Synthesis and structure-linear and structure-nonlinear optical properties of multi-dipolar zigzag oligoaryleneethynylenes

A novel series of monodisperse, multi-dipolar zigzag oligoaryleneethynylenes DA(n) and D-Ar-A(n), bearing electron-donating dibenzothiophene and electron-accepting dibenzothiophene dioxide as arenes, with up to six charge-transfer (dipolar) units have been designed and synthesized by palladium-catalyzed Sonogashira coupling reactions. The linear and nonlinear optical properties of these multi-dipolar oligoaryleneethynylenes can easily be modified or enhanced by incorporating/extending with various central aryleneethynyl moieties such as phenylethynyl, oligo(9,9-dibutylfluorenyl)ethynyl, and oligothienylethynyl within the donor-acceptor units. Interestingly, the absorption and emission of these zigzag oligoaryleneethynylenes are not dependent on the number of covalently linked dipolar chromophores; however, the fluorescence quantum efficiencies consistently decrease with increased number of covalently linked dipolar units. These zigzag oligoaryleneethynylenes exhibit a linear increase in the two-photon absorption (TPA) cross-sections with increased number of covalently linked dipolar units without red-shifting the absorption and emission spectra. In addition, very large TPA cross-sections in the femtosecond regime (sigma(800) = 1306 GM in DMF or sigma(750) = 1522 GM in CH(2)Cl(2)) were obtained for D-TF-A(4) despite the moderate strength of the donor-acceptor pair. Our results suggest that the TPA properties of these zigzag oligoaryleneethynylenes including TPA wavelength and TPA cross-section can easily be tuned by means of modifying the central aryleneethynylene units and increasing the number of dipolar units, respectively. This approach provides an alternative means to tune or enhance the TPA cross-section at a specific wavelength.     

Droplet-based microfluidics with nonaqueous solvents and solutions

In droplet-based ("digital") microfluidics, liquid droplets in contact with dielectric surfaces are created, moved, merged and mixed by applying AC or DC potentials across electrodes patterned beneath the dielectric. We show for the first time that it is possible to manipulate droplets of organic solvents, ionic liquids, and aqueous surfactant solutions in air by these mechanisms using only modest voltages (<100 V) and frequencies (<10 kHz). The feasibility of moving any liquid can be predicted empirically from its frequency-dependent complex permittivity, epsilon*. The threshold for droplet actuation in air with our two-plate device configuration is /epsilon*/>8x10(-11). The mechanistic implications of these results are discussed, along with the greatly expanded range of applications for digital microfluidics that these results suggest are now feasible.     

Structural flexibility of a helical peptide regulates vibrational energy transport properties

Applying ultrafast vibrational spectroscopy, we find that vibrational energy transport along a helical peptide changes from inefficient but mostly ballistic below approximately 270 K into diffusive and significantly more efficient above. On the basis of molecular dynamics simulations, we attribute this change to the increasing flexibility of the helix above this temperature, similar to the glass transition in proteins. Structural flexibility enhances intramolecular vibrational energy redistribution, thereby refeeding energy into the few vibrational modes that delocalize over large parts of the structure and therefore transport energy efficiently. The paper outlines concepts how one might regulate vibrational energy transport properties in ultrafast photobiological processes, as well as in molecular electronic devices, by engineering the flexibility of their components.     

Linear and non-linear dynamics of entangled linear polymer melts by modified tunable coarse-grained level dissipative particle dynamics

Dissipative particle dynamics (DPD) is a well-known simulation method for soft materials and has been applied to a variety of systems. However, doubts have been cast recently on its adequacy because of upper coarse-graining limitations, which could prevent the method from being applicable to the whole mesoscopic range. This paper proposes a modified coarse-grained level tunable DPD method and demonstrates its performance for linear polymeric systems. The method can reproduce both static and dynamic properties of entangled linear polymer systems well. Linear and non-linear viscoelastic properties were predicted and despite being a mesoscale technique, the code is able to capture the transition from the plateau regime to the terminal zone with decreasing angular frequency, the transition from the Rouse to the entangled regime with increasing molecular weight and the overshoots in both shear stress and normal-stress differences upon start-up of steady shear.     

High-performance hydrogen production and oxidation electrodes with hydrogenase supported on metallic single-wall carbon nanotube networks

We studied the electrocatalytic activity of an [FeFe]-hydrogenase from Clostridium acetobutylicum (CaH2ase) immobilized on single-wall carbon nanotube (SWNT) networks. SWNT networks were prepared on carbon cloth by ultrasonic spraying of suspensions with predetermined ratios of metallic and semiconducting nanotubes. Current densities for both proton reduction and hydrogen oxidation electrocatalytic activities were at least 1 order of magnitude higher when hydrogenase was immobilized onto SWNT networks with high metallic tube (m-SWNT) content in comparison to hydrogenase supported on networks with low metallic tube content or when SWNTs were absent. We conclude that the increase in electrocatalytic activities in the presence of SWNTs was mainly due to the m-SWNT fraction and can be attributed to (i) substantial increases in the active electrode surface area, and (ii) improved electronic coupling between CaH2ase redox-active sites and the electrode surface.     

Catalyst volume to surface area constraints for nucleating carbon nanotubes

In this Article, we describe a carbon nanotube formation model in which sp2 carbon hemispheres form the embryonic caps from which a nanotube can grow. This requirement leads to a single wall carbon nanotube formation window concomitant with our systematic experimental findings, which show upper and lower diameter limits. Further, the successful formation of a nucleation cap (hemisphere) is governed by catalyst particle volume to surface area considerations. Single wall carbon nanotubes are only obtained when both the nanotube formation window and the precipitating catalyst size distribution cross over. The extent to which these two windows overlap establishes the mean diameter and diameter distribution of the obtained single wall carbon nanotubes.     

Unraveling the absorption spectra of alkali metal atoms attached to helium nanodroplets

The absorption spectra of the first electronic exited state of alkali metal atoms on helium nanodroplets formed of both 4He and 3He isotopes were studied experimentally as well as theoretically. In the experimental part new data on the 2p<--2s transition of lithium on 3He nanodroplets are presented. The absorption spectrum changes drastically when compared to 4He droplets, in contrast to sodium where only marginal differences were observed in former studies. To explain these large differences and to answer some still open questions concerning the interaction of alkali metal atoms with helium nanodroplets, a model calculation was performed. New helium density profiles as well as a refined model allowed us to achieve good agreement with the experimental findings. For the first time the red-shifted intensities in the lithium and sodium spectra are explained in terms of enhanced binding configurations in the excited state displaced spatially from the ground state configurations.     

Tensile strengths and Young’s modulus of thin copper and copper-nickel (CuNi44) substrates

In this paper we report a method to determine tensile strengths and Young’s modulus of cubic biaxial textured metal tapes used as substrate materials for coated conductors (CC). Simplicity, rapidity and reproducibility of the procedure are important for the evaluation of continuous in-house productions. Our approach is based on the EN 10002-1 B tensile test method. A key role for satisfactory results is the sample preparation of 100–250 μm thick tapes, which will be described in detail. Copper (E-Cu57) can be successfully transformed to cubic biaxial textured substrates. Best results were achieved by annealing between 750°C and 850°C in reducing atmosphere. Best FWHM values for the ψ scan are 5.51° and for the ϕ scan are 4.5°. Pole figure analysis verified the sharp {001} <100> texture of the tape. Vickers hardness measurements (HV 0.1) for the cold worked material yielded values of 135 and for the annealed tape, values of 37. The ultimate tensile yield strength Rm of the textured substrate is 150 MPa and thus significantly lower than that for the cold worked material (413 MPa). Cubic biaxial substrates could be manufactured from Isotan CuNi44 (WM49) bars. Best results were achieved by annealing at 1200°C in reducing atmosphere. Pole figure analysis verified the {001} <100> texture with other low intensity texture components. Vickers hardness measurements (HV 0.1) for the cold worked material yielded values of 236 and for the annealed tape values of 92. The ultimate tensile yield strength R _m of the textured substrate is 300 MPa and thus significantly lower than that for the cold worked material (723 MPa).      

Scroll wave filaments terminate in the back of traveling fronts

Experiments with the 1,4-cyclohexanedione Belousov-Zhabotinsky reaction demonstrate that three-dimensional scroll waves can rotate around filaments that end in the wake of a traveling excitation pulse. The vortex structures nucleate during the collision of three nonrotating excitation pulses. The nucleation process and the wave-termination of filaments are direct consequences of the system's anomalous dispersion relation. Vortex filaments are found to expand with about twice the speed of their anchoring wave fronts. Filament expansion is accompanied by the build-up of phase differences in spiral rotation creating strongly twisted wave structures. Experiments employ optical tomography for the reconstruction of the three-dimensional wave patterns.     

Two cationic metal-organic frameworks based on cadmium and α,ω-alkanedisulfonate anions and their photoluminescent properties

We have successfully synthesized three cadmium-based metal-organic frameworks by utilizing two separate organic linkers to direct the structure. The first material is a three-dimensional neutral framework based on 2D cadmium ethanedisulfonate layers pillared by a 4,4'-bipyridine linker. The other two materials are 3D cationic frameworks and are the first with propanedisulfonate and butanedisulfonate as extraframework charge balancing anions. Both structures occupy a high symmetry hexagonal crystal system where Cd-bipy chains are arranged into three crystallographically distinct layers that stack spirally along [001]. The framework is stabilized by alkanesulfonate anions that are electrostatically and hydrogen bonded to the framework. Each material was characterized by single-crystal and powder X-ray diffraction. The thermal and luminescent properties were also investigated by thermogravimetric analysis and photoluminescence spectroscopy, respectively. All three materials exhibit high thermal stability to above 300 °C and efficient blue emissive photoluminescence centered at 425 nm to 450 nm upon 350 nm excitation.