Revisiting differential calculus in the light of an uncanny function

A metric jet can be linear without being the metric jet of a continuous linear map. We begin with giving such an amazing example and then we get interested in tangentiable maps whose tangent jet at a point is precisely a linear metric jet. For such maps, a local inversion theorem is still true.     

1,2,5,6-Tetrakis(guanidino)-Naphthalenes: Electron Donors,Fluorescent Probes and Redox-Active Ligands

New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps.     

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays.     

Inter-laboratory exercise with an aim to compare methods for 90Sr and 239,240Pu determination in environmental soil samples

In order to deliver reliable results for a multitude of different scenarios, e.g. emergency preparedness, environmental monitoring, nuclear decommissioning and waste management, there is a constant process of method development in the field of radioanalytical chemistry. This work presents the results of a method comparison exercise aimed at quantifying ⁹⁰Sr and ^239,240Pu in environmental soil samples, with the intention of evaluating the performance and applicability of different methods. From the methods examined in this work, recommendations are given in order to find a radioanalytical measurement procedure, for ⁹⁰Sr and ^239,240Pu analysis, which is fit-for-purpose for a particular scenario.

     

Comparison of direct mass spectrometry methods for the on‐line analysis of volatile compounds in foods

For the on‐line monitoring of flavour compound release, atmospheric pressure chemical ionization (APCI) and proton transfer reaction (PTR) combined to mass spectrometry (MS) are the most often used ionization technologies. APCI‐MS was questioned for the quantification of volatiles in complex mixtures, but direct comparisons of APCI and PTR techniques applied on the same samples remain scarce. The aim of this work was to compare the potentialities of both techniques for the study of in vitro and in vivo flavour release. Aroma release from flavoured aqueous solutions (in vitro measurements in Teflon bags and glass vials) or flavoured candies (in vivo measurements on six panellists) was studied using APCI‐ and PTR‐MS. Very similar results were obtained with both techniques. Their sensitivities, expressed as limit of detection of 2,5‐dimethylpyrazine, were found equivalent at 12 ng/l air. Analyses of Teflon bag headspace revealed a poor repeatability and important ionization competitions with both APCI‐ and PTR‐MS, particularly between an ester and a secondary alcohol. These phenomena were attributed to dependency on moisture content, gas/liquid volume ratio, proton affinities and product ion distribution, together with inherent drawbacks of Teflon bags (adsorption, condensation of water and polar molecules). Concerning the analyses of vial headspace and in vivo analyses, similar results were obtained with both techniques, revealing no competition phenomena. This study highlighted the equivalent performances of APCI‐MS and PTR‐MS for in vitro and in vivo flavour release investigations and provided useful data on the problematic use of sample bags for headspace analyses. Copyright © 2013 John Wiley & Sons, Ltd.     

Estimation of the surface sulfur content of cellulose nanocrystals prepared by sulfuric acid hydrolysis

The conditions required for the accurate measurement of the sulfur content of cellulose nanocrystals (CNCs) by conductometric titration are discussed. CNCs from sulfuric acid hydrolysis are electrostatically stabilized in aqueous suspension due to the introduction of charged sulfate ester groups onto the surface of the crystallites during reaction. The sulfur content thus largely reflects the surface charge of the crystals, and is crucial to the characterization and understanding of material properties. Conductometric titration is commonly used to quantify the sulfur content of CNCs, however, the exhaustive removal of free acid by dialysis and the necessity, type, quantity and duration of ion-exchange resin treatments are not always consistent. Here we explore the standard conditions of dialysis, ion-exchange, and the reproducibility of titration results. Extensive dialysis is found to be effective in the removal of free acid, but similar results are also achieved in shorter times and with less water using membrane ultrafiltration. It is also shown that the conditions of ion-exchange most commonly employed in the literature can lead to inaccurate sulfur contents. Finally, good agreement is obtained between the sulfur contents of different CNC batches prepared using the same hydrolysis conditions, and from titration and elemental analysis when thoroughly purified, well-dispersed samples, and appropriate resin conditions are used.