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161.
162.
Gifted with novel chemical features and extraordinary biological activity, sceptrin has remained a prominent unanswered synthetic challenge since its characterization in 1981 by Faulkner and Clardy. A concise and practical solution to the myriad of chemical challenges posed by sceptrin is reported in this Communication. Thus, through a sequence involving rearrangement of an oxaquadricyclane, a new method for chemo- and regioselective halogenation, a mild sequence for 2-aminoimidazole formation, and careful synthetic choreography, (+/-)-sceptrin is obtained in a minimum of steps and in 24% overall yield from dimethyl acetylenedicarboxylate without a single use of chromatography. 相似文献
163.
Alexandros E. Koumbis Apostolos D. Kaitaidis Stefanos S. Kotoulas 《Tetrahedron letters》2006,47(48):8479-8481
A short and efficient approach was applied to the total synthesis of erythro-saccharinic acid lactone and the leaf-closing substance potassium (2R,3R)-2,3,4-trihydroxy-2-methylbutanoate from a 2-C-hydroxymethyl-d-erythrose derivative, using a combined strategy. 相似文献
164.
Proton and carbon-13 nmr spectra for cis- and trans-2-ethyl-3,3-diphenyl-4-methyltetrahydrofurans and 2-ethylidene-3,3-diphenyl-4-methyltetrahydrofuran, derived from the pyrolysis of the quaternary ammonium salts of the diastereomeric isomethadols and isomethadone, respectively, are reported. 1H and 13C chemical shifts and 1H-1H coupling constants have been assigned in each case. The isomeric teterahydrofurans have been analyzed in terms of a half-chair conformation, and an envelope conformation for the ethylidene derivative. 相似文献
165.
Alexandros Ch PappasConstantine D Stalikas Yannis Ch FiamegosMiltiades I Karayannis 《Analytica chimica acta》2002,455(2):305-313
The development of a highly sensitive method for the determination of nanomolar concentrations of hydrogen peroxide in the liquid phase is described. This paper demonstrates for the first time a flow injection analysis (FIA) system with immobilized enzyme reactor combined with a total internal reflective cell (a liquid waveguide capillary cell (LWCC)) and spectrophotometric detection, for the development of an improved procedure for the determination of hydrogen peroxide. Moreover, the newly synthesized 4-aminopyrazolone derivative, 4-amino-5-(p-aminophenyl)-1-methyl-2-phenyl-pyrazol-3-one (DAP), is used as a color coupler in its oxidative condensation with the sodium salt of N-ethyl-N-sulphopropylaniline sodium salt (ALPS) which acts as a hydrogen donor. Immobilization of peroxidase is achieved by coupling the periodate-treated enzyme to aminopropyl controlled-pore glass (CPG) beads. The determination of hydrogen peroxide is carried out in a 0.1 M phosphate buffer and the product is monitored at 590 nm with a charge-coupled device (CCD) detector equipped with fiber optics in a fully computerized system. The interference of different species, mainly ionic, was investigated.The method permits detection down to 4 nmol l−1 hydrogen peroxide (signal-to-noise ratio=3). A linear calibration graph was obtained over the range 20-700 nmol l−1. The relative standard deviation (R.S.D.) at 300 nmol l−1 H2O2 is 1.7% (n=7). The method was successfully applied for the determination of hydrogen peroxide in samples from a vat-cleaning process. 相似文献
166.
Pantos A Tsiourvas D Paleos CM Nounesis G 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6696-6702
Unilamellar PC-based liposomes bearing a recognizable moiety were loaded either with the hydrophilic drug doxorubicin (DXR) or with the hydrophobic drug tamoxiphen (TMX) and allowed to interact with multilamellar PC-based liposomes bearing complementary recognizable groups. It has been established that, due to molecular recognition of these complementary liposomes, effective and fast transport of the drugs occurs from unilamellar to multilamellar liposomes. The transport of TMX is more effective compared to that of DXR. This behavior was observed for both PEGylated and non-PEGylated unilamellar liposomes, and it was attributed to the different sites of solubilization of the drugs in the unilamellar liposomes. PEGylation reduces the transport of both drugs since it inhibits to some extent the molecular recognition effectiveness of the complementary moieties. 相似文献
167.
[reaction: see text] Abyssomicins, a novel class of polyketide antibiotics, are characterized by an unprecedented spirotetronic tricyclic subunit in their structure. In this letter, a short synthesis of a suitably functionalized tricyclic precursor of abyssomicins is reported. Key steps of the synthesis are (i) the highly stereoselective Al(III)-tethered Diels-Alder reaction and (ii) the tandem Dieckmann cyclization/TBS trapping of the C9 hydroxyl group followed by a regioselective intramolecular epoxide opening for the assembly of the target tricyclic structure. 相似文献
168.
The reductive decarboxylation of α-alkenyl derivatives of allyl-β-ketoesters was achieved by use of palladium(0) catalyst generated in situ from Pd(OAc)2 and PPh3, with triethylammonium formate as the hydride source, in THF. The reaction proceeds smoothly and cleanly, with linear alkenyl derivatives of allyl-β-ketoesters, to afford (E)-3-alkenones in good to excellent yields (73-92%) and high stereoselectivity (>98%). 相似文献
169.
Dimitra Kovala-Demertzi Alexandros Alexandratos Athanassios Papageorgiou Paras Nath Yadav Panagiotis Dalezis Mavroudis A. Demertzis 《Polyhedron》2008
The present paper includes synthesis and spectral characterization of the novel prepared palladium(II) and zinc(II) complexes with 2-formyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone, HFo4Npypipe, 1 and the 2-acetyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone, HAc4Npypipe, 2. The Pd(II) complexes [PdCl(Fo4Npypipe)], 3, [PdCl(Ac4Npypipe)], 4 and the Zn(II) complexes [ZnCl2(Fo4Npypipe)], 5 and [ZnCl2(Ac4Npypipe)], 6 have been characterized by elemental analyses and spectroscopic studies. The crystal structure of the complexes [PdCl(Fo4Npippy)], 3 and [PdCl(Ac4Npippy)], 4, have been solved by single-crystal X-ray diffraction. The electronic, IR, UV/Vis, and NMR spectroscopic data of the complexes are reported. The results of the cytotoxic activity of 1–6 have been evaluated in vitro against the cells of three human cancer cell lines: MCF-7, T24, A-549 and a mouse L-929 (a fibroblast-like cell line cloned from strain L). For selected compounds 2 and 6 the acute toxicity and antitumor activity were evaluated on leukemia P388-bearing mice. The Zn(II) compounds 5 and 6 are considered as agents with potential antitumor activity, and can therefore be candidates for further stages of screening in vitro and/or in vivo. 相似文献
170.
A systematic approach to construct a low-dimensional free energy landscape from a classical molecular dynamics (MD) simulation is presented. The approach is based on the recently proposed dihedral angle principal component analysis (dPCA), which avoids artifacts due to the mixing of internal and overall motions in Cartesian coordinates and circumvents problems associated with the circularity of angular variables. Requiring that the energy landscape reproduces the correct number, energy, and location of the system's metastable states and barriers, the dimensionality of the free energy landscape (i.e., the number of essential components) is obtained. This dimensionality can be determined from the distribution and autocorrelation of the principal components. By performing an 800 ns MD simulation of the folding of hepta-alanine in explicit water and using geometric and kinetic clustering techniques, it is shown that a five-dimensional dPCA energy landscape is a suitable and accurate representation of the full-dimensional landscape. In the second step, the dPCA energy landscape can be employed (e.g., in a Langevin simulation) to facilitate a detailed investigation of biomolecular dynamics in low dimensions. Finally, several ways to visualize the multidimensional energy landscape are discussed. 相似文献