Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Isolation of lanthanides from spent nuclear fuel by means of high performance ion chromatography (HPIC) prior to mass spectrometric analysis

Pure and complete fractions of neodymium, samarium, europium, gadolinium and dysprosium were isolated by means of high performance ion chromatography, using a cation exchange column and gradient elution with alpha-hydroxyisobutyric acid solutions (α-HIBA). Intermediate precision and robustness of the isolation method was investigated, identifying eluent pH as the most important parameter. Investigation of the elution behaviour of the most important fission and activation products and actinides indicated that preventing the accumulation of cesium on the cation exchange column required further isocratic elution with a higher concentrated α-HIBA solution after elution of the lanthanides. A sample matrix free of carbon was achieved by means of acid digestion, followed by UV photo-oxidation, resulting in samples suitable for mass spectrometric analysis.

     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

Factor probabilistic distance clustering (FPDC): a new clustering method

Factor clustering methods have been developed in recent years thanks to improvements in computational power. These methods perform a linear transformation of data and a clustering of the transformed data, optimizing a common criterion. Probabilistic distance (PD)-clustering is an iterative, distribution free, probabilistic clustering method. Factor PD-clustering (FPDC) is based on PD-clustering and involves a linear transformation of the original variables into a reduced number of orthogonal ones using a common criterion with PD-clustering. This paper demonstrates that Tucker3 decomposition can be used to accomplish this transformation. Factor PD-clustering alternatingly exploits Tucker3 decomposition and PD-clustering on transformed data until convergence is achieved. This method can significantly improve the PD-clustering algorithm performance; large data sets can thus be partitioned into clusters with increasing stability and robustness of the results. Real and simulated data sets are used to compare FPDC with its main competitors, where it performs equally well when clusters are elliptically shaped but outperforms its competitors with non-Gaussian shaped clusters or noisy data.     

Synthesis of Aminopyridines and Aminopyridones by Cobalt‐Catalyzed [2+2+2] Cycloadditions Involving Yne‐Ynamides: Scope,Limitations, and Mechanistic Insights

An in‐depth study of the cobalt‐catalyzed [2+2+2] cycloaddition between yne‐ynamides and nitriles to afford aminopyridines has been carried out. About 30 nitriles exhibiting a broad range of steric demand and electronic properties have been evaluated, some of which open new perspectives in metal‐catalyzed arene formation. In particular, the use of [CpCo(CO)(dmfu)] (dmfu=dimethyl fumarate) as a precatalyst made possible the incorporation of electron‐deficient nitriles into the pyridine core. Modification of the substitution pattern at the yne‐ynamide allows the regioselectivity to be switched toward 3‐ or 4‐aminopyridines. Application of this synthetic methodology to the construction of the aminopyridone framework using a yne‐ynamide and an isocyanate was also briefly examined. DFT computations suggest that 3‐aminopyridines are formed by formal [4+2] cycloaddition between the nitrile and the intermediate cobaltacyclopentadiene, whereas 4‐aminopyridines arise from an insertion pathway.     

Electrochemical determination of traces lead ions using a new nanocomposite of polypyrrole/carbon nanofibers

Journal of Solid State Electrochemistry - In this paper, a new nanocomposite of polypyrrole (PPy) and carbon nanofibers (CNFs)-modified carbon paste electrode (CPE) has been reported for the...