Non-invasive analysis of natural textile dyes using fluorescence excitation-emission matrices.

Multidimensional fluorescence spectroscopy was assessed as a non-invasive and non-destructive method for the analysis of components in natural textile dyes. Results demonstrate that components in the natural dyes fluoresce and wool's intrinsic fluorescence is, in many cases, not a considerable analytical interferent. In the case of some self-dyed reference yarns, like those dyed with northern and lady's bedstraws, wood horsetail, safflower, salted shield lichen, dyer's madder and cochineal, the fluorescence excitation-emission matrices (EEMs) are sufficiently characteristic for using them as a primary means of identification (or assignment to a family of dyes). With most of the studied yellow and green dyes (heather, silver birch, some bloodred webcap treatments, alkanet), however, the spectra can be used as additional information for identification. This study reports multidimensional fluorescence data for a collection of wools dyed with natural dyes (31 dyed wool yarn samples that were self-dyed with 18 different natural dyes) that were used as references in a case study of two historical textiles for which liquid chromatography-mass spectrometry was used as a confirmatory technique. Given its utility as a rapid and non-destructive/non-invasive method with information-rich multidimensional EEM output, the front-face fluorescence spectroscopy of surfaces using a fiber optic probe is a promising technique for the analysis of dyes on cultural heritage textiles.

Experimental and Computational Study of Aminoacridines as MALDI(-)-MS Matrix Materials for the Analysis of Complex Samples.

Monoaminoacridines (1-, 2-, 3-, 4-, and 9-aminoacridine) were studied for suitability as matrices in the negative ion mode matrix-assisted laser desorption/ionization mass spectrometry (MALDI(-)-MS) analysis of various samples. This is the first study to examine 1-, 2-, and 4-aminoacridine as potential matrix material candidates for MALDI(-)-MS. In addition, spectral (UV-Vis absorption and fluorescence), proton transfer-related (basicity and autoprotolysis), and crystallization properties of these compounds were characterized experimentally and/or computationally. For testing the capabilities of these aminoacridines as matrix materials, four samples related to cultural heritage materials-stearic acid, colophony resin, dyer's madder dye, and a resinous case-study sample from a shipwreck-were analyzed with MALDI(-)-MS. A novel algorithm (implemented as an executable Python script) for MS data analysis was developed to compare the five matrix materials and to help mass spectrometrists rapidly identify peaks originating from the sample and matrix material. It was determined that all five of the studied aminoacridines can successfully be used as matrix materials in MALDI(-)-MS analysis. As an interesting finding, in several cases, the best mass spectra were obtained by using a relatively small amount of matrix material mixed with an excess amount of sample. 3- and 4-aminoacridine outperformed the other aminoacridines in the ease of obtaining acceptable spectra, average number of ions identified in the mass spectra, and low dependence of the sample-to-matrix mass ratio on experimental results.

Comparative validation of amperometric and optical analyzers of dissolved oxygen: a case study.

A comprehensive comparative validation for two different types of dissolved oxygen (DO) analyzers, amperometric and optical, is presented on two representative commercial DO analyzers. A number of performance characteristics were evaluated including drift, intermediate precision, accuracy of temperature compensation, accuracy of reading (under different measurement conditions), linearity, flow dependence of the reading, repeatability (reading stability), and matrix effects of dissolved salts. The matrix effects on readings in real samples were evaluated by analyzing the dependence of the reading on salt concentration (at saturation concentration of DO). The analyzers were also assessed in DO measurements of a number of natural waters. The uncertainty contributions of the main influencing parameters were estimated under different experimental conditions. It was found that the uncertainties of results for both analyzers are quite similar but the contributions of the uncertainty sources are different. Our results imply that the optical analyzer might not be as robust as is commonly assumed; however, it has better reading stability, lower stirring speed dependence, and typically requires less maintenance. On the other hand, the amperometric analyzer has a faster response and wider linear range. Both analyzers seem to have issues with the accuracy of temperature compensation. The approach described in this work will be useful to practitioners carrying out DO measurements for ensuring reliability of their measurements.

Qualitative Analysis of E-Liquid Emissions as a Function of Flavor Additives Using Two Aerosol Capture Methods.

This work investigates emissions sampling methods employed for qualitative identification of compounds in e-liquids and their resultant aerosols to assess what capture methods may be sufficient to identify harmful and potentially harmful constituents present. Three popular e-liquid flavors (cinnamon, mango, vanilla) were analyzed using qualitative gas chromatography-mass spectrometry (GC-MS) in the un-puffed state. Each liquid was also machine-puffed under realistic-use flow rate conditions and emissions were captured using two techniques: filter pads and methanol impingers. GC-MS analysis was conducted on the emissions captured using both techniques from all three e-liquids. The e-liquid GC-MS analysis resulted in positive identification of 13 compounds from the cinnamon flavor e-liquid, 31 from mango, and 19 from vanilla, including a number of compounds observed in all e-liquid experiments. Nineteen compounds were observed in emissions which were not present in the un-puffed e-liquid. Qualitative GC-MS analysis of the emissions samples identify compounds observed in all three samples: e-liquid, impinge, and filter pads, and each subset thereof. A limited number of compounds were observed in emissions captured with impingers, but were not observed in emissions captured using filter pads; a larger number of compounds were observed on emissions collected from the filter pads, but not those captured with impingers. It is demonstrated that sampling methods have different sampling efficiencies and some compounds might be missed using only one method. It is recommended to investigate filter pads, impingers, thermal desorption tubes, and solvent extraction resins to establish robust sampling methods for emissions testing of e-cigarette emissions.

Inflammatory Response and Barrier Dysfunction by Different e-Cigarette Flavoring Chemicals Identified by Gas Chromatography-Mass Spectrometry in e-Liquids and e-Vapors on Human Lung Epithelial Cells and Fibroblasts.

Recent studies suggest that electronic cigarette (e-cig) flavors can be harmful to lung tissue by imposing oxidative stress and inflammatory responses. The potential inflammatory response by lung epithelial cells and fibroblasts exposed to e-cig flavoring chemicals in addition to other risk-anticipated flavor enhancers inhaled by e-cig users is not known. The goal of this study was to evaluate the release of the proinflammatory cytokine (interleukin-8 [IL-8]) and epithelial barrier function in response to different e-cig flavoring chemicals identified in various e-cig e-liquid flavorings and vapors by chemical characterization using gas chromatography-mass spectrometry analysis. Flavorings, such as acetoin (butter), diacetyl, pentanedione, maltol (malt), ortho-vanillin (vanilla), coumarin, and cinnamaldehyde in comparison with tumor necrosis factor alpha (TNFα), were used in this study. Human bronchial epithelial cells (Beas2B), human mucoepidermoid carcinoma epithelial cells (H292), and human lung fibroblasts (HFL-1) were treated with each flavoring chemical for 24 hours. The cells and conditioned media were then collected and analyzed for toxicity (viability %), lung epithelial barrier function, and proinflammatory cytokine IL-8 release. Cell viability was not significantly affected by any of the flavoring chemicals tested at a concentration of 10 µM to 1 mM. Acetoin and diacetyl treatment induced IL-8 release in Beas2B cells. Acetoin- and pentanedione-treated HFL-1 cells produced a differential, but significant response for IL-8 release compared to controls and TNFα. Flavorings, such as ortho-vanillin and maltol, induced IL-8 release in Beas2B cells, but not in H292 cells. Of all the flavoring chemicals tested, acetoin and maltol were more potent inducers of IL-8 release than TNFα in Beas2B and HFL-1 cells. Flavoring chemicals rapidly impaired epithelial barrier function in human bronchial epithelial cells (16-HBE) as measured by electric cell surface impedance sensing. Our findings suggest that some of the e-cig liquids/aerosols containing flavoring chemicals can cause significant loss of epithelial barrier function and proinflammatory response in lung cells.

Determination of Nicotine Content and Delivery in Disposable Electronic Cigarettes Available in the United States by Gas Chromatography-Mass Spectrometry.

INTRODUCTION: Electronic cigarettes (E-Cigs) are popular alternatives to conventional tobacco cigarettes. Disposable E-Cigs are single-use devices that emit aerosols from a nicotine-containing solution (e-liquid) by activating a heating coil during puffing. However, due to lack of regulations and standards, it is unclear how product claims are aligning with actual content and performance. Some analytical methods for characterizing E-Cigs are still in an exploratory phase. METHODS: Five products of disposable E-Cigs (purchased March-April, 2014 from a local smoke shop and an on-line US distributor) were studied for nicotine content, number of puffs obtained before depletion, portion of nicotine delivered via aerosolization, and e-liquid pH. Protocols were developed to consistently extract e-liquid from puffed and unpuffed E-Cigs. An in-house mechanical puffing machine was used to consistently puff E-Cig aerosols onto filter pads. A gas chromatography-mass spectrometry method was developed that produced sensitive and repeatable nicotine determinations. RESULTS: Under our experimental parameters, results showed a disparity between nicotine content and number of puffs achieved relative to what was claimed on product packaging. The portion of nicotine delivered to filter pads was often less than half that which was available, indicating much of the nicotine may be left in the E-Cig upon depletion. CONCLUSIONS: Analyses of unpuffed E-Cigs by gas chromatography-mass spectrometry indicate the nicotine content of these products can be considerably different from manufacture's labeling. Furthermore, a large portion of the nicotine in E-Cigs may not be transferred to the user, and that which is transferred, may often be in the less bioavailable form.

Laboratory Activity for the Determination of Nicotine in Electronic Cigarette Liquids using Gas Chromatography-Mass Spectrometry.

In recent years the prevalence and popularity of electronic cigarettes (ECs) has increased noticeably and a large market for their refillable nicotine solutions (e-liquids) has also rapidly increased. These e-liquids contain nicotine, an addictive and potentially dangerous stimulant, but often the actual nicotine content differs significantly from manufacturers' labelling, due in part to lack of regulation for these products. A laboratory activity for undergraduate students was developed to directly test e-liquids for nicotine content using gas chromatography combined with mass spectrometry (GC-MS) as a means for teaching the instrumentation to undergraduate students using an authentic, real-world example. The activity introduces and/or re-emphasizes the theory and operation of GC-MS, standard/sample preparation, calibration curves, internal standards, selected ion monitoring mode of MS operation, and method validation. The laboratory experiment is designed for students enrolled in Quantitative Analysis courses (like Analytical Chemistry or Instrumental Analysis), but portions are also suitable for lower level chemistry courses or even those designed for allied health professionals or non-chemistry majors. Given the current popularity of ECs, this activity can provide the chemistry curriculum with a timely, real-world, and contemporary application in which crucial course content is taught. Students can also benefit from the inherent discussion of ECs, regulations, and related social aspects of smoking and EC vaping - which can serve as a secondary learning outcome.

Investigation of the fluorescence quenching of 1-aminoanthracene by dissolved oxygen in cyclohexane.

This study provides a detailed investigation of the fluorescence quenching mechanisms of the fluorophore, 1-aminoanthracene, by dissolved oxygen in cyclohexane. Dynamic/collisional quenching dominates in the system studied, but there is also a small component of static quenching. Stern-Volmer plots revealed that the dynamic quenching constant is 0.445 ± 0.014 mM(-1) and represents ∼95% of total quenching in the system. The static quenching rate constant is 0.024 ± 0.001 mM(-1), and mechanisms by complex formation and "sphere of action" static quenching were examined. Compensation of steady-state fluorescence data for solvent loss during the gradual deoxygenation period of the experiment was found to be important in order to conduct a thorough evaluation of the different quenching mechanisms of the system. The enhancement factors, (F(o)/F) and (τ(o)/τ), for 1-aminoanthracene were determined to be 2.20 ± 0.01 and 2.08 ± 0.01, respectively, and the diffusion-controlled bimolecular rate constant was found to be 2.1 × 10(10) ± 0.2 × 10(10) M(-1) s(-1). The work involved the development of a novel instrumental setup that simultaneously measures several important spectroscopic parameters (steady-state fluorescence intensity, absorbance, fluorescence lifetime, and dissolved oxygen concentration) for the careful study of oxygen quenching mechanisms of 1-aminoanthracene in a cyclohexane solution.

Multidimensional fluorescence studies of the phenolic content of dissolved organic carbon in humic substances.

Indicators suggest that the amount of dissolved organic carbon (DOC) in natural waters may be increasing. Climate change has been proposed as a potential contributor to the trend, and under such a mechanism, the phenolic content of DOC may also be increasing. This study explores the assessment of the phenolic character of DOC using multidimensional fluorescence spectroscopy as a more convenient alternative to traditional wet chemistry methods. Parallel factor analysis (PARAFAC) is applied to fluorescence excitation emission matrices (EEMs) of humic samples to analyze inherent phenolic content. The PARAFAC results are correlated with phenol concentrations derived from the Folin-Ciocalteau reagent-based method. The reagent-based method reveals that the phenolic content of five International Humic Substance Society (IHSS) samples varies from approximately 5.2 to 22 ppm Tannic Acid Equivalents (TAE). A four-component PARAFAC fit is applied to the EEMs of the IHSS sample dataset and it is determined by PARAFAC score correlations with phenol concentrations from the reagent-based method that components C2, C3, and C4 have the highest probability of containing phenolic groups. The results show the potential for PARAFAC analysis of multidimensional fluorescence data for monitoring the phenolic content of DOC.

Nitrogen gas purging for the deoxygenation of polyaromatic hydrocarbon solutions in cyclohexane for routine fluorescence analysis.

During routine fluorescence analysis, the presence of dissolved oxygen in solutions can result in the dynamic quenching of a fluorophore's emission through collisional deexcitation of the fluorophore's excited state. In order to avoid this type of fluorescence quenching, dissolved oxygen is often removed from solutions by an inert gas purging procedure. However, the details and quantification of this purging process are often limited in fluorescence studies. In this work, standard 10 mm x 10 mm fluorescence cuvettes are filled with polyaromatic hydrocarbon (PAH) solutions in cyclohexane and purged using nitrogen gas, and the experimental purging parameters (nitrogen flow rate, amount of volatile solvent loss, and rate of oxygen removal) are measured and analyzed. For experimental conditions similar to those used in this study, we are able to provide useful guidelines for the deoxygenation of solutions, specifically the purge times required for solutions of fluorophores with various fluorescence lifetimes. Enhancement factors, or F(0)/F values (the ratio of fluorescence intensity of a completely deoxygenated solution to the fluorescence intensity of an aerated solution), for chrysene, phenanthrene, naphthalene, and pyrene solutions in cyclohexane were found to be 3.61 +/- 0.02, 4.17 +/- 0.02, 7.63 +/- 0.07, and 21.81 +/- 0.35, respectively.