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171.
We describe the first studies on the chemistry of 2-(2-oxo-3-phenylpropyl)benzaldehydes, which were converted into 3-benzylisochromen-1-ones via the corresponding 2-(2-oxo-3-phenylpropyl)benzoic acid. The 2-(2-oxo-3-phenylpropyl)benzaldehydes proved to be convenient starting materials for the synthesis of 3-phenyl-2-naphthols. Oxidation of the latter compounds resulted in a novel, efficient synthesis of 3-phenyl-1,2-naphthoquinones, which were efficiently transformed into 2-hydroxy-3-phenyl-1,4-naphthoquinones. 相似文献
172.
Martin JN Muñoz EM Schwergold C Souard F Asensio JL Jiménez-Barbero J Cañada J Vicent C 《Journal of the American Chemical Society》2005,127(26):9518-9533
Sugar-oligoamides have been designed and synthesized as structurally simple carbohydrate-based ligands to study carbohydrate-DNA interactions. The general design of the ligands 1-3 has been done as to favor the bound conformation of Distamycin-type gamma-linked covalent dimers which is a hairpin conformation. Indeed, NMR analysis of the sugar-oligoamides in the free state has indicated the presence of a percentage of a hairpin conformation in aqueous solution. The DNA binding activity of compounds 1-3 was confirmed by calf thymus DNA (ct-DNA) NMR titration. Interestingly, the binding of the different sugar-oligoamides seems to be modulated by the sugar configuration. Semiquantitative structural information about the DNA ligand complexes has been derived from NMR data. A competition experiment with Netropsin suggested that the sugar-oligoamide 3 bind to DNA in the minor groove. The NMR titrations of 1-3 with poly(dA-dT) and poly(dG-dC) suggested preferential binding to the ATAT sequence. TR-NOE NMR experiments for the sugar-oligoamide 3-ct-DNA complex both in D(2)O and H(2)O have confirmed the complex formation and given information on the conformation of the ligand in the bound state. The data confirmed that the sugar-oligoamide ligand is a hairpin in the bound state. Even more relevant to our goal, structural information on the conformation around the N-glycosidic linkage has been accessed. Thus, the sugar asymmetric centers pointing to the NH-amide and N-methyl rims of the molecule have been characterized. 相似文献
173.
Samuel N. Sanders Elango Kumarasamy Kealan J. Fallon Matthew Y. Sfeir Luis M. Campos 《Chemical science》2020,11(4):1079
Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law. 相似文献
174.
Bustamante JJ Garcia M Gonzalez L Garcia J Flores R Aguilar RM Trevino A Benavides L Martinez AO Haro LS 《Electrophoresis》2005,26(23):4389-4395
A method for separating proteins with a molecular mass difference of 2 kDa using SDS-PAGE under nonreducing conditions is presented. A sample mixture containing several human growth hormone (hGH) isoforms was initially separated on a weak anion-exchange column. Fractions rich in 24 kDa hGH as determined by analytical SDS-PAGE were pooled and further separated by cation-exchange chromatography. The fractions pooled from the cation-exchange chromatography contained two hGH isoforms with a 2 kDa molecular mass difference according to SDS-PAGE analysis, 22 and 24 kDa hGH. The 22 and 24 kDa hGH were separated using continuous-elution preparative double-inverted gradient PAGE (PDG-PAGE) under nonreducing conditions. The preparative electrophoresis gel was composed of three stacked tubular polyacrylamide matrices, a 4% stacking gel, a 13-18% linear gradient gel, and a 15-10% linear inverted gradient gel. Fractions containing purified 24 kDa hGH were pooled and Western blot analysis displayed immunoreactivity to antihGH antibodies. PDG-PAGE provides researchers with an electrophoretic technique to preparatively purify proteins under nonreducing conditions with molecular mass differences of 2 kDa. 相似文献
175.
Luis R. Kahn 《International journal of quantum chemistry》1984,25(1):149-183
A one-component approach to molecular electronic structure is discussed that includes the dominant relativistic effects on valence electrons and yet allows the use of the traditional quantum-chemistry techniques. The approach starts with one-component Cowan–Griffin relativistic orbitals that successfully incorporate the effects of the mass-velocity and Darwin terms present in more complicated wave functions such as the Dirac–Hartree–Fock. The approach then constructs “relativistic” effective core potentials (RECPS ) from these orbitals, and uses these to bring the relativistic effects into the molecular electronic calculations. The use of effective one-electron spin-orbit operators in conjunction with these one-component wave functions to include the effects of spin-orbit coupling is discussed. Applications to molecular systems involving heavy atoms and comparisons with available spectroscopic data on molecular geometries and excitation energies are presented. Finally, a new approach to the construction of RECPS encompassing the Hamiltonian and shapeconsistent approach is presented together with a novel analysis of the long-range behavior of the RECPS . 相似文献
176.
Miguel A. Esteso Luis Fernandez-Merida Felipe F. Hernandez-Luis 《Journal of Electroanalytical Chemistry》1987,230(1-2)
Values of the emf for the cell: Na-glass|Na2Succ(m), Hg2Succ|Hg, have been measured. These values of E have been used with Hückel's extended Debye and Hückel equation to obtain the mean ionic activity coefficient values for Na2Succ in aqueous solutions of several concentrations, m. The values of γ± thus obtained have been adjusted to Pitzer's equation, with b = 1.2 and α = 2.0 to find Pitzer's parameters and then the values for both the osmotic coefficients and the activity of water. Finally, the standard potential of the Hg2Succ|Hg electrode has been determined and from this value the solubility-product equilibrium constant for mercurous succinate has also been calculated. 相似文献
177.
Brunetto R Gutiérrez L Delgado Y Gallignani M Burguera JL Burguera M 《Analytical and bioanalytical chemistry》2003,375(4):534-538
A column-switching high-performance liquid chromatographic method with UV detection for the determination of cocaine (COC) and benzoylecgonine (BZE) in human blood plasma samples is described. The method uses an alkyl-diol-silica ADS-C18 extraction precolumn. A 50- micro L plasma sample was introduced to the ADS precolumn in order to separate the analytes from proteins and endogenous compounds. The fraction containing COC and BZE was back-flushed and transferred to an Alltech mixed-mode C(18)/cation-exchange analytical column for final separation. The validation of the method revealed quantitative recoveries from 95.0 to 99.0% for COC at three different concentrations (0.5, 1.0 and 2.0 micro g mL(-1)), and from 96.0 to 99.0% for BZE at the same concentration levels with coefficients of variation <4.00% (n=5). The detection limit (signal to noise ratio (S/N)>3) was 0.03 micro g mL(-1) for all the compounds with an injection volume of 50 micro L. However, it was possible to enhance the sensitivity further by injecting larger plasma volumes, up to 200 micro L, at the same optimal conditions. The overlap of sample preparation, analysis and reconditioning of the extraction column, increase the overall sample throughput to 5 samples h(-1). The developed method has been applied to human blood plasma samples from subjects suspected of cocaine abuse. 相似文献
178.
Water adsorption and absorption on crystalline polyvinylidene fluoride with 30% trifluoroethylene, P(VDF-TrFE, 70:30), was examined by thermal desorption spectroscopy. Two distinctly different water adsorption sites are identified: one adsorbed species that resembles ice and another species that interacts more strongly with the polymer thin film. The existence of the latter species is consistent with X-ray diffraction studies of water absorbed into the bulk of copolymers of polyvinylidene fluoride with trifluoroethylene crystalline thin films. There are strong steric effects observed in the angle-resolved thermal desorption that may be a result of the large polymer thin film surface dipoles. 相似文献
179.
180.
Summary The colored substance given by nicotine under special oxidizing conditions and subsequent treatment of the resulting product with concentrated sulfuric acid proved to be pyrido-pyrylium sulfate.
Dedicated to ProfessorHans Lieb on occasion of his 70th birthday. Further details of this proof of structure will be published in an appropriate journal on organic chemistry. 相似文献
Zusammenfassung Der Farbstoff, der sich unter speziellen Oxydationsbedingungen und nachfolgender Behandlung des resultierenden Produktes mit konz. Schwefelsäure aus Nikotin bildet, erwies sich als Pyridopyrylium-Sulfat.
Eesumen El colorante formado de nicotina, usando condiciones especiales de oxidación y tratamento con acido sulfurico concentrado del producto resultando, se revela ser el sulfato de un compuesto de tipo pyrido-pyrylium.
Résumé La substance colorée obtenue par oxydation de la nicotine dans des conditions particulières et traitement ultérieur du produit résultant par l'acide sulfurique concentré s'est avérée être le sulfate de pyrido-pyrylium.
Dedicated to ProfessorHans Lieb on occasion of his 70th birthday. Further details of this proof of structure will be published in an appropriate journal on organic chemistry. 相似文献