Cholesterol-armed cyclens for helical metal complexes offering chiral self-aggregation and sensing of amino acid anions in aqueous solutions

Cholesterol-armed cyclens worked as octadentate receptors for Na+, Ca2+, and Y3+ complexes in which four chiral cholesterol-functionalized sidearms were bundled and asymmetrically twisted above cyclen-metal complex platforms. Since the resulting helical metal complexes included chiral, hydrophobic cholesterol residues and charged, hydrophilic metal sites as well as asymmetric coordination geometries, they exhibited unique amphiphilic properties and provided chiral self-aggregates in aqueous solutions. Light scattering, fluorescence, and TEM characterizations demonstrated that Na+ complex with cholesterol-armed cyclen gave a particularly stable self-aggregate in aqueous solution and offered supramolecular environments effective for sensing and detection of amino acid anions. Various dansylamino acid derivatives (dansyl = 5-(dimethylamino)-1-naphthalenesulfonyl) were nicely accommodated in the helicate aggregates to give highly enhanced fluorescence signals, which could be detected by the naked eye at 10(-7) mol/L level. Their inclusion behaviors were analyzed by a Langmuir-type equation, indicating that enantiomer-selective inclusion occurred. MM/MD calculations and circular dichroism (CD) studies further suggested that cholesterol-armed cyclen helicates have chiral and hydrophobic cavities upon self-aggregation, in which the dansylamino acid anions were specifically accommodated. Since these helicates exhibited nonselective binding abilities in solvent extraction experiments of dansylamino acid anions, uncommon chiral recognition and sensing functions were generated by supramolecular alignments of the chiral metal helicates in the aqueous solutions.     

Aerobic catechol oxidation catalyzed by a bis(mu-oxo)dimanganese(III,III) complex via a manganese(II)-semiquinonate complex

A 3,5-di-tert-butyl-1,2-semiquinonato (DTBSQ) adduct of Mn(II) was prepared by a reaction between Mn(II)(TPA)Cl(2) (TPA = tris(pyridin-2-ylmethyl)amine) and DTBSQ anion and was isolated as a tetraphenylborate salt. The X-ray crystal structure revealed that the complex is formulated as a manganese(II)-semiquinonate complex [Mn(II)(TPA)(DTBSQ)](+) (1). The electronic spectra in solution also indicated the semiquinonate coordination to Mn. The exposure of 1 in acetonitrile to dioxygen afforded 3,5-di-tert-butyl-1,2-benzoquione and a bis(mu-oxo)dimanganese(III,III) complex [Mn(III)(2)(mu-oxo)(2)(TPA)(2)](2+) (2). The reaction of 2 with 3,5-di-tert-butylcatechol (DTBCH(2)) quantitatively afforded two equivalents of 1 under anaerobic conditions. The highly efficient catalytic oxidation of DTBCH(2) with dioxygen was achieved by combining the above two reactions, that is, by constructing a catalytic cycle involving both manganese complexes 1 and 2. It was revealed that dioxygen is reduced to water but not to hydrogen peroxide in the catalytic cycle.     

Formation and High Reactivity of the anti‐Dioxo Form of High‐Spin μ‐Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C−H Bonds

Recently, it was shown that μ‐oxo‐μ‐peroxodiiron(III) is converted to high‐spin μ‐oxodioxodiiron(IV) through O?O bond scission. Herein, the formation and high reactivity of the anti‐dioxo form of high‐spin μ‐oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic‐absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ‐oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluene<ethylbenzene≈cumene<trans‐β‐methylstyrene. The rate constants increased proportionally to the substrate concentration at low substrate concentration. At high substrate concentration, however, the rate constants converge to the same value regardless of the kind of substrate. This is explained by a two‐step mechanism in which anti‐μ‐oxodioxodiiron(IV) is formed by syn‐to‐anti transformation of the syn‐dioxo form and reacts with substrates as the oxidant. The anti‐dioxo form is 620 times more reactive in the C?H bond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE for the reaction with toluene/[D₈]toluene is 95 at ?30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H₂O₂.     

Interval solution of nonlinear equations using linear programming

A new computational test is proposed for nonexistence of a solution to a system of nonlinear equations in a convex polyhedral regionX. The basic idea proposed here is to formulate a linear programming problem whose feasible region contains all solutions inX. Therefore, if the feasible region is empty (which can be easily checked by Phase I of the simplex method), then the system of nonlinear equations has no solution inX. The linear programming problem is formulated by surrounding the component nonlinear functions by rectangles using interval extensions. This test is much more powerful than the conventional test if the system of nonlinear equations consists of many linear terms and a relatively small number of nonlinear terms. By introducing the proposed test to interval analysis, all solutions of nonlinear equations can be found very efficently. This work was partially supported by the Japanese Ministry of Education.     

Electrical conductivity and local structure of lithium tin iron vanadate glass

A relationship between electrical conductivity (σ) and local structure of 15Li₂O·10Fe₂O₃·xSnO₂·(70–x)V₂O₅·5P₂O₅ glass (x = 0–20 mol%), abbreviated as xLFSVP glass, was investigated by ⁵⁷Fe- and ¹¹⁹Sn-Mössbauer spectroscopies, differential thermal analysis (DTA) and dc-four probe method. A small increase in quadrupole splitting (Δ) for Fe^III was observed from 0.70 to 0.74_{± 0.02} mm s^???1 with an increase of “x”, whereas isomer shift (Δ) values of 0.40_±0.01 mm s^???1 were independent of “x”. This result suggests that local distortion of Fe^IIIO₄ tetrahedra was slightly increased in SnO₂-containing vanadate glasses, which was reflected as an increase in glass transition temperature (T_g) from 266 to 285_±5 °C. A slope of 675 K / (mm s^???1) obtained in ‘T_g vs. Δ plot’ proved that Fe^III occupied the site of network former (NWF). An isothermal annealing of 10LFSVP glass at 500 °C for 100 min resulted in a marked decrease of Δ from 0.72 to 0.56_±0.02 mm s^???1, indicating that local distortion of FeO₄ tetrahedra was reduced by the structural relaxation of 3D-network. In contrast, identical δ and Δ values of 0.07_±0.01 and 0.53_±0.02 mms^???1, respectively, were observed in ¹¹⁹Sn-Mössbauer spectra of 10LFSVP glass before and after the annealing. These results indicate that Sn^IVO₆ octahedra are loosely bound in the glass matrix as a network modifier (NWM). A marked increase in σ from 7.4 × 10^???7 to 9.1 × 10^???3 S cm^???1 was observed in 20LFSVP glass after the isothermal annealing, indicating that structural relaxation of 3D-network evidently causes a marked increase in σ.     

Phenolic Compounds Isolated from the Bark of Abies sachalinensis

Eight spiro‐biflavonoids named abiesinols A–H, along with three neolignans, quercetin, and protocatechuic acid were isolated from the MeOH extract of the bark of Abies sachalinensis. The structures of these phenolic compounds were characterized by spectroscopic methods including NMR and MS. The absolute configurations of the abiesinols were determined by Mosher's method, CD, and NOESY data.