Protein-cleaving catalyst selective for protein substrate

A protein-cleaving catalyst specific for a disease-related protein can be used as a catalytic drug. As the first protein-cleaving catalyst selective for a protein substrate, a catalyst for myoglobin was designed by attaching Cu(II) or Co(III) complex of cyclen to a binding site searched by a combinatorial method using peptide nucleic acid monomers as building units. [reaction: see text]     

Synthesis and characterization of nano titania powder with high photoactivity for gas-phase photo-oxidation of benzene from TiOCl(2) aqueous solution at low temperatures

Nano rutile, anatase, and bicrystalline (anatase + brookite) titania powders with an average crystal size of below 10 nm are prepared from aqueous TiOCl(2) solution at low temperatures by adjusting pH values of the starting solution and adding different additives. Adding a small amount of octyl phenol poly(ethylene oxide) into aqueous TiOCl(2) solution leads to the change of particle morphologies of obtained nano titania from needlelike to nano spherical rutile crystals. Amorphous-anatase transformation of titania could proceed in liquid-solid reaction at low temperatures, even at room temperature. A formation mechanism of rutile, anatase, and brookite titania was proposed. It is found that H(+) or H(3)O(+) plays a catalytic role in the phase transformation from amorphous to anatase titania and that the presence of a small amount of SO(4)(2)(-) ion is unfavorable to the formation of both rutile and brookite. By carefully adjusting preparation conditions, nano pure anatase with higher surface area, good crystallinity, and a lower recombination rate of photoexcited electrons and holes was obtained. This nano pure anatase showed a very good photocatalytic activity for gas-phase photo-oxidation of benzene.     

Long-lived charge-separation by retarding reverse flow of charge-balancing cation and zeolite-encapsulated Ru(bpy)(3)(2+) as photosensitized electron pump from zeolite framework to externally placed viologen

K(+)-exchanged, Ru(bpy)(3)(2+)-encapsulating zeolite-Y [K(+)-Ru(bpy)(3)(2+)Y] and N-[3-(dicyclohexylmethyl)oxypropyl-N'-methyl-4,4'-bipyridinium [DCH-MV(2+)] were prepared, and visible light-induced electron transfer from the zeolite-encapsulated Ru(II) complex to the size-excluded viologen was studied in acetonitrile. Addition of a series of crown ethers (CEs) into the heterogeneous solution leads to over a 10-fold increase in the yield of DCH-MV(*)(+), where the yield linearly increases as the formation constant of CE with K(+) [K(f)(K(+))(CE)] increases. The following two sequential events are attributed to be responsible for the above novel phenomenon. First, K(+) ions are liberated from the zeolite to solution during interfacial electron transfer from the photoexcited Ru(II) complexes to DCH-MV(2+). Second, the liberated K(+) ions form strong host-guest complexes with the added CE molecules, which leads to retardation of the reverse flow of the cations, hence the charge-balancing electrons, from the solution to the zeolite. Surprisingly, the yield of DCH-MV(*)(+) reaches more than approximately 50 times the amount of Ru(bpy)(3)(2+) situated in the outermost supercages, despite the absence of electron relay in the zeolite. This is attributed to photosensitized electron pumping from the zeolite framework to viologen by the outermost Ru(bpy)(3)(2+) ions. In support of the above conclusion, Ru(bpy)(3)(3+) does not accumulate in the zeolite host while DCH-MV(*)(+) accumulates in the supernatant solution. Consistent with the above, the independently prepared hexafluorophosphate salt of Ru(bpy)(3)(3+) is reduced to Ru(bpy)(3)(2+) in acetonitrile upon contact with Ru(bpy)(3)(2+)-free M(+)Y (M(+) = Li(+), Na(+), K(+), Rb(+), and Cs(+)), where the yield increases as the donor strength of the framework oxygen increases. Although small, thermal electron transfer also takes place from the zeolite framework to DCH-MV(2+), where the yield increases upon increasing the donor strength of the framework, concentration of DCH-MV(2+), temperature, and K(f)(K(+))(CE) (when K(+)Y is the zeolite host). The photoyield is always higher than the thermal yield by 4-30 times, confirming that the zeolite-encapsulated Ru(bpy)(3)(2+) serves as the photosensitized electron pump.     

Studies of rhodium-catalyzed ring opening of vinyl epoxides

The stereoselective 6-endo mode cyclization of vinyl epoxides has been achieved by the use of a catalytic amount of [Rh(CO)₂Cl]₂ affording six-membered heterocycle systems, such as piperidines and tetrahydropyrans. The scope and limitations of the reaction are discussed.     

Existence of intramolecular triplet excimer of bis(9-fluorenyl)methane: phosphorescence and delayed fluorescence spectroscopic and ab initio studies

A concerted computational and experimental study has been undertaken to probe the conformational structure and excited-state dynamics of bis(9-fluorenyl)methane (BFM). We have observed that the relative intensity of the delayed excimer fluorescence of BFM is greatly enhanced in comparison with that of the normal fluorescence. This is presumably because the relative concentration of the triplet excimer is enhanced in comparison with the singlet excimer. B3LYP DFT/6-31G(d) calculations indicate that the sandwich conformer of BFM in the singlet ground state is unstable, whereas that in the triplet excited state has a bound state, being very slightly higher in internal and Gibbs free energies than that of the lowest state of the near-orthogonal conformer.     

Analysis of tofisopam in human serum by column-switching semi-micro high-performance liquid chromatography and evaluation of tofisopam bioequivalency

A rapid and sensitive column-switching semi-micro HPLC method is described for the direct analysis of tofisopam in human serum. The sample (100 microL) was directly injected onto the precolumn (Capcell Pak MF Ph-1), where unretained proteins were eluted to waste. Tofisopam was then eluted into an enrichment column using 13% acetonitrile in 50 mM phosphate buffer (pH 7.0) containing 5 mM sodium octanesulfonate and subsequently into the analytical column using 43% acetonitrile in 0.1% phosphoric acid containing 5 mM sodium octanesulfonate. The detection limit (2 ng/mL), good precision (CV < or = 4.2%) and speed (total analysis time 24 min) of the present method were sufficient for drug monitoring. This method was successfully applied to a bioequivalence test of two commercial tofisopam tablets.     

Phase- and size-controlled synthesis of hexagonal and cubic CoO nanocrystals

Highly crystalline, phase- and size-controlled CoO nanocrystals of hexagonal and cubic phases have been prepared by thermal decomposition of Co(acac)3 in oleylamine under an inert atmosphere. Kinetic and thermodynamic control for the precursor formation leads to two different seeds of hexagonal and cubic phases at higher temperatures. The crystal size of both CoO phases can be easily manipulated by changing the precursor concentration and reaction temperature.     

Synthesis of the proposed structure of feigrisolide C

[reaction: see text] Possible structures of feigrisolide C were synthesized via ring-closing olefin metathesis reaction of a diester derivative prepared from 8-epi-nonactic acid, but physical characteristics of the synthetic samples did not match with those of the natural sample of feigrisolide C.