Transformation of schiff bases derived from alpha‐naphthaldehyde. Synthesis,spectral data and biological activity of new‐3‐aryl‐2‐(α‐naphtyl)‐4‐thiazolidinones and N‐aryl‐N‐[1‐(α‐naphthyl)but‐3‐enyl]amines

New N‐aryl substituted 2‐(α‐naphthyl)‐4‐thiazolidinones were prepared by the cyclocondensation of α‐mercaptoacetic acid and corresponding N‐(α‐naphthyliden)anilines. The same starting materials were utilized to obtain a new series of N‐aryl‐N‐[1‐(α‐naphthyl)but‐3‐enyl]amines, which was synthesized through an addition of the Grignard reagent (allylmagnesium bromide) to the double bond C?N of the aldimines. The antichagasic and trichomonacidal in vitro activity, as well as, the antifungal and cytotoxic properties of some of these compounds were evaluated.     

Structure, chemical composition, and reactivity correlations during the in situ oxidation of 2-propanol

Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (～1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions.     

Air-water interfacial behavior of linear-dendritic block copolymers containing PEG and azobenzene chromophores

Fabrication of Langmuir films at the air-water interface of four linear-dendritic block copolymers (LDBCs) is described. The LDBCs are composed of a linear hydrophilic chain of poly(ethylene glycol) (PEG) and the first four generations of hydrophobic aliphatic polyester dendrons functionalized at the periphery with cyanoazobenzene chromophores. Langmuir films of the LDBCs, coded as PEG-AZOn (n indicates the number of cyanoazobenzene units at the periphery of the dendritic block), have been characterized by a combination of surface pressure versus area per molecule isotherms, UV-vis reflection spectroscopy and Brewster angle microscopy. The observed PEG-AZOn Langmuir film behavior depends strongly on the hydrophilic/hydrophobic ratio. A typical transition, related to PEG chains desorption from the air-water interface into the water subphase is observed for all the LDBCs, except for PEG-AZO16. In addition, PEG-AZO2 and PEG-AZO4 show a second transition whose nature has been studied in detail. Azobenzene chromophore interactions have been shown to be relevant in the organization of PEG-AZOn (n=4, 8 and 16) Langmuir films. Moreover, for PEG-AZO16 the orientation of the azobenzene units has been determined, revealing the formation of a well organized structure of azobenzene moieties at the air-water interface.     

Sequential stir bar extraction,thermal desorption and retention time locked GC–MS for determination of pesticides in water

A method based on sequential stir bar sorptive extraction followed by automated thermal desorption–GC–MS for the determination of pesticides in underground and superficial water samples has been developed. Retention time locked GC–MS and deconvolution Automated Mass Spectral Deconvolution and Identification System software allows the use of pesticide databases for identification and quantification in routine applications. Quantitation limits and repetitivity using full scan mass spectrometric determination guarantee the applicability of the method, which enables considerable savings to be made in total analysis time, with data processing times of around 2 min/sample.     

Crisis curves in nonlinear business cycles

Intermittent behavior of economic dynamics is studied by a nonlinear model of business cycles when two of its control parameters, amplitude and frequency of a periodic exogenous driving force, are changed. This study points out how similar wanted situations may be reached by changing any of both parameters, and it gives a deeper understanding of what happens in actual economic data when some control parameters are changed at the same time.     

Solid-phase microextraction coupled with high performance liquid chromatography using on-line diode-array and electrochemical detection for the determination of fenitrothion and its main metabolites in environmental water samples

The aim of this study was to develop a methodology for the analysis of the insecticide fenitrothion and its two main environmental metabolites, fenitrooxon and 3-methyl-4-nitrophenol. For this purpose, a solid-phase microextraction (SPME) method coupled to high performance liquid chromatography (LC) was optimized. Two on-line detectors, diode array (DAD) and direct current amperometrical (DCAD) were used in order to determine sensitivity and selectivity. The effects of the extraction parameters, including exposure and desorption time, pH, temperature, salt concentration and desorption mode on the extraction efficiency were studied. A satisfactory reproducibility for extractions from samples at 20 ppb-level with RSD < 12.5% (n = 10) was obtained. The calibration graphs were linear in the range of 10-1000 microg l(-1) and detection limits for the target compounds were between 1.2 and 11.8 microg l(-1) depending on which detector was used. The method was applied for determining fenitrothion and both its metabolites in river waters which run through forest areas near to aerial application of the pesticide.     

Multiple crossed isopolymorphism: two-component systems CCl4 +CBr2Cl2 and CBrCl3 + CBr2Cl2; inference of a metastable rhombohedral phase of CBr2Cl2

The phases diagrams of the two-component systems CCl4 +CBr2Cl2 and CBrCl3 + CBr2Cl2 have been determined by means of X-ray powder diffraction and thermal analysis techniques from the low-temperature ordered phase to the liquid state. The isomorphism relationship between the stable orientationally disordered (OD) face-centered cubic (FCC) phases of CBrCl3 and CBr2Cl2 and the metastable OD FCC phase (monotropic behavior with respect to the OD rhombohedral stable phase) of CCl4 has been put into evidence throughout the continuous evolution of the lattice parameters and the existence of the two-phase equilibrium [FCC + L] for the whole range of composition in both two-component systems. This equilibrium interferes, for the CCl4 +CBr2Cl2 system, with a rhombohedral (R) plus liquid ([R + L]) equilibrium giving rise to a peritectic invariant. In addition, whatever the system, [R + FCC] equilibrium also interferes with the low-temperature equilibria between the low-temperature monoclinic (C2/c) phase and the OD R and FCC phases. In regards to the low-temperature monoclinic phases, isomorphism is evidenced, and by means of Rietveld profile refinement, any ordering of the molecules by varying the fractional occupancy of the halogen sites has been detected. The thermodynamic assessment, conducted by means of the concept of crossed isopolymorphism, coherently reproduces all the involved equilibria and provides a coherent set of data for the thermodynamic properties of nonexperimentally available phase transitions of pure compound CBr2Cl2 which enables us to obtain the topological properties of its pressure-temperature phase diagram and to infer the existence of a high-pressure R phase for such a compound.