Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces

One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy of surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.     

An External Matrix-Assisted Laser Desorption Ionization Source for Flexible FT-ICR Mass Spectrometry Imaging with Internal Calibration on Adjacent Samples

We describe the construction and application of a new MALDI source for FT-ICR mass spectrometry imaging. The source includes a translational X-Y positioning stage with a 10×10 cm range of motion for analysis of large sample areas, a quadrupole for mass selection, and an external octopole ion trap with electrodes for the application of an axial potential gradient for controlled ion ejection. An off-line LC MALDI MS/MS run demonstrates the utility of the new source for data- and position-dependent experiments. A FT-ICR MS imaging experiment of a coronal rat brain section yields ～200 unique peaks from m/z 400-1100 with corresponding mass-selected images. Mass spectra from every pixel are internally calibrated with respect to polymer calibrants collected from an adjacent slide.     

Self-assembly and conductivity of hydrogen-bonded oligothiophene nanofiber networks

Symmetric oligothiophene derivatives containing hydrogen bond forming segments create self-supporting organogels consisting of self-assembled 1D nanostructures at low concentrations. Hydrogen bond formation and π-π stacking were both found to be crucial for the formation of conductive supramolecular networks of 1D nanostructures.     

Mass anomalous dimension in SU(2) with six fundamental fermions

We simulate SU(2) gauge theory with six massless fundamental Dirac fermions. We measure the running of the coupling and the mass in the Schrödinger Functional scheme. We observe very slow running of the coupling constant. We measure the mass anomalous dimension γ, and find it is between 0.135 and 1.03 in the range of couplings consistent with the existence of an IR fixed point.     

Optimization of coronary whole-heart MRA free-breathing technique at 3 Tesla

Four different techniques for 3-T whole-heart coronary magnetic resonance angiography (MRA) using free-breathing three-dimensional segmented parallel imaging and adiabatic T2-preparation were assessed. Coronary MRA at 3 T is improved by shortening the acquisition window more than employing the highest spatial resolution. Double-oblique whole-heart acquisitions result in better overall image quality and allow for better delineation of the left anterior descending coronary artery. It is possible to attain shorter acquisition windows and a smaller voxel size at 3 T than previously reported at 1.5 T.     

Third-harmonic generation in slow-light chalcogenide glass photonic crystal waveguides

We demonstrate third-harmonic generation (THG) in a dispersion-engineered slow-light photonic crystal waveguide fabricated in AMTIR-1 chalcogenide glass. Owing to the relatively low loss and low dispersion in the slow-light (c/30) regime, combined with the high nonlinear figure of merit of the material (～2), we obtain a relatively large conversion efficiency (1.4×10(-8)/W(2)), which is 30× higher than in comparable silicon waveguides, and observe a uniform visible light pattern along the waveguide. These results widen the number of applications underpinned by THG in slow-light platforms, such as the direct observation of the spatial evolution of the propagating mode.     

Temporary silicon connection strategies in intramolecular allylation of aldehydes with allylsilanes

Three gamma-(amino)silyl-substituted allylsilanes 14a-c have been prepared in three steps from the corresponding dialkyldichlorosilane. The aminosilyl group has been used to link this allylsilane nucleophile to a series of beta-hydroxy aldehydes through a silyl ether temporary connection. The size of the alkyl substituents at the silyl ether tether governs the outcome of the reaction on exposure to acid. Thus, treatment of aldehyde (E)-9aa, which contains a dimethylsilyl ether connection between the aldehyde and allylsilane, with a range of Lewis and Br?nsted acid activators provides an (E)-diene product. The mechanism of formation of this undesired product is discussed. Systems containing a sterically more bulky diethylsilyl ether connection react differently: thus in the presence of TMSOTf and a Br?nsted acid scavenger, intramolecular allylation proceeds smoothly to provide two out of the possible four diastereoisomeric oxasilacycles, 23 (major) and 21 (minor). A diene product again accounts for the remaining mass balance in the reaction. This side product can be completely suppressed by using a sterically even more bulky diisopropylsilyl ether connection in the cyclization precursor, although this is now at the expense of a slight erosion in the 1,3-stereoinduction in the allylation products. The sense of 1,3-stereoinduction observed in these intramolecular allylations has been rationalized by using an electrostatic argument, which can also explain the stereochemical outcome of a number of related reactions. Levels of 1,4-stereoinduction in the intramolecular allylation are more modest but can be significantly improved in some cases by using a tethered (Z)-allylsilane in place of its (E)-stereoisomer. Oxidation of the major diastereoisomeric allylation product 23 under Tamao-Kumada conditions provides an entry into stereodefined 1,2-anti-2,4-syn triols 28.     

A Brønsted acid mediated cascade enone synthesis from aldehydes containing a tethered propargylsilane

MeSO3H effects the intramolecular allenylation of a series of aldehydes 1 to provide allenyl alcohol product 3 as a single diastereoisomer. Cyclization proceeds rapidly at -78 degrees C. However, when the reaction is performed at room temperature, aldehyde 1 provides enone product 7 instead. A mechanism for the formation of this product is proposed in which the initially formed allenyl alcohol 3 undergoes dehydration to provide an allyl carbocation, which is trapped with water, thereby installing the enone.     

Heterocyclic Chromophore Amphiphiles and their Supramolecular Polymerization

Supramolecular polymerization of π-conjugated amphiphiles in water is an attractive approach to create functional nanostructures. Here, we report on the synthesis, optoelectronic and electrochemical properties, aqueous supramolecular polymerization, and conductivity of polycyclic aromatic dicarboximide amphiphiles. The chemical structure of the model perylene monoimide amphiphile was modified with heterocycles, essentially substituting one fused benzene ring with thiophene, pyridine or pyrrole rings. All the heterocycle-containing monomers investigated underwent supramolecular polymerization in water. Large changes to the monomeric molecular dipole moments led to nanostructures with low electrical conductivity due to diminished interactions. Although the substitution of benzene with thiophene did not notably change the monomer dipole moment, it led to crystalline nanoribbons with 20-fold higher electrical conductivity, due to enhanced dispersion interactions as a result of the presence of sulfur atoms.     

Hybrid Monomer Design Synergizing Property Trade-offs in Developing Polymers for Circularity and Performance

Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability to monomer for a circular plastics economy and desirable performance that can rival or even exceed today's non-recyclable or hard-to-recycle petroleum-based incumbents. However, within a traditional monomer framework it is challenging to optimize, concurrently, contrasting polymerizability/depolymerizability and recyclability/performance properties. Here, we highlight the emerging hybrid monomer design strategy to develop intrinsically circular polymers with tunable performance properties, aiming to unify desired, but otherwise conflicting, properties in a single monomer. Conceptually, this design hybridizes parent monomer pairs of contrasting, mismatching, or matching properties into offspring monomers that not only unify the above-described conflicting properties but also radically alter the resultant polymer properties far beyond the limits of what either parent homopolymers or their copolymers can achieve.