Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

Sonochemical immobilization of noble metal nanoparticles on the surface of maghemite: mechanism and morphological control of the products

Aqueous sample solutions containing noble metal ions (HAuCl₄, Na₂PdCl₄, H₂PtCl₆), polyethyleneglycol monostearate, and magnetic maghemite nanoparticles were irradiated with high power ultrasound. Analyses of the products showed that noble metal ions were reduced by the effects of ultrasound, and the formed noble metal nanoparticles were uniformly immobilized on the surface of the maghemite. The present “one pot process” significantly simplifies the immobilization of noble metal nanoparticles on the surface of supports, compared with the conventional impregnation method. The average diameter of immobilized Au was 7–13 nm, and the diameters of Pd and Pt were several nm. The diameters depended upon the concentration of polyethyleneglycol monostearate and the concentration of noble metal ions, but not upon the maghemite concentration, indicating the possibility of the morphological controls of the products by adjusting these preparation conditions. The measurements of the average diameters and the numbers of immobilized Au nanoparticles obtained under various conditions suggest that the nucleation of Au does not occur on the surface of maghemite, but it might occur in the homogeneous bulk solution.     

Applications of CE-ESI-MS/MS analysis to structural elucidation of methylenecyclohexane ozonolysis products in the particle phase

The composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of methylenecyclohexane was analyzed in a series of indoor aerosol chamber experiments. Capillary electrophoresis-electrospray ionization-ion trap mass spectrometry (CE/ESI-ITMS) was used for qualitative and quantitative analysis of SOA constituents. A number of dicarboxylic acids in the range of C(5)-C(6), such as adipic acid and glutaric acid, were found as major components of the organic products. Besides these smaller compounds, the formation of higher-molecular-weight compounds were observed under both neutral and acidic conditions. MS/MS experiments were carried out in order to obtain information on the monomer units and the structure of the dimers. MS(2) experiments of the two most prominent dimers with a mass-to-charge ratio (m/z) of 257 and m/z 273 yielded common fragments of m/z 83, 129 or 145. Based on the fragmentation patterns, these dimers are tentatively identified as carboxylate ester acids containing a unit of adipic acid in the structure. The dimer with m/z 257 was nearly 60% of the total detected compounds for both the neutral and acidic seed particle experiments.     

The Weight-Bearing Rate on the Paretic Limb of Cerebrovascular Hemiplegic Patients Necessary for an Independent Obstacle Negotiation Gait

Purpose: The obstacle negotiation gait (ONG) is a fundamental activity of daily living. In cerebrovascular hemiplegic patients (stroke patients), the weight-bearing rate (WBR) on the paretic limb necessary for an independent ONG was studied. Methods: One hundred and seventeen stroke patients were involved. The patients'' average age at the time of the study was 67 years, and the average time from stroke onset was 102 days. There were 68 men and 49 women. Seventy patients were right hemiplegics, and 47 were left hemiplegics. The correlations between ONG and age, sex, body mass index (BMI), time from stroke onset, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation, and the WBR on both the paretic and non-paretic limbs were studied. Patients who could perform ONG independently and safely were categorized as the independent group (IG), and those who needed observation or any assistance were categorized as the dependent group (DG). Results: The BMI, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation and the WBR for both the paretic and non-paretic limbs were significantly different between the IG and DG groups. In particular, the WBR on the paretic limb was found to correlate significantly with the ONG, and a WBR value of 80.5% on the paretic limb gave a clear cut-off value. Conclusion: Although multiple factors influenced the ONG of stroke patients, the WBR on the paretic limb was the most influential.     

Contribution of the π electron to the N-HO[double bond, length as m-dash]C hydrogen bond: IR spectroscopic studies of the jet-cooled pyrrole-acetone binary clusters

To investigate the π bonding electron contribution to N-HO[double bond, length as m-dash]C hydrogen-bond (H-bond) formation, we applied IR cavity ringdown spectroscopy to jet-cooled pyrrole-acetone (Py-Ac) binary clusters. The observed NH stretching vibrations were analyzed by density functional theory (DFT), in which the energetically optimized structures, harmonic frequencies, and interaction energies were calculated for various sizes of binary clusters. We observed three NH stretching vibrations, ascribed to binary clusters at 3406, 3388, and 3335 cm(-1). These were assigned to H-bonded NH stretches of the Py(2)-Ac(1), Py(1)-Ac(1), and Py(1)-Ac(2) clusters, respectively. The Py(1)-Ac(1) cluster has a single N-HO[double bond, length as m-dash]C H-bonded structure with C(s) symmetry, while the Py(1)-Ac(2) cluster has a cyclic structure formed by a single N-HO[double bond, length as m-dash]C H-bond, dipole-dipole interactions, and weak CH H-bonds. A natural bond orbital (NBO) analysis was performed to reveal the H-bond strength in Py-Ac binary clusters. For the Py(1)-Ac(2) cluster, we found that the donor-acceptor interactions are not only the n →σ* type (O atom lone pair to the NH anti-bonding orbitals), but also the π→σ* type (the CO π bonding to the NH anti-bonding orbitals). By analyzing the relationship between the frequency shift and the stabilization energy in donor-acceptor interactions, we concluded that larger red-shift of the NH stretching vibration in the Py(1)-Ac(2) can be explained by not only the lone pair and the π electron contributions to the N-HO[double bond, length as m-dash]C H-bond, but also the dipole-interaction between Py and non-H-bonded Ac. We also discussed the structures of Py(2)-Ac(1) clusters.     

Mechanism of the alkali degradation of (6-4) photoproduct-containing DNA

The (6-4) photoproduct is one of the major damaged bases produced by ultraviolet light in DNA. This lesion is known to be alkali-labile, and strand breaks occur at its sites when UV-irradiated DNA is treated with hot alkali. We have analyzed the product obtained by the alkali treatment of a dinucleoside monophosphate containing the (6-4) photoproduct, by HPLC, NMR spectroscopy, and mass spectrometry. We previously found that the N3-C4 bond of the 5' component was hydrolyzed by a mild alkali treatment, and the present study revealed that the following reaction was the hydrolysis of the glycosidic bond at the 3' component. The sugar moiety of this component was lost, even when a 3'-flanking nucleotide was not present. Glycosidic bond hydrolysis was also observed for a dimer and a trimer containing 5-methyl-2-pyrimidinone, which was used as an analog of the 3' component of the (6-4) photoproduct, and its mechanism was elucidated. Finally, the alkali treatment of a tetramer, d(GT(6-4)TC), yielded 2'-deoxycytidine 5'-monophosphate, while 2'-deoxyguanosine 3'-monophosphate was not detected. This result demonstrated the hydrolysis of the glycosidic bond at the 3' component of the (6-4) photoproduct and the subsequent strand break by β-elimination. It was also shown that the glycosidic bond at the 3' component of the Dewar valence isomer was more alkali-labile than that of the (6-4) photoproduct.     

Novel strategic lipase-catalyzed asymmetrization of 1,3-propanediacetate in supercritical carbon dioxide

In lipase-catalyzed asymmetrization of 1,3-propanediacetate no enantioselectivity was observed in conventional organic solvents, whereas in supercritical carbon dioxide (scCO₂) enantioselectivities were observed up to 50% ee, which probably arose from a conformational changing of lipase at the active site due to a transformation of the amino group of lysine into carbamic acid.     

The synthesis and properties of a methylviologen analogue

A novel derivative of methylviologen, prepared by transannular reaction of [2.2] (3,5) pyridinophane, shows large bathochromic shift in the electronic spectrum and nearly equal redox potential compared with methylviologen.