Multivariate Association of Graph-Theoretic Variables and Physicochemical Properties

Abstract

We used canonical correlation analysis to examine the multivariate association between two distinct data sets commonly measured or calculated for approximately 600 chemicals: (1) measured or calculated values of select physieochemical properties (i.e., K _ow, boiling point, heat of vaporization, molecular weight, water solubility, molecular volume, hydrogen bonding potential, and vapor pressure) and (2) calculated algorithmically-derived variables (i.e., topological and neighborhood indices derived from graph theory). Canonical correlation analysis identified eight highly significant associations between linear combinations of graph-theoretic variables and linear combinations of physicochemical properties. The set of graph theoretic variables was significantly related to all physieochemical properties, explaining 55% to 99% of the variation in these properties.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.     

An investigation of calibration materials for the measurement of metals in ambient particulate matter on filters by LA-ICP-MS

Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques.     

Trace elements in sediments and bioaccumulation in European silver eels (Anguilla anguilla L.) from a Mediterranean lagoon (SE Italy)

Samples of surface sediments and tissues (liver and muscle) of commercially available European silver eels (Anguilla anguilla L.) collected from Varano lagoon (Italy) were analysed to determine trace element contents. Univariate and multivariate analyses were performed to highlight both the differences between sampling sites and the influence of channel discharges. Atomic ratios indices for sediment data and biological enrichment factors (BEF) for eel tissues were calculated in order to evaluate the enrichment factor due to human activities. The highest levels of As (11.9?µg?g^?1) and Zn (14.1?µg?g^?1) were observed in the south-eastern zone of the lagoon, which is influenced by urban and agricultural discharges. The low levels of Hg observed in this study (0.04?µg?g^?1) led us to exclude both natural and human local sources of this element. Trace element concentrations of all elements were lower in muscle than in liver tissue. Significant enrichment of Cu and Zn was found in livers.     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Review on the thickness measurement of ultrathin oxide films by mutual calibration method

Mutual calibration was suggested as a method to determine the absolute thickness of ultrathin oxide films. It was motivated from the large offset values in the reported thicknesses in the Consultative Committee for Amount of Substance (CCQM) pilot study P-38 for the thickness measurement of SiO₂ films on Si(100) and Si(111) substrates in 2004. Large offset values from 0.5 to 1.0 nm were reported in the thicknesses by ellipsometry, X-ray reflectometry (XRR), medium-energy ion scattering spectrometry (MEIS), Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), and transmission electron microscopy (TEM). However, the offset value for the thicknesses by X-ray photoelectron spectroscopy (XPS) was close to zero (−0.013 nm). From these results, the mutual calibration method was reported for the thickness measurement of SiO₂ films on Si(100) by combination of TEM and XPS. The mutual calibration method has been applied for the thickness measurements of hetero oxide films such as Al₂O₃ and HfO₂. Recently, the effect of surface contamination was reported to be critical to the thickness measurement of HfO₂ films by XPS. On the other hand, MEIS was proved to be a powerful zero offset method which is not affected by the surface contamination. As a result, the reference thicknesses in the CCQM pilot study P-190 for the thickness measurement of HfO₂ films on Si(100) substrate were determined by mutual calibration method from the average XRR data and MEIS analysis. Conclusively, the thicknesses of ultrathin oxide films can be traceably certified by mutual calibration method and most thickness measurement methods can be calibrated from the certified thicknesses.     

A two-point calibration method for quantifying organic binary mixtures using secondary ion mass spectrometry in the presence of matrix effects

Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′-bis(9-carbazolyl) biphenyl and tris(2-phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two-point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one-point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two-point calibration method could be of significant benefit to SIMS analysts.     

Interpretation of TOF-SIMS data based on information entropy of spectra

Time-of-flight secondary ion mass spectrometry (TOF-SIMS), when used for the analysis of complex material samples, typically provides data that are complicated and challenging to understand. Therefore, additional data analysis techniques, such as multivariate analysis, are often required to facilitate the interpretation of TOF-SIMS data. In this study, a new method based on the information entropy (Shannon entropy) is proposed as an indicator of the outline characteristics of an unknown sample, such as changes in the material within the sample and mixing conditions. The Shannon entropy values are calculated using the relative intensity of every secondary ion normalized to the total ion count and reflect the diversity of secondary ions in the spectrum. Mixed samples containing two organic electroluminescence materials of different ratios, multilayers of Irganox 1010, and other organic materials were employed to evaluate the utility of Shannon entropy in the analysis of TOF-SIMS data. The findings demonstrate that the Shannon entropy of a spectrum indicates differences in materials and changes in the conditions of a material in a sample without the need for peak identification or the knowledge of specific peaks corresponding to the materials in the sample.