Photoluminescent Ferroelastic Molecular Crystals

Ferroelasticity has been reported for several types of molecular crystals, which show mechanical‐stress‐induced shape change under twinning and/or spontaneous formation of strain. Aiming to create materials that exhibit both ferroelasticity and light‐emission characteristics, we discovered the first examples of ferroelastic luminescent organometallic crystals. Crystals of arylgold(I)(N‐heterocyclic carbene)(NHC) complexes bend upon exposure to anisotropic mechanical stress. X‐ray diffraction analyses and stress‐strain measurements on these ferroelastic crystals confirmed typical ferroelastic behavior, mechanical twinning, and the spontaneous build‐up of strain. A comparison with single‐crystal structures of related gold‐NHC complexes that do not show ferroelasticity shed light on the structural origins of the ferroelastic behavior.     

Optical modulator using metal-oxide-semiconductor type Si ring resonator

Electric-field drive optical modulators using a Si ring resonator were fabricated on silicon-on-insulator (SOI) wafers. The fabricated resonators consisted of Si waveguides with width and thickness of 1.0 and 0.3 μm, respectively. In order to induce the linear electro-optic (EO) effect in the Si core layer, the strain was applied by covering the layer with Si₃N₄ film (0.26 μm thick) deposited by low pressure chemical vapor deposition (LPCVD) at 750 °C. The vertical electric-field was applied to the Si waveguide through the top and bottom cladding layers, and the optical output from the drop port at the resonance wavelength was measured. At a wavelength of 1501.6 nm, the optical modulation of 33% was obtained at 200V (electric-field at the silicon surface ∼3 × 10⁵ V/cm, nearly the breakdown field). The resonance wavelength was shifted toward the short wavelength side by applying both positive and negative voltages, this shift was explained by carrier concentration modulation. The linear EO effect in the Si core layer was not observed, presumably because the strain in the Si core layer was too small.     

GPU-accelerated molecular dynamics simulation for study of liquid crystalline flows

We have developed a GPU-based molecular dynamics simulation for the study of flows of fluids with anisotropic molecules such as liquid crystals. An application of the simulation to the study of macroscopic flow (backflow) generation by molecular reorientation in a nematic liquid crystal under the application of an electric field is presented. The computations of intermolecular force and torque are parallelized on the GPU using the cell-list method, and an efficient algorithm to update the cell lists was proposed. Some important issues in the implementation of computations that involve a large number of arithmetic operations and data on the GPU that has limited high-speed memory resources are addressed extensively. Despite the relatively low GPU occupancy in the calculation of intermolecular force and torque, the computation on a recent GPU is about 50 times faster than that on a single core of a recent CPU, thus simulations involving a large number of molecules using a personal computer are possible. The GPU-based simulation should allow an extensive investigation of the molecular-level mechanisms underlying various macroscopic flow phenomena in fluids with anisotropic molecules.     

Synthesis of aspergillide A via proline-catalyzed trans-to-cis isomerization of a substituted tetrahydropyran

The transformation of a common synthetic intermediate of aspergillides B and C into aspergillide A, a cytotoxin produced by a marine-derived fungus, has been accomplished in an eleven-step sequence involving an efficient proline-catalyzed isomerization of a 2,6-trans-substituted tetrahydropyran-2-acetaldehyde intermediate into the corresponding cis isomer and the Yamaguchi macrolactonization as the key steps.     

Titanocene(II)-promoted carbonyl allenation utilizing 1,1-dichloroalk-1-enes

Treatment of 1,1-dichloroalk-1-enes with Cp2Ti[P(OEt)3]2 produced organotitanium species, which afford allenes on treatment with aldehydes and ketones.     

Attenuation and depolarization of millimeter waves due to incoherent scattering in tropical rainfall

The radiative transfer equation has been applied to investigate the effects of multiple scattering on communication at the millimeter wavelength in tropical rain. Horizontal linearly polarized incident waves are assumed. The scattering characteristics are calculated using the Mie theory at frequencies of 16, 34.8, 82, 140 and and at rainfall rates of 12.5, 50 and . Some results of the directional patterns of the incoherent intensities at various points in the rain medium are presented. The frequency dependence of the propagation distance, attenuation coefficient and the variation of incoherent specific intensities in tropical rainfall are investigated. The incoherent power at the receiver relative to the coherent power, which is important in assessing the quality of signal in the receiver, is also investigated. It is observed that the maximum incoherent copolarized received power is about in tropical rainfall at rainfall rate. Also the difference between the copolarized incoherent power in tropical and temperate rainfall is about at frequencies higher than , and about for the cross-polarized incoherent power components. It may therefore be safely said that multiple scattering may not result in serious degradation of the coherent wave component even in the most intense tropical precipitation. It also appears that it is independent of regional rainfall climatology.     

Enhancement of water solubility of fullerene by cogrinding with mixture of cycloamyloses, novel cyclic alpha-1,4-glucans, via solid-solid mechanochemical reaction

Improvement of solubility for fullerene (C60) was studied by cogrinding with cycloamyloses using a ball mill in the solid state. Cycloamylose is a novel cyclic alpha-1,4-glucan produced from synthetic amylose by enzymatic reaction. Although sample solutions showed a pale yellow for the initial period of cogrinding with cycloamyloses and C60, the color varied to brown after 48 h. Subsequently, the solubility of C60 was improved markedly to 560 (microg/ml) at 96 h. From powder X-ray diffraction analysis, the peak intensity of crystalline C60 decreased as the cogrinding time was extended. The UV-VIS absorption spectrum of C60 shows absorption bands at 262 and 340 nm in water with cycloamyloses, and 258 and 328 nm in n-hexane. These results suggested that C60 molecules were dispersed into cycloamyloses micellar system and the red-shift of the UV-VIS spectra was due to an intermolecular interaction between C60 and cycloamyloses.     

Photochemical ligation of DNA conjugates through anthracene cyclodimer formation and its fidelity to the template sequences

Anthracene readily forms photoadducts, anthracene dimers, and this photodimerization reaction has been well characterized. In general, however, the reaction requires close proximity and certain spatial alignment of both reaction partners. DNA could provide an ideal scaffold for accelerating the photocyclic addition. We synthesized a number of anthracene-DNA conjugates. The sequences of the conjugates, 5'AntODNn and 3'AntODNn (the length of methylene linkers: n = 3 or 6), were designed to bind adjacent sequences of the template with the anthracene units directed such that they stacked with each other. The conjugates were only dimerized in the presence of the template by light irradiation. The efficiency was affected by one-base displacement in the template sequence.