Metrological traceability in laboratory medicine

 The establishment of a reference examination system necessary for metrological traceability of the many types of sophisticated examination result in laboratory medicine is a daunting task, which has been made mandatory by the EU Directive on in vitro diagnostic medical devices and the requirements for accreditation. Following a definition of examinand and allowed examination uncertainty, a dedicated calibration hierarchy is established from stated reference through alternating reference examination procedures and calibrators providing a traceability chain from examination result to the reference, often a definition of a measurement unit. The various types of possible calibration hierarchy are outlined in EN ISO Standards. Recent efforts by national and international stakeholders to establish a global reference examination system have led to the creation of a Joint Committee on Traceability in Laboratory Medicine with the International Committee for Weights and Measures, International Bureau of Weights and Measures, International Federation of Clinical Chemistry and Laboratory Medicine, International Laboratory Accreditation Cooperation, and World Health Organization as the principal promoters. This structure will identify reference procedures, reference materials, and reference laboratories, and seek support for further prioritised and coordinated development of the system. Received: 1 August 2002 Accepted: 22 November 2002 Based on a lecture at an IUPAC Seminar, EC JRC Institute for Reference Materials and Measurements, Geel, BE, 2001–12–18 Correspondence to R. Dybkaer     

The relation between structure and reactivity in five-membered heteroaromatic compounds—I: Effect of assumed molecular geometry on CNDO/2 electron distribution for some tetrazole derivatives

Two parallel sets of CNDO/2 calculations have been carried out for 1H-5-aminotetrazole (1), 2-methyl-5-aminotetrazole (2), 1,3-dimethyl-5-aminotetrazolium cation (3) and the tetrazolate anion (4). In one set, the molecular geometry was represented by a regular pentagon 1·33 Å on a side, and in the other the experimentally determined molecular geometries were used. The calculated electronic structures from the two sets of calculations are compared; both sets predict similar trends in variation of atomic charges and bond indices with structure. Where comparison is possible, these trends seem to be generally in agreement with expectations based on classical concepts such as resonance. It is noted that the relative magnitudes of σ-electron bond indices seem to parallel those of the π-electron bond indices in many cases, although the σ-bond indices show much smaller variation in absolute magnitude as compared with the π-bond indices. A brief discussion of the relative merits of various geometrical models is presented; it is suggested that, in order to combine the advantages of both approaches, standard and experimentally-determined geometries should be used side-by-side whenever possible. A procedure for speeding convergence by use of a damping factor is described.     

The photodissociative ionization of amorphous ice

Within the energy range 17 hv < 35 eV, the ionic species desorbed and their excitation spectra are reported. The only positive ion desorbed is H⁺. A model for the surface is suggested which explains the absence of OH⁺ desorption. The desorption mechanisms are discussed in terms of an energy analysis.     

Use of ir and 13c-nmr data in the retrieval of functional groups for computer-aided structure determination

Computer-aided interpretation of ¹³C-n.m.r. and i.r. spectra of organic molecules (m.w. ? 500) is done by an artificial intelligence approach. The output of the proposed ASSIGNER system is a list of functional groups which are reasonable candidates for the final structural isomers. The procedure of finding possible functional groups and the main features of the filtering steps are outlined. One search is worked out in detail to demonstrate the capability of the system.     

Efficiency control in large-scale genotyping using analysis of variance

The efficiency of the genotyping process is determined by many simultaneous factors. In actual genotyping, a production run is often preceded by small-scale experiments to find optimal conditions. We propose to use statistical analysis of production run data as well, to gain insight into factors important for the outcome of genotyping. As an example, we show that analysis of variance (ANOVA) applied to the first-pass results of a genetic study reveals important determinants of genotyping success. The largest factor limiting genotyping appeared to be interindividual variation among DNA samples, explaining 20% of the variance, and a smaller reaction volume, sizing failure, and differences among markers all explained ∼10%. Other potentially important factors, such as sample position within the plate and reusing electrophoresis matrix, appeared to be of minor influence. About 55% of the total variance could be explained by systematic factors. These results show that ANOVA can provide valuable feedback to improve genotyping efficiency. We propose to adjust genotype production runs using principles of experimental design in order to maximize genotyping efficiency at little additional cost.     

Flavonoids from Tephrosia—VII : The constitution and absolute configuration of lupinifolin and lupinifolinol,two flavanones from Tephrosia lupinifolia Burch (DC)

The structure and absolute configuration of lupinifolin, (2S) - 4′,5 - dihydroxy - 8 - (3? - methyl - 2? - butenyl) - 2″, 2″ - dimethylpyrano[5″.6″ - g]flavanone, and lupinifolinol, (2R,3R) - 8 - (3? - methyl - 2? - butenyl) - 3,4′,5 - trihydroxy - 2″,2″ - dimethylpyrano[5″.6″ - g]flavanone, have been deduced from spectroscopic and chemical evidence.     

Magnetic properties of iron-intercalated titanium diselenide

Powder samples of Fe_xTiSe₂ (0.00 ≤ x ≤ 0.50) have been prepared by direct reaction of high purity elements. Crystal parameters were determined by the Debye-Scherrer powder diffraction technique. Magnetic susceptibility measurements were made by the Faraday method in the temperature range 1.5–300 K and indicated magnetic odering for compositions with x > 0.03. The magnetic ordering temperature, T_m, was observed to move to higher temperature with increasing iron concentration. These results have been interpreted in terms of a spin-glass model for low iron concentrations (x < 0.2) and antiferromagnetism for high concentrations (x > 0.2).     

Twenty years of the Me.Tos. Project: an Italian national external quality assessment scheme for trace elements in biological fluids

The Me.Tos. Project, started in 1983 and still running, is an external quality assessment (EQA) scheme for laboratories performing specialized analyses in occupational and environmental laboratory medicine. Besides the organization of EQA exercises, initiatives for further education of the participants and the harmonization of EQA procedures at a European level are carried out. Participation in EQA schemes allows laboratories to comply with the international standards for the quality and competence of testing and clinical laboratories. The organization of the scheme includes the preparation of control materials, their distribution to the participants, according to strategies aimed to avoid identification of the samples, the statistical analysis of the results and the evaluation of laboratories' performance according to international guidelines and criteria set by the organizers. An overview of the scheme operation and the current performances of participants will be given.     

Vibrattonal excitation of molecules by collisions with “hot” hydrogen atoms from laser photolysis

Excimer laser (ArF) photolysis of diatomic and triatomic hydrides produces hydrogen atoms with translational energies in excess of 15000 cm^?1 per atom. Subsequent collisions of these “hot” atoms with CO₂ and N₂O produces vibrationally excited molecules which can be detected by their characteristic infrared emission.