Calibration of laser-ablation ICP-MS. Can we use synthetic standards with pneumatic nebulization?

An approach for the determination of trace element concentrations in high purity metals, using an inductively coupled plasma mass spectrometer (ICP-MS) with a laser-ablation system for direct solid sample introduction after calibration with nebulized liquid standards was made. Due to the inherent differences in the rate of sample introduction with laser-ablation and pneumatic nebulization, a matrix element must be used as an internal standard. This is problematical for elements that have no isotope with a relative abundance of less than 0.1 %, since the ion signals would be too high for direct measurement, and reduction of the ablation rate would compromise the sensitivity for trace elements. Due to the high stability of ICP-unit and mass filter of the instrument used, it was found that the tail of a mass-peak of the matrix element could be used as an internal standard. Therefore, a position at –0.5 amu from the matrix-isotope (e.g. ^62.5Cu in copper samples) was used for internal standardization. The standard deviation of this signal in a period of 2.5 h was 3.6% RSD with no notable drift when the laser ablation was used for sample introduction. The calibration of the matrix-element by nebulizing liquid standards showed that the ion signal measured on the peak-tail is directly proportional to the element concentration in the ICP. This indicates that the peak shape is not only stable, but also independent of the peak height. The advantages of this method lie in the easy preparation of calibration standards for quantitative measurements with a laser-ablation system and access to homogeneous standards for materials, that are difficult to homogenize in the solid state. The calibration of the traces is performed relatively to a fixed concentration of the matrix element. Calibrations were carried out for trace concentrations in high purity copper and good recoveries were obtained for high-purity reference standards. Received: 23 February 1998 / Revised: 20 July 1998 / Accepted: 25 July 1998     

Aminocarbonylthioformiate – Darstellung und Reaktionen

Aminocarbonylthioformates — Preparation and Reactivity Sodium aminocarbonylthioformate NaSCOCONH₂ (II) is obtained by reaction of sodium cyanodithioformate with acetone in presence of a secondary amine and water. II permits to produce the acid HSCOCONH₂ · H₂O (IX) and salts M^II(SCOCONH₂)₂ · 2H₂O. In basic aqueous solutions hydrolysis of II to oxaminate and oxalate, respectively, takes place, an excess of aqueous ammonia leads to amidino formic acid. In organic solvents the reaction of IX with N-bases yields stable ammonium salts. The results of i.r. spectroscopic and thermogravimetric measurements are discussed.     

Two new flavonoids from Andrographis rothii

Two new flavonoids, 5, 7, 2', 5'-tetramethoxyflavanone (1) and 5-hydroxy-7, 2'-dimethoxyflavone (2), together with two known flavones, skullcapflavone I (3) and echioidin (4) were isolated from the whole plant of Andrographis rothii. The structures of the new compounds were established by extensive one- and two-dimensional (1D- and 2D-) NMR spectral studies.     

Acyclic stereoselection—13 : Aryl esters: reagents for threo-aldolization

Preformed Li enolates of hindered aryl esters condense with aldehydes to give predominantly threo aldols. The method has been explored with esters 3 (DMP propionate), 4 (BHT propionate), and 5 (DBHA propionate). DMP propionate reacts with benzaldehyde and α-unbranched aliphatic aldehydes to give threo:erythro ratios of about 6.5:1. However, with α-branched aliphatic aldehydes, ester 3 gives only threo-aldols. BHT propionate and DBHA propionate give only threo-aldols with all aldehydes studied. The DMP aldols may be converted into β-hydroxy acids by simple hydrolysis with KOH in aqueous methanol. BHT aldols cannot be hydrolyzed without retroaldolization. However, these aldols can be reduced to diastereomerically pure 1,3-diols. The DBHA aldols can be converted into β-hydroxy acids by a method involving oxidation with ceric ammonium nitrate (CAN) in aqueous acetonitrile. Threo-selectivity is also seen in the condensations of DMP butyrate (15), DBHA butyrate (16), DMP pentenoate (17), and BHT pentenoate (18). The approach has been utilized in a stereoselective synthesis of racemic methyl corynomycolate (30).     

Rotational cooling of Li 2 ( 1 S g + ) molecules by ultracold collisions with a helium gas buffer

The very weak interaction of Li₂ with He atoms has been obtained from accurate ab initio calculations and is here analyzed in terms of its anisotropic features. Quantum scattering calculations of the rotational inelastic de-excitation cross sections are carried out using a recently proposed multichannel treatment, the modified variable phase method, implemented by the authors and applied here to ultralow collision energies. General conclusions on the low efficiency of a He buffer gas in cooling down molecular rotations in this system are presented and analyzed.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail.This work is affectionately dedicated to Prof. Jean-Louis Rivail on the occasion of his university retirement. We wish our friend many more happy years of research and the continued opportunity of guiding young scientists.