Human errors and reliability of test results in analytical chemistry

The present paper is a review of the main theoretical and technical aspects of human error treatment (error modelling, reduction and quantification) as applied in aviation, engineering, medicine and other fields. The aim of the review is to attract the attention of analysts and specialists in metrology and quality in chemistry to the human error problem and its influence on the reliability of test results of chemical composition and associated measurement uncertainty. Therefore, the subject of human error is interpreted in the review in application to the conditions of a chemical analytical laboratory.     

Electrochemical evidences and consequences of significant differences in ions diffusion rate in polyacrylate-based ion-selective membranes

The origin and effect of surface accumulation of primary ions within the ion-selective poly(n-butyl acrylate)-based membrane, obtained by thermal polymerization, is discussed. Using a new method, based on the relation between the shape of a potentiometric plot and preconditioning time, the diffusion of copper ions in the membrane was found to be slow (the diffusion coefficient estimated to be close to 10(-11) cm(2) s(-1)), especially when compared to ion-exchanger counter ions--sodium cations diffusion (a diffusion coefficient above 10(-9) cm(2) s(-1)). The higher mobility of sodium ions than those of the copper-ionophore complex results in exposed ion-exchanger role leading to undesirably exposed sensitivity to sodium or potassium ions.     

Metabolic fingerprinting of high-fat plasma samples processed by centrifugation- and filtration-based protein precipitation delineates significant differences in metabolite information coverage

Metabolomics and metabolic fingerprinting are being extensively employed for improved understanding of biological changes induced by endogenous or exogenous factors. Blood serum or plasma samples are often employed for metabolomics studies. Plasma protein precipitation (PPP) is currently performed in most laboratories before LC–MS analysis. However, the impact of fat content in plasma samples on metabolite coverage has not previously been investigated. Here, we have studied whether PPP procedures influence coverage of plasma metabolites from high-fat plasma samples. An optimized UPLC-QTOF/MS metabolic fingerprinting approach and multivariate modeling (PCA and OPLS-DA) were utilized for finding characteristic metabolite changes induced by two PPP procedures; centrifugation and filtration. We used 12-h fasting samples and postprandial samples collected at 2 h after a standardized high-fat protein-rich meal in obese non-diabetic subjects recruited in a dietary intervention. The two PPP procedures as well as external and internal standards (ISs) were used to track errors in response normalization and quantification. Remarkably and sometimes uniquely, the fPPP, but not the cPPP approach, recovered not only high molecular weight (HMW) lipophilic metabolites, but also small molecular weight (SMW) relatively polar metabolites. Characteristic SMW markers of postprandial samples were aromatic and branched-chain amino acids that were elevated (p < 0.001) as a consequence of the protein challenge. In contrast, some HMW lipophilic species, e.g. acylcarnitines, were moderately lower (p < 0.001) in postprandial samples. LysoPCs were largely unaffected. In conclusion, the fPPP procedure is recommended for processing high-fat plasma samples in metabolomics studies. While method improvements presented here were clear, use of several ISs revealed substantial challenges to untargeted metabolomics due to large and variable matrix effects.     

Validity and reliability of two standard test devices in assessing mechanical properties of different sport surfaces

The Artificial Athlete (AA) and the Advanced Artificial Athlete (AAA) devices are the two key test methods for the assessment of shock absorption (SA) and vertical deformation (VD) of sports surfaces. The aim of this study was to investigate the relationship between them. Laboratory tests were carried out in accordance with international regulations and standards on 50 athletics tracks and 44 artificial turf systems using both test methods. No significant differences between methods were observed. Measurements with the AA and the AAA were compared using intraclass correlation coefficients (ICCs), showing acceptable to excellent inter-method reliability (ICC ranged from 0.47 to 0.91). The Bland-Altman test revealed an overall SA overestimation and VD underestimation with the AAA. Linear regression analysis was performed, obtaining excellent agreement between test methods for the assessment of SA (R² = 0.994) and VD (R² = 0.985). It is concluded that, by applying Equations (1) and (2) in this study, the AA and the AAA could be used interchangeably when assessing SA and VD on athletics tracks and artificial turf surfaces.     

Cytochemical differences in bacterial glycocalyx.

To examine new cytochemical aspects of the bacterial adhesion, a strain 41452/01 of the oral commensal Streptococcus sanguis and a wild strain of Staphylococcus aureus were grown with and without sucrose supplementation for 6 days. Osmiumtetraoxyde (OsO4), uranyl acetate (UA), ruthenium red (RR), cupromeronic blue (CB) staining with critical electrolytic concentrations (CECs), and the tannic acid-metal salt technique (TAMST) were applied for electron microscopy. Cytochemically, only RR-positive fimbriae in S. sanguis were visualized. By contrast, some types of fimbriae staining were observed in S. aureus glycocalyx: RR-positive, OsO4-positive, tannophilic and CB-positive with ceasing point at 0.3 M MgCl2. The CB staining with CEC, used for the first time for visualization of glycoproteins of bacterial glycocalyx, also reveals intacellular CB-positive substances-probably the monomeric molecules, that is, subunits forming the fimbriae via extracellular assembly. Thus, glycosylated components of the biofilm matrix can be reliably related to single cells. The visualization of intracellular components by CB with CEC enables clear distinction between S. aureus and other bacteria, which do not produce CB-positive substances. The small quantities of tannophilic substances found in S. aureus makes the use of TAMST for the same purpose difficult. The present work protocol enables, for the first time, a partial cytochemical differentiation of the bacterial glycocalyx.     

Nascent particle sizes and degrees of entanglement are responsible for the significant differences in impact strength of ultrahigh molecular weight polyethylene

The physical properties of ultrahigh molecular weight polyethylene (UHMWPE) are generally highly dependent on its molecular weight. However, in our study, it was found that two UHMWPE samples of similar molecular weight, SLL‐5 and GUR 4150, have significantly different impact strengths, with the Charpy impact strength of GUR 4150 being almost 3.4 times that of SLL‐5. To reveal the reasons, the structure–property relations of these UHMWPE materials were investigated. Morphologies of the nascent particles and impact fracture surfaces, the melting behavior, rheological behavior, and three‐phase (crystalline, amorphous, and interphase) contents were characterized by scanning electron microscopy, differential scanning calorimetry, advanced rotary rheometer, and Raman spectroscopy, respectively. It was observed that no significant differences in the crystal structures of SLL‐5 and GUR 4150, but GUR 4150 had smaller nascent particles sizes and a lower degree of entanglement when compared with those of SLL‐5. Accordingly, a mechanism to clarify the significant difference in the impact strengths of GUR 4150 and SLL‐5 was developed. More importantly, this work may be useful for improving the preparation technologies and industrial applications of UHMWPE. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 632–641     

Radiationless transitions. Quantitative interpretation of some experiments.

The Green function method is used to calculate the rate of radiationless transitions. The obtained formula is applied for quantitative interpretation of the fluorescence quenching of anthracene, pyrene, methylanthracene in various solvents. The vibrational relaxation rates of small molecules substituted to the noble gas crystalline hosts are evaluated. The agreement with experiment is satisfactory.     

Perspectives and limitations of resolutions-reconstitution experiments.

Reconstitutions of membranous activities can tell us how many components are required and what their functions are. The mitochondrial proton pump is used as an example. Moreover, the biological activity, such as Pi transport, can be used in reconstituted vesicles as an assay during the isolation of the transporter. Reconstitution experiments reveal the importance of membrane asymmetry and allow us to study conditions of vectorial assembly. The mechanism of action of ion pumps has been successfully analyzed in reconstituted liposomes. We can study the movement of ions and the electrogenicity of the system without interference by other unrelated processes. Based on studies with the resolved Ca2+-ATPase of sarcoplasmic reticulum, we propose a novel formulation of the mechanism of ATP-driven ion pumps in which cyclic binding of Mg2+ plays a key role.     

A test for the reliability of the controlled potential coulometric method to determine plutonium in uranium-plutonium mixtures

Summary A method has been developed for the determination of trimethylsilyl groups in N-silylated compounds and in trimethylsilyl esters of carboxylic acids. The method is based on the desilylation of the compound to be analysed with phenol followed by gas-chromatographic determination of the trimethylphenoxysilane formed. The relative error of the determination is around 1% and the standard deviation is 1.20 × 10^–3 (3.12%). A single determination takes less than 2 h.

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Gas-chromatographische Bestimmung von Trimethylsilyl-Gruppen in N-silylierten Verbindungen und in Trimethylsilyl-Estern von Carbonsäuren

Zusammenfassung Das Verfahren beruht auf der Desilylierung der zu analysierenden Verbindung mit Phenol und der anschlie\enden gas-chromatographischen Bestimmung des gebildeten Trimethylphenoxysilans. Der relative Fehler der Bestimmung beträgt ca. 1% und die Standardabweichung 1,20 × 10^–3 (3,12%). Die Bestimmungszeit ist kürzer als 2 h.

     

Electron-transfer reactions with significant changes in structure. Unsymmetrical crowded ethylenes

The electrochemical reduction mechanisms of xanthylideneanthrone, 6, thioxanthylideneanthrone, 7, 10-(diphenylmethylene)anthrone, 8, and 9-(diphenylmethylene)-9H-fluorene, 9, have been studied in dimethylformamide. The reduction of the first two compounds proceeds from folded forms of the neutral to twisted forms of the anion radical according to a square scheme. The data for reduction of 8 can be well accounted for by the same square scheme. However, one-step reduction with concerted electron transfer and structural change cannot be ruled out. Compound 9, whose fluorene ring system cannot fold, exists only in twisted forms in the neutral, anion radical, and dianion. Consequently, there are no major changes in structure upon reduction, and the compound is reduced in two reversible steps with the second complicated by rapid loss of the dianion that is probably due to protonation by components of the medium.     

An 227Ac-211Pb generator for test experiments of solution chemistry of element 114

A simple and effective method has been developed for the continuous production of the short-lived isotope Pb as a homolog of element 114 on the principle of a radionuclide generator. The method is based on the initial sorption of ²²⁷Ac or ²²³Ra on a small cation-exchange column, with subsequent “milking” of ²¹¹Pb (36.1 m) by a mixture of HCl/CH₃OH. The optimum conditions for the repeated separation of ²¹¹Pb from radionuclides strongly sorbed by the cation-exchanger (Ac, Th, Ra, Pu, TPE) have been determined. Possibilities of using the ²¹¹Pb generator for test experiments on the solution chemistry of element 114 have been shown. Advantages of aqueous alcohol HCl solutions for the isolation of ²¹¹Pb (element 114) are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Improvement in energy conversion of electrostrictive composite materials by new approach via piezoelectric effect: Modeling and experiments

This study proposes a new model that couples the piezoelectric and electrostrictive behavior to minimize the polarization power of composite polymer. The development of this model is capable to predict the energy harvesting abilities of an electrostrictive composite. To improve the dielectric permittivity of electrostrictive polymer, the particles of PZT have been incorporated in order to increase the conversion efficiency of the composite. Dielectric characterization tests showed an increase in dielectric permittivity by a factor of 4.5 compared to pure polymer. Experimental measurements of harvested power validate the analytical model and demonstrate a good correlation between the two data. An equivalent of an electrical scheme has been developed, which allows modeling the two behaviors. The harvested power density under low frequency at 2% of strain can reach 0.30 μW/cm³ for 33% of PZT without the polarization field, including the conversion efficiency becomes higher. The energy harvester property of this material composite has excellent potential for several self‐powered applications such as wireless sensor networks and the internet of things.     

Synchrotron X-ray experiments in pulsed high magnetic fields.

Recent developments of the techniques for measurements of X-ray diffraction and X-ray absorption spectroscopy in very high magnetic fields are reviewed. Miniature pulsed magnets allow us to conduct various kinds of high-field X-ray experiments rather easily; the magnets can be readily installed on a conventional apparatus such as a diffractometer and a cryostat because of its smallness. The results of some experiments on the field-induced phase transition of a rare-earth intermetallic compound (YbInCu4) are also presented.     

Low-cost nanomanipulator for in situ experiments in a SEM.

Here, we describe the development of an inexpensive and versatile manipulation system for in situ experiments in a field emission scanning electron microscope based on a parallel-guiding plate-spring mechanism and low cost materials. The system has been tested for a wide range of applications, such as collecting, moving, and positioning particles, fabricating atomic force microscopy tips based on carbon nanotubes, and characterizing individual nanobjects. The nanomanipulation results demonstrate that there are many opportunities for the use of physical manipulation in the bottom-up approach to fabrication of nanodevices.     

Improvement of the partial least squares model performance for oral glucose intake experiments by inside mean centering and inside multiplicative signal correction.

Near infrared (NIR) spectroscopy has become a promising technique for the in vivo monitoring of glucose. Several capillary-rich locations in the body, such as the tongue, forearm, and finger, have been used to collect the in vivo spectra of blood glucose. For such an in vivo determination of blood glucose, collected NIR spectra often show some dependence on the measurement conditions and human body features at the location on which a probe touches. If NIR spectra collected for different oral glucose intake experiments, in which the skin of different patients and the measurement conditions may be quite different, are directly used, partial least squares (PLS) models built by using them would often show a large prediction error because of the differences in the skin of patients and the measurement conditions. In the present study, the NIR spectra in the range of 1300-1900 nm were measured by conveniently touching an optical fiber probe on the forearm skin with a system that was developed for in vivo measurements in our previous work. The spectra were calibrated to resolve the problem derived from the difference of patient skin and the measurement conditions by two proposed methods, inside mean centering and inside multiplicative signal correction (MSC). These two methods are different from the normal mean centering and normal multiplicative signal correction (MSC) that are usually performed to spectra in the calibration set, while inside mean centering and inside MSC are performed to the spectra in every oral glucose intake experiment. With this procedure, spectral variations resulted from the measurement conditions, and human body features will be reduced significantly. More than 3000 NIR spectra were collected during 68 oral glucose intake experiments, and calibrated. The development of PLS calibration models using the spectra show that the prediction errors can be greatly reduced. This is a potential chemometric technique with simplicity, rapidity and efficiency in the pretreatment of NIR spectra collected during oral glucose intake experiments.     

Statistical and probabilistic approaches to confidence intervals of linear calibration in liquid chromatography.

The aim of this paper is to compare the reliability of two approaches to estimate the 95% confidence intervals of linear calibration in real situations. One is the statistical approach, which is well known in statistics, and the other is the probabilistic approach, which is based on a theory to predict the precision of instrumental analyses mainly from signal and noise, called FUMI (Function of Mutual Information) theory. The high-performance liquid chromatographic determination of quisalofop and maltose is taken as an example. Calibration lines obtained under the same experimental conditions are superimposed on the 95% confidence intervals to investigate whether the resulting confidence intervals can include all the calibration lines reasonably. A pair of 95% confidence intervals (upper and lower limits) can be calculated from each calibration line, but varies from calibration line to calibration line, although obtained under the same experimental conditions. The variability and reliability of the 95% intervals are also examined.     

Improvement of double pulsed field gradient spin‐echo ROESY experiments for identification of bound waters

A novel pulse sequence incorporating the double pulsed field gradient spin‐echo (DPFGSE) and the gradient‐tailored excitation WATERGATE techniques is presented that has particular use for identifying bound waters in ¹⁵N‐labeled macromolecules. This sequence, DPFGSE–ROESY–HSQC, affords greater spectral sensitivity than the DPFGSE–ROESY–HMQC experiment which was previously presented and is consequently useful for rapidly obtaining reliable information for characterizing macromolecular bound water molecules. A significant enhancement in the sensitivity is achieved by using the gradient‐tailored excitation WATERGATE sequence in the reverse INEPT step as it allows the use of much higher receiver gains. Since coherence selection is not used, the sequence has improved sensitivity together with less spectral artifacts. The advantage of this pulse sequence is illustrated using ¹⁵N‐labeled ribonuclease T₁. Copyright © 2003 John Wiley & Sons, Ltd.     

Extraction of kinetic information from single-molecule experiments.

We discuss two possible approaches for extracting kinetic information from single-molecule experiments. The first approach is based on computing correlation functions from measured fluorescence signals, and the second on studying the statistics of on and off times of the same fluorescence signal. We show that in both cases it is possible to extract kinetic information about the nature of intramolecular fluctuations of the single molecule. We show that for single-molecule kinetics the intramolecular fluctuations produce stochastic memory effects which lead to new dynamic features that do not exist in traditional chemical kinetics. In particular, we investigate a new type of chemical oscillations in correlation functions observed experimentally by Edman and Rigler (Proc. Natl. Acad. Sci. USA 2000, 97, 8266).