Controlling Energy Gaps of π-Conjugated Polymers by Multi-Fluorinated Boron-Fused Azobenzene Acceptors for Highly Efficient Near-Infrared Emission

We demonstrate that multi-fluorinated boron-fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor-acceptor (D-A) type π-conjugated polymers. Position-dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near-infrared (NIR) emission (λ_PL=758–847 nm) with high absolute photoluminescence quantum yield (Φ_PL=7–23%) originating from low-lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid-state emissive properties of the BAz units, deeper NIR emission (λ_PL=852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D-A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron-accepting unit through fine-tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials.     

Regulation of Multicolor Fluorescence Changes Found in Donor-acceptor-type Mechanochromic Fluorescent Dyes

The regulation of multicolor fluorescence changes in mechanochromic fluorescence (MCF) remains a challenging task. Herein, we report the regulation of MCF using a donor-acceptor structure. Two crystal polymorphs, BTD-pCHO(O) and BTD-pCHO(R) produced by the introduction of formyl groups to an MCF dye, respond to a mechanical stimulus, allowing a three-color fluorescence change. Specifically, the orange-colored fluorescence of the metastable BTD-pCHO(O) polymorph changed to a deep-red color in the amorphous-like state to finally give a red color in the stable BTD-pCHO(R) polymorph. This change occurred by mechanical grinding followed by vapor fuming. The two different crystal packing patterns were selectively regulated by the electronic effect of the introduced functional groups. The two types of selectively formed crystals in BTD(F)-pCHO bearing fluorine atoms, and BTD(OMe)-pCHO bearing methoxy groups, respond to mechanical grinding, allowing for the regulation of multicolor MCL from a three-color change to two different types of two-color changes.     

Cross‐sectional structural characterization of the surface of exfoliated HOPG using HRTEM‐EELS

We analyzed the surface atomic structure of highly oriented pyrolytic graphite (HOPG) substrate exfoliated with adhesive tape, using high‐resolution transmission electron microscopy and scanning transmission electron microscopy‐electron energy‐loss spectroscopy (STEM‐EELS). The surface step height of the exfoliated HOPG substrate was determined using high‐angle annular dark‐field‐scanning transmission electron microscopy (HAADF‐STEM) images and the depth profiles of the EELS spectra of a cross‐sectioned thin foil specimen prepared via focused ion beam milling. The exfoliated surface of the HOPG substrate presented disordered and curved graphene layers. The STEM‐EELS measurements indicated that upon exfoliation, the surface of the HOPG substrate reacted with atmospheric water and oxygen molecules.     

A new micromechanical formulation of martensite kinetics driven by temperature and/or stress

Summary Martensitic transformation behavior of alloys is studied under the arbitrary action of a thermal and/or a triaxial mechanical load-stress state by solving a transformation kinetic equation presented recently by the same authors. Numerical and analytical solutions reveal that the transformation behavior is almost path-independent. Lines of constant volume fraction of martensite are nearly parallel in the stress-temperature plane. Some new analytical formulae for martensitic transformation kinetics are presented.

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Eine neue mikromechanische Formulierung der Martensit-Kinetik unter Temperatur- und/order Spannungsbelastung

Übersicht Es wird das Verhalten der martensitischen Umwandlung von Legierungen unter beliebiger thermischer und/oder dreiachsiger mechanischer Spannungsbelastung untersucht, indem eine neue Gleichung der Umwandlungskinetik gelöst wird. Diese Gleichung wurde vor kurzem von denselben Autoren vorgestellt. Die numerischen und die analytischen Lösungen zeigen, daß das Transformationsverhalten nahezu pfadunabhängig ist. Die Linien gleicher Volumsfraktion von Martensit sind nahezu parallel im Spannungs-Temperatur-Diagramm. Es werden auch einige neue analytische Formeln für die Umwandlungskinetik von Martensit präsentiert.

     

A correction method for measuring turbulence kinetic energy dissipation rate by PIV

The accuracy of turbulent kinetic energy (TKE) dissipation rate measured by PIV is studied. The critical issue for PIV-based dissipation measurements is the strong dependency on the spatial resolution, Δx, as reported by Saarenrinne and Piirto (Exp Fluids Suppl:S300–S307, 2000). When the PIV spacing is larger than the Kolmogorov scale, η, the dissipation is underestimated because the small scale fluctuations are filtered. For the case of Δx smaller than the Kolmogorov scale, the error rapidly increases due to noise. We introduce a correction method to eliminate the dominant error for the small Δx case. The correction method is validated by using a novel PIV benchmark, random Oseen vortices synthetic image test (ROST), in which quasi-turbulence is generated by randomly superposing multiple Oseen vortices. The error of the measured dissipation can be more than 1,000% of the analytical dissipation for the small Δx case, while the dissipation rate is underestimated for the large Δx case. Though the correction method does not correct the underestimate due to the low resolution, the dissipation was accurately obtained within a few percent of the true value by using the correction method for the optimal resolution of η/10 < Δx < η/2.     

Meshless method for nonlinear heat conduction analysis of nano-composites

Carbon nanotubes (CNTs) may become ideal reinforcing materials for high-performance nano-composites due their exceptional properties. Still, much work is needed to be done before the potentials of CNT based composites can be fully realized. The evaluation of effective material properties of nano-composites is one of many difficult tasks. Simulations using continuum mechanics approach can play a significant role in the analysis of these composites. In the present work, nonlinear heat conduction analysis of CNT based composites has been carried out using continuum mechanics approach. Element free Galerkin method has been applied as a numerical tool. Thermal conductivities of nanotube and polymer matrix are assumed to vary quadratically with temperature. Picard and quasi-linearization schemes have been utilized to obtain the solution of a system of nonlinear equations. Cylindrical representative volume element has been used to evaluate the thermal properties of nano-composites. Present simulations show that the temperature dependent matrix thermal conductivity has a significant effect on the equivalent thermal conductivity of the composite, whereas temperature dependent nanotube thermal conductivity has a small effect on the equivalent thermal conductivity of the composite. The results obtained by Picard method have been found almost similar with those obtained by quasi-linearization approach.     

Turning characteristics of multi-axle vehicles

This paper presents a mathematical model for multi-axle vehicles operating on level ground. Considering possible factors related to turning motion such as vehicle configuration and tire slip velocities, equations of motion were constructed to predict steerability and driving efficiency of such vehicles. Turning radius, slip angle at the mass center, and each wheel velocity were obtained by numerically solving the equations with steering angles and average wheel velocity as numerical inputs. To elucidate the turning characteristics of multi-axle vehicles, the effect of fundamental parameters such as vehicle speed, steering angles and type of driving system were examined for a sample of multi-axle vehicles. Additionally, field tests using full-scale vehicles were carried out to evaluate the basic turning characteristics on level ground.     

Two‐dimensional replica‐exchange method for predicting protein–ligand binding structures

We have developed a two‐dimensional replica‐exchange method for the prediction of protein–ligand binding structures. The first dimension is the umbrella sampling along the reaction coordinate, which is the distance between a protein binding pocket and a ligand. The second dimension is the solute tempering, in which the interaction between a ligand and a protein and water is weakened. The second dimension is introduced to make a ligand follow the umbrella potential more easily and enhance the binding events, which should improve the sampling efficiency. As test cases, we applied our method to two protein‐ligand complex systems (MDM2 and HSP 90‐alpha). Starting from the configuration in which the protein and the ligand are far away from each other in each system, our method predicted the ligand binding structures in excellent agreement with the experimental data from Protein Data Bank much faster with the improved sampling efficiency than the replica‐exchange umbrella sampling method that we have previously developed. © 2013 Wiley Periodicals, Inc.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.