Boric Acid as Highly Efficient Catalyst for the Synthesis of Phenols from Arylboronic Acids

A simple, efficient, and environmentally benign boric acid catalyzed methodology for the ipso‐hydroxylation of arylboronic acid to phenol has been developed using aqueous hydrogen peroxide as an oxidizing agent and ethanol as the solvent. The versatility of this protocol is that the reactions were performed at room temperature in short reaction time under metal‐, ligand‐, and base‐free conditions.     

51V solid-state NMR and density functional theory studies of vanadium environments in V(V)O2 dipicolinic acid complexes

(51)V solid-state NMR and density functional theory (DFT) investigations are reported for a series of pentacoordinate dioxovanadium(V)-dipicolinate [V(V)O(2)-dipicolinate] and heptacoordinate aquahydroxylamidooxovanadium(V)-dipicolinate [V(V)O-dipicolinate] complexes. These compounds are of interest because of their potency as phosphatase inhibitors as well as their insulin enhancing properties and potential for the treatment of diabetes. Experimental solid-state NMR results show that the electric field gradient tensors in the V(V)O(2)-dipicolinate derivatives are affected significantly by substitution on the dipicolinate ring and range from 5.8 to 8.3 MHz. The chemical shift anisotropies show less dramatic variations with respect to the ligand changes and range between -550 and -600 ppm. To gain insights on the origins of the NMR parameters, DFT calculations were conducted for an extensive series of the V(V)O(2)- and V(V)O-dipicolinate complexes. To assess the level of theory required for the accurate calculation of the (51)V NMR parameters, different functionals, basis sets, and structural models were explored in the DFT study. It is shown that the original x-ray crystallographic geometries, including all counterions and solvation water molecules within 5 A of the vanadium, lead to the most accurate results. The choice of the functional and the basis set at a high level of theory has a relatively minor impact on the outcome of the chemical shift anisotropy calculations; however, the use of large basis sets is necessary for accurate calculations of the quadrupole coupling constants for several compounds of the V(V)O(2) series. These studies demonstrate that even though the vanadium compounds under investigations exhibit distorted trigonal bipyramidal coordination geometry, they have a "perfect" trigonal bipyramidal electronic environment. This observation could potentially explain why vanadate and vanadium(V) adducts are often recognized as potent transition state analogs.     

Nanotribological and nanomechanical properties of skin with and without cream treatment using atomic force microscopy and nanoindentation

Various beauty care products involve surface interaction between the product and the skin surface they are applied to. Friction, adhesion and wear during sliding between the treated surface and the rubbing surfaces need to be optimized. Skin cream is used to improve skin health and create a smooth, soft, and flexible surface with moist perception by altering the surface roughness, friction, adhesion, elastic modulus, and surface charge of the skin surface. Rheology of skin cream as a function of cream thickness and strain rate and the binding interaction between skin cream and skin surface and operating environment are some of the important factors affecting the smooth feel and repair of the skin surface. Atomic force microscopy (AFM) and nanoindentation have recently become important tools for studying the micro/nanoscale properties of human hair, hair conditioner, skin, and skin cream. In this paper, we present an overview of the nanotribological and nanomechanical properties of skin with and without cream treatment as a function of operating environment. Relevant mechanisms are discussed. Next, the result of a triboelectrification study of skin with and without cream treatment is presented. Finally, an overview of attempts to develop a synthetic skin for research purposes is presented.     

Wear-resistant rose petal-effect surfaces with superhydrophobicity and high droplet adhesion using hydrophobic and hydrophilic nanoparticles

Surfaces exhibiting the so-called "petal effect" (superhydrophobicity with high droplet adhesion) have potential for applications such as the transport of small volumes of liquid. It is known that the microstructure pitch value and nanostructure density are important in achieving this effect, both in rose petals themselves and in synthetic petal-effect surfaces. However, the effect of the surface energy of materials on these values has not been systematically studied. In addition, wear resistance, which is critical for industrial applications, has rarely been examined for petal-effect surfaces. In this study, surfaces of varying microstructure pitch and nanostructure density were fabricated by depositing ZnO nanoparticles onto micropatterned substrates. The prepared surfaces were then modified with octadecylphosphonic acid (ODP) in order to hydrophobize the ZnO nanoparticles. The wettability of the surfaces was characterized both before and after ODP modification. The effect of hydrophobizing the nanostructure was examined with regards to the values of microstructure pitch and nanostructure density necessary to achieve the petal effect. In addition, to study wear resistance for industrial applications, a wear experiment was performed using an atomic force microscope (AFM).     

Didocosyl selenide stabilized recyclable Pd(0) nanoparticles and coordinated palladium(II) as efficient catalysts for Suzuki-Miyaura coupling

First selenium ligand stabilized Pd(0) nanoparticles (～3-5 nm) catalyze Suzuki-Miyaura C-C coupling in short time and are recyclable (up to 94% yield after 5 reuses). The air stable compound [PdCl(2)(L1)(2)] shows high catalytic efficiency for this coupling as its 3 × 10(-5) mol% is sufficient for activated ArBr.     

Transparent, Superhydrophobic, and Wear-Resistant Coatings on Glass and Polymer Substrates Using SiO(2), ZnO, and ITO Nanoparticles

It is of significant interest to create surfaces that simultaneously exhibit high water contact angle, low contact angle hysteresis, and high transmission of visible light, as well as mechanical wear resistance for industrial applications. The fabrication of such surfaces has often involved complex or expensive processes, required techniques that were not suitable for a variety of substrates and particles, required surface post-treatment, or lacked wear resistance. A systematic study has been performed in which transparent superhydrophobic surfaces were created on glass, polycarbonate, and poly(methyl methacrylate) (PMMA) substrates using surface-functionalized SiO(2), ZnO, and indium tin oxide (ITO) nanoparticles. The contact angle, contact angle hysteresis, and optical transmittance were measured for samples using all particle-substrate combinations. To examine wear resistance, multiscale wear experiments were performed using an atomic force microscope (AFM) and a water jet apparatus.     

Molecular nesting in co-crystals of tetrabenzoquadrannulene and C(60): application of the sphere in a cone model

We report the X-ray crystal structure of TMS(4)-TBQ with C(60) and analyse their interaction using a sphere in a cone model.     

Synthesis of the aminocyclitol units of (-)-hygromycin A and methoxyhygromycin from myo-inositol

Concise and efficient syntheses of the aminocyclitol cores of hygromycin A (HMA) and methoxyhygromycin (MHM) have been achieved starting from readily available myo-inositol. Reductive cleavage of myo-inositol orthoformate to the corresponding 1,3-acetal, stereospecific introduction of the amino group via the azide, and resolution of a racemic cyclitol derivative as its diastereomeric mandelate esters are the key steps in the synthesis. Synthesis of the aminocyclitol core of hygromycin A involved chromatography in half of the total number of steps, and the aminocyclitol core of methoxyhygromycin involved only one chromatography.     

Chiral crystals from an achiral molecule: 4,6‐di‐O‐benzyl‐1,3‐O‐benzylidene‐2‐O‐(4‐methoxybenzyl)‐myo‐5‐inosose

The title achiral compound, C₃₅H₃₄O₇, crystallizes in the chiral monoclinic space group P2₁. The molecules are densely packed to form a helical assembly along the crystallographic twofold screw axis via C—H...O and C—H...π interactions. Interestingly, the unit‐translated helical chains are loosely connected via a rather uncommon edge‐to‐edge Ph—H...H—Ph short contact (H...H = 2.33 Å).