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91.
92.
Miguel Guerrero Josefina Pons Mercè Font-Bardia Teresa Calvet Josep Ros 《Journal of chemical crystallography》2011,41(5):721-726
Abstract
The crystal structure of the title compound C22H30N4O2·H2O (L), has been determined using X-ray diffraction at 293 K. The crystal of 1,2-bis[4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-oxobutyl]benzene is in triclinic crystal system with space group P(−1) (Z = 2), lattice parameters a = 8.225(6) ?, b = 10.967(6) ?, c = 12.903(6) ?, V = 1119.1(11) ?3. Analyses of single crystals of L, crystallized from dichloromethane/diethyl ether (1:1), revealed that the molecules are arranged in couples, which adopt a pseudo chair conformation, by means of intermolecular O–H···N hydrogen bonding interactions. Moreover, the extended structure revealed a 1D chain caused by several C–H···N intermolecular interactions. 相似文献93.
Pavithran R Saleesh Kumar NS Biju S Reddy ML Junior SA Freire RO 《Inorganic chemistry》2006,45(5):2184-2192
Three new europium complexes, [Eu(PBI)3.3H2O] (1), [Eu(PBI)3.2TOPO] (2), and [Eu(PBI)3.2TPPO.H2O] (3) (where HPBI, TOPO, and TPPO stand for 3-phenyl-4-benzoyl-5-isoxazolone, tri-n-octylphosphine oxide, and triphenylphosphine oxide, respectively), with different neutral ligands were synthesized and characterized by elemental analysis, Fourier transform infrared, (1)H NMR, thermogravimetric analysis, and photoluminescence (PL) spectroscopy. The coordination geometries of the complexes were calculated using the Sparkle/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes within the Austin Model 1) model. The ligand-Eu3+ energy-transfer rates were calculated in terms of a model of the intramolecular energy-transfer process in lanthanide coordination compounds reported in the literature. The room-temperature PL spectra of the europium(III) complexes are composed of the typical Eu3+ red emission, assigned to transitions between the first excited state (5D0) and the multiplet (7F(0-4)). On the basis of emission spectra and lifetimes of the 5D0-emitting level, the emission quantum efficiency (eta) was determined. The results clearly show that the substitution of water molecules by TOPO leads to greatly enhanced quantum efficiency (i.e., 26% vs 92%) and longer 5D0 lifetimes (250 vs 1160 micros). This can be ascribed to a more efficient ligand-to-metal energy transfer and a less nonradiative 5D0 relaxation process. Judd-Ofelt intensity parameters (Omega2 and Omega4) were determined from the emission spectra for the Eu3+ ion based on the 5D0 --> 7F2 and 5D0 --> 7F4 electronic transitions, respectively, and the 5D0 --> 7F1 magnetic-dipole-allowed transition was taken as the reference. A point to be noted in these results is the relatively high value of the Omega2 intensity parameter for all of the complexes. This may be interpreted as being a consequence of the hypersensitive behavior of the 5D0 --> 7F2 transition. The dynamic coupling mechanism is, therefore, dominant, indicating that the Eu3+ ion is in a highly polarizable chemical environment. 相似文献
94.
Pozo OJ Guerrero C Sancho JV Ibáñez M Pitarch E Hogendoorn E Hernández F 《Journal of chromatography. A》2006,1103(1):83-93
The potential of solid-phase extraction coupled on-line to liquid chromatography/electrospray tandem mass spectrometry (SPE-LC-ESI-MS/MS) has been investigated in this paper for the efficient sensitive quantification and confirmation of 16 antibiotics in water. The list of targeted analytes included 10 quinolones (oxolinic acid (OXO), nalidixic acid (NAL), flumequine (FLU), marbofloxacine (MAR), ofloxacine (OFLO), enrofloxacine (ENR), pefloxacine (PEF), ciprofloxacine (CIP), pipemidic acid (PIPE), norfloxacine (NOR)) and 6 penicillins (penicillin G (PEN), oxacillin (OXA), dicloxacillin (DIC), piperacillin (PIP), cloxacillin (CLO) and ampicillin (AMP)) that were determined in ground and surface water. The procedure is based on the injection of 9.8 mL of sample into the SPE-LC-MS/MS system and the measurement of antibiotics by selected reaction monitoring mode, using a triple quadrupole analyser. The method has been validated at realistic low concentrations that might be present in environmental water, i.e. 10 and 100 ng L(-1), obtaining recoveries between 74% and 123% with relative standard deviation lower than 14%. Matrix effects were not relevant in most of cases, except for ampicillin in surface water, where notable signal suppression was observed. The limits of detection were as low as 0.4-4.3 ng L(-1). The method developed allows the rapid screening and quantification of all the analytes selected by acquiring one MS/MS transition (normally the most sensitive) for each compound. It was applied to a number of actual surface and groundwater samples with several compounds being detected, mainly quinolones, at low ng L(-1) levels. Special attention was given to the confirmation of compounds detected in water due to the difficulties of obtaining confident confirmation at low ng L(-1). This matter has been of growing concern in the last few years as reflected by recent papers and correspondence. The acquisition of several MS/MS transitions for each compound detected in a second independent analysis allowed the unequivocal confirmation of identity, avoiding reporting false-positives. Finally, the potential of QTOF instruments to confirm positive samples has also been evaluated and compared with triple quadrupole analysers. 相似文献
95.
Bernardo?Nu?ez-MoraledaEmail author Joaquin?Pizarro Elisa?Guerrero Maria?P.?Guerrero-Lebrero Andres?Yá?ez Sergio?Ignacio?Molina Pedro?Luis?Galindo 《The European Physical Journal B - Condensed Matter and Complex Systems》2014,87(11):263
In this paper, stress fields at the surface of the capping layer of self-assembled InAsP quantum wires grown on an InP (001) substrate have been determined from atomistic models using molecular dynamics and Stillinger-Weber potentials. To carry out these calculations, the quantum wire compositional distribution was extracted from previous works, where the As and P distributions were determined by electron energy loss spectroscopy and high-resolution aberration-corrected Z-contrast imaging. Preferential sites for the nucleation of wires on the surface of the capping layer were studied and compared with (i) previous simulations using finite element analysis to solve anisotropic elastic theory equations and (ii) experimentally measured locations of stacked wires. Preferential nucleation sites of stacked wires were determined by the maximum stress location at the MD model surface in good agreement with experimental results and those derived from finite element analysis. This indicates that MD simulations based on empirical potentials provide a suitable and flexible tool to study strain dependent atom processes. 相似文献
96.
José Manoel Balthazar Dailhane Grabowski Bassinello Angelo Marcelo Tusset Átila Madureira Bueno Bento Rodrigues de Pontes Junior 《Meccanica》2014,49(8):1859-1867
The electromechanical transducer considered in this work is composed of a mechanical oscillator linked to an electronic circuit. Simulations results have determined that for some combination of parameters the electromechanical system is subject to chaotic motion with resonant transient behavior, and after the resonant transient the mechanical system (MS) synchronizes with the electrical system (ES). In order to improve the transient response, avoiding both the chaotic and resonant behaviors, a nonlinear control system is designed, a feedback control strategy is used to drive the system into the desired periodic orbit, and a nonlinear feedforward strategy is used to keep the system into the periodic orbit, obtained by the Fourier series. Two control techniques are used and compared, namely: the state dependent Ricatti equation and the optimal linear feedback control. Numerical simulations results are shown in order to compare the results, considering parametric uncertainties. Additionally, the energy transfer “pumping” between the ES and the MS is also analysed. 相似文献
97.
A.I. Figueroa J. Bartolomé J.M. García del Pozo A. Arauzo E. Guerrero P. Téllez F. Bartolomé L.M. García 《Journal of magnetism and magnetic materials》2012
A transverse susceptibility (TS) measurement system based on a simple inverter CMOS cell oscillator cross-coupled to a LC tank is presented. The system has been implemented to operate at a Quantum Design Physical Properties Measurement System (PPMS). We introduce several improvements with respect to similar currently operating TS measurement equipments. The electronics have been redesigned to use CMOS transistors as active devices, which simplifies the circuit design and enlarge the tuning range, thus making the proposed electronic block more feasible, predictable, and precise. Additionally, we propose a newly designed sample holder, which facilitates the procedure to change a sample and improves reproducibility of the circuit. Our design minimizes the thermal leak of the measuring probe by one order of magnitude, allowing to measure from 1.8 K in standard PPMS systems, thanks to the use of a low temperature beryllium–copper coaxial cable instead of the conventional RG402 Cu coaxial cable employed in the insert for the PPMS in similar systems. The data acquisition method is also simplified, so that the measuring sequences are implemented directly in the PPMS controller computer by programming them in the Quantum Design MultiVu software that controls the PPMS. We present the test measurements performed on the system without sample to study the background signal and stability of the circuit. Measurements on a Gd2O3 calibrating sample yield to the estimation of the system sensitivity, which is found to be on the order of 10−6 emu. Finally, measurements on a TmCo2 Laves phase sample with a ferrimagnetic transition temperature around 4 K are described, demonstrating that the developed system is well suited to explore interesting magnetic phenomena at this temperature scale. 相似文献
98.
Dávalos JZ Herrero R Chana A Guerrero A Jiménez P Santiuste JM 《The journal of physical chemistry. A》2012,116(9):2261-2267
We have studied the energetics and structural properties of trans-cinnamic acid (CA), o-, m-, and p-coumaric acids (2-, 3-, and 4-hydroxycinnamic acids), caffeic acid (3,4-dihydroxycinnamic acid), ferulic acid (4-hydroxy-3-methoxycinnamic acid), iso-ferulic acid (3-hydroxy-4-methoxycinnamic acid), and sinapic acid (3,5-dimethoxy-4-hydroxycinnamic acid). The experimental values of Δ(f)H(m)°(g), determined (in kJ·mol(-1)) for CA (-229.8 ± 1.9), p-coumaric acid (-408.0 ± 4.4), caffeic acid (-580.0 ± 5.9), and ferulic acid (-566.4 ± 5.7), allowed us to derive Δ(f)H(m)°(g) of o-coumaric acid (-405.6 ± 4.4), m-coumaric acid (-406.4 ± 4.4), iso-ferulic acid (-565.2 ± 5.7), and sinapic acid (-698.8 ± 4.1). From these values and by use of isodesmic/homodesmotic reactions, we studied the energetic effects of π-donor substituents (-OH and -OCH(3)) in cinnamic acid derivatives and in the respective benzene analogues. Our results indicate that the interaction between -OCH(3) and/or -OH groups in hydroxycinnamic acids takes place without significant influence of the propenoic fragment. 相似文献
99.
dos Anjos JV Srivastava RM Costa-Silva JH Scotti L Scotti MT Wanderley AG Leite ES de Melo SJ Mendonça Junior FJ 《Molecules (Basel, Switzerland)》2012,17(1):809-819
In this study, the antinociceptive properties of 3,4-dihydro-2,6-diaryl-4-oxo-pyrimidine-5-carbonitrile derivatives 5a-i at doses of 25 and 50 mg/kg were evaluated in mice, using the abdominal constriction test. Molecular modeling studies were also performed using density functional theory calculations. These data provided information about the electrostatic and ionization potentials and were used to compare the antinociceptive activity of the title compounds. The most active compounds were 3,4-dihydro-2-(4-chlorophenyl)-6-(4-methoxyphenyl)-4-oxo-pyrimidine-5-carbonitrile (5b) and 3,4-dihydro-2,6-diphenyl-4-oxo-pyrimidine-5-carbonitrile (5i), which inhibited the number of abdominal constrictions, at 50 mg/kg dose, in 88.6% and 88% of the sample, respectively. A preliminary SAR study demonstrated that halogen replacement in the phenyl rings of the compounds under study reduces the antinociceptive activity. DFT calculations showed that there is a high correlation between the ionization potentials and the analgesic properties of the compounds. It was found that compounds with a positive ionization potential (compounds 5b and 5i) were found to be the best analgesic drugs in this series. 相似文献
100.
Palimécio G. Guerrero Jr. Paulo R. de OliveiraAdriano C.M. Baroni Francisco A. MarquesRicardo Labes Gabriela R. HurtadoMiguel J. Dabdoub 《Tetrahedron letters》2012,53(39):5302-5305
An efficient and novel total synthesis of the two bioactive retinoids temarotene and arotinoid acid (TTNPB) is described. The key steps in this process include the regio and stereoselective hydrotelluration of thioacetylene 9 and Te/Li transmetalation of mixed (Z)-1,2-bis(organylchalcogene)-1-alkene (Z)-3. The subsequent reaction involving the β-phenylthio vinyl lithiated intermediate 10 with dimethyl sulfate gave the (E)-vinyl sulfide 11. The Ni+2 cross-coupling of 11 with the corresponding phenylzinc bromide and p-oxazoline phenylzinc bromide 12 afforded the respective temarotene 2 and retinoid-oxazoline substituted 13. Finally, compound 13 was deprotected with HCl to furnish arotinoid acid (TTNPB) 1. 相似文献