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11.
[structure: see text] The first total synthesis of rollicosin, a member of a rare subgroup of Annonaceous acetogenins containing two terminal gamma-lactones, is reported. The approach features a highly regio- and stereoselective tandem ring-closing/cross-metathesis reaction for construction of the east-wing lactone and incorporation of the alkyl spacer. Establishment of the C4 stereocenter and addition of the west-wing lactone were achieved by Sharpless asymmetric dihydroxylation and enolate alkylation. 相似文献
12.
María S. García Tasende Maria I. Surez Gimeno A. Snchez J.S. Casas J. Sordo 《Journal of organometallic chemistry》1990,390(3):293-300
Compounds of type RnMH2Tb (R = Me, Ph; n = 1 (M = Hg), 2 (M = Tl), H3Tb = 2-thiobarbituric acid) have been prepared, and studied by vibrational (IR and Raman) and NMR (1H, 13C, 199Hg and 205Tl) spectroscopy. The organomercury derivatives have the metal bound to the deprotonated thiol sulphur atom of the ligand in both the solid state and in DMSO solution. The organothallium compounds, however, while having the metal bound to the sulphur atom and possibly to one of the nitrogen atoms of the ligand pyrimidine ring in the solid state, in DMSO form conducting solutions containing H2Tb− and R2Tl+ ions. 相似文献
13.
Simple and rapid micellar electrokinetic capillary chromatographic method for simultaneous determination of four antiepileptics in human serum 总被引:1,自引:0,他引:1
A very rapid and simple MEKC method was developed for the simultaneous determination of four antiepileptic drugs, ethosuximide (Etho), primidone (Pri), phenytoin (Pht) and carbamazepine (Cbz) in human serum. Sample analysis required only 100 microL of human serum which only needed to be centrifuged, decanted and combined with the running buffer [5.3 mM Na(2)HPO(4)/3.2 mM borax buffer (pH 9.5) containing 55 mM SDS and 3.5% (v/v) acetone]. The analysis was performed in only 10 min into fused-silica capillaries (57 cm total length with 50 microm i.d. and 50 cm to the detector) using the MEKC methodology with diode-array detection at 220 nm. The calibration graphs were established for ethoximide, primidone, phenytoin and carbamazepine between 0 and 20 mg/L. Recoveries were between 85 and 87%. The simplicity of the proposed methodology makes it suitable for routine clinical use, especially for epileptic patients on polytherapy. 相似文献
14.
15.
Stephanie Frank Singer 《Letters in Mathematical Physics》1996,38(2):195-201
This Letter contains constructions of complex action variables for both the full Kostant-Toda Lattice in sl(n, ) and the generalized nonperiodic tridiagonal Toda lattice associated to an arbitrary complex semisimple Lie algebra g. The main tool is the explicit factorization solution for certain Hamiltonian flows. The Letter also contains a generalization of the standard factorization solution theorem necessary for the analysis of the full Kostant-Toda lattice. 相似文献
16.
Casas JS Castaño MV García-Tasende MS Rodríguez-Castellón E Sánchez A Sanjuán LM Sordo J 《Dalton transactions (Cambridge, England : 2003)》2004,(13):2019-2026
Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature. 相似文献
17.
Chen D Wang R Arachchige I Mao G Brock SL 《Journal of the American Chemical Society》2004,126(50):16290-16291
This communication describes a spin-coating method to nucleate organic molecular rods of uniform size from an inorganic nanoparticle at a solid surface. The particle-rod hybrid structure spontaneously forms when a film is spin coated from a mixed 2-propanol solution of arachidic acid (AA) and nanoparticles of cadmium selenide capped by mercaptoundecanoic acid (MUA-CdSe) on graphite. AFM images show that MUA-CdSe nanoparticles nucleate single crystalline rods of AA with a cross section of a single unit cell of the C-form. The solution-based process potentially allows the precise tuning of the wetting profile of the solution on the surface-attached nanoparticle, which provides the reservoir for the growth of the single crystalline rods. The results suggest that nanoparticles can be regarded as nanoseeds for the nucleation of guest crystals. It should be possible to further functionalize the AA rods by electrostatic complexation with metal or organic ions. 相似文献
18.
Seasonal fluctuation of DNA photodamage in marine plankton assemblages at Palmer Station, Antarctica
Meador J Jeffrey WH Kase JP Pakulski JD Chiarello S Mitchell DL 《Photochemistry and photobiology》2002,75(3):266-271
Ultraviolet radiation-induced DNA damage frequencies were measured in DNA dosimeters and natural plankton communities during the austral spring at Palmer Station, Antarctica, during the 1999-2000 field season. We found that the fluence of solar ultraviolet-B radiation (UV-B) at the earth's surface correlated with stratospheric ozone concentrations, with significant ozone depletion observed because of "ozone hole" conditions. To verify the interdependence of ozone depletion and DNA damage in natural microbial communities, seawater was collected daily or weekly from Arthur Harbor at Palmer Station, Antarctica, throughout "ozone season," exposed to ambient sunlight between 0600 and 1800 h and fractionated using membrane filtration to separate phytoplankton and bacterioplankton populations. DNA from these fractions was isolated and DNA damage measured using radioimmunoassay. Under low-ozone conditions cyclobutane dimer concentrations in bacterioplankton and phytoplankton communities were maximal. DNA damage measured in dosimeters correlated closely with ozone concentrations and UV-B fluence. Our studies offer further support to the theory that stratospheric deozonation is detrimental to marine planktonic organisms in the Southern Ocean. 相似文献
19.
Goldschmidt RJ Wetzel SJ Blair WR Guttman CM 《Journal of the American Society for Mass Spectrometry》2000,11(12):1095-1106
Various secondary series are observed in matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectra of polystyrene. The number and positions of the series depend on the choice of matrix and added cation. For a given treatment, series observed in linear mode are not necessarily observed in reflectron mode, and vice versa. Post-source decay analysis was used to determine that the secondary series arise at least in part from formation and decay of adducts of polystyrene with matrix species. There is some treatment-to-treatment variation, but adduct formation and decay were observed for all tested treatments. The multiplicity of secondary series makes it unclear whether post-source decay occurs for the main series (polystyrene + cation)+ ions under the conditions normally used for polystyrene analysis. Such ions do undergo post-source decay at laser fluences greater than normally used. Although only polystyrene was investigated in this work, other polymers may also produce adduct and decay series in MALDI analysis. Their presence can mask the presence of minor components in a sample, but at least as observed here, do not have a strong influence on molecular mass determinations. 相似文献
20.
A third generation Frechet-type dendrimer containing 24 allyl ether end-groups was synthesized, cross-linked using the ring-closing metathesis (RCM) reaction, and the core was removed hydrolytically without significant fragmentation. The results are analogous to those previously reported for homoallyl ether dendrimers (Wendland, M. S.; Zimmerman, S. C. J. Am. Chem. Soc. 1999, 121, 1389-1390) suggesting that the less readily available homoallyl ether dendrimers can be replaced by their allyl ethers analogues in a range of applications. 相似文献