Unraveling the mechanism of catalytic reactions through combined kinetic and thermodynamic analyses: Application to the condensation of ethanol

The combination of kinetic and thermodynamic analyses can provide an in-depth knowledge of the crucial steps of catalyzed reactions. Earlier examples are recalled to stress how a reaction mechanism can be supported or rejected based on trivial reactant and product concentration analyses. The method is then applied to the important reaction of alcohol condensation, the so-called Guerbet reaction, which enables converting ethanol, a renewable feedstock, into higher alcohols. Important conclusions regarding the design of ethanol condensation processes can be drawn, as the main reaction mechanism occurring at high temperatures (ca. 350–420 °C) appears to be different from that proposed at low temperatures (< 250 °C). In the former case, the pathway involving acetaldehyde is negligible, and therefore a multi-step process based on ethanol dehydrogenation followed by acetaldehyde self-aldolization would be irrelevant.     

Validated Stability-Indicating GC-MS Method for Characterization of Forced Degradation Products of Trans-Caffeic Acid and Trans-Ferulic Acid

When dealing with simple phenols such as caffeic acid (CA) and ferulic acid (FA), found in a variety of plants, it is very important to have control over the most important factors that accelerate their degradation reactions. This is the first report in which the stabilities of these two compounds have been systematically tested by exposure to various different factors. Forced degradation studies were performed on pure standards (trans-CA and trans-FA), dissolved in different solvents and exposed to different oxidative, photolytic and thermal stress conditions. Additionally, a rapid, sensitive, and selective stability-indicating gas chromatographic-mass spectrometric method was developed and validated for determination of trans-CA and trans-FA in the presence of their degradation products. Cis-CA and cis-FA were confirmed as the only degradation products in all the experiments performed. All the compounds were perfectly separated by gas chromatography (GC) and identified using mass spectrometry (MS), a method that additionally elucidated their structures. In general, more protic solvents, higher temperatures, UV radiation and longer storage times led to more significant degradation (isomerization) of both trans-isomers. The most progressive isomerization of both compounds (up to 43%) was observed when the polar solutions were exposed to daylight at room temperature for 1 month. The method was validated for linearity, precision as repeatability, limit of detection (LOD) and limit of quantitation (LOQ). The method was confirmed as linear over tested concentration ranges from 1−100 mg L⁻¹ (r²s were above 0.999). The LOD and LOQ for trans-FA were 0.15 mg L⁻¹ and 0.50 mg L⁻¹, respectively. The LOD and LOQ for trans-CA were 0.23 mg L⁻¹ and 0.77 mg L⁻¹, respectively.     

New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

A quantum chemical study on structure of 1,2-bis(diphenylphosphinoyl)ethane and phenol cocrystal

The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol.     

A thermodynamic approach with internal variables using Lagrange formalism. Part I: General framework

We present some reflections on the application of the Lagrangian formalism for continuous media locally uniform subjected to internal irreversible evolutions. The Lagrangian density, defined as the time derivative of a non-equilibrium thermodynamic potential, [Thermodynamics of Relaxation Processes using Internal variables within a Lagrange-formalism. P. Germain’s Anniversary Volume 2000. Contiuum Thermomechanics: the Art and Science of Modeling Matter’s Behaviour, 2000], contains all the symmetry properties of the system. The generalised Lagrange co-ordinates correspond to the state and internal variables of the time derivative of the generalised Gibbs potential. The latter being used within the framework of the De Donder’s method, must also account for the memory effect of the physical medium.This first part is devoted to the thermodynamic framework called the distribution of non-linear relaxations approach (DNLR) developed by C. Cunat on the basis of the generalised Gibbs’ relation.     

Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10^?3 mol L^?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004     

Preparation and characterization of finely dispersed drugs. 5. Ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate

Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica.     

Thermodynamic study of sodium-iron oxides: Part II. Ternary phase diagram of the Na-Fe-O system

Studies on ternary phase diagrams of the Na-Fe-O system have been carried out from the thermodynamic point of view. Thermodynamic data of main ternary Na-Fe oxides Na₄FeO₃(s), Na₃FeO₃(s), Na₅FeO₄(s) and Na₈Fe₂O₇(s) have been assessed. A user database has been created by reviewing literature data together with recent DSC and vapor pressure measurements by the present authors. New ternary phase diagrams of the Na-Fe-O system have been constructed from room temperature to 1000 K. Stable conditions of the ternary oxides at 800 K were presented in predominance diagram as functions of oxygen pressure and sodium pressure.