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1
Ditto, Jenna C., Megan He, Tori N. Hass-Mitchell, Samar G. Moussa, Katherine Hayden, Shao-Meng Li, John Liggio, et al. "Atmospheric evolution of emissions from a boreal forest fire: the formation of highly functionalized oxygen-, nitrogen-, and sulfur-containing organic compounds." Atmospheric Chemistry and Physics 21, no. 1 (January 14, 2021): 255–67. http://dx.doi.org/10.5194/acp-21-255-2021.
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Abstract. Forest fires are major contributors of reactive gas- and particle-phase organic compounds to the atmosphere. We used offline high-resolution tandem mass spectrometry to perform a molecular-level speciation of gas- and particle-phase compounds sampled via aircraft from an evolving boreal forest fire smoke plume in Saskatchewan, Canada. We observed diverse multifunctional compounds containing oxygen, nitrogen, and sulfur (CHONS), whose structures, formation, and impacts are understudied. The dilution-corrected absolute ion abundance of particle-phase CHONS compounds increased with plume age by a factor of 6.4 over the first 4 h of downwind transport, and their relative contribution to the observed functionalized organic aerosol (OA) mixture increased from 19 % to 40 %. The dilution-corrected absolute ion abundance of particle-phase compounds with sulfide functional groups increased by a factor of 13 with plume age, and their relative contribution to observed OA increased from 4 % to 40 %. Sulfides were present in up to 75 % of CHONS compounds and the increases in sulfides were accompanied by increases in ring-bound nitrogen; both increased together with CHONS prevalence. A complex mixture of intermediate- and semi-volatile gas-phase organic sulfur species was observed in emissions from the fire and depleted downwind, representing potential precursors to particle-phase CHONS compounds. These results demonstrate CHONS formation from nitrogen- and oxygen-containing biomass burning emissions in the presence of reduced sulfur species. In addition, they highlight chemical pathways that may also be relevant in situations with elevated emissions of nitrogen- and sulfur-containing organic compounds from residential biomass burning and fossil fuel use (e.g., coal), respectively.
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Zhao, Y., A. G. Hallar, and L. R. Mazzoleni. "Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh resolution FT-ICR mass spectrometry." Atmospheric Chemistry and Physics Discussions 13, no. 8 (August 7, 2013): 20561–610. http://dx.doi.org/10.5194/acpd-13-20561-2013.
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Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gaseous and particulate phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at Storm Peak Laboratory near Steamboat Spring, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh resolution mass spectra of the samples after using a reverse phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen containing compounds (CHNO compounds), sulfur containing compounds (CHOS and CHNOS compounds) and other oxygen containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ~0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. We observed multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite indicating the significance of nighttime emissions or NOx oxidation on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur containing compounds) were also observed, however further investigation is needed to determine the origin of the reduced sulfur containing compounds. Overall, the molecular composition determined using ultrahigh resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic composition in the Rocky Mountain area which could help to improve the understanding of aqueous phase processes.
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Zhao, Y., A. G. Hallar, and L. R. Mazzoleni. "Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry." Atmospheric Chemistry and Physics 13, no. 24 (December 18, 2013): 12343–62. http://dx.doi.org/10.5194/acp-13-12343-2013.
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Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.
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Ditto, Jenna C., Jo Machesky, and Drew R. Gentner. "Analysis of reduced and oxidized nitrogen-containing organic compounds at a coastal site in summer and winter." Atmospheric Chemistry and Physics 22, no. 5 (March 8, 2022): 3045–65. http://dx.doi.org/10.5194/acp-22-3045-2022.
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Abstract. Nitrogen-containing organic compounds, which may be directly emitted into the atmosphere or which may form via reactions with prevalent reactive nitrogen species (e.g., NH3, NOx, NO3), have important but uncertain effects on climate and human health. Using gas and liquid chromatography with soft ionization and high-resolution mass spectrometry, we performed a molecular-level speciation of functionalized organic compounds at a coastal site on the Long Island Sound in summer (during the 2018 Long Island Sound Tropospheric Ozone Study – LISTOS – campaign) and winter. This region often experiences poor air quality due to the emissions of reactive anthropogenic, biogenic, and marine-derived compounds and their chemical transformation products. We observed a range of functionalized compounds containing oxygen, nitrogen, and/or sulfur atoms resulting from these direct emissions and chemical transformations, including photochemical and aqueous-phase processing that was more pronounced in summer and winter, respectively. In both summer and winter, nitrogen-containing organic aerosols dominated the observed distribution of functionalized particle-phase species ionized by our analytical techniques, with 85 % and 68 % of total measured ion abundance containing a nitrogen atom, respectively. Nitrogen-containing particles included reduced nitrogen functional groups (e.g., amines, imines, azoles) and common NOz contributors (e.g., organonitrates). Reduced nitrogen functional groups observed in the particle phase were frequently paired with oxygen-containing groups elsewhere on the molecule, and their prevalence often rivaled that of oxidized nitrogen groups detected by our methods. Supplemental gas-phase measurements, collected on adsorptive samplers and analyzed with a novel liquid chromatography-based method, suggest that gas-phase reduced nitrogen compounds are possible contributing precursors to the observed nitrogen-containing particles. Altogether, this work highlights the prevalence of reduced nitrogen-containing compounds in the less-studied northeastern US and potentially in other regions with similar anthropogenic, biogenic, and marine source signatures.
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Li, Y., U. Pöschl, and M. Shiraiwa. "Molecular corridors and parameterizations of volatility in the evolution of organic aerosols." Atmospheric Chemistry and Physics Discussions 15, no. 19 (October 15, 2015): 27877–915. http://dx.doi.org/10.5194/acpd-15-27877-2015.
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Abstract. The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the volatility of organic compounds containing oxygen, nitrogen and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.
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Li, Ying, Ulrich Pöschl, and Manabu Shiraiwa. "Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols." Atmospheric Chemistry and Physics 16, no. 5 (March 14, 2016): 3327–44. http://dx.doi.org/10.5194/acp-16-3327-2016.
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Abstract. The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.
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Sham, Simon, and Gang Wu. "Zinc-67 NMR study of tetrahedral and octahedral zinc sites with symmetrical oxygen, nitrogen, and sulfur ligands." Canadian Journal of Chemistry 77, no. 11 (November 1, 1999): 1782–87. http://dx.doi.org/10.1139/v99-154.
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We report a 67Zn nuclear magnetic resonance (NMR) study of compounds containing zinc ions coordinated by oxygen, nitrogen, and sulfur ligands. New information concerning 67Zn nuclear quadrupole coupling constants (NQCC) and chemical shift was obtained from magic-angle spinning (MAS) spectra of solid compounds containing both natural abundance and enriched 67Zn isotopes. Rapid ligand exchange processes of [Zn(thiourea)4]2+ in aqueous solutions were also observed.Key words: 67Zn NMR, nuclear quadrupolar coupling constant, ligand exchange.
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Li, Ying, Douglas A. Day, Harald Stark, Jose L. Jimenez, and Manabu Shiraiwa. "Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions." Atmospheric Chemistry and Physics 20, no. 13 (July 13, 2020): 8103–22. http://dx.doi.org/10.5194/acp-20-8103-2020.
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Abstract. Volatility and viscosity are important properties of organic aerosols (OA), affecting aerosol processes such as formation, evolution, and partitioning of OA. Volatility distributions of ambient OA particles have often been measured, while viscosity measurements are scarce. We have previously developed a method to estimate the glass transition temperature (Tg) of an organic compound containing carbon, hydrogen, and oxygen. Based on analysis of over 2400 organic compounds including oxygenated organic compounds, as well as nitrogen- and sulfur-containing organic compounds, we extend this method to include nitrogen- and sulfur-containing compounds based on elemental composition. In addition, parameterizations are developed to predict Tg as a function of volatility and the atomic oxygen-to-carbon ratio based on a negative correlation between Tg and volatility. This prediction method of Tg is applied to ambient observations of volatility distributions at 11 field sites. The predicted Tg values of OA under dry conditions vary mainly from 290 to 339 K and the predicted viscosities are consistent with the results of ambient particle-phase-state measurements in the southeastern US and the Amazonian rain forest. Reducing the uncertainties in measured volatility distributions would improve predictions of viscosity, especially at low relative humidity. We also predict the Tg of OA components identified via positive matrix factorization of aerosol mass spectrometer (AMS) data. The predicted viscosity of oxidized OA is consistent with previously reported viscosity of secondary organic aerosols (SOA) derived from α-pinene, toluene, isoprene epoxydiol (IEPOX), and diesel fuel. Comparison of the predicted viscosity based on the observed volatility distributions with the viscosity simulated by a chemical transport model implies that missing low volatility compounds in a global model can lead to underestimation of OA viscosity at some sites. The relation between volatility and viscosity can be applied in the molecular corridor or volatility basis set approaches to improve OA simulations in chemical transport models by consideration of effects of particle viscosity in OA formation and evolution.
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Altieri, K. E., M. G. Hastings, A. J. Peters, and D. M. Sigman. "Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry." Atmospheric Chemistry and Physics Discussions 11, no. 11 (November 29, 2011): 31283–321. http://dx.doi.org/10.5194/acpd-11-31283-2011.
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Abstract. Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties, and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W), which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2455 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+), CHON compounds that contained sulfur (CHONS+), CHON compounds that contained phosphorous (CHONP+), CHON compounds that contained both sulfur and phosphorous (CHONSP+), and compounds that contained only carbon, hydrogen, and nitrogen (CHN+). No organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March) which have anthropogenic air mass origins and samples collected during the warm season (April to September) with remote marine air mass origins. This, in conjunction with patterns identified in van Krevelen diagrams, suggests that the cold season WSON is a mixture of organic matter with both marine and anthropogenic sources while in the warm season the WSON appears to be dominated by marine sources. These findings indicate that, although the concentrations and percent contribution of WSON to total N is fairly consistent across diverse geographic regions, the chemical composition of WSON varies strongly as a function of source region and atmospheric environment.
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Altieri, K. E., M. G. Hastings, A. J. Peters, and D. M. Sigman. "Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry." Atmospheric Chemistry and Physics 12, no. 7 (April 12, 2012): 3557–71. http://dx.doi.org/10.5194/acp-12-3557-2012.
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Abstract. Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W), which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+), CHON compounds that contained sulfur (CHONS+), CHON compounds that contained phosphorus (CHONP+), CHON compounds that contained both sulfur and phosphorus (CHONSP+), and compounds that contained only carbon, hydrogen, and nitrogen (CHN+). Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March) which have anthropogenic air mass origins and samples collected during the warm season (April to September) with remote marine air mass origins. This, in conjunction with patterns identified in van Krevelen diagrams, suggests that the cold season WSON is a mixture of organic matter with both marine and anthropogenic sources while in the warm season the WSON appears to be dominated by marine sources. These findings indicate that, although the concentrations and percent contribution of WSON to total N is fairly consistent across diverse geographic regions, the chemical composition of WSON varies strongly as a function of source region and atmospheric environment.
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Kobotaeva, Natalia, Tatiana Skorokhodova, Oleg Andrienko, Elena Marakina, and Victor Sachkov. "Extractants Based on Coordinating Liquid Polar Solvents for Removal of Sulfur Compounds from Diesel Fuels." Applied Sciences 8, no. 8 (July 30, 2018): 1259. http://dx.doi.org/10.3390/app8081259.
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To remove sulfur-containing compounds (SCC) from the diesel fraction 200–360 °C extraction systems have been created based on coordinating organic solvents—dimethylformamide and dimethylsulfoxide, metal chlorides (CoCl2, CuCl2, CdCl2, MnCl2 and CrCl3), and metal trifluoroacetates (Co(TFA)2, Cu(TFA)2 and Mn(TFA)2). Using PMR spectroscopy the coordination of metal chloride and metal trifluoroacetate on the oxygen atom in the carbonyl group of DMF was shown to redistribute electron density in the solvent molecule and to enhance properties of the acceptor center localized on the nitrogen atom. The removal of sulfur-containing compounds from the diesel fraction proceeded under mild conditions—at the temperature of 25 °C and atmospheric pressure. The degree of SCC removal from the diesel fraction in 30 minutes extraction was more than 90%. The interaction of organic solvents with metal salts and sulfur-containing compounds of the diesel fraction was considered within the framework of the concept of “hard and soft acids and bases” (HSAB). The most complete SCC extraction was carried out with DMF-Mn(TFA)2, MnCl2 and CrCl3 systems, that was probably connected with the implementation of the ‘hard base–hard acid’ system.
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Zhu, Yannan, and You Huang. "Organocatalyzed [3+3] Annulations for the Construction of Heterocycles." Synthesis 52, no. 08 (February 5, 2020): 1181–202. http://dx.doi.org/10.1055/s-0039-1690810.
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Six-membered heterocyclic systems are widely distributed in many natural products and pharmaceuticals, and the construction of highly functionalized six-membered heterocyclic compounds is an important topic in modern organic synthesis. Organocatalyzed [3+3] annulations represents an important method for assembling a substantial variety of six-membered cycles that contain one or more heteroatoms. This review describes the development of organocatalyzed [3+3] annulations for the synthesis of six-membered heterocycles, including organocatalysis using secondary amines, tertiary amines, phosphines, chiral phosphoric acids and N-heterocyclic carbenes.1 Introduction2 Secondary Amine Catalyzed [3+3] Annulations2.1 Synthesis of Nitrogen Heterocycles2.2 Synthesis of Oxygen Heterocycles2.3 Synthesis of Sulfur Heterocycles3 Tertiary Amine Catalyzed [3+3] Annulations3.1 Catalysis through Multiple Hydrogen-Bonding Interactions3.2 Catalysis of Tertiary Amines as Lewis Bases4 Phosphine-Catalyzed [3+3] Annulations4.1 Synthesis of Nitrogen Heterocycles4.2 Synthesis of Oxygen Heterocycles4.3 Synthesis of Heterocycles Containing Two or More Heteroatoms5 Chiral Phosphoric Acid Catalyzed [3+3] Annulations5.1 Synthesis of Nitrogen Heterocycles5.2 Synthesis of Heterocycles Containing Two or More Heteroatoms6 N-Heterocyclic Carbene Catalyzed [3+3] Annulations6.1 Synthesis of Nitrogen Heterocycles6.2 Synthesis of Oxygen Heterocycles6.3 Synthesis of Heterocycles Containing Two or More Heteroatoms7 Conclusion and Outlook
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Altieri, K. E., B. J. Turpin, and S. P. Seitzinger. "Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry." Atmospheric Chemistry and Physics 9, no. 7 (April 7, 2009): 2533–42. http://dx.doi.org/10.5194/acp-9-2533-2009.
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Abstract. Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.
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Cook, Ryan D., Ying-Hsuan Lin, Zhuoyu Peng, Eric Boone, Rosalie K. Chu, James E. Dukett, Matthew J. Gunsch, et al. "Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water." Atmospheric Chemistry and Physics 17, no. 24 (December 21, 2017): 15167–80. http://dx.doi.org/10.5194/acp-17-15167-2017.
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Abstract. Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August–September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C10−12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.
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Singh, Kuldeep, Kulbir Kulbir, Tarang Gupta, Rajneesh Kaur, and Raman Singh. "Applications of Rozen’s Reagent in Oxygen-Transfer and C–H Activation Reactions." Synthesis 51, no. 02 (November 22, 2018): 371–83. http://dx.doi.org/10.1055/s-0037-1609638.
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Rozen’s reagent (hypofluorous acid–acetonitrile complex, HOF·MeCN) is a robust nonspecific oxygen-transfer reagent and became a proven tool for the oxidation of difficult-to-oxidize molecules. It has been applied to instant oxygen transfers to functional groups such as alkenes, alkynes, and aromatic hydrocarbons, epoxidation, oxidation of alcohols, amines, and alkynes, oxygen-transfer reactions with nitrogen, phosphorus, and sulfur-containing substrates, and α-hydroxylation of carbonyl groups. Apart from being a potential green oxidizing agent, the complex has applications in 18O-labeling and C–H functionalization strategies. Recent uses of Rozen’s reagent in developing nanomaterials and oxidized expanded graphite indicate the enormous potential of the reagent. These aspects are discussed in this review.1 Introduction2 Synthesis and Physical Properties3 Safety and Handling4 Oxygen-Transfer Reactions4.1 General Mechanism of Oxygen Transfer4.2 Epoxidation4.3 Oxidation of Alkynes4.4 Oxidation of Aromatic Alcohols and Phenols4.5 Oxidation of Nitrogen-Containing Compounds4.6 Conversion of Aldehydes into Nitriles4.7 Oxidation of Alcohols and Ethers4.8 Oxidation of Sulfur-Containing Compounds4.9 Oxygen-Transfer Reaction with Phosphine, Phosphite, and Phosphinite Compounds5 C–H Activation Reactions5.1 Hydroxylation of Nonactivated Tertiary Saturated Carbon Center5.2 Hydroxylation of Aromatic Carbon Center5.3 α-Hydroxylation of Carbonyl Group5.4 Activation of α-Hydrogens of α-Amino Acids6 Other Uses7 Green Chemistry and Rozen’s Reagent8 Experimental Problems9 Further Applications10 Conclusions
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Hauser, P. C., and M. W. Blades. "Atomization of Organic Compounds in the Inductively Coupled Plasma." Applied Spectroscopy 42, no. 4 (May 1988): 595–98. http://dx.doi.org/10.1366/0003702884429373.
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The problem of incomplete atomization when nonmetals are being determined in aspirated organic solutions was studied. Abel inverted spatial profiles of C2, CN, C(I) and S(I) emission were acquired at several heights. It was found that molecular emission caused by the analyte is restricted to the lower aerosol channel. Nonmetal atomic emission is found in the toroidal region and higher up in the aerosol channel. Compounds that contained nonmetals comprised of either oxygen, nitrogen, or sulfur, which were dissolved in xylene, exhibited nonmetal emission intensities independent of the structure of the compound.
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China, Hideyasu, Ravi Kumar, Kotaro Kikushima, and Toshifumi Dohi. "Halogen-Induced Controllable Cyclizations as Diverse Heterocycle Synthetic Strategy." Molecules 25, no. 24 (December 18, 2020): 6007. http://dx.doi.org/10.3390/molecules25246007.
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In organic synthesis, due to their high electrophilicity and leaving group properties, halogens play pivotal roles in the activation and structural derivations of organic compounds. Recently, cyclizations induced by halogen groups that allow the production of diverse targets and the structural reorganization of organic molecules have attracted significant attention from synthetic chemists. Electrophilic halogen atoms activate unsaturated and saturated hydrocarbon moieties by generating halonium intermediates, followed by the attack of carbon-containing, nitrogen-containing, oxygen-containing, and sulfur-containing nucleophiles to give highly functionalized carbocycles and heterocycles. New transformations of halogenated organic molecules that can control the formation and stereoselectivity of the products, according to the difference in the size and number of halogen atoms, have recently been discovered. These unique cyclizations may possibly be used as efficient synthetic strategies with future advances. In this review, innovative reactions controlled by halogen groups are discussed as a new concept in the field of organic synthesis.
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Altieri, K. E., B. J. Turpin, and S. P. Seitzinger. "Oligomers, organosulfates, and nitroxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry." Atmospheric Chemistry and Physics Discussions 8, no. 5 (September 23, 2008): 17439–66. http://dx.doi.org/10.5194/acpd-8-17439-2008.
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Abstract. Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Three main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, and S- and nitrogen containing CHONS compounds. Organic acids commonly identified in precipitation were detected, as well as linear alkylbenzene sulfonates, which are persistent pollutants commonly measured in river water, seawater, and sediments, but to our knowledge, not previously documented in atmospheric samples. Within the three main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitroxy-organosulfates were identified. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.
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Pashev, Aleksandar, Nikola Burdzhiev, and Elena Stanoeva. "One-step route to tricyclic fused 1,2,3,4-tetrahydroisoquinoline systems via the Castagnoli–Cushman protocol." Beilstein Journal of Organic Chemistry 16 (June 24, 2020): 1456–64. http://dx.doi.org/10.3762/bjoc.16.121.
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The Castagnoli–Cushman reaction of 3,4-dihydroisoquinolines with glutaric anhydride, its oxygen and sulfur analogues was investigated as a one-step approach to the benzo[a]quinolizidine system and its heterocyclic analogs. An extension towards the pyrrolo[2,1-a]isoquinoline system was achieved with the use of succinic anhydride. The results are evidence of an unexplored method for the access of the aforementioned tricyclic annelated systems incorporating a bridgehead nitrogen atom. The structures and relative configurations of the new compounds were established by means of 1D and 2D NMR techniques. The reactions between 1-methyldihydroisoquinoline and glutaric, diglycolic and succinic anhydrides yielded unexpected isoquinoline derivatives containing an exocyclic double bond. The compounds prepared bear the potential to become building blocks for future synthetic bioactive molecules.
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Li, Jian, Taiju Di, and Jinhe Bai. "Distribution of Volatile Compounds in Different Fruit Structures in Four Tomato Cultivars." Molecules 24, no. 14 (July 17, 2019): 2594. http://dx.doi.org/10.3390/molecules24142594.
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Distribution of volatile compounds in different fruit structures were analyzed in four tomato cultivars by headspace-solid-phase microextraction (SPME)-gas chromatography-mass spectrometry (GC-MS). A total of 36 volatile compounds were identified in fruit samples, which were primarily aldehydes, hydrocarbons, alcohols, ketones, furans, esters, nitrogen compounds, and sulfur and nitrogen-containing heterocyclic compounds. The volatile compositions in pericarp (PE), septa and columella (SC), locular gel and seeds (LS), and stem end (SE) tissues showed different profiles. The PE tissue showed the highest total volatile concentration due to a high abundance of aldehydes, especially cis-3-hexenal and benzaldehyde. Meanwhile, it showed higher aromatic proportion and herbaceous series intensity than other tissues. Floral and fruity series showed higher intensity in SC and LS tissues. The concentration of alcohols in the LS was higher than that in other tissues in association with the higher abundances of 2-methyl propanol, 3-methyl butanol, and 2-methyl butanol. However, the numbers and concentrations of volatile compounds, especially cis-3-hexenal, benzaldehyde, and geranyl acetone were lower in SE than in the other tissues, indicating less tomato aromas in SE. SE tissues were also lacking in floral and fruity characteristic compounds, such as geranyl acetone, 1-nitro-pentane, and 1-nitro-2-phenylethane. “FL 47” contained more volatile compounds than the other three, and the contents of aldehydes, ketones and oxygen-containing heterocyclic compounds in the “Tygress” fruit were higher than the other cultivars.
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Oh, Ji Ye, Kiho Park, Yangsoo Kim, Tae-Yun Park, and Dae Ryook Yang. "A Quantitative Structure-Property Relationship Model for Predicting the Critical Pressures of Organic Compounds Containing Oxygen, Sulfur, and Nitrogen." Journal of Chemical Engineering of Japan 50, no. 6 (2017): 397–407. http://dx.doi.org/10.1252/jcej.16we367.
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Stewart, Frank J. "Dissimilatory sulfur cycling in oxygen minimum zones: an emerging metagenomics perspective." Biochemical Society Transactions 39, no. 6 (November 21, 2011): 1859–63. http://dx.doi.org/10.1042/bst20110708.
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Biological diversity in marine OMZs (oxygen minimum zones) is dominated by a complex community of bacteria and archaea whose anaerobic metabolisms mediate key steps in global nitrogen and carbon cycles. Molecular and physiological studies now confirm that OMZs also support diverse micro-organisms capable of utilizing inorganic sulfur compounds for energy metabolism. The present review focuses specifically on recent metagenomic data that have helped to identify the molecular basis for autotrophic sulfur oxidation with nitrate in the OMZ water column, as well as a cryptic role for heterotrophic sulfate reduction. Interpreted alongside marker gene surveys and process rate measurements, these data suggest an active sulfur cycle with potentially substantial roles in organic carbon input and mineralization and critical links to the OMZ nitrogen cycle. Furthermore, these studies have created a framework for comparing the genomic diversity and ecology of pelagic sulfur-metabolizing communities from diverse low-oxygen regions.
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Tsay, Shwu-Chen, Himatkumar V. Patel, and Jih Ru Hwu. "Recent Developments of Compounds Containing the Nitrogen-Oxygen Moiety in Organic Synthesis." Synlett 1998, no. 9 (September 1998): 939–49. http://dx.doi.org/10.1055/s-1998-1827.
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Bąchor, Urszula, and Marcin Mączyński. "Selected β2-, β3- and β2,3-Amino Acid Heterocyclic Derivatives and Their Biological Perspective." Molecules 26, no. 2 (January 15, 2021): 438. http://dx.doi.org/10.3390/molecules26020438.
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Heterocyclic moieties, especially five and six-membered rings containing nitrogen, oxygen or sulfur atoms, are broadly distributed in nature. Among them, synthetic and natural alike are pharmacologically active compounds and have always been at the forefront of attention due to their pharmacological properties. Heterocycles can be divided into different groups based on the presence of characteristic structural motifs. The presence of β-amino acid and heterocyclic core in one compound is very interesting; additionally, it very often plays a vital role in their biological activity. Usually, such compounds are not considered to be chemicals containing a β-amino acid motif; however, considering them as this class of compounds may open new routes of their preparation and application as new drug precursors or even drugs. The possibility of their application as nonproteinogenic amino acid residues in peptide or peptide derivatives synthesis to prepare a new class of compounds is also promising. This review highlights the actual state of knowledge about β-amino acid moiety-containing heterocycles presenting antiviral, anti-inflammatory, antibacterial compounds, anaplastic lymphoma kinase (ALK) inhibitors, as well as agonist and antagonists of the receptors.
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Zhang, Jingyi, Bin Jiang, Zhiheng Wang, Yongmei Liang, Yahe Zhang, Chunming Xu, and Quan Shi. "Molecular characterisation of ambient aerosols by sequential solvent extractions and high-resolution mass spectrometry." Environmental Chemistry 15, no. 3 (2018): 150. http://dx.doi.org/10.1071/en17197.
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Environmental contextOrganic compounds generally make a large contribution to ambient aerosol fine particles, and can influence atmospheric chemistry. Solvent extraction before mass spectrometry is widely used for the determination of organic compounds in aerosols, but the molecular selectivity of different solvents is unclear. We extracted an aerosol sample with various solvents and show how the organic compound profile obtained by mass spectrometry changes depending on the extracting solvent. AbstractFor a comprehensive characterisation of organic compounds in aerosols, samples collected on a hazy day from Beijing were sequentially extracted with various solvents and analysed by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Electrospray ionisation (ESI) was used for the MS analysis. Aerosol samples were extracted in an apolar-to-polar solvent order of n-hexane (n-C6), dichloromethane (DCM), acetonitrile (ACN) and water, and also extracted in reverse sequence. The separated fractions were defined as non-polar, low-polarity, mid-polarity and high-polarity organic compounds respectively. Approximately 70 % of the total organic carbon (TOC) was extractable, of which the water-soluble organic carbon (WSOC) and non-polar organic carbon accounted for 30 and 25 % of the TOC respectively. Non-polar and low-polarity compounds with a high degree of molecular condensation such as oxidised polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing compounds (CHN) were extracted by n-C6 and DCM. Water-soluble organic matter (WSOM) was predominant with aliphatic and aromatic organosulfates (CHOS) and nitrooxy-organosulfates (CHONS). Most oxygen-containing compounds (CHO) and oxygen- and nitrogen-containing compounds (CHON) with high double-bond equivalents (DBEs) and long carbon chains tended to be extracted into organic solvents.
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Kumar, Palanichamy Santhosh, Dhanaraj Premnath, Asir Obadiah, Arulappan Durairaj, Subramanian Ramanathan, and Samuel Vasanthkumar. "Synthesis, Structural Characterization and Biological Evaluation of 3-Amino-5-(5-oxo-5H-benzo[a]phenoxazin-6-ylamino)benzoic acid Derivatives." Asian Journal of Chemistry 31, no. 12 (November 16, 2019): 2886–94. http://dx.doi.org/10.14233/ajchem.2019.22253.
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1,4-Naphthoquinones are exceptional building blocks in organic synthesis and have been used to synthesize several well-known pharmaceutically active agents. Compounds containing oxygen, nitrogen or sulfur atoms inside the rings are attracting much attention and interest due to their biological importance. A series of 3-amino-5-(3-chloro-1,4-dioxo-1,4-dihydronaphthalen-2-ylamino)benzoic acid derivatives were synthesized by the Michael addition of 2,3-dichloronaphthalene-1,4-dione and 3,5-diaminobenzoic acid. All the synthesized compounds are screened for their bioactivity through molecular docking, cytotoxicity (against HeLa) and antioxidant activity. DPPH and ABTS evaluation procedures are employed to assess the antioxidant activity. Among the synthesized 3-amino-5-(3-chloro-1, 4-dioxo-1, 4-dihydronaphthalen-2-ylamino)benzoic acid derivatives (1, 2, 3a-g), compound 3d exhibited the highest inhibition of 75 % and 83 % in the DPPH and ABTS antioxidant activity evaluation, respectively. Compound 3d exhibited better glide energy and E model scores when docked with HDAC8 using GLIDE program. Cytotoxicity of the synthesized compounds was studied against cervical cancer cell line (HeLa) and compound 3d showed the maximum inhibition and displayed a better activity than the standard drug.
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Uher, M., A. Korenova, D. Vegh, M. Giurga, and J. Mlochowski. "Convenient method for introduction of cyano group into nitrogen, sulfur, and oxygen heterocyclic compounds." Chemistry of Heterocyclic Compounds 31, no. 10 (October 1995): 1186–87. http://dx.doi.org/10.1007/bf01185587.
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BOYKIN, D. W., and A. L. BAUMSTARK. "ChemInform Abstract: 17O NMR Spectroscopy of Organic Compounds Containing Oxygen Bound to Nitrogen and Oxygen Bound to Oxygen." ChemInform 22, no. 31 (August 22, 2010): no. http://dx.doi.org/10.1002/chin.199131327.
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Zhang, Jie, Ping Liu, and Peipei Sun. "Synthesis of Oxygen- or Nitrogen-Containing Heterocyclic Compounds via Radical Addition Cascade Cyclization." Chinese Journal of Organic Chemistry 41, no. 1 (2021): 185. http://dx.doi.org/10.6023/cjoc202006010.
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Ginzburg, B., I. Dor, and O. Lev. "Odorous Compounds in Wastewater Reservoir Used for Irrigation." Water Science and Technology 40, no. 6 (September 1, 1999): 65–71. http://dx.doi.org/10.2166/wst.1999.0263.
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The objective of this study was to investigate the odor and physicochemical characteristics of a model deep wastewater reservoir (the Na'an reservoir). Depth sampling of the reservoir revealed depletion of oxygen and increase of hydrogen sulfide and organic nitrogen and sulfur odorous compounds at deeper levels of the reservoir. TOC, TON, BOD5 and chromatographic fingerprinting by MSD and Olfactory/GC of the semi-volatile organic compounds in the reservoir were found to be season dependent. Late summer was found to be the most odorous period and the richest in semi-volatile compounds. A list of volatile compounds, which were identified by gas chromatography, in the reservoir water and in the surrounding atmosphere was compiled.
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Kapsomenos, George S., and Pericles D. Akrivos. "Computational study of heterocyclic thione ligands. Part I. Five-membered heteroatomic thiones possessing an α-nitrogen heteroatom." Canadian Journal of Chemistry 66, no. 11 (November 1, 1988): 2835–38. http://dx.doi.org/10.1139/v88-439.
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A SCF-MNDO study is made of the equilibrium between the "thiol" and "thione" tautomers of four species possessing a five-membered heterocyclic ring, where nitrogen and oxygen or sulfur are the α-heteroatoms. Based on the computationally derived Δ(ΔHf) values for each pair of forms, evidence is presented for the possibility of co-occurrence of the two forms in solution. The tautomerism is particularly interesting in this class of compounds, since it offers the possibility for a sulfur, nitrogen, or sulfur and nitrogen coordination. The nucleophilicity of each specific site in both forms is discussed in terms of net atomic charges and the HOMO constitution of the molecules. Results concerning the study of metal complexes are generally in accordance with these considerations, since the preference for a specific donation scheme is governed by an HSAB criterion.
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Slivka, Mikhailo, and Mikhailo Onysko. "The Use of Electrophilic Cyclization for the Preparation of Condensed Heterocycles." Synthesis 53, no. 19 (May 19, 2021): 3497–512. http://dx.doi.org/10.1055/s-0040-1706036.
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AbstractCondensed heterocycles are well-known for their excellent biological effects and they are undeniably important compounds in organic chemistry. Electrophilic cyclization reactions are widely used for the synthesis of mono-heterocyclic compounds. This review highlights the utility of electrophilic cyclization reactions as an effective generic tool for the synthesis of various condensed heterocycles containing functional groups that are able to undergo further chemical transformations, such as nucleophilic substitution, elimination, re-cyclization, cleavage, etc. This review describes the reactions of unsaturated derivatives of different heterocycles with various electrophilic agents (halogens, arylsulfanyl chlorides, mineral acids) resulting in annulation of an additional partially saturated heterocycle. The electrophilic reaction conditions, plausible mechanisms and the use of such transformations in organic synthesis are also discussed. The review mainly focuses on research published since 2002 in order to establish the current state of the art in this area. 1 Introduction2 Electrophilic Cyclization Pathways Involving a Nitrogen Nucleophilic Center3 Electrophilic Cyclization Pathways Involving a Chalcogen Nucleophilic Center3.1 Sulfur Centers3.2 Oxygen Centers3.3 Selenium Centers4 Strategies and Mechanisms5 Conclusion
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Yao, Zhen Xing, Yong Fang Zhang, Da Wei Fan, Xiao Dong Xin, Jie Zhao, Guo Dong Chen, Bin Du, and Qin Wei. "Advances in Biosensor Application for Environmental Monitoring." Advanced Materials Research 306-307 (August 2011): 31–36. http://dx.doi.org/10.4028/www.scientific.net/amr.306-307.31.
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A review is provided dealing with the definitions and classifications of biosensors, as well as their basic working principles. Then, their applications to the environmental monitoring, which include the monitor of biochemical oxygen demand (BOD), bacterial count and various organic and inorganic pollutants, e.g. nitrogen compounds, heavy metal ions, organophosphorus pesticides, phenolic compounds, toxic compounds, carcinogens, teratogens, benzenes, sulfur dioxide, aldehydes and ethanols are presented. In the end, some suggestions were given with respect to the current problems of biosensors and the future applications of biosensors were also discussed.
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Kang, Jun Yong, and Hai Huang. "Triflic Anhydride (Tf2O)-Activated Transformations of Amides, Sulfoxides and Phosphorus Oxides via Nucleophilic Trapping." Synthesis 54, no. 05 (October 27, 2021): 1157–202. http://dx.doi.org/10.1055/a-1679-8205.
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AbstractTrifluoromethanesulfonic anhydride (Tf2O) is utilized as a strong electrophilic activator in a wide range of applications in synthetic organic chemistry, leading to the transient generation of a triflate intermediate. This versatile triflate intermediate undergoes nucleophilic trapping with diverse nucleophiles to yield novel compounds. In this review, we describe the features and applications of triflic anhydride in organic synthesis reported in the past decade, especially in amide, sulfoxide, and phosphorus oxide chemistry through electrophilic activation. A plausible mechanistic pathway for each important reaction is also discussed.1 Introduction2 Amide Chemistry2.1 Carbon Nucleophiles2.2 Hydrogen Nucleophiles2.3 Nitrogen Nucleophiles2.4 Oxygen and Sulfur Nucleophiles2.5 hosphorus Nucleophiles2.6 A Vilsmeier-Type Reagent2.7 Umpolung Reactivity in Amides3 Sulfoxide Chemistry3.1 Oxygen Nucleophiles3.2 Carbon Nucleophiles3.3 Nitrogen Nucleophiles3.4 Thionium Reagents4 Phosphorus Chemistry4.1 Hendrickson’s Reagent4.2 Diaryl Phosphine Oxides4.3 Phosphonates, Phosphates and Phosphinates5 Conclusion and Outlook
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Ito, Masato M., Kazuyuki Akita, and Hakuai Inoue. "Wet oxidation of oxygen- and nitrogen-containing organic compounds catalyzed by cobalt(III) oxide." Industrial & Engineering Chemistry Research 28, no. 7 (July 1989): 894–99. http://dx.doi.org/10.1021/ie00091a003.
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TSAY, S. C., H. V. PATEL, and J. R. HWU. "ChemInform Abstract: Recent Developments of Compounds Containing the Nitrogen-Oxygen Moiety in Organic Synthesis." ChemInform 29, no. 48 (June 18, 2010): no. http://dx.doi.org/10.1002/chin.199848306.
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Poturay, V. A. "ORGANIC MATTER IN THERMAL, COLD GROUND AND SURFACE WATERS OF THE FAR EAST SOUTH CONTINENTAL PART (OXYGEN-CONTAINING COMPOUNDS)." REGIONAL PROBLEM 24, no. 4 (2021): 50–62. http://dx.doi.org/10.31433/2618-9593-2021-24-4-50-62.
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This article presents the composition and molecular weight distribution of medium volatility oxygen-containing organic compounds in the thermal, cold ground and surface waters of the continental part of the Far East south. Using the method of capillary gas chromatography-mass spectrometry, it is found 71 oxygen-containing compounds in thermal waters, belonging to 10 homologous series, and in cold ground and surface waters – 36 compounds, belonging to 7 homologous series. Their relative content in the medium volatility organic matter composition is about 55% in thermal waters and about 45% in cold ground and surface waters. Esters, carboxylic acids and aldehydes are widespread in hot waters. These compounds are widely produced in the biosphere and are probably of biogenic origin. The features of the carboxylic acids and aldehydes molecular weight distribution (the predominance of homologues with an even number of carbon atoms in the molecule) also show their biogenic genesis. The formation of ethers can as well be associated with the oxidation of organic matter in water-bearing rocks, and aromatic and nitrogen-containing components – with thermogenic processes occurring in hydrothermal systems. Esters, steroids and ketones also reach their maximum relative concentrations in cold waters. Steroids predominate in the oxygen-containing organic compounds composition in cold ground and surface waters where the carboxylic acids distribution is insignificant. Among the revealed compounds, in thermal waters there are some components – indicators of technogenic pollution. These are the compounds containing a tert-butyl group and DETA. However, their share in the composition of medium volatility organic matter is insignificant.
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Anshakov, A. S., P. V. Domarov, A. I. Aliferov, and V. A. Faleev. "INVESTIGATION OF PLASMA-OHMIC ELECTRIC FURNACES FOR GASIFYING CARBONACEOUSE WASTES." Bulletin of Toraighyrov University. Energetics series, no. 2021.3 (September 11, 2021): 6–17. http://dx.doi.org/10.48081/ljwi2657.
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For the first time, the processes of reducing energy consumption of a plasma-ohmic electric furnace for the gasification of various carbon-containing wastes (municipal, biological, agricultural, and other organic wastes) were investigated. The effect of reducing the humidity, morphological composition of waste on energy consumption during plasma gasification of carbon-containing materials is shown. The possibility to exclude the process of preliminary drying from the production cycle of waste gasification has been revealed. In the modern world, one of the global trends in technology development is the continuous increase in the efficiency and environmental friendliness of carbon-containing waste management methods. The carbon-containing industrial waste includes: municipal (municipal solid waste (MSW)), agricultural (rice husk, etc.), industrial (wood waste, coal slimes, etc.) and biological (medical, biological sludge deposits (BIO) and etc.) Despite the different nature of this waste, they all consist of the same chemical elements: carbon, hydrogen, oxygen, nitrogen, chlorine, sulfur, ash (a complex of inorganic elements and compounds), water (moisture), but contain elements and compounds dangerous for the environment (pathogens, heavy metals, etc.). Gasification of carbon-containing wastes is a complex physico-chemical process with a large number of effects, a complete scientific explanation of which is far from completion.
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Imran, Dr Aed Jaber. "AL – Mansuriya gas fields associated liquid and its role to increase the potential capacity of gasoline fuel in Daura oil refinery." Journal of Petroleum Research and Studies 7, no. 1 (May 6, 2021): 107–17. http://dx.doi.org/10.52716/jprs.v7i1.167.
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Hydrotreating processing is commonly used to remove platforming catalyst poisons from straight run or cracked naphthas prior to charging to the platforming Process unit. It can be seen that the primary function of the naphtha Hydrotreating Process can be characterized as a “Clean up” Operation. The catalyst used in the Naphtha Hydrotreating Process is composed of an alumina base impregnated with compounds of cobalt or nickel and molybdenum. The catalyst is insensitive to most poisons which affect dehydrogenation reactions. A relatively high percentage of carbon on the catalyst does not materially affect its sensitivity or selectivity. Volumetric recoveries of products depend on the sulfur and olefin contents [1].
The Naphtha Hydrotreating Process is a catalytic refining process employing a selected catalyst and a hydrogen-rich gas stream to decompose organic sulfur, oxygen and nitrogen compounds contained in hydrocarbon fractions. In addition, hydrotreating removes organo-metallic compounds and saturates olefinic compounds.
Organo-metallic compounds, notably arsenic and lead compounds, are known to be permanent poisons to platinum catalysts. "The complete removal of these materials by Hydrotreating processing gives longer catalyst life in the platforming unit.
Sulfur, above a critical level, is a temporary poison to platforming catalysts and causes an unfavorable change in the product distribution. Organic nitrogen is also a temporary poison to platforming catalyst. It is an extremely potent one, however, and relatively small amounts of nitrogen compounds in the Platformer feed can cause large deactivation effects, as well as the deposition of ammonium chloride salts in the platforming unit cold sections.
Oxygen compounds are detrimental to the operation of a Platformer. Any oxygen compounds which are not removed in the hydrotreater will be converted to water in the platforming unit, thus affecting the water/ chloride balance of the platforming catalyst. Large amounts of olefins contribute to increase coking of the platforming catalyst. Also, olefins can polymerize at platforming operating conditions which can result in exchanger and reactor fouling.
The Naphtha Hydrotreating Process makes a major contribution to the ease of operation and economy of platforming. Much greater flexibility is afforded in choice of allowable charge stocks to the platforming unit. Because this unit protects the platforming catalyst, it is important to maintain consistently good operation in the Hydrotreating Unit.
In addition to treating naphtha for Platformer feed, naphthas produced from thermal cracking processes, such as delayed coking and visbreaking, are usually high in olefinic content and other contaminants, and may not be stable in storage. These naphthas may be hydrotreated to stabilize the olefins and to remove organic or metallic contaminants, thus providing a marketable product.
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Rahayu, Yuni Sri. "Isolation and Identification of Hydrocarbon Degradation Bacteria and Phosphate Solubilizing Bacteria in Oil Contaminated Soil in Bojonegoro, East Java, Indonesia." Indonesian Journal of Science and Technology 4, no. 1 (March 7, 2019): 134. http://dx.doi.org/10.17509/ijost.v4i1.14923.
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Petroleum is a mixture of hydrocarbon complexes with organic compounds from sulfur, oxygen, nitrogen and metal-containing compounds. These organic compounds can be used as substrate for bacterial growth. This study aimed to isolate and identify hydrocarbon degrading bacteria and phosphate solubilizing bacteria in oil-contaminated soil in Bojonegoro. This study used an exploration method to find each of the two types of hydrocarbon degrading bacteria and phosphate solubilizing bacteria from soil samples in Bojonegoro that contaminated by oil. Identification of isolates bacterial included macroscopic observations of bacteria, gram staining on bacterial cells and physiological tests. Macroscopic observations include the form of colonies, colony diameter, colony color, colony edge, and elevation. The physiological test using Microbact Identification System to determine the physiological characteristics of bacteria so that genera and types of bacteria can be known. The identification of organisms was based on changes in pH and use of the substrate. The results of data analysis were obtained from five types of bacteria from soil samples that contaminated by oil which were successfully isolated. After identification of species was done, four species of bacteria were obtained, namely Pseudomonas pseudomallei, Pseudomonas fluorescens-25, Flavobacterium odoratum, and Enterococcus sp.
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Zou, Song, Sheng Wang, and Chanjuan Xi. "ROTf-induced annulation of heteroatom reagents and unsaturated substrates leading to cyclic compounds." Royal Society Open Science 5, no. 11 (November 2018): 181389. http://dx.doi.org/10.1098/rsos.181389.
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The development of metal-free organic reactions is one of the hotspots in the synthesis of cyclic compounds. ROTf (alkyl trifluoromethanesulfonates), due to their good electrophilicity, are powerful alkylating reagents at heteroatoms such as nitrogen, oxygen, sulfur and phosphorus to induce an electrophilic centre for carbon–carbon or carbon–heteroatom bond formation. Inspired by this chemistry, a variety of research concentrating on heterocycles synthesis has been carried out. In this review, we mainly summarize the ROTf-induced annulation of heteroatom reagents such as nitriles, carbodiimides, azobenzenes, isothiocyanates, aldehydes, isocyanates and phosphaalkene with themselves or alkynes to afford cyclic compounds.
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Novotortsev, Vladimir K., Maxim E. Kukushkin, Viktor A. Tafeenko, Dmitry A. Skvortsov, Marina A. Kalinina, Roman V. Timoshenko, Nelly S. Chmelyuk, et al. "Dispirooxindoles Based on 2-Selenoxo-Imidazolidin-4-Ones: Synthesis, Cytotoxicity and ROS Generation Ability." International Journal of Molecular Sciences 22, no. 5 (March 5, 2021): 2613. http://dx.doi.org/10.3390/ijms22052613.
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A regio- and diastereoselective synthesis of two types of dispiro derivatives of 2-selenoxoimidazolidin-4-ones, differing in the position of the nitrogen atom in the central pyrrolidine ring of the spiro-fused system—namely, 2-selenoxodispiro[imidazolidine-4,3′-pyrrolidine-2′,3″-indoline]-2″,5-diones (5a-h) and 2-senenoxodispiro[imidazolidine-4,3′-pyrrolidine-4′,3″-indoline]-2″,5-diones (6a-m)—were developed based on a 1,3-dipolar cycloaddition of azomethine ylides generated from isatin and sarcosine or formaldehyde and sarcosine to 5-arylidene or 5-indolidene-2-selenoxo-tetrahydro-4H-imidazole-4-ones. Selenium-containing dispiro indolinones generally exhibit cytotoxic activity near to the activity of the corresponding oxygen and sulfur-containing derivatives. Compounds 5b, 5c, and 5e demonstrated considerable in vitro cytotoxicity in the 3-(4,5-dimethylthiazol-2-yl)2,5-diphenyl tetrazolium bromide (MTT) test (concentration of compounds that caused 50% death of cells (CC50) 7.6–8.7 μM) against the A549 cancer cell line with the VA13/A549 selectivity index 5.2–6.9; some compounds (5 and 6) increased the level of intracellular reactive oxygen species (ROS) in the experiment on A549 and PC3 cells using platinized carbon nanoelectrode. The tests for p53 activation for compounds 5 and 6 on the transcriptional reporter suggest that the investigated compounds can only have an indirect p53-dependent mechanism of action. For the compounds 5b, 6b, and 6l, the ROS generation may be one of the significant mechanisms of their cytotoxic action.
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Nielsen, Per Halkjaer, Kamma Raunkjær, Niels Henrik Norsker, Niels Aagaard Jensen, and Thorkild Hvitved-Jacobsen. "Transformation of Wastewater in Sewer Systems – A Review." Water Science and Technology 25, no. 6 (March 1, 1992): 17–31. http://dx.doi.org/10.2166/wst.1992.0111.
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Many chemical, physical and biological transformations of wastewater in sewer systems may take place and cause significant changes in the composition during transportation. This paper focuses on the methods for measuring changes in wastewater composition (organic matter, dissolved oxygen, nitrogen and sulfur compounds), characteristics for changes in wastewater composition and empirical equations for oxygen uptake rates, sulfide production rates and BOD removal rates in both pressure mains and gravity sewers. Simple and more complicated biofilm models are evaluated for use in sewer systems, but so far no suitable advanced model for sewer biofilms exists, due to a lack of quantitative information about the transformations in such high-loaded multispecies biofilms.
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Zang, Lijie, Yi Wan, Haifeng Zhang, Yu Zhang, Yingxin Gao, Yupeng He, Jianying Hu, Yuehui Kang, Dong Cao, and Min Yang. "Characterization of non-volatile organic contaminants in coking wastewater using non-target screening: Dominance of nitrogen, sulfur, and oxygen-containing compounds in biological effluents." Science of The Total Environment 837 (September 2022): 155768. http://dx.doi.org/10.1016/j.scitotenv.2022.155768.
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Amos, Stephanie G. E., Marion Garreau, Luca Buzzetti, and Jerome Waser. "Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis." Beilstein Journal of Organic Chemistry 16 (May 29, 2020): 1163–87. http://dx.doi.org/10.3762/bjoc.16.103.
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Organic dyes have emerged as a reliable class of photoredox catalysts. Their great structural variety combined with the easy fine-tuning of their electronic properties has unlocked new possibilities for the generation of reactive intermediates. In this review, we provide an overview of the available approaches to access reactive intermediates that employ organophotocatalysis. Our contribution is not a comprehensive description of the work in the area but rather focuses on key concepts, accompanied by a few selected illustrative examples. The review is organized along the type of reactive intermediates formed in the reaction, including C(sp3) and C(sp 2 ) carbon-, nitrogen-, oxygen-, and sulfur-centered radicals, open-shell charged species, and sensitized organic compounds.
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Malysheva, Alla G., N. Yu Kozlova, E. G. Rastyannikov, A. A. Ermakov, and V. A. Shokhin. "PHYSICO-CHEMICAL INVESTIGATIONS FOR THE ASSESSMENT OF THE CHEMICAL SAFETY AND EFFICACY OF APPLICATION OF A NEW SYSTEM OF LANDFILL GAS PURIFICATION AT THE SOLID DOMESTIC GARBAGE DUMP." Hygiene and sanitation 96, no. 11 (March 27, 2019): 1103–8. http://dx.doi.org/10.18821/0016-9900-2017-96-11-1103-1108.
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Landfills of municipal solid waste (MSW) have a negative impact on the environment and people: air, soil, surface water and groundwater are polluted. During the storage of MSW in the body of the landfill natural anaerobic decomposition of organic waste takes place under conditions of oxygen lack, high temperature and humidity. One product of this process is landfill gas - a mixture of methane and carbon dioxide with small amounts of impurities (nitrogen, silicon, sulfur, hydrogen sulfide). Tens and hundreds of different organic compounds are also included as a compound of landfill gas. The composition and content of the individual components in landfill gas depends on the composition of landfilled waste at the solid domestic garbage dump. The landfill gas and odor run to great distances. Construction, operation and closure of landfills give rise to a number of environmental problems associated with such a classification of landfills as a secondary source of pollution of the urban environment. The solution of such environmental problems offers a variety of options for the “recovery”, “remediation” and protective measures in areas of placement of landfills. For example, in the landfill “Timokhovo” there were studied the efficacy and safety of a new chemical treatment technologies and disposal of landfill gas As a result of the installation of the system for landfill gas purification there was established the decline in the total concentration of polluting compounds, as hydrocarbons (including saturated and aromatic), alcohols, oxygen and sulfur containing compounds by from 63 to 2200 times. There was reached 100% disposal of mercaptanes, sulfides, di- and trisulfides, naphthenic and terpenic hydrocarbons and chlorinated compounds. The number of identified compounds was reduced by more than 2 times. However, at the output of the purification system there were revealed compounds not identified at the input of this system. It can be regarded due to the appearance of transformation products of flaring hydrocarbons. Gas chromatography-mass spectrometry studies directed to the identification with quantitative assessment of air emissions before and after the new system of utilization allow both perform monitoring emissions taking into account the real content and changes in group and component structure under the influence of the chemical impact of the new technologies and make recommendations for further improvement of gas purification systems in terms of environmental aspects.
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Furin, G. G., M. A. Fedotov, G. G. Yakobson, and A. V. Zibarev. "15N and 17O NMR spectra of some nitrogen- and oxygen-containing polyfluoroaromatic compounds." Journal of Fluorine Chemistry 28, no. 3 (July 1985): 273–90. http://dx.doi.org/10.1016/s0022-1139(00)80540-0.
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Bugaeva, Aleksandra I., and Yuriy G. Slizhov. "SILICA GEL MODIFICATION BY NICKEL(II) COMPLEXES WITH NITROGEN- AND OXYGEN-CONTAINING ORGANIC LIGANDS FOR GAS CHROMATOGRAPHY." IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA 64, no. 1 (December 9, 2020): 59–66. http://dx.doi.org/10.6060/ivkkt.20216401.6299.
Full textAbstract:
Gas chromatographic sorbents based on Siloсhrome S-80 adsorptively modified with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate and 2-nitroso-1-naphtholate of nickel(II) have been obtained. It has been established that the thermal stability (up to 170–350 °C) of chelate-containing sorbents is sufficient for carrying out gas chromatographic separations. The IR and Raman spectra of the obtained materials confirmed the success of the complexation processes in the synthesis of complex nickel(II) compounds and the retention of coordination bonds after the deposition of chelates on silica gel. The characteristics of the surface and the porous structure of the prepared sorbents are investigated. As a result of adsorptive modification of Silochrome S-80 with nickel(II) chelates, it’s specific surface area (84 m2/g) decreases by 12–32 m2/g along with a decrease in the average pore size, which indicates the fixation of modifiers at the edges of large pores. It was shown that modification of Silochrome S-80 with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate, 2-nitroso-1-naphtholate of nickel(II) has a significant effect on the chromatographic polarity and selectivity of sorbents. The presence of a polar nitroso-groups in the composition of nickel(II) 2-nitroso-1-naphtholate makes the metal center more accessible for donor-acceptor interactions with sorbates (pyridine, carbonyl compounds). Also, the nitroso-group is active in the formation of hydrogen bonds with alcohols, which complicates their elution at column temperatures below 170 °C. The greatest affinity to the homologous of arenes is shown by silochrome modified by a nickel(II) complex with the least bulky 8-hydroxyquinolinate ligands, which leads to an increase in the retention times of aromatic and polyaromatic compounds along with an increase of the sorbent selectivity. The possibility of practical application of a chromatographic column filled with Silochrome S-80 with deposited nickel(II) 8-hydroxyquinolinate for gas chromatographic (FID) separation of mixtures of polyaromatic compounds in the temperature programming mode is shown.
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Bugaeva, Aleksandra I., and Yuriy G. Slizhov. "SILICA GEL MODIFICATION BY NICKEL(II) COMPLEXES WITH NITROGEN- AND OXYGEN-CONTAINING ORGANIC LIGANDS FOR GAS CHROMATOGRAPHY." IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA 64, no. 1 (December 9, 2020): 59–66. http://dx.doi.org/10.6060/ivkkt.20216401.6299.
Full textAbstract:
Gas chromatographic sorbents based on Siloсhrome S-80 adsorptively modified with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate and 2-nitroso-1-naphtholate of nickel(II) have been obtained. It has been established that the thermal stability (up to 170–350 °C) of chelate-containing sorbents is sufficient for carrying out gas chromatographic separations. The IR and Raman spectra of the obtained materials confirmed the success of the complexation processes in the synthesis of complex nickel(II) compounds and the retention of coordination bonds after the deposition of chelates on silica gel. The characteristics of the surface and the porous structure of the prepared sorbents are investigated. As a result of adsorptive modification of Silochrome S-80 with nickel(II) chelates, it’s specific surface area (84 m2/g) decreases by 12–32 m2/g along with a decrease in the average pore size, which indicates the fixation of modifiers at the edges of large pores. It was shown that modification of Silochrome S-80 with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate, 2-nitroso-1-naphtholate of nickel(II) has a significant effect on the chromatographic polarity and selectivity of sorbents. The presence of a polar nitroso-groups in the composition of nickel(II) 2-nitroso-1-naphtholate makes the metal center more accessible for donor-acceptor interactions with sorbates (pyridine, carbonyl compounds). Also, the nitroso-group is active in the formation of hydrogen bonds with alcohols, which complicates their elution at column temperatures below 170 °C. The greatest affinity to the homologous of arenes is shown by silochrome modified by a nickel(II) complex with the least bulky 8-hydroxyquinolinate ligands, which leads to an increase in the retention times of aromatic and polyaromatic compounds along with an increase of the sorbent selectivity. The possibility of practical application of a chromatographic column filled with Silochrome S-80 with deposited nickel(II) 8-hydroxyquinolinate for gas chromatographic (FID) separation of mixtures of polyaromatic compounds in the temperature programming mode is shown.
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Lyčka, Antonín, Jaroslav Holeček, and Karel Handlíř. "119Sn, 13C and 1H NMR studies of aryloxy- and arylthio(1-butyl)stannanes." Collection of Czechoslovak Chemical Communications 54, no. 9 (1989): 2386–98. http://dx.doi.org/10.1135/cccc19892386.
Full textAbstract:
Two series of compounds have been prepared and studied by means of 119Sn, 13C, and 1H NMR spectroscopy, viz. aryloxy- and N-heteroaryloxytris(1-butyl)stannanes and their thio analogues Bu3SnER, and diaryloxy- and di(N-heteroaryloxy)bis(1-butyl)stannanes and their thio analogues Bu2Sn(ER)2, where E means oxygen or sulfur, Bu is 1-butyl, R = phenyl, 1-naphthyl, or 8-quinolyl. On the basis of mutual comparison of NMR spectral parameters of both series of organotin compounds and their comparison with NMR spectral parameters of analogous, purely organic compounds CH3ER it is possible to discuss the consequences of the presence of tin atoms in the organotin substituents and of nitrogen heteroatoms in the aromatic systems, and the therefrom following structure of the organotin compounds studied.