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991.
Estrader M Ribas J Tangoulis V Solans X Font-Bardía M Maestro M Diaz C 《Inorganic chemistry》2006,45(20):8239-8250
The reaction of Ln(NO3)3.aq with K3[Cr(CN)6] and 2,2'-bipyridine (bpy) in a water/ethanol solution led to two families of complexes: 4 one-dimensional (1D) complexes of the formula trans-[Cr(CN)4(mu-CN)2Ln(H2O)3(bpy)2]n.4nH2O.3.5nbpy (Ln3+ = La, Ce, Pr, and Nd) and 10 1D complexes of the formula trans-[Cr(CN)4(mu-CN)2Ln(H2O)4(bpy)]n.3.5nH2O.1.5nbpy (Ln3+ = Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu). The structures for the fourteen complexes [LaCr]n (1), [CeCr]n (2), [PrCr]n (3), [NdCr]n (4), [NdCr]n (4'), [SmCr]n (5), [EuCr]n (6), [TbCr]n (7), [DyCr]n (8), [HoCr]n (9), [ErCr]n (10), [TmCr]n (11), [YbCr]n (12), and [LuCr]n (13) have been solved. Complexes 1-4 crystallize in the orthorhombic space group Pbam and are isomorphous; complexes 4'-13 crystallize in the triclinic space group PI and are isomorphous. The X-ray structural characterization of complexes 1-4 shows the presence of a discrete decameric water cluster built around a cyclic hexameric core stabilized by the solid-state structure, which represents another new mode of association of water molecules. The Ln3+-Cr3+ magnetic interaction is negligible in 6 and 12, antiferromagnetic in 2, 4', 7, 8, 9, 10, and 11, and unresolved for 3. The complex 5 is a ferrimagnet because its magnetic studies suggest the onset of a very weak ferromagnetic three-dimensional ordering. 相似文献
992.
Sre?ko I. Kirin Xavier de Hatten Thomas Weyhermüller 《Journal of organometallic chemistry》2006,691(16):3451-3457
An experimental and computational study on the conformational preference of 1,n′-disubstituted ferrocenoyl amino acids and dipeptides is presented. Only l-amino acids were used for the synthesis of Fe[C5H4-CO-Met-Met-OMe]2 (4), but according to the X-ray structure a 4:1 mixture of l,d,M,d,l and l,d,M,l,l isomers is obtained (l describes amino acid chirality and M the helical chirality of the ferrocene core). This result is in agreement with IR and CD solution phase data and can be explained with a racemization by 1 M NaOH during the synthesis. In order to determine the relative stabilities of the different conformations, DFT calculations on model compounds Fe[C5H4-CO-Gly-NH2]2 (5) and Fe[C5H4-CO-Ala-OMe]2 (6) were performed using the B3LYP/LanL2DZ method with ECPs on the heavy atoms. Conformers 5A-5C with different hydrogen bond patterns have significantly different stabilities with a stabilization by about 30 kJ mol−1 per hydrogen bond. The “Herrick conformation” 5A with two hydrogen bonds is the most stable in the gas phase, in accordance with the solution and solid phase data. In contrast, only small energetic differences (less than 10 kJ mol−1) were calculated for conformers l,P,l-6A, l,P,d-6A and d,P,d-6A, which differ only in amino acid chirality. 相似文献
993.
A high performance liquid chromatography (HPLC) method has been developed for the simultaneous determination of four fluoroquinolones. The studied compounds have been enoxacin (ENO), norfloxacin (NOR), ofloxacin (OFLO) and enrofloxacin (ENRO). An isocratic elution method, using a mixture of tetrahydrofuran (8%) and phosphate buffer (pH 3.00, 30.0 mM, 92%) as mobile phase, has been developed. Fluorimetric detection, exciting at 277 nm, and multiemission scan (407 nm for ENO, 444 nm for both NOR and ENRO and 490 nm for OFLO) has been used. Detection limits of 500, 14.7, 25.2 and 15.0 ng mL−1 for ENO, NOR, OFLO and ENRO, respectively, have been obtained. The proposed method has been satisfactorily applied to analyze NOR, OFLO and ENRO in human urine and serum samples. 相似文献
994.
A novel one-dimensional coordination polymer made up of Fe(II), 3-cyanopyridine (3CNpy), and the singular in situ formed [Cu(I)(3CNpy)(CN)2]- anionic bridge has been synthesized. This compound undergoes a spin-crossover behavior according to its magnetic and calorimetric properties. The crystal structure of the title compound has been studied in the high- and low-spin states and correlated with the character of the spin conversion. Evidence for intense spin-state-dependent Cu....Cu interactions between the chains is also reported. 相似文献
995.
A novel method of inline coupling of microdialysis (MD) with CE has been investigated. A polysulfone MD membrane was in situ prepared at the inlet end of the separation capillary, which endued the capillary with an additional function of clean-up sampling and made the pretreatment of complex matrices simple. The properties of the membrane and its influence on electrophoresis were evaluated. The membrane cut off macromolecules and particles efficiently and persistently, and changing the components of membrane-casting solution could control the molecular weight cutoff of the membrane. Using the capillary having the MD membrane in electrophoresis, column efficiency with little reduction was achieved. The mixture of chlorpheniramine (CPA) and BSA was used to verify the analytical characteristics. Only the peak of CPA appears in the electropherograms and the RSDs of migration times and peak areas of CPA were 0.8 and 4.6%, respectively. The method was applied for the determination of glucose in human blood using an electrochemical detector. Whole blood containing glucose and macromolecules was electrokinetically injected directly into the capillary without pretreatment, and the concentration of glucose in human blood was 5.5 mmol/L. Equilibrium dialysis injection is also investigated in this paper. The results show that the method may be further used for in vivo sampling to monitor the endogenous or exogenous small molecules and their metabolites. 相似文献
996.
997.
Mercère P Idir M Moreno T Cauchon G Dovillaire G Levecq X Couvet L Bucourt S Zeitoun P 《Optics letters》2006,31(2):199-201
We present what we believe to be the first automatic alignment of a synchrotron beamline by the Hartmann technique. Experiments were performed, in the soft-x-ray range (E=3 keV, lambda=0.414 nm), by using a four-actuator Kirkpatrick-Baez (KB) active optic. A system imaging the KB focal spot and a soft-x-ray Hartmann wavefront sensor were used alternatively to control the KB optic. The beam corrected with the help of the imaging system was used to calibrate the wavefront sensor. With both closed loops, we focused the beam into a 6.8 microm x 9 microm FWHM focal spot. 相似文献
998.
John S. Fletcher Xavier A. Conlan Nicholas P. Lockyer John C. Vickerman 《Applied Surface Science》2006,252(19):6513-6516
Atomic depth profiling using secondary ion mass spectrometry, SIMS, is common in the field micro-electronics; however, the generation of molecular information as a function of sample depth is difficult due to the accumulation of damage both on and beneath the sample surface. The introduction of polyatomic ion beams such as SF5 and C60 have raised the possibility of overcoming this problem as they deposit the majority of their energy in the upper surface of the sample resulting in increased sputter yields but with a complimentary reduction in sub-surface damage accumulation. In this paper we report the depth profile analysis of the bio-polymer polycaprolactone, PCL, using the polyatomic ions and and the monoatomic Au+. Results are compared to recent analysis of a similar sample using . depth profiling of cellulose is also demonstrated, an experiment that has been reported as unsuccessful when attempted with implications for biological analysis are discussed. 相似文献
999.
Effect of an adverse pressure gradient on the streamwise Reynolds stress profile maxima in a turbulent boundary layer 总被引:1,自引:0,他引:1
It is widely accepted that in a turbulent boundary layer (TBL) with adverse pressure gradient (APG) an outer peak usually appears in the profile of streamwise Reynolds stress. However, the effect of APG on this outer peak is not clearly understood. In this paper, the effect of APG is analysed using the numerical and experimental results in the literature. Because the effect of upstream flow is inherent in the TBL, we first analyse this effect in TBLs with zero pressure gradient on flat plates. Under the individual effect of upstream flow, an outer peak already appears in the profile of streamwise Reynolds stress when the TBL continues developing in the streamwise direction. The APG accelerates the appearance of the outer peak, instead of being a trigger. 相似文献
1000.
Emanuela Bianchi Janetti Ishai Dror Monica Riva Alberto Guadagnini Xavier Sanchez-Vila Brian Berkowitz 《Transport in Porous Media》2013,97(3):295-315
We study the mobility and interaction under competing conditions observed for copper ( $\text{ Cu}^{2+}$ ) and zinc ( $\text{ Zn}^{2+}$ ) ions in the context of laboratory-scale experiments performed in natural soil columns. The experiments focus on the analysis of solute breakthrough curves (BTCs) obtained after injection of an aqueous solution containing similar concentrations of the two metal ions into a soil column fully saturated with double deionized water. Transport of the competing ions is tested for the same soil under aerobic and anaerobic conditions. Measurements show that the species with lower affinity for the soil, $\text{ Zn}^{2+}$ , migrates occupying all available adsorption sites, and is then progressively replaced by the ion with higher affinity, $\text{ Cu}^{2+}$ . The two ions are displaced in the system with different effective retardation. The slowest species replaces the sorbed ions, resulting in observed $\text{ Zn}^{2+}$ concentrations that display a non-monotonic behavior in time and which, for a certain period, are larger than the concentration supplied continuously at the inlet. In the absence of a complete geochemical characterization of the system, we show that the measured concentrations of both metals can be interpreted through simple models based on a set of coupled partial differential and algebraic equations, involving a small subset of aqueous and adsorbed species that are present in the system. Depending on the model considered, the relationship between aqueous and adsorbed ion concentrations is described at equilibrium by a Gaines–Thomas (GT) formulation, a competitive Sheindorf–Rebhun–Sheintuch (SRS) isotherm, or an Extended Langmuir (EL) isotherm, respectively. The GT formulation provides the best interpretation of the observed behavior among the models tested. We find that employing these simple models, which account only for the main governing reactive processes, allows reasonable estimation of the observed BTCs in experiments where only partial geochemical datasets are available. 相似文献