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101.
Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate 总被引:1,自引:0,他引:1
Vione D Barra S De Gennaro G De Rienzo M Gilardoni S Perrone MG Pozzoli L 《Annali di chimica》2004,94(4):257-268
This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts. 相似文献
102.
The application of an experimental approach based on the load separation criterion for the determination of the point of fracture initiation in a fracture test on a ductile polymer was critically examined. To this aim, the fracture process outlined by the application of this method was related to that described by the visual analysis of the fracture surfaces obtained in fracture tests on nominally identical specimens, in which different levels of crack extension were produced. The material examined was an acrylonitrile-butadiene-styrene (ABS) resin, and the fracture tests were performed at low loading rate on single-edge notched in bending specimens.The results demonstrated that this load separation criterion based methodology is a promising approach for the determination of the point of fracture initiation, and for material fracture resistance, JIc, evaluation. The method also has experimental simplicity and a high degree of repeatability. 相似文献
103.
104.
Ghitti M Spitaleri A Valentinis B Mari S Asperti C Traversari C Rizzardi GP Musco G 《Angewandte Chemie (International ed. in English)》2012,51(31):7702-7705
Ain't got that swing(-out): The cyclopeptide isoDGR is emerging as a new αvβ3 integrin binding motif. Agreement between the results of computational and biochemical studies reveals that isoDGR-containing cyclopeptides are true αvβ3 integrin antagonists that block αvβ3 in its inactive conformation (see scheme). isoDGR-based ligands may give αvβ3 antagonists without paradoxical effects. 相似文献
105.
Simona Bronco Giambattista Consiglio Silvia Di Benedetto Matthias Fehr Felix Spindler Antonio Togni 《Helvetica chimica acta》1995,78(4):883-886
Cationic Pd-complexes modified by dicyclohexyl{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}phosphine ( 1a ) give very active catalytic systems for the regioregular isotactic specific copolymerization of propene with CO. Other alk-1-enes also give stereoregular and regioregular copolymers, even if with lower productivity. The copolymers are isolated as poly(4-alkyl-tetrahydrofuran-2,2,5,5-tetrayl-2-oxy-2-methylenes) B in the solid state and give the isomeric poly(2-alkyl-1-oxopropane-1,3-diyls) A by dissolution in (CF3)2CHOH. Solid polymer A (R = Et) is formed back at least partially when the dissolved material is reprecipitated from MeOH. The use of the related (ferrocenyl)diphosphine ligands 1b ? e and 2 as the catalyst modifier shows that the presence of both elements of chirality and of large substituents on the P-atoms of the ligand is necessary to achieve good stereocontrol, and that the large difference in basicity between the two P-atoms is probably the reason for the good catalytic activity. 相似文献
106.
Reboredo S Reyes E Vicario JL Badía D Carrillo L de Cózar A Cossío FP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7179-7188
The catalytic enantioselective [3+2] cycloaddition between azomethine ylides and α,β-unsaturated aldehydes catalyzed by α,α-diphenylprolinol has been studied in detail. In particular, the reaction has been extended to the use of 2-alkenylidene aminomalonates generated in situ as azomethine ylide precursors. These reactions lead to the formation of pyrrolidines containing a 5-alkenyl side chain with potential for chemical manipulation. Moreover, a detailed and concise computational study has been carried out to understand the exact nature of the mechanism of this reaction and especially the consequences derived from the incorporation of the chiral secondary amine catalyst on the reaction pathway. 相似文献
107.
Terbuthylazine (TBA) is a widely applied herbicide and an environmental contaminant. Following its use, humans, such as agricultural workers and rural residents, may be exposed. An isotope-dilution liquid chromatography coupled to electrospray-tandem mass spectrometry method for the determination of TBA, and its metabolite desethylterbuthylazine (DET) in human urine and hair was developed and validated. Under the optimised conditions, analytes were extracted from urine using a solid phase cartridge or from hair by sonication in methanol. Analytes were separated using a C18 reversed-phase chromatographic column and quantified, after positive ionization using a heated electrospray source, by a triple quadrupole mass detector in the selected reaction monitoring mode. Validation showed linear dynamic ranges up to 100 μg/L or 5.00 ng/mg hair, inter- and intra-run precisions <7%, and accuracies within 12% of spiked concentrations. Limits of quantification were 0.25 μg/L in urine and 0.01 ng/mg hair for both TBA and DET. Matrix effect evaluation showed that the isotope dilution approach allowed for the control of bias sources. TBA and DET were determined in specimens of agriculture workers exposed to TBA using the validated method. Hair samples contained TBA levels in the low nanogram per milligram range, and urine samples contained DET levels in the low microgram per liter range. Conversely, TBA levels in urine samples and DET levels in hair samples were always below the limit of quantification. 相似文献
108.
The title compound crystallizes in the monoclinic P2(1)/c space group with a = 11.2470(3) ?, b = 5.9034(2) ?, c = 12.0886(3) ?, β = 115.143(1)°, and V = 726.58(4) ?(3) and consists of discrete monomeric NiCl(2)(o-phenylendiamine)(2) molecules. Each o-phen ligand coordinates in a bidentate mode with the chloride ions occupying trans positions in the resulting tetragonally distorted octahedral coordination sphere. Two discrete sets of N-H···Cl hydrogen bonds link the octahedral molecules into a two-dimensional network, with type 1 interactions linking adjacent monomers along the c axis and type 2 interactions linking monomers along the diagonals in the bc plane. Analysis of the magnetic data reveals the existence of weak antiferromagnetic coupling within the layers via these hydrogen bonds, in addition to the presence of zero field splitting, with the best fit obtained for a 1d antiferromagnetic model with g = 2.0917(7), J/k = -2.11(4) K [J = -1.47(3) cm(-1)], and D = 1.05(3) cm(-1) [β = D/|J| = 0.72(6)] for the model with D > 0 and g = 2.0911(6), J/k = -2.26(1) K [J = -1.57(1) cm(-1)], and D = -0.86(1) cm(-1) [β = D/|J| = 0.55(6)] for the model with D < 0. Theoretical calculations of the exchange coupling confirm the experimental results, yielding values of J(1) = -1.39 cm(-1) for the type 1 hydrogen bonds and J(2)/k = -0.56 cm(-1) for the type 2 hydrogen bonds. 相似文献
109.
Sreedevi KC Thomas AP Ramakrishnan S Salini PS Holaday MG Reddy ML Srinivasan A 《Organic & biomolecular chemistry》2012,10(18):3600-3605
Synthesis, spectral and structural characterization of a pyrroloindolizine derivative having structural similarity with calix[2]pyrrole is described. Here, two pyrrole rings are connected with two meso-carbon atoms having an N,α-linkage and an α,β-linkage to afford the smallest analogue in the calixpyrrole family. Detailed NMR spectroscopic studies along with single crystal X-ray analysis confirm the assigned structure of the molecule. 相似文献
110.
Inmaculada Robina Silvia Gómez-Bujedo José G. Fernández-Bolaños José Fuentes 《合成通讯》2013,43(13):2379-2397
To prepare C-sulfonate derivatives of disaccharides two different strategies were followed. Thus 6- and 6′-C-sulfocellobiosides 4 and 10–12 were prepared starting from a suitably protected cellobioside. The 6′-C-sulfoaminocellobioside 18 was prepared by construction of the molecule through a glycosylation reaction. In both cases, the synthetic pathway involves regioselective tosylation, introduction of a sulfur atom by nucleophilic displacement with potassium thioacetate and oxidation with hydrogen peroxide. 相似文献