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The aerobic oxidation of C(sp3)–H bonds is an important issue in organic synthesis, and hydrogen atom transfer (HAT) is an effective process to initiate the oxidation reaction. Here, we demonstrate an innovative strategy for the oxidation of C(sp3)–H bonds based on γ-valerolactone, which can be produced from biomass. This reaction system promotes the aerobic oxidation of various benzylic and allylic C(sp3)–H bonds and alcohols. Excellent chemoselectivity for 1-isochromanone was achieved with the assistance of Ni2Al-layered double hydroxide by increasing the difference in bond dissociation energy between the 1- and 4-C–H bonds of isochroman. The excellent application potential of the reaction system has been demonstrated via the synthesis of pharmaceutical molecules, modification of steroidal substrates, scaled-up oxidation experiments, and the ready availability of γ-valerolactone from biomass. This work also reports on a new carbon-centered radical for the activation of C(sp3)–H bonds. [ABSTRACT FROM AUTHOR]

Black carbon (BC) mass size distribution (BCMSD) is crucial in both the environment and the climate system due to BC's intense size-dependent absorption of solar radiation. BC-containing particles larger than 700 nm (BC >700) could contribute to more than half of bulk BC mass concentration. Unfortunately, previous methods concentrated on BC-containing particles of less than 700 nm because of technical limitations. The contribution of BC to absorption and the radiative effect might be underestimated without consideration of BC >700. In this study, equivalent BCMSD (eBCMSD) from 150 nm up to 1.5 µm was measured at high time resolution of 1 h for the first time by an aerodynamic aerosol classifier in tandem with an aethalometer in two field campaigns over eastern China, namely Changzhou located in the Yangtze River Delta and Beijing located in the North China Plain. The results revealed that the pattern of eBCMSD in Changzhou (Beijing) was mostly bimodal (unimodal) peaking at 240 and 1249 nm (427 nm). The peak diameter of eBCMSD in Changzhou did not shift significantly with increasing pollution (240 to 289 nm). In contrast, the peak diameter of eBCMSD in Beijing shifted towards larger sizes, from 347 to 527 nm, with increasing pollution, indicating that the aging process at the urban site was different from that at the regional background site. eBCMSD in both Changzhou and Beijing had a significant diurnal cycle with a smaller (larger) value of eBCMSD during daytime (nighttime). Equivalent BC >700 (eBC >700) was ubiquitous and varied significantly with different locations and pollution levels. The campaign-averaged contribution of eBC >700 to bulk eBC mass concentration (meBC,bulk), bulk absorption coefficient (σab,bulk) and estimated direct radiative forcing of eBC (DRF eBC) in Changzhou and Beijing were 27.8 % (20.9 %–36.5 %) and 24.1 % (17.5 %–34.2 %), 19.6 % (15.8 %–24.6 %) and 25.9 % (19.6 %–33.7 %) and 20.5 % (18.4 %–22.2 %) and 21.0 % (16.3 %–26.1 %), respectively. meBC,bulk , σab,bulk and DRF eBC of eBC >700 in Changzhou (Beijing) increased by a factor of 3.6 (5.1) from 0.11 (0.07) to 0.40 (0.36) µgm-3 , by a factor of 3.2 (5.5) from 0.54 (0.63) to 1.75 (3.45) Mm -1 and by a factor of 2.4 (4.7) from 0.1 (0.1) to 0.24 (0.47) W m -2 , respectively, with the aggravation of pollution. The contribution of eBC >700 to meBC,bulk and σab,bulk had a significant diurnal cycle with a higher (lower) fraction during daytime (nighttime) in both Changzhou and Beijing. A case study indicated that the contribution of eBC >700 to meBC,bulk , σab,bulk and DRF eBC could reach up to 50 %, 50 % and 40 %, respectively. It was highly recommended to consider the whole size range of BC-containing particles in model estimation of the BC radiative effect. [ABSTRACT FROM AUTHOR]

Ozone and its precursors were measured from 15 June 2006 to 14 June 2007 at an urban site in Shanghai and used to characterize photochemical oxidant production in this region. During the observation period, ozone displays a seasonal variation with a maximum in spring. Observed nitrogen oxides (NOx) and carbon monoxide (CO) reached a maximum in winter and a minimum in summer. NOx and CO has a similar double-peak diurnal cycle, implying that they are largely of motor vehicle origin. Total nonmethane organic compounds (NMOC) concentrations averaged over the morning, and the 24-hour periods have a large day-to-day variation with no apparent seasonal cycle. Aromatics play a dominant role in contributing to total NMOC reactivity and ozone-forming potential. Anthropogenic NMOC of diverse sources are major components of total NMOC and consist mainly of moderate and low reactivity species. In contrast, relatively low levels of biogenic NMOC concentrations were observed in urban Shanghai. The early morning NMOC/NOx ratios are typically below 8:1 with an average of around 4:1, indicating that the sampling location is situated in a NMOC-limited regime. Model simulations confirm that potential photochemical ozone production in Shanghai is NMOC-sensitive. It is presently difficult to predict the impact of future human activities, such as the increase of automobiles and vegetation-covered landscapes and the reduction of aerosol on ozone pollution in the fast developing megacities of China, and additional studies are needed to better understand the highly nonlinear ozone problem. © 2009., the American Geophysical Union.