2,2':6',2'-terpyridine substituted in the 4'-position by the solubilizing and sterically demanding tert-butyl group: a surprisingly new ligand

We describe the synthesis and characterization of 4'-tert-butyl-2,2':6',2'-terpyridine (4'-(t)Butpy, 1), a convergent tpy ligand that exhibits both a sterically demanding and solubilizing 4'-substituent. In the solid state, molecules of 1 pack with alternating tpy and tert-butyl domains, and the bulky alkyl substituents prevent the molecules from engaging in the face-to-face π-interactions which are typical of simple tpy ligands. Instead, the predominant packing forces involve CH···N hydrogen bonds and weak CH···π contacts. The syntheses of the homoleptic complexes [M(1)(2)][PF(6)](2) (M = Fe, Co, Zn and Ru) and the heteroleptic [Ru(tpy)(1)][PF(6)](2) are described. The complexes have been fully characterized in solution, including the (1)H NMR spectroscopic characterization of the paramagnetic [Co(1)(2)][PF(6)](2). Cyclic voltammetric data are consistent with the tert-butyl substituent being slightly electron releasing. The single crystal structures of [Zn(1)(2)][PF(6)](2) and [Ru(1)(2)][PF(6)](2) have been determined; the compounds are essentially isomorphous. The packing of the cations is such that the tert-butyl substituents are accommodated in pockets between the tpy domains of adjacent cations, and as a consequence, the {M(tpy)(2)}-embrace that is a ubiquitous feature of many related structures is not observed.     

Non-singular dislocation loops in gradient elasticity

Using gradient elasticity, we give in this Letter the non-singular fields produced by arbitrary dislocation loops in isotropic media. We present the ‘modified’ Mura, Peach–Koehler and Burgers formulae in the framework of gradient elasticity theory.     

Triphenylene silanes for direct surface anchoring in binary mixed self-assembled monolayers

New triphenylene-based silanes 2-(ω-(chlorodimethylsilyl)-n-alkyl)-3,6,7,10,11-penta-m-alkoxytriphenylene 4 (Tm-Cn) with n = 8 or 9 and m = 7, 8, 9, 10, or 11 were synthesized, and their self-assembly behavior in the liquid state and at glass and silicon oxide surfaces was investigated. The mesomorphic properties of triphenylene silanes 4 (Tm-Cn) and their precursors 3 (Tm-Cn) were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. From the small-angle X-ray scattering (SAXS) regime, a preferential discotic lamellar mesophase can be deduced, and wide-angle X-ray scattering (WAXS) highlights the liquid-like characteristics of the alkyl side chains. To transfer these bulk structural properties to thin films, self-assembled monolayers (SAMs) were obtained by adsorption from solution and characterized by water contact angle measurements, null ellipsometry, and atomic force microscopy (AFM). Employing the concentration as an additional degree of freedom, binary SAMs of 2-(ω-(chlorodimethylsilyl)-undecyl)-3,6,7,10,11-penta-decyloxytriphenylene 4 (T10-C11) were coassembled with chlorodecyldimethylsilane or chlorodimethyloctadecylsilane, and their capability as model systems for organic templating was evaluated. The structure of the resulting binary mixed SAMs was analyzed by water contact angle measurements, null ellipsometry, and X-ray reflectivity (XRR) in combination with theoretical modeling by a multidimensional Parratt algorithm and AFM. The composition dependence of film thickness and roughness can be explained by a microscopic model including the steric hindrance of the respective molecular constituents.     

Self-assembly of class II hydrophobins on polar surfaces

Hydrophobins are structural proteins produced by filamentous fungi that are amphiphilic and function through self-assembling into structures such as membranes. They have diverse roles in the growth and development of fungi, for example in adhesion to substrates, for reducing surface tension to allow aerial growth, in forming protective coatings on spores and other structures. Hydrophobin membranes at the air-water interface and on hydrophobic solids are well studied, but understanding how hydrophobins can bind to a polar surface to make it more hydrophobic has remained unresolved. Here we have studied different class II hydrophobins for their ability to bind to polar surfaces that were immersed in buffer solution. We show here that the binding under some conditions results in a significant increase of water contact angle (WCA) on some surfaces. The highest contact angles were obtained on cationic surfaces where the hydrophobin HFBI has an average WCA of 62.6° at pH 9.0, HFBII an average of 69.0° at pH 8.0, and HFBIII had an average WCA of 61.9° at pH 8.0. The binding of the hydrophobins to the positively charged surface was shown to depend on both pH and ionic strength. The results are significant for understanding the mechanism for formation of structures such as the surface of mycelia or fungal spore coatings as well as for possible technical applications.     

Supported lipopolysaccharide bilayers

In this report, the formation of supported lipopolysaccharide bilayers (LPS-SLBs) is studied with extracted native and glycoengineered LPS from Escherichia coli ( E. coli ) and Salmonella enterica sv typhimurium ( S. typhimurium ) to assemble a platform that allows measurement of LPS membrane structure and the detection of membrane tethered saccharide-protein interactions. We present quartz crystal microbalance with dissipation monitoring (QCM-D) and fluorescence recovery after photobleaching (FRAP) characterization of LPS-SLBs with different LPS species, having, for example, different molecular weights, that show successful formation of SLBs through vesicle fusion on SiO(2) surfaces with LPS fractions up to 50 wt %. The thickness of the LPS bilayers were investigated with AFM force-distance measurements which showed only a slight thickness increase compared to pure POPC SLBs. The E. coli LPS were chosen to study the saccharide-protein interaction between the Htype II glycan epitope and the Ralstonia solanacearum lectin (RSL). RSL specifically recognizes fucose sugars, which are present in the used Htype II glycan epitope and absent in the epitopes LPS1 and EY2. We show via fluorescence microscopy that the specific, but weak and multivalent interaction can be detected and discriminated on the LPS-SLB platform.     

The impact of plant-pathogen studies on medicinal drug discovery

The pharmaceutical industry is reliant on a constant supply of new chemical entities and molecular targets for disease intervention. In this tutorial review, we want to illustrate that basic research studies on the biological function of natural products involved in plant-pathogen interactions can serve as an inspiring source for the identification of new bioactive entities as well as of strategies on how to achieve small molecule manipulation of biological systems. An application of findings from plant-pathogen interaction studies might therefore display a significant impact on drug discovery.     

Phase resolved near-field imaging of propagating waves in infrared tapered slot antennas

Tapered slot antennas (TSAs) consist of a planar non-resonant structure which couples incident radiation to a propagating waveguide mode. They are commonly used at microwave and radio frequencies because they are fundamentally broadband and have small profiles. Because of their planar layout and broadband response they have recently been scaled to infrared frequencies where they have advantages for sensing and energy harvesting. We use scattering-type scanning near-field optical microscopy (s-SNOM) to study the mode transformation of two types of TSA operating in the thermal infrared (λ₀ = 10.6 μm) with respect to electric field amplitude and phase. The results agree well with simulation showing both the phase reversal across the tapered slot and the traveling of wave fronts along the tapered slot, yet they also reveal high sensitivity of device performance to inhomogeneities in the geometry or illumination. This study will aid future design and analysis of practical non-resonant antennas operating at optical and infrared frequencies.     

Ultrastrong coupling regime and plasmon polaritons in parabolic semiconductor quantum wells

Ultrastrong coupling is studied in a modulation-doped parabolic potential well coupled to an inductance-capacitance resonant circuit. In this system, in accordance to Kohn's theorem, strong reduction of the energy level separation caused by the electron-electron interaction compensates the depolarization shift. As a result, a very large ratio of 27% of the Rabi frequency to the center resonance frequency as well as a polariton gap of width 2π × 670 GHz are observed, suggesting parabolic quantum wells as the system of choice in order to explore the ultrastrong coupling regime.     

3D FEM–BEM-coupling method to solve magnetostatic Maxwell equations

3D magnetostatic Maxwell equations are solved using the direct Johnson–Nédélec FEM–BEM coupling method and a reduced scalar potential approach. The occurring BEM matrices are calculated analytically and approximated by H-matrices using the ACA+ algorithm. In addition a proper preconditioning method is suggested that allows to solve large-scale problems using iterative solvers.