how the intraband and interband transitions in graphene can be modified through electrostatic gating. We describe plasmonic resonances arising from the free-carrier (intraband) response and excitonic effects that are manifested in the interband absorption. Light emission, the reverse process of absorption, is weak in graphene due to the absence of a band gap. We show that photoluminescence from hot electrons can, however, become observable either through femtosecond laser excitation or strong electrostatic gating.     

Depth‐integrated free‐surface flow with a two‐layer non‐hydrostatic formulation

This paper presents the derivation of a depth‐integrated wave propagation and runup model from a system of governing equations for two‐layer non‐hydrostatic flows. The governing equations are transformed into an equivalent, depth‐integrated system, which separately describes the flux‐dominated and dispersion‐dominated processes. The depth‐integrated system reproduces the linear dispersion relation within a 5 error for water depth parameter up to kd = 11, while allowing direct implementation of a momentum conservation scheme to model wave breaking and a moving‐waterline technique for runup calculation. A staggered finite‐difference scheme discretizes the governing equations in the horizontal dimension and the Keller box scheme reconstructs the non‐hydrostatic terms in the vertical direction. An semi‐implicit scheme integrates the depth‐integrated flow in time with the non‐hydrostatic pressure determined from a Poisson‐type equation. The model is verified with solitary wave propagation in a channel of uniform depth and validated with previous laboratory experiments for wave transformation over a submerged bar, a plane beach, and fringing reefs. Copyright © 2011 John Wiley & Sons, Ltd.     

Recent advances in SALDI-MS techniques and their chemical and bioanalytical applications

Although laser desorption mass spectrometry was introduced in the 1960s, the potential of laser mass spectrometry was not realised until the introduction of matrix-assisted laser desorption/ionisation (MALDI) in the 1980s. The technique relies on light-absorbing compounds called matrices that are co-crystallised with the analyte to achieve high ionisation and desorption efficiencies. MALDI offers a lot of advantages and is an indispensable tool in macromolecule analysis. However, the presence of the matrix also produces a high chemical background in the region below m/z 700 in the mass spectrum. Surface-assisted laser desorption/ionisation (SALDI) substitutes the chemical matrix of MALDI for an active surface, which means that matrix interference can be eliminated. SALDI mass spectrometry has evolved in recent years into a technique with great potential to provide insight into many of the challenges faced in modern research, including the growing interest in “omics” and the demands of pharmaceutical science. A great variety of materials have been reported to work in SALDI. Examples include a number of nanomaterials and surfaces. The unique properties of nanomaterials greatly facilitate analyte desorption and ionisation. This article reviews recent advances made in relation to carbon- and semiconductor-based SALDI strategies. Examples of their environmental, chemical and biomedical applications are discussed with the aim of highlighting progression in the field and the robustness of the technique, as well as to evaluate the strengths and weaknesses of individual approaches. In addition, this article describes the physical and chemical processes involved in SALDI and explains how the unique physical and electronic properties of nanostructured surfaces allow them to substitute for the matrix in energy transfer processes.