Twenty five years of reference material activity at Agriculture and Agri-Food Canada

In the mid 1970s, the available RMs, notably Bowen’s Kale and Orchard Leaves and Bovine liver from National Bureau of Standards (NBS), although of great benefit, were overwhelmingly insufficiently representative, in respect of matrix and elemental composition, of the wide range of natural products submitted for analysis and in worldwide commerce. To provide additional coverage, an RM development project was initiated with input from cooperating analysts leading to an Agriculture and Agri-Food Canada/National Institute of Standards and Technology (NIST) cooperative venture and development of a total of 12 different agricultural/food RMs. With a total of 303 concentration values for 34 elements and a wide range of matrix components such as ash, silica, protein, fat, carbohydrate and fiber, these RMs significantly augment the world repertoire of biological control materials. A final material under consideration is a highly reliable, discrete, synthetic RM for quality control and calibration. This paper summarizes the research and developmental activities undertaken during the past quarter of a century related to RM development at Agriculture and Agri-Food Canada and includes a short historical background, conceptual considerations, preparation, physical characterization, homogeneity estimation, chemical characterization, calculation of recommended reference values and associated uncertainties, methodology development and application, and performance of inorganic analytical methods in a multielement, multilaboratory, collaborative characterization campaign.     

Twenty years of gibberellin research

This review covers research into the chemistry and biology of the gibberellin family of plant bioregulators carried out in the author's laboratory over the past 20 years and has 231 references.     

Polyfluorenes: Twenty years of progress

Polyfluorenes are an important class of electroactive and photoactive materials. In the last three years this research field has literally exploded because of polyfluorenes' exceptional electrooptical properties for applications in light‐emitting diodes. This is the only family of conjugated polymers that emit colors spanning the entire visible range with high efficiency and low operating voltage. Other unusual optical and electrical properties are made possible with polyfluorene derivatives, such as thermochromism and conducting base‐doped polyelectrolytes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2867–2873, 2001     

Development of a potential reference material for evaluating antioxidant activity

Phenolic phytochemical are known to perform several functions ranging from phytoprotectants, to protecting lipids in food products, to antioxidant activity in animals and humans. The need for a common standard mixture containing multiple phenolic phytochemicals is critical for the development of a robust validation assay for accurately quantifying antioxidant activity in various matrixes. Different research groups have used A wide array of single purified reference phenolic compounds in this regard. A 5 compound mixture (caffeic acid, morin hydrate, hesperetin, catechin hydrate, and epigallocatechin gallate) containing phenolic compounds from 4 subgroups (phenolic acid, flavone, flavanone, and flavan-3-ol) was prepared. The mixture was assayed for stability evaluation by high-performance liquid chromatography (HPLC) using a diode array detection procedure for a 3 month time interval. HPLC analysis confirmed that there was no significant interaction between different components of the mixture. The among-sample relative standard deviation (RSD) of all 5 phenolic compounds, as well as the total HPLC area, was < 1%. The RSD due to instrument variation was < 2% and the total RSD among-days was < 5%. These results unambiguously suggest that the sample was stable for a 3 month time interval in an amber vial stored in a refrigerator below 5 degrees C. This mixture is currently being used for the single-laboratory validation study for the assay of total phenolic content by the Folin-Ciocalteu method and the antioxidant capacity by oxygen radical absorbing capacity procedure.     

Uncertainty of measurement. Twenty years afterwards

The application of the concept "uncertainty" causes considerable difficulties. In this paper an analysis of the intrinsic contradictions of the concept itself and its relationship with the statements of metrology is given with the aim of establishing possible reasons for these difficulties. As a result of this analysis several examples are presented to demonstrate the conflicts of the concept and its several statements in the general fundamental notions of metrology.     

Uncertainty of measurement. Twenty years afterwards

The application of the concept “uncertainty” causes considerable difficulties. In this paper an analysis of the intrinsic contradictions of the concept itself and its relationship with the statements of metrology is given with the aim of establishing possible reasons for these difficulties. As a result of this analysis several examples are presented to demonstrate the conflicts of the concept and its several statements in the general fundamental notions of metrology. Received: 16 February 2001 / Revised: 2 April 2001 / Accepted: 9 April 2001     

Production of reference material

Summary Carbon has been determined in the certified reference sample Euro CRM Pure Iron 097-1 to 3.98 g C/g (R = 0.15 at P = 95%) by combustion of the sample portion with subsequent indication of the CO₂ by coulometry. A calibration material based on primary sources of carbon was used with a sufficient small interval of uncertainty of the accuracy and an adequate weighing system. The blank could be kept sufficiently small with a fraction of 23% of the total analytical signal. The surface carbon of the 097-1 was determined to approximately 50% of the total carbon. This result of total carbon is considerably lower than the values in the certificate reading up to 20 g/g. This reflects the strong tendency to too high values in the certificates of reference steels with contents of carbon up to 100 g/g. Examples are given.

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Herstellung von Referenzmaterial — Bestimmung von Kohle in Stählen und reinem Eisen im Bereich von 1–100 g/g mit primärer Kalibrierung

     

Biosensors in Russia: Twenty years of research

The main achievements of Russian researchers in the field of biosensors from 1991 till nowadays are considered. The biosensors are classified according to the nature of the biochemical component. The most important reviews of Russian scientists devoted to enzyme, microbe, immune, and DNA-sensors are revised together with the most interesting results acquired within the field.     

Production of certified reference material

Summary Carbon has been determined in 31 European reference steels in the range of 11–2561 g/g C, using an absolute calibration method.High-purity calcium carbonate was used as the calibration material and weighing was carried out by means of a balance with extremely small weighing error. Both synthetic calibration samples and test samples were processed alternatingly under identical conditions, and the analyses were completed in the shortest possible time.In 28 of the cases examined, results were lower than the certificate values, by an average of 27 g/g. The interval of uncertainty of the accuracy was 6 g/g (probability 99%).

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Herstellung zertifizierter ReferenzmaterialienGenaue Bestimmung von Kohlenstoff in Stählen im Bereich von 11–2561g/g

Zusammenfassung Die Kohlenstoffgehalte von 31 europäischen zertifizierten Referenzstählen im Arbeitsbereich von 11–2561 g/g Kohlenstoff wurden durch absolute Eichung überprüft.Die hinreichende Reinheit des Eichmittels Calciumcarbonat wurde sichergestellt und ein Wägesystem mit einem hinreichend kleinen Wägefehler benutzt.Das gleiche Verhalten von synthetischen Eichproben und Analysenproben im Analysenprozeß wurde hergestellt und beide Probearten wechselweise unter konstanten Systembedingungen innerhalb kürzester Zeitspanne untersucht. In 28 der untersuchten Fällen wurden im Mittel um 27 ppm tiefere Werte gefunden als in den Zertifikaten angegeben. Das Unsicherheitsintervall der Richtigkeit der gefundenen Werte lag mit einer Wahrscheinlichkeit von 99% im Mittel bei 6 g/g.

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Abbreviations CRM Certified reference material - ppm g/g The author thanks Mr. E. Weichert for his excellent direction of the practical work.     

Accreditation of reference material producers

 The use of reference materials is the most pragmatic means by which the analyst can achieve comparability of data. Reference material producers therefore need to have adequate quality systems in place for ensuring the reliability of their materials. In order to provide guidance to both producers and assessors, ISO Guide 34 has recently been produced detailing the quality system requirements for the production of reference materials. CITAC, REMCO and ILAC are now collaborating in the revision of this guide to produce a free-standing document detailing the general requirements for the competence of reference material producers. This paper discusses some of the more important issues described in these documents. The possible formation of an international register containing details of a reference material producer's quality system status is also discussed.     

Production of standard reference material

Summary Deviations were reproduced repeatedly between certified and observed low phosphorus values in commercial standard reference steel samples when being analyzed thoroughly by photometry of the yellow phosphorus vanadato molybdenum complex after extraction by methyl isobutyl ketone. The values observed were by 14 ppm (min 2, max 26) lower as certified. The accuracy of these results on a choice of those samples was achieved and proved by primary calibration with pure substances with an interval of uncertainty of only 1.4ppm (95% confidence interval). As demonstrated this fact demands imparatively the documented application of primary calibration substances and suitable calibration methods when standard reference material is produced.

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Zur Herstellung von StandardreferenzmaterialÜberprüfung des Phosphorgehaltes in Standardreferenzstählen im Bereich von 59–125 ppm P durch Primäreichung

Zusammenfassung Aufgrund von wiederholten und reproduzierbaren Abweichungen zwischen den Soll- und Ist-Gehalten niedriger Phosphorwerte in käuflichen Standardreferenzstählen wurde eine Auswahl dieser Proben sorgfältig durch Photometrie des gelben Phosphorvanadatomolybdänkomplexes nach MIBK-Extraktion untersucht. Die Richtigkeit der Ergebnisse, die etwa 14 ppm (min. 2, max. 26) unter den Angaben der Zertifikate liegen, wurde durch Primäreichung mit Reinsubstanzen mit einem Unsicherheitsbereich von nur 1,4 ppm (P=95%) nachgewiesen. Dieser Sachverhalt legt, wie gezeigt wird, die dokumentierte Anwendung von primären Eichsubstanzen und geeigneten Eichmethoden bei der Untersuchung künftiger Standardreferenzproben zwingend nahe.

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The author thanks E. Weichert for efficient assistance with the practical work.     

Twenty years of research on silica-based chiral stationary phases

This review provides an overview of twenty years of pioneering work (from 1985 to 2005) of our research group in the preparation and application of enantioselective packing materials for HPLC. After a brief introduction to the rational design of a new chiral stationary phase, a detailed presentation in chronological order of appearance in the literature is given of the currently developed repertoire of chiral stationary phases and their typical applications. Emphasis is placed on the different synthetic strategies exploited to obtain highly efficient, stable, and versatile chiral stationary phases.     

Twenty three years of dicarbollide extraction of metals research and applications

The history of the development of solvent extraction investigations with dicarbollides for the separation of metals is briefly treated and some inaccuracies in previous reviews are commented on.     

Twenty years of interface development for capillary electrophoresis-electrospray ionization-mass spectrometry

Capillary electrophoresis-electrospray ionization-mass spectrometry has the potential to become a preferred tool for the analysis of biological mixtures and other complex samples. The development of improved interfaces in the past twenty years has been critical in demonstrating the feasibility of this technique. However, a compromise still exists between interfaces that give optimal performance and those that are practical for commercial applications. The first section of this review focuses on the technological advances in CE-ESI-MS as they relate to the key interface features for both sheath-flow and sheathless systems: delivery of the sheath liquid, shaping of the emitter tip, formation of electrical contact, and practicality in terms of ease of use and lifetime. In the second section, we review the fundamental processes that affect interface performance. Because of the complex natures of both capillary electrophoresis and electrospray ionization, flow rate, arrangement of the electrical circuit, electrochemistry, tip geometry and location of electrical contact must all be carefully managed in the design of a successful interface.     

Preparation of a lichen reference material

For preparation of a multielement lichen reference material for environmental studies, 25 kg of the epyphitic lichen Evernia prunastri (L.) Ach. was collected in unpolluted regions of Portugal. The lichen was removed from Cistus ladanifer and Quercus spp. The material was ground to a mesh size 125 m. The material homogeneity was evaluated by determining Na, K, Mn, Br, As, La and Sm on two samples of 100 mg taken at each of 20 locations of the bulk material; the locations were randomly chosen. The k₀-based INAA was used. The material is homogeneous for fractions 100 mg, as shown by the evaluation of the heterogeneity of the subsampling operation in the 20 locations and by the results of a one-way analysis of variance for the data obtained. The composition of Evernia prunastri varies neither with the region where it grows nor with the date of collection. This work was accomplished under contract with the IAEA.     

Value assignment of nutrient concentrations in five standard reference materials and six reference materials

A number of food-matrix reference materials (RMs) are available from the National Institute of Standards and Technology (NIST) and from Agriculture Canada through NIST. Most of these materials were originally value-assigned for their elemental composition (major, minor, and trace elements), but no additional nutritional information was provided. Two of the materials were certified for selected organic constituents. Ten of these materials (Standard Reference Material [SRM] 1,563 Cholesterol and Fat-Soluble Vitamins in Coconut Oil [Natural and Fortified], SRM 1,566b Oyster Tissue, SRM 1,570a Spinach Leaves, SRM 1,974a Organics in Mussel Tissue (Mytilus edulis), RM 8,415 Whole Egg Powder, RM 8,418 Wheat Gluten, RM 8,432 Corn Starch, RM 8,433 Corn Bran, RM 8,435 Whole Milk Powder, and RM 8,436 Durum Wheat Flour) were recently distributed by NIST to 4 laboratories with expertise in food analysis for the measurement of proximates (solids, fat, protein, etc.), calories, and total dietary fiber, as appropriate. SRM 1846 Infant Formula was distributed as a quality control sample for the proximates and for analysis for individual fatty acids. Two of the materials (Whole Egg Powder and Whole Milk Powder) were distributed in an earlier interlaboratory comparison exercise in which they were analyzed for several vitamins. Value assignment of analyte concentrations in these 11 SRMs and RMs, based on analyses by the collaborating laboratories, is described in this paper. These materials are intended primarily for validation of analytical methods for the measurement of nutrients in foods of similar composition (based on AOAC INTERNATIONAL's fat-protein-carbohydrate triangle). They may also be used as "primary control materials" in the value assignment of in-house control materials of similar composition. The addition of proximate information for 10 existing reference materials means that RMs are now available from NIST with assigned values for proximates in 6 of the 9 sectors of the AOAC triangle. Five of these materials have values assigned for total dietary fiber-the first such information provided for materials available from NIST.     

Preparation and certification of tea leaves reference material

Summary Tea leaves reference material was prepared and certified for elemental composition. Japanese green tea leaves were ground, sieved to pass a 80-mesh screen, blended and bottled. The prepared material satisfied the homogeneity criteria for a reference material. Trace element analysis of the material was carried out by flame and graphite furnace atomic absorption and inductively coupled plasma atomic emission spectrometry.Certification of the material was performed using the data obtained by various analytical techniques and certified values are provided for Al, Ca, Cd, Cu, K, Mg, Mn, Na, Ni, Pb and Zn. The elemental composition of the tea leaves reference material is considered typical of Japanese green tea leaves.