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971.
Aqueous-phase chemistry of glyoxal may play an important role in the formation of highly oxidized secondary organic aerosol (SOA) in the atmosphere. In this work, we use a novel design of photochemical reactor that allows for simultaneous photo-oxidation and atomization of a bulk solution to study the aqueous-phase OH oxidation of glyoxal. By employing both online aerosol mass spectrometry (AMS) and offline ion chromatography (IC) measurements, glyoxal and some major products including formic acid, glyoxylic acid, and oxalic acid in the reacting solution were simultaneously quantified. This is the first attempt to use AMS in kinetics studies of this type. The results illustrate the formation of highly oxidized products that likely coexist with traditional SOA materials, thus, potentially improving model predictions of organic aerosol mass loading and degree of oxidation. Formic acid is the major volatile species identified, but the atmospheric relevance of its formation chemistry needs to be further investigated. While successfully quantifying low molecular weight organic oxygenates and tentatively identifying a reaction product formed directly from glyoxal and hydrogen peroxide, comparison of the results to the offline total organic carbon (TOC) analysis clearly shows that the AMS is not able to quantitatively monitor all dissolved organics in the bulk solution. This is likely due to their high volatility or low stability in the evaporated solution droplets. This experimental approach simulates atmospheric aqueous phase processing by conducting oxidation in the bulk phase, followed by evaporation of water and volatile organics to form SOA. 相似文献
972.
Oh HS Kim TD Koh YH Lee KS Cho S Cartwright A Prasad PN 《Chemical communications (Cambridge, England)》2011,47(31):8931-8933
New donor-acceptor alternating conjugated polymers were synthesized and characterized. Among them, PCPBBT exhibited a band-gap of 1.01 eV and ambipolar characteristics with μ(h) = 7.1 × 10(-4) cm(2) V(-1) s(-1) and μ(e) = 3.3 × 10(-3) cm(2) V(-1) s(-1). 相似文献
973.
Li CZ Chien SC Yip HL Chueh CC Chen FC Matsuo Y Nakamura E Jen AK 《Chemical communications (Cambridge, England)》2011,47(36):10082-10084
A facile synthesis was employed to make a 56π-electron methano-PC(61)BM with a very small 1,2-dihydromethano (CH(2)) group. This new fullerene derivative possesses high electron mobility (0.014 cm(2) V(-1) s(-1)) and higher LUMO energy level (0.15 eV) than PC(61)BM. Bulk hetero-junction devices based on using poly(3-hexylthiophene) and methano-PC(61)BM as active layer exhibited better performance and thermal stability than those using the PC(61)BM analogue. 相似文献
974.
Silvers WC Payne AS McCarley RL 《Chemical communications (Cambridge, England)》2011,47(40):11264-11266
A new quinone propionic acid-cloaked rhodamine fluorophore has its fluorescence revealed (de-cloaked) upon activation by human NAD(P)H:quinone oxidoreductase 1 (hNQO1), an upregulated enzyme in cancer cells and tumors. 相似文献
975.
Avila F Fernandez DJ Arenas JF Otero JC Soto J 《Chemical communications (Cambridge, England)》2011,47(14):4210-4212
Quantum mechanical calculations of the ground and excited electronic states of several [Ag(n)-pyridine](q) complexes yield a linear dependence of the energies of the surface states, especially the metal-to-molecule charge transfer states, on q(eff) = q/n. This is the first theoretical approach to modelling the effect of the electrode potential on SERS. 相似文献
976.
The first example of the enantioselective methyl C-H activation by an intramolecular ArPdX species and subsequent cyclisation was developed. Palladium catalysts using commercially available chiral diphosphines yield good ee's (up to 93% ee) in the synthesis of 2-methyl indolines from 2-halo N-isopropyl anilides. This approach was also employed for the synthesis of enantioenriched cyclohexyl fused indolines with moderate enantioselectivities. 相似文献
977.
978.
Fletcher JS Rabbani S Henderson A Lockyer NP Vickerman JC 《Rapid communications in mass spectrometry : RCM》2011,25(7):925-932
Time-of-flight secondary ion mass spectrometry (ToFSIMS) is being applied increasingly to the study of biological systems where the chemical specificity of mass spectrometry and the high lateral resolution imaging capabilities can be exploited. Here we report a comparison of two cell sample preparation methods and demonstrate how they influence the outcome of the ToFSIMS analysis for three-dimensional (3D) imaging of biological cells using our novel buncher-ToF instrument (J105 3D Chemical Imager) equipped with a C(60) primary ion beam. Cells were analysed fixed and freeze-dried and non-fixed, frozen-hydrated. It is concluded that maintaining the cells in a non-fixed frozen-hydrated state during the analysis helps reduce chemical redistribution, producing cleaner spectra and improved chemical contrast in both 2D and 3D imaging. Insights into data interpretation are included and we present methods for 3D reconstruction of the data using multivariate analysis techniques. 相似文献
979.
Castro JL Lopez-Ramirez MR Arenas JF Soto J Otero JC 《Langmuir : the ACS journal of surfaces and colloids》2012,28(24):8926-8932
The surface-enhanced raman scattering (SERS) of benzoic acid/benzamide and salicylic acid/salicylamide on silver colloids show important wavenumber shifts with respect to the Raman spectrum of the band assigned to mode 1;ν(ring) when adsorbed on the metal surface (ca. +50 cm(-1)). In the case of the acids, this shift is originated by the deprotonation of the carboxylic group in agreement with the well-known fact that aromatic acids are adsorbed on silver as carboxylates. However, the main conclusion of this work is that a similar behavior is found for the respective amides that do not behave as acids in water solution. The here studied aromatic amides are adsorbed as azanions on silver nanoparticles even at pH 7 and link to the metal through the nitrogen and oxygen atoms of the ionized carboxamide group. This is a very surprising result given that amides are not significantly ionized even at pH 13-14. The deprotonation of these amides is not determined exclusively by the pH, but it is mainly caused by the strong affinity of the anionic species to the metal. Therefore, the SERS must be cautiously used as a universal pH sensor if the adsorption occurs through the ionizable group. In order to support this conclusion, theoretical DFT force field calculations have been carried out, confirming that deprotonated benzamide and salicylamide interact with the metallic surface. 相似文献
980.
Michael J. Silva Alex O. Sanches Luiz F. Malmonge Eliton S. Medeiros Morsyleide F. Rosa Colleen M. McMahan José A. Malmonge 《Macromolecular Symposia》2012,319(1):196-202
Summary: Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI-DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet-visible-near infrared (UV-Vis - NIR) and Fourier-transform infrared (FTIR) spectroscopies and X-ray diffraction (XRD). FTIR and UV-Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10−1 S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X-ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils. 相似文献