Determination of molecular weight distributions of novolac resins by gel permeation chromatography

The number- and weight-average molecular weights of several statistical and high ortho novolac resins were determined using gel permeation chromatography (GPC). The standards used were pure compounds having between 2 and 12 phenol units bridged via methylene linkages. Three series of compounds were studied: (i) those with methylene linkages substituted in only the ortho positions relative to the phenolic hydroxyl group; (ii) those in which all para positions, together with sufficient ortho positions, were used to synthesize the compounds; and (iii) those in which the methylene linkages were substituted at a mixture of ortho and para positions. Such compounds, having known molecular architecture and units similar to the segments of industrial novolac resins, provide for a more exact measurement of the molecular weight than do the commonly used poly(styrene) standards. Using these new standards the number average molecular weights of the resins determined by GPC were in good agreement with the average molecular weight obtained by ¹H-NMR spectra of the resins, particularly for low molecular weight resins. GPC analysis of higher molecular weight resins tends to underestimate the molecular weights because of complications introduced by hydrogen bonding. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1399–1407, 1997     

Accreditation system for reference material producers and certified reference materials for iron and steel in Japan

  ISO 9000 series strictly requires traceability to national or international measurement standards. It is becoming more necessary to make clear the concept of traceability of measurement standards with respect to chemical composition and to accredit the reference material producers. In Japan, the accreditation system for reference material producers is considered to satisfy the requirement of ISO Guide 34, ISO 9000 series and ISO/IEC Guide 25, while the producer fulfills the concept of traceability of measurement standards. This paper describes the production of iron and steel reference materials in Japan relating to the international standardization of methods (written standards) and accreditation of reference material producers. Received: 11 October 1996 Accepted: 5 December 1996     

Implementation of Statistical Process Control for Proteomic Experiments Via LC MS/MS

Statistical process control (SPC) is a robust set of tools that aids in the visualization, detection, and identification of assignable causes of variation in any process that creates products, services, or information. A tool has been developed termed Statistical Process Control in Proteomics (SProCoP) which implements aspects of SPC (e.g., control charts and Pareto analysis) into the Skyline proteomics software. It monitors five quality control metrics in a shotgun or targeted proteomic workflow. None of these metrics require peptide identification. The source code, written in the R statistical language, runs directly from the Skyline interface, which supports the use of raw data files from several of the mass spectrometry vendors. It provides real time evaluation of the chromatographic performance (e.g., retention time reproducibility, peak asymmetry, and resolution), and mass spectrometric performance (targeted peptide ion intensity and mass measurement accuracy for high resolving power instruments) via control charts. Thresholds are experiment- and instrument-specific and are determined empirically from user-defined quality control standards that enable the separation of random noise and systematic error. Finally, Pareto analysis provides a summary of performance metrics and guides the user to metrics with high variance. The utility of these charts to evaluate proteomic experiments is illustrated in two case studies.

The Japanese traceability system and the role of uncertainty evaluation in measurement

 The new traceability system of measurement standards based on the Japanese Measurement Law has been established since November 1993. Some reference materials such as metal standard solutions, pH standard solutions and standard gas mixtures are included in the system together with relevant physical quantities. In this system, primary measurement standard instruments or primary reference materials are designated by the regulation for each quantity. For the practical dissemination of each quantity, accreditation of calibration bodies is recognized by the steering committee under the supervision of the government. In the course of assessment of a candidate calibration body, the concepts of ISO/IEC Guide 25 and ISO/IEC Guide 58 are effectively introduced. For the estimation of reliability, the concept of how to introduce the statistical approach is effectively considered. The method of uncertainty evaluation described in the ISO document entitled "Guide to the expression of uncertainty in measurement" is adopted.     

Understanding the meaning of accuracy,trueness and precision

Clear definitions of basic terms, used to describe the quality of measurements, is essential for communication among scientists as well as when reporting measurement results to clients. Even if appropriate definitions are given in international standards and guidelines, the understanding of some basic terms sometimes proves difficult. The reasons for this are various, e.g., the same words being defined rather differently in encyclopaedias and in international standards as well as concepts, well established in some languages, that may be relatively new in other national communities and at large in the international one. Here we present a matrix intended to clarify the relationships between the type of error affecting an analytical measurement, the respective qualitative concepts (performance characteristics) and their quantitative expression.

Integration of metrological principles in a proficiency-testing scheme in the field of water analysis

Measurement traceability is universally recognised as one of the basic prerequisites for comparability of results obtained in different laboratories and is a basic aspect of metrological sciences such as analytical chemistry. This requirement is underscored by the increasing adoption of standards and measurement quality systems, such as laboratory accreditation against ISO/IEC 17025. Testing laboratories ensure traceability of their measurement results by using appropriate reference standards for calibration of instruments and control of measurement processes. For routine work in the field of water analysis, these standards are usually commercial solutions or in-house solutions prepared from pure products. Therefore, laboratories should demonstrate that their use of reference standards is appropriate and sufficient, which can be done by participation in an appropriate proficiency-testing scheme. The paper reports how measurement traceability of results from field laboratories (nitrite nitrogen, nitrate nitrogen, chloride and sulphate; all in water) can be demonstrated by participation in a proficiency-testing scheme based on reference values.     

Detection limits and quantitation limits in the view of international harmonization and the consequences for analytical laboratories

 In the literature and in daily work there exist many different models to describe detection limits and quantitation limits in the chemical measurement process (CMP). It is still an open question whether the evaluation of detection and quantitation limits should be an one-off process carried out during the validation of a CMP, or whether it should be a continuous process. Because of these reasons many laboratories have difficulties to interprete such values. It is necessary that the official standardization bodies should do some efforts in the international harmonization of the special standards concerning detection and quantitation limits. Received: 3 November 1997 · Accepted: 25 January 1998     

Metrology in laboratory medicine – Reference measurement systems

 The medical laboratory must provide results of measurements that are comparable over space and time in order to aid medical diagnosis and therapy. Thus, metrological traceability, preferably to the SI, is necessary. The task is formidable due to the many disciplines involved, the high production rate, short request-to-report time, small sample volumes, microheterogeneity of many analytes, and complex matrices. The prerequisite reference measurement systems include definition of measurand, unit of measurement (when applicable), consecutive levels of measurement procedures and calibrators in a calibration hierarchy, international organizations, reference measurement laboratories, dedicated manufacturers, written standards and guides for the medical laboratory, production of reference materials, internal and external quality control schemes, and increasingly accreditation. The present availability of reference measurement procedures and primary calibrators is shown to be insufficient to obtain international comparability of all types of quantity in laboratory medicine. Received: 19 April 2000 / Accepted: 3 July 2000     

Clinical reference materials for the validation of the performance of photometric systems used for clinical analyses

 There are a wide variety of spectrophotometric devices nowadays used in health services with various qualities of manufacture methods of measurement and metrological characteristics for performing the necessary measurements. Therefore, to meet the accuracy and repeatability requirements needed in medical diagnosis and treatment, the validation of the performance of such systems by clinical chemistry laboratories is essential. However, the validation of a spectrophotometric system for clinical analyses requires several reference materials, according to the end use of the measurement results. This paper discusses some characteristics required of the clinical reference materials needed and used by Romanian Institute of Metrology for validation work. Types of clinical reference materials developed in the national area for this purpose are also presented. Received: 23 April 1997 · Accepted: 7 July 1997     

Rapid and simultaneous determination of U,F, Al,Ca and V in phosphate rocks by a combination of delayed neutron and γ-ray spectrometry techniques

Delayed neutron counting for uranium assay was coupled with -ray spectrometry in order to measure radionuclides of F, Al, Ca and V produced by neutron activation. For this measurement, the delay time required for U determination was exploited. Calibration of the method was provided by standards based on a CaCO₃ matrix and validity of results was verified against other analytical methods. A single sample can be analyzed for the five elements in 3 min with a precision of ±10%. The method developed was applied in the exploration of phosphate ores. The measured total concentrations permitted the disclosure of correlations between various elements and constituents in the samples. Chemical and mineralogical properties were obtained as well.     

Optimized Gaussian basis sets for use with relativistic effective (core) potentials: K,Ca, Ga—Kr

Correlation-consistent valence basis sets were developed for the third-row main block elements (K, Ca, Ga—Kr) for use with relativistic effective core potentials. These basis sets are somewhat larger than double-zeta in size, with polarization functions, and are balanced for use in both Hartree–Fock and correlation calculations. Spin–orbit splittings for atoms and molecules are calculated and compared to experiment. These calculations use the approximate spin–orbit operator from the relativistic effective core potentials. The use of these results in the calculation of accurate thermochemical data is discussed. © 1997 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Computation of general multipole moment expansions for N atoms by MAPLE

A program written in the MAPLE symbolic computational language was written to compute analytic and numerical expressions for the long-range multipole moment expansion of the electrostatic (Coulombic) perturbation operator for a system of N atoms in arbitrary orientations in space. These expressions are written in terms of the multipole moment operators on individual interacting atoms. The program was tested on a system consisting of a ground-state hydrogen atom interacting with two protons in three different configurations, and the results were found to be in agreement with manual calculations. This approach can produce, with relative ease, the long-range multipole expansion for systems with large numbers of interacting atoms or ions. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 62 : 343–351, 1997     

On practical metrology and chemical analysis: legal,institutional and technical evolutions in the Australian national measurement system

 Economic and technological change, regional and international trade and the globalisation of industry have led to intense pressures for improvements to analytical quality, reliability and comparability. Of central importance are national traceability structures connecting chemical measurements in the field with internationally accepted measurement units and their practical realisations. Australia has a developed physical and engineering measurement system, a legislative framework for analytical traceability and, in the National Association of Testing Authorities, a recognised laboratory accreditation system. The need has been identified to develop the technical capability to perform matrix-independent reference measurements for the certification of traceable reference materials, useable as practical analytical etalons to establish metrological control systems in field measurements for amounts of substance. Recently, a unique collaborative consortium has proposed a National Analytical Reference Laboratory (NARL). The NARL is designed to be a metrological mass spectrometry facility for the transference of measurement units to more widely useable chemical measurement standards and reference materials. Received: 10 October 1995 Accepted: 26 October 1995     

Quality assurance system for a decomposition method as demonstrated for the Wickbold combustion technique

 A five-step model for a quality assurance system is developed for an internal quality control check. It includes the quality control of the decomposition method and the detection method as steps belonging together. The Wickbold combustion technique as decomposition method in combination with atomic absorption spectrometry was chosen. The vaporization of the elements mercury, arsenic, lead, antimony and selenium is based on combustion in an oxyhydrogen flame. To check the efficiency of the analytical system, the uncertainty of results was calculated on the basis of the "Guide to the Expression of Uncertainty in Measurement". Received: 13 January 1997 · Accepted: 29 March 1997     

A Web-Based Molecular-Level Inquiry Laboratory Activity

This paper presents a new computer-based atomic level simulation of an ideal gas. The simulation is written in Java and is accessed by students through a Web browser. This software is used in conjunction with a written laboratory experiment developed within the framework of an inquiry instructional strategy. This molecular-level laboratory experiment is used in combination with a parallel macroscopic laboratory experiment. We hypothesize that students exposed to these kinds of parallel activities will be better able to link the macroscopic, microscopic, and symbolic understanding of chemical concepts.Presented at the ACS Division of Chemical Education sponsored symposium on web-assisted learning in chemistry at its 221st national meeting in San Diego, CA April 1–5, 2001.     

The application of the measurement uncertainty concept to in-process control in pharmaceutical development

 Any analytical data is used to provide information about a sample. The "possible error" of the measurement can be of extreme importance in order to have complete information. The measurement uncertainty concept is a way to achieve quantitative information about this "possible error" using an estimation procedure. On the basis of the analytical result, the chemist makes a decision on the next step of the development process. If the uncertainty is unknown, the information is not complete; therefore this decision might be impossible. The major problem for the in-process control (IPC) procedure is that not only the repeatability but also the intermediate precision (which expresses the variations within laboratories related to different days, different analysts, different equipment, etc.) has to be good enough to make a decision. Unfortunately, the statistical information achieved from one single analytical run only gives information about the repeatability. This paper shows that the estimation of the measurement uncertainty for IPC is a way to solve the problem and gives the necessary information about the quality of the procedure. An example demonstrates that an estimate of uncertainty based on the standard deviations of an analytical method gives a value similar to one based on the standard deviations obtained from a control chart. Therefore, the estimation is both a very useful and also a very cost-effective tool. Though measurement uncertainty cannot replace validation in general, it is a viable alternative to validation for all methods that will never be used routinely. Received: 24 May 1996 Accepted: 10 August 1996     

Determination of copper, lead, cadmium, zinc, and iron in calcium fluoride and other fluoride-containing samples by means of direct solid sampling GF-AAS

Direct solid sampling graphite furnace AAS (SS-GF-AAS) provides an advantageous alternative to the conventional AAS which requires wet digestion of the samples. This method is suitable for trace element determination in calcium fluoride and other fluoride-containing samples. Matrix effects were studied by using calibration standards, certified reference materials with different matrices and by means of three-dimensional calibration. 3D calibration is suitable for selection of calibration samples for more reliable analyses. Cu, Pb, Cd, Zn, and Fe were determined by means of calibration with variation of sample weight using certified reference materials and suitable fluoride-containing calibration samples. Received: 25 July 1997 / Revised: 15 December 1997 / Accepted: 20 December 1997     

Determination of copper, lead, cadmium, zinc, and iron in calcium fluoride and other fluoride-containing samples by means of direct solid sampling GF-AAS

Direct solid sampling graphite furnace AAS (SS-GF-AAS) provides an advantageous alternative to the conventional AAS which requires wet digestion of the samples. This method is suitable for trace element determination in calcium fluoride and other fluoride-containing samples. Matrix effects were studied by using calibration standards, certified reference materials with different matrices and by means of three-dimensional calibration. 3D calibration is suitable for selection of calibration samples for more reliable analyses. Cu, Pb, Cd, Zn, and Fe were determined by means of calibration with variation of sample weight using certified reference materials and suitable fluoride-containing calibration samples. Received: 25 July 1997 / Revised: 15 December 1997 / Accepted: 20 December 1997     

Determination of titanium and zirconium wear debris in blood serum by means of HNO3/HF pressurized digestion using ICP – optical emission spectrometry

A ‘one bottle’ method to determine particulate debris of titanium and zirconium in blood serum was developed. Inductively coupled plasma – optical emission spectrometry (ICP-OES) was used to simultaneously detect both elements at concentrations above 50 ng/mL. Pressurized digestion by means of nitric and hydrofluoric acid in PTFE^TM-containers in a specific time-heat-pressure protocol apparatus was applied to assure complete solvation of particles including oxides. Total decomposition of the matrix was achieved and reasonable detection limits were accomplished. The amount of remaining carbon did not cause any matrix problems during measurement. Received: 10 October 1997 / Revised: 5 December 1997 / Accepted: 9 December 1997