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201.
Alberto Milani Jacopo Zanetti Chiara Castiglioni Elena Di Dedda Stefano Radice Giorgio Canil Claudio Tonelli 《European Polymer Journal》2012,48(2):391-403
Perfluoropolyether (PFPE) fluids constitute a class of polymers that fulfil a wide range of requirements for hi-tech applications, due to their pefluorinated backbone. For some of these applications they are requested to bear polar end groups, and the combination of a chemical inert backbone and a reactive end group can produce peculiar conformations and supramolecular structures. The molecular structure and the vibrational properties of the ethoxyl-terminated PFPE FLUOROLINK®E10H in solution are here investigated by means of IR spectroscopy. It is shown that the complex spectral features of the OH-stretching region cannot be explained without a thorough computational study, involving the investigation of the conformational space of an isolated model molecule by means of semiempirical AM1 calculations and DFT calculations. The most relevant conformers were singled out, showing a high degree of conformational disorder for FLUOROLINK®E10H. Furthermore, it is shown that intra- and intermolecular H-bonding affects significantly the molecular structure and the vibrational spectrum. Several interactions are shown to be relevant, such as OH…F interactions and complexes with residual water. Theoretical values of the absolute intensities of OH stretching IR bands, relevant for the analytical applications, are obtained. 相似文献
202.
Pier Luigi Ferrarini Claudio Mori Giuliana Biagi Oreste Livi Imperio Tonetti 《Journal of heterocyclic chemistry》1984,21(2):417-419
Some 1,8-naphthyridine nitrogen mustards have been synthesized for studies of their antitumor potentialities. All the tested intermediate and target compounds are devoid of antitumor properties. 相似文献
203.
Calza P Baudino S Aigotti R Baiocchi C Branca P Pelizzetti E 《Journal of mass spectrometry : JMS》2002,37(6):566-576
Tebuconazole is a widely used fungicide. The formation of by-products on irradiated titanium dioxide as a photocatalyst was evaluated. Several species derived from tebuconazole degradation were identified and characterized by HPLC/MS(n). A pattern of reactions accounting for the observed intermediates is proposed. Different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds), leading to a wide range of intermediate compounds. All these molecules are more hydrophylic than tebuconazole. The main steps involved are (1) the hydroxylation of the molecule with the formation of three species having [M + H](+) 324; the hydroxylation occurs on the C-1 carbon and on the aromatic ring in the two ortho-positions; (2) the cleavage of a C--C bond with the release of the tert-butyl moiety and the formation of a species having m/z 250; analogously to step 1, also on this species a further hydroxylation reaction occurs; (3) through the loss of the triazole moiety with the formation of a structure with m/z 257. 相似文献
204.
Claudio Bianchini Carlo A. Ghilardi Andrea Meli Stefano Midollini Annabella Orlandini 《Journal of organometallic chemistry》1983,255(2):C27-C30
CO2, COS, and SCNPh react under very mild conditions with the copper(I)-tetrahydroborate complexes [(PR3)2Cu(η2-BH4)] (R = Ph, Cy); CO2 and COS give the complexes [(PR3)2Cu(η2-O2CH)] and [(PR3)2Cu(η2-OSCH)] respectively, whereas SCNPh gives the η2-dithiocarbamate complexes [(PR3)2Cu-(η2-S2CNHPh)]. Addition of PPh3 under CO2 to solutions of [(PPh3)2Cu-(η2-BH4)] gives [(PPh3)3Cu(η1-O2CH)] while addition of PPh3 and NBu4ClO4 under CO2 gives [(PPh3)3Cu(η-O2CH)Cu(PPh3)3] ClO4. 相似文献
205.
The electronic structures of complexes and one‐dimensional metallomacrocycles with cyanide as bridged ligand, such as [MacM(CN)2]? and [MacM(CN)]n [Mac=phthalocyanine, tetrabenzoporphyrine; M=Co(III), Rh(III)] have been investigated using density functional theory. The results of this study show that the intrinsic semiconductivity properties depend on the frontier bands. The valence band is composed by the π‐macrocycle orbital. The conduction band for the cobalt polymers is a mixture of orbitals between this metal and the cyanide ligand along of the stacking direction. However, in the rhodium polymers such a band is exclusively composed of the π* system of the macrocycles. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 相似文献
206.
Morgado CA Svozil D Turner DH Sponer J 《Physical chemistry chemical physics : PCCP》2012,14(36):12580-12591
Preceding NMR experiments show that the conformation of tandem GA base pairs, an important recurrent non-canonical building block in RNA duplexes, is context dependent. The GA base pairs adopt "sheared" N3(G)-N6(A), N2(G)-N7(A) geometry in the r(CGAG)(2) and r(iGGAiC)(2) contexts while switching to "imino" N1(G)-N1(A), O6(G)-N6(A) geometry in the r(GGAC)(2) and r(iCGAiG)(2) contexts (iC and iG stand for isocytosine and isoguanine, respectively). As base stacking is likely to be one of the key sources of the context dependence of the conformation of GA base pairs, we calculated base stacking energies in duplexes containing such base pairs, to see if this dependence can be predicted by stacking energy calculations. When investigating the context dependence of the GA geometry two different conformations of the same duplex were compared (imino vs. sheared). The geometries were generated via explicit solvent MD simulations of the respective RNA duplexes, while the subsequent QM energy calculations focused on base stacking interactions of the four internal base pairs. Geometrical relaxation of nucleobase atoms prior to the stacking energy computations has a non-negligible effect on the results. The stacking energies were derived at the DFT-D/6-311++G(3df,3pd) level. We show a rather good correspondence between the intrinsic gas-phase stacking energies and the NMR-determined GA geometries. The conformation with more favorable gas-phase stacking is in most cases the one observed in experiments. This correlation is not improved when including solvent effects via the COSMO method. On the other side, the stacking calculations do not predict the relative thermodynamic stability of duplex formation for different sequences. 相似文献
207.
208.
209.
NMR screening techniques in drug discovery and drug design 总被引:7,自引:0,他引:7
Brian J. Stockman Claudio Dalvit 《Progress in Nuclear Magnetic Resonance Spectroscopy》2002,41(3-4):187-231
210.
Rosa IL Filho PC Neri CR Serra OA de Figueiredo AT Varela JA Longo E 《Journal of fluorescence》2011,21(4):1575-1583
This work reports on the synthesis and characterization of a new complex of Eu3+ with the 3-hydroxypicolinamide ligand (Hhpa). Here we present an approach for obtaining bis[2-carbamoyl(κO)pyridin-3-olato(κO’)]
lanthanide complexes, which were characterized through elemental analysis, thermal analysis, infrared and photoluminescence
spectroscopies (emission, excitation, luminescence lifetimes, quantum efficiencies, Judd-Ofelt parameters and quantum yields).
Although hpa can act as a bidentate ligand in different conformations, the results attest for the occurrence of a unique coordination
site of low symmetry for the Eu3+ ions, in which two anionic hpa ligands coordinate the cations through an O/O chelating system. The phosphorescence of the
synthesized gadolinium complex provides the energy of the triplet state, which is determined to be at 20,830 cm-1 over the ground state. This makes the Hhpa ligand very adequate for sensitizing the Eu3+ luminescence, which leads to a very efficient antenna effect and opens a wide range of applications for the complex in light
emitting organic-inorganic devices. 相似文献