Spin Density Distribution in 2,4,6-Triphenylphenoxyl

The distribution of the unpaired electron over the oxygen and the 24 carbon atoms in the free 2,4,6-triphenylphenoxy radical was determined by electron spin resonance spectroscopy and quantum-mechanical approximation methods. The hyperfine splitting was evaluated with the aid of the spectra of triphenylphenoxyls deuterated in some or all of the substituent phenyl groups. The results of the quantum-mechanical approximations were checked by recording the ESR spectra of triphenylphenoxyls labeled with ¹³C in positions 1,2,3, or 4 of the central ring. The spin density distribution permits a first discussion of the ¹⁷O-coupling constants of correspondingly labeled triphenylphenoxyl and other organic free radicals.     

Vergleichende atomabsorptionsspektrometrische untersuchungen zur elementspurenbestimmung in Urin

When using a direct determination procedure with graphite-furnace a.a.s. (e.t.a.a.s.), it is sufficient to make an addition of nitric acid in order to arrive at the optimal reduction of the spectral background. A “matrix modifier” (NH₄NO₃, (NH₄)₂HPO₄) produces a background which often cannot be compensated completely. Detection limits of the direct determination technique are: Cd 0.1, Co 8, Cu 4, Ni 5, Pb 2 and Tl 3 (μg l^?1). A similar power of detection can be achieved as with flame-a.a.s. due to a preceding preconcentration step (trace adsorption on highly dispersed silicic acid). After preconcentration and determination with e.t.a.a.s., the detection limits are: Cd 0.002, Co 0.1, Cu 0.05, Ni 0.09, Pb 0.09 and Tl 0.06 (μg l^?1). The trace concentrations in urine of healthy persons were found to be: Cd 0.2–0.8, Co ? 0.1, Cu 4–10, Ni 1–3, Pb 6–10 and Tl 0.7–1.3 (μg l^?1). Direct e.t.-a.a.s. is, therefore, found to be suitable for the determination of Cd, Cu and Pb. For the determination of Co, Ni and Tl concentrations, a preconcentration is required. Cobalt was not found in any of the urine samples at the limit of detection of 0.1 μg l^?1.     

Determination of Cd and Pb at microg/L levels by HHPN-beam injection flame furnace-AAS

Flame-heated tubes are widespread in flame-AAS, mainly for the determination of hydride-forming elements. Instead of the introduction of gaseous compounds liquids can also be introduced continuously in such an absorption cell. With the aid of an HPLC pump the liquid is forced through a very fine nozzle, generating an aerosol beam less than 0.5 mm in diameter. This beam travels a distance of 10cm as a "free-flying aerosol jet" into the sample introduction hole of a metal tube furnace placed in the flame. Both introduction of the entire sample and the long residence time lead to a considerable improvement in power of detection. The detection limit for 100 microL samples amounts to 7 microg/L (Pb) and to 0.2 microg/L (Cd), which means an increase in power of detection of between one and two orders of magnitude compared to conventional flame-AAS. The relative standard deviation (100 microL sample volume, N = 10) was found to be 1.3% (signal area) for 600 microg/L Pb and to be 1.5% (signal-area) for 15 microg/L Cd. RSD values from measurements in peak-height amounted to 2.2% (Pb) and to 1.7% (Cd).     

A contribution to the trace analysis of high-purity iron by atomic spectrometry (flame-AAS, furnace-AAS, ICP-OES)

Summary Various possibilities for the determination of trace impurities in high-purity iron by atomic spectrometry were investigated in detail. For Ba, Bi, Cd, Co, Cr, Cu, Mn, Ni, Pb, Ti and V, flame AAS, furnace AAS and ICP-OES were firstly evaluated in terms of their power of detection. Detection limits in the g/g-range could be achieved by direct determination. For determination in the ng/g-range a removal of iron by a solvent extraction technique prior to the instrumental measurement was required. The power of detection of direct determination, and of combined procedures were compared with regard to routine applicability and a minimization of systematic errors.     

Flame AAS/flame AES for trace determination in fresh and used lubricating oils with sample introduction by hydraulic high-pressure nebulization

In hydraulic high-pressure nebulization (HHPN) an aerosol is produced by means of an HPLC-pump and a special nebulization nozzle, applying a pressure of about 200 bar. This spray technique has been employed for sample introduction of mineral oil samples in flame atomic absorption/flame emission spectrometry. The determination of the trace elements Al, Cr, Cu, Fe, K, Na, Ni, Pb, Si and V has been investigated. Viscosity hardly acts upon the sensitivity of the determination, thereby avoiding a time consuming dilution of oil samples. By means of two interconnecting sampling valves a calibration method based on the standard addition technique can be performed which is both simple and easy to carry out. In samples of used oils, results for Cu and Pb equalled those of XRF-analysis. Regarding Fe traces, data obtained from AAS and XRF measurement correlate. In comparison with sample uptake by pneumatic nebulization, which is restricted to diluted oil samples, detection limits decrease by a factor of 2 to 4, indicating the dilution required in pneumatic nebulization.     

Comparison of quantitative methods for analysis of polyphasic pharmaceuticals

Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important the purity of standards and their proper storage, what is a challenge for metastable forms. Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry. The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add confidence in the analytical results.     

Thermal synthesis of the optical pure pentapeptide derivative Z-(L)-Ala-(L)-Phe-Gly-(L)-Phe-Gly-OMe

The pentapeptide Z-(L)-Ala-(L)-Phe-Gly-(L)-Phe-Gly-OMe was obtained by reacting the activated dipeptide derivative Z-(L)-Ala-(L)-Phe-OPcp with the amino peptide derivative TFA·H-Gly-(L)-Phe-Gly-OMe at 100–105°C under reduced pressure (10^?2-10-^?3 Torr) without using solvents. The product obtained by bulk condensation showed no racemization, whereas the product obtained by a matrix mediated condensation contained 5,5 % diastereomer Z-(L)-Ala-(D)-Phe-Gly-(L)-Phe-Gly-OMe. Separation of diastereomers was achieved by HPLC on a silicagel column.