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81.
Koichi Itoh Takeji Takui 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2004,80(2):29
This review paper deals with an overview of molecule-based magnetism as a rapidly developing interdisciplinary field, topological symmetry rule as the first principle of spin alignment in organic open-shell systems in the ground state, the proposal of organic through-bond 1D and 2D ferro- and superparamagnets and the detection of the first organic high-spin molecule, m-phenylenebis(phenylmethylene) in the quintet ground state (S = 2), followed by extended organic high-spin systems with π-conjugation such as aromatic hydrocarbons having S = 3, 4, 5. The paper also describes a theoretical approach to the understanding of electronic spin structures of organic high-spin molecules by invoking both Heisenberg and Hubbard model Hamiltonians, weakly interacting intramolecular high-spin systems from both experimental and theoretical sides, the spin density distribution of the first organic high-spin molecule in terms of electron- nuclear multiple resonance spectroscopy and the detection and characterization of ionic high-spin hydrocarbons, emphasizing the establishment of high spin chemistry underlying organic molecular magnetism. 相似文献
82.
《Journal of separation science》2003,26(5):402-408
When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities. 相似文献
83.
Three four-step enantiospecific syntheses of different diastereomers of AES, a new biodegradable chelating agent, are described. The stereocenters in each of the isomers are accessible from l- and d-malic and aspartic acids. 相似文献
84.
《Magnetic resonance in chemistry : MRC》2003,41(12):975-982
The reaction of 2,4‐pentanedione ( 1 ) with (R)‐(—)‐2‐phenylglycine methyl ester ( 2 ), (R)‐(—)‐2‐phenylglycinol ( 3 ) and the proteinogenic amino acids (2S,3R)‐(—)‐2‐amino‐3‐hydroxybutyric acid (L ‐threonine) ( 4 ) and (R)‐(—)‐2‐amino‐3‐mercaptopropionic acid (L ‐cysteine) ( 5 ) methyl esters was investigated. The corresponding enamines 6 , 7 and 8 were isolated and characterized spectroscopically whereas 9 , which is unstable, was transformed in situ into 13 . Treatment of 7 , 8 and 9 with boron trifluoride etherate afforded the new [1,4]oxazepines 10 , 11 and [1,4]thiazepine ( 12 ) as their BF3O? salts. The structures of the enamines and their corresponding seven‐membered heterocycles were assessed by 1D and 2D NMR spectroscopy. Variable‐temperature experiments revealed different molecular mobility behavior among these heterocycles. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
85.
Valérie Michaut Jean-Marc Paris Jean-Christophe Plaquevent 《Journal of fluorine chemistry》2007,128(8):889-895
Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure. 相似文献
86.
Biological transformation of volatile organic compounds is one of the key factors that influence contaminant-plume evolution
and thus natural attenuation. In this study we investigate the effect of biological transformation on the transport of contaminants
in the aqueous and gaseous phases. The analysis includes the study of the effect of density-driven advection of contaminants
in the gaseous phase on multiphase and multispecies flow, fate and transport modeling in the subsurface. Trichloroethylene
(TCE) and its two byproducts, dichloroethylene and vinyl chloride, are analyzed as the target contaminants. Our results indicate
that density-driven advection of the gaseous phase, which is initiated by evaporation of TCE as a nonaqueous phase liquid,
increases the downward and also the lateral migration of TCE within the unsaturated zone. This process also influences the
location of high-concentration zones of the byproducts of TCE in the unsaturated and the saturated zones. Biotransformation
of TCE contributes to the reduction of dissolved TCE plume development as expected. The daughter byproducts, which are introduced
into the subsurface system, show distinct transport patterns as they are affected by their independent degradation kinetics
and density-driven advection. These observations, which are based on our simulation results for biotransformation and transport
of TCE and its byproducts, are useful in evaluating the natural attenuation processes, its potential health hazards and also
the evaluation of potential plume development at contaminated sites. 相似文献
87.
A. V. Tarasov P. O. Yablonsky Yu. A. Moskvichev 《Chemistry of Heterocyclic Compounds》2003,39(1):119-122
Various methods were studied for the oxidation of 2-methyl-5-(phenylsulfonyl)benzenesulfamide and its derivatives. The oxidation by sodium dichromate in sulfuric acid was found most efficient. The effects of temperature, concentration, reagent ratio, and time of the oxidation reaction on the yield of the desired product were investigated. Conditions were proposed for obtaining the desired product in yields up to 95%. A synthesis was developed for a series of new saccharin derivatives. 相似文献
88.
Investigation on ultrafast thrid—order optical nonlinearity of metal(dmit)2/mnt)2 Charge transfer complexes
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We have investigated the transient third-order optical nonlinearity of the solutions of Metal(dmit)2/(mnt)2 salts in acetone by employing femtosecond optical Kerr gate measurement at 830nm wavelength.An order of enhancement on the second-order hyperppolarizability is found for the above salts with central atoms of Cu and Ni.We have suggested an explanation for the enhancement based on the extension of electronic conjugation by the entring Cu or Ni atom. 相似文献
89.
Inés CarrancoJosé Luis D?&#x;az Oscar JiménezRodolfo Lavilla 《Tetrahedron letters》2003,44(46):8449-8452
The Lewis acid-catalyzed interaction of dihydropyridines with ethyl glyoxalate and primary aliphatic amines yields, depending on the reaction conditions, bicyclic aminals or rearranged tetrahydropyridines in one-pot multicomponent reactions. 相似文献
90.
G. I. Nikishin L. L. Sokova V. D. Makhaev N. I. Kapustina 《Russian Chemical Bulletin》2008,57(1):118-123
The solid-phase oxidation of cinnamic, 4-methoxy- and 3,4-dimethoxycinnamic acids with Ce(NH4)2(NO3)6—MHal system leads to β-halostyrenes. Similar procedure in the absence of a metal halide results in a cleavage of the C=C
bond giving the corresponding benzaldehydes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 114–118, January, 2008. 相似文献