Coprecipitation of gold(III) complex ions with manganese(II) hydroxide and their stoichiometric reduction to atomic gold (Au(0)): analysis by Mössbauer spectroscopy and XPS

To elucidate the formation process of precursor of gold-supported manganese dioxide (MnO2), the coprecipitation behavior of [AuCl4-n(OH)n](-) (n=0-4) (Au(III)) complex ions with manganese(II) hydroxide (Mn(OH)2 and the change in their chemical state were examined. The Au(III) complex ions were rapidly and effectively coprecipitated with Mn(OH)(2) at pH 9. According to the M?ssbauer spectra for gold (Au) coprecipitated with Mn(OH)2, below an Au content of 60 wt% in the coprecipitates, all of the coprecipitated Au existed in the atomic state (Au(0)), while, above an Au content of 65 wt%, part of the gold existed in the Au(III) state, and the proportion increased with increasing coprecipitated Au content. Based on the results of X-ray photoelectron spectroscopy, Mn(II) in Mn(OH)2 converted to Mn(IV) in conjunction with coprecipitation of Au(III) complex ions. These results indicate that the rapid stoichiometric reduction of Au(III) to Au(0) is caused by electron transfer from Mn(II) in Mn(OH)2 to the Au(III) complex ion through an Mn-O-Au bond.     

Synthesis of an Octacyclic C60 Fragment

Fragments of buckminsterfullerene (C₆₀) include the monumental three compounds corannulene, sumanene, and truxene. These three have served as leading molecules in ongoing research for curved, fused, and π-extended polyaromatic materials. Achieving more structural variations that join the ranks of these three archetypes remains challenging. Herein we report synthesis of an octacyclic hydrocarbon that is an unexplored C₆₀-fragment, namely, a 4,11-dihydrodiindeno[7,1,2-ghi:7′,1′,2′-pqr]chrysene (C₂₈H₁₆, which we named Metelykene). The key to success was solution-compatible synthesis in which double pentagonal rings flank hexagonal ones. This solution-phase approach, coupled with the resulting non-planar π-conjugation, is so straightforward that it offers an entry to a derivative such as a cardo aromatic monomer.     

New cytotoxic 14-membered macrolides from marine-derived fungus Aspergillus ostianus

Three new 14-membered macrolides, named aspergillides A, B, and C (1, 5, and 7), were isolated from marine-derived fungus Aspergillus ostianus strain 01F313, cultured in a medium composed of bromine-modified artificial seawater. The structures of the new compounds were determined by analyses of 1D and 2D NMR spectra. Their absolute configurations were elucidated by the modified Mosher's method and chemical conversions. The new compounds showed cytotoxic activity against mouse lymphocytic leukemia cells (L1210).     

meso-Phbox-Pd(II) catalyzed tandem carbonylative cyclization of 1-ethynyl-1-propargyl acetate

Palladium(ii) catalyzed carbonylation of 1-ethynyl-1-propargyl acetate is described; in the absence of the bisoxazoline (box) ligand, the second triple bond did not react, affording cyclic orthoesters and . The use of meso-Phbox-Pd(ii) strikingly changed the course of the reaction, yielding bicyclic lactone by tandem carbonylative cyclization as a result of insertion of the second triple bond.     

Counting the number of independent sets in chordal graphs

We study some counting and enumeration problems for chordal graphs, especially concerning independent sets. We first provide the following efficient algorithms for a chordal graph: (1) a linear-time algorithm for counting the number of independent sets; (2) a linear-time algorithm for counting the number of maximum independent sets; (3) a polynomial-time algorithm for counting the number of independent sets of a fixed size. With similar ideas, we show that enumeration (namely, listing) of the independent sets, the maximum independent sets, and the independent sets of a fixed size in a chordal graph can be done in constant time per output. On the other hand, we prove that the following problems for a chordal graph are #P-complete: (1) counting the number of maximal independent sets; (2) counting the number of minimum maximal independent sets. With similar ideas, we also show that finding a minimum weighted maximal independent set in a chordal graph is NP-hard, and even hard to approximate.     

Multielectron-transfer reactions at single Cu(II) centers embedded in polyoxotungstates driven by photo-induced metal-to-metal charge transfer from anchored Ce(III) to framework W(VI)

Using carbon monoxide as a probe molecule for the oxidation state of Cu ions, we demonstrated that anchored polynuclear charge-transfer complexes consisting of Ce(III) ions and Cu(II)-substituted Keggin-type polyoxotungstates function as efficient visible-light-driven multielectron-transfer catalysts.     

1,3-indane-based chromogenic calixpyrroles with push-pull chromophores: synthesis and anion sensing

[structure: see text]. Knoevenagel condensation of 2-formyl-octamethylcalix[4]pyrrole with selected 1,3-indanedione derivatives yields calix[4]pyrrole anion sensors with push-pull chromophores displaying strong intramolecular charge transfer. The push-pull feature results in augmented signal output as well as in dramatic changes in anion selectivity exemplified by a 50-fold increase in acetate vs chloride selectivity compared to the parent calix[4]pyrrole.     

Photogenerated hole mobility in DNA measured by time-resolved microwave conductivity

We report the first direct observation of charge transport dynamics using time-resolved microwave conductivity and transient absorption spectroscopy techniques on the photolysis of an anthraquinone-bound DNA complex.     

Synthesis, structure, anion binding, and sensing by calix[4]pyrrole isomers

The synthesis, structure, and anion binding properties of chromogenic octamethylcalix[4]pyrroles (OMCPs) and their N-confused octamethylcalix[4]pyrrole isomers (NC-OMCPs) containing an inverted pyrrole ring connected via alpha'- and beta-positions are described. X-ray diffraction analyses proved the structures of two synthesized isomeric pairs of OMCPs and NC-OMCPs. The addition of anions to solutions of chromogenic OMCPs and NC-OMCPs resulted in different colors suggesting different anion-binding behaviors. The chromogenic NC-OMCPs showed significantly stronger anion-induced color changes compared to the corresponding chromogenic OMCP, and the absorption spectroscopy titrations indicated that chromogenic OMCPs and NC-OMCPs also possess different anion binding selectivity. Detailed NMR studies revealed that this rather unusual feature stems from a different anion-binding mode in OMCPs and NC-OMCPs, one where the beta-pyrrole C-H of the inverted pyrrole moiety participates in the hydrogen-bonded anion-NC-OMCP complex. Preliminary colorimetric microassays using synthesized chromogenic calixpyrroles embedded in partially hydrophilic polyurethane matrices allow for observation of analyte-specific changes in color when the anions are administered in the form of their aqueous solutions and in the presence of weakly competing anions.     

Selective mono-acylation of 1,2- and 1,3-diols using (α,α-difluoroalkyl)amines

In the reaction of N,N-diethyl-α,α-difluorobenzylamine (DFBA) with 1,2- or 1,3-diols, selective mono-benzoylation occurs to afford mono-esters of the diols in good yield. The reaction is completed under mild conditions in a short reaction time. Further, prim-, sec-, and tert-diols and catechol can be converted to the corresponding mono-benzoates. DFBA is used for the protection of the hydroxy group in sugars. The selective mono-nicotinylation, formylation and pivaloylation of diols are also performed by using the corresponding difluoroalkylamines.