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排序方式: 共有502条查询结果,搜索用时 31 毫秒
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CAS SCF and CCI calculations have been performed in order to establish the existence or non-existence of the HO3 radical. The potential surface for the dissociation reaction, HO3 → O2(3Σ) + OH, along one chosen coordinate has been calculated. The calculations show that although the wavefunctions describing the short-distance and long-distance states are of different character, the energies are the same and the curve connecting the states is very flat. There is probably no barrier towards dissociation of the radical. However, the existence of HO3 can still not be excluded. 相似文献
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Nordesferriferrithiocin, NDFFTH(2), is a derivative of the siderophore desferriferrithiocin, DFFTH(2), in which the methyl group is substituted by a hydrogen atom. Both compounds show high oral activity as possible drugs for the treatment of iron overload. While DFFTH(2) is significantly toxic, NDFFTH(2) exhibits a lower toxicity and offers a much better therapeutic window than other orally active iron chelators. In this study, complexes of DFFTH(2) and NDFFTH(2) with various trivalent metals have been synthesized and characterized. Five isomers (the maximum possible) have been observed in the case of [Co(DFFT)(2)](-) in solution, as proved by (1)H-NMR measurements. Although normally labile, complexes of Al(3+) ([Al(DFFT)(2)](-)) have been separated by HPLC. In general, DFFTH(2) forms kinetically inert complexes whereas complexes of NDFFTH(2) tend to isomerize quickly in solution, as indicated by CD spectroscopy of separated HPLC fractions of [Cr(NDFFT)(2)](-). The most stable isomers of the aluminum complexes of both ligands have been characterized by X-ray crystallography; K[Al(DFFT)(2)] crystallizes from methanol/diethyl ether in the orthorhombic space group P2(1)2(1)2 with a = 11.238(3) ?, b = 31.719(11) ?, c = 7.684(2) ?, V = 2739.2(24) ?(3), and Z = 4. This isomer has the mer-(N,O-Lambda)(S,S) configuration, while K[Al(NDFFT)(2)] crystallizes from methanol/diethyl ether in the space group P6(1) (a = 21.269(8) ?, c = 9.643(3) ?, V = 3777.8(42) ?(3), Z = 6) and has the same coordination geometry. The solution thermodynamics of the Al(3+), Ga(3+), and Fe(3+) complexes have been studied by spectrophotometric titration. The stability constants (log K) are 23.6(1), 29.2(3), and 31.04(3), respectively, for the DFFTH(2) complexes and 22.0(1), 27.8(2), and 29.09(3), respectively, for the NDFFTH(2) complexes. Cyclic voltammograms of both iron complexes have been recorded in water at a carbon disk working electrode and in DMF at a graphite working electrode. The reduction waves measured in DMF indicate no reversibility whereas in water a quasi-reversible reduction is observed. The reduction potentials (E(1/2)'s) in water are -166 mV for [Fe(DFFT)(2)](-) and -97 mV for [Fe(NDFFT)(2)](-) versus NHE. These potentials are well in the range for biological reductants, which makes possible an in vivo reduction mechanism for the iron removal from the siderophore. 相似文献
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Genson KL Hoffman J Teng J Zubarev ER Vaknin D Tsukruk VV 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9044-9052
An amphiphilic heteroarm star polymer containing 12 alternating hydrophobic/hydrophilic arms of polystyrene (PS) and poly(acrylic acid) (PAA) connected to a well-defined rigid aromatic core was studied at the air-water and the air-solid interfaces. At the air-water interface, the molecules spontaneously form pancakelike micellar aggregates which measure up to several microns in diameter and 5 nm in thickness. Upon reduction of the surface area per molecule to 7 nm2, the two-dimensional micelles merged into a dense monolayer. We suggest that confined phase separation of dissimilar polymer arms occurred upon their segregation on the opposite sides of the rigid disklike aromatic core, forcing the rigid cores to adopt a face-on orientation with respect to the interface. Upon transfer onto solid supports the PS chains face the air-film interface making it completely hydrophobic, and the PAA chains were found to collapse and form a thin flattened underlayer. This study points toward new strategies to create large 2D microstructures with facial amphiphilicity and suggests a profound influence of star molecular architecture on the self-assembly of amphiphiles at the air-water interface. 相似文献
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From analysis by gas chromatography/mass spectrometry (GC/MS), the presence of either 2,4,5-tribromo-1H-imidazole (1) or 3,4,5-tribromo-1H-pyrazole (2) was tentatively identified in lipophilic extracts from the egg masses of three muricid molluscs. Synthesis of these compounds, followed by comparison of the GC retention times and fragmentation patterns from electron impact MS, with those of the natural products, indicated that it was 2,4,5-tribromo-1H-imidazole rather than the pyrazole. This imidazole is likely to be responsible for some of the antimicrobial activity observed in the egg extracts. This is the first report of this compound from a natural source. 相似文献
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Bao J Baker RK Doss GA Kayser F Kotliar A Miao S Parsons WH Rupprecht KM 《Organic letters》2002,4(11):1871-1873
[reaction: see text] Pentacyclic triterpenoid natural product correolide (1) was converted to ketone 2 via ozonolysis. An unusual fragmentation reaction of ketone 2 with LiCl was discovered. This reaction is general among several similar substrates examined and appears to be specific for the correolide-type E-ring structure (ketone). A mechanism involving a retroaldol reaction, a nucleophilic opening of the epoxide, and a subsequent acetoxy elimination reaction was proposed. 相似文献
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Hau Sun Sam Chan Amber L. Thompson Kirsten E. Christensen Jonathan W. Burton 《Chemical science》2020,11(42):11592
Laurefurenynes C–F are four natural products isolated from Laurencia species whose structures were originally determined on the basis of extensive nuclear magnetic resonance experiments. On the basis of a proposed biogenesis, involving a tricyclic oxonium ion as a key intermediate, we have reassigned the structures of these four natural products and synthesized the four reassigned structures using a biomimetic approach demonstrating that they are the actual structures of the natural products. In addition, we have developed a synthesis of the enantiomers of the natural products laurencin and deacetyllaurencin from the enantiomer of (E)-laurefucin using an unusual retrobiomimetic strategy. All of these syntheses have been enabled by the use of tricyclic oxonium ions as pivotal synthetic intermediates.The synthesis and structural reassignment of laurefurenynes C–F has been achieved, with the new structures fitting with a proposed biosynthesis. Also reported is the synthesis of ent-laurencin and ent-deacetyllaurencin via a retrobiomimetic approach. 相似文献
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