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A secondary phosphine oxide (SPO)-nickel catalyst allowed the activation of otherwise inert C-F bonds of unactivated arenes in terms of challenging couplings with primary and secondary alkyl Grignard reagents. The C-F activation is characterized by mild reaction conditions and high levels of branched selectivity. Electron-rich and electron-deficient arenes were suitable electrophiles for this transformation. In addition, this strategy also proved suitable to heterocycles and for the activation of C-O bonds under slightly modified conditions.An efficient method for the synthesis of (hetero)arene-fused 2,2-difluoro-2,3-dihydrothiophene derivatives using readily available sodium chlorodifluoroacetate (ClCF2CO2Na) has been developed. Ribociclib price This transformation is achieved through a combination of a thiolate with difluorocarbene, followed by intramolecular nucleophilic addition to a ketone, cyano, or ester functional group.The first palladium-catalyzed, ligand-controlled chemoselective synthesis of imides has been achieved. An orthogonal set of conditions has been developed for multicomponent reaction of various olefin-tethered aryl iodides, isocyanides, and carboxylic acids. Alkylimides ("cyclization on" products) via arylimidation of tethered unactivated alkenes and aryl imides ("cyclization off" products) via direct imidation of aryl iodides were obtained in good to excellent yields with good to excellent selectivity. Computational studies were performed to gain insight into the origin of the high levels of chemoselectivity observed.We re-evaluate two key steps in the mechanism of CO2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. We optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT's inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO2 reduction, which is the subject of ongoing work.In this paper, we propose a polarization-selective color filter that can generate two different color informations simultaneously depending on the polarization direction. The proposed color filter is mainly composed of the etalon structure to generate the color by the structural resonance properties while the upper layer of the etalon is made of plasmonic nanogratings to promote polarization-dependent color properties. When the duty ratio of the silver nanogratings is fixed, the proposed color filter can maintain identical optical properties for orthogonal polarization, while the etalon structure of the proposed color filter can manipulate different color information depending on the cavity height for the horizontal polarization. Finally, we experimentally confirm that polarization-dependent security images can be generated using the proposed color filters with a fixed duty ratio of various nanograting arrays.Developing a rapid fabrication of colloidal crystal film is one of the technical issues to apply to wide and various fields. We have been investigating a drying process of colloidal aqueous ethanol (EtOH) suspension formed by electrophoretic deposition (EPD). Here, the detailed formation mechanism of the colloidal crystal films with the closest packing structure was investigated by optical microscope and spectroscopy. The growth mechanism from the colloidal suspension to the colloidal crystal film was found to consist of four stages. In the first stage, concentrated colloidal suspension changed to order structure, i.e., nonclosely packed colloidal crystal by Alder phase transition. After this crystallization, we observed Bragg's diffraction peak and structural color. In the second stage, the diffraction peak shifts toward the shorter-wavelength direction (blue shift) due to the reduction of the interparticle distance of the nonclosely packed colloidal crystal. Finally, this peak shift continued until the closely packed colloidal crystal film was formed. In the third stage, the diffraction peak kept almost a similar wavelength due to the liquid film of aqueous EtOH covering on the colloidal crystal film. In the fourth stage, the colloidal crystal film changed from wet to dry condition. The structural color changes from green to blue by the evaporation of the solvent from the interspace of the colloidal crystal film. This color change is explained by the change in the refractive index of the interparticle medium from solvent to air. One of the key findings in our process is a rapid crystal growth using concentrated colloid aqueous EtOH suspension. Drying the concentrated suspension formed a closely packed colloidal crystal film within 55 s. This process has the potential for high-speed deposition of the colloidal crystalline thin films.Understanding the structure of the stratum corneum (SC) is essential to understand the skin barrier process. The long periodicity phase (LPP) is a unique trilayer lamellar structure located in the SC. Adjustments in the composition of the lipid matrix, as in many skin abnormalities, can have severe effects on the lipid organization and barrier function. Although the location of individual lipid subclasses has been identified, the lipid conformation at these locations remains uncertain. Contrast variation experiments via small-angle neutron diffraction were used to investigate the conformation of ceramide (CER) N-(tetracosanoyl)-sphingosine (NS) within both simplistic and porcine mimicking LPP models. To identify the lipid conformation of the twin chain CER NS, the chains were individually deuterated, and their scattering length profiles were calculated to identify their locations in the LPP unit cell. In the repeating trilayer unit of the LPP, the acyl chain of CER NS was located in the central and outer layers, while the sphingosine chain was located exclusively in the middle of the outer layers.
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