Pd-P(t-Bu)(3)-catalyzed consecutive cross-coupling of p-phenylenedizinc compound with two different electrophiles leading to unsymmetrically 1,4-disubstituted benzenes

Pd-P(t-Bu)3 was found to be a chemoselective catalyst for the reaction of p-phenylenedizinc compound with equimolar amounts of carbon electrophiles to afford the single cross-coupling products in good yields, effectively suppressing the formation of double cross-coupling products. The subsequent additions of other electrophiles to the resulting solutions caused the second cross-coupling of the incipient products to take place, achieving a novel and efficient one-pot synthesis of unsymmetrically 1,4-disubstituted benzenes. The origin of the observed high chemoselectivity was speculated.     

Self-assembly of acridine orange dye at a mica/solution interface: formation of nanostripe supramolecular architectures

Optical waveguide spectroscopy and atomic force microscopy (AFM) have been used to characterize the supramolecular architectures of acridine orange (AO) dye self-assembled at a mica/aqueous solution interface. Under the saturated adsorption conditions, optical waveguide spectroscopy revealed that the dye formed H-type aggregates at the interface. In situ AFM visualized interesting morphology of the dye aggregates showing nanosized meandering stripes with the width of approximately 1.5 nm (or brightness periodicity of approximately 3 nm). Electrostatic adsorption of the dye cations onto a mica surface as well as the intermolecular pi-pi stacking brought about the ordered nanostructures. We propose an interfacial aggregation model that shows a meandering staircase structure with the intermolecular slip angle of 60 degrees. According to the model, the AO molecule occupies a surface area of about 1.0 nm2.     

Theoretical analysis of concerted and stepwise mechanisms of Diels-Alder reactions of butadiene with silaethylene and disilene

The concerted and the stepwise mechanisms of the Diels-Alder reactions of butadiene with silaethylene and disilene were studied by ab initio MO methods. For the reaction of butadiene and silaethylene, an asymmetric concerted process that is almost stepwise and two stepwise processes were located. For the first step of the stepwise process, the C-Si bond formation is more favorable than the C-C bond formation. The activation energy barrier of the concerted transition state is only 0.89 kcal/mol lower than that of the first-step transition state of the C-Si bond formation for the stepwise process by the CASPT2 calculation level. For the reaction of butadiene and disilene, the activation energy barrier of the concerted-type transition state constrained with Cs symmetry is about 9 kcal/mol higher than that of the stepwise transition state by the CASSCF method. The energy barrier of the first step of the stepwise reaction disappears at the CASPT2/6-311++G(d,p) calculation level including the nondynamical correlation energy, although the reaction of the butadiene with disilene occurs through the stepwise-like process.     

Performance comparison of bilinear interpolation, bicubic interpolation, and B-spline interpolation in parallel phase-shifting digital holography

To improve the quality of reconstructed images, we apply bicubic interpolation and B-spline interpolation to parallel phase-shifting digital holography for the first time. The effectiveness of bilinear interpolation, bicubic interpolation, and B-spline interpolation in parallel phase-shifting digital holography is shown by a numerical simulation. In the simulation result, the application of bicubic interpolation and B-spline interpolation succeeded in decreasing the rootmean- square error of the reconstructed image by 12.6 and 11.9%, respectively.     

Mode of action and biosynthesis of the azabicycle-containing natural products azinomycin and ficellomycin

Only a handful of aziridine-containing natural products have been identified out of the more than 100,000 natural products characterized to date. Among this class of compounds, only the azinomycins (azinomycin A and B) and ficellomycin contain an unusual 1-azabicyclo[3.1.0]hexane ring system, which has been reported to be the reason for theDNAcrosslinking abilities and cytotoxicity of these metabolites. Both families of natural products are produced by Streptomyces species, Streptomyces sahachiroi and Streptomyces ficellus, respectively. Up until recently, much of the work on these molecules has focused on the synthesis of these natural products or their corresponding analogs for in vitro investigations evaluating their DNA selectivity. While one of the most intriguing aspects of these natural products is their biosynthesis, progress made in this area was largely impeded by difficulties with obtaining a reliable culture method and securing a consistent source of these natural products. In this review, we will cover the discovery and biological activity of the azinomycins, their mode of action, related synthetic analogs and biosynthesis, and finish with a discussion on the less studied metabolite, ficellomycin.     

Polysulfone Functionalized With Phosphonated Poly(pentafluorostyrene) Grafts for Potential Fuel Cell Applications

A multi‐step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne‐end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting of PFS onto PSU backbone is performed via the “click”‐chemistry approach. In a final step, the PFS‐grafts are subjected to the post phosphonation. The copolymers are evaluated as membranes for potential fuel cell applications through thermal analyses, water uptake, and conductivity measurements. The proposed synthetic route opens the possibility to tune copolymers’ hydrophilic–hydrophobic balance to obtain membranes with an optimal balance between proton conductivity and mechanical properties.     

Mechanistic study on the reaction of pinB-BMes2 with alkynes based on experimental investigation and DFT calculations: gradual change of mechanism depending on the substituent

Transition metal-free direct and base-catalyzed 1,2-diborations of arylacetylenes using pinB-BMes₂ provided a syn/anti-isomeric mixture of diborylalkenes. The kinetic analysis showed that the reaction rate and isomer ratio were affected by reaction conditions and substituents on the aryl ring. DFT calculations indicated that direct addition proceeded via the interaction of acetylene-π with the BMes₂ fragment. In contrast, for the base-catalyzed diboration, the previously isolated sp²–sp³ diborane and borataallene were confirmed as stable intermediates by calculations. The whole reaction pathways can be divided into the Bpin-migration and deprotonation steps, where the borataallene should be considered as a common intermediate. It should be noted that the deprotonation step is reversible and affords the kinetically less favoured isomer under the thermodynamic conditions. As a result, the composition of isomeric products, in the base-catalyzed diboration, is attributed to the small difference of activation barriers between direct and base-catalyzed systems.

Combination of kinetic and DFT studies revealed a subtle balance for substituent effect toward the regioselectivity of the product in metal-free and base-catalyzed diboration of arylacetylenes.     

Polarization-independent guided-mode resonance filter with cross-integrated waveguide resonators

A cavity-resonator-integrated guided-mode resonance filter (CRIGF) has been proposed and investigated in order to realize high-efficiency narrowband reflection with a small aperture. The CRIGF consists of a grating coupler integrated in a cavity resonator constructed by a pair of distributed Bragg reflectors on a thin-film waveguide. This time, orthogonally crossed integration of two CRIGFs was demonstrated in order to obtain polarization-independent reflection spectrum. An SiO₂-based device with 10?μm aperture was designed and fabricated for around 850?nm wavelength operation, and narrowband polarization-independent reflection was confirmed experimentally.     

Parallel phase-shifting dual-illumination phase unwrapping

We propose a single-shot phase unwrapping technique using a single wavelength and parallel phase-shifting interferometry. In the proposed technique, an object is illuminated by two laser beams, which are emitted from the same laser, and have different illumination angles and polarizations. Two types of object waves generated by the two beams are separately and simultaneously recorded by a polarization-imaging camera. In the path of the reference wave, an array of phase retarders is placed to implement the parallel phase-shifting technique. A highly accurate three-dimensional shape is reconstructed from a single hologram. We numerically simulated the proposed technique and conducted a preliminary experiment to verify its effectiveness. It was confirmed that millimeter-order height, which was several thousand times the wavelength of the laser, can be reconstructed by the proposed technique without wrapping.     

Parallel two-step phase-shifting digital holography using polarization

We propose an optical implementation of a parallel two-step phase-shifting digital holography that utilizes a polarization technique. The implementation uses a phase-shifting array device consisting of a retarder array attached to an image sensor, and does not require the optical system to image the phase-shifting array device onto the image sensor required for the previously reported optical implementation of the parallel two-step phase-shifting digital holography. Then, the proposed implementation is essentially simple to align and compose. A preliminary experiment showed that the parallel two-step phase-shifting digital holography based on the proposed implementation can remove the conjugate image clinging to the image reconstructed by Fresnel transform alone with DC term suppression. Also, when the reconstruction distance was changed, the qualities of the reconstructed images were quantitatively evaluated by using normalized root-mean-square error. It was clarified that the proposed implementation was superior to other parallel phase-shifting digital holographies and Fresnel transform alone. Thus, the validity of the proposed implementation was confirmed.