Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.     

Wavelength effect on the photoinduced reaction of polymethylmethacrylate

Polymethylmethacrylate (PMMA) containing benzophenone (BP) was photo-irradiated with monochromatic radiation of wavelength 260–360 nm using the Okazaki Large Spec-trograph (OLS). On irradiation of PMMA films containing BP in air, the sensitized main-chain scission and photocrosslinking of PMMA took place simultaneously. These reactions are dependent on irradiation wavelength. The threshold wavelength for both reactions is found to be ca. 380 nm. The number of main-chain scission and amount of gel increased with the increase of BP concentration in PMMA. Photosensitized main-chain scission favors the irradiation of radiation at ca. 280 nm and photocrosslinking takes place efficiently with the exposure of 340 nm radiation. A possible mechanism for photosensitized reaction is proposed. © 1995 John Wiley & Sons, Inc.     

Analysis of phenothiazines in human body fluids using disk solid-phase extraction and liquid chromatography

Seven phenothiazine derivatives, perazine, perphenazine, prochlorperazine, propericiazine, thioproperazine, trifluoperazine, and flupentixol, have been found to be extractable from human plasma and urine samples using disk solid-phase extraction (SPE) with an Empore C18 cartridge. Human plasma and urine (1 mL each) containing the 7 phenothiazine derivatives were mixed with 2 mL of 0.1M NaOH and 7 mL distilled water and then poured into the disk SPE cartridges. The drugs were eluted with 1 mL chloroform- acetonitrile (8 + 2) and determined by liquid chromatography with ammonium formate/formic acid-acetonitrile gradient elution. The detection was performed by ultraviolet absorption at 250 nm. The separation of the 7 phenothiazine derivatives from each other and from impurities was generally satisfactory using a SymmetryShield RP8 column (150 x 2.1 mm id, 3.5 microm particle size). The recoveries of the 7 phenothiazine derivatives spiked into plasma and urine samples were 64.0-89.9% and 65.1-92.1%, respectively. Regression equations for the 7 phenothiazine derivatives showed excellent linearity, with detection limits of 0.021-0.30 microg/mL for plasma and 0.017-0.30 microg/mL for urine. The within-day and day-to-day coefficients of variation for both samples were commonly below 9.0 and 14.9%, respectively.     

The system BaOGeO2 at high pressures and temperatures,with special reference to high-pressure transformations in BaGeO3, BaGe2O5, and Ba2Ge5O12

Phase relations in the system BaOGeO₂ were investigated in the pressure range 20–70 kbar in the temperature range 750–1200°C. Several new phases were identified in this system: an atmospheric phase of BaGe₂O₅ (monoclinic BaGe₂O₅ I), two high-pressure phases of BaGe₂O₅ (monoclinic BaGe₂O₅ II and tetragonal BaGe₂O₅ III), and a high-pressure phase of Ba₂Ge₅O₁₂. The phase boundary curve between BaGe₂O₅ II and BaGe₂O₅ III was preliminarily determined as P(kbar) = 7.7 + 0.047T (°C). The high-pressure phases of BaGeO₃, which were previously reported by Y. Shimizu, Y. Syono, and S. Akimoto (High Temp.-High Pressures2, 113 (1970)) in the pressure range 15–95 kbar, were interpreted to be not single-phase materials but complicated mixtures of more than two phases in the system BaOGeO₂. X-Ray powder diffraction data for the new compounds synthesized in this study are given.     

Catalytic enantioselective Michael addition of 1,3-dicarbonyl compounds to nitroalkenes catalyzed by well-defined chiral ru amido complexes

Well-defined chiral Ru amido complexes promoted asymmetric Michael addition of 1,3-dicarbonyl compounds including malonates, beta-keto esters, and 1,3-diketones to nitroalkenes to give the corresponding adducts with excellent ees and in excellent yields.     

Preparation and characterization of polypropylene/mesoporous silica nanocomposites with confined polypropylene

Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C₄H₉)₃ catalyst. The cross polarization/magic angle spinning (CP/MAS) ¹³C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N₂ adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (M_w) and molecular weight distribution (M_w/M_n) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (M_w = 200,000–450,000, M_w/M_n = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003     

Kinetic Studies of Heterogeneous Reaction of HO2 Radical by Dicarboxylic Acid Particles

The HO₂ uptake coefficients (γ) for organic submicron aerosol particles were measured using an aerosol flow tube coupled with a chemical conversion/laser‐induced fluorescence technique under ambient conditions (760 Torr and 296 ± 2 K) and different values of relative humidity (RH) (28% and 68%). Determined uptake coefficients for succinic, glutaric, adipic, and pimelic acid aerosol particles at 28% RH were 0.07 ± 0.02, 0.07 ± 0.03, 0.02 ± 0.01, and 0.06 ± 0.03, respectively, whereas the γ values for those particles at 68% RH were 0.18 ± 0.07, 0.15 ± 0.04, 0.06 ± 0.01, and 0.13 ± 0.04, respectively. An increase in γ with increasing RH was observed for all the dicarboxylic acids, suggesting a contribution by water amount in the particle, aqueous phase chemistry, and uptake of HO₂–H₂O. The anomalously low γ values for adipic acid are likely related to its high crystallization RH and thus provide a new clue that the water amount and/or RH have a significant influence on HO₂ uptake.     

Effect of Hexamethyi Phosphoric Acid Triamide on the Polymerization of Epichlorohydrin-Methyl Methacryiate Initiated with Alkylaluminum

Abstract

The effect of hexamethyi phosphoric acid triamide on the rate of polymerization of AlEt₃-initiated polymerization of epichloro-hydrin and methyl methacryiate was examined. Benzene was used as solvent and the experiments covered AlEt₃ /hexamethyi phosphoric acid triamide ratios from 1:0 to 1:2. Rate of polymerization increased to a maximum at AlEt₃/ hexamethyi phosphoric acid triamide ratio of 1:0.2 and then decreased.

The reaction of hexamethyi phosphoric acid triamide with AlEt, appears to modify the catalytic nature and copolymeriza-tion of epichlorohydrin with methyl methacryiate as demonstrated by enhanced methyl methacryiate reactivity in the presence of hexamethyi phosphoric acid triamide.