Interaction between peroxide ion and phenol group which are coordinated to the same iron(III) ion

We have prepared several new iron(III) complexes with ligands which contain a phenol group; these are tetradentate [(X-phpy)H, X and H(phpy) represent the substituents on the phenol ring and N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine, respectively] and pentadentate ligands [(R-enph-X)H; R=ethyl(Et) or methyl(Me) derivative and H(Me-enph) denotes N,N-bis(2-pyridylmethyl)-N″-methyl-N″-(2″-hydroxyl-benzylamine)ethylenediamine] and have determined the crystal structures of Fe(phpy)Cl₂, Fe(5-NO₂-phpy)Cl₂, and Fe(Me-enph)ClPF₆, which are of a mononuclear six-coordinate iron(III) complex with coordination of one or two chloride ion(s). These compounds are highly colored (dark violet) due to the coordination of phenol group to an iron(III) atom. When hydrogen peroxide was added to the solution of the iron(III) complex, a color change occurs with bleaching of the violet color, indicating that oxidative degradation of the phenol moiety occurred in the ligand system. The bleaching of the violet color was also observed by the addition of t-butylhydroperoxide. The rate of the disappearance of the violet color is highly dependent on the substituent on the phenol ring; introduction of an electron-withdrawing group in the phenol ring decreases the rate of bleaching, suggesting that disappearance of the violet band should be due to a chemical reaction between the phenol group and a peroxide adduct of the iron(III) species with an η¹-coordination mode and that in this reaction the peroxide adduct acts as an electrophile towards phenol ring. The intramolecular interaction between the phenol moiety and an iron(III)-peroxide adduct may induce activation of the peroxide ion, and this was supported by several facts that the solution containing an iron(III) complex and hydrogen peroxide exhibits high activities for degradation of nucleosides and albumin.     

Synthesis of functionalized hydroquinones via [Cp*RuCl2]2-catalyzed cocyclization of alkynes, alpha,beta-unsaturated carbonyl compounds, and carbon monoxide

[reaction: see text] Catalytic [2 + 2 + 1 + 1] cocyclization reaction of an alkyne, an alkene, and two molecules of carbon monoxide, leading to functionalized hydroquinones, was studied. Using [Cp*RuCl2]2 as a catalyst, we found that a variety of electron-deficient alkenes, such as alpha,beta-unsaturated ketones, esters, amides, and nitriles, can be employed as an alkene coupling partner to give the corresponding hydroquinones.     

Self-organized lipid-porphyrin bilayer membranes in vesicular form: nanostructure,photophysical properties,and dioxygen coordination

An amphiphilic tetraphenylporphyrin and its iron complex bearing four phospholipid substituents, in which a trimethylolethane residue connects the two acyl chains (lipid-porphyrins), have been synthesized. The free-base lipid-porphyrin 6a self-organizes in aqueous media to form spherical unilamellar vesicles with a diameter of 100 nm and a uniform thickness of 10 nm, which corresponds to twice the length of the molecule. In the visible absorption spectrum, the porphyrin Soret band was significantly red-shifted (12 nm) relative to that of the monomer in benzene/MeOH solution due to the excitonic interaction of the porphyrin chromophores. The [symbol: see text]-A isotherm of 6a gave an area per molecule of 2.2 nm2, which allowed the estimation of the number of molecules in a single vesicle (2.3 x 10(4)). Double-layered Langmuir-Blodgett (LB) films of 6a on a glass surface exhibited an absorption spectrum identical to that of the 6a vesicles in bulk aqueous solution, and this suggests that they contain similar geometric arrangements of the porphyrin moieties. Exciton calculations on the basis of our structural model reproduced the bathochromic shift of the Soret band well. In the photophysical properties of the 6a vesicles, the characteristics of J-aggregated porphyrins substantially predominate: strong fluorescence and extremely short triplet lifetime. The iron complex 6b with a small molar excess of 1-dodecylimidazole (DIm) also formed spherical unilamellar vesicles (100 nm phi). Scanning force microscopy after evaporation on a graphite surface revealed 6b/DIm vesicles with a vertical height of 19.8 nm, which coincided with the thickness of the double bilayer membranes. The ferrous 6c formed a bis(DIm)-coordinated low-spin FeII complex under an N2 atmosphere. Upon addition of O2 to this solution, a kinetically stable O2 adduct was formed at 37 degrees C with a half-life of 17 h. Distinct gel-phase (liquid-crystal) transitions of the lipid-porphyrin membranes were clearly observed; the free base 6a displayed a higher transition temperature (56 degrees C) than the iron complex. Magnetic circular dichroism and infrared spectroscopic studies proved that molecular O2 coordinates to the self-organized lipid-porphyrinatoiron(II) vesicles in aqueous media.     

Induced long-range attractive potentials of human serum albumin by ligand binding

Small-angle x-ray scattering and dielectric spectroscopy investigation on the solutions of recombinant human serum albumin and its heme hybrid revealed that heme incorporation induces a specific long-range attractive potential between protein molecules. This is evidenced by the enhanced forward intensity upon heme binding, despite no hindrance to rotatory Brownian motion, unbiased colloid osmotic pressure, and discontiguous nearest-neighbor distance, confirming monodispersity of the proteins. The heme-induced potential may play a trigger role in recognition of the ligand-filled human serum albumins in the circulatory system.     

Influence of bubble clustering on multibubble sonoluminescence

Influence of clustering of cavitation bubbles on multibubble sonoluminescence (MBSL) in standing wave fields is studied through measurement of MBSL intensity with a photomultiplier tube and observation of corresponding bubble behavior with a high-speed video camera and an intensified charge-coupled device one. It is clarified that, when the SL is quenched suddenly at excessive ultrasonic power, the behavior of bubbles clearly changes; the bubbles which form dendritic branches of filaments change into clusters due to the secondary Bjerknes force. The cluster is composed of several bubbles surrounded by many tiny bubbles, in which bubbles repeatedly coalesce and fragment, and run away from pressure antinodes. When the clusters are broken up by forced fluid motion, the quenching of MBSL is suppressed.     

Synthesis and structural characterisation of a cationic trinuclear organobismuth complex with an unprecedented coordination mode of hydrotris(2-mercaptoimidazolyl)borate ligands

A new coordination mode of hydrotris(2-mercaptoimidazolyl)borate ligands was found in the reaction of [Na(Tm(tBu))] with Me(2)BiCl to form a trinuclear organobismuth complex [(Me(2)Bi)(3)(Tm(tBu))(2)](+)[Me(2)BiCl(2)](-)(Tm(tBu)= hydrotris(2-mercapto-1-tert-butylimidazolyl)borate).     

Author Index

Authors Index

Author Index     

Scaling algorithms for the calculation of solar radiative fluxes

We derived new scaling formulae based on the method of successive orders of scattering to calculate solar radiative flux. In this report, we demonstrate a multiple scaling method, in which we introduce scaling factors for each scattering order independently. The formula of radiative transfer by the method of successive orders of scattering cannot be solved rapidly except in the case of optically thin atmospheres. Then we further derived a double scaling method, which scales the ordinary radiative transfer equation by two scaling factors. We applied the double scaling method to two-stream and four-stream approximations of the discrete ordinates method. Comparing the results of the double scaling method with those of the delta-M method, we found that the double scaling method improved the accuracy of radiative fluxes at large solar zenith angles, especially in the optically thin region, and that in the region where multiple scattering dominates, its accuracy was comparable to that of the delta-M method. Once we determined the scaling factors appropriately, the double scaling method calculated radiative fluxes as rapidly as the delta-M method in the two-stream and four-stream approximations. This method, therefore, is useful for accurate computation of solar radiative fluxes in general circulation models.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.