Direct analysis of reference biofluids by coupled in situ electrodeposition-electrothermal atomic absorption spectrometry

The application of coupled in situ electrodeposition-electrothermal atomic absorption spectrometry (ED-ETAAS) to the determination of Pb in biological standard reference materials is described. In situ electrodeposition at a cell voltage of 3.0 V from 25-μl samples onto electrodeposited Pd is used to quantitatively separate the analyte from blood and urine matrices. With subsequent withdrawal of spent electrolyte, this overcomes the atomisation problems inherent with high salt and organic contents. ED-ETAAS is applied with minimal sample pre-treatment (acidification). The electrolysis process aids decomposition of the organic matrix, and the release of trace elements. Evolution of H₂ at the cathode counters fouling of the Pd modifier surface. The palladium deposit is renewed in situ for each determination. For AMI certified lyophilised blood, diluted 1+3 with 0.1 M HCl (18.1 μg/l Pb), the R.S.D. was 3.0% (peak height; n=5) and the detection limit (3 σ_blank; n=5) was 1.5 μg/l. Results for certified blood samples were AMI 72.3±4.3 μg/l (certified 76.2±7.6 μg/l) and Seronorm 34.2±2.0 μg/l (36±4 μg/l). The result for NIST SRM 2670 normal urine acidified to 1% HNO₃ was 8.1±0.6 μg/l (recommended value 10 μg/l).     

L,L‐Lactide and ε‐Caprolactone Block Copolymers by a ‘Poly(L,L‐lactide) Block First’ Route

L,L ‐lactide (LA) and ε‐caprolactone (CL) block copolymers have been prepared by initiating the poly(ε‐caprolactone) (PCL) block growth with living poly(L,L ‐lactide) (PLA*). In the previous attempts to prepare block copolymers this way only random copolyesters were obtained because the PLA* + CL cross‐propagation rate was lower than that of the PLA–CL* + PLA transesterification. The present paper shows that application of Al‐alkoxide active centers that bear bulky diphenolate ligands results in efficient suppression of the transesterification. Thus, the corresponding well‐defined di‐ and triblock copolymers could be prepared.

     

Optimierung der quantitativen röntgenographischen Phasenanalyse

A new procedure for an absolute quantitative X-ray phase analysis is presented, based on the square programming guaranting optimum analytical results. Theoretical conclusions are illustrated by a practical example.     

Matrices related to interpolatory quadratures

Summary An explicit formula for the coefficients of interpolatory quadratures with knots of arbitrary multiplicity which uses the eigenvectors and principal vectors of certain matrices is derived. The construction and properties of such matrices are discussed, and applications for the evaluation of Gauss and generalized Gauss-Lobatto quadratures are indicated.     

A mathematical model of realistic constitutional chemistry. A synthon approach. I: An algebraic model of a synthon

A mathematical model of a synthon is suggested. The synthon is modelled by a special so-calledS-matrix. The notion of isomeric synthons on the set of atoms A and that of a Family of Isomeric SynthonsFIS (A) is introduced. The chemical reaction is represented by a matrix equation and it is modelled by the so-calledSR-matrix. The notion of the reaction distance (RD) between two isomeric synthons is defined. A mathematical theory of the S andSR-matrices is developed.     

Spectroscopic measurements in nitrogen arcs with respect to local thermodynamic equilibrium

A wall-stabilized nitrogen arc at atmospheric pressure was studied spectroscopically in the current range from 20 to 70 A with the aim of detecting departures from LTE. Measurements of the relative intensity of several N(I) lines showed that the populations of the upper excited states are in equilibrium for currents greater than approx. 25 A. Comparisons of the excitation temperatures obtained from relative intensities with the electron temperature and with the temperature curves calculated for different departures from LTE show that deviations from equilibrium are small at the arc center for electron densities above approx. 4 × 10¹⁶ cm^-3. Deviations between the radial profiles of the electron and excitation temperatures were observed for currents between 35 and 55 A.