Porous Protein Crystals as Catalytic Vessels for Organometallic Complexes

Porous protein crystals, which are protein assemblies in the solid state, have been engineered to form catalytic vessels by the incorporation of organometallic complexes. Ruthenium complexes in cross‐linked porous hen egg white lysozyme (HEWL) crystals catalyzed the enantioselective hydrogen‐transfer reduction of acetophenone derivatives. The crystals accelerated the catalytic reaction and gave different enantiomers based on the crystal form (tetragonal or orthorhombic). This method represents a new approach for the construction of bioinorganic catalysts from protein crystals.     

Control of the coordination structure of organometallic palladium complexes in an apo-ferritin cage

We report the preparation of organometallic Pd(allyl) dinuclear complexes in protein cages of apo-Fr by reactions with [Pd(allyl)Cl]2 (allyl = eta3-C3H5). One of the dinuclear complexes is converted to a trinuclear complex by replacing a Pd-coordinated His residue to an Ala residue. These results suggest that multinuclear metal complexes with various coordination structures could be prepared by the deletion or introduction of His, Cys, and Glu at appropriate positions on protein surface.     

Practical synthesis of pinacolborane for one-pot synthesis of unsymmetrical biaryls via aromatic C-H borylation-cross-coupling sequence

A method for practical preparation of pinacolborane from borane-diethylaniline and pinacol was newly developed. Aromatic C-H borylation of arenes with pinacolborane or bis(pinacolato)diboron catalyzed by 1/2[Ir(OMe)(COD)]₂-(4,4′-di-tert-butyl-2,2′-bipyridine) at 25 °C in hexane to give arylboronic esters was directly followed by cross-coupling with aromatic bromides at 60 °C in the presence of PdCl₂(dppf) (3.0 mol %) and K₃PO₄ in DMF. This one-pot, two-step procedure provided a variety of unsymmetrical biaryls in high yields.     

Rapid micropatterning of mesoporous silica film by site-selective low-energy electron beam irradiation

Rapid microfabrication of mesoporous silica film at low temperature was achieved with low-energy electron beam (LEEB) irradiation. A mesostructured film (thickness approximately 200 nm), which was prepared through hydrolysis and condensation of tetramethoxysilane in the presence of hexadecyltrimethylammonium chloride, was irradiated with LEEB at 25 kV and 300 microA under pressures of 10 and 1000 Pa. The surfactant molecules can be eliminated completely at temperatures less than 40 degrees C after only 10 min (10 Pa) and 5 min (1000 Pa) of irradiation, resulting in conversion to a highly ordered mesoporous silica film without cracking. The LEEB-irradiated film also showed reasonable chemical resistance toward dilute hydrofluoric acid solution due to sufficient consolidation by cross-linking of silicate networks during the irradiation. The unirradiated regions were etched away preferentially to the irradiated areas; therefore, rapid micropatterning of the mesoporous silica film was possible by area-selective LEEB irradiation followed by chemical etching.     

Selective adsorption of bacterial cells onto zeolites

Zeolites adsorb microbial cells on their surfaces and selective adsorption for specific microorganisms was seen with certain zeolites. Tests for the adsorption ability of zeolites were conducted using various established microbial cell lines. Specific cell lines were shown to selectively absorb to certain zeolites, species to species.

In order to understand the selectivity of adsorption, we tested adsorption under various pH conditions and determined the zeta-potentials of zeolites and cells. The adsorption of some cell lines depended on the pH, and some microorganisms were preferentially adsorbed at acidic pH. The values of zeta-potentials were used for calculating the electric double layer interaction energy between zeolites and microbial cells. There was a correlation between the experimental adsorption results and the interaction energy. Moreover, we evaluated the surface hydrophobicity of bacterial cells by using the microbial adherence to hydrocarbon (MATH) assay. In addition, we also applied this method for zeolites to quantify relative surface hydrophobicity. As a result, we found a correlation between the adsorption results and the hydrophobicity of bacterial cells and zeolites. These results suggested that adsorption could be explained mainly by electric double layer interactions and hydrophobic interactions.

Finally, by using the zeolites Na-BEA and H-Y, we succeeded in clearly separating three representative microbes from a mixture of Escherichia coli, Bacillus subtilis and Staphylococcus aureus. Zeolites could adsorb each of the bacterial cell species with high selectivity even from a mixed suspension. Zeolites can therefore be used as effective carrier materials to provide an easy, rapid and accurate method for cell separation.     

Vinylic C?H Borylation of Cyclic Vinyl Ethers with Bis(pinacolato)diboron Catalyzed by an Iridium(I)‐dtbpy Complex

Borylation of the vinylic C? H bond of 1,4‐dioxene, 2,3‐dihydrofuran, 3,4‐dihydro‐2H‐pyran and their γ‐substituted analogs was carried out in the presence of bis(pinacolato)diboron (B₂pin₂) and a catalytic amount of Ir^I‐dtbpy (dtbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine) complex. The two boron atoms in B₂pin₂ participated in the coupling, thus giving two equivalents of the coupling product from one equivalent of B₂pin₂. The borylation of 1,4‐dioxene in hexane resulted in 81 % yield at room temperature. The borylation of 2,3‐dihydrofurans at 80 °C in octane suffered from low regioselectivity, and gave a mixture of α‐ and β‐coupling products even for hindered γ‐disubstituted analogs, but γ‐substituted analogs of 3,4‐dihydro‐2H‐pyran achieved high α‐selectivity, giving single coupling products. This protocol was applied to the syntheses of a key precursor of vineomycinone B2 methyl ester and other C‐substituted D ‐glucals by borylation of protected D ‐glucals with B₂pin₂ to give α‐boryl glucal followed by cross‐coupling with haloarenes, benzyl bromide, and allyl bromide. A catalytic cycle that involves the oxidative addition of sp² C? H bond to iridium(III)‐trisboryl intermediate as the rate‐determining step has been proposed.     

Alternating Layers of Iron(III) Tetra(N‐methyl‐4‐pyridyl)‐porphyrin and Copper Tetrasulfonated Phthalocyanine for Amperometric Detection of 4‐Nitrophenol in Nanomolar Levels

The present work describes the development of a highly sensitive amperometric sensor for 4‐NP in nanomolar levels using a glassy carbon electrode modified with alternating layers of CuTSPc and FeT4MPyP. After optimizing the operational conditions, the sensor provided a linear response range for 4‐NP from 5 up to 100 nmol L^?1 with sensitivity, detection, and quantification limits of 14 nA L nmol^?1, 1.9 nmol L^?1, and 5.4 nmol L^?1, respectively. The proposed sensor showed a stable response for at least 200 successive determinations. This modified electrode can be used to the determination of 4‐NP in water samples.     

Total synthesis of spiruchostatin B, a potent histone deacetylase inhibitor, from a microorganism

The first total synthesis of spiruchostatin B, a potent histone deacetylase inhibitor, was achieved in a convergent manner; the synthesis established stereochemistry at the C5' position.     

Properties of nitride‐based photovoltaic cells under concentrated light illumination

We investigated the properties of nitride‐based solar cells under concentrated light illumination from 1 to 200 suns. The conversion efficiency of our solar cells increased with increasing concentration up to 200 suns. The short‐circuit cur‐ rent density, open‐circuit voltage, fill factor, and conversion efficiency were 510 mA/cm², 1.9 V, 70%, and 3.4%, respectively, under an air mass filter of 1.5G at 200 suns and room temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)