Recyclable Magnetic Cu-MOF-74-Catalyzed C(sp2)-N Coupling and Cyclization under Microwave Irradiation: Synthesis of Imidazo[1,2-c]quinazolines and Their Analogues.

Magnetic Cu-MOF-74 (Fe3O4@SiO2@Cu-MOF-74) was synthesized for the first time by grafting MOF-74 (copper as the metal center) on the surface of core-shell magnetic carboxyl-functionalized silica gel (Fe3O4@SiO2-COOH), which was prepared by coating core Fe3O4 nanoparticles with hydrolyzed 2-(3-(triethoxysilyl)propyl)succinic anhydride and tetraethyl orthosilicate. The structure of Fe3O4@SiO2@Cu-MOF-74 nanoparticles was characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). The prepared Fe3O4@SiO2@Cu-MOF-74 nanoparticles could be applied as a recyclable catalyst to the synthesis of N-fused hybrid scaffolds. 2-(2-Bromoaryl)imidazoles and 2-(2-bromovinyl)imidazoles were coupled and cyclized with cyanamide in DMF in the presence of a catalytic amount of Fe3O4@SiO2@Cu-MOF-74 along with a base to give imidazo[1,2-c]quinazolines and imidazo[1,2-c]pyrimidines, respectively, in good yields. The Fe3O4@SiO2@Cu-MOF-74 catalyst could be easily recovered by a super magnetic bar and recycled more than four times while almost maintaining catalytic activity.

Synthesis of Imidazo[1,2-f]phenanthridines by Recyclable Magnetic MOF-Catalyzed Coupling and Cyclization of 2-(2-Bromoaryl)imidazoles with Cyclohexane-1,3-diones Followed by Aromatization.

2-(2-Bromoaryl)imidazoles react with cyclohexane-1,3-diones in the presence of a catalytic amount of recyclable Fe3O4@SiO2@MOF-199 and a base to give the corresponding C-C coupled and cyclized products 6,7-dihydroimidazo[1,2-f]phenanthridin-8(5H)-ones in high yields. The magnetic MOF catalyst could be easily recovered and reused four times without any significant loss of catalytic activity. The coupled and cyclized scaffolds were aromatized to imidazo[1,2-f]phenanthridines in high yields by a one-pot sequential procedure including reduction, dehydration, and oxidation. The present protocol could be applied to the synthesis of Zephycandidine A, which is known to exhibit anti-tumor activity.

Role of various factors affecting the photochemical treatment of N-nitrosamines related to CO2 capture.

Post-combustion CO2 capture using amine solvents is the most feasible method of reducing anthropogenic CO2 emissions, which are the largest contributor to global warming. The formation of carcinogenic N-nitrosamines (i.e. by-products) can hinder the industrial application of this technology. In this study, the effects of direct UV photolysis (N-nitrosamine concentration and amines) and advanced oxidation processes (UV/H2O2 and UV/O3) on the three specific N-nitrosamines that are commonplace in amine-based CO2 capture (i.e. N-nitrosodiethylamine (NDEA), N-nitrosodiethanolamine (NDELA), and N-nitrosomorpholine (NMOR)) were examined. A significant decrease in the photodegradation rate constants was observed for NDEA (1.02 × 100 to 2.94 × 10-1 min-1), NDELA (1.52 × 100 to 3.32 × 10-1 min-1), and NMOR (1.93 × 100 to 2.20 × 10-1 min-1) as their concentrations increased within 1-50 mg/L. This is the first report of a significant increase in the degradation rate constants of N-nitrosamine with an increase in amine concentrations (i.e. monoethanolamine, diethanolamine, and morpholine) within 10-200 mM. The photodegradation rate constants increased as the molar ratio of H2O2 to N-nitrosamine increased to 20, but then decreased at molar ratios beyond this. O3 had a negligible effect on the photodegradation of N-nitrosamines.

Microwave-Assisted Cyclization under Mildly Basic Conditions: Synthesis of 6 H-Benzo[ c]chromen-6-ones and Their 7,8,9,10-Tetrahydro Analogues.

Aryl 2-bromobenzoates and aryl 2-bromocyclohex-1-enecarboxylates are cyclized by microwave irradiation in dimethylformamide in the presence of K2CO3 to give the corresponding 6 H-benzo[ c]chromen-6-ones and their 7,8,9,10-tetrahydro analogues, respectively, in 50-72% yields. Aryl 3-bromoacrylates are also converted into 2 H-chromen-2-ones under the employed conditions.

Weak Base-Promoted Lactamization under Microwave Irradiation: Synthesis of Quinolin-2(1H)-ones and Phenanthridin-6(5H)-ones.

Quinolin-2(1H)-ones and phenanthridin-6(5H)-ones are synthesized in high yields by K2CO3-promoted cyclization of N-aryl-ß-bromo-α,ß-unsaturated amides and N-aryl-2-bromobenzamides in dimethylformamide under microwave irradiation.

Naphthalene emissions from moth repellents or toilet deodorant blocks determined using head-space and small-chamber tests.

The present study investigated the emissions of naphthalene and other compounds from several different moth repellents (MRs) and one toilet deodorant block (TDB) currently sold in Korea, using a headspace analysis. The emission factors and emission rates of naphthalene were studied using a small-scale environmental chamber. Paper-type products emitted a higher concentration of the total volatile organic compounds (VOCs) (normalized to the weight of test piece) than ball-type products, which in turn emitted higher concentration than a gel-type product. In contrast, naphthalene was either the most or the second highest abundant compound for the four ball products, whereas for paper and gel products it was not detected or was detected at much lower levels. The abundance of naphthalene ranged between 18.4% and 37.3% for ball products. The results showed that the lower the air changes per hour (ACH) level was, the higher the naphthalene concentrations became. In general, a low ACH level suggests a low ventilation rate. The emission factor for naphthalene was nearly 100 times higher for a ball MR than for a gel or a paper MR. For the ball MR, the lower ACH level resulted in higher emission rate.

Volatile pollutants emitted from selected liquid household products.

BACKGROUND, AIM, AND SCOPE: To identify household products that may be potential sources of indoor air pollution, the chemical composition emitted from the products should be surveyed. Although this kind of survey has been conducted by certain research groups in Western Europe and the USA, there is still limited information in scientific literature. Moreover, chemical components and their proportions of household products are suspected to be different with different manufacturers. Consequently, the current study evaluated the emission composition for 42 liquid household products sold in Korea, focusing on five product classes (deodorizers, household cleaners, color removers, pesticides, and polishes). MATERIALS AND METHODS: The present study included two phase experiments. First, the chemical components and their proportions in household products were determined using a gas chromatograph and mass spectrometer system. For the 19 target compounds screened by the first phase of the experiment and other selection criteria, the second phase was done to identify their proportions in the purged-gas phase. RESULTS: The number of chemicals in the household products surveyed ranged from 9 to 113. Eight (product class of pesticides) to 17 (product class of cleaning products) compounds were detected in the purged-gas phase of each product class. Several compounds were identified in more than one product class. Six chemicals (acetone, ethanol, limonene, perchloroethylene (PCE), phenol, and 1-propanol) were identified in all five product classes. There were 13 analytes occurring with a frequency of more than 10% in the household products: limonene (76.2%), ethanol (71.4%), PCE (66.7%), phenol (40.5%), 1-propanol (35.7%), decane (33%), acetone (28.6%), toluene (19.0%), 2-butoxy ethanol (16.7%), o-xylene (16.7%), chlorobenzene (14.3%), ethylbenzene (11.9%), and hexane (11.9%). All of the 42 household products analyzed were found to contain one or more of the 19 compounds. DISCUSSION: The chemical composition varied broadly along with the product classes or product categories, and it was different from that reported in other studies abroad, although certain target chemicals were identified in both studies. This finding supports an assertion that chemical components emitted from household products may be different in different products and with different manufacturers. The chlorinated pollutants identified in the present study have not been reported to be components of cleaning products in papers published since the early 1990s. Limonene was identified as having the highest occurrence in the household products in the present study, although it was not detected in any of 67 household products sold in the U.S. CONCLUSIONS: The emission composition of selected household products was successfully examined by purge-and-trap analysis. Along with other exposure information such as use pattern of household products and the indoor climate, this composition data can be used to estimate personal exposure levels of building occupants. This exposure data can be employed to link environmental exposure to health risk. It is noteworthy that many liquid household products sold in Korea emitted several toxic aromatic and chlorinated organic compounds. Moreover, the current finding suggests that product types and manufacturers should be considered, when evaluating building occupants' exposure to chemical components emitted from household products. RECOMMENDATIONS AND PERSPECTIVES: The current findings can provide valuable information for the semiquantitative estimation of the population inhalation exposure to these compounds in indoor environments and for the selection of safer household products. However, although the chemical composition is known, the emissions of household products might include compounds formed during the use of the product or compounds not identified as ingredients by this study. Accordingly, further studies are required, and testing must be done to determine the actual composition being emitted. Similar to eco-labeling of shampoos, shower gels, and foam baths proposed by a previous study, eco-labeling of other household products is suggested.

Pulmonary effects of inhaled limonene ozone reaction products in elderly rats.

d-Limonene is an unsaturated volatile organic chemical found in cleaning products, air fresheners and soaps. It is oxidized by ozone to secondary organic aerosols consisting of aldehydes, acids, oxidants and fine and ultra fine particles. The lung irritant effects of these limonene ozone reaction products (LOP) were investigated. Female F344 rats (2- and 18-month-old) were exposed for 3 h to air or LOP formed by reacting 6 ppm d-limonene and 0.8 ppm ozone. BAL fluid, lung tissue and cells were analyzed 0 h and 20 h later. Inhalation of LOP increased TNF-alpha, cyclooxygenase-2, and superoxide dismutase in alveolar macrophages (AM) and Type II cells. Responses of older animals were attenuated when compared to younger animals. LOP also decreased p38 MAP kinase in AM from both younger and older animals. In contrast, while LOP increased p44/42 MAP kinase in AM from younger rats, expression decreased in AM and Type II cells from older animals. NF-kappaB and C/EBP activity also increased in AM from younger animals following LOP exposure but decreased or was unaffected in Type II cells. Whereas in younger animals LOP caused endothelial cell hypertrophy, perivascular and pleural edema and thickening of alveolar septal walls, in lungs from older animals, patchy accumulation of fluid within septal walls in alveolar sacs and subtle pleural edema were noted. LOP are pulmonary irritants inducing distinct inflammatory responses in younger and older animals. This may contribute to the differential sensitivity of these populations to pulmonary irritants.

Characterization of emissions composition for selected household products available in Korea.

The present study investigated the emission composition for 59 household products currently sold in Korea, using a headspace analysis. The chemical composition and concentrations of total volatile organic compounds (VOCs) broadly varied along with products, even within the same product category. Up to 1-17 organic compounds were detected in the headspace gas phase of any one of the products. The chemical composition of certain household products determined in the current study was different from that of other studies from other countries. Between 4 and 37 compounds were detected in the headspace gas phase of each product class. Several compounds were identified in more than one product class. Of the 59 household products analyzed, 58 emitted one or more of the 72 compounds at chromatographic peak areas above 10(4). There were 11 analytes which occurred with a frequency of more than 10%: limonene (44.2%), ethanol (30.5%), acetone (18.6%), alpha-pinene (18.6%), o,m,p-xylenes (18.6%), decane (17.0%), toluene (17.0%), beta-myrcene (11.9%), ammonia (10.2%), ethylbenzene (10.2%), and hexane (10.2%).

Evidence for oligomer formation in clouds: reactions of isoprene oxidation products.

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate product formation in laboratory experiments designed to study secondary organic aerosol (SOA) formation in clouds. It has been proposed that water soluble aldehydes derived from aromatics and alkenes, including isoprene, oxidize further in cloud droplets forming organic acids and, upon droplet evaporation, SOA. Pyruvic acid is an important aqueous-phase intermediate. Time series samples from photochemical batch aqueous phase reactions of pyruvic acid and hydrogen peroxide were analyzed for product formation. In addition to the monomers predicted by the reaction scheme, products consistent with an oligomer system were found when pyruvic acid and OH radical were both present. No evidence of oligomer formation was found in a standard mix composed of pyruvic, glyoxylic, and oxalic acids prepared in the same matrix as the samples analyzed using the same instrument conditions. The distribution of high molecular weight products is consistent with oligomers composed of the mono-, oxo-, and di-carboxylic acids expected from the proposed reaction scheme.

Isoprene forms secondary organic aerosol through cloud processing: model simulations.

Isoprene accounts for more than half of non-methane volatile organics globally. Despite extensive experimentation, homogeneous formation of secondary organic aerosol (SOA) from isoprene remains unproven. Herein, an incloud process is identified in which isoprene produces SOA. Interstitial oxidation of isoprene produces water-soluble aldehydes that react in cloud droplets to form organic acids. Upon cloud evaporation new organic particulate matter is formed. Cloud processing of isoprene contributes at least 1.6 Tg yr(-1) to a global biogenic SOA production of 8-40 Tg yr(-1). We conclude that cloud processing of isoprene is an important contributor to SOA production, altering the global distribution of hygroscopic organic aerosol and cloud condensation nuclei.

Assessing truck driver exposure at the World Trade Center disaster site: personal and area monitoring for particulate matter and volatile organic compounds during October 2001 and April 2002.

The destruction of the World Trade Center (WTC) in New York City on September 11, 2001, created a 16-acre debris field composed of pulverized and burning material significantly impacting air quality. Site cleanup began almost immediately. Cleanup workers were potentially exposed to airborne contaminants, including particulate matter, volatile organic compounds, and asbestos, at elevated concentrations. This article presents the results of the exposure assessment of one important group of WTC workers, truck drivers, as well as area monitoring that was conducted directly on site during October 2001 and April 2002. In cooperation with a local labor union, 54 drivers (October) and 15 drivers (April) were recruited on site to wear two monitors during their 12-hour work shifts. In addition, drivers were administered a questionnaire asking for information ranging from "first day at the site" to respirator use. Area monitoring was conducted at four perimeter locations during October and three perimeter locations during April. During both months, monitoring was also conducted at one location in the middle of the rubble. Contaminants monitored for included total dust (TD), PM10, PM2.5, and volatile organic compounds. Particle samples were analyzed for mass, as well as elemental and organic carbon content. During October, the median personal exposure to TD was 346 microg/m3. The maximum area concentration, 1742 microg/m3, was found in middle of the debris. The maximum TD concentration found at the perimeter was 392 microg/m3 implying a strong concentration gradient from the middle of debris outward. PM2.5/PM10 ratios ranged from 23% to 100% suggesting significant fire activity during some of the sampled shifts. During April, the median personal exposure to TD was 144 microg/m3, and the highest area concentration, 195 microg/m3, was found at the perimeter. During both months, volatile organic compounds concentrations were low.

Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment.

Time-resolved ambient particulate organic (OC) and elemental carbon (EC) data measured in Atlanta, GA, during the Atlanta Supersite Experiment (August3-September 1, 1999) were investigated to determine the temporal trends of atmospheric carbonaceous aerosol and to examine the relative contributions of primary and secondary OC to measured particulate OC. Mean 1-h average concentrations (ranges in parentheses) of PM2.5 OC, EC, and total carbon were 8.3 (3.6-15.8), 2.3 (0.3-9.6), and 10.6 (4.6-24.6) microg of C m(-3), respectively, based on Rutgers University/Oregon Graduate Institute in situ thermal-optical carbon analyzer measurements. Carbonaceous matter (organic material 40%; EC 8%) comprised approximately 48% of PM2.5 mass in Atlanta. Primary and secondary OC concentrations were estimated using an EC tracer method. Secondary OC contributed approximately 46% of measured particulate OC, and 1-h average contributions ranged up to 88%. Vehicle emissions appear to be the dominant contributors to measured EC and primary OC concentrations based on temporal patterns of EC, primary OC, and CO. This research suggests that secondary OC concentrations in Atlanta were influenced by (1) "fresh" secondary organic aerosol formed by photochemical reactions locally in the early afternoons as seen in the Los Angeles air basin and (2) "aged" secondary organic aerosol transported from upwind regions or formed on previous days. Nocturnal peaks in secondary OC and ozone concentrations were observed on several days. The most probable explanation for this is the favorable partitioning of semivolatile organic compounds to the particulate phase driven by temperature decreases and relative humidity increases at night and vertical transport of regional pollutants from above to ground level.