Fast liquid chromatography-electrochemistry-mass spectrometry of ferrocenecarboxylic acid esters

Rapid liquid chromatographic separations of ferrocenecarboxylic esters of various alcohols and phenols have been achieved on reversed-phase columns of 20 mm length. After separation, the ferrocene derivatives are oxidized electrochemically under formation of the charged ferrocinium species, which are easily detected by mass spectrometry using an atmospheric pressure chemical ionization source operated in the heated nebulizer mode. While a series of nine phenol derivatives was separated within less than 1.5 min, six alcohol derivatives eluted within 1 min. Limits of detection using a single quadrupole mass analyzer ranged from 60 to 190 nmol/l. Additional work was directed on the use of a graphite in-line filter instead of a silica-based reversed-phase column to achieve the separation.     

Wet ashing of coal with perchloric acid mixed with periodic acid for the determination of sulphur and certain other constituents

A method is described for the determination of sulphur and some other inorganic constituents of coal. Organic matter is destroyed by wet combustion with perchloric acid and periodic acid. The method is rapid and efficient. Silica and sulphur are determined gravimetrically, iron, aluminium, vanadium, titanium, phosphorus, and arsenic spectrophotometrically, and calcium and magnesium volumetrically. No loss occurred by volatilisation. The complete analysis scheme devised was applied to a bituminous coal of Iowa origin.     

On the use of a focusing spectrometer with a Cambridge Electron Probe

Summary A focusing X-ray spectrometer has been installed on a Cambridge Electron Probe. Significant improvements in peak intensities, peak to background ratios and resolution were obtained and the quantitative capabilities of the instrument correspondingly enhanced. The difficulties encountered due to increased focusing sensitivity are discussed.

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Zusammenfassung Ein fokussierendes Röntgenstrahlenspektrometer wurde in einem Cambridge-Elektronenstrahlmikroanalysator eingebaut. Damit ergaben sich signifikante Verbesserungen der Peak-Höhen, der Peak-Hintergrundverhältnisse und der Auflösung. Die quantitative Leistung des Instruments wurde damit entsprechend vergrößert. Die sich aus der erhöhten Empfindlichkeit ergebenden Schwierigkeiten wurden diskutiert.

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Résumé On a fixé un spectromètre à rayons X à focalisation une microsonde electronic Cambridge. Des progrès significatifs ont été obtenus en matière de maximums d'intensité, de rapports de pointes à fond et de résolution; les possibilités quantitatives de l'instrument s'en trouvent accrues en conséquence. Les difficultés qui découlent de la délicatesse de focalisation du spectromètre lors de son emploi avec des cristaux de haute résolution sont passées en revue.

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Presented in part at the Second National Conference on Electron Microprobe Analysis, Boston, Mass., June 14–16, 1967.     

The structure of the proton skeleton in 1,3-butadieneiron Tricarbonyl as determined from the NMR spectra of oriented molecules

¹H NMR spectra of 1,3-butadieneiron tricarbonyl oriented in a nematic liquid crystal solvent have been analysed and used to derive the structure of the proton skeleton, which is found to be non-planar. The distance of the anti protons from the plane defined by the remaining four protons is 0.77 ± 0.06 ±.     

Measurement of multiple psi torsion angles in uniformly 13C,15N-labeled alpha-spectrin SH3 domain using 3D 15N-13C-13C-15N MAS dipolar-chemical shift correlation spectroscopy

We demonstrate the simultaneous measurement of several backbone torsion angles psi in the uniformly (13)C,(15)N-labeled alpha-Spectrin SH3 domain using two different 3D 15N-13C-13C-15N dipolar-chemical shift magic-angle spinning (MAS) NMR experiments. The first NCCN experiment utilizes double quantum (DQ) spectroscopy combined with the INADEQUATE type 13C-13C chemical shift correlation. The decay of the DQ coherences formed between 13C'(i) and 13C(alphai) spin pairs is determined by the "correlated" dipolar field due to 15N(i)-13C(alphai) and 13C'(i)-15N(i+1) dipolar couplings and is particularly sensitive to variations of the torsion angle in the regime |psi| > 140 degrees. However, the ability of this experiment to constrain multiple psi-torsion angles is limited by the resolution of the 13C(alpha)-(13)CO correlation spectrum. This problem is partially addressed in the second approach described here, which is an NCOCA NCCN experiment. In this case the resolution is enhanced by the superior spectral dispersion of the 15N resonances present in the 15N(i+1)-13C(alphai) part of the NCOCA chemical shift correlation spectrum. For the case of the 62-residue alpha-spectrin SH3 domain, we determined 13 psi angle constraints with the INADEQUATE NCCN experiment and 22 psi constraints were measured in the NCOCA NCCN experiment.     

Evaluation of sample preparation methods for elastomer digestion for further halogens determination

In this work, three sample preparation methods were evaluated for further halogen determination in elastomers containing high concentrations of carbon black. Samples of nitrile-butadiene rubber, styrene-butadiene rubber, and ethylene-propylene-diene monomer elastomers were decomposed using oxygen flask combustion and microwave-induced combustion (MIC) for further Br and Cl determination by ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma mass spectrometry (ICP-MS). Extraction assisted by microwave radiation in closed vessels was also evaluated using water or alkaline solution. Digestion by MIC was carried out using 50 mmol l⁻¹ (NH₄)₂CO₃ as the absorbing solution. The effect of the reflux step was also evaluated. Accuracy was evaluated using certified reference materials with polymeric matrix composition and by comparison of results using neutron activation analysis. Agreement for Br and Cl was better than 95% by MIC using 5 min of reflux, and no statistical difference was found using IC, ICP OES, and ICP-MS for determination of both analytes. For MIC, the relative standard deviation (RSD) was lower than 5%. Using extraction in closed vessels, a high amount of residues was observed, and recoveries were lower than 45% for both analytes. For oxygen flask combustion, the agreement was similar using MIC but RSD was higher (20%). The residual carbon content, an important parameter used to evaluate the digestion efficiency, was always below 1% for MIC. Using MIC, it was possible to digest elastomers with high efficiency, resulting in a single solution suitable for halogen determination by different techniques.