Oxalic acid is often the single most abundant watersoluble organic compound identified in ambient aerosols, but its precursors have not been identified, and its formation mechanism is not well understood. On the contrary, sulfate as a major aerosol component, its formation pathways have been established, and in-cloud processing is recognized as its major production pathway. Our measurements of aerosol sulfate and oxalate collected across a wide geographical span in the East Asia region, up to Beijing in the north and down to Hong Kong in the south, indicate that the two species are highly correlated among samples collected at the same location and among samples collected at different locations in the Pearl River Delta region. This good correlation is also found in measurements made elsewhere by other researchers. We argue that a common dominant formation pathway, likely in-cloud processing, explains the close tracking of the two chemically distinct species. This also highlights the potential importance of in-cloud processing as a pathway leading to formation of secondary organic aerosols.

The charring of organic materials during carbon analysis bythermal methods makes it difficult to differentiate elemental carbon (EC) from organic carbon (OC). Failure to correct for charring results in the overestimation of EC and the underestimation of OC. The charring characteristics andthermal behaviors of aerosol OC are studied by subjecting hexane and water extracts of ambient aerosols to various analysis conditions. The complete evolution of water-soluble organic carbon (WSOC) aerosol materials is found to require a temperature as high as 850 degrees C and the presence of oxygen. EC would be oxidized under these thermal conditions as well. As a result, thermal methods relying only on temperature for the differentiation of EC and OC would give unreliable OC and EC concentrations. Our investigation also reveals that WSOC accounts for a large fraction (13-66%) of charring, while hexane extractable organic compounds produce little charring. The extent of charring from WSOC, defined as the ratio between pyrolytically generated EC to the total WSOC, is found to increase with the WSOC loading in each analysis when the loadings are below a certain value. This ratio remains constant when the loadings are above this value. This may account for the high variability in the extent of charring among aerosol samples from different locations as well as among samples from a single location collected at different times. Charring is reduced if the residence time at each temperature step in a helium atmosphere is sufficiently long to allow for maximum C evolution at each step. Charring is also influenced by the presence of inorganic constituents such as ammonium bisulfate. For the few tested organic materials, it is observed that ammonium bisulfate enhances the charring of starch and cellulose but reduces the charring of levoglucosan.

PM 2.5 samples were collected at an urban and a suburban site in Nanjing, China in 2001. They were analyzed for inorganic ions, elemental carbon, organic carbon (OC), water-soluble organic carbon (WSOC), and individual WSOC and nonpolar organic species. Sulfate and organic matter were the two most abundant constituents in these samples. Sulfate accounted for an average of 23% (urban site) and 30% (suburban site) of the identified aerosol mass.Organic matter accounted for an average of 37% (urban) and 28% (suburban) of the identified aerosol mass. WSOC was a significant portion of OC, accounting for about one-third of OC at the urban site and 45% of OC at the suburban site. The suburban-urban gradient in the WSOC/OC ratio also reflected that the aerosol OC was more aged at the suburban location. The correlations of WSOC with sulfate and nitrate suggest that the WSOC fraction was dominated by secondary organics. More than 30 individual WSOC species in the compound classes of organic anions, amino acids, aliphatic amines, and carbohydrates were quantified, accounting for approximately 8% of the WSOC on a carbon mass basis. In addition, 46 individual nonpolar organic compounds in the compound classes of n-alkanes, hopanes, and polycyclic aromatic hydrocarbons were quantified using an in-injection port thermal desorption technique. These nonpolar organic species accounted for less than 7% of the OC on a carbon mass basis. The quantification of individual compounds allowed the identification of major aerosol sources through principal component analysis. Coal combustion, vehicular emissions, secondary inorganic and organic aerosols, and road/sea salt were the major contributing sources to the identified PM 2.5 aerosol mass.

Since the seminal work of Zhang in 2016, donor–acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis­(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from −1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri­(9H-carbazol-9-yl)-6-(ethyl­(phenyl)­amino)­isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN•–*, which can be used to activate reductively recalcitrant aryl chlorides (E red ≈ −1.9 to −2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C–B, C–P, and C–C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.

We present herein the first visible-light-driven hydrocarboxylation as well as carbocarboxylation of alkynes using CO via an iridium/cobalt dual catalysis. Such transformations provide access to various pharmaceutically important heterocycles in a one-pot procedure from readily available alkynes. Coumarins, 2-quinolones, and 2-benzoxepinones were directly accessed through a one-pot alkyne hydrocarboxylation/alkene isomerization/cyclization sequence in which the Ir photocatalyst serves a dual role to promote single-electron transfer in alkyne hydrocarboxylation and energy transfer in the subsequent alkene isomerization. Moreover, an unprecedented cobalt carboxylation/acyl migration cascade enables alkyne difunctionalization to introduce γ-hydroxybutenolides with high efficiency. We expect that this cascade strategy will inspire new perspectives for alkyne and alkene difunctionalization.

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/anie.201811266. Scheme 1. Difunctionalization of simple alkenes via CÀHorSi ÀH activation. BPO = benzoyl peroxide;TBHP = tert-butyl hydroperoxide; DTBP = di-tert-butyl peroxide.

Limited by the size of microelectronics, as well as the space of electrical vehicles, there are tremendous demands for lithium-ion batteries with high volumetric energy densities. Current lithium-ion batteries, however, adopt graphite-based anodes with low tap density and gravimetric capacity, resulting in poor volumetric performance metric. Here, by encapsulating nanoparticles of metallic tin in mechanically robust graphene tubes, we show tin anodes with high volumetric and gravimetric capacities, high rate performance, and long cycling life. Pairing with a commercial cathode material LiNi0.6Mn0.2Co0.2O2, full cells exhibit a gravimetric and volumetric energy density of 590 W h Kg−1 and 1,252 W h L−1, respectively, the latter of which doubles that of the cell based on graphite anodes. This work provides an effective route towards lithium-ion batteries with high energy density for a broad range of applications.

[1] During the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia), samples of carbonaceous aerosols were collected on board the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) De Havilland DHC-6 Twin Otter aircraft. The samples were analyzed to determine their total carbon (TC) and water-soluble organic compound (WSOC) contents as well as to identify the individual compounds comprising the WSOC fraction of the aerosol. The TC concentrations varied from 3.5 to 14.3 mg C m À3 ; the highest TC levels were observed for samples collected in pollution layers that originated over mainland China. WSOC concentrations ranged from 0.54 to 7.2 mg C m À3, with the WSOC fraction contributing from 10 to 50% of the carbon mass. About 50% of the carbonaceous aerosol mass in pollution layers could be attributed to WSOC. For samples collected in dust layers the WSOC fraction of TC was much lower than that observed in pollution layers. The sum of all the detected organic ions accounted for 6.9-19% of the WSOC. In the six samples collected by the Twin Otter during ACEAsia, of the organic ions identified in the WSOC fraction, oxalate had the highest concentration. Samples collected from pollution layers exhibited a slightly higher ratio of formate to oxalate as compared to the other samples. Two samples had a relatively high ratio of lactate to oxalate, which might be a signature of some currently unidentified source of carbonaceous aerosol. The sum of the masses of sulfate and nitrate ions exceeded the sum of the masses of the identified organic ions by a factor of 9 to 17. The chemical levoglucosan, a tracer for biomass burning, comprised from 0.1 to 0.4% of TC mass. Comparing this ratio to the ratio measured directly in wood-burning studies it was determined that biomass burning may have represented from %2 to 10% of the carbonaceous aerosol collected during ACE-Asia.