Thermal behaviour of some dibenzobicyclo[2.2.2]octane derivatives

A number of dibenzobicyclo[2.2.2]octane derivatives have been studied due to the interest of such compounds as ligands for coordination compounds with potential biological activity. Their thermal behaviour has been analyzed in order to find out more information about their fragmentation. A connection between the bridge substituents and the fragmentation process has been observed.     

Amine oxidase amperometric biosensor coupled to liquid chromatography for biogenic amines determination

A selective and sensitive method is presented for biogenic amines (BA) determination. The novelty consists in coupling a highly selective electrochemical biosensor to a weak acid cation-exchange column for online detection of amines. A bienzyme design, based on a recently isolated amine oxidase from grass pea and commercial horseradish peroxidase, was used for the biosensor construction. The enzymes were co-immobilized on the surface of a graphite electrode together with the electrochemical mediator (Os-redox polymer). The electrochemical detection was performed at a low applied potential (?50 mV vs. Ag/AgCl, KCl_0.1 M), where biases from interferences are minimal. The separation and determination of six BA, with relevance in food analysis (tyramine, putrescine, cadaverine, histamine, agmatine and spermidine), were investigated. Irrespective of the BA nature, the amine oxidase-based biosensor showed a linear response up to 5 mM, and its sensitivity decreases in the following order: cadaverine, putrescine, spermidine, agmatine, histamine and tyramine. The approach was used to estimate the BA content in fish samples, after their extraction with methanesulfonic acid.     

Assessment of collagen-based materials which are supports of cultural and historical objects

The thermal degradation of collagen-based materials, viz. collagen, recently manufactured parchments and tanned leathers, a heritage parchment and patrimonial (historical) leathers, was investigated by thermal analysis methods. With progressive heating, all these materials exhibit three main successive processes, associated with dehydration, protein denaturation and pyrolysis/oxidation. The analysis of both denaturation and thermo-oxidation revealed significant differences between aged leather, collagen, recently manufactured parchments and tanned leathers in terms of the number of overlapping processes (reflected in the number of peaks recorded at denaturation) and of the oxidative degradation rates, given by the normalised curves of differential thermal gravimetry (DTG). The various observations are proposed as qualitative indices for assessing the age and storage conditions of leather. A three-phase model was used for explaining the results. This consists of crystalline collagen filaments that are embedded in an amorphous matrix with an interface zone between the crystalline and amorphous regions. Solid-state ¹H NMR investigations corroborate the thermal analysis results and enhance the understanding of the ageing processes.     

Metal-Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S-Oxides

Benzothiophenes, activated by oxidation to the corresponding S-oxides, undergo C−H/C−H-type coupling with phenols to give C4 arylation products. While an electron-withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π-complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron-rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal-free arylation process.     

Mechanistically inspired design of Fe(III)-TAML peroxide-activating catalysts

Recent broad-ranging mechanistic studies of FeIII-TAML peroxide activators enable a strategy for designing catalysts with improved (i) hydrolytic and (ii) operational stabilities, (iii) faster activation of H2O2 and other peroxides, and (iv) a pH of highest activity closer to 7. Combining all items of insight leads to [Fe{1-NO2C6H3-3,4-(NCOCMe2NCO)2CF2}(OH2)]- (1a) which exhibits the most desirable technical performance in its class.     

Precision of Raman depolarization and optical attenuation measurements of sound tooth enamel

The demineralization of enamel that is associated with early caries formation affects the optical properties of the enamel. Polarized Raman spectroscopy and optical coherence tomography have been used to detect these changes and potentially offer a means to detect and monitor early caries development. The total optical attenuation coefficient as measured by optical coherence tomography and the polarization anisotropy of the Raman peak arising from the symmetric ν₁ vibration of at approximately 959 cm⁻¹ have been demonstrated as being sensitive markers of early caries. This ex vivo study on extracted human teeth demonstrates that these measurements can be made with reasonable precision with concomitantly good repeatability and reproducibility in sound enamel. Such reliability is crucial for these techniques to have a practical clinical value.     

Per-O-methylation of neutral carbohydrates directly from aqueous samples for gas chromatography and mass spectrometry analysis

Per-O-methylation of neutral carbohydrates in one step by adding dimethyl sulfoxide, powdered sodium hydroxide, and methyl iodide directly to aqueous sample is described. The influence of the water on the methylation reaction is investigated. Solid powdered sodium hydroxide is very hygroscopic and can scavenge the water from sample if an additional excess of sodium hydroxide is added. The degree of per-O-methylation of carbohydrates is checked by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Gas chromatography-mass spectrometry analysis of mono- and disaccharides from grape juice is presented.     

Economic Cycles of Carnot Type

Originally, the Carnot cycle was a theoretical thermodynamic cycle that provided an upper limit on the efficiency that any classical thermodynamic engine can achieve during the conversion of heat into work, or conversely, the efficiency of a refrigeration system in creating a temperature difference by the application of work to the system. The first aim of this paper is to introduce and study the economic Carnot cycles concerning Roegenian economics, using our thermodynamic–economic dictionary. These cycles are described in both a Q−P diagram and a E−I diagram. An economic Carnot cycle has a maximum efficiency for a reversible economic “engine”. Three problems together with their solutions clarify the meaning of the economic Carnot cycle, in our context. Then we transform the ideal gas theory into the ideal income theory. The second aim is to analyze the economic Van der Waals equation, showing that the diffeomorphic-invariant information about the Van der Waals surface can be obtained by examining a cuspidal potential.     

Tight and Scalable Side-Channel Attack Evaluations through Asymptotically Optimal Massey-like Inequalities on Guessing Entropy

The bounds presented at CHES 2017 based on Massey’s guessing entropy represent the most scalable side-channel security evaluation method to date. In this paper, we present an improvement of this method, by determining the asymptotically optimal Massey-like inequality and then further refining it for finite support distributions. The impact of these results is highlighted for side-channel attack evaluations, demonstrating the improvements over the CHES 2017 bounds.     

Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL

The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed.