Orthogonality and similarity within silica-based reversed-phased chromatographic systems

The starting point of this study was a current set of 32 chromatographic systems used to select initial conditions for method development to determine the impurity profile of a drug. The system exhibiting the best selectivity is then selected for further method development. In this current set eight silica-based phases are applied in conjunction with four mobile phases at different pH. In order to save time and resources, the possibilities for a meaningful subset selection were investigated. The most differing systems in terms of selectivity, in other words only the most orthogonal systems, need to be selected. Since the stationary phases are all silica-based, the selectivity differences are examined within a more homogeneous group than if, for instance, also zirconia- or polymer-based columns would be involved. To select the subset of systems also the best overall separation performances are taken into account. The selection is based both on the HPLC-DAD data of a generic set of 68 drugs, and on the LC-MS-DAD results for a mixture of 15 drugs, less different in structure. The orthogonality is evaluated using weighted-average-linkage dendrograms and color maps, both created from the Pearson-correlation coefficients r between normalized retention times r. The Derringer's desirability functions are applied to define the systems with the best overall separation performances. Proposals for different representative subsets of the initial 32 systems are made.     

Selection of reversed-phase liquid chromatographic columns with diverse selectivity towards the potential separation of impurities in drugs

To select appropriate stationary phases from the continuously expanding supply of potentially suitable HPLC columns, the properties of 28 frequently applied stationary phases were determined by measuring several chromatographic parameters. From these results, based on chromatographic expertise, eight stationary phases with different properties and selectivities were selected. The aim of this study is to apply chemometric tools to evaluate the initially selected set of columns, i.e. a more systematic approach for making such a selection is examined. Starting from the information obtained on the 28 stationary phases, the re-evaluation was performed independently based on the chemometric techniques Pareto-optimality, principal component analysis (PCA), and Derringer's desirability functions. The aim was to select a set of efficient columns exhibiting large selectivity differences. The chemometrically selected stationary phases were divided in groups based on hydrophobicity, a critical retention-determining property in reversed-phase chromatography. This allowed to further reducing the selection to three columns. It is demonstrated that the selection by the chemometric approaches in general is fairly comparable with the initial selection.     

Experimental determination of k 0 , Q 0 , \bar{E}_{r} factors and neutron cross-sections for 41 isotopes of interest in Neutron Activation Analysis

The k ₀ -literature has been reviewed every decade but some of its nuclear data is still more than 30 years old. Sometimes Q ₀ values were adopted from the nuclear data at that time or were experimentally determined by only 1 laboratory. Other isotopes were listed with accurate pairs of (k ₀ , Q ₀ ) values but were also quoted as candidates for redetermination for different reasons (i.e. imprecise cadmium transmission factors, half-lives). In this work we aim at the experimental re-determination of k ₀ and Q ₀ values for 41 isotopes of analytical interest while introducing a methodology for simultaneous $ \bar{E}_{r} $ and Q ₀ determination employing N irradiation channels. In order to satisfy the metrological level required, up to 12 repeats per standard were irradiated in up to 4 irradiation channels of the Belgian Reactor 1 (BR1, SCK?CEN) having a wide spread in neutron characteristics. Our relative percentile differences to the literature values were usually ≤10 % for Q ₀ factors, ≥25 % for $ \bar{E}_{r} $ values and ≤4 % for k ₀ values. Our precision and accuracy are discussed thoroughly.     

Experimental k 0 and k 0-fission factors for the determination of the n(235U)/n(238U) enrichment levels and correction for 235U fission interferences in samples containing uranium

In 2010 we investigated the applicability of the current k ₀ and k ₀-fission factors for the determination of the n(²³⁵U)/n(²³⁸U) isotopic ratio in multi-elemental samples containing uranium. An overestimation 3–4 % was observed in our determinations when employing the recommended 2003 k ₀-literature. After a recalibration of all our laboratory instruments, a 3 % overestimation was still observed in this work when employing this nuclear data. Therefore we aimed at the experimental re-determination of these composite nuclear constants in order to enhance the reliability of the isotopic ratio determination method and the accuracy of our data-filtering algorithms. New k ₀-fission factors are given for 7 nuclides that are not currently present in the 2012 k ₀-database. Several additional k ₀ factors are introduced for some nuclides in this library. Our k ₀ results are also compared with those recently reported by Blaauw et al.     

Microstructure characterization of titanium dioxide nanodispersions and thin films for dye-sensitized solar cell devices

This article reports on the microstructure characterization of titanium dioxide nanodispersions and thin films made thereof for dye-sensitized solar cell devices. Structure–property relationships have been investigated mainly using electron microscopy to assess how microstructure (crystalline structure, defects) and morphological (e.g. heterogeneities, inclusions, voids) features in the electron transport element of the solar cell device correlate with electrical performance, namely, short-circuit photocurrent density (J_sc). This work shows that for a nanodispersion synthesized in the laboratory different electrical performances are measurable depending on the thin film forming process, more specifically, heat-sintering at 450 °C or pressure-sintering at 500 bar. For the heat-sintered device J_sc is about 7.3 mA/cm² whereas for the pressure-sintered one this value is much lower, this difference being attributed to the existence of inclusions in the titanium dioxide matrix, which are spatially isolated from the rest of the electron transport element thereby limiting the charge transport process by promoting their premature recombination. PACS 68.37.Lp; 73.61.Le; 81.40.-z; 84.60.Jt     

The impact of polyethylene vials on reactor channel characterization in k 0 -NAA

Reactor channel characterization is commonly performed by irradiating bare and cadmium-covered “fluence rate monitors”, avoiding as much as possible the use of irradiation vials and spacers to position the monitors inside the channel. However, in routine k ₀ -Neutron Activation Analysis often samples are packed in small polyethylene vials prior to irradiation. This work aims at studying the impact of typical NAA polyethylene vials (~1 mm wall thickness) on the determination of the f and α channel-specific parameters through the “Bare”, “Cadmium-Covered” and “Cadmium-Ratio” methods. The impact of these vials on each method was studied for 3 irradiation channels of the Belgian Reactor 1 at SCK·CEN (Mol, Belgium) with low to high f and α-values. The net impact was 1% on each parameter. Inconsistencies between the different methods were found when the impact of the polyethylene was neglected, implying that all determination methods must be pooled and thin monitors should be used for an accurate channel characterization.     

Neutron spectrum calibration using the Cd-ratio for multi-monitor method with a synthetic multi-element standard

Several methods are in use for the determination of the thermal to epithermal neutron fluence rate ratio (f) and the deviation of the epithermal neutron spectrum from the 1/E shape parameter (α). In our former work, it was proven that the recently developed and characterized Synthetic Multi-ELement Standard (SMELS) can be used for the fast verification of the stability of the irradiation parameters using the Au-Zr bare monitor method. However, this latter method using SMELS had a too low precision for an accurate determination of f and α. Therefore, the Cd-ratio for multi-monitor method using SMELS was investigated for two irradiation channels. As shown the material can also be used as a monitor for the calibration of an irradiation facility.     

Trace element determination in beauty products by k0-instrumental neutron activation analysis

A recent study on trace elements in beauty products and cosmetics sold on the Asian market has shown the presence of high levels of U, Th and rare earth elements in so called “Hormesis cosmetics.” For the purpose of comparison, some more information about trace elements in European cosmetics would be useful. In this paper the results obtained using k ₀-standardised Instrumental Neutron Activation Analysis (k ₀-INAA) for more than 20 trace elements in 20 different beauty products collected from the European market are presented. We found traces of Ba, As and Sb which is in breach with European legislation. For some of the other elements like Cr and Co further speciation is needed in order to evaluate their presence in beauty products.     

Influence of Porosity on the Electrical Sensing Zone and Laser Diffraction Sizing of Silicas. A collaborative study

The objective of a continuing study by the Belgian Particle Technology Group involves difficulties in practical size determinations. This part describes the behaviour of silicas with different porosities during sizing by electrical sensing zone and laser diffraction methods. Anisotropy and porosity were identified to be important particle characteristics in understanding the differences between the two methods. Especially large pore diameters and pore volumes were found to be responsible for shifts in size distribution of 50 to 100%. The use of optical values and optical models was shown to influence these shifts considerably. In the case of spherical silica particles with moderate porosity, no significant differences could be found between the two sizing methods.     

A theoretical introduction to “Combinatory SYBR®Green qPCR Screening”, a matrix-based approach for the detection of materials derived from genetically modified plants

The detection of genetically modified (GM) materials in food and feed products is a complex multi-step analytical process invoking screening, identification, and often quantification of the genetically modified organisms (GMO) present in a sample. “Combinatory qPCR SYBR®Green screening” (CoSYPS) is a matrix-based approach for determining the presence of GM plant materials in products. The CoSYPS decision-support system (DSS) interprets the analytical results of SYBR®GREEN qPCR analysis based on four values: the C _t- and T _m values and the LOD and LOQ for each method. A theoretical explanation of the different concepts applied in CoSYPS analysis is given (GMO Universe, “Prime number tracing”, matrix/combinatory approach) and documented using the RoundUp Ready soy GTS40-3-2 as an example. By applying a limited set of SYBR®GREEN qPCR methods and through application of a newly developed “prime number”-based algorithm, the nature of subsets of corresponding GMO in a sample can be determined. Together, these analyses provide guidance for semi-quantitative estimation of GMO presence in a food and feed product.