Ni(0)-promoted hydroxycarboxylation of 1,2-dienes by reaction with CO2 and O2

[structure: see text]. A novel method for the preparation of hydroxy carboxylic acid derivatives has been developed by O2-oxidation of pi-allylnickel intermediates generated by Ni(0)-mediated coupling of 1,2-dienes with CO2.     

Controlled Synthesis of Nanoporous Nickel Oxide with Two‐Dimensional Shapes through Thermal Decomposition of Metal–Cyanide Hybrid Coordination Polymers

The urgent need for nanoporous metal oxides with highly crystallized frameworks is motivating scientists to try to discover new preparation methods, because of their wide use in practical applications. Recent work has demonstrated that two‐dimensional (2D) cyanide‐bridged coordination polymers (CPs) are promising materials and appropriate for this purpose (Angew. Chem. Int. Ed.­ 2013 , 52, 1235). After calcination, 2D CPs can be transformed into nanoporous metal oxides with a highly accessible surface area. Here, this strategy is adopted in order to form 2D nanoporous nickel oxide (NiO) with tunable porosity and crystallinity, using trisodium citrate dihydrate as a controlling agent. The presence of trisodium citrate dihydrate plays a key role in the formation of 2D nanoflakes by controlling the nucleation rate and the crystal growth. The size of the nanoflakes gradually increases by augmenting the amount of trisodium citrate dihydrate in the reaction. After heating the as‐prepared CPs in air at different temperatures, nanoporous NiO can be obtained. During this thermal treatment, organic units (carbon and nitrogen) are completely removed and only the metal content remains to take part in the formation of nanoporous NiO. In the case of large‐sized 2D CP nanoflakes, the original 2D flake‐shapes are almost retained, even after thermal treatment at low temperature, but they are completely destroyed at high temperature because of further crystallization in the framework. Nanoporous NiO with high surface area shows significant efficiency and interesting results for supercapacitor application.     

Quick screening for new flux pinning materials in YBCO films with the combinatorial-PLD method

An effective way to improve the superconducting properties in REBa₂Cu₃O_y (REBCO) films under a magnetic field is to dope artificial pinning centers (APC). The pinning performance depends on the content of the APC materials. Usually, the optimal APC content is explored by preparing films one at a time from the REBCO target using different APC material content, which is an extremely time-consuming process.The combinatorial-PLD (C-PLD) method allowed us to prepare films that continuously changed in composition across a single substrate. In this study, we used the C-PLD method to prepare BaSnO₃ (BSO)-doped YBCO films. The films were deposited on SrTiO₃ substrate using a fourth-harmonic Nd:YAG laser. From the results of the J_c–B curves at 77 K and B//c, the film that contained 3.2 vol.% of BSO exhibited the best pinning performance in this study. We showed that the C-PLD method was efficient for quick screening of the optimal APC content with only one deposition. We also used the C-PLD method to explore new APC materials, and proved that it can quickly evaluate the new APC materials Ba₃Cu₃In₄O₁₂ and BaTbO₃.     

Isomerization of spirobenzopyrans bearing electron-donating and electron-withdrawing groups in acidic aqueous solutions

Spirobenzopyrans, which are well known as photochromic compounds, exist as thermodynamically stable protonated ring-opened isomers (protonated merocyanine form, McH) in an acidic aqueous solution in the dark. In the present study, we investigated effects of substitution of the spirobenzopyrans on a ring-opening behavior in an aqueous system. We prepared five polymerizable spirobenzopyrans that are substituted with a methoxy group or a nitro group at the 6'- or 8'-positions and without a substituent. These monomers were copolymerized with N,N-dimethylacrylamide to evaluate the spirobenzopyrans in aqueous solution. Correlation between ring-opening rates and the kind and position of the substitution can be summarized as follows: the substitution of an electron-donating methoxy group and the substitution at the 8'-position increased the ring-opening rate, whereas the substitution of an electron-withdrawing nitro group decreased the rate. The effects of the substitution can be explained by changes in the electron density of the oxygen atom of the spirobenzopyrans.     

Tungsten(0)- and rhenium(I)-catalyzed tandem cyclization of acetylenic dienol silyl ethers based on geminal carbo-functionalization of alkynes

Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)(6)] or [ReCl(CO)(5)] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2-azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO)(4)(PPh(3))], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)(5)]/AgSbF(6) . Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO)(6)].     

Wettability characterization of transparent MgF<Subscript>2</Subscript> nanoparticle coatings with SiO<Subscript>2</Subscript> binder covered with fluoroalkylsilane self-assembled monolayers

SiO₂-added MgF₂ nanoparticle coatings with various surface roughness properties were formed on silica-glass substrates from autoclaved sols prepared at 100–180 °C. The samples were exposed to fluoro-alkyl silane (FAS) vapor to give hydrophobicity. All nanoparticle samples before FAS treatment had transmittances higher than 93% and such values were preserved even after FAS treatment. We examined root mean square roughnesses of the nanoparticle coatings with a Scanning Probe Microscope. We also examined their static and dynamic wettabilities with a contact angle meter and calculated their adhesive energies and surface free energies (SFEs). The surface roughness of the nanoparticle coating increased with the increase of the autoclave temperature. In addition, higher autoclave temperature caused increases in the sliding angle and decreases in the SFE. Interestingly, the higher the contact angle was, the larger the sliding angle was, although smaller sliding angle was expected with a larger contact angle.     

Spherical phospholipid polymer hydrogels for cell encapsulation prepared with a flow-focusing microfluidic channel device

To prepare spherical polymer hydrogels, we used a flow-focusing microfluidic channel device for mixing aqueous solutions of two water-soluble polymers. Continuous encapsulation of cells in the hydrogels was also examined. The polymers were bioinspired 2-methacryloyloxyethyl phosphorylcholine polymer bearing phenyl boronic acid groups (PMBV) and poly(vinyl alcohol) (PVA), which spontaneously form a hydrogel in aqueous medium via specific molecular complexation upon mixing, even when they were in cell culture medium. The microfluidic device was prepared with polydimethylsiloxan, and the surface of the channel was treated with fluoroalkyl compound to prevent sticking of the polymers on the surface. The microfluidic channel process could control the diameter of the spherical hydrogels in the range of 30-90 μm and generated highly monodispersed diameter spherical hydrogels. We found that the polymer distribution in the hydrogel was influenced by the PVA concentration and that the hydrogel could be dissociated by the addition of d-sorbitol to the suspension. The single cells could be encapsulated and remain viable in the hydrogels. The localized distribution of polymers in the hydrogel may provide an environment for modulating cell function. It is concluded that the spontaneous hydrogel formation between PMBV and PVA in the flow-focusing microfluidic channel device is applicable for continuous preparation of a spherical hydrogel-encapsulating living cell.     

Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin–Chemically Converted Graphene Composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl‐functionalized CCG and porphyrin boronic ester. The covalently linked CCG–porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady‐state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin‐linked CCG revealed a short‐lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO₂ electrode coated with the porphyrin‐linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π‐conjugated systems in the excited and ground states.