Coexistence of Two Thermally Induced Intramolecular Electron Transfer Processes in a Series of Metal Complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2] (M=Co,Fe, and Ni) bearing Non‐Innocent Catechol‐Based Ligands: A Combined Experimental and Theoretical Study

The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)₂], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ^?) or dinegative (Cat‐N‐SQ^2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IET^LM) and ligand‐to‐ligand (IET^LL). IET^LL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes.     

Ferrocenyl-substituted α,β-unsaturated ketones in synthesis of tetrahydropyrimidinones

Ferrocenyltetrahydropyrimidin-2-ones were prepared by reactions of linear and cyclic ,-unsaturated ketones of the ferrocene series with urea in i-PrOH in the presence of t-BuOK. The structures of the compounds prepared were studied by ¹H and ¹³C NMR and IR spectroscopy, and also by single crystal X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1887–1893.Original Russian Text Copyright © 2004 by E. Klimova, Lorez, T. Klimova, Garcia, Hernandez, Ramirez.This revised version was published online in April 2005 with a corrected cover date.     

Rapid and sensitive method for determining free amino acids in honey by gas chromatography with flame ionization or mass spectrometric detection

This paper describes a rapid, sensitive and specific method for determination of free amino acids in honey involving a new reaction of derivatization and gas chromatography (GC) with flame ionization (FID) and mass spectrometric (MS) detection. The method allows the determination of 22 free amino acids in honey samples in a short time: 8 and 5 min for GC-FID and GC-MS, respectively. Quantitation was performed using Norvaline as internal standard, with detection limits ranging between 0.112 and 1.795 mg/L by GC-FID and between 0.001 and 0.291 mg/L by GC-MS in the selected-ion monitoring mode. The method was validated and applied to a set of 74 honey samples belonging to four different botanical origins: eucaliptus, rosemary, orange and heather. The statistical treatment of data shows a correct classification of different origins over 90%.     

Ultra-Shallow Chemical Characterization of Organic Thin Films Deposited by Plasma and Vacuum-Ultraviolet, Using Angle- and Excitation Energy-Resolved XPS

Nitrogen (N)-rich organic thin films were deposited using both low-pressure plasma- and vacuum-ultraviolet-based techniques, from mixtures of ammonia (NH₃) and ethylene (C₂H₄). These films were investigated using angle-resolved and excitation energy resolved X-ray photoelectron spectroscopy (ARXPS and ERXPS, respectively) in order to determine their sub-surface chemical profiles. These two techniques enable one to tune the ??XPS 95%?? information depth, z _95%, by varying either the angle or the excitation energy. Using a combination of both techniques, z _95% can be varied continuously from 0.7 to 11 nm. The surface-near chemistry is investigated using both high-resolution C 1s spectra and elemental concentrations derived from elemental peak intensities. Results show that while laboratory XPS, and even ARXPS, suggest homogenous surface chemistries, the novel combination of ARXPS and ERXPS points to the existence of a compositional profile in the extreme outer surface layer. Our conclusions are supported by simulations using SESSA software.     

Computational study of the thermal decomposition and the thermochemistry of allyl ethers and allyl sulfides

In spite of the several experimental and computational studies on the thermal decomposition of allyl ethers and allyl sulfides, there are still disagreements on aspects of the reaction mechanism, such as the true nature of the transition states and the grade of synchronicity of the reactions. This work presents a computational study of the gas-phase thermolysis reaction of allyl ethers and allyl sulfides substituted at α-carbon, at the M05-2X/6-31+G(d,p) level of theory and a temperature range from 586.15 to 673.15 K. The substituent groups were methyl, ethyl, n-propyl, i-propyl, allyl, benzyl and acetonyl. It was found that the sulfides react faster than the homologous ethers and that the substituent groups with the capacity of delocalize charge increase the reaction rate. Through natural bond orbital calculations, the transition states were characterized. The synchronicities and atomic charges of the studied reactions were determined. A computational study at the G3 level of theory on the thermochemistry of allyl ethers and sulfides was also carried out.     

Localized Orbitals vs. Pseudopotential-Plane Waves Basis Sets: Performances and Accuracy for Molecular Magnetic Systems

 Density functional theory, in combination with a) a careful choice of the exchange-correlation part of the total energy and b) localized basis sets for the electronic orbitals, has become the method of choice for calculating the exchange-couplings in magnetic molecular complexes. Orbital expansion on plane waves can be seen as an alternative basis set especially suited to allow optimization of newly synthesized materials of unknown geometries. However, little is known on the predictive power of this scheme to yield quantitative values for exchange coupling constants J as small as a few hundredths of eV (50–300 cm⁻¹). We have used density functional theory and a plane waves basis set to calculate the exchange couplings J of three homodinuclear Cu-based molecular complexes with experimental values ranging from +40 cm⁻¹ to −300 cm⁻¹. The plane waves basis set proves as accurate as the localized basis set, thereby suggesting that this approach can be reliably employed to predict and rationalize the magnetic properties of molecular-based materials. Corresponding author. E-mail: Carlo.Massobrio@ipcms.u-strasbg.fr Received August 5, 2002; accepted August 9, 2002     

Characterization of a few Mexican clays

The characterization of a few Mexican clays with chemical treatmentfor possible application as catalysers is shown. The natural clays are treatedwith H₂ SO₄ , HF, F₃ CSO₃ H, ClSO₃ H, HClO₄ and their behavior in reactions with some alcoholswas recorded. The analysis were made before and after using the clays as catalysers.The clays were characterized by Mössbauer spectroscopy, X-ray diffraction,X-ray fluorescence analysis, and differential thermo analysis. The predominantmineral species are: montmorillonite, christobalite and quartz. The main elementsare: Si, Al, Fe, Ca, K, etc. The Mössbauer results show mainly a paramagneticdoublet of Fe₃₊ . The clays behave similarly as described in theliterature.     

Solving incomplete inorganic chemical systems through a fuzzy knowledge frame

A model for the completion and balancing of inconsistent inorganic reactions is presented. A series of fuzzy parameters is proposed. These parameters are considered within a knowledge frame representing inorganic reactions via a semantic/functional network and, through the calculation of possibility measures, allow the completion and solution of such reactions by considering new inorganic species to be added to the reaction. Species to be added are formulated on the basis of atoms present and/or absent in the reaction, along with valence, system features, and a series of flags that determines the cardinality of the possible solution set. Incorporation of the proposed model into an inorganic chemistry formulation system would contribute to the development of powerful computer-assisted learning systems, given the extent of information extracted from a reaction.     

Self-assembled films based on polypyrrole and carbon nanotubes composites for the determination of Diuron pesticide

In this work, polypyrrole (PPy) and its respective composite with functionalized multi-walled carbon nanotubes (MWCNT) were obtained by chemical polymerization of the monomer pyrrole in aqueous solution. The obtained PPy as well as its composite (PPy-MWCNT) were characterized by Fourier transform infrared spectroscopy (FTIR) and were used to produce nanostructured self-assembled (SA) films deposited onto glass substrates covered with indium tin oxide (ITO). The SA films were produced with alternated layers of polystyrene sulphonated (PSS) and were characterized by UV-visible, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) analyses. The applicability of the SA films was evaluated by square wave voltammetry (SWV) with standard additions of aliquots of Diuron pesticide in Britton-Robinson buffer solutions (pH = 2.0). The results showed an oxidation peak at 0.23 V which increases in function of the Diuron concentration for both the SA films. It was also observed that the SA film based on the composite (PPy-MWCNT/PSS) showed a peak current intensity about ten times higher in comparison with its unmodified counterpart (PPy/PSS) for a Diuron concentration of 4.29 × 10^?5 mol L^?1, indicating a synergic effect between PPy and MWCNT in the composite. The limits of quantification (LOQ) and limits of detection (LOD) were respectively 8.6 × 10^?7 mol L^?1 and 2.6 × 10^?7 mol L^?1.