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101.
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
102.
Chisvert A Salvador A Pascual-Martí MC March JG 《Fresenius' Journal of Analytical Chemistry》2001,369(7-8):684-689
Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI. 相似文献
103.
The first total synthesis of racemic perophoramidine is described. The key step features the highly stereoselective introduction of the vicinial quaternary centers via base-promoted carbon-carbon bond formation between a 3-alkylindole and a 3-bromo-3-alkylindolin-2-one. This transformation presumably proceeds through a conjugate addition or Diels-Alder cycloaddition of the 3-alkylindole with a 3-alkylindol-2-one intermediate. 相似文献
104.
Evans PA Sawyer JR Lai KW Huffman JC 《Chemical communications (Cambridge, England)》2005,(31):3971-3973
The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
105.
Andreas Manz Elisabeth Verpoorte Carlo S. Effenhauser Norbert Burggraf Daniel E. Raymond D. Jed Harrison H. Michael Widmer 《Journal of separation science》1993,16(7):433-436
Miniaturization of separation columns implies equally reduced vol- umes of injectors, detectors, and the connecting channels. Planar chip technology provides a powerful means for the fabrication of micron-sized structures such as channels. This is demonstrated by two examples. An optical absorbance detector chip exhibits the expected behavior of a 1 mm optical path length cell despite its volume of 1 nL. A capillary electrophoresis device allows integrated injections of 100 pL samples, efficiencies of 70,000 to 160,000 theoretical plates in 10 to 20 seconds, and external laser-induced fluorescence detection at any capillary length of choice between 5 and 50 mm. 相似文献
106.
The transferability of the first and second order electric moments of localized orbitals have been shown. Some moment characteristics have also been investigated. The standard deviation of first order localized moments is less than 2.0%. The standard deviation of second order electric moment components are larger: although they do not exceed 4.0% for bond orbitals, for lone pair ones they vary about 1.5–10.1%. 相似文献
107.
3-(1-Methylethyl)-7-methyl2,6-octadienal, was prepared from 1,1,3-triethoxy-3,4-dimethylpentane and 3-methyl-2-buten-l-ol in a one-pot procedure utilising Claisen and Cope rearrangement of an intermediate dienol-allyl ether. 相似文献
108.
Crystal and Molecular Structure of Macrocyclic Musks. III. Muscone and its 2, 4-Diuitrophenylhydrazone Muscone (3-methylcyclopentadecanone C16H30O) forms orthorhombic plastic-crystals with Z = 2 (a = 5.560(4), b = 8.176(6), c = 17,168(20) Å). Single crystals are obtained by zone melting at 258 °K. The high degree of disorder and the ambiguity of space group have precluded a structural determination by X-ray diffraction methods. The crystal structure of muscone 2,4-dinitrophenylhydrazone (DNPHM; C22H34N4O4, triclinic, space group P¯, a = 8.015 (4), b = 8.235 (2), c = 17.409 (4) Å. α = 102.69 (4), β; = 93.86 (3), γ = 96.03 (3)° Z = 2) was solved by direct methods and refined to a final R of 0.155 (Rω = 0.102). The macrocycle shows static disorder, which could be partially resolved by analysis of the anisotropy of the atomic vibrational parameters. Eight possible conformers with reasonable geometries emerged from the subsequent refinements and were used as starting models in force-field calculations, which converged to four quinquangular conformations ([25233]; [34233]; [21423*4]; [3423*4]) with similar energies. In the molecular packing, the interactions between macrocycles and substituents are minimized. They are comparable to those described for the cis- and trans-civetone DNPH derivatives [1] [2]. 相似文献
109.
Siya Ram William Evans Dean S. Wise Leroy B. Townsend John W. Mccall 《Journal of heterocyclic chemistry》1989,26(4):1053-1059
A series of methyl 2-substituted purine 8-carbamates was prepared and evaluated for antifilarial activity. These purines were synthesized as aza congeners of benzimidazole carbamates which have shown significant anthelmintic activity to determine the effect that this modification might have on anthelmintic activity. The compounds were tested against the filarial infection, B. pahangi, in jirds. None of the compounds prepared in this study demonstrated antifilarial activity. 相似文献
110.
Raymond J. Abraham Lee Griffiths Philip Loftus 《Journal of computational chemistry》1982,3(3):407-416
Alternative methods of estimating atomic charges in haloalkanes are presented, derived from quantum mechanical and classical treatments. A scheme based on a breakdown of the transmission of charge by polar atoms into one-bond, two-bond, and three-bond additive contributions is given, in which the one-bond effect is proportional to the difference in the electronegativities of the bonded atoms, and the two- and three-bond effects functions of the atomic electronegativity and polarizability. Suitable developments of the basic scheme, including an iterative self-consistent process, give calculated dipole moments for a variety of haloalkanes in good agreement with the observed values. The atomic charges obtained by this scheme are compared with other estimates of these charges. They are similar to those derived from a simple LCAO –MO scheme but differ from those obtained by population analysis of more refined quantum mechanical calculations. 相似文献