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161.
Manuela Martín‐Zarco Santiago Toribio Joaquín C. García‐Martínez Julián Rodríguez‐López 《Journal of polymer science. Part A, Polymer chemistry》2009,47(23):6409-6419
A series of polyamido amine (PAMAM) dendrimers (Generations 2, 3, 4, and 6) fully functionalized at their periphery with first‐ and second‐generation poly (phenylenevinylene) (PPV) dendrons have been efficiently prepared. MALDI‐TOF mass spectrometry proved to be particularly useful for the characterization of the new hybrid dendrimers as well as for the estimation of the average number of PPV dendrons attached to the surface. The optical absorption and emission properties of these systems were studied. The materials display extremely high molar extinction coefficients and emit blue light with only slightly lower fluorescence quantum yields than the corresponding free dendrons. Self‐quenching interactions between PPV units were not observed in THF. However, the luminescence properties underwent a dramatic change when toluene was used as the solvent. The lower polarity of toluene caused shrinkage of the PAMAM structure and brought the PPV chromophores closer together, leading to self‐quenching interactions and excimer formation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6409–6419, 2009 相似文献
162.
Reyes Malavé Osuna Rocio Ponce Ortiz Mari Carmen Ruiz Delgado Valentin G Nenajdenko Viktor V Sumerin Elizabeth S Balenkova Víctor Hernández Juan Teodomiro López Navarrete 《Chemphyschem》2007,8(5):745-750
Herein, we study the conjugation properties of three different thienoacenes, each of which has three or four fused thiophene rings, by means of Fourier transform Raman spectroscopy. The B3LYP/6-31G** vibrational analysis of all of the collected spectroscopic data evidences that the selective enhancement of a limited number of Raman scatterings is related to the occurrence in the three thienoacenes of a vibronic coupling between the lowest unoccupied frontier molecular orbital (LUMO) and some Raman-active skeletal nu(C==C) stretching modes of 1600-1300 cm(-1). 相似文献
163.
Parvaneh Dastoorani Malek Taher Maghsoodlou Mohammad A. Khalilzadeh Santiago García‐Granda Laura Torre‐Fernndez Evan Sarina 《Heteroatom Chemistry》2016,27(2):102-107
An efficient, simple, and diastereoselective synthesis of novel benzofuran phosphonato ester derivatives has been achieved via a one‐pot three‐component reaction of euparin as a natural product, trialkyl phosphate, and dimethyl acetylenedicarboxylate (DMAD) in diethyl ether without using any catalyst at room temperature. NMR spectroscopic data and X‐ray crystallography analysis are in agreement with the anti arrangement for the two vicinal protons in the structures, and only one diastereoisomer (2S,3R) or (2R,3S) was obtained for the products. The advantage of our research is that this is the first report for the diastereoselective synthesis of phosphonato ester derivatives from a green natural product. This one‐pot reaction occurs in high yields with easy work‐up under mild conditions. All pure products were obtained by recrystallization from ethanol, and there was no need for column chromatography. 相似文献
164.
An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF
Monica Nardi Natividad Herrera Cano Antonio De Nino Maria Luisa Di Gioia Loredana Maiuolo Manuela Oliverio Ana Santiago Diletta Sorrentino Antonio Procopio 《Tetrahedron letters》2017,58(18):1721-1726
Er(OTf)3 in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles.The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-d-glucal and different nucleophiles affording good results in a short time. 相似文献
165.
Dario Delgado Manickam Minakshi Dong-Jin Kim Chung Kyeong W 《Analytical letters》2017,50(15):2386-2401
The influence of oxides in the hydrogen evolution on Raney nickel electrocatalysts was characterized by electrochemical impedance measurements. In addition, these materials show competitive overpotentials for hydrogen evolution with a modified Watts bath as a binder for the Raney nickel. The optimum result was ?190?mV of overpotential at 100?mA?cm?2. Oxygen in the Raney Ni catalyst affects its electroactivity toward hydrogen evolution. The source of oxygen is related to the presence of chloride ions in the modified Watts bath. A Watts bath binds Raney Ni particles to the surface of the catalysts and chloride regulates the oxygen content in the nickel binder during electrodeposition. High oxygen content increases the hydrogen evolution overpotential of the electrode. The electroactivity of the synthesized porous coatings was evaluated by polarization curves and impedance plots. In addition, surface characterization by X-ray diffraction, field emission–scanning electron microscopy equipped with energy-dispersive analysis, and X-ray photoelectron spectroscopy is reported. 相似文献
166.
In this work, new UNIQUAC structural parameters r and q for the ionic liquids were determined by quantum chemistry calculations performed with the Gaussian 03 and GAMESS 7.1 packages, including the density functional theory (DFT) for the optimization of the structures and the polarizable continuum method (PCM) for the calculation of molecular areas and volumes. Data liquid–liquid equilibrium (LLE) of 41 ternary systems involving 15 different ionic liquids, comprising 379 experimental tie-lines, was correlated by the UNIQUAC model for the activity coefficient. The results, expressed by deviations between experimental and calculated compositions, are very satisfactory, with deviation values about 1.93%. 相似文献
167.
Ternary liquid–liquid equilibria (LLE) data in systems involving ionic liquids has been investigated by several years, mainly due to the innovative role of ionic liquids as extraction solvents. The thermodynamic modeling of these systems has been performed almost invariably with the well-known NRTL model. In recent years, the UNIQUAC model has also been used, with structural parameters for ionic liquids determined either by empirical correlations or, more recently, through quantum mechanics calculations. In this work, the structural group volume and area parameters for the group-contribution UNIFAC method have been calculated for six ionic liquids following the quantum mechanics approach. The Density Functional Theory (DFT) was used to optimize the molecular geometry and the Polarizable Continuum Method (PCM) was used to calculate the area and volume. The obtained parameters were used to correlate LLE data for twenty-four ternary systems, totalizing 169 tie-lines. New interaction parameters were also estimated between the solvent and ionic liquid functional groups. The results are very satisfactory, with root mean square deviations between experimental and calculated compositions about 1.6%. 相似文献
168.
Ignacio Alfonso Dr. Miriam Bru Dr. M. Isabel Burguete Dr. Eduardo García‐Verdugo Dr. Santiago V. Luis Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(4):1246-1255
The self‐assembling abilities of several pseudopeptidic macrocycles have been thoroughly studied both in the solid (SEM, TEM, FTIR) and in solution (NMR, UV, CD, FTIR) states. Detailed microscopy revealed large differences in the morphology of the self‐assembling micro/nanostructures depending on the macrocyclic chemical structures. Self‐assembly was triggered by the presence of additional methylene groups or by changing from para to meta geometry of the aromatic phenylene backbone moiety. More interestingly, the nature of the side chain also plays a fundamental role in some of the obtained nanostructures, thus producing structures from long fibers to hollow spheres. These nanostructures were obtained in different solvents and on different surfaces, thus implying that the chemical information for the self‐assembly is contained in the molecular structure. Dilution NMR studies (chemical shift and self‐diffusion rates) suggest the formation of incipient aggregates in solution by a combination of hydrogen‐bonding and π–π interactions, thus implicating amide and aryl groups, respectively. Electronic spectroscopy further supports the π–π interactions because the compounds that lead to fibers show large hypochromic shifts in the UV spectra. Moreover, the fiber‐forming macrocycles also showed a more intense CD signature. The hydrogen‐bonding interactions within the nanostructures were also characterized by attenuated total‐reflectance FTIR spectroscopy, which allowed us to monitor the complete transition from the solution to the dried nanostructure. Overall, we concluded that the self‐assembly of this family of pseudopeptidic macrocycles is dictated by a synergic action of hydrogen‐bonding and π–π interactions. The feasibility and geometrical disposition of these interactions finally render a hierarchical organization, which has been rationalized with a proposal of a model. The understanding of the process at the molecular level has allowed us to prepare hybrid soft materials. 相似文献
169.
Roman N. Naumov Artem V. Kozlov Santiago Gómez-Ruiz Evamarie Hey-Hawkins Andrey A. Karasik 《Tetrahedron letters》2010,51(7):1034-1037
The rac stereoisomer of a novel cryptand containing two bridgehead nitrogen and four asymmetric phosphorus atoms in the 16-membered core cycle was obtained stereoselectively via the reaction of bis(mesitylphosphino)propane, formaldehyde, and meta-xylylenediamine in the course of a covalent self-assembly process. 相似文献
170.
Víctor Delgado 《Journal of mathematical chemistry》2010,48(4):1001-1009
When a chemical sample composed of N elements is analyzed using sequential selective excitation by a tunable polyenergetic
X-ray beam and selective measurement of the characteristic X-rays, the production of secondary fluorescence does not interfere
with the measurements. This experimental situation leads to a particular case of the Sherman equations which can be written
as a set of non-linear equations. The same kind of equations are also obtained when we excite a chemical sample with a polyenergetic
X-ray beam and neglect the production of secondary fluorescence. This set of equations can be regarded as a non-linear eigenvalue
problem. A non-linear extension of the Perron Frobenious theorem ensures that there is one and only one physically acceptable
solution, and also leads to a method to obtaining it. The propagation off measurements errors of sample fluorescence to errors
in the calculated sample concentrations, has been simulated, and the results show that the solution is well conditioned. The
case of production of secondary fluorescence can not be treated, in general, as a nonlinear Perron eigenvalue problem, but
it has been shown that it is rather plausible that Sherman equations corresponding to the actual chemical elements and that
include the production of secondary fluorescence have one and only one physically acceptable solution. An exhaustive search
could elucitate the existence and unicity of solutions for the equations corresponding to the actual chemical elements. 相似文献