NGS-based likelihood ratio for identifying contributors in two- and three-person DNA mixtures.

PubMed

Chan Mun Wei, Joshua; Zhao, Zicheng; Li, Shuai Cheng; Ng, Yen Kaow

2018-06-01

DNA fingerprinting, also known as DNA profiling, serves as a standard procedure in forensics to identify a person by the short tandem repeat (STR) loci in their DNA. By comparing the STR loci between DNA samples, practitioners can calculate a probability of match to identity the contributors of a DNA mixture. Most existing methods are based on 13 core STR loci which were identified by the Federal Bureau of Investigation (FBI). Analyses based on these loci of DNA mixture for forensic purposes are highly variable in procedures, and suffer from subjectivity as well as bias in complex mixture interpretation. With the emergence of next-generation sequencing (NGS) technologies, the sequencing of billions of DNA molecules can be parallelized, thus greatly increasing throughput and reducing the associated costs. This allows the creation of new techniques that incorporate more loci to enable complex mixture interpretation. In this paper, we propose a computation for likelihood ratio that uses NGS (next generation sequencing) data for DNA testing on mixed samples. We have applied the method to 4480 simulated DNA mixtures, which consist of various mixture proportions of 8 unrelated whole-genome sequencing data. The results confirm the feasibility of utilizing NGS data in DNA mixture interpretations. We observed an average likelihood ratio as high as 285,978 for two-person mixtures. Using our method, all 224 identity tests for two-person mixtures and three-person mixtures were correctly identified. Copyright © 2018 Elsevier Ltd. All rights reserved.

"Unresolved Complex Mixture" (UCM): A brief history of the term and moving beyond it.

PubMed

Farrington, John W; Quinn, James G

2015-07-15

The term "Unresolved Complex Mixture" (UCM) has been used extensively for decades to describe a gas chromatographic characteristic indicative of the presence of fossil fuel hydrocarbons (mainly petroleum hydrocarbons) in hydrocarbons isolated from aquatic samples. We chronicle the origin of the term. While it is still a useful characteristic for screening samples, more modern higher resolution two dimensional gas chromatography and gas chromatography coupled with advanced mass spectrometry techniques (Time-of-Flight or Fourier Transform-Ion Cyclotron Resonance) should be employed for analyses of petroleum contaminated samples. This will facilitate advances in understanding of the origins, fates and effects of petroleum compounds in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Prospective power calculations for the Four Lab study of a multigenerational reproductive/developmental toxicity rodent bioassay using a complex mixture of disinfection by-products in the low-response region.

PubMed

Dingus, Cheryl A; Teuschler, Linda K; Rice, Glenn E; Simmons, Jane Ellen; Narotsky, Michael G

2011-10-01

In complex mixture toxicology, there is growing emphasis on testing environmentally representative doses that improve the relevance of results for health risk assessment, but are typically much lower than those used in traditional toxicology studies. Traditional experimental designs with typical sample sizes may have insufficient statistical power to detect effects caused by environmentally relevant doses. Proper study design, with adequate statistical power, is critical to ensuring that experimental results are useful for environmental health risk assessment. Studies with environmentally realistic complex mixtures have practical constraints on sample concentration factor and sample volume as well as the number of animals that can be accommodated. This article describes methodology for calculation of statistical power for non-independent observations for a multigenerational rodent reproductive/developmental bioassay. The use of the methodology is illustrated using the U.S. EPA's Four Lab study in which rodents were exposed to chlorinated water concentrates containing complex mixtures of drinking water disinfection by-products. Possible experimental designs included two single-block designs and a two-block design. Considering the possible study designs and constraints, a design of two blocks of 100 females with a 40:60 ratio of control:treated animals and a significance level of 0.05 yielded maximum prospective power (~90%) to detect pup weight decreases, while providing the most power to detect increased prenatal loss.

Prospective Power Calculations for the Four Lab Study of A Multigenerational Reproductive/Developmental Toxicity Rodent Bioassay Using A Complex Mixture of Disinfection By-Products in the Low-Response Region

PubMed Central

Dingus, Cheryl A.; Teuschler, Linda K.; Rice, Glenn E.; Simmons, Jane Ellen; Narotsky, Michael G.

2011-01-01

In complex mixture toxicology, there is growing emphasis on testing environmentally representative doses that improve the relevance of results for health risk assessment, but are typically much lower than those used in traditional toxicology studies. Traditional experimental designs with typical sample sizes may have insufficient statistical power to detect effects caused by environmentally relevant doses. Proper study design, with adequate statistical power, is critical to ensuring that experimental results are useful for environmental health risk assessment. Studies with environmentally realistic complex mixtures have practical constraints on sample concentration factor and sample volume as well as the number of animals that can be accommodated. This article describes methodology for calculation of statistical power for non-independent observations for a multigenerational rodent reproductive/developmental bioassay. The use of the methodology is illustrated using the U.S. EPA’s Four Lab study in which rodents were exposed to chlorinated water concentrates containing complex mixtures of drinking water disinfection by-products. Possible experimental designs included two single-block designs and a two-block design. Considering the possible study designs and constraints, a design of two blocks of 100 females with a 40:60 ratio of control:treated animals and a significance level of 0.05 yielded maximum prospective power (~90%) to detect pup weight decreases, while providing the most power to detect increased prenatal loss. PMID:22073030

Estimation of affinities of ligands in mixtures via magnetic recovery of target-ligand complexes and chromatographic analyses: chemometrics and an experimental model

PubMed Central

2011-01-01

Abstract Background The combinatorial library strategy of using multiple candidate ligands in mixtures as library members is ideal in terms of cost and efficiency, but needs special screening methods to estimate the affinities of candidate ligands in such mixtures. Herein, a new method to screen candidate ligands present in unknown molar quantities in mixtures was investigated. Results The proposed method involves preparing a processed-mixture-for-screening (PMFS) with each mixture sample and an exogenous reference ligand, initiating competitive binding among ligands from the PMFS to a target immobilized on magnetic particles, recovering target-ligand complexes in equilibrium by magnetic force, extracting and concentrating bound ligands, and analyzing ligands in the PMFS and the concentrated extract by chromatography. The relative affinity of each candidate ligand to its reference ligand is estimated via an approximation equation assuming (a) the candidate ligand and its reference ligand bind to the same site(s) on the target, (b) their chromatographic peak areas are over five times their intercepts of linear response but within their linear ranges, (c) their binding ratios are below 10%. These prerequisites are met by optimizing primarily the quantity of the target used and the PMFS composition ratio. The new method was tested using the competitive binding of biotin derivatives from mixtures to streptavidin immobilized on magnetic particles as a model. Each mixture sample containing a limited number of candidate biotin derivatives with moderate differences in their molar quantities were prepared via parallel-combinatorial-synthesis (PCS) without purification, or via the pooling of individual compounds. Some purified biotin derivatives were used as reference ligands. This method showed resistance to variations in chromatographic quantification sensitivity and concentration ratios; optimized conditions to validate the approximation equation could be applied to different mixture samples. Relative affinities of candidate biotin derivatives with unknown molar quantities in each mixture sample were consistent with those estimated by a homogenous method using their purified counterparts as samples. Conclusions This new method is robust and effective for each mixture possessing a limited number of candidate ligands whose molar quantities have moderate differences, and its integration with PCS has promise to routinely practice the mixture-based library strategy. PMID:21545719

Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments

USGS Publications Warehouse

Alvarez, D.A.; Petty, J.D.; Huckins, J.N.; Jones-Lepp, T. L.; Getting, D.T.; Goddard, J.P.; Manahan, S.E.

2004-01-01

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log KowS < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

DEVELOPMENT OF A PASSIVE, IN SITU, INTEGRATIVE ...

EPA Pesticide Factsheets

Until recently, hydrophobic, bioconcentratable compounds have been the primary focus of most environmental organic contaminant investigations, There is an increasing realization that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants as well. This group of compounds includes a wide variety of chemicals, including potentially endocrine disrupting and estrogenic contaminants which have been shown to contribute to numerous abnormalities such as impaired reproduction in aquatic organisms exposed in environmental waters. To address this issue, we developed a passive, in situ, sampling device (the Polar Organic Chemical Integrative Sampler or POCIS) which integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations and provides a screening assessment of the toxicological significance of the complex mixture of waterborne contaminants. Using a prototype sampler (effective membrane sampling surface area = 18.2 cm 2) linear uptake of selected herbicides and pharmaceuticals was observed for up to 56 days. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS chemical sampling rates. The research focused on in the subtasks is the development and application of state-of

Quantifying mineral abundances of complex mixtures by coupling spectral deconvolution of SWIR spectra (2.1-2.4 μm) and regression tree analysis

USGS Publications Warehouse

Mulder, V.L.; Plotze, Michael; de Bruin, Sytze; Schaepman, Michael E.; Mavris, C.; Kokaly, Raymond F.; Egli, Markus

2013-01-01

This paper presents a methodology for assessing mineral abundances of mixtures having more than two constituents using absorption features in the 2.1-2.4 μm wavelength region. In the first step, the absorption behaviour of mineral mixtures is parameterised by exponential Gaussian optimisation. Next, mineral abundances are predicted by regression tree analysis using these parameters as inputs. The approach is demonstrated on a range of prepared samples with known abundances of kaolinite, dioctahedral mica, smectite, calcite and quartz and on a set of field samples from Morocco. The latter contained varying quantities of other minerals, some of which did not have diagnostic absorption features in the 2.1-2.4 μm region. Cross validation showed that the prepared samples of kaolinite, dioctahedral mica, smectite and calcite were predicted with a root mean square error (RMSE) less than 9 wt.%. For the field samples, the RMSE was less than 8 wt.% for calcite, dioctahedral mica and kaolinite abundances. Smectite could not be well predicted, which was attributed to spectral variation of the cations within the dioctahedral layered smectites. Substitution of part of the quartz by chlorite at the prediction phase hardly affected the accuracy of the predicted mineral content; this suggests that the method is robust in handling the omission of minerals during the training phase. The degree of expression of absorption components was different between the field sample and the laboratory mixtures. This demonstrates that the method should be calibrated and trained on local samples. Our method allows the simultaneous quantification of more than two minerals within a complex mixture and thereby enhances the perspectives of spectral analysis for mineral abundances.

Role of an Oxidant Mixture as Surface Modifier of Porous Silicon Microstructures Evaluated by Spectroscopic Ellipsometry

PubMed Central

Montiel-González, Zeuz; Escobar, Salvador; Nava, Rocío; del Río, J. Antonio; Tagüeña-Martínez, Julia

2016-01-01

Current research on porous silicon includes the construction of complex structures with luminescent and/or photonic properties. However, their preparation with both characteristics is still challenging. Recently, our group reported a possible method to achieve that by adding an oxidant mixture to the electrolyte used to produce porous silicon. This mixture can chemically modify their microstructure by changing the thickness and surface passivation of the pore walls. In this work, we prepared a series of samples (with and without oxidant mixture) and we evaluated the structural differences through their scanning electron micrographs and their optical properties determined by spectroscopic ellipsometry. The results showed that ellipsometry is sensitive to slight variations in the porous silicon structure, caused by changes in their preparation. The fitting process, based on models constructed from the features observed in the micrographs, allowed us to see that the mayor effect of the oxidant mixture is on samples of high porosity, where the surface oxidation strongly contributes to the skeleton thinning during the electrochemical etching. This suggests the existence of a porosity threshold for the action of the oxidant mixture. These results could have a significant impact on the design of complex porous silicon structures for different optoelectronic applications. PMID:27097767

Role of an Oxidant Mixture as Surface Modifier of Porous Silicon Microstructures Evaluated by Spectroscopic Ellipsometry.

PubMed

Montiel-González, Zeuz; Escobar, Salvador; Nava, Rocío; del Río, J Antonio; Tagüeña-Martínez, Julia

2016-04-21

Current research on porous silicon includes the construction of complex structures with luminescent and/or photonic properties. However, their preparation with both characteristics is still challenging. Recently, our group reported a possible method to achieve that by adding an oxidant mixture to the electrolyte used to produce porous silicon. This mixture can chemically modify their microstructure by changing the thickness and surface passivation of the pore walls. In this work, we prepared a series of samples (with and without oxidant mixture) and we evaluated the structural differences through their scanning electron micrographs and their optical properties determined by spectroscopic ellipsometry. The results showed that ellipsometry is sensitive to slight variations in the porous silicon structure, caused by changes in their preparation. The fitting process, based on models constructed from the features observed in the micrographs, allowed us to see that the mayor effect of the oxidant mixture is on samples of high porosity, where the surface oxidation strongly contributes to the skeleton thinning during the electrochemical etching. This suggests the existence of a porosity threshold for the action of the oxidant mixture. These results could have a significant impact on the design of complex porous silicon structures for different optoelectronic applications.

Constituent bioconcentration in rainbow trout exposed to a complex chemical mixture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Linder, G.; Bergman, H.L.; Meyer, J.S.

1984-09-01

Classically, aquatic contaminant fate models predicting a chemical's bioconcentration factor (BCF) are based upon single-compound derived models, yet such BCF predictions may deviate from observed BCFs when physicochemical interactions or biological responses to complex chemical mixture exposures are not adequately considered in the predictive model. Rainbow trout were exposed to oil-shale retort waters. Such a study was designed to model the potential biological effects precluded by exposure to complex chemical mixtures such as solid waste leachates, agricultural runoff, and industrial process waste waters. Chromatographic analysis of aqueous and nonaqueous liquid-liquid reservoir components yielded differences in mixed extraction solvent HPLC profilesmore » of whole fish exposed for 1 and 3 weeks to the highest dilution of the complex chemical mixture when compared to their corresponding control, yet subsequent whole fish extractions at 6, 9, 12, and 15 weeks into exposure demonstrated no qualitative differences between control and exposed fish. Liver extractions and deproteinized bile samples from exposed fish were qualitatively different than their corresponding controls. These findings support the projected NOEC of 0.0045% dilution, even though the differences in bioconcentration profiles suggest hazard assessment strategies may be useful in evaluating environmental fate processes associated with complex chemical mixtures. 12 references, 4 figures, 2 tables.« less

Performance characterizations of asphalt binders and mixtures incorporating silane additive ZycoTherm

NASA Astrophysics Data System (ADS)

Hasan, Mohd Rosli Mohd; Hamzah, Meor Othman; Yee, Teh Sek

2017-10-01

Experimental works were conducted to evaluate the properties of asphalt binders and mixtures produced using a relatively new silane additive, named ZycoTherm. In this study, 0.1wt% ZycoTherm was blended with asphalt binder to enable production of asphalt mixture at lower than normal temperatures, as well as improve mix workability and compactability. Asphalt mixture performances towards pavement distresses in tropical climate region were also investigated. The properties of control asphalt binders (60/70 and 80/10 penetration grade) and asphalt binders incorporating 0.1% ZycoTherm were reported based on the penetration, softening point, rotational viscosity, complex modulus and phase angle. Subsequently, to compare the performance of asphalt mixture incorporating ZycoTherm with the control asphalt mixture, cylindrical samples were prepared at recommended temperatures and air voids depending on the binder types and test requirements. The samples were tested for indirect tensile strength (ITS), resilient modulus, dynamic creep, Hamburg wheel tracking and moisture induced damage. From compaction data using the Servopak gyratory compactor, specimen prepared using ZycoTherm exhibit higher workability and compactability compared to the conventional mixture. From the mixture performance test results, mixtures prepared with ZycoTherm showed comparable if not better performance than the control sample in terms of the resistance to moisture damage, permanent deformation and cracking.

Application of stored waveform ion modulation 2D-FTICR MS/MS to the analysis of complex mixtures.

PubMed

Ross, Charles W; Simonsick, William J; Aaserud, David J

2002-09-15

Component identification of complex mixtures, whether they are from polymeric formulations or combinatorial synthesis, by conventional MS/MS techniques generally requires component separation by chromatography or mass spectrometry. An automated means of acquiring simultaneous MS/MS data from a complex mixture without prior separation is obtained from stored waveform ion modulation (SWIM) two-dimensional FTICR MS/MS. The technique applies a series of SWIFT excitation waveforms whose frequency domain magnitude spectrum is a sinusoid increasing in frequency from one waveform to the next. The controlled dissociation of the precursor ions produces an associated modulation of the product ion abundances. Fourier transformation of these abundances reveals the encoded modulation frequency from which connectivities of precursor and product ions are observed. The final result is total assignment of product ions for each precursor ion in a mixture from one automated experiment. We demonstrated the applicability of SWIM 2D-FTICR MS/MS to two diverse samples of industrial importance. We characterized structured polyester oligomers and products derived from combinatorial synthesis. Fragmentation pathways identified in standard serial ion isolation MS/MS experiments were observed for trimethylolpropane/methyl hexahydrophthalic anhydride. A 20-component sample derived from combinatorial synthesis was fragmented, and the template ion along with another key fragment ion was identified for each of the 20 components.

Using Ion Exchange Chromatography to Separate and Quantify Complex Ions

ERIC Educational Resources Information Center

Johnson, Brian J.

2014-01-01

Ion exchange chromatography is an important technique in the separation of charged species, particularly in biological, inorganic, and environmental samples. In this experiment, students are supplied with a mixture of two substitution-inert complex ions. They separate the complexes by ion exchange chromatography using a "flash"…

Cumulative assessment of steroid receptor mediated activity of contaminants in water samples using in vitro bioassays.

EPA Science Inventory

Cell-based assays could serve as a useful tool in the regulatory screening toolbox due to their high sensitivity and the ability to assess complex mixtures in which unknown compounds may be present. We have completed 3 major projects in collaboration with USGS: 1) Chemical Mixtur...

Massively parallel sequencing-enabled mixture analysis of mitochondrial DNA samples.

PubMed

Churchill, Jennifer D; Stoljarova, Monika; King, Jonathan L; Budowle, Bruce

2018-02-22

The mitochondrial genome has a number of characteristics that provide useful information to forensic investigations. Massively parallel sequencing (MPS) technologies offer improvements to the quantitative analysis of the mitochondrial genome, specifically the interpretation of mixed mitochondrial samples. Two-person mixtures with nuclear DNA ratios of 1:1, 5:1, 10:1, and 20:1 of individuals from different and similar phylogenetic backgrounds and three-person mixtures with nuclear DNA ratios of 1:1:1 and 5:1:1 were prepared using the Precision ID mtDNA Whole Genome Panel and Ion Chef, and sequenced on the Ion PGM or Ion S5 sequencer (Thermo Fisher Scientific, Waltham, MA, USA). These data were used to evaluate whether and to what degree MPS mixtures could be deconvolved. Analysis was effective in identifying the major contributor in each instance, while SNPs from the minor contributor's haplotype only were identified in the 1:1, 5:1, and 10:1 two-person mixtures. While the major contributor was identified from the 5:1:1 mixture, analysis of the three-person mixtures was more complex, and the mixed haplotypes could not be completely parsed. These results indicate that mixed mitochondrial DNA samples may be interpreted with the use of MPS technologies.

Capacity building and predictors of success for HIV-1 drug resistance testing in the Asia-Pacific region and Africa

PubMed Central

Land, Sally; Zhou, Julian; Cunningham, Philip; Sohn, Annette H; Singtoroj, Thida; Katzenstein, David; Mann, Marita; Sayer, David; Kantor, Rami

2013-01-01

Background The TREAT Asia Quality Assessment Scheme (TAQAS) was developed as a quality assessment programme through expert education and training, for laboratories in the Asia-Pacific and Africa that perform HIV drug-resistance (HIVDR) genotyping. We evaluated the programme performance and factors associated with high-quality HIVDR genotyping. Methods Laboratories used their standard protocols to test panels of human immunodeficiency virus (HIV)-positive plasma samples or electropherograms. Protocols were documented and performance was evaluated according to a newly developed scoring system, agreement with panel-specific consensus sequence, and detection of drug-resistance mutations (DRMs) and mixtures of wild-type and resistant virus (mixtures). High-quality performance was defined as detection of ≥95% DRMs. Results Over 4.5 years, 23 participating laboratories in 13 countries tested 45 samples (30 HIV-1 subtype B; 15 non-B subtypes) in nine panels. Median detection of DRMs was 88–98% in plasma panels and 90–97% in electropherogram panels. Laboratories were supported to amend and improve their test outcomes as appropriate. Three laboratories that detected <80% DRMs in early panels demonstrated subsequent improvement. Sample complexity factors – number of DRMs (p<0.001) and number of DRMs as mixtures (p<0.001); and laboratory performance factors – detection of mixtures (p<0.001) and agreement with consensus sequence (p<0.001), were associated with high performance; sample format (plasma or electropherogram), subtype and genotyping protocol were not. Conclusion High-quality HIVDR genotyping was achieved in the TAQAS collaborative laboratory network. Sample complexity and detection of mixtures were associated with performance quality. Laboratories conducting HIVDR genotyping are encouraged to participate in quality assessment programmes. PMID:23845227

Paper SERS chromatography for detection of trace analytes in complex samples

NASA Astrophysics Data System (ADS)

Yu, Wei W.; White, Ian M.

2013-05-01

We report the application of paper SERS substrates for the detection of trace quantities of multiple analytes in a complex sample in the form of paper chromatography. Paper chromatography facilitates the separation of different analytes from a complex sample into distinct sections in the chromatogram, which can then be uniquely identified using SERS. As an example, the separation and quantitative detection of heroin in a highly fluorescent mixture is demonstrated. Paper SERS chromatography has obvious applications, including law enforcement, food safety, and border protection, and facilitates the rapid detection of chemical and biological threats at the point of sample.

Separation and screening of short-chain chlorinated paraffins in environmental samples using comprehensive two-dimensional gas chromatography with micro electron capture detection.

PubMed

Xia, Dan; Gao, Lirong; Zhu, Shuai; Zheng, Minghui

2014-11-01

Short-chain chlorinated paraffins (SCCPs) are highly complex technical mixtures with thousands of isomers and numerous homologs. They are classified as priority candidate persistent organic pollutants under the Stockholm Convention for their persistence, bioaccumulation, and toxicity. Analyzing SCCPs is challenging because of the complexity of the mixtures. Chromatograms of SCCPs acquired using one-dimensional (1D) gas chromatography (GC) contain a large characteristic "peak" with a broad and unresolved profile. Comprehensive two-dimensional GC (GC×GC) shows excellent potential for separating complex mixtures. In this study, GC×GC coupled with micro electron capture detection (μECD) was used to separate and screen SCCPs. The chromatographic parameters, including the GC column types, oven temperature program, and modulation period, were systematically optimized. The SCCP congeners were separated into groups using a DM-1 column connected to a BPX-50 column. The SCCP congeners in technical mixtures were separated according to the number of chlorine substituents for a given carbon chain length and according to the number of carbon atoms plus chlorine atoms for different carbon chain lengths. A fish tissue sample was analyzed to illustrate the feasibility of the GC×GC-μECD method in analyzing biological samples. Over 1,500 compounds were identified in the fish extract, significantly more than were identified using 1D GC. The detection limits for five selected SCCP congeners were between 1 and 5 pg/L using the GC×GC method, and these were significantly lower than those achieved using 1D GC. This method is a good choice for analysis of SCCPs in environmental samples, exhibiting good separation and good sensitivity.

Characterizing the bioactivity of complex environmental ...

EPA Pesticide Factsheets

Bioassays can be employed to evaluate the integrated effects of complex mixtures of both known and unidentified contaminants present in environmental samples. However, such methods have typically focused on one or a few bioactivities despite the fact that the chemicals in a mixture may exhibit a wide range of activities. High throughput toxicology approaches that can rapidly screen samples for a broad diversity of biological activities offer a means to provide a more comprehensive characterization. To test this concept, twenty-four ambient water samples were collected, extracted, and screened for their ability to interact with or modulate over 80 different transcription factors using the Attagene subset of assays utilized by the US EPA’s ToxCast Program. Samples evaluated included water collected at five sites along a spatial gradient centered around a wastewater discharge into the Maumee River, Ohio, USA; 10 samples were collected in varying proximity to a wastewater discharge within the St. Louis River Area of Concern (AOC), MN; and eight samples were associated with a nation-wide US Geological Survey Mixture Study. Samples collected along the Maumee River showed a gradient response in the number of observed activities, ranging from three positive assay responses observed far upstream of discharge to seven positive responses in water from the mixing zone. TGFb signaling and the aryl hydrocarbon receptor (AhR) activation were the biological activities obser

Application of the high throughput Attagene Factorial TM ...

EPA Pesticide Factsheets

Bioassays can be employed to evaluate the integrated effects of complex mixtures of both known and unidentified contaminants present in environmental samples. However, such methods have typically focused on one or a few pathways despite the fact that the chemicals in a mixture may exhibit a wide range of activities. High throughput toxicology approaches that can rapidly screen samples for a broad diversity of biological activities offer a means to provide a more comprehensive characterization of complex mixtures. To test this concept, twenty-four ambient water samples were collected, extracted, and screened for their ability to interact with or modulate over 80 different transcription factors using the Attagene FactorialTM platform utilized by the US EPA’s ToxCast Program. Samples evaluated included 10 water samples collected in varying proximity to a wastewater discharge into the St. Louis River, MN; water collected at five sites along a gradient centered on a wastewater discharge into the Maumee River, Ohio, USA; and eight samples collected in association with a nation-wide USGS surface streams study. For samples collected along the St. Louis River, the greatest number of biological activities were observed at locations closest to wastewater discharge with up to 13 endpoints responding. The Maumee River showed a gradient response in the number of observed activities, ranging from three positive responses observed far upstream of a wastewater discharge to 10

Detection of High Levels of Endocrine Activity in Selected Environmental Surface Water Samples Using ER, AR, and GR-mediated In Vitro Bioassays

EPA Science Inventory

Determining the associated health risks of exposure to complex mixtures in the environment is a recognized challenge. The Chemical Mixtures project, a collaborative effort between USEPA and USGS, is making a step in that direction by examining the co-occurrence of chemicals and b...

Rapid Quadrupole-Time-of-Flight Mass Spectrometry Method Quantifies Oxygen-Rich Lignin Compound in Complex Mixtures

NASA Astrophysics Data System (ADS)

Boes, Kelsey S.; Roberts, Michael S.; Vinueza, Nelson R.

2018-03-01

Complex mixture analysis is a costly and time-consuming task facing researchers with foci as varied as food science and fuel analysis. When faced with the task of quantifying oxygen-rich bio-oil molecules in a complex diesel mixture, we asked whether complex mixtures could be qualitatively and quantitatively analyzed on a single mass spectrometer with mid-range resolving power without the use of lengthy separations. To answer this question, we developed and evaluated a quantitation method that eliminated chromatography steps and expanded the use of quadrupole-time-of-flight mass spectrometry from primarily qualitative to quantitative as well. To account for mixture complexity, the method employed an ionization dopant, targeted tandem mass spectrometry, and an internal standard. This combination of three techniques achieved reliable quantitation of oxygen-rich eugenol in diesel from 300 to 2500 ng/mL with sufficient linearity (R2 = 0.97 ± 0.01) and excellent accuracy (percent error = 0% ± 5). To understand the limitations of the method, it was compared to quantitation attained on a triple quadrupole mass spectrometer, the gold standard for quantitation. The triple quadrupole quantified eugenol from 50 to 2500 ng/mL with stronger linearity (R2 = 0.996 ± 0.003) than the quadrupole-time-of-flight and comparable accuracy (percent error = 4% ± 5). This demonstrates that a quadrupole-time-of-flight can be used for not only qualitative analysis but also targeted quantitation of oxygen-rich lignin molecules in complex mixtures without extensive sample preparation. The rapid and cost-effective method presented here offers new possibilities for bio-oil research, including: (1) allowing for bio-oil studies that demand repetitive analysis as process parameters are changed and (2) making this research accessible to more laboratories. [Figure not available: see fulltext.

Rapid Quadrupole-Time-of-Flight Mass Spectrometry Method Quantifies Oxygen-Rich Lignin Compound in Complex Mixtures

NASA Astrophysics Data System (ADS)

Boes, Kelsey S.; Roberts, Michael S.; Vinueza, Nelson R.

2017-12-01

Complex mixture analysis is a costly and time-consuming task facing researchers with foci as varied as food science and fuel analysis. When faced with the task of quantifying oxygen-rich bio-oil molecules in a complex diesel mixture, we asked whether complex mixtures could be qualitatively and quantitatively analyzed on a single mass spectrometer with mid-range resolving power without the use of lengthy separations. To answer this question, we developed and evaluated a quantitation method that eliminated chromatography steps and expanded the use of quadrupole-time-of-flight mass spectrometry from primarily qualitative to quantitative as well. To account for mixture complexity, the method employed an ionization dopant, targeted tandem mass spectrometry, and an internal standard. This combination of three techniques achieved reliable quantitation of oxygen-rich eugenol in diesel from 300 to 2500 ng/mL with sufficient linearity (R2 = 0.97 ± 0.01) and excellent accuracy (percent error = 0% ± 5). To understand the limitations of the method, it was compared to quantitation attained on a triple quadrupole mass spectrometer, the gold standard for quantitation. The triple quadrupole quantified eugenol from 50 to 2500 ng/mL with stronger linearity (R2 = 0.996 ± 0.003) than the quadrupole-time-of-flight and comparable accuracy (percent error = 4% ± 5). This demonstrates that a quadrupole-time-of-flight can be used for not only qualitative analysis but also targeted quantitation of oxygen-rich lignin molecules in complex mixtures without extensive sample preparation. The rapid and cost-effective method presented here offers new possibilities for bio-oil research, including: (1) allowing for bio-oil studies that demand repetitive analysis as process parameters are changed and (2) making this research accessible to more laboratories. [Figure not available: see fulltext.

Rapid Quadrupole-Time-of-Flight Mass Spectrometry Method Quantifies Oxygen-Rich Lignin Compound in Complex Mixtures.

PubMed

Boes, Kelsey S; Roberts, Michael S; Vinueza, Nelson R

2018-03-01

Complex mixture analysis is a costly and time-consuming task facing researchers with foci as varied as food science and fuel analysis. When faced with the task of quantifying oxygen-rich bio-oil molecules in a complex diesel mixture, we asked whether complex mixtures could be qualitatively and quantitatively analyzed on a single mass spectrometer with mid-range resolving power without the use of lengthy separations. To answer this question, we developed and evaluated a quantitation method that eliminated chromatography steps and expanded the use of quadrupole-time-of-flight mass spectrometry from primarily qualitative to quantitative as well. To account for mixture complexity, the method employed an ionization dopant, targeted tandem mass spectrometry, and an internal standard. This combination of three techniques achieved reliable quantitation of oxygen-rich eugenol in diesel from 300 to 2500 ng/mL with sufficient linearity (R 2 = 0.97 ± 0.01) and excellent accuracy (percent error = 0% ± 5). To understand the limitations of the method, it was compared to quantitation attained on a triple quadrupole mass spectrometer, the gold standard for quantitation. The triple quadrupole quantified eugenol from 50 to 2500 ng/mL with stronger linearity (R 2 = 0.996 ± 0.003) than the quadrupole-time-of-flight and comparable accuracy (percent error = 4% ± 5). This demonstrates that a quadrupole-time-of-flight can be used for not only qualitative analysis but also targeted quantitation of oxygen-rich lignin molecules in complex mixtures without extensive sample preparation. The rapid and cost-effective method presented here offers new possibilities for bio-oil research, including: (1) allowing for bio-oil studies that demand repetitive analysis as process parameters are changed and (2) making this research accessible to more laboratories. Graphical Abstract ᅟ.

Modern analytics for synthetically derived complex drug substances: NMR, AFFF-MALS, and MS tests for glatiramer acetate.

PubMed

Rogstad, Sarah; Pang, Eric; Sommers, Cynthia; Hu, Meng; Jiang, Xiaohui; Keire, David A; Boyne, Michael T

2015-11-01

Glatiramer acetate (GA) is a mixture of synthetic copolymers consisting of four amino acids (glutamic acid, lysine, alanine, and tyrosine) with a labeled molecular weight range of 5000 to 9000 Da. GA is marketed as Copaxone™ by Teva for the treatment of multiple sclerosis. Here, the agency has evaluated the structure and composition of GA and a commercially available comparator, Copolymer-1. Modern analytical technologies which can characterize these complex mixtures are desirable for analysis of their comparability and structural "sameness." In the studies herein, a molecular fingerprinting approach is taken using mass-accurate mass spectrometry (MS) analysis, nuclear magnetic resonance (NMR) (1D-(1)H-NMR, 1D-(13)C-NMR, and 2D NMR), and asymmetric field flow fractionation (AFFF) coupled with multi-angle light scattering (MALS) for an in-depth characterization of three lots of the marketplace drug and a formulated sample of the comparator. Statistical analyses were applied to the MS and AFFF-MALS data to assess these methods' ability to detect analytical differences in the mixtures. The combination of multiple orthogonal measurements by liquid chromatography coupled with MS (LC-MS), AFFF-MALS, and NMR on the same sample set was found to be fit for the intended purpose of distinguishing analytical differences between these complex mixtures of peptide chains.

(1)H NMR spectroscopy for profiling complex carbohydrate mixtures in non-fractionated beer.

PubMed

Petersen, Bent O; Nilsson, Mathias; Bøjstrup, Marie; Hindsgaul, Ole; Meier, Sebastian

2014-05-01

A plethora of biological and biotechnological processes involve the enzymatic remodelling of carbohydrates in complex mixtures whose compositions affect both the processes and products. In the current study, we employed high-resolution (1)H NMR spectroscopy for the analysis of cereal-derived carbohydrate mixtures as exemplified on six beer samples of different styles. Structural assignments of more than 50 carbohydrate moieties were obtained using (1)H1-(1)H2 groups as structural reporters. Spectroscopically resolved carbohydrates include more than ''20 different'' small carbohydrates with more than 38 isomeric forms in addition to cereal polysaccharide fragments with suspected organoleptic and prebiotic function. Structural motifs at the cleavage sites of starch, β-glucan and arabinoxylan fragments were identified, showing different extent and specificity of enzymatic polysaccharide cleavage during the production of different beer samples. Diffusion ordered spectroscopy supplied independent size information for the characterisation and identification of polysaccharide fragments, indicating the presence especially of high molecular weight arabinoxylan fragments in the final beer. Copyright © 2013 Elsevier Ltd. All rights reserved.

Transferring mixtures of chemicals from sediment to a bioassay using silicone-based passive sampling and dosing.

PubMed

Mustajärvi, Lukas; Eriksson-Wiklund, Ann-Kristin; Gorokhova, Elena; Jahnke, Annika; Sobek, Anna

2017-11-15

Environmental mixtures of chemicals consist of a countless number of compounds with unknown identity and quantity. Yet, chemical regulation is mainly built around the assessment of single chemicals. Existing frameworks for assessing the toxicity of mixtures require that both the chemical composition and quantity are known. Quantitative analyses of the chemical composition of environmental mixtures are however extremely challenging and resource-demanding. Bioassays may therefore serve as a useful approach for investigating the combined toxicity of environmental mixtures of chemicals in a cost-efficient and holistic manner. In this study, an unknown environmental mixture of bioavailable semi-hydrophobic to hydrophobic chemicals was sampled from a contaminated sediment in a coastal Baltic Sea area using silicone polydimethylsiloxane (PDMS) as an equilibrium passive sampler. The chemical mixture was transferred to a PDMS-based passive dosing system, and its applicability was demonstrated using green algae Tetraselmis suecica in a cell viability assay. The proportion of dead cells increased significantly with increasing exposure level and in a dose-response manner. At an ambient concentration, the proportion of dead cells in the population was nearly doubled compared to the control; however, the difference was non-significant due to high inter-replicate variability and a low number of replicates. The validation of the test system regarding equilibrium sampling, loading efficiency into the passive dosing polymer, stability of the mixture composition, and low algal mortality in control treatments demonstrates that combining equilibrium passive sampling and passive dosing is a promising tool for investigating the toxicity of bioavailable semi-hydrophobic and hydrophobic chemicals in complex environmental mixtures.

Application of Biologically Based Lumping To Investigate the Toxicokinetic Interactions of a Complex Gasoline Mixture.

PubMed

Jasper, Micah N; Martin, Sheppard A; Oshiro, Wendy M; Ford, Jermaine; Bushnell, Philip J; El-Masri, Hisham

2016-03-15

People are often exposed to complex mixtures of environmental chemicals such as gasoline, tobacco smoke, water contaminants, or food additives. We developed an approach that applies chemical lumping methods to complex mixtures, in this case gasoline, based on biologically relevant parameters used in physiologically based pharmacokinetic (PBPK) modeling. Inhalation exposures were performed with rats to evaluate the performance of our PBPK model and chemical lumping method. There were 109 chemicals identified and quantified in the vapor in the chamber. The time-course toxicokinetic profiles of 10 target chemicals were also determined from blood samples collected during and following the in vivo experiments. A general PBPK model was used to compare the experimental data to the simulated values of blood concentration for 10 target chemicals with various numbers of lumps, iteratively increasing from 0 to 99. Large reductions in simulation error were gained by incorporating enzymatic chemical interactions, in comparison to simulating the individual chemicals separately. The error was further reduced by lumping the 99 nontarget chemicals. The same biologically based lumping approach can be used to simplify any complex mixture with tens, hundreds, or thousands of constituents.

An assessment of the information content of likelihood ratios derived from complex mixtures.

PubMed

Marsden, Clare D; Rudin, Norah; Inman, Keith; Lohmueller, Kirk E

2016-05-01

With the increasing sensitivity of DNA typing methodologies, as well as increasing awareness by law enforcement of the perceived capabilities of DNA typing, complex mixtures consisting of DNA from two or more contributors are increasingly being encountered. However, insufficient research has been conducted to characterize the ability to distinguish a true contributor (TC) from a known non-contributor (KNC) in these complex samples, and under what specific conditions. In order to investigate this question, sets of six 15-locus Caucasian genotype profiles were simulated and used to create mixtures containing 2-5 contributors. Likelihood ratios were computed for various situations, including varying numbers of contributors and unknowns in the evidence profile, as well as comparisons of the evidence profile to TCs and KNCs. This work was intended to illustrate the best-case scenario, in which all alleles from the TC were detected in the simulated evidence samples. Therefore the possibility of drop-out was not modeled in this study. The computer program DNAMIX was then used to compute LRs comparing the evidence profile to TCs and KNCs. This resulted in 140,000 LRs for each of the two scenarios. These complex mixture simulations show that, even when all alleles are detected (i.e. no drop-out), TCs can generate LRs less than 1 across a 15-locus profile. However, this outcome was rare, 7 of 140,000 replicates (0.005%), and associated only with mixtures comprising 5 contributors in which the numerator hypothesis includes one or more unknown contributors. For KNCs, LRs were found to be greater than 1 in a small number of replicates (75 of 140,000 replicates, or 0.05%). These replicates were limited to 4 and 5 person mixtures with 1 or more unknowns in the numerator. Only 5 of these 75 replicates (0.004%) yielded an LR greater than 1,000. Thus, overall, these results imply that the weight of evidence that can be derived from complex mixtures containing up to 5 contributors, under a scenario in which no drop-out is required to explain any of the contributors, is remarkably high. This is a useful benchmark result on top of which to layer the effects of additional factors, such as drop-out, peak height, and other variables. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Enzyme-coupled nanoparticles-assisted laser desorption ionization mass spectrometry for searching for low-mass inhibitors of enzymes in complex mixtures.

PubMed

Salwiński, Aleksander; Da Silva, David; Delépée, Raphaël; Maunit, Benoît

2014-04-01

In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: 'ion fading' (IF-ENALDI), based on superficial adsorption of inhibitors and 'ion hunting' (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme-inhibitor pairs: tyrosinase-glabridin and trypsin-leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin-leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.

Improving Toxicity Assessment of Pesticide Mixtures: The Use of Polar Passive Sampling Devices Extracts in Microalgae Toxicity Tests

PubMed Central

Kim Tiam, Sandra; Fauvelle, Vincent; Morin, Soizic; Mazzella, Nicolas

2016-01-01

Complexity of contaminants exposure needs to be taking in account for an appropriate evaluation of risks related to mixtures of pesticides released in the ecosystems. Toxicity assessment of such mixtures can be made through a variety of toxicity tests reflecting different level of biological complexity. This paper reviews the recent developments of passive sampling techniques for polar compounds, especially Polar Organic Chemical Integrative Samplers (POCIS) and Chemcatcher® and the principal assessment techniques using microalgae in laboratory experiments. The progresses permitted by the coupled use of such passive samplers and ecotoxicology testing as well as their limitations are presented. Case studies combining passive sampling devices (PSD) extracts and toxicity assessment toward microorganisms at different biological scales from single organisms to communities level are presented. These case studies, respectively, aimed (i) at characterizing the “toxic potential” of waters using dose-response curves, and (ii) at performing microcosm experiments with increased environmental realism in the toxicant exposure in term of cocktail composition and concentration. Finally perspectives and limitations of such approaches for future applications in the area of environmental risk assessment are discussed. PMID:27667986

An innovative approach to sampling complex industrial emissions for use in animal toxicity tests: application to iron casting operations.

PubMed

Palmer, W G; Scholz, R C; Moorman, W J

1983-03-01

Sampling of complex mixtures of airborne contaminants for chronic animal toxicity tests often involves numerous sampling devices, requires extensive sampling time, and yields forms of collected materials unsuitable for administration to animals. A method is described which used a high volume, wet venturi scrubber for collection of respirable fractions of emissions from iron foundry casting operations. The construction and operation of the sampler are presented along with collection efficiency data and its application to the preparation of large quantities of samples to be administered to animals by intratracheal instillation.

Screening Complex Effluents for Estrogenic Activity with the T47D-Kbluc Cell Bioassay: Assay Optimization and Comparison to In Vivo Responses in Fish

EPA Science Inventory

The endocrine activity of complex mixtures of chemicals associated with wastewater treatment plant effluents, runoff from concentrated animal feeding operations (CAFOs), and/or other environmental samples can be difficult to characterize based on analytical chemistry. In vitro bi...

Production, Characterization, and Stability of Orange or Eucalyptus Essential Oil/β-Cyclodextrin Inclusion Complex.

PubMed

Kringel, Dianini Hüttner; Antunes, Mariana Dias; Klein, Bruna; Crizel, Rosane Lopes; Wagner, Roger; de Oliveira, Roberto Pedroso; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

2017-11-01

The aim of this study was to produce and characterize inclusion complexes (IC) between β-cyclodextrin (β-CD) and orange essential oil (OEO) or eucalyptus essential oil (EEO), and to compare these with their pure compounds and physical mixtures. The samples were evaluated by chemical composition, morphology, thermal stability, and volatile compounds by static headspace-gas chromatography (SH-GC). Comparing the free essential oil and physical mixture with the inclusion complex, of both essential oils (OEO and EEO), it was observed differences occurred in the chemical composition, thermal stability, and morphology. These differences show that there was the formation of the inclusion complex and demonstrate the necessity of the precipitation method used to guarantee the interaction between β-CD and essential oils. The slow loss of the volatile compounds from both essential oils, when complexed with β-CD, showed a higher stability when compared with their physical mixtures and free essential oils. Therefore, the results showed that the chemical composition, molecular size, and structure of the essential oils influence the characteristics of the inclusion complexes. The application of the β-CD in the formation of inclusion complexes with essential oils can expand the potential applications in foods. © 2017 Institute of Food Technologists®.

A new tunable dispersive liquid-liquid micro extraction method developed for the simultaneous preconcentration of lead and cadmium from lakes water: a multivariate study

NASA Astrophysics Data System (ADS)

Bilal, Muhammad; Kazi, Tasneem Gul; Afridi, Hassan Imran; Ali, Jamshed; Baig, Jameel Ahmed; Arain, Mohammad Balal; Khan, Mustafa

2017-08-01

A green tunable dispersive liquid-liquid micro extraction (TDLLME) technique was established for the simultaneous enrichment of lead (Pb) and cadmium (Cd) from different lakes water before analysis by flame atomic absorption spectrometry (FAAS). A solvent known as tunable polarity solvent (TPS), mixture of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1-decanol, has been employed as extractant in aqueous medium. In first step this mixture can be made polar by slowly bubbling the antisolvent trigger (CO2) through the solution, which makes a monophasic solution. During this step hydrophobic complexes of the metals with 8-hydroxy quinoline (8-HQ) were extracted by TPS. Then the mixture was switched back to hydrophobic one by heating and/or bubbling nitrogen, turning the mixture into two phases again. In second phase the metals were leached out from the complexes entrapped in TPS, by treating with a solution of nitric acid and exposing the mixture to CO2, which switched the mixture into single phase. Then N2 purging and/or heating again turned the mixture into two phases. The acidic aqueous phase containing the metals was introduced to FAAS for analysis, whereas TPS was recycled for next experiment. Different parameters, affecting the efficiency the technique, were optimized by multivariate approach. The method was applied to certified reference material of water and to a real sample spiked with standards of known concentration, to confirm its validity and accuracy. LOD obtained for Pb and Cd were 0.560 and 0.056 μg L- 1 respectively. The developed method was applied successfully to the real water samples of two lakes of Sindh, Pakistan.

Peptide Identification by Database Search of Mixture Tandem Mass Spectra*

PubMed Central

Wang, Jian; Bourne, Philip E.; Bandeira, Nuno

2011-01-01

In high-throughput proteomics the development of computational methods and novel experimental strategies often rely on each other. In certain areas, mass spectrometry methods for data acquisition are ahead of computational methods to interpret the resulting tandem mass spectra. Particularly, although there are numerous situations in which a mixture tandem mass spectrum can contain fragment ions from two or more peptides, nearly all database search tools still make the assumption that each tandem mass spectrum comes from one peptide. Common examples include mixture spectra from co-eluting peptides in complex samples, spectra generated from data-independent acquisition methods, and spectra from peptides with complex post-translational modifications. We propose a new database search tool (MixDB) that is able to identify mixture tandem mass spectra from more than one peptide. We show that peptides can be reliably identified with up to 95% accuracy from mixture spectra while considering only a 0.01% of all possible peptide pairs (four orders of magnitude speedup). Comparison with current database search methods indicates that our approach has better or comparable sensitivity and precision at identifying single-peptide spectra while simultaneously being able to identify 38% more peptides from mixture spectra at significantly higher precision. PMID:21862760

Notes on lunar ilmenite

NASA Technical Reports Server (NTRS)

Hutson, M. L.

1989-01-01

Opaques (mostly ilmenite) make up 0 to 5 percent of highland rocks, 1 to 11 percent of low-Ti mare basalts, and 10 to 34 percent of high-Ti mare basalts (Carter 1988). Apollos 11 and 17 sampled high-Ti basalts. Apollos 12 and 14 sampled low-Ti basalts. Apollo 15 sampled a complex mixture of mare and highland material. Apollo 16 sampled mainly highland material (Taylor 1975).

Novel selective TOCSY method enables NMR spectral elucidation of metabolomic mixtures

NASA Astrophysics Data System (ADS)

MacKinnon, Neil; While, Peter T.; Korvink, Jan G.

2016-11-01

Complex mixture analysis is routinely encountered in NMR-based investigations. With the aim of component identification, spectral complexity may be addressed chromatographically or spectroscopically, the latter being favored to reduce sample handling requirements. An attractive experiment is selective total correlation spectroscopy (sel-TOCSY), which is capable of providing tremendous spectral simplification and thereby enhancing assignment capability. Unfortunately, isolating a well resolved resonance is increasingly difficult as the complexity of the mixture increases and the assumption of single spin system excitation is no longer robust. We present TOCSY optimized mixture elucidation (TOOMIXED), a technique capable of performing spectral assignment particularly in the case where the assumption of single spin system excitation is relaxed. Key to the technique is the collection of a series of 1D sel-TOCSY experiments as a function of the isotropic mixing time (τm), resulting in a series of resonance intensities indicative of the underlying molecular structure. By comparing these τm -dependent intensity patterns with a library of pre-determined component spectra, one is able to regain assignment capability. After consideration of the technique's robustness, we tested TOOMIXED firstly on a model mixture. As a benchmark we were able to assign a molecule with high confidence in the case of selectively exciting an isolated resonance. Assignment confidence was not compromised when performing TOOMIXED on a resonance known to contain multiple overlapping signals, and in the worst case the method suggested a follow-up sel-TOCSY experiment to confirm an ambiguous assignment. TOOMIXED was then demonstrated on two realistic samples (whisky and urine), where under our conditions an approximate limit of detection of 0.6 mM was determined. Taking into account literature reports for the sel-TOCSY limit of detection, the technique should reach on the order of 10 μ M sensitivity. We anticipate this technique will be highly attractive to various analytical fields facing mixture analysis, including metabolomics, foodstuff analysis, pharmaceutical analysis, and forensics.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

NASA Astrophysics Data System (ADS)

Zhul'Kina, A. L.; Ivantsova, E. L.; Filatova, A. G.; Kosenko, R. Yu.; Gumargalieva, K. Z.; Iordanskii, A. L.

2009-05-01

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhul'kina, A. L.; Ivantsova, E. L.; Filatova, A. G.

2009-05-15

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Application of the Attagene FACTORIAL™ assay to ...

EPA Pesticide Factsheets

Bioassays can be used to evaluate the integrated effects of complex mixtures from both known and unidentified contaminants present in environmental samples. However, such bio-monitoring approaches have typically focused only on one or a few pathways (e.g. estrogen receptor, androgen receptor) despite the fact that the chemicals in a mixture may exhibit a range of biological activities. High-throughput screening approaches that can rapidly assess samples for a broad diversity of biological activities offer a means to provide a more comprehensive characterization of complex mixtures. The Attagene FactorialTM platform is a high-throughput, cell based assay utilized by US EPA’s ToxCast Program, which provides high-content assessment of over 90 different gene regulatory pathways and all 48 human nuclear receptors (NRs). This assay has previously been used in a preliminary screening of surface water extracts from sites across the Great Lakes. In the current study, surface waters samples from 38 sites were collected, extracted, and screened through the Factorial assay as part of a USGS nationwide stream assessment. All samples were evaluated in a six point, 3-fold dilution series and analyzed using the ToxCast Data Pipeline (TCPL) to generate dose-response curves and corresponding half-maximal activity concentration (AC50) estimates. A total of 27 assay endpoints responded to extracts from one or more sites, with up to 14 assays active for a single extract. The four

Mixture-based gatekeeping procedures in adaptive clinical trials.

PubMed

Kordzakhia, George; Dmitrienko, Alex; Ishida, Eiji

2018-01-01

Clinical trials with data-driven decision rules often pursue multiple clinical objectives such as the evaluation of several endpoints or several doses of an experimental treatment. These complex analysis strategies give rise to "multivariate" multiplicity problems with several components or sources of multiplicity. A general framework for defining gatekeeping procedures in clinical trials with adaptive multistage designs is proposed in this paper. The mixture method is applied to build a gatekeeping procedure at each stage and inferences at each decision point (interim or final analysis) are performed using the combination function approach. An advantage of utilizing the mixture method is that it enables powerful gatekeeping procedures applicable to a broad class of settings with complex logical relationships among the hypotheses of interest. Further, the combination function approach supports flexible data-driven decisions such as a decision to increase the sample size or remove a treatment arm. The paper concludes with a clinical trial example that illustrates the methodology by applying it to develop an adaptive two-stage design with a mixture-based gatekeeping procedure.

Comparative Characterization of Crofelemer Samples Using Data Mining and Machine Learning Approaches With Analytical Stability Data Sets.

PubMed

Nariya, Maulik K; Kim, Jae Hyun; Xiong, Jian; Kleindl, Peter A; Hewarathna, Asha; Fisher, Adam C; Joshi, Sangeeta B; Schöneich, Christian; Forrest, M Laird; Middaugh, C Russell; Volkin, David B; Deeds, Eric J

2017-11-01

There is growing interest in generating physicochemical and biological analytical data sets to compare complex mixture drugs, for example, products from different manufacturers. In this work, we compare various crofelemer samples prepared from a single lot by filtration with varying molecular weight cutoffs combined with incubation for different times at different temperatures. The 2 preceding articles describe experimental data sets generated from analytical characterization of fractionated and degraded crofelemer samples. In this work, we use data mining techniques such as principal component analysis and mutual information scores to help visualize the data and determine discriminatory regions within these large data sets. The mutual information score identifies chemical signatures that differentiate crofelemer samples. These signatures, in many cases, would likely be missed by traditional data analysis tools. We also found that supervised learning classifiers robustly discriminate samples with around 99% classification accuracy, indicating that mathematical models of these physicochemical data sets are capable of identifying even subtle differences in crofelemer samples. Data mining and machine learning techniques can thus identify fingerprint-type attributes of complex mixture drugs that may be used for comparative characterization of products. Copyright © 2017 American Pharmacists Association®. All rights reserved.

Simultaneous quantification of Aroclor mixtures in soil samples by gas chromatography/mass spectrometry with solid phase microextraction using partial least-squares regression.

PubMed

Zhang, Mengliang; Harrington, Peter de B

2015-01-01

Multivariate partial least-squares (PLS) method was applied to the quantification of two complex polychlorinated biphenyls (PCBs) commercial mixtures, Aroclor 1254 and 1260, in a soil matrix. PCBs in soil samples were extracted by headspace solid phase microextraction (SPME) and determined by gas chromatography/mass spectrometry (GC/MS). Decachlorinated biphenyl (deca-CB) was used as internal standard. After the baseline correction was applied, four data representations including extracted ion chromatograms (EIC) for Aroclor 1254, EIC for Aroclor 1260, EIC for both Aroclors and two-way data sets were constructed for PLS-1 and PLS-2 calibrations and evaluated with respect to quantitative prediction accuracy. The PLS model was optimized with respect to the number of latent variables using cross validation of the calibration data set. The validation of the method was performed with certified soil samples and real field soil samples and the predicted concentrations for both Aroclors using EIC data sets agreed with the certified values. The linear range of the method was from 10μgkg(-1) to 1000μgkg(-1) for both Aroclor 1254 and 1260 in soil matrices and the detection limit was 4μgkg(-1) for Aroclor 1254 and 6μgkg(-1) for Aroclor 1260. This holistic approach for the determination of mixtures of complex samples has broad application to environmental forensics and modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Determination method of polysorbates in powdered soup by HPLC].

PubMed

Takeda, Y; Abe, Y; Ishiwata, H; Yamada, T

2001-04-01

A method for qualitative and quantitative analyses of polysorbates in powdered soup by HPLC was studied. Polysorbates in samples were extracted with acetonitrile after rinsing with n-hexane to remove fats and oils. The extract was cleaned up using a Bond Elut silica gel cartridge (500 mg). The cartridge was washed with ethyl acetate and polysorbates were eluted with a small amount of acetonitrile-methanol (1:2) mixture. The eluate was treated with cobalt thiocyanate solution to form a blue complex with polysorbate. In order to determine polysorbate, the complex was subjected to HPLC with a GPC column, using a mixture of acetonitrile-water (95:5) as a mobile phase, with a detection wavelength of 620 nm. The recoveries of polysorbate 80 added to powdered soups were more than 75% and the determination limit was 0.04 mg/g. When the proposed method was applied to the determination of polysorbates in 16 commercial samples of powdered soup for instant noodles and seasoning consomme, no polysorbates were detected in any sample.

Analytical Scheme Leading to Integrated High-Sensitivity Profiling of Glycosphingolipids Together with N- and O-Glycans from One Sample

NASA Astrophysics Data System (ADS)

Benktander, John D.; Gizaw, Solomon T.; Gaunitz, Stefan; Novotny, Milos V.

2018-05-01

Glycoconjugates are directly or indirectly involved in many biological processes. Due to their complex structures, the structural elucidation of glycans and the exploration of their role in biological systems have been challenging. Glycan pools generated through release from glycoprotein or glycolipid mixtures can often be very complex. For the sake of procedural simplicity, many glycan profiling studies choose to concentrate on a single class of glycoconjugates. In this paper, we demonstrate it feasible to cover glycosphingolipids, N-glycans, and O-glycans isolated from the same sample. Small volumes of human blood serum and ascites fluid as well as small mouse brain tissue samples are sufficient to profile sequentially glycans from all three classes of glycoconjugates and even positively identify some mixture components through MALDI-MS and LC-ESI-MS. The results show that comprehensive glycan profiles can be obtained from the equivalent of 500-μg protein starting material or possibly less. These methodological improvements can help accelerating future glycomic comprehensive studies, especially for precious clinical samples.

Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

PubMed

Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

2016-06-21

Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the ion source is compact, can be powered with a 10 V battery, and is tolerant of complex mixtures.

Preliminary construction of integral analysis for characteristic components in complex matrices by in-house fabricated solid-phase microextraction fibers combined with gas chromatography-mass spectrometry.

PubMed

Tang, Zhentao; Hou, Wenqian; Liu, Xiuming; Wang, Mingfeng; Duan, Yixiang

2016-08-26

Integral analysis plays an important role in study and quality control of substances with complex matrices in our daily life. As the preliminary construction of integral analysis of substances with complex matrices, developing a relatively comprehensive and sensitive methodology might offer more informative and reliable characteristic components. Flavoring mixtures belonging to the representatives of substances with complex matrices have now been widely used in various fields. To better study and control the quality of flavoring mixtures as additives in food industry, an in-house fabricated solid-phase microextraction (SPME) fiber was prepared based on sol-gel technology in this work. The active organic component of the fiber coating was multi-walled carbon nanotubes (MWCNTs) functionalized with hydroxyl-terminated polydimethyldiphenylsiloxane, which integrate the non-polar and polar chains of both materials. In this way, more sensitive extraction capability for a wider range of compounds can be obtained in comparison with commercial SPME fibers. Preliminarily integral analysis of three similar types of samples were realized by the optimized SPME-GC-MS method. With the obtained GC-MS data, a valid and well-fit model was established by partial least square discriminant analysis (PLS-DA) for classification of these samples (R2X=0.661, R2Y=0.996, Q2=0.986). The validity of the model (R2=0.266, Q2=-0.465) has also approved the potential to predict the "belongingness" of new samples. With the PLS-DA and SPSS method, further screening out the markers among three similar batches of samples may be helpful for monitoring and controlling the quality of the flavoring mixtures as additives in food industry. Conversely, the reliability and effectiveness of the GC-MS data has verified the comprehensive and efficient extraction performance of the in-house fabricated fiber. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous Detection of Metalloprotease Activities in Complex Biological Samples Using the PrAMA (Proteolytic Activity Matrix Assay) Method.

PubMed

Conrad, Catharina; Miller, Miles A; Bartsch, Jörg W; Schlomann, Uwe; Lauffenburger, Douglas A

2017-01-01

Proteolytic Activity Matrix Analysis (PrAMA) is a method for simultaneously determining the activities of specific Matrix Metalloproteinases (MMPs) and A Disintegrin and Metalloproteinases (ADAMs) in complex biological samples. In mixtures of unknown proteases, PrAMA infers selective metalloproteinase activities by using a panel of moderately specific FRET-based polypeptide protease substrates in parallel, typically monitored by a plate-reader in a 96-well format. Fluorescence measurements are then quantitatively compared to a standard table of catalytic efficiencies measured from purified mixtures of individual metalloproteinases and FRET substrates. Computational inference of specific activities is performed with an easily used Matlab program, which is provided herein. Thus, we describe PrAMA as a combined experimental and mathematical approach to determine real-time metalloproteinase activities, which has previously been applied to live-cell cultures, cellular lysates, cell culture supernatants, and body fluids from patients.

Optimization of the high-performance liquid chromatographic separation of a complex mixture containing urinary steroids, boldenone and bolasterone: application to urine samples.

PubMed

Gonzalo-Lumbreras, R; Izquierdo-Hornillos, R

2000-05-26

An HPLC separation of a complex mixture containing 13 urinary anabolics and corticoids, and boldenone and bolasterone (synthetic anabolics) has been carried out. The applied optimization method involved the use of binary, ternary and quaternary mobile phases containing acetonitrile, methanol or tetrahydrofuran as organic modifiers. The effect of different reversed-phase packings and temperature on the separation was studied. The optimum separation was achieved by using a water-acetonitrile (60:40, v/v) mobile phase in reversed-phase HPLC at 30 degrees C, allowing the separation of all the analytes in about 24 min. Calibration graphs were obtained using bolasterone or methyltestosterone as internal standards. Detection limits were in the range 0.012-0.107 microg ml(-1). The optimized separation was applied to the analysis, after liquid-liquid extraction, of human urine samples spiked with steroids.

Colloidal properties of single component naphthenic acids and complex naphthenic acid mixtures.

PubMed

Mohamed, Mohamed H; Wilson, Lee D; Peru, Kerry M; Headley, John V

2013-04-01

Tensiometry was used to provide estimates of the critical micelle concentration (cmc) values for three sources of naphthenic acids (NAs) and three examples of single component NAs (S1-S3) in aqueous solution at pH 10.5 and 295 K. Two commercially available mixtures of NAs and an industrially derived mixture of NAs obtained from Alberta oil sands process water (OSPW) were investigated. The three examples of single component NAs (C(n)H(2n+z)O2) were chosen with variable z-series to represent chemical structures with 0-2 rings, as follows: 2-hexyldecanoic acid (z=0; S1), trans-4-pentylcyclohexanecarboxylic acid (z=-2; S2) and dicyclohexylacetic acid (z=-4; S3). The estimated cmc values for S1 (35.6 μM), S2 (0.545 mM), and S3 (4.71 mM) vary over a wide range according to their relative lipophile characteristics of each carboxylate anion. The cmc values for the three complex mixtures of NAs were evaluated. Two disctinct cmc values were observed (second listed in brackets) as follows: Commercial sample 1; 50.9 μM (109 μM), Commercial sample 2; 22.3 μM (52.2 μM), and Alberta derived OSPW; 154 μM (417 μM). These results provide strong support favouring two general classes of NAs in the mixtures investigated with distinct cmc values. We propose that the two groups may be linked to a recalcitrant fraction with a relatively large range of cmc values (52.2-417 μM) and a readily biodegradable fraction with a relatively low range of cmc values (22.3-154 μM) depending on the source of NAs in a given mixture. Copyright © 2013 Elsevier Inc. All rights reserved.

Aqueous two-phase extraction of nickel dimethylglyoximato complex and its application to spectrophotometric determination of nickel in stainless steel.

PubMed

Yoshikuni, Nobutaka; Baba, Takayuki; Tsunoda, Natsuki; Oguma, Koichi

2005-03-31

A polyethylene glycol (PEG)-based aqueous two-phase system has been established for the extraction of Ni-dimethylglyoximato complex. Appropriate amounts of PEG solution and solid (NH(4))(2)SO(4) were added to the Ni-dimethylglyoximato complex which had been formed in the presence of sodium tartrate and K(2)S(2)O(8) at pH 12 in a separatory funnel and shaken vigorously for about 1min. The mixture was allowed to stand for 10min and then the absorbance of the extracted complex in the upper PEG-rich phase was measured at 470nm. Beer's law was obeyed over the range of 0.26-2.1ppm Ni. The proposed extraction method has been applied to the determination of Ni in steel. A steel sample was decomposed with an appropriate acid mixture. An aliquot of the sample solution was taken, treated with H(3)PO(4) and most of the iron and copper were removed by hydroxide precipitation using solid BaCO(3) to control the pH of the sample solution in advance of the extraction of Ni. The analytical results obtained for Ni in steel certified reference material JSS 650-10 (The Japan Iron and Steel Federation), BCS 323 (Bureau of Analysed Samples Ltd.) and NIST SRM 361 and 362 (National Institute of Standards and Technology) were in good agreement with certified values.

Benchmarking Water Quality from Wastewater to Drinking Waters Using Reduced Transcriptome of Human Cells.

PubMed

Xia, Pu; Zhang, Xiaowei; Zhang, Hanxin; Wang, Pingping; Tian, Mingming; Yu, Hongxia

2017-08-15

One of the major challenges in environmental science is monitoring and assessing the risk of complex environmental mixtures. In vitro bioassays with limited key toxicological end points have been shown to be suitable to evaluate mixtures of organic pollutants in wastewater and recycled water. Omics approaches such as transcriptomics can monitor biological effects at the genome scale. However, few studies have applied omics approach in the assessment of mixtures of organic micropollutants. Here, an omics approach was developed for profiling bioactivity of 10 water samples ranging from wastewater to drinking water in human cells by a reduced human transcriptome (RHT) approach and dose-response modeling. Transcriptional expression of 1200 selected genes were measured by an Ampliseq technology in two cell lines, HepG2 and MCF7, that were exposed to eight serial dilutions of each sample. Concentration-effect models were used to identify differentially expressed genes (DEGs) and to calculate effect concentrations (ECs) of DEGs, which could be ranked to investigate low dose response. Furthermore, molecular pathways disrupted by different samples were evaluated by Gene Ontology (GO) enrichment analysis. The ability of RHT for representing bioactivity utilizing both HepG2 and MCF7 was shown to be comparable to the results of previous in vitro bioassays. Finally, the relative potencies of the mixtures indicated by RHT analysis were consistent with the chemical profiles of the samples. RHT analysis with human cells provides an efficient and cost-effective approach to benchmarking mixture of micropollutants and may offer novel insight into the assessment of mixture toxicity in water.

An approach toward quantification of organic compounds in complex environmental samples using high-resolution electrospray ionization mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Tran B.; Nizkorodov, Sergey; Laskin, Alexander

2013-01-07

Quantitative analysis of individual compounds in complex mixtures using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) is complicated by differences in the ionization efficiencies of analyte molecules in the mixture, resulting in signal suppression during ionization. However, the ability to obtain concentration estimates of compounds in an environmental sample is important for data interpretation and comparison. We introduce an approach for estimating mass concentrations of analytes observed in a multicomponent mixture by HR-ESI-MS, without prior separation. The approach relies on a calibration of the instrument using appropriate standards added to the mixture of studied analytes. An illustration of how the proposedmore » calibration can be applied in practice is provided for aqueous extracts of isoprene photooxidation organic aerosol, with multifunctional organic acids standards. We show that the observed ion sensitivities in ESI-MS are positively correlated with the “adjusted mass,” defined as a product of the molecular mass and the H/C ratio in the molecule (adjusted mass = H/C x molecular mass). The correlation of the observed ESI sensitivity with adjusted mass is justified by considering trends of the physical and chemical properties of organic compounds that affect ionization in the positive ion mode, i.e., gas-phase basicity, polarizability, and molecular size.« less

Dielectric properties of binary mixtures of methyl iso butyl ketone and amino silicone oil

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Trivedi, C. M.; Vankar, H. P.

2017-05-01

Dielectric permittivity ɛ*(ω) = ɛ' - jɛ″ of the binary mixtures of the methyl iso butyl ketone and amino silicone oil in the frequency range 100 Hz to 2 MHz were measured using precision LCR meter at 305.15 K. Relative complex permittivity spectra in the frequency range 100 Hz to 2 MHz, of the mixture solutions of varying concentrations is reported. Determined values of the permittivity at optical frequency of all the samples are also reported. The dielectric parameters are used to gain information about the effect of concentration variation of components of the mixtures on the dielectric properties. It also provides the information about electrode polarization phenomena taking place under the low frequency A.C. electric field.

Analysis of macromolecules, ligands and macromolecule-ligand complexes

DOEpatents

Von Dreele, Robert B [Los Alamos, NM

2008-12-23

A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

Comprehensive Metabolite Identification Strategy Using Multiple Two-Dimensional NMR Spectra of a Complex Mixture Implemented in the COLMARm Web Server

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bingol, Kerem; Li, Da-Wei; Zhang, Bo

Identification of metabolites in complex mixtures represents a key step in metabolomics. A new strategy is introduced, which is implemented in a new public web server, COLMARm, that permits the co-analysis of up to three 2D NMR spectra, namely 13C-1H HSQC, 1H-1H TOCSY, and 13C-1H HSQC-TOCSY for the comprehensive, accurate, and efficient performance of this task. The highly versatile and interactive nature of COLMARm permits its application to a wide range of metabolomics samples independent of the magnetic field. Database query is performed using the HSQC spectrum and the top metabolite hits are then validated against the TOCSY-type experiment(s) bymore » superimposing the expected cross-peaks on the mixture spectrum. In this way the user can directly accept or reject candidate metabolites by taking advantage of the complementary spectral information offered by these experiments and their different sensitivities. The power of COLMARm is demonstrated for a human serum sample uncovering the existence of 14 metabolites that hitherto were not identified by NMR.« less

Fast 2D NMR Spectroscopy for In vivo Monitoring of Bacterial Metabolism in Complex Mixtures.

PubMed

Dass, Rupashree; Grudzia Ż, Katarzyna; Ishikawa, Takao; Nowakowski, Michał; Dȩbowska, Renata; Kazimierczuk, Krzysztof

2017-01-01

The biological toolbox is full of techniques developed originally for analytical chemistry. Among them, spectroscopic experiments are very important source of atomic-level structural information. Nuclear magnetic resonance (NMR) spectroscopy, although very advanced in chemical and biophysical applications, has been used in microbiology only in a limited manner. So far, mostly one-dimensional 1 H experiments have been reported in studies of bacterial metabolism monitored in situ . However, low spectral resolution and limited information on molecular topology limits the usability of these methods. These problems are particularly evident in the case of complex mixtures, where spectral peaks originating from many compounds overlap and make the interpretation of changes in a spectrum difficult or even impossible. Often a suite of two-dimensional (2D) NMR experiments is used to improve resolution and extract structural information from internuclear correlations. However, for dynamically changing sample, like bacterial culture, the time-consuming sampling of so-called indirect time dimensions in 2D experiments is inefficient. Here, we propose the technique known from analytical chemistry and structural biology of proteins, i.e., time-resolved non-uniform sampling. The method allows application of 2D (and multi-D) experiments in the case of quickly varying samples. The indirect dimension here is sparsely sampled resulting in significant reduction of experimental time. Compared to conventional approach based on a series of 1D measurements, this method provides extraordinary resolution and is a real-time approach to process monitoring. In this study, we demonstrate the usability of the method on a sample of Escherichia coli culture affected by ampicillin and on a sample of Propionibacterium acnes , an acne causing bacterium, mixed with a dose of face tonic, which is a complicated, multi-component mixture providing complex NMR spectrum. Through our experiments we determine the exact concentration and time at which the anti-bacterial agents affect the bacterial metabolism. We show, that it is worth to extend the NMR toolbox for microbiology by including techniques of 2D z-TOCSY, for total "fingerprinting" of a sample and 2D 13 C-edited HSQC to monitor changes in concentration of metabolites in selected metabolic pathways.

Application of Biologically-Based Lumping To Investigate the ...

EPA Pesticide Factsheets

People are often exposed to complex mixtures of environmental chemicals such as gasoline, tobacco smoke, water contaminants, or food additives. However, investigators have often considered complex mixtures as one lumped entity. Valuable information can be obtained from these experiments, though this simplification provides little insight into the impact of a mixture's chemical composition on toxicologically-relevant metabolic interactions that may occur among its constituents. We developed an approach that applies chemical lumping methods to complex mixtures, in this case gasoline, based on biologically relevant parameters used in physiologically-based pharmacokinetic (PBPK) modeling. Inhalation exposures were performed with rats to evaluate performance of our PBPK model. There were 109 chemicals identified and quantified in the vapor in the chamber. The time-course kinetic profiles of 10 target chemicals were also determined from blood samples collected during and following the in vivo experiments. A general PBPK model was used to compare the experimental data to the simulated values of blood concentration for the 10 target chemicals with various numbers of lumps, iteratively increasing from 0 to 99. Large reductions in simulation error were gained by incorporating enzymatic chemical interactions, in comparison to simulating the individual chemicals separately. The error was further reduced by lumping the 99 non-target chemicals. Application of this biologic

Differential Attenuation of NMR Signals by Complementary Ion-Exchange Resin Beads for De Novo Analysis of Complex Metabolomics Mixtures.

PubMed

Zhang, Bo; Yuan, Jiaqi; Brüschweiler, Rafael

2017-07-12

A primary goal of metabolomics is the characterization of a potentially very large number of metabolites that are part of complex mixtures. Application to biofluids and tissue samples offers insights into biochemical metabolic pathways and their role in health and disease. 1D 1 H and 2D 13 C- 1 H HSQC NMR spectra are most commonly used for this purpose. They yield quantitative information about each proton of the mixture, but do not tell which protons belong to the same molecule. Interpretation requires the use of NMR spectral databases, which naturally limits these investigations to known metabolites. Here, a new method is presented that uses complementary ion exchange resin beads to differentially attenuate 2D NMR cross-peaks that belong to different metabolites. Based on their characteristic attenuation patterns, cross-peaks could be clustered and assigned to individual molecules, including unknown metabolites with multiple spin systems, as demonstrated for a metabolite model mixture and E. coli cell lysate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of the photoprotective effect of β-cyclodextrin on the emission of volatile degradation products of ranitidine.

PubMed

Jamrógiewicz, Marzena; Wielgomas, Bartosz; Strankowski, Michał

2014-09-01

The process of the photo-excitation of ranitidine hydrochloride (RAN) in a solid state makes visible changes to its colour and generates an unpleasant odour. The purpose of the present study was to observe the protective effects of β-cyclodextrin (CD) complexation as well as the effect of the mixture of two stoichiometries 1:1 and 1:2 (RAN:CD, IC) on the photostability of samples in a solid state. Samples of inclusion complexes (IC) and physical mixtures (PM) were prepared and irradiated for 48h in a Suntest CPS+ chamber. Irradiated samples were analyzed using nuclear magnetic resonance ((1)H NMR), infrared spectroscopy (FT-IR), the differential scanning calorimetry method (DSC) and thermogravimetry analysis (TGA). Volatiles were monitored with the use of headspace-solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS). The protective effect of CD was noticed with respect to IC, and also PM. Achieved photostabilization of complexed RAN against photodegradation could be explained due to either the inclusion of the furan part of RAN into the CD cavity as shown by the (1)H NMR ROESY (rotation frame nuclear Overhauser effect spectroscopy) spectrum or the screening effect of CD. FT-IR spectra, DSC curves and microscope images of irradiated samples of protected RAN did not indicate any physical changes, such as phase transfer. Copyright © 2014 Elsevier B.V. All rights reserved.

Breccia 66055 and related clastic materials from the Descartes region, Apollo 16

NASA Technical Reports Server (NTRS)

Fruchter, J. S.; Kridelbaugh, S. J.; Robyn, M. A.; Goles, G. G.

1974-01-01

Trace and major element contents obtained by instrumental neutron activation are reported for a number of Apollo 16 soil samples and miscellaneous breccia fragments. In addition, data obtained by instrumental neutron activation and electron microprobe techniques along with petrographic descriptions are presented for selected subsamples of breccia 66055. The compositions of our soil samples can be modeled by mixtures of various amounts of anorthosite, anorthositic gabbro and low-K Fra Mauro basalt components. These mixtures are typical of those found in a number of petrographic surveys of the fines. Breccia 66055 is a complex regolith breccia which consists of at least four distinct types of microbreccias. No systematic relation with respect to stratigraphic age among the various microbreccia types was observed. Compositionally and texturally, the clasts which compose breccia 66055 are similar to a number of previously reported rock types from the Apollo 16 area. The entire breccia appears to have undergone a complex history of thermal metamorphism. We conclude from the study of these samples that the Cayley Formation is probably homogeneous in its gross compositional and petrographic aspects.

Integrative two-dimensional correlation spectroscopy (i2DCOS) for the intuitive identification of adulterated herbal materials

NASA Astrophysics Data System (ADS)

Chen, Jianbo; Wang, Yue; Rong, Lixin; Wang, Jingjuan

2018-07-01

IR, Raman and other separation-free and label-free spectroscopic techniques have been the promising methods for the rapid and low-cost quality control of complex mixtures such as food and herb. However, as the overlapped signals from different ingredients usually make it difficult to extract useful information, chemometrics tools are often needed to find out spectral features of interest. With designed perturbations, two-dimensional correlation spectroscopy (2DCOS) is a powerful technique to resolve the overlapped spectral bands and enhance the apparent spectral resolution. In this research, the integrative two-dimensional correlation spectroscopy (i2DCOS) is defined for the first time overcome some disadvantages of synchronous and asynchronous correlation spectra for identification. The integrative 2D correlation spectra weight the asynchronous cross peaks by the corresponding synchronous cross peaks, which combines the signal-to-noise ratio advantage of synchronous correlation spectra and the spectral resolution advantage of asynchronous correlation spectra. The feasibility of the integrative 2D correlation spectra for the quality control of complex mixtures is examined by the identification of adulterated Fritillariae Bulbus powders. Compared with model-based pattern recognition and multivariate calibration methods, i2DCOS can provide intuitive identification results but not require the number of samples. The results show the potential of i2DCOS in the intuitive quality control of herbs and other complex mixtures, especially when the number of samples is not large.

Bayesian mixture analysis for metagenomic community profiling.

PubMed

Morfopoulou, Sofia; Plagnol, Vincent

2015-09-15

Deep sequencing of clinical samples is now an established tool for the detection of infectious pathogens, with direct medical applications. The large amount of data generated produces an opportunity to detect species even at very low levels, provided that computational tools can effectively profile the relevant metagenomic communities. Data interpretation is complicated by the fact that short sequencing reads can match multiple organisms and by the lack of completeness of existing databases, in particular for viral pathogens. Here we present metaMix, a Bayesian mixture model framework for resolving complex metagenomic mixtures. We show that the use of parallel Monte Carlo Markov chains for the exploration of the species space enables the identification of the set of species most likely to contribute to the mixture. We demonstrate the greater accuracy of metaMix compared with relevant methods, particularly for profiling complex communities consisting of several related species. We designed metaMix specifically for the analysis of deep transcriptome sequencing datasets, with a focus on viral pathogen detection; however, the principles are generally applicable to all types of metagenomic mixtures. metaMix is implemented as a user friendly R package, freely available on CRAN: http://cran.r-project.org/web/packages/metaMix sofia.morfopoulou.10@ucl.ac.uk Supplementary data are available at Bionformatics online. © The Author 2015. Published by Oxford University Press.

Classification of narcotics in solid mixtures using principal component analysis and Raman spectroscopy.

PubMed

Ryder, Alan G

2002-03-01

Eighty-five solid samples consisting of illegal narcotics diluted with several different materials were analyzed by near-infrared (785 nm excitation) Raman spectroscopy. Principal Component Analysis (PCA) was employed to classify the samples according to narcotic type. The best sample discrimination was obtained by using the first derivative of the Raman spectra. Furthermore, restricting the spectral variables for PCA to 2 or 3% of the original spectral data according to the most intense peaks in the Raman spectrum of the pure narcotic resulted in a rapid discrimination method for classifying samples according to narcotic type. This method allows for the easy discrimination between cocaine, heroin, and MDMA mixtures even when the Raman spectra are complex or very similar. This approach of restricting the spectral variables also decreases the computational time by a factor of 30 (compared to the complete spectrum), making the methodology attractive for rapid automatic classification and identification of suspect materials.

An inexpensive, temporally-integrated system for monitoring occurrence and biological effects of aquatic contaminants in the field

EPA Science Inventory

Assessment of potential ecological risks of complex contaminant mixtures in the environment requires integrated chemical and biological approaches. Instrumental analysis of environmental samples alone can identify contaminants, but provides only limited insights as to possible a...

MONITORING OF WATERWAYS FOR EMERGING CONTAMINANTS USING INTEGRATIVE SAMPLING COUPLED WITH LIQUID CHROMATOGRAPHY-ELECTROSPRAY/MASS SPECTROMETRY

EPA Science Inventory

Assessing the potential impact to the aquatic environment from emerging contaminants, entails monitoring a complex mixture (pharmaceuticals, polar pesticides, industrial by- products and degradation products) in natural waters. The presence of these chemicals, often at ultra-trac...

Next Generation Spectrometers for Rapid Analysis of Complex Mixtures

DTIC Science & Technology

2014-05-29

digitizer by collecting 1 and 100 million averages of a molecular sample ( nitromethane ) and verifying the expected factor of 10 improvement in signal-to...spectra of nitromethane . The positive-going spectrum represents 100 million averages while the negative-going spectrum represents 1 million averages

Used tire recycling to produce granulates: evaluation of occupational exposure to chemical agents.

PubMed

Savary, Barbara; Vincent, Raymond

2011-10-01

Exposure was assessed in four facilities where used tires are turned into rubber granulates. Particulate exposure levels were measured using filter samples and gravimetric analysis. In parallel, volatile organic compounds (VOCs) screening was carried out using samples taken on activated carbon supports, followed by an analysis using a gas chromatograph coupled to a spectrometric detector. The exposure level medians are between 0.58 and 3.95 mg m(-3). Clogging of the textile fiber separation systems can lead to worker exposure; in this case, the measured concentrations can reach 41 mg m(-3). However, in contrast to the data in the literature, VOC levels >1 p.p.m. were not detected. The particulate mixtures deposited on the installation surfaces are complex; some of the chemical agents are toxic to humans. The results of this study indicate significant exposure to complex mixtures of rubber dust. Optimizing exhaust ventilation systems inside the shredders, with a cyclone for example, is essential for reducing the exposure of workers in this rapidly developing sector.

Effective Ion Mobility Peak Width as a New Isomeric Descriptor for the Untargeted Analysis of Complex Mixtures Using Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Farenc, Mathilde; Paupy, Benoit; Marceau, Sabrina; Riches, Eleanor; Afonso, Carlos; Giusti, Pierre

2017-07-01

Ion mobility coupled with mass spectrometry was proven to be an efficient way to characterize complex mixtures such as petroleum samples. However, the identification of isomeric species is difficult owing to the molecular complexity of petroleum and no availability of standard molecules. This paper proposes a new simple indicator to estimate the isomeric content of highly complex mixtures. This indicator is based on the full width at half maximum (FWHM) of the extracted ion mobility peak measured in millisecond or square angstrom that is corrected for instrumental factors such as ion diffusion. This value can be easily obtained without precisely identifying the number of isomeric species under the ion mobility peaks. Considering the Boduszynski model, the ion mobility profile for a particular elemental composition is expected to be a continuum of various isomeric species. The drift time-dependent fragmentation profile was studied and confirmed this hypothesis, a continuous evolution of the fragmentation profile showing that the larger alkyl chain species were detected at higher drift time values. This new indicator was proven to be a fast and efficient method to compare vacuum gas oils for which no difference was found using other analytical techniques.

Complex mixtures of dissolved pesticides show potential aquatic toxicity in a synoptic study of Midwestern U.S. streams

USGS Publications Warehouse

Nowell, Lisa H.; Moran, Patrick W.; Schmidt, Travis S.; Norman, Julia E.; Nakagaki, Naomi; Shoda, Megan E.; Mahler, Barbara J.; Van Metre, Peter C.; Stone, Wesley W.; Sandstrom, Mark W.; Hladik, Michelle L.

2018-01-01

Aquatic organisms in streams are exposed to pesticide mixtures that vary in composition over time in response to changes in flow conditions, pesticide inputs to the stream, and pesticide fate and degradation within the stream. To characterize mixtures of dissolved-phase pesticides and degradates in Midwestern streams, a synoptic study was conducted at 100 streams during May–August 2013. In weekly water samples, 94 pesticides and 89 degradates were detected, with a median of 25 compounds detected per sample and 54 detected per site. In a screening-level assessment using aquatic-life benchmarks and the Pesticide Toxicity Index (PTI), potential effects on fish were unlikely in most streams. For invertebrates, potential chronic toxicity was predicted in 53% of streams, punctuated in 12% of streams by acutely toxic exposures. For aquatic plants, acute but likely reversible effects on biomass were predicted in 75% of streams, with potential longer-term effects on plant communities in 9% of streams. Relatively few pesticides in water—atrazine, acetochlor, metolachlor, imidacloprid, fipronil, organophosphate insecticides, and carbendazim—were predicted to be major contributors to potential toxicity. Agricultural streams had the highest potential for effects on plants, especially in May–June, corresponding to high spring-flush herbicide concentrations. Urban streams had higher detection frequencies and concentrations of insecticides and most fungicides than in agricultural streams, and higher potential for invertebrate toxicity, which peaked during July–August. Toxicity-screening predictions for invertebrates were supported by quantile regressions showing significant associations for the Benthic Invertebrate-PTI and imidacloprid concentrations with invertebrate community metrics for MSQA streams, and by mesocosm toxicity testing with imidacloprid showing effects on invertebrate communities at environmentally relevant concentrations. This study documents the most complex pesticide mixtures yet reported in discrete water samples in the U.S. and, using multiple lines of evidence, predicts that pesticides were potentially toxic to nontarget aquatic life in about half of the sampled streams.

Chemical composition and mixing-state of ice residuals sampled within mixed phase clouds

NASA Astrophysics Data System (ADS)

Ebert, M.; Worringen, A.; Benker, N.; Mertes, S.; Weingartner, E.; Weinbruch, S.

2010-10-01

During an intensive campaign at the high alpine research station Jungfraujoch, Switzerland, in February/March 2006 ice particle residuals within mixed-phase clouds were sampled using the Ice-counterflow virtual impactor (Ice-CVI). Size, morphology, chemical composition, mineralogy and mixing state of the ice residual and the interstitial (i.e., non-activated) aerosol particles were analyzed by scanning and transmission electron microscopy. Ice nuclei (IN) were identified from the significant enrichment of particle groups in the ice residual (IR) samples relative to the interstitial aerosol. In terms of number lead-bearing particles are enriched by a factor of approximately 25, complex internal mixtures with silicates or metal oxides as major components by a factor of 11, and mixtures of secondary aerosol and soot (C-O-S particles) by a factor of 2. Other particle groups (sulfates, sea salt, Ca-rich particles, external silicates) observed in the ice-residual samples cannot be assigned unambiguously as IN. Between 9 and 24% of all IR are Pb-bearing particles. Pb was found as major component in around 10% of these particles (PbO, PbCl2). In the other particles, Pb was found as some 100 nm sized agglomerates consisting of 3-8 nm sized primary particles (PbS, elemental Pb). C-O-S particles are present in the IR at an abundance of 17-27%. The soot component within these particles is strongly aged. Complex internal mixtures occur in the IR at an abundance of 9-15%. Most IN identified at the Jungfraujoch station are internal mixtures containing anthropogenic components (either as main or minor constituent), and it is concluded that admixture of the anthropogenic component is responsible for the increased IN efficiency within mixed phase clouds. The mixing state appears to be a key parameter for the ice nucleation behaviour that cannot be predicted from the separate components contained within the individual particles.

Effect of fish gelatin-gum arabic interactions on structural and functional properties of concentrated emulsions.

PubMed

Anvari, Mohammad; Joyner Melito, Helen S

2017-12-01

Concentrated emulsions containing both proteins and polysaccharides are the basis for many commercial products; however, the effects of protein-polysaccharide interactions on the functional properties of these complex systems are often poorly understood from a fundamental standpoint. Hence, the objective of this study was to determine the effects of fish gelatin (FG)-gum arabic (GA) complexation at different aqueous phase pH (3.6, 5.0, and 9.0) on concentrated emulsion structure-function relationships. Concentrated emulsions were prepared using FG-GA mixtures and characterized by rheometry and confocal scanning laser microscopy (CSLM). CSLM images showed that all samples were O/W emulsions; emulsions with lower pH showed smaller oil droplets, greater homogeneity in size distribution, and higher stability. This was attributed to an increased number of FG-GA complexes in the emulsification. Electrostatic attractive interactions and charge neutralization created biopolymer associations with increased emulsification capacity. Samples with FG-GA mixtures at lower pH showed higher elastic moduli under small deformation and exhibited greater deviation between apparent and complex viscosities under the Cox-Merz rule, indicating increased gel network extension and greater intermolecular connectivity between adsorbed layers of adjacent oil droplets. These results can be used to incorporate protein-polysaccharide complexes as a suitable emulsifier in materials comprising concentrated emulsions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazurek, M.A.; Hildemann, L.M.; Cass, G.R.

1990-04-01

Extractable organic compounds having between 6 to 40 carbon atoms comprise an important mass fraction of the fine particulate matter samples from major urban emission sources. Depending on the emission source type, this solvent-soluble fraction accounts for <20% to 100% of the total organic aerosol mass, as measured by quantitative high-resolution has chromatography (HRGC) with flame ionization detection. In addition to total extract quantitation, HRGC can be applied to further analyses of the mass distributions of elutable organics present in the complex aerosol extract mixtures, thus generating profiles that serve as fingerprints'' for the sources of interest. This HRGC analyticalmore » method is applied to emission source samples that contain between 7 to 12,000 {mu}g/filter organic carbon. It is shown to be a sensitive technique for analysis of carbonaceous aerosol extract mixtures having diverse mass loadings and species distributions. This study describes the analytical chemical methods that have been applied to: the construction of chemical mass balances based on the mass of fine organic aerosol emitted for major urban sources of particulate carbon; and the generation of discrete emission source chemical profiles derived from chromatographic characteristics of the organic aerosol components. 21 refs., 1 fig., 2 tabs.« less

Quantification of acidic compounds in complex biomass-derived streams

DOE PAGES

Karp, Eric M.; Nimlos, Claire T.; Deutch, Steve; ...

2016-05-10

Biomass-derived streams that contain acidic compounds from the degradation of lignin and polysaccharides (e.g. black liquor, pyrolysis oil, pyrolytic lignin, etc.) are chemically complex solutions prone to instability and degradation during analysis, making quantification of compounds within them challenging. Here we present a robust analytical method to quantify acidic compounds in complex biomass-derived mixtures using ion exchange, sample reconstitution in pyridine and derivatization with BSTFA. The procedure is based on an earlier method originally reported for kraft black liquors and, in this work, is applied to identify and quantify a large slate of acidic compounds in corn stover derived alkalinemore » pretreatment liquor (APL) as a function of pretreatment severity. Analysis of the samples is conducted with GCxGC-TOFMS to achieve good resolution of the components within the complex mixture. The results reveal the dominant low molecular weight components and their concentrations as a function of pretreatment severity. Application of this method is also demonstrated in the context of lignin conversion technologies by applying it to track the microbial conversion of an APL substrate. Here as well excellent results are achieved, and the appearance and disappearance of compounds is observed in agreement with the known metabolic pathways of two bacteria, indicating the sample integrity was maintained throughout analysis. Finally, it is shown that this method applies more generally to lignin-rich materials by demonstrating its usefulness in analysis of pyrolysis oil and pyrolytic lignin.« less

METHODS AND TECHNIQUES FOR DEALING WITH THE UNIDENTIFIED FRACTION OF COMPLEX MIXTURES

EPA Science Inventory

For the vast majority of highly complex environmental mixtures to which humans are exposed, significant portions of the mixture are unidentified. Although toxicological data on the mixture itself are desired for risk assessment, such data, even on a similar mixture, are rarely a...

Protein Stains to Detect Antigen on Membranes.

PubMed

Dsouza, Anil; Scofield, R Hal

2015-01-01

Western blotting (protein blotting/electroblotting) is the gold standard in the analysis of complex protein mixtures. Electroblotting drives protein molecules from a polyacrylamide (or less commonly, of an agarose) gel to the surface of a binding membrane, thereby facilitating an increased availability of the sites with affinity for both general and specific protein reagents. The analysis of these complex protein mixtures is achieved by the detection of specific protein bands on a membrane, which in turn is made possible by the visualization of protein bands either by chemical staining or by reaction with an antibody of a conjugated ligand. Chemical methods employ staining with organic dyes, metal chelates, autoradiography, fluorescent dyes, complexing with silver, or prelabeling with fluorophores. All of these methods have differing sensitivities and quantitative determinations vary significantly. This review will describe the various protein staining methods applied to membranes after western blotting. "Detection" precedes and is a prerequisite to obtaining qualitative and quantitative data on the proteins in a sample, as much as to comparing the protein composition of different samples. "Detection" is often synonymous to staining, i.e., the reversible or irreversible binding by the proteins of a colored organic or inorganic chemical.

Protein stains to detect antigen on membranes.

PubMed

D'souza, Anil; Scofield, R Hal

2009-01-01

Western blotting (protein blotting/electroblotting) is the gold standard in the analysis of complex protein mixtures. Electroblotting drives protein molecules from a polyacrylamide (or less commonly, of an agarose) gel to the surface of a binding membrane, thereby facilitating an increased availability of the sites with affinity for both general and specific protein reagents. The analysis of these complex protein mixtures is achieved by the detection of specific protein bands on a membrane, which in turn is made possible by the visualization of protein bands either by chemical staining or by reaction with an antibody of a conjugated ligand. Chemical methods employ staining with organic dyes, metal chelates, autoradiography, fluorescent dyes, complexing with silver, or prelabeling with fluorophores. All of these methods have differing sensitivities and quantitative determinations vary significantly. This review will describe the various protein staining methods applied to membranes after electrophoresis. "Detection" precedes and is a prerequisite to obtaining qualitative and quantitative data on the proteins in a sample, as much as to comparing the protein composition of different samples. Detection is often synonymous to staining, i.e., the reversible or irreversible binding by the proteins of a colored organic or inorganic chemical.

Western blotting using chemiluminescent substrates.

PubMed

Alegria-Schaffer, Alice

2014-01-01

Western blotting is a powerful and commonly used tool to identify and quantify a specific protein in a complex mixture (Towbin et al., 1979). The technique enables indirect detection of protein samples immobilized on a nitrocellulose or polyvinylidene fluoride (PVDF) membrane. Copyright © 2014 Elsevier Inc. All rights reserved.

A rapid, ideal, and eco-friendlier protocol for quantifying proline.

PubMed

Shabnam, Nisha; Tripathi, Indu; Sharmila, P; Pardha-Saradhi, P

2016-11-01

Proline, a stress marker, is routinely quantified by a protocol that essentially uses hazardous toluene. Negative impacts of toluene on human health prompted us to develop a reliable alternate protocol for proline quantification. Absorbance of the proline-ninhydrin condensation product formed by reaction of proline with ninhydrin at 100 °C in the reaction mixture was significantly higher than that recorded after its transfer to toluene, revealing that toluene lowers sensitivity of this assay. λ max of the proline-ninhydrin complex in the reaction mixture and toluene were 508 and 513 nm, respectively. Ninhydrin in glacial acetic acid yielded higher quantity of the proline-ninhydrin condensation product compared to ninhydrin in mixture of glacial acetic acid and H 3 PO 4 , indicating negative impact of H 3 PO 4 on proline quantification. Further, maximum yield of the proline-ninhydrin complex with ninhydrin in glacial acetic acid and ninhydrin in mixture of glacial acetic acid and H 3 PO 4 was achieved within 30 and 60 min, respectively. This revealed that H 3 PO 4 has negative impact on the reaction rate and quantity of the proline-ninhydrin complex formed. In brief, our proline quantification protocol involves reaction of a 1-ml proline sample with 2 ml of 1.25 % ninhydrin in glacial acetic acid at 100 °C for 30 min, followed by recording absorbance of the proline-ninhydrin condensation product in the reaction mixture itself at 508 nm. Amongst proline quantification protocols known till date, our protocol is the most simple, rapid, reliable, cost-effective, and eco-friendlier.

A Statistical Approach for Judging Stability of Whole Mixture Chemical Composition over Time for Highly Complex Disinfection By-Product Mixtures from EPA's Four Lab Study

EPA Science Inventory

Chemical characterization of complex mixtures and assessment of stability over time of the characterized chemicals is crucial both to characterize exposure and to use data from one mixture as a surrogate for other similar mixtures. The chemical composition of test mixtures can va...

Automatic differential analysis of NMR experiments in complex samples.

PubMed

Margueritte, Laure; Markov, Petar; Chiron, Lionel; Starck, Jean-Philippe; Vonthron-Sénécheau, Catherine; Bourjot, Mélanie; Delsuc, Marc-André

2018-06-01

Liquid state nuclear magnetic resonance (NMR) is a powerful tool for the analysis of complex mixtures of unknown molecules. This capacity has been used in many analytical approaches: metabolomics, identification of active compounds in natural extracts, and characterization of species, and such studies require the acquisition of many diverse NMR measurements on series of samples. Although acquisition can easily be performed automatically, the number of NMR experiments involved in these studies increases very rapidly, and this data avalanche requires to resort to automatic processing and analysis. We present here a program that allows the autonomous, unsupervised processing of a large corpus of 1D, 2D, and diffusion-ordered spectroscopy experiments from a series of samples acquired in different conditions. The program provides all the signal processing steps, as well as peak-picking and bucketing of 1D and 2D spectra, the program and its components are fully available. In an experiment mimicking the search of a bioactive species in a natural extract, we use it for the automatic detection of small amounts of artemisinin added to a series of plant extracts and for the generation of the spectral fingerprint of this molecule. This program called Plasmodesma is a novel tool that should be useful to decipher complex mixtures, particularly in the discovery of biologically active natural products from plants extracts but can also in drug discovery or metabolomics studies. Copyright © 2017 John Wiley & Sons, Ltd.

ABRF-PRG07: advanced quantitative proteomics study.

PubMed

Falick, Arnold M; Lane, William S; Lilley, Kathryn S; MacCoss, Michael J; Phinney, Brett S; Sherman, Nicholas E; Weintraub, Susan T; Witkowska, H Ewa; Yates, Nathan A

2011-04-01

A major challenge for core facilities is determining quantitative protein differences across complex biological samples. Although there are numerous techniques in the literature for relative and absolute protein quantification, the majority is nonroutine and can be challenging to carry out effectively. There are few studies comparing these technologies in terms of their reproducibility, accuracy, and precision, and no studies to date deal with performance across multiple laboratories with varied levels of expertise. Here, we describe an Association of Biomolecular Resource Facilities (ABRF) Proteomics Research Group (PRG) study based on samples composed of a complex protein mixture into which 12 known proteins were added at varying but defined ratios. All of the proteins were present at the same concentration in each of three tubes that were provided. The primary goal of this study was to allow each laboratory to evaluate its capabilities and approaches with regard to: detection and identification of proteins spiked into samples that also contain complex mixtures of background proteins and determination of relative quantities of the spiked proteins. The results returned by 43 participants were compiled by the PRG, which also collected information about the strategies used to assess overall performance and as an aid to development of optimized protocols for the methodologies used. The most accurate results were generally reported by the most experienced laboratories. Among laboratories that used the same technique, values that were closer to the expected ratio were obtained by more experienced groups.

WATER QUALITY MONITORING OF PHARMACEUTICALS ...

EPA Pesticide Factsheets

The demand on freshwater to sustain the needs of the growing population is of worldwide concern. Often this water is used, treated, and released for reuse by other communities. The anthropogenic contaminants present in this water may include complex mixtures of pesticides, prescription and nonprescription drugs, personal care and common consumer products, industrial and domestic-use materials and degradation products of these compounds. Although, the fate of these pharmaceuticals and personal care products (PPCPs) in wastewater treatment facilities is largely unknown, the limited data that does exist suggests that many of these chemicals survive treatment and some others are returned to their biologically active form via deconjugation of metabolites.Traditional water sampling methods (i.e., grab or composite samples) often require the concentration of large amounts of water to detect trace levels of PPCPs. A passive sampler, the polar organic chemical integrative sampler (POCIS), has been developed to integratively concentrate the trace levels of these chemicals, determine the time-weighted average water concentrations, and provide a method of estimating the potential exposure of aquatic organisms to these complex mixtures of waterborne contaminants. The POCIS (U.S. Patent number 6,478,961) consists of a hydrophilic microporous membrane, acting as a semipermeable barrier, enveloping various solid-phase sorbents that retain the sampled chemicals. Sampling rates f

INTEGRATED AND REAL-TIME DIFFUSION DENUDER SAMPLE FOR PM2.5. (R825367)

EPA Science Inventory

Abstract

Particulate matter (PM) is a complex mixture of stable condensed phases, adsorbed or dissolved gases, and semi-volatile materials, i.e. compounds that transfer between the gas and condensed phases. Fine particles in both rural and urban environments contain su...

Evaluation of in vitro bioactivity of surface waters from a nationwide assessment of United States streams

EPA Science Inventory

Bioassays can be used to evaluate the integrated effects of complex mixtures of both known and unidentified contaminants present in environmental samples. Most bio-monitoring approaches have historically focused only on one or a few pathways (e.g. estrogen receptor, androgen rece...

Application of the Attagene FACTORIAL™ assay to characterization of surface waters from a nationwide assessment of streams

EPA Science Inventory

Bioassays can be used to evaluate the integrated effects of complex mixtures from both known and unidentified contaminants present in environmental samples. However, such bio-monitoring approaches have typically focused only on one or a few pathways (e.g. estrogen receptor, andro...

Sensitivity of the immature rat uterotrophic assay to mixtures of estrogens.

PubMed Central

Tinwell, Helen; Ashby, John

2004-01-01

We have evaluated whether mixtures of estrogens, present in the mix at doses that are individually inactive in the immature rat uterotrophic assay, can give a uterotrophic response. Seven chemicals were evaluated: nonylphenol, bisphenol A (BPA), methoxychlor, genistein (GEN), estradiol, diethylstilbestrol, and ethinyl estradiol. Dose responses in the uterotrophic assay were constructed for each chemical. The first series of experiments involved evaluating binary mixtures of BPA and GEN at dose levels that gave moderate uterotrophic responses when tested individually. The mixtures generally showed an intermediate or reduced uterotrophic effect compared with when the components of the mixture were tested alone at the dose used in the mixture. The next series of experiments used a multicomponent (complex) mixture of all seven chemicals evaluated at doses that gave either weakly positive or inactive uterotrophic responses when tested individually in the assay. Doses that were nominally equi-uterotrophic ranged over approximately six orders of magnitude for the seven chemicals. Doses of agents that gave a weak uterotrophic response when tested individually gave a marginally enhanced positive response in the assay when tested combined as a mixture. Doses of agents that gave a negative uterotrophic response when tested individually gave a positive response when tested as a mixture. These data indicate that a variety of different estrogen receptor (ER) agonists, present individually at subeffective doses, can act simultaneously to evoke an ER-regulated response. However, translating these findings into the process of environmental hazard assessment will be difficult. The simple addition of the observed, or predicted, activities for the components of a mixture is confirmed here to be inappropriate and to overestimate the actual effect induced by the mixture. Equally, isobole analysis is only suitable for two- or three-component mixtures, and concentration addition requires access to dose-response data and EC50 values (concentration giving 50% of the maximum response) for the individual components of the mixture--requirements that will rarely be fulfilled for complex environmental samples. Given these uncertainties, we conclude that it may be most expedient to select and bioassay whole environmental mixtures of potential concern. PMID:15064164

A mixture model with a reference-based automatic selection of components for disease classification from protein and/or gene expression levels

PubMed Central

2011-01-01

Background Bioinformatics data analysis is often using linear mixture model representing samples as additive mixture of components. Properly constrained blind matrix factorization methods extract those components using mixture samples only. However, automatic selection of extracted components to be retained for classification analysis remains an open issue. Results The method proposed here is applied to well-studied protein and genomic datasets of ovarian, prostate and colon cancers to extract components for disease prediction. It achieves average sensitivities of: 96.2 (sd = 2.7%), 97.6% (sd = 2.8%) and 90.8% (sd = 5.5%) and average specificities of: 93.6% (sd = 4.1%), 99% (sd = 2.2%) and 79.4% (sd = 9.8%) in 100 independent two-fold cross-validations. Conclusions We propose an additive mixture model of a sample for feature extraction using, in principle, sparseness constrained factorization on a sample-by-sample basis. As opposed to that, existing methods factorize complete dataset simultaneously. The sample model is composed of a reference sample representing control and/or case (disease) groups and a test sample. Each sample is decomposed into two or more components that are selected automatically (without using label information) as control specific, case specific and not differentially expressed (neutral). The number of components is determined by cross-validation. Automatic assignment of features (m/z ratios or genes) to particular component is based on thresholds estimated from each sample directly. Due to the locality of decomposition, the strength of the expression of each feature across the samples can vary. Yet, they will still be allocated to the related disease and/or control specific component. Since label information is not used in the selection process, case and control specific components can be used for classification. That is not the case with standard factorization methods. Moreover, the component selected by proposed method as disease specific can be interpreted as a sub-mode and retained for further analysis to identify potential biomarkers. As opposed to standard matrix factorization methods this can be achieved on a sample (experiment)-by-sample basis. Postulating one or more components with indifferent features enables their removal from disease and control specific components on a sample-by-sample basis. This yields selected components with reduced complexity and generally, it increases prediction accuracy. PMID:22208882

Evaluating porewater polycyclic aromatic hydrocarbon-related toxicity at a contaminated sediment site using a spiked field-sediment approach.

PubMed

Hartzell, Sharon E; Unger, Michael A; Vadas, George G; Yonkos, Lance T

2018-03-01

Although the complexity of contaminant mixtures in sediments can confound the identification of causative agents of adverse biological response, understanding the contaminant(s) of primary concern at impacted sites is critical to sound environmental management and remediation. In the present study, a stock mixture of 18 polycyclic aromatic hydrocarbon (PAH) compounds was prepared to reflect the variety and relative proportions of PAHs measured in surface sediment samples collected from discrete areas of a historically contaminated industrial estuary. This site-specific PAH stock mixture was spiked into nontoxic in-system and out-of-system field-collected reference sediments in dilution series spanning the range of previously measured total PAH concentrations from the region. Spiked sediments were evaluated in 10-d Leptocheirus plumulosus tests to determine whether toxicity in laboratory-created PAH concentrations was similar to the toxicity found in field-collected samples with equivalent PAH concentrations. The results show that toxicity of contaminated sediments was not explained by PAH exposure, while indicating that toxicity in spiked in-system (fine grain, high total organic carbon [TOC]) and out-of-system (course grain, low TOC) sediments was better explained by porewater PAH concentrations, measured using an antibody-based biosensor that quantified 3- to 5-ring PAHs, than total sediment PAH concentrations. The study demonstrates the application of site-specific spiking experiments to evaluate sediment toxicity at sites with complex mixtures of multiple contaminant classes and the utility of the PAH biosensor for rapid sediment-independent porewater PAH analysis. Environ Toxicol Chem 2018;37:893-902. © 2017 SETAC. © 2017 SETAC.

Metabolomics Tools for Describing Complex Pesticide Exposure in Pregnant Women in Brittany (France)

PubMed Central

Bonvallot, Nathalie; Tremblay-Franco, Marie; Chevrier, Cécile; Canlet, Cécile; Warembourg, Charline; Cravedi, Jean-Pierre; Cordier, Sylvaine

2013-01-01

Background The use of pesticides and the related environmental contaminations can lead to human exposure to various molecules. In early-life, such exposures could be responsible for adverse developmental effects. However, human health risks associated with exposure to complex mixtures are currently under-explored. Objective This project aims at answering the following questions: What is the influence of exposures to multiple pesticides on the metabolome? What mechanistic pathways could be involved in the metabolic changes observed? Methods Based on the PELAGIE cohort (Brittany, France), 83 pregnant women who provided a urine sample in early pregnancy, were classified in 3 groups according to the surface of land dedicated to agricultural cereal activities in their town of residence. Nuclear magnetic resonance-based metabolomics analyses were performed on urine samples. Partial Least Squares Regression-Discriminant Analysis (PLS-DA) and polytomous regressions were used to separate the urinary metabolic profiles from the 3 exposure groups after adjusting for potential confounders. Results The 3 groups of exposure were correctly separated with a PLS-DA model after implementing an orthogonal signal correction with pareto standardizations (R2 = 90.7% and Q2 = 0.53). After adjusting for maternal age, parity, body mass index and smoking habits, the most statistically significant changes were observed for glycine, threonine, lactate and glycerophosphocholine (upward trend), and for citrate (downward trend). Conclusion This work suggests that an exposure to complex pesticide mixtures induces modifications of metabolic fingerprints. It can be hypothesized from identified discriminating metabolites that the pesticide mixtures could increase oxidative stress and disturb energy metabolism. PMID:23704985

A novel sample preparation and on-line HPLC-DAD-MS/MS-BCD analysis for rapid screening and characterization of specific enzyme inhibitors in herbal extracts: case study of α-glucosidase.

PubMed

Li, D Q; Zhao, J; Xie, J; Li, S P

2014-01-01

Drug discovery from complex mixture like Chinese herbs is a challenge and extensive false positives make the obtainment of specific bioactive compounds difficult. In the present study, a novel sample preparation method was proposed to rapidly reveal the specific bioactive compounds from complex mixtures using α-glucosidase as a case. Firstly, aqueous and methanol extracts of 500 traditional Chinese medicines were carried out with the aim of finding new sources of α-glucosidase inhibitors. As a result, the extracts of fruit of Terminalia chebula (FTC), flowers of Rosa rugosa (FRR) and Eugenia caryophyllata (FEC) as well as husk of Punica granatum (HPG) showed high inhibition on α-glucosidase. On-line liquid chromatography-diode array detection-tandem mass spectrometry and biochemical detection (HPLC-DAD-MS/MS-BCD) was performed to rapidly screen and characterize α-glucosidase inhibitors in these four extracts. After tentative identification, most of compounds with inhibitory activity in the investigated crude extracts were found to be tannins commonly recognized as non-specific enzyme inhibitors in vitro. Subsequently, the four extracts were treated with gelatin to improve specificity of the on-line system. Finally, two compounds with specific α-glucosidase inhibition were identified as corilagin and ellagic acid. The developed method could discover specific α-glucosidase inhibitors in complex mixtures such as plant extracts, which could also be used for discovery of specific inhibitors of other enzymes. Copyright © 2013 Elsevier B.V. All rights reserved.

Detection of bacteria from biological mixtures using immunomagnetic separation combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

USGS Publications Warehouse

Madonna, A.J.; Basile, F.; Furlong, E.; Voorhees, K.J.

2001-01-01

A rapid method for identifying specific bacteria from complex biological mixtures using immunomagnetic separation coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been developed. The technique employs commercially available magnetic beads coated with polycolonal antibodies raised against specific bacteria and whole cell analysis by MALDI-MS. A suspension of a bacterial mixture is mixed with the immunomagnetic beads specific for the target microorganism. After a short incubation period (20 mins) the bacteria captured by the beads are washed, resuspended in deionized H2O and directly applied onto a MALDI probe. Liquid suspensions containing bacterial mixtures can be screened within 1 h total analysis time. Positive tests result in the production of a fingerprint mass spectrum primarily consisting of protein biomarkers characteristic of the targeted microorganism. Using this procedure, Salmonella choleraesuis was isolated and detected from standard bacterial mixtures and spiked samples of river water, human urine, and chicken blood. Copyright ?? 2001 John Wiley & Sons, Ltd.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE PAGES

Geier, Mitra C.; James Minick, D.; Truong, Lisa; ...

2018-04-01

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geier, Mitra C.; James Minick, D.; Truong, Lisa

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Elucidating the Chemical Complexity of Organic Aerosol Constituents Measured During the Southeastern Oxidant and Aerosol Study (SOAS)

NASA Astrophysics Data System (ADS)

Yee, L.; Isaacman, G. A.; Spielman, S. R.; Worton, D. R.; Zhang, H.; Kreisberg, N. M.; Wilson, K. R.; Hering, S. V.; Goldstein, A. H.

2013-12-01

Thousands of volatile organic compounds are uniquely created in the atmosphere, many of which undergo chemical transformations that result in more highly-oxidized and often lower vapor pressure species. These species can contribute to secondary organic aerosol, a complex mixture of organic compounds that is still not chemically well-resolved. Organic aerosol collected on filters taken during the Southeastern Oxidant and Aerosol Study (SOAS) constitute hundreds of unique chemical compounds. Some of these include known anthropogenic and biogenic tracers characterized using standardized analytical techniques (e.g. GC-MS, UPLC, LC-MS), but the majority of the chemical diversity has yet to be explored. By employing analytical techniques involving sample derivatization and comprehensive two-dimensional gas chromatography (GC x GC) with high-resolution-time-of-flight mass spectrometry (HR-ToF-MS), we elucidate the chemical complexity of the organic aerosol matrix along the volatility and polarity grids. Further, by utilizing both electron impact (EI) and novel soft vacuum ultraviolet (VUV) ionization mass spectrometry, a greater fraction of the organic mass is fully speciated. The GC x GC-HR-ToF-MS with EI/VUV technique efficiently provides an unprecedented level of speciation for complex ambient samples. We present an extensive chemical characterization and quantification of organic species that goes beyond typical atmospheric tracers in the SOAS samples. We further demonstrate that complex organic mixtures can be chemically deconvoluted by elucidation of chemical formulae, volatility, functionality, and polarity. These parameters provide insight into the sources (anthropogenic vs. biogenic), chemical processes (oxidation pathways), and environmental factors (temperature, humidity), controlling organic aerosol growth in the Southeastern United States.

Application of Biologically-Based Lumping To Investigate the Toxicological Interactions of a Complex Gasoline Mixture

EPA Science Inventory

People are often exposed to complex mixtures of environmental chemicals such as gasoline, tobacco smoke, water contaminants, or food additives. However, investigators have often considered complex mixtures as one lumped entity. Valuable information can be obtained from these exp...

Laser Time-of-Flight Mass Spectrometry for Future In Situ Planetary Missions

NASA Technical Reports Server (NTRS)

Getty, S. A.; Brinckerhoff, W. B.; Cornish, T.; Ecelberger, S. A.; Li, X.; Floyd, M. A. Merrill; Chanover, N.; Uckert, K.; Voelz, D.; Xiao, X.;

Database searching and accounting of multiplexed precursor and product ion spectra from the data independent analysis of simple and complex peptide mixtures.

PubMed

Li, Guo-Zhong; Vissers, Johannes P C; Silva, Jeffrey C; Golick, Dan; Gorenstein, Marc V; Geromanos, Scott J

2009-03-01

A novel database search algorithm is presented for the qualitative identification of proteins over a wide dynamic range, both in simple and complex biological samples. The algorithm has been designed for the analysis of data originating from data independent acquisitions, whereby multiple precursor ions are fragmented simultaneously. Measurements used by the algorithm include retention time, ion intensities, charge state, and accurate masses on both precursor and product ions from LC-MS data. The search algorithm uses an iterative process whereby each iteration incrementally increases the selectivity, specificity, and sensitivity of the overall strategy. Increased specificity is obtained by utilizing a subset database search approach, whereby for each subsequent stage of the search, only those peptides from securely identified proteins are queried. Tentative peptide and protein identifications are ranked and scored by their relative correlation to a number of models of known and empirically derived physicochemical attributes of proteins and peptides. In addition, the algorithm utilizes decoy database techniques for automatically determining the false positive identification rates. The search algorithm has been tested by comparing the search results from a four-protein mixture, the same four-protein mixture spiked into a complex biological background, and a variety of other "system" type protein digest mixtures. The method was validated independently by data dependent methods, while concurrently relying on replication and selectivity. Comparisons were also performed with other commercially and publicly available peptide fragmentation search algorithms. The presented results demonstrate the ability to correctly identify peptides and proteins from data independent acquisition strategies with high sensitivity and specificity. They also illustrate a more comprehensive analysis of the samples studied; providing approximately 20% more protein identifications, compared to a more conventional data directed approach using the same identification criteria, with a concurrent increase in both sequence coverage and the number of modified peptides.

Application of hierarchical Bayesian unmixing models in river sediment source apportionment

NASA Astrophysics Data System (ADS)

Blake, Will; Smith, Hugh; Navas, Ana; Bodé, Samuel; Goddard, Rupert; Zou Kuzyk, Zou; Lennard, Amy; Lobb, David; Owens, Phil; Palazon, Leticia; Petticrew, Ellen; Gaspar, Leticia; Stock, Brian; Boeckx, Pacsal; Semmens, Brice

2016-04-01

Fingerprinting and unmixing concepts are used widely across environmental disciplines for forensic evaluation of pollutant sources. In aquatic and marine systems, this includes tracking the source of organic and inorganic pollutants in water and linking problem sediment to soil erosion and land use sources. It is, however, the particular complexity of ecological systems that has driven creation of the most sophisticated mixing models, primarily to (i) evaluate diet composition in complex ecological food webs, (ii) inform population structure and (iii) explore animal movement. In the context of the new hierarchical Bayesian unmixing model, MIXSIAR, developed to characterise intra-population niche variation in ecological systems, we evaluate the linkage between ecological 'prey' and 'consumer' concepts and river basin sediment 'source' and sediment 'mixtures' to exemplify the value of ecological modelling tools to river basin science. Recent studies have outlined advantages presented by Bayesian unmixing approaches in handling complex source and mixture datasets while dealing appropriately with uncertainty in parameter probability distributions. MixSIAR is unique in that it allows individual fixed and random effects associated with mixture hierarchy, i.e. factors that might exert an influence on model outcome for mixture groups, to be explored within the source-receptor framework. This offers new and powerful ways of interpreting river basin apportionment data. In this contribution, key components of the model are evaluated in the context of common experimental designs for sediment fingerprinting studies namely simple, nested and distributed catchment sampling programmes. Illustrative examples using geochemical and compound specific stable isotope datasets are presented and used to discuss best practice with specific attention to (1) the tracer selection process, (2) incorporation of fixed effects relating to sample timeframe and sediment type in the modelling process, (3) deriving and using informative priors in sediment fingerprinting context and (4) transparency of the process and replication of model results by other users.

COMPARATIVE TUMOR-INITIATING ACTIVITY OF COMPLEX MIXTURES FROM ENVIRONMENTAL PARTICULATE EMISSIONS ON SENCAR MOUSE SKIN

EPA Science Inventory

The value of the SENCAR mouse for testing tumorigenic properties of complex mixtures on mouse skin was studied. Seven complex mixtures were obtained as dichloromethane extracts of collected particulate emissions from three diesel-fueled automobiles, a heavy-duty diesel engine, a ...

Comparison of Chemical Composition of Complex Disinfection Byproduct (DBP) Mixtures Produced by Different Treatment Methods - slides

EPA Science Inventory

Analyses of the chemical composition of complex DBP mixtures, produced by different drinking water treatment processes, are essential to generate toxicity data required for assessing their risks to humans. For mixture risk assessments, whole mixture toxicology studies generally a...

Comparison of Chemical Composition of Complex Disinfection Byproduct (DBP) Mixtures Produced by Different Treatment Methods

EPA Science Inventory

Analyses of the chemical composition of complex DBP mixtures, produced by different drinking water treatment processes, are essential to generate toxicity data required for assessing their risks to humans. For mixture risk assessments, whole mixture toxicology studies generally a...

Preservation of commonly applied fluorescent tracers in complex water samples

NASA Astrophysics Data System (ADS)

Cao, Viet; Schaffer, Mario; Jin, Yulan; Licha, Tobias

2017-06-01

Water sample preservation and pre-treatment are important steps for achieving accurate and reproductive results from tracer tests. However, this is particularly challenging for complex water mixtures prior to fluorescence analysis. In this study, the interference of iron and calcium precipitation with nine commonly applied conservative tracers, uranine, eosin, 1-naphthalene sulfonate, 1,5-naphthalene disulfonate, 2,6-naphthalene disulfonate, 4-amino-1-naphthalene sulfonate, 6-hydroxy-2-naphthalene sulfonate, 1,3,6-naphthalene trisulfonate, and 1,3,6,8-pyrene tetrasulfonate, was investigated in batch experiments. In general, the observed results are influenced by precipitates. A technique consisting of pH adjustment and centrifugation is described for preserving samples and avoiding the impact of these precipitates on the tracer test results.

Comparison of two common adsorption materials for thermal desorption gas chromatography - mass spectrometry of biogenic volatile organic compounds.

PubMed

Marcillo, Andrea; Jakimovska, Viktorija; Widdig, Anja; Birkemeyer, Claudia

2017-09-08

Volatile organic compounds (VOCs) are commonly collected from gaseous samples by adsorption to materials such as the porous polymer Tenax TA. Adsorbed compounds are subsequently released from these materials by thermal desorption (TD) and separated then by gas chromatography (GC) with flame ionization (FID) or mass spectrometry (MS) detection. Tenax TA is known to be particularly suitable for non-polar to semipolar volatiles, however, many volatiles from environmental and biological samples possess a rather polar character. Therefore, we tested if the polymer XAD-2, which so far is widely used to adsorb organic compounds from aqueous and organic solvents, could provide a broader coverage for (semi)polar VOCs during gas-phase sampling. Mixtures of volatile compounds covering a wide range of volatility (bp. 20-256°C) and different chemical classes were introduced by liquid spiking into sorbent tubes with one of the two porous polymers, Tenax TA or XAD-2, and analyzed by TD/GC-MS. At first, an internal standard mixture composed of 17 authentic standards was used to optimize desorption temperature with respect to sorbent degradation and loading time for calibration. Secondly, we tested the detectability of a complex standard mixture composed of 57 volatiles, most of them common constituents of the body odor of mammals. Moreover, the performance of XAD-2 compared with Tenax TA was assessed as limit of quantitation and linearity for the internal standard mixture and 33 compounds from the complex standard mixture. Volatiles were analyzed in a range between 0.01-∼250ng/tube depending on the compound and material. Lower limits of quantitation were between 0.01 and 3 ng±<25% RSD (R 2 >0.9). Interestingly, we found different kinetics for compound adsorption with XAD-2, and a partially better sensitivity in comparison with Tenax TA. For these analytes, XAD-2 might be recommended as an alternative of Tenax TA for TD/GC-MS analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Sample displacement chromatography as a method for purification of proteins and peptides from complex mixtures

PubMed Central

Gajdosik, Martina Srajer; Clifton, James; Josic, Djuro

2012-01-01

Sample displacement chromatography (SDC) in reversed-phase and ion-exchange modes was introduced approximately twenty years ago. This method takes advantage of relative binding affinities of components in a sample mixture. During loading, there is a competition among different sample components for the sorption on the surface of the stationary phase. SDC was first used for the preparative purification of proteins. Later, it was demonstrated that this kind of chromatography can also be performed in ion-exchange, affinity and hydrophobic-interaction mode. It has also been shown that SDC can be performed on monoliths and membrane-based supports in both analytical and preparative scale. Recently, SDC in ion-exchange and hydrophobic interaction mode was also employed successfully for the removal of trace proteins from monoclonal antibody preparations and for the enrichment of low abundance proteins from human plasma. In this review, the principals of SDC are introduced, and the potential for separation of proteins and peptides in micro-analytical, analytical and preparative scale is discussed. PMID:22520159

Recent progress in the design and clinical development of electronic-nose technologies

Treesearch

Dan Wilson

2016-01-01

Electronic-nose (e-nose) devices are instruments designed to detect and discriminate between precise complex gaseous mixtures of volatile organic compounds derived from specific organic sources, such as clinical test samples from patients, based on electronic aroma signature patterns (distinct digital sensor responses) resulting from the combined outputs of a...

Synthesis, characterisation and computational studies on a novel one-dimensional arrangement of Schiff-base Mn3 single-molecule magnet.

PubMed

Lin, Po-Heng; Gorelsky, Serge; Savard, Didier; Burchell, Tara J; Wernsdorfer, Wolfgang; Clérac, Rodolphe; Murugesu, Muralee

2010-09-07

The syntheses, structures and magnetic properties are reported for three new manganese complexes containing the Schiff-base ((2-hydroxy-3-methoxyphenyl)methylene)isonicotinohydrazine (H(2)hmi) ligand. Complex [Mn(II)(H(2)hmi)(2)(MeOH)(2)Cl(2)] (1) was obtained from the reaction of H(2)hmi with MnCl(2) in a MeOH-MeCN mixture. Addition of triethylamine to the previous reaction mixture followed by diethyl ether diffusion yielded a dinuclear manganese [Mn(III)(2)(hmi)(2)(OMe)(2)](infinity).2MeCN.2OEt(2) (2) compound. Upon increasing the MnCl(2)/H(2)hmi ratio, the mixed valence complex [Mn(III)(2)Mn(II)(hmi)(2)(OMe)(2)Cl(2)](infinity).MeOH (3) was obtained. Dc and ac magnetic measurements were carried out on all three samples. The ac susceptibility and field dependence of the magnetisation measurements confirmed that complex 3 exhibits a single-molecule magnet behaviour with an effective energy barrier of 8.1 K and an Arrhenius pre-exponential factor of 3 x 10(-9) s.

A chromatographic objective function to characterise chromatograms with unknown compounds or without standards available.

PubMed

Alvarez-Segura, T; Gómez-Díaz, A; Ortiz-Bolsico, C; Torres-Lapasió, J R; García-Alvarez-Coque, M C

2015-08-28

Getting useful chemical information from samples containing many compounds is still a challenge to analysts in liquid chromatography. The highest complexity corresponds to samples for which there is no prior knowledge about their chemical composition. Computer-based methodologies are currently considered as the most efficient tools to optimise the chromatographic resolution, and further finding the optimal separation conditions. However, most chromatographic objective functions (COFs) described in the literature to measure the resolution are based on mathematical models fitted with the information obtained from standards, and cannot be applied to samples with unknown compounds. In this work, a new COF based on the automatic measurement of the protruding part of the chromatographic peaks (or peak prominences) that indicates the number of perceptible peaks and global resolution, without the need of standards, is developed. The proposed COF was found satisfactory with regard to the peak purity criterion when applied to artificial peaks and simulated chromatograms of mixtures built using the information of standards. The approach was applied to mixtures of drugs containing unknown impurities and degradation products and to extracts of medicinal herbs, eluted with acetonitrile-water mixtures using isocratic and gradient elution. Copyright © 2015 Elsevier B.V. All rights reserved.

Application of headspace solid-phase microextraction (HS-SPME) and comprehensive two-dimensional gas chromatography (GC x GC) for the chemical profiling of volatile oils in complex herbal mixtures.

PubMed

Di, Xin; Shellie, Robert A; Marriott, Philip J; Huie, Carmen W

2004-04-01

The coupling of headspace solid-phase microextraction (HS-SPME) with comprehensive two-dimensional gas chromatography (GC x GC) was shown to be a powerful technique for the rapid sampling and analysis of volatile oils in complex herbal materials. When compared to one-dimensional (1-D) GC, the improved analytical capabilities of GC x GC in terms of increased detection sensitivity and separation power were demonstrated by using HS-SPME/GC x GC for the chemical profiling (fingerprinting) of essential/volatile oils contained in herbal materials of increasing analytical complexity. More than 20 marker compounds belonging to Panax quinquefolius (American ginseng) can be observed within the 2-D contour plots of ginseng itself, a mixture of ginseng and another important herb (P. quinquefolius/Radix angelicae sinensis), as well as a mixture of ginseng and three other herbs (P. quinquefolius /R. angelicae sinensis/R. astragali/R. rehmanniae preparata). Such analytical capabilities should be important towards the authentication and quality control of herbal products, which are receiving increasing attention as alternative medicines worldwide. In particular, the presence of Panax in the herb formulation could be readily identified through its specific peak pattern in the 2-D GC x GC plot.

Honeybees Learn Odour Mixtures via a Selection of Key Odorants

PubMed Central

Reinhard, Judith; Sinclair, Michael; Srinivasan, Mandyam V.; Claudianos, Charles

2010-01-01

Background The honeybee has to detect, process and learn numerous complex odours from her natural environment on a daily basis. Most of these odours are floral scents, which are mixtures of dozens of different odorants. To date, it is still unclear how the bee brain unravels the complex information contained in scent mixtures. Methodology/Principal Findings This study investigates learning of complex odour mixtures in honeybees using a simple olfactory conditioning procedure, the Proboscis-Extension-Reflex (PER) paradigm. Restrained honeybees were trained to three scent mixtures composed of 14 floral odorants each, and then tested with the individual odorants of each mixture. Bees did not respond to all odorants of a mixture equally: They responded well to a selection of key odorants, which were unique for each of the three scent mixtures. Bees showed less or very little response to the other odorants of the mixtures. The bees' response to mixtures composed of only the key odorants was as good as to the original mixtures of 14 odorants. A mixture composed of the other, non-key-odorants elicited a significantly lower response. Neither an odorant's volatility or molecular structure, nor learning efficiencies for individual odorants affected whether an odorant became a key odorant for a particular mixture. Odorant concentration had a positive effect, with odorants at high concentration likely to become key odorants. Conclusions/Significance Our study suggests that the brain processes complex scent mixtures by predominantly learning information from selected key odorants. Our observations on key odorant learning lend significant support to previous work on olfactory learning and mixture processing in honeybees. PMID:20161714

Pesticide mixtures in the Swedish streams: Environmental risks, contributions of individual compounds and consequences of single-substance oriented risk mitigation.

PubMed

Gustavsson, Mikael; Kreuger, Jenny; Bundschuh, Mirco; Backhaus, Thomas

2017-11-15

This paper presents the ecotoxicological assessment and environmental risk evaluation of complex pesticide mixtures occurring in freshwater ecosystems in southern Sweden. The evaluation is based on exposure data collected between 2002 and 2013 by the Swedish pesticide monitoring program and includes 1308 individual samples, detecting mixtures of up to 53 pesticides (modal=8). Pesticide mixture risks were evaluated using three different scenarios for non-detects (best-case, worst-case and using the Kaplan-Meier method). The risk of each scenario was analyzed using Swedish Water Quality Objectives (WQO) and trophic-level specific environmental thresholds. Using the Kaplan-Meier method the environmental risk of 73% of the samples exceeded acceptable levels, based on an assessment using Concentration-Addition and WQOs for the individual pesticides. Algae were the most sensitive organism group. However, analytical detection limits, especially for insecticides, were insufficient to analyze concentrations at or near their WQO's. Thus, the risk of the analyzed pesticide mixtures to crustaceans and fish is systematically underestimated. Treating non-detects as being present at their individual limit of detection increased the estimated risk by a factor 100 or more, compared to the best-case or the Kaplan-Meier scenario. Pesticide mixture risks are often driven by only 1-3 compounds. However, the risk-drivers (i.e., individual pesticides explaining the largest share of potential effects) differ substantially between sites and samples, and 83 of the 141 monitored pesticides need to be included in the assessment to account for 95% of the risk at all sites and years. Single-substance oriented risk mitigation measures that would ensure that each individual pesticide is present at a maximum of 95% of its individual WQO, would also reduce the mixture risk, but only from a median risk quotient of 2.1 to a median risk quotient of 1.8. Also, acceptable total risk levels would still be exceeded in more than 70% of the samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluating differential effects using regression interactions and regression mixture models

PubMed Central

Van Horn, M. Lee; Jaki, Thomas; Masyn, Katherine; Howe, George; Feaster, Daniel J.; Lamont, Andrea E.; George, Melissa R. W.; Kim, Minjung

2015-01-01

Research increasingly emphasizes understanding differential effects. This paper focuses on understanding regression mixture models, a relatively new statistical methods for assessing differential effects by comparing results to using an interactive term in linear regression. The research questions which each model answers, their formulation, and their assumptions are compared using Monte Carlo simulations and real data analysis. The capabilities of regression mixture models are described and specific issues to be addressed when conducting regression mixtures are proposed. The paper aims to clarify the role that regression mixtures can take in the estimation of differential effects and increase awareness of the benefits and potential pitfalls of this approach. Regression mixture models are shown to be a potentially effective exploratory method for finding differential effects when these effects can be defined by a small number of classes of respondents who share a typical relationship between a predictor and an outcome. It is also shown that the comparison between regression mixture models and interactions becomes substantially more complex as the number of classes increases. It is argued that regression interactions are well suited for direct tests of specific hypotheses about differential effects and regression mixtures provide a useful approach for exploring effect heterogeneity given adequate samples and study design. PMID:26556903

Applicability study of classical and contemporary models for effective complex permittivity of metal powders.

PubMed

Kiley, Erin M; Yakovlev, Vadim V; Ishizaki, Kotaro; Vaucher, Sebastien

2012-01-01

Microwave thermal processing of metal powders has recently been a topic of a substantial interest; however, experimental data on the physical properties of mixtures involving metal particles are often unavailable. In this paper, we perform a systematic analysis of classical and contemporary models of complex permittivity of mixtures and discuss the use of these models for determining effective permittivity of dielectric matrices with metal inclusions. Results from various mixture and core-shell mixture models are compared to experimental data for a titanium/stearic acid mixture and a boron nitride/graphite mixture (both obtained through the original measurements), and for a tungsten/Teflon mixture (from literature). We find that for certain experiments, the average error in determining the effective complex permittivity using Lichtenecker's, Maxwell Garnett's, Bruggeman's, Buchelnikov's, and Ignatenko's models is about 10%. This suggests that, for multiphysics computer models describing the processing of metal powder in the full temperature range, input data on effective complex permittivity obtained from direct measurement has, up to now, no substitute.

Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

NASA Astrophysics Data System (ADS)

Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

2010-02-01

Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

Investigation of thermal and optical properties of some quartet mixed hydrogen-bonded liquid crystals

NASA Astrophysics Data System (ADS)

Okumuş, Mustafa

2017-11-01

In this study, the thermal and optical properties of quartet mixtures formed at different weight ratios (1:1:1:1 and 1.5:1:1:1) from liquid crystals 4-octyloxy-4‧-cyanobiphenyl (8OCB), 4-hexylbenzoic acid, 4-(octyloxy)benzoic acid and 4-(decyloxy)benzoic acid were investigated by differential scanning calorimeter (DSC) and polarized optic microscopy (POM). The phase transition temperatures of the novel quartet mixtures measured in the DSC experiments are in line with the POM experiments. The experimental results clearly show that the novel liquid crystal mixtures have displayed pure liquid crystalline properties. According to the phase diagram drawn from DSC results, the nematic range of the novel mixture at the eutectic point is larger than the nematic ranges of the components. The mesomorphic structures of produced homolog complex mixtures are found to be smectic and nematic phases. But the smectic phase cannot be observed in the novel complex 1.5:1:1:1 mixture during continuous cooling. The nematic range of the novel complex 1.5:1:1:1 mixture is bigger than the nematic range of the novel complex 1:1:1:1 mixture with increasing 8OCB. Also, the nematic-to-isotropic phase transition temperature decreases with increasing the weight ratio of 8OCB in the complex quartet mixture. Another interesting result is that the produced mixtures are to be like a medical cream at room temperatures. Furthermore, order parameter and thermal stability factor of the transitions are also calculated.

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams

USGS Publications Warehouse

Barber, Larry B.; Keefe, Steffanie H.; Brown, Greg K.; Furlong, Edward T.; Gray, James L.; Kolpin, Dana W.; Meyer, Michael T.; Sandstrom, Mark W.; Zaugg, Steven D.

2013-01-01

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L–1) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L–1), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

Automating data analysis for two-dimensional gas chromatography/time-of-flight mass spectrometry non-targeted analysis of comparative samples.

PubMed

Titaley, Ivan A; Ogba, O Maduka; Chibwe, Leah; Hoh, Eunha; Cheong, Paul H-Y; Simonich, Staci L Massey

2018-03-16

Non-targeted analysis of environmental samples, using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC/ToF-MS), poses significant data analysis challenges due to the large number of possible analytes. Non-targeted data analysis of complex mixtures is prone to human bias and is laborious, particularly for comparative environmental samples such as contaminated soil pre- and post-bioremediation. To address this research bottleneck, we developed OCTpy, a Python™ script that acts as a data reduction filter to automate GC × GC/ToF-MS data analysis from LECO ® ChromaTOF ® software and facilitates selection of analytes of interest based on peak area comparison between comparative samples. We used data from polycyclic aromatic hydrocarbon (PAH) contaminated soil, pre- and post-bioremediation, to assess the effectiveness of OCTpy in facilitating the selection of analytes that have formed or degraded following treatment. Using datasets from the soil extracts pre- and post-bioremediation, OCTpy selected, on average, 18% of the initial suggested analytes generated by the LECO ® ChromaTOF ® software Statistical Compare feature. Based on this list, 63-100% of the candidate analytes identified by a highly trained individual were also selected by OCTpy. This process was accomplished in several minutes per sample, whereas manual data analysis took several hours per sample. OCTpy automates the analysis of complex mixtures of comparative samples, reduces the potential for human error during heavy data handling and decreases data analysis time by at least tenfold. Copyright © 2018 Elsevier B.V. All rights reserved.

Evaluating the aquatic toxicity of complex organic chemical mixtures: lessons learned from polycyclic aromatic hydrocarbon and petroleum hydrocarbon case studies.

PubMed

Landrum, Peter F; Chapman, Peter M; Neff, Jerry; Page, David S

2012-04-01

Experimental designs for evaluating complex mixture toxicity in aquatic environments can be highly variable and, if not appropriate, can produce and have produced data that are difficult or impossible to interpret accurately. We build on and synthesize recent critical reviews of mixture toxicity using lessons learned from 4 case studies, ranging from binary to more complex mixtures of primarily polycyclic aromatic hydrocarbons and petroleum hydrocarbons, to provide guidance for evaluating the aquatic toxicity of complex mixtures of organic chemicals. Two fundamental requirements include establishing a dose-response relationship and determining the causative agent (or agents) of any observed toxicity. Meeting these 2 requirements involves ensuring appropriate exposure conditions and measurement endpoints, considering modifying factors (e.g., test conditions, test organism life stages and feeding behavior, chemical transformations, mixture dilutions, sorbing phases), and correctly interpreting dose-response relationships. Specific recommendations are provided. Copyright © 2011 SETAC.

Sequential elution process

DOEpatents

Kingsley, I.S.

1987-01-06

A process and apparatus are disclosed for the separation of complex mixtures of carbonaceous material by sequential elution with successively stronger solvents. In the process, a column containing glass beads is maintained in a fluidized state by a rapidly flowing stream of a weak solvent, and the sample is injected into this flowing stream such that a portion of the sample is dissolved therein and the remainder of the sample is precipitated therein and collected as a uniform deposit on the glass beads. Successively stronger solvents are then passed through the column to sequentially elute less soluble materials. 1 fig.

Purification and Quantification of an Isomeric Compound in a Mixture by Collisional Excitation in Multistage Mass Spectrometry Experiments.

PubMed

Jeanne Dit Fouque, Dany; Maroto, Alicia; Memboeuf, Antony

2016-11-15

The differentiation, characterization, and quantification of isomers and/or isobars in mixtures is a recurrent problem in mass spectrometry and more generally in analytical chemistry. Here we present a new strategy to assess the purity of a compound that is susceptible to be contaminated with another isomeric side-product in trace levels. Providing one of the isomers is available as pure sample, this new strategy allows the detection of isomeric contamination. This is done thanks to a "gas-phase collisional purification" inside an ion trap mass spectrometer paving the way for an improved analysis of at least similar samples. This strategy consists in using collision induced dissociation (CID) multistage mass spectrometry (MS 2 and MS 3 ) experiments and the survival yield (SY) technique. It has been successfully applied to mixtures of cyclic poly( L -lactide) (PLA) with increasing amounts of its linear topological isomer. Purification in gas phase of PLA mixtures was established based on SY curves obtained in MS 3 mode: all samples gave rise to the same SY curve corresponding then to the pure cyclic component. This new strategy was sensitive enough to detect traces of linear PLA (<3%) in a sample of cyclic PLA that was supposedly pure according to other characterization techniques ( 1 H NMR, MALDI-HRMS, and size-exclusion chromatography). Moreover, in this case, the presence of linear isomer was undetectable according to MS/MS or MS/MS/MS analysis only as fragment ions are also of the same m/z values. This type of approach could easily be implemented in hyphenated mass spectrometric techniques to improve the structural and quantitative analysis of complex samples.

COMPONENT-BASED AND WHOLE-MIXTURE ASSESSMENTS IN ADDRESSING THE UNIDENTIFIED FRACTION OF COMPLEX MIXTURES: DRINKING WATER AS AN EXAMPLE

EPA Science Inventory

Component-Based and Whole-Mixtures Assessments in Addressing the Unidentified Fraction of Complex Mixtures: Drinking Water as an Example

J. E. Simmons; L. K. Teuschler; C. Gennings; T. F. Speth; S. D. Richardson; R. J. Miltner; M. G. Narotsky; K. D. Schenck; G. Rice

Liquid class predictor for liquid handling of complex mixtures

DOEpatents

Seglke, Brent W [San Ramon, CA; Lekin, Timothy P [Livermore, CA

2008-12-09

A method of establishing liquid classes of complex mixtures for liquid handling equipment. The mixtures are composed of components and the equipment has equipment parameters. The first step comprises preparing a response curve for the components. The next step comprises using the response curve to prepare a response indicator for the mixtures. The next step comprises deriving a model that relates the components and the mixtures to establish the liquid classes.

DETECTION OF HIGH MOLECULAR WEIGHT ORGANIC TRACERS IN VEGETATION SMOKE SAMPLES BY HIGH-TEMPERATURE GAS CHROMATOGRAPHY-MASS SPECTROMETRY. (R823990)

EPA Science Inventory

High-temperature high-resolution gas chromatography
(HTGC) is an established technique for the separation of
complex mixtures of high molecular weight (HMW) compounds
which do not elute when analyzed on conventional GC
columns. The combination of this technique wit...

Group specific internal standard technology (GSIST) for simultaneous identification and quantification of small molecules

DOEpatents

Adamec, Jiri; Yang, Wen-Chu; Regnier, Fred E

2014-01-14

Reagents and methods are provided that permit simultaneous analysis of multiple diverse small molecule analytes present in a complex mixture. Samples are labeled with chemically identical but isotopically distince forms of the labeling reagent, and analyzed using mass spectrometry. A single reagent simultaneously derivatizes multiple small molecule analytes having different reactive functional groups.

Sequential derivatization of polar organic compounds in cloud water using O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride, N,O-bis(trimethylsilyl)trifluoroacetamide, and gas-chromatography/mass spectrometry analysis.

PubMed

Sagona, Jessica A; Dukett, James E; Hawley, Harmonie A; Mazurek, Monica A

2014-10-03

Cloud water samples from Whiteface Mountain, NY were used to develop a combined sampling and gas chromatography-mass spectrometric (GCMS) protocol for evaluating the complex mixture of highly polar organic compounds (HPOC) present in this atmospheric medium. Specific HPOC of interest were mono- and di keto-acids which are thought to originate from photochemical reactions of volatile unsaturated hydrocarbons from biogenic and manmade emissions and be a major fraction of atmospheric carbon. To measure HPOC mixtures and the individual keto-acids in cloud water, samples first must be derivatized for clean elution and measurement, and second, have low overall background of the target species as validated by GCMS analysis of field and laboratory blanks. Here, we discuss a dual derivatization method with PFBHA and BSTFA which targets only organic compounds that contain functional groups reacting with both reagents. The method also reduced potential contamination by minimizing the amount of sample processing from the field through the GCMS analysis steps. Once derivatized only gas chromatographic separation and selected ion monitoring (SIM) are needed to identify and quantify the polar organic compounds of interest. Concentrations of the detected total keto-acids in individual cloud water samples ranged from 27.8 to 329.3ngmL(-1) (ppb). Method detection limits for the individual HPOC ranged from 0.17 to 4.99ngmL(-1) and the quantification limits for the compounds ranged from 0.57 to 16.64ngmL(-1). The keto-acids were compared to the total organic carbon (TOC) results for the cloud water samples with concentrations of 0.607-3.350mgL(-1) (ppm). GCMS analysis of all samples and blanks indicated good control of the entire collection and analysis steps. Selected ion monitoring by GCMS of target keto-acids was essential for screening the complex organic carbon mixtures present at low ppb levels in cloud water. It was critical for ensuring high levels of quality assurance and quality control and for the correct identification and quantification of key marker compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

Genetic evidence of local exploitation of Atlantic salmon in a coastal subsistence fishery in the Northwest Atlantic

USGS Publications Warehouse

Bradbury, Ian R.; Hamilton, Lorraine C.; Rafferty, Sara; Meerburg, David; Poole, Rebecca; Dempson, J. Brian; Robertson, Martha J.; Reddin, David G.; Bourret, Vincent; Dionne, Mélanie; Chaput, Gerald J.; Sheehan, Timothy F.; King, Tim L.; Candy, John R.; Bernatchez, Louis

2014-01-01

Fisheries targeting mixtures of populations risk the over utilization of minor stock constituents unless harvests are monitored and managed. We evaluated stock composition and exploitation of Atlantic salmon in a subsistence fishery in coastal Labrador, Canada using genetic mixture analysis and individual assignment with a microsatellite baseline (15 loci, 11 829 individuals, 12 regional groups) encompassing the species western Atlantic range. Bayesian and maximum likelihood mixture analyses of fishery samples over six years (2006-2011; 1 772 individuals) indicate contributions of adjacent stocks of 96-97%. Estimates of fishery associated exploitation were highest for Labrador salmon (4.2-10.6% per year) and generally < 1% for other regions. Individual assignment of fishery samples indicated non-local contributions to the fishery (e.g., Quebec, Newfoundland) were rare and primarily in southern Labrador, consistent with migration pathways utilizing the Strait of Belle Isle. This work illustrates how genetic analysis of mixed stock Atlantic salmon fisheries in the northwest Atlantic using this new baseline can disentangle exploitation and reveal complex migratory behaviours.

Advanced statistical analysis of Raman spectroscopic data for the identification of body fluid traces: semen and blood mixtures.

PubMed

Sikirzhytski, Vitali; Sikirzhytskaya, Aliaksandra; Lednev, Igor K

2012-10-10

Conventional confirmatory biochemical tests used in the forensic analysis of body fluid traces found at a crime scene are destructive and not universal. Recently, we reported on the application of near-infrared (NIR) Raman microspectroscopy for non-destructive confirmatory identification of pure blood, saliva, semen, vaginal fluid and sweat. Here we expand the method to include dry mixtures of semen and blood. A classification algorithm was developed for differentiating pure body fluids and their mixtures. The classification methodology is based on an effective combination of Support Vector Machine (SVM) regression (data selection) and SVM Discriminant Analysis of preprocessed experimental Raman spectra collected using an automatic mapping of the sample. This extensive cross-validation of the obtained results demonstrated that the detection limit of the minor contributor is as low as a few percent. The developed methodology can be further expanded to any binary mixture of complex solutions, including but not limited to mixtures of other body fluids. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Rapid Characterization of Microalgae and Microalgae Mixtures Using Matrix-Assisted Laser Desorption Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF MS)

PubMed Central

Barbano, Duane; Diaz, Regina; Zhang, Lin; Sandrin, Todd; Gerken, Henri; Dempster, Thomas

2015-01-01

Current molecular methods to characterize microalgae are time-intensive and expensive. Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) may represent a rapid and economical alternative approach. The objectives of this study were to determine whether MALDI-TOF MS can be used to: 1) differentiate microalgae at the species and strain levels and 2) characterize simple microalgal mixtures. A common protein extraction sample preparation method was used to facilitate rapid mass spectrometry-based analysis of 31 microalgae. Each yielded spectra containing between 6 and 56 peaks in the m/z 2,000 to 20,000 range. The taxonomic resolution of this approach appeared higher than that of 18S rDNA sequence analysis. For example, two strains of Scenedesmus acutus differed only by two 18S rDNA nucleotides, but yielded distinct MALDI-TOF mass spectra. Mixtures of two and three microalgae yielded relatively complex spectra that contained peaks associated with members of each mixture. Interestingly, though, mixture-specific peaks were observed at m/z 11,048 and 11,230. Our results suggest that MALDI-TOF MS affords rapid characterization of individual microalgae and simple microalgal mixtures. PMID:26271045

Direct Maximization of Protein Identifications from Tandem Mass Spectra*

PubMed Central

Spivak, Marina; Weston, Jason; Tomazela, Daniela; MacCoss, Michael J.; Noble, William Stafford

2012-01-01

The goal of many shotgun proteomics experiments is to determine the protein complement of a complex biological mixture. For many mixtures, most methodological approaches fall significantly short of this goal. Existing solutions to this problem typically subdivide the task into two stages: first identifying a collection of peptides with a low false discovery rate and then inferring from the peptides a corresponding set of proteins. In contrast, we formulate the protein identification problem as a single optimization problem, which we solve using machine learning methods. This approach is motivated by the observation that the peptide and protein level tasks are cooperative, and the solution to each can be improved by using information about the solution to the other. The resulting algorithm directly controls the relevant error rate, can incorporate a wide variety of evidence and, for complex samples, provides 18–34% more protein identifications than the current state of the art approaches. PMID:22052992

Chemical mixtures and environmental effects: a pilot study to assess ecological exposure and effects in streams

USGS Publications Warehouse

Buxton, Herbert T.; Reilly, Timothy J.; Kuivila, Kathryn; Kolpin, Dana W.; Bradley, Paul M.; Villeneuve, Daniel L.; Mills, Marc A.

2015-01-01

Assessment and management of the risks of exposure to complex chemical mixtures in streams are priorities for human and environmental health organizations around the world. The current lack of information on the composition and variability of environmental mixtures and a limited understanding of their combined effects are fundamental obstacles to timely identification and prevention of adverse human and ecological effects of exposure. This report describes the design of a field-based study of the composition and biological activity of chemical mixtures in U.S. stream waters affected by a wide range of human activities and contaminant sources. The study is a collaborative effort by the U.S. Geological Survey and the U.S. Environmental Protection Agency. Scientists sampled 38 streams spanning 24 States and Puerto Rico. Thirty-four of the sites were located in watersheds impacted by multiple contaminant sources, including industrial and municipal wastewater discharges, crop and animal agricultural runoff, urban runoff, and other point and nonpoint contaminant sources. The remaining four sites were minimally development reference watersheds. All samples underwent comprehensive chemical and biological characterization, including sensitive and specific direct analysis for over 700 dissolved organic and inorganic chemicals and field parameters, identification of unknown contaminants (environmental diagnostics), and a variety of bioassays to evaluate biological activity and toxicity.

Solid-phase cadmium speciation in soil using L3-edge XANES spectroscopy with partial least-squares regression.

PubMed

Siebers, Nina; Kruse, Jens; Eckhardt, Kai-Uwe; Hu, Yongfeng; Leinweber, Peter

2012-07-01

Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least-square (PLS) regression was tested for its capability to deconvolute Cd L(3)-edge X-ray absorption near-edge structure (XANES) spectra of multi-compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R(2)) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi-compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd-contaminated soil revealing Cd(3)(PO(4))(2) (36.1%), Cd(NO(3))(2)·4H(2)O (24.5%), Cd(OH)(2) (21.7%), CdCO(3) (17.1%) and CdCl(2) (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.

COMPLEX MIXTURES OF CHEMICAL CARCINOGENS: PRINCIPLES OF ACTION AND HUMAN CANCER

EPA Science Inventory

There is strong epidemiological evidence supported by experimental animal data that complex environmental mixtures pose a risk to human health producing increases in cancer incidence. Understanding the chemical and biological properties of these mixtures leads to a clearer unde...

Co-elution phenomena in polymer mixtures studied by asymmetric flow field-flow fractionation.

PubMed

Zielke, Claudia; Fuentes, Catalina; Piculell, Lennart; Nilsson, Lars

2018-01-12

Most polymers generally have complex characteristics. Analysis and understanding of these characteristics is crucial as they, for instance, influence functionality. Separation and analysis of samples of polymers, biopolymers in particular, is challenging since they often display broad distributions in size, structure and molar mass (M) and/or a tendency to form aggregates. Only few analytical techniques are suitable for the task. AF4-MALS-dRI is highly suited for the task, but the analysis can nevertheless be especially challenging for heterogeneous mixtures of polymers that exhibit wide size distributions or aggregation. For such systems, systematic and thorough method development is clearly a requirement. This is the purpose of the present work, where we approach the problem of heterogeneous polymer samples systematically by analyzing mixtures of two different polymers which are also characterized individually. An often observed phenomenon in AF4 of samples with a high polydispersity is a downturn in M vs. elution time, especially common at high retention. This result is often dismissed as an artifact attributed to various errors in detection and data processing. In this work, we utilize AF4-MALS-dRI to separate and analyze binary mixtures of the well-known polysaccharides pullulan and glycogen, or pullulan and poly(ethylene oxide), respectively, in solution. The results show that an observed downturn - or even an upturn - in M can be a correct result, caused by inherent properties of the analyzed polymers. Copyright © 2017 Elsevier B.V. All rights reserved.

Diversifying mechanisms in the on-farm evolution of crop mixtures.

PubMed

Thomas, Mathieu; Thépot, Stéphanie; Galic, Nathalie; Jouanne-Pin, Sophie; Remoué, Carine; Goldringer, Isabelle

2015-06-01

While modern agriculture relies on genetic homogeneity, diversifying practices associated with seed exchange and seed recycling may allow crops to adapt to their environment. This socio-genetic model is an original experimental evolution design referred to as on-farm dynamic management of crop diversity. Investigating such model can help in understanding how evolutionary mechanisms shape crop diversity submitted to diverse agro-environments. We studied a French farmer-led initiative where a mixture of four wheat landraces called 'Mélange de Touselles' (MDT) was created and circulated within a farmers' network. The 15 sampled MDT subpopulations were simultaneously submitted to diverse environments (e.g. altitude, rainfall) and diverse farmers' practices (e.g. field size, sowing and harvesting date). Twenty-one space-time samples of 80 individuals each were genotyped using 17 microsatellite markers and characterized for their heading date in a 'common-garden' experiment. Gene polymorphism was studied using four markers located in earliness genes. An original network-based approach was developed to depict the particular and complex genetic structure of the landraces composing the mixture. Rapid differentiation among populations within the mixture was detected, larger at the phenotypic and gene levels than at the neutral genetic level, indicating potential divergent selection. We identified two interacting selection processes: variation in the mixture component frequencies, and evolution of within-variety diversity, that shaped the standing variability available within the mixture. These results confirmed that diversifying practices and environments maintain genetic diversity and allow for crop evolution in the context of global change. Including concrete measurements of farmers' practices is critical to disentangle crop evolution processes. © 2015 John Wiley & Sons Ltd.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish.

PubMed

Geier, Mitra C; James Minick, D; Truong, Lisa; Tilton, Susan; Pande, Paritosh; Anderson, Kim A; Teeguardan, Justin; Tanguay, Robert L

2018-04-06

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. We constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilization (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures. Copyright © 2018 Elsevier Inc. All rights reserved.

FTIR gas chromatographic analysis of perfumes

NASA Astrophysics Data System (ADS)

Diederich, H.; Stout, Phillip J.; Hill, Stephen L.; Krishnan, K.

1992-03-01

Perfumes, natural or synthetic, are complex mixtures consisting of numerous components. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) techniques have been extensively utilized for the analysis of perfumes and essential oils. A limited number of perfume samples have also been analyzed by FT-IR gas chromatographic (GC-FTIR) techniques. Most of the latter studies have been performed using the conventional light pipe (LP) based GC-FTIR systems. In recent years, cold-trapping (in a matrix or neat) GC-FTIR systems have become available. The cold-trapping systems are capable of sub-nanogram sensitivities. In this paper, comparison data between the LP and the neat cold-trapping GC- FTIR systems is presented. The neat cold-trapping interface is known as Tracer. The results of GC-FTIR analysis of some commercial perfumes is also presented. For comparison of LP and Tracer GC-FTIR systems, a reference (synthetic) mixture containing 16 major and numerous minor constituents was used. The components of the mixture are the compounds commonly encountered in commercial perfumes. The GC-FTIR spectra of the reference mixture was obtained under identical chromatographic conditions from an LP and a Tracer system. A comparison of the two sets of data thus generated do indeed show the enhanced sensitivity level of the Tracer system. The comparison also shows that some of the major components detected by the Tracer system were absent from the LP data. Closer examination reveals that these compounds undergo thermal decomposition on contact with the hot gold surface that is part of the LP system. GC-FTIR data were obtained for three commercial perfume samples. The major components of these samples could easily be identified by spectra search against a digitized spectral library created using the Tracer data from the reference mixture.

Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

PubMed

Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

2015-10-20

Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.

Simultaneous separation of inorganic anions and metal-citrate complexes on a zwitterionic stationary phase with on-column complexation.

PubMed

Nesterenko, Ekaterina P; Nesterenko, Pavel N; Paull, Brett

2008-12-05

The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.

Ozone Modulation/Membrane Introduction Mass Spectrometry for Analysis of Hydrocarbon Pollutants in Air

NASA Astrophysics Data System (ADS)

Atkinson, D. B.

2001-12-01

Modulation of volatile hydrocarbons in two-component mixtures is demonstrated using an ozonolysis pretreatment with membrane introduction mass spectrometry (MIMS). The MIMS technique allows selective introduction of volatile and semivolatile analytes into a mass spectrometer via processes known collectively as pervaporation [Kotiaho and Cooks, 1992]. A semipermeable polymer membrane acts as an interface between the sample (vapor or solution) and the vacuum of the mass spectrometer. This technique has been demonstrated to allow for sensitive analysis of hydrocarbons and other non-polar volatile organic compounds (VOC`s) in air samples[Cisper et al., 1995] . The methodology has the advantages of no sample pretreatment and short analysis time, which are promising for online monitoring applications but the chief disadvantage of lack of a separation step for the different analytes in a mixture. Several approaches have been investigated to overcome this problem including use of selective chemical ionization [Bier and Cooks, 1987] and multivariate calibration techniques[Ketola et al., 1999] . A new approach is reported for the quantitative measurement of VOCs in complex matrices. The method seeks to reduce the complexity of mass spectra observed in hydrocarbon mixture analysis by selective pretreatment of the analyte mixture. In the current investigation, the rapid reaction of ozone with alkenes is used, producing oxygenated compounds which are suppressed by the MIMS system. This has the effect of removing signals due to unsaturated analytes from the compound mass spectra, and comparison of the spectra before and after the ozone treatment reveals the nature of the parent compounds. In preliminary investigations, ozone reacted completely with cyclohexene from a mixture of cylohexene and cyclohexane, and with β -pinene from a mixture of toluene and β -pinene, suppressing the ion signals from the olefins. A slight attenuation of the cyclohexane and toluene in those mixtures was also observed. Despite this problem, the hydrocarbon signal response can be calibrated and the method can be used for quantitative analysis of volatile hydrocarbon compounds in air samples. This methodology should augment the efficiency of the MIMS approach in online and onsite monitoring of VOC emissions. Bier, M.R., and R.G. Cooks, Membrane Interface for Selective Introduction of Volatile Compounds Directly into The Ionization Chamber of a Mass Spectrometer, Anal. Chem., 59 (4), 597, 1987. Cisper, M.E., C.G. Gill, L.E. Townsend, and P.H. Hemberger, On-Line Detection of Volatile Organic Compounds in Air at Parts-per-Trillion Levels by Membrane Introduction Mass Spectrometry, Anal. Chem., 67 (8), 1413-1417, 1995. Ketola, R.A., M. Ojala, and J. Heikkonen, A Non-linear Asymmetric Error Function-based Least Mean Square Approach for the Analysis of Multicomponent Mass Spectra Measured by Membrane Inlet Mass Spectrometry, Rapid Commun. Mass Spectrom., 13 (8), 654, 1999. Kotiaho, T., and R.G. Cooks, Membrane Introduction Mass Spectrometry in Environmental Analysis, in: J.J. Breen, M. J. Dellarco, (Eds), Pollution in Industrial processes, 126 pp., ACS Symp. Ser., Washington, D.C. 508, 1992.

OPC Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langton, C.

2014-11-01

The study presented in this report focused on a low-activity wasteform containing a high-pH pore solution with a significant level of sulfate. The purpose of the study was to improve understanding of the complex concrete/wasteform reactive transport problem, in particular, the role of pH in sulfate attack. Paste samples prepared at three different water-to-cement ratios were tested. The mixtures were prepared with ASTM Type I cement, without additional admixtures. The samples were exposed to two different sodium sulfate contact solutions. The first solution was prepared at 0.15M Na 2SO 4. The second solution also incorporated 0.5M NaOH, to mimic themore » high pH conditions found in Saltstone. The data collected indicated that, in Na 2SO 4 solution, damage occurs to the pastes. In the case of the high-pH sulfate solution (Na 2SO 4 + NaOH), no signs of damage were observed on any of the paste mixtures. These results indicate that the high sulfate content found in the wasteform pore solution will not necessarily lead to severe damage to concrete. Good-quality mixtures could thus prove durable over the long term, and act as an effective barrier to prevent radionuclides from reaching the environment.« less

Quantification of Terpenes by 1DGC-MS and 2DGC-TOF-MS

NASA Astrophysics Data System (ADS)

Flores, R. M.; Perlinger, J. A.; Doskey, P. V.

2009-12-01

Biogenic emissions are the primary source of volatile organic compounds in the global troposphere. Deciduous and coniferous forests are the principal emitters of a complex mixture of isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24). Sesquiterpenes are readily oxidized in the atmosphere producing secondary organic aerosols (SOA) with 100% yields. The SOA are hydrophilic and scatter light, and thus, increase albedo and lead to a cooling effect. In addition, both monoterpene and sesquiterpene generated SOA are effective cloud condensation nuclei leading to an increase in the particle number concentration and to the formation of clouds that also increase albedo. To quantify the complex mixture of terpenes and their oxidation products requires development of on-line extraction and comprehensive two-dimensional gas chromatographic techniques. One objective of this work was to compare one-dimensional gas chromatography-mass spectrometry (1DGC-MS) and two-dimensional gas chromatography time-of-flight mass spectrometry (2DGC-TOFMS) for quantifying eight monoterpenes (alpha- and beta-pinene, limonene, 3-carene, linalool, terpinolene, myrcene and ocimene) and eight sesquiterpenes (beta-caryophyllene, humulene, alpha-cedrene, cis-nerolidol, trans-nerolidol, cedrol, camphene and farnesene) in air samples collected in Northern Michigan. Future research involves coupling thermal desorption and supercritical fluid extraction devices to a GC×2GC for routine quantification of the complex mixture of terpenes and their oxidation products in rural and urban air.

The use of zeta potential as a tool to study phase transitions in binary phosphatidylcholines mixtures.

PubMed

Sierra, M B; Pedroni, V I; Buffo, F E; Disalvo, E A; Morini, M A

2016-06-01

Temperature dependence of the zeta potential (ZP) is proposed as a tool to analyze the thermotropic behavior of unilamellar liposomes prepared from binary mixtures of phosphatidylcholines in the absence or presence of ions in aqueous suspensions. Since the lipid phase transition influences the surface potential of the liposome reflecting a sharp change in the ZP during the transition, it is proposed as a screening method for transition temperatures in complex systems, given its high sensitivity and small amount of sample required, that is, 70% less than that required in the use of conventional calorimeters. The sensitivity is also reflected in the pre-transition detection in the presence of ions. Plots of phase boundaries for these mixed-lipid vesicles were constructed by plotting the delimiting temperatures of both main phase transition and pre-transition vs. the lipid composition of the vesicle. Differential scanning calorimetry (DSC) studies, although subject to uncertainties in interpretation due to broad bands in lipid mixtures, allowed the validation of the temperature dependence of the ZP method for determining the phase transition and pre-transition temperatures. The system chosen was dipalmitoylphosphatidylcholine/dimyristoyl phosphatidylcholine (DMPC/DPPC), the most common combination in biological membranes. This work may be considered as a starting point for further research into more complex lipid mixtures with functional biological importance. Copyright © 2016 Elsevier B.V. All rights reserved.

Persistent activation of DNA damage signaling in response to complex mixtures of PAHs in air particulate matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Ian W.H., E-mail: Ian.Jarvis@ki.se; Bergvall, Christoffer, E-mail: Christoffer.Bergvall@anchem.su.se; Bottai, Matteo, E-mail: Matteo.Bottai@ki.se

2013-02-01

Complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are present in air particulate matter (PM) and have been associated with many adverse human health effects including cancer and respiratory disease. However, due to their complexity, the risk of exposure to mixtures is difficult to estimate. In the present study the effects of binary mixtures of benzo[a]pyrene (BP) and dibenzo[a,l]pyrene (DBP) and complex mixtures of PAHs in urban air PM extracts on DNA damage signaling was investigated. Applying a statistical model to the data we observed a more than additive response for binary mixtures of BP and DBP on activation of DNAmore » damage signaling. Persistent activation of checkpoint kinase 1 (Chk1) was observed at significantly lower BP equivalent concentrations in air PM extracts than BP alone. Activation of DNA damage signaling was also more persistent in air PM fractions containing PAHs with more than four aromatic rings suggesting larger PAHs contribute a greater risk to human health. Altogether our data suggests that human health risk assessment based on additivity such as toxicity equivalency factor scales may significantly underestimate the risk of exposure to complex mixtures of PAHs. The data confirms our previous findings with PAH-contaminated soil (Niziolek-Kierecka et al., 2012) and suggests a possible role for Chk1 Ser317 phosphorylation as a biological marker for future analyses of complex mixtures of PAHs. -- Highlights: ► Benzo[a]pyrene (BP), dibenzo[a,l]pyrene (DBP) and air PM PAH extracts were compared. ► Binary mixture of BP and DBP induced a more than additive DNA damage response. ► Air PM PAH extracts were more potent than toxicity equivalency factor estimates. ► Larger PAHs (> 4 rings) contribute more to the genotoxicity of PAHs in air PM. ► Chk1 is a sensitive marker for persistent activation of DNA damage signaling from PAH mixtures.« less

Chemometric comparison of polychlorinated biphenyl residues and toxicologically active polychlorinated biphenyl congeners in the eggs of Forster's Terns (Sterna fosteri)

USGS Publications Warehouse

Schwartz, Ted R.; Stalling, David L.

1991-01-01

The separation and characterization of complex mixtures of polychlorinated biphenyls (PCBs) is approached from the perspective of a problem in chemometrics. A technique for quantitative determination of PCB congeners is described as well as an enrichment technique designed to isolate only those congener residues which induce mixed aryl hydrocarbon hydroxylase enzyme activity. A congener-specific procedure is utilized for the determination of PCBs in whichn-alkyl trichloroacetates are used as retention index marker compounds. Retention indices are reproducible in the range of ±0.05 to ±0.7 depending on the specific congener. A laboratory data base system developed to aid in the editing and quantitation of data generated from capillary gas chromatography was employed to quantitate chromatographic data. Data base management was provided by computer programs written in VAX-DSM (Digital Standard MUMPS) for the VAX-DEC (Digital Equipment Corp.) family of computers.In the chemometric evaluation of these complex chromatographic profiles, data are viewed from a single analysis as a point in multi-dimensional space. Principal Components Analysis was used to obtain a representation of the data in a lower dimensional space. Two-and three-dimensional proections based on sample scores from the principal components models were used to visualize the behavior of Aroclor® mixtures. These models can be used to determine if new sample profiles may be represented by Aroclor profiles. Concentrations of individual congeners of a given chlorine substitution may be summed to form homologue concentration. However, the use of homologue concentrations in classification studies with environmental samples can lead to erroneous conclusions about sample similarity. Chemometric applications are discussed for evaluation of Aroclor mixture analysis and compositional description of environmental residues of PCBs in eggs of Forster's terns (Sterna fosteri) collected from colonies near Lake Poygan and Green Bay, Wisconsin. The application of chemometrics is extended to the comparison of: a) Aroclors and PCB-containing environmental samples; to b) fractions of Aroclors and of environmental samples that have been enriched in congeners which induce mixed aryl hydrocarbon hydroxylase enzyme activity.

A low-cost gradient system for high-performance liquid chromatography. Quantitation of complex pharmaceutical raw materials.

PubMed

Erni, F; Frei, R W

1976-09-29

A device is described that makes use of an eight-port motor valve to generate step gradients on the low-pressure side of a piston pump with a low dead volume. Such a gradient device with an automatic control unit, which also permits repetition of previous steps, can be built for about half the cost of a gradient system with two pumps. Applications of this gradient unit to the separation of complex mixtures of glycosides and alkaloids are discussed and compared with separations systems using two high-pressure pumps. The gradients that are used on reversed-phase material with solvent mixtures of water and completely miscible organic solvents are suitable for quantitative routine control of pharmaceutical products. The reproducibility of retention data is excellent over several months and, with the use of loop injectors, major components can be determined quantitatively with a reproducibility of better than 2% (relative standard deviation). The step gradient selector valve can also be used as an introduction system for very large sample volumes. Up to 11 can be injected and samples with concentrations of less than 1 ppb can be determined with good reproducibilities.

MONITORING OF WATERWAYS FOR EMERGING ...

EPA Pesticide Factsheets

Assessing the potential impact to the aquatic environment from emerging contaminants, entails monitoring a complex mixture (pharmaceuticals, polar pesticides, industrial by- products and degradation products) in natural waters. The presence of these chemicals, often at ultra-trace levels, may be responsible for development of sub-lethal toxic effects in aquatic organisms (i.e., reproductive dysfunction, immune dysfunction, neurological disorders). Conventional sampling techniques (i.e., grab sampling) often are insufficient for detecting these trace levels. An integrative sampler, the Polar Organic Chemical Integrative Sampler (POCIS), developed by the USGS Columbia Environmental Research Center, provided a way to measure the time-weighted average concentrations of these complex mixtures of contaminants. When POCIS was combined with liquid chromatography/mass spectrometry (LC/MS), it proved to be a powerful tool in identification and quantification of polar anthropogenic contaminants. Data from a pilot study showed the antibiotic azithromycin, illicit drugs [methamphetamine and MDMA (Ecstasy)], polyfluorinated organic acids (PFOA and PFOS) (essential ingredients in the manufacture of fluoropolymers), and surfactants [i.e., diethanolamine polyethylene glycols (DAPGs), polyethylene glycols (PEGs), and nonylphenol ethoxylates (NPEOs)] were all present in the extracts from the effluents of three wastewater treatment plants and other bodies of natural waters. Althoug

Qualitative and quantitative assessment of unresolved complex mixture in PM2.5 of Bakersfield, CA

NASA Astrophysics Data System (ADS)

Nallathamby, Punith Dev; Lewandowski, Michael; Jaoui, Mohammed; Offenberg, John H.; Kleindienst, Tadeusz E.; Rubitschun, Caitlin; Surratt, Jason D.; Usenko, Sascha; Sheesley, Rebecca J.

2014-12-01

The 2010 CalNex (California Nexus) field experiment offered an opportunity for detailed characterization of atmospheric particulate carbon composition and sources in Bakersfield, CA. In the current study, the authors describe and employ a new protocol for reporting unresolved complex mixture (UCM) in over 30 daily samples. The Bakersfield, CA site has significant contribution from UCM, 2.9 ± 2.2% of the daily OC, which makes it an ideal first application. The new protocol reports two UCM peaks for Bakersfield with unique mean vapor pressure, retention time, mass spectra and daily ambient concentration trends. The first UCM peak, UCM-A, was comprised of semi-volatile compounds including alkanes, alkenes, and alkynes, with a mean vapor pressure of 2E-04 Torr and medium to heavy-duty diesel exhaust as a likely source. The second UCM peak, UCM-B, was comprised of linear, branched, and cyclic alkanes, with a mean vapor pressure of 1E-08 Torr. UCM-B had strong similarities to UCM in the NIST Standard Reference Material 1649b (urban dust) and to previously reported, detailed UCM for a representative Bakersfield sample, with possible sources including: motor vehicle exhaust, agricultural activities, and construction activities.

Characterization of conducting cellulose acetate based polymer electrolytes doped with "green" ionic mixture.

PubMed

Ramesh, S; Shanti, R; Morris, Ezra

2013-01-02

Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced. Copyright © 2012 Elsevier Ltd. All rights reserved.

Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

Hollow silica microspheres for buoyancy-assisted separation of infectious pathogens from stool.

PubMed

Weigum, Shannon E; Xiang, Lichen; Osta, Erica; Li, Linying; López, Gabriel P

2016-09-30

Separation of cells and microorganisms from complex biological mixtures is a critical first step in many analytical applications ranging from clinical diagnostics to environmental monitoring for food and waterborne contaminants. Yet, existing techniques for cell separation are plagued by high reagent and/or instrumentation costs that limit their use in many remote or resource-poor settings, such as field clinics or developing countries. We developed an innovative approach to isolate infectious pathogens from biological fluids using buoyant hollow silica microspheres that function as "molecular buoys" for affinity-based target capture and separation by floatation. In this process, antibody functionalized glass microspheres are mixed with a complex biological sample, such as stool. When mixing is stopped, the target-bound, low-density microspheres float to the air/liquid surface, which simultaneously isolates and concentrates the target analytes from the sample matrix. The microspheres are highly tunable in terms of size, density, and surface functionality for targeting diverse analytes with separation times of ≤2min in viscous solutions. We have applied the molecular buoy technique for isolation of a protozoan parasite that causes diarrheal illness, Cryptosporidium, directly from stool with separation efficiencies over 90% and low non-specific binding. This low-cost method for phenotypic cell/pathogen separation from complex mixtures is expected to have widespread use in clinical diagnostics as well as basic research. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetics and mechanism of catalytic hydroprocessing of components of coal-derived liquids. Sixteenth quarterly report, February 16, 1983-May 15, 1983.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gates, B. C.; Olson, H. H.; Schuit, G. C.A.

1983-08-22

A new method of structural analysis is applied to a group of hydroliquefied coal samples. The method uses elemental analysis and NMR data to estimate the concentrations of functional groups in the samples. The samples include oil and asphaltene fractions obtained in a series of hydroliquefaction experiments, and a set of 9 fractions separated from a coal-derived oil. The structural characterization of these samples demonstrates that estimates of functional group concentrations can be used to provide detailed structural profiles of complex mixtures and to obtain limited information about reaction pathways. 11 references, 1 figure, 7 tables.

Enhanced Mass Defect Filtering To Simplify and Classify Complex Mixtures of Lignin Degradation Products.

PubMed

Dier, Tobias K F; Egele, Kerstin; Fossog, Verlaine; Hempelmann, Rolf; Volmer, Dietrich A

2016-01-19

High resolution mass spectrometry was utilized to study the highly complex product mixtures resulting from electrochemical breakdown of lignin. As most of the chemical structures of the degradation products were unknown, enhanced mass defect filtering techniques were implemented to simplify the characterization of the mixtures. It was shown that the implemented ionization techniques had a major impact on the range of detectable breakdown products, with atmospheric pressure photoionization in negative ionization mode providing the widest coverage in our experiments. Different modified Kendrick mass plots were used as a basis for mass defect filtering, where Kendrick mass defect and the mass defect of the lignin-specific guaiacol (C7H7O2) monomeric unit were utilized, readily allowing class assignments independent of the oligomeric state of the product. The enhanced mass defect filtering strategy therefore provided rapid characterization of the sample composition. In addition, the structural similarities between the compounds within a degradation sequence were determined by comparison to a tentatively identified product of this compound series. In general, our analyses revealed that primarily breakdown products with low oxygen content were formed under electrochemical conditions using protic ionic liquids as solvent for lignin.

Evaluating the similarity of complex drinking-water disinfection by-product mixtures: overview of the issues.

PubMed

Rice, Glenn E; Teuschler, Linda K; Bull, Richard J; Simmons, Jane E; Feder, Paul I

2009-01-01

Humans are exposed daily to complex mixtures of environmental chemical contaminants, which arise as releases from sources such as engineering procedures, degradation processes, and emissions from mobile or stationary sources. When dose-response data are available for the actual environmental mixture to which individuals are exposed (i.e., the mixture of concern), these data provide the best information for dose-response assessment of the mixture. When suitable data on the mixture itself are not available, surrogate data might be used from a sufficiently similar mixture or a group of similar mixtures. Consequently, the determination of whether the mixture of concern is "sufficiently similar" to a tested mixture or a group of tested mixtures is central to the use of whole mixture methods. This article provides an overview for a series of companion articles whose purpose is to develop a set of biostatistical, chemical, and toxicological criteria and approaches for evaluating the similarity of drinking-water disinfection by-product (DBPs) complex mixtures. Together, the five articles in this series serve as a case study whose techniques will be relevant to assessing similarity for other classes of complex mixtures of environmental chemicals. Schenck et al. (2009) describe the chemistry and mutagenicity of a set of DBP mixtures concentrated from five different drinking-water treatment plants. Bull et al. (2009a, 2009b) describe how the variables that impact the formation of DBP affect the chemical composition and, subsequently, the expected toxicity of the mixture. Feder et al. (2009a, 2009b) evaluate the similarity of DBP mixture concentrates by applying two biostatistical approaches, principal components analysis, and a nonparametric "bootstrap" analysis. Important factors for determining sufficient similarity of DBP mixtures found in this research include disinfectant used; source water characteristics, including the concentrations of bromide and total organic carbon; concentrations and proportions of individual DBPs with known toxicity data on the same endpoint; magnitude of the unidentified fraction of total organic halides; similar toxicity outcomes for whole mixture testing (e.g., mutagenicity); and summary chemical measures such as total trihalomethanes, total haloacetic acids, total haloacetonitriles, and the levels of bromide incorporation in the DBP classes.

Development and validation of a multi-locus DNA metabarcoding method to identify endangered species in complex samples

PubMed Central

Arulandhu, Alfred J.; Staats, Martijn; Hagelaar, Rico; Voorhuijzen, Marleen M.; Prins, Theo W.; Scholtens, Ingrid; Costessi, Adalberto; Duijsings, Danny; Rechenmann, François; Gaspar, Frédéric B.; Barreto Crespo, Maria Teresa; Holst-Jensen, Arne; Birck, Matthew; Burns, Malcolm; Haynes, Edward; Hochegger, Rupert; Klingl, Alexander; Lundberg, Lisa; Natale, Chiara; Niekamp, Hauke; Perri, Elena; Barbante, Alessandra; Rosec, Jean-Philippe; Seyfarth, Ralf; Sovová, Tereza; Van Moorleghem, Christoff; van Ruth, Saskia; Peelen, Tamara

2017-01-01

Abstract DNA metabarcoding provides great potential for species identification in complex samples such as food supplements and traditional medicines. Such a method would aid Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) enforcement officers to combat wildlife crime by preventing illegal trade of endangered plant and animal species. The objective of this research was to develop a multi-locus DNA metabarcoding method for forensic wildlife species identification and to evaluate the applicability and reproducibility of this approach across different laboratories. A DNA metabarcoding method was developed that makes use of 12 DNA barcode markers that have demonstrated universal applicability across a wide range of plant and animal taxa and that facilitate the identification of species in samples containing degraded DNA. The DNA metabarcoding method was developed based on Illumina MiSeq amplicon sequencing of well-defined experimental mixtures, for which a bioinformatics pipeline with user-friendly web-interface was developed. The performance of the DNA metabarcoding method was assessed in an international validation trial by 16 laboratories, in which the method was found to be highly reproducible and sensitive enough to identify species present in a mixture at 1% dry weight content. The advanced multi-locus DNA metabarcoding method assessed in this study provides reliable and detailed data on the composition of complex food products, including information on the presence of CITES-listed species. The method can provide improved resolution for species identification, while verifying species with multiple DNA barcodes contributes to an enhanced quality assurance. PMID:29020743

Development and validation of a multi-locus DNA metabarcoding method to identify endangered species in complex samples.

PubMed

Arulandhu, Alfred J; Staats, Martijn; Hagelaar, Rico; Voorhuijzen, Marleen M; Prins, Theo W; Scholtens, Ingrid; Costessi, Adalberto; Duijsings, Danny; Rechenmann, François; Gaspar, Frédéric B; Barreto Crespo, Maria Teresa; Holst-Jensen, Arne; Birck, Matthew; Burns, Malcolm; Haynes, Edward; Hochegger, Rupert; Klingl, Alexander; Lundberg, Lisa; Natale, Chiara; Niekamp, Hauke; Perri, Elena; Barbante, Alessandra; Rosec, Jean-Philippe; Seyfarth, Ralf; Sovová, Tereza; Van Moorleghem, Christoff; van Ruth, Saskia; Peelen, Tamara; Kok, Esther

2017-10-01

DNA metabarcoding provides great potential for species identification in complex samples such as food supplements and traditional medicines. Such a method would aid Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) enforcement officers to combat wildlife crime by preventing illegal trade of endangered plant and animal species. The objective of this research was to develop a multi-locus DNA metabarcoding method for forensic wildlife species identification and to evaluate the applicability and reproducibility of this approach across different laboratories. A DNA metabarcoding method was developed that makes use of 12 DNA barcode markers that have demonstrated universal applicability across a wide range of plant and animal taxa and that facilitate the identification of species in samples containing degraded DNA. The DNA metabarcoding method was developed based on Illumina MiSeq amplicon sequencing of well-defined experimental mixtures, for which a bioinformatics pipeline with user-friendly web-interface was developed. The performance of the DNA metabarcoding method was assessed in an international validation trial by 16 laboratories, in which the method was found to be highly reproducible and sensitive enough to identify species present in a mixture at 1% dry weight content. The advanced multi-locus DNA metabarcoding method assessed in this study provides reliable and detailed data on the composition of complex food products, including information on the presence of CITES-listed species. The method can provide improved resolution for species identification, while verifying species with multiple DNA barcodes contributes to an enhanced quality assurance. © The Authors 2017. Published by Oxford University Press.

Characterization of the Androgen-sensitive MDA-kb2 Cell Line for Assessing Complex Environmental Mixtures, Presentation

EPA Science Inventory

Synthetic and natural steroidal androgens and estrogens and many other non-steroidal endocrine-active compounds commonly occur as complex mixtures in aquatic environments. It is important to understand the potential interactive effects of these mixtures to properly assess their r...

Integrated Disinfection By-Products Research: Assessing Reproductive and Developmental Risks Posed by Complex Disinfection By-Product Mixtures

EPA Science Inventory

This article presents a toxicologically-based risk assessment strategy for identifying the individual components or fractions of a complex mixture that are associated with its toxicity. The strategy relies on conventional component-based mixtures risk approaches such as dose addi...

Sworn testimony of the model evidence: Gaussian Mixture Importance (GAME) sampling

NASA Astrophysics Data System (ADS)

Volpi, Elena; Schoups, Gerrit; Firmani, Giovanni; Vrugt, Jasper A.

2017-07-01

What is the "best" model? The answer to this question lies in part in the eyes of the beholder, nevertheless a good model must blend rigorous theory with redeeming qualities such as parsimony and quality of fit. Model selection is used to make inferences, via weighted averaging, from a set of K candidate models, Mk; k=>(1,…,K>), and help identify which model is most supported by the observed data, Y>˜=>(y˜1,…,y˜n>). Here, we introduce a new and robust estimator of the model evidence, p>(Y>˜|Mk>), which acts as normalizing constant in the denominator of Bayes' theorem and provides a single quantitative measure of relative support for each hypothesis that integrates model accuracy, uncertainty, and complexity. However, p>(Y>˜|Mk>) is analytically intractable for most practical modeling problems. Our method, coined GAussian Mixture importancE (GAME) sampling, uses bridge sampling of a mixture distribution fitted to samples of the posterior model parameter distribution derived from MCMC simulation. We benchmark the accuracy and reliability of GAME sampling by application to a diverse set of multivariate target distributions (up to 100 dimensions) with known values of p>(Y>˜|Mk>) and to hypothesis testing using numerical modeling of the rainfall-runoff transformation of the Leaf River watershed in Mississippi, USA. These case studies demonstrate that GAME sampling provides robust and unbiased estimates of the evidence at a relatively small computational cost outperforming commonly used estimators. The GAME sampler is implemented in the MATLAB package of DREAM and simplifies considerably scientific inquiry through hypothesis testing and model selection.

Decoding 2D-PAGE complex maps: relevance to proteomics.

PubMed

Pietrogrande, Maria Chiara; Marchetti, Nicola; Dondi, Francesco; Righetti, Pier Giorgio

2006-03-20

This review describes two mathematical approaches useful for decoding the complex signal of 2D-PAGE maps of protein mixtures. These methods are helpful for interpreting the large amount of data of each 2D-PAGE map by extracting all the analytical information hidden therein by spot overlapping. Here the basic theory and application to 2D-PAGE maps are reviewed: the means for extracting information from the experimental data and their relevance to proteomics are discussed. One method is based on the quantitative theory of statistical model of peak overlapping (SMO) using the spot experimental data (intensity and spatial coordinates). The second method is based on the study of the 2D-autocovariance function (2D-ACVF) computed on the experimental digitised map. They are two independent methods that are able to extract equal and complementary information from the 2D-PAGE map. Both methods permit to obtain fundamental information on the sample complexity and the separation performance and to single out ordered patterns present in spot positions: the availability of two independent procedures to compute the same separation parameters is a powerful tool to estimate the reliability of the obtained results. The SMO procedure is an unique tool to quantitatively estimate the degree of spot overlapping present in the map, while the 2D-ACVF method is particularly powerful in simply singling out the presence of order in the spot position from the complexity of the whole 2D map, i.e., spot trains. The procedures were validated by extensive numerical computation on computer-generated maps describing experimental 2D-PAGE gels of protein mixtures. Their applicability to real samples was tested on reference maps obtained from literature sources. The review describes the most relevant information for proteomics: sample complexity, separation performance, overlapping extent, identification of spot trains related to post-translational modifications (PTMs).

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

NASA Astrophysics Data System (ADS)

Kassem, Mohammed A.; Amin, Alaa S.

2015-02-01

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

Chemical characterization of organic aerosol above a mid-latitude forest reveals a complex mixture of highly-functionalized chemical species and diverse structural features with temporal variability

NASA Astrophysics Data System (ADS)

Gentner, D. R.; Ditto, J.; Barnes, E.; Khare, P.

2017-12-01

Highly-functionalized organic compounds are known to be a major component of the complex mixture of the particle-phase compounds that comprise organic aerosol, yet little is known about the identity of many of these compounds, and their formation pathways and roles in atmospheric processes are poorly understood. We present results from the comprehensive chemical speciation of PM10 organic aerosols collected in July 2016 at the remote mid-latitude forest field site during PROPHET. Samples were analyzed via liquid and gas chromatography coupled with a quadrupole time-of-flight tandem mass spectrometry (MS×MS) following electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). 8 hr samples were collected during day- and night-time sampling periods rather than more typical 24-hour samples. This analysis of the organic aerosol yielded over 12,000 unique compounds for which we have high accuracy molecular masses, formulas, and additional information on structural features using MS×MS. O:C ratios were 0.3 on average, yet the top 10% of compounds ranged 0.7-2.3. 70% and 69% of day- and night-time samples were nitrogen-containing, whereas 26% and 24% contained sulfur, respectively. Within these broader molecular categories, we observed a wide variety of molecular features that reveal a diversity of functional groups and moieties. In this presentation, we present the results of our speciation, temporal variability, connections to air parcel back trajectories and other bulk properties, and potential formation pathways.

Mixture and odorant processing in the olfactory systems of insects: a comparative perspective.

PubMed

Clifford, Marie R; Riffell, Jeffrey A

2013-11-01

Natural olfactory stimuli are often complex mixtures of volatiles, of which the identities and ratios of constituents are important for odor-mediated behaviors. Despite this importance, the mechanism by which the olfactory system processes this complex information remains an area of active study. In this review, we describe recent progress in how odorants and mixtures are processed in the brain of insects. We use a comparative approach toward contrasting olfactory coding and the behavioral efficacy of mixtures in different insect species, and organize these topics around four sections: (1) Examples of the behavioral efficacy of odor mixtures and the olfactory environment; (2) mixture processing in the periphery; (3) mixture coding in the antennal lobe; and (4) evolutionary implications and adaptations for olfactory processing. We also include pertinent background information about the processing of individual odorants and comparative differences in wiring and anatomy, as these topics have been richly investigated and inform the processing of mixtures in the insect olfactory system. Finally, we describe exciting studies that have begun to elucidate the role of the processing of complex olfactory information in evolution and speciation.

Mineralogical and geochemical anomalous data of the K-T boundary samples

NASA Technical Reports Server (NTRS)

Miura, Y.; Shibya, G.; Imai, M.; Takaoka, N.; Saito, S.

1988-01-01

Cretaceous-Tertiary boundary problem has been discussed previously from the geological research, mainly by fossil changes. Although geochemical bulk data of Ir anomaly suggest the extraterrestrial origin of the K-T boundary, the exact formation process discussed mainly by mineralogical and geochemical study has been started recently, together with noble gas contents. The K-T boundary sample at Kawaruppu River, Hokkaido was collected, in order to compare with the typical K-T boundary samples of Bubbio, Italy, Stevns Klint, Denmark, and El Kef, Tunisia. The experimental data of the silicas and calcites in these K-T boundary samples were obtained from the X-ray unit-cell dimension (i.e., density), ESR signal and total linear absorption coefficient, as well as He and Ne contents. The K-T boundary samples are usually complex mixture of the terrestrial activities after the K-T boundary event. The mineralogical and geochemical anomalous data indicate special terrestrial atmosphere at the K-T boundary formation probably induced by asteroid impact, followed the many various terrestrial activities (especially the strong role of sea-water mixture, compared with terrestrial highland impact and impact craters in the other earth-type planetary bodies).

Enhanced bioavailability of process-induced fast-dissolving ibuprofen cogranulated with beta-cyclodextrin.

PubMed

Ghorab, Mohamed K; Adeyeye, Moji Christianah

2003-08-01

The objectives of this study were to evaluate the bioavailability of cogranulated and oven-dried ibuprofen (IBU) and beta-cyclodextrin (betaCD), in comparison to a physical mixture, and to examine the effect of endogenous bile on the bioavailability of the drug. In vitro dissolution studies were performed using USP type 2 apparatus. The granules and physical mixture were administered perorally in a crossover fashion, to male Wistar bile duct-nonligated rats. The granules were also perorally administered to bile duct-ligated rats. Blood samples were taken at different time intervals and the plasma analyzed for IBU. Dissolution of granules was faster than the physical mixture due to faster IBU-betaCD complex formation in solution from the former than the latter. The in vivo study showed that C(max), AUC(0-8), and the absolute bioavailability for the granules (49.0 microg/mL, 57.0 h x microg/mL and 80.6%, respectively) were almost one and half times that of the physical mixture (32.2 microg/mL, 38.4 h x microg/mL and 53.1%, respectively). However, in bile duct-ligated rats, lower C(max) and AUC(0-8) (15.9 microg/mL and 14.4 h x microg/mL, respectively) were obtained for the granules. Phase solubility study of IBU in an aqueous betaCD solution in the presence of the bile salt (sodium cholate), showed an increase in the solubility of IBU. Moreover, the stability constant value for the IBU-betaCD complex was also found to decrease as the sodium cholate concentration increased. These results indicated that the enhancement in the bioavailability of IBU was due to faster in-solution complex formation, and micelllar solubilization by the bile salt. Copyright 2003 Wiley-Liss, Inc.

Definition and characterization of a "trypsinosome" from specific peptide characteristics by nano-HPLC-MS/MS and in silico analysis of complex protein mixtures.

PubMed

Le Bihan, Thierry; Robinson, Mark D; Stewart, Ian I; Figeys, Daniel

2004-01-01

Although HPLC-ESI-MS/MS is rapidly becoming an indispensable tool for the analysis of peptides in complex mixtures, the sequence coverage it affords is often quite poor. Low protein expression resulting in peptide signal intensities that fall below the limit of detection of the MS system in combination with differences in peptide ionization efficiency plays a significant role in this. A second important factor stems from differences in physicochemical properties of each peptide and how these properties relate to chromatographic retention and ultimate detection. To identify and understand those properties, we compared data from experimentally identified peptides with data from peptides predicted by in silico digest of all corresponding proteins in the experimental set. Three different complex protein mixtures extracted were used to define a training set to evaluate the amino acid retention coefficients based on linear regression analysis. The retention coefficients were also compared with other previous hydrophobic and retention scale. From this, we have constructed an empirical model that can be readily used to predict peptides that are likely to be observed on our HPLC-ESI-MS/MS system based on their physicochemical properties. Finally, we demonstrated that in silico prediction of peptides and their retention coefficients can be used to generate an inclusion list for a targeted mass spectrometric identification of low abundance proteins in complex protein samples. This approach is based on experimentally derived data to calibrate the method and therefore may theoretically be applied to any HPLC-MS/MS system on which data are being generated.

Generalized Wishart Mixtures for Unsupervised Classification of PolSAR Data

NASA Astrophysics Data System (ADS)

Li, Lan; Chen, Erxue; Li, Zengyuan

2013-01-01

This paper presents an unsupervised clustering algorithm based upon the expectation maximization (EM) algorithm for finite mixture modelling, using the complex wishart probability density function (PDF) for the probabilities. The mixture model enables to consider heterogeneous thematic classes which could not be better fitted by the unimodal wishart distribution. In order to make it fast and robust to calculate, we use the recently proposed generalized gamma distribution (GΓD) for the single polarization intensity data to make the initial partition. Then we use the wishart probability density function for the corresponding sample covariance matrix to calculate the posterior class probabilities for each pixel. The posterior class probabilities are used for the prior probability estimates of each class and weights for all class parameter updates. The proposed method is evaluated and compared with the wishart H-Alpha-A classification. Preliminary results show that the proposed method has better performance.

Detection of anabolic androgenic steroid abuse in doping control using mammalian reporter gene bioassays.

PubMed

Houtman, Corine J; Sterk, Saskia S; van de Heijning, Monique P M; Brouwer, Abraham; Stephany, Rainer W; van der Burg, Bart; Sonneveld, Edwin

2009-04-01

Anabolic androgenic steroids (AAS) are a class of steroid hormones related to the male hormone testosterone. They are frequently detected as drugs in sport doping control. Being similar to or derived from natural male hormones, AAS share the activation of the androgen receptor (AR) as common mechanism of action. The mammalian androgen responsive reporter gene assay (AR CALUX bioassay), measuring compounds interacting with the AR can be used for the analysis of AAS without the necessity of knowing their chemical structure beforehand, whereas current chemical-analytical approaches may have difficulty in detecting compounds with unknown structures, such as designer steroids. This study demonstrated that AAS prohibited in sports and potential designer AAS can be detected with this AR reporter gene assay, but that also additional steroid activities of AAS could be found using additional mammalian bioassays for other types of steroid hormones. Mixtures of AAS were found to behave additively in the AR reporter gene assay showing that it is possible to use this method for complex mixtures as are found in doping control samples, including mixtures that are a result of multi drug use. To test if mammalian reporter gene assays could be used for the detection of AAS in urine samples, background steroidal activities were measured. AAS-spiked urine samples, mimicking doping positive samples, showed significantly higher androgenic activities than unspiked samples. GC-MS analysis of endogenous androgens and AR reporter gene assay analysis of urine samples showed how a combined chemical-analytical and bioassay approach can be used to identify samples containing AAS. The results indicate that the AR reporter gene assay, in addition to chemical-analytical methods, can be a valuable tool for the analysis of AAS for doping control purposes.

Separation system suitability (3S): a new criterion of chromatogram classification in HPLC based on cross-evaluation of separation capacity/peak symmetry and its application to complex mixtures of anthraquinones.

PubMed

Nowik, Witold; Héron, Sylvie; Bonose, Myriam; Tchapla, Alain

2013-10-07

A comparison of chromatograms obtained in a series of separation conditions for a given complex mixture may be done with a series of chromatographic descriptors. In this study, we used two descriptors: the number of critical pairs and symmetry of peaks, further rescaled and converted to the corresponding critical pairs' coefficient (CPc) and symmetry coefficient (Sc). Considering the difficulty of appreciating global separation quality using CPc and Sc criteria separately, as their respective values are usually uncorrelated, a double-criteria cross-evaluation system was required. For that purpose we tested the commonly used multi-criteria decision-making method - Derringer's desirability function (D) - as well as the recently introduced sum of ranking differences (SRD). To facilitate the graphical comparison of both approaches, the desirability function (D) was used in the inverse form (Dinv). The advantages and drawbacks of both evaluation methods, especially the respective under- or over-evaluation of outliers, caused us to introduce a new ranking approach, separation system suitability (3S). The obtained suitability rankings for the three tested approaches (Dinv, SRD and 3S) are different; nevertheless, 3S appears to be the most balanced and the easiest to interpret as well. The approach developed for selection of suitable systems was applied to the problem of separation of complex mixtures through the analysis of a series of standards of anthraquinone derivatives. To judge the pertinence of this evaluation, a sample containing a number of natural anthraquinones extracted from the bark of Indian mulberry (Morinda citrifolia) was analysed. In conclusion, the proposed methodology for the cross-evaluation of the series of chromatograms using single specific descriptors (CPc and Sc) through a global composite descriptor (3S) significantly simplifies the decision that separation systems are the most suitable for the separation of complex target mixtures of compounds.

The volatile compound BinBase mass spectral database.

PubMed

Skogerson, Kirsten; Wohlgemuth, Gert; Barupal, Dinesh K; Fiehn, Oliver

2011-08-04

Volatile compounds comprise diverse chemical groups with wide-ranging sources and functions. These compounds originate from major pathways of secondary metabolism in many organisms and play essential roles in chemical ecology in both plant and animal kingdoms. In past decades, sampling methods and instrumentation for the analysis of complex volatile mixtures have improved; however, design and implementation of database tools to process and store the complex datasets have lagged behind. The volatile compound BinBase (vocBinBase) is an automated peak annotation and database system developed for the analysis of GC-TOF-MS data derived from complex volatile mixtures. The vocBinBase DB is an extension of the previously reported metabolite BinBase software developed to track and identify derivatized metabolites. The BinBase algorithm uses deconvoluted spectra and peak metadata (retention index, unique ion, spectral similarity, peak signal-to-noise ratio, and peak purity) from the Leco ChromaTOF software, and annotates peaks using a multi-tiered filtering system with stringent thresholds. The vocBinBase algorithm assigns the identity of compounds existing in the database. Volatile compound assignments are supported by the Adams mass spectral-retention index library, which contains over 2,000 plant-derived volatile compounds. Novel molecules that are not found within vocBinBase are automatically added using strict mass spectral and experimental criteria. Users obtain fully annotated data sheets with quantitative information for all volatile compounds for studies that may consist of thousands of chromatograms. The vocBinBase database may also be queried across different studies, comprising currently 1,537 unique mass spectra generated from 1.7 million deconvoluted mass spectra of 3,435 samples (18 species). Mass spectra with retention indices and volatile profiles are available as free download under the CC-BY agreement (http://vocbinbase.fiehnlab.ucdavis.edu). The BinBase database algorithms have been successfully modified to allow for tracking and identification of volatile compounds in complex mixtures. The database is capable of annotating large datasets (hundreds to thousands of samples) and is well-suited for between-study comparisons such as chemotaxonomy investigations. This novel volatile compound database tool is applicable to research fields spanning chemical ecology to human health. The BinBase source code is freely available at http://binbase.sourceforge.net/ under the LGPL 2.0 license agreement.

The volatile compound BinBase mass spectral database

PubMed Central

2011-01-01

Background Volatile compounds comprise diverse chemical groups with wide-ranging sources and functions. These compounds originate from major pathways of secondary metabolism in many organisms and play essential roles in chemical ecology in both plant and animal kingdoms. In past decades, sampling methods and instrumentation for the analysis of complex volatile mixtures have improved; however, design and implementation of database tools to process and store the complex datasets have lagged behind. Description The volatile compound BinBase (vocBinBase) is an automated peak annotation and database system developed for the analysis of GC-TOF-MS data derived from complex volatile mixtures. The vocBinBase DB is an extension of the previously reported metabolite BinBase software developed to track and identify derivatized metabolites. The BinBase algorithm uses deconvoluted spectra and peak metadata (retention index, unique ion, spectral similarity, peak signal-to-noise ratio, and peak purity) from the Leco ChromaTOF software, and annotates peaks using a multi-tiered filtering system with stringent thresholds. The vocBinBase algorithm assigns the identity of compounds existing in the database. Volatile compound assignments are supported by the Adams mass spectral-retention index library, which contains over 2,000 plant-derived volatile compounds. Novel molecules that are not found within vocBinBase are automatically added using strict mass spectral and experimental criteria. Users obtain fully annotated data sheets with quantitative information for all volatile compounds for studies that may consist of thousands of chromatograms. The vocBinBase database may also be queried across different studies, comprising currently 1,537 unique mass spectra generated from 1.7 million deconvoluted mass spectra of 3,435 samples (18 species). Mass spectra with retention indices and volatile profiles are available as free download under the CC-BY agreement (http://vocbinbase.fiehnlab.ucdavis.edu). Conclusions The BinBase database algorithms have been successfully modified to allow for tracking and identification of volatile compounds in complex mixtures. The database is capable of annotating large datasets (hundreds to thousands of samples) and is well-suited for between-study comparisons such as chemotaxonomy investigations. This novel volatile compound database tool is applicable to research fields spanning chemical ecology to human health. The BinBase source code is freely available at http://binbase.sourceforge.net/ under the LGPL 2.0 license agreement. PMID:21816034

Binary gaseous mixture and single component adsorption of methane and argon on exfoliated graphite

NASA Astrophysics Data System (ADS)

Russell, Brice Adam

Exfoliated graphite was used as a substrate for adsorption of argon and methane. Adsorption experiments were conducted for both equal parts mixtures of argon and methane and for each gas species independently. The purpose of this was to compare mixture adsorption to single component adsorption and to investigate theoretical predictions concerning the kinetics of adsorption made by Burde and Calbi.6 In particular, time to reach pressure equilibrium of a single dose at a constant temperature for the equal parts mixture was compared to time of adsorption for each species by itself. It was shown that mixture adsorption is a much more complex and time consuming process than single component adsorption and requires a much longer amount of time to reach equilibrium. Information about the composition evolution of the mixture during the times when pressure was going toward equilibrium was obtained using a quadrupole mass spectrometer. Evidence for initial higher rate of adsorption for the weaker binding energy species (argon) was found as well as overall composition change which clearly indicated a higher coverage of methane on the graphite sample by the time equilibration was reached. Effective specific surface area of graphite for both argon and methane was also determined using the Point-B method.2

Assessment of health effects in epidemiologic studies of air pollution.

PubMed Central

Samet, J M; Speizer, F E

1993-01-01

As we increasingly recognize the complexity of the pollutants in indoor and outdoor microenvironments, a broad array of inhaled mixtures has assumed scientific, public health, and regulatory importance. Few adverse effects of environmental pollutants are specific, that is, uniquely associated with a single agent; the adverse effects that might be considered in an investigation of the consequences of exposure to an inhaled complex mixture are generally nonspecific. In the context of this paper, we will refer to binary mixtures as complex, though we realize that a more precise definition of complexity would restrict the term to mixtures of three or more constituents. Their causes potentially include not only pollutant exposures through the medium of inhaled air but other environmental agents, such as infectious organisms and radiation, and inherent characteristics of the exposed persons, such as atopy. We review the outcome measures that have been used in epidemiologic studies of the health effects of single pollutants and complex mixtures. Some of these outcome measures have been carefully standardized, whereas others need similar standardization and modification to improve sensitivity and specificity for investigating the health effects of air pollution. PMID:8206024

Molecular identification of organic compounds in atmospheric complex mixtures and relationship to atmospheric chemistry and sources.

PubMed

Mazurek, Monica A

2002-12-01

This article describes a chemical characterization approach for complex organic compound mixtures associated with fine atmospheric particles of diameters less than 2.5 m (PM2.5). It relates molecular- and bulk-level chemical characteristics of the complex mixture to atmospheric chemistry and to emission sources. Overall, the analytical approach describes the organic complex mixtures in terms of a chemical mass balance (CMB). Here, the complex mixture is related to a bulk elemental measurement (total carbon) and is broken down systematically into functional groups and molecular compositions. The CMB and molecular-level information can be used to understand the sources of the atmospheric fine particles through conversion of chromatographic data and by incorporation into receptor-based CMB models. Once described and quantified within a mass balance framework, the chemical profiles for aerosol organic matter can be applied to existing air quality issues. Examples include understanding health effects of PM2.5 and defining and controlling key sources of anthropogenic fine particles. Overall, the organic aerosol compositional data provide chemical information needed for effective PM2.5 management.

Embryotoxic and genotoxic effects of sewage effluents in zebrafish embryo using multiple endpoint testing.

PubMed

Babić, Sanja; Barišić, Josip; Višić, Hrvoje; Sauerborn Klobučar, Roberta; Topić Popović, Natalija; Strunjak-Perović, Ivančica; Čož-Rakovac, Rozelindra; Klobučar, Göran

2017-05-15

Wastewater treatment plant (WWTP) effluents are often complex mixtures of various organic and inorganic substances. Quality control of wastewaters and sludges has been regulated with measuring several physico-chemical parameters and sometimes using biological methods with non-specific responses, while synergistic action mechanisms of contaminants in such complex mixtures is still unknown. Toxic effects of wastewaters within and downstream of the WWTP in City of Virovitica, Croatia, were tested on zebrafish Danio rerio using a set of biomarkers that enabled an insight in wastewaters toxic potential on embryos at the cellular, tissue and the whole organism level during an early ontogenesis (24 and 48 hpf). Exposure of embryos to the wastewater samples from WWTP Virovitica increased mortality and abnormality rate. Heart rate, spontaneous movements and pigmentation formation were also markedly affected. Biochemical markers confirmed the presence of MXR inhibitors in all tested wastewater samples, indicating the increase of pollutant accumulation in the cell/organism. Also, a tendency of DNA damage decrease measured with Comet assay was evident in wastewater samples downstream from WWTP although control levels were not reached in any environmental sample. Histopathological analysis showed that exposure to tested samples resulted in impaired muscle organization, notochord malformation and retardation in eye and brain development at embryos 48 hpf. Furthermore, semi-quantitative histopathology assessment indicated increased percentage of embryo defects in river water sampled several kilometers downstream from the WWTP, confirming toxic potential of WWTP effluents. Extension of the zebrafish embryotoxicity test (ZET) with biochemical and histopathological biomarkers could serve as a guiding principle in biomonitoring of wastewater contamination. Copyright © 2017 Elsevier Ltd. All rights reserved.

Application of quality by design concept to develop a dual gradient elution stability-indicating method for cloxacillin forced degradation studies using combined mixture-process variable models.

PubMed

Zhang, Xia; Hu, Changqin

2017-09-08

Penicillins are typical of complex ionic samples which likely contain large number of degradation-related impurities (DRIs) with different polarities and charge properties. It is often a challenge to develop selective and robust high performance liquid chromatography (HPLC) methods for the efficient separation of all DRIs. In this study, an analytical quality by design (AQbD) approach was proposed for stability-indicating method development of cloxacillin. The structures, retention and UV characteristics rules of penicillins and their impurities were summarized and served as useful prior knowledge. Through quality risk assessment and screen design, 3 critical process parameters (CPPs) were defined, including 2 mixture variables (MVs) and 1 process variable (PV). A combined mixture-process variable (MPV) design was conducted to evaluate the 3 CPPs simultaneously and a response surface methodology (RSM) was used to achieve the optimal experiment parameters. A dual gradient elution was performed to change buffer pH, mobile-phase type and strength simultaneously. The design spaces (DSs) was evaluated using Monte Carlo simulation to give their possibility of meeting the specifications of CQAs. A Plackett-Burman design was performed to test the robustness around the working points and to decide the normal operating ranges (NORs). Finally, validation was performed following International Conference on Harmonisation (ICH) guidelines. To our knowledge, this is the first study of using MPV design and dual gradient elution to develop HPLC methods and improve separations for complex ionic samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Sediment unmixing using detrital geochronology

USGS Publications Warehouse

Sharman, Glenn R.; Johnstone, Samuel

2017-01-01

Sediment mixing within sediment routing systems can exert a strong influence on the preservation of provenance signals that yield insight into the influence of environmental forcings (e.g., tectonism, climate) on the earth’s surface. Here we discuss two approaches to unmixing detrital geochronologic data in an effort to characterize complex changes in the sedimentary record. First we summarize ‘top-down’ mixing, which has been successfully employed in the past to characterize the different fractions of prescribed source distributions (‘parents’) that characterize a derived sample or set of samples (‘daughters’). Second we propose the use of ‘bottom-up’ methods, previously used primarily for grain size distributions, to model parent distributions and the abundances of these parents within a set of daughters. We demonstrate the utility of both top-down and bottom-up approaches to unmixing detrital geochronologic data within a well-constrained sediment routing system in central California. Use of a variety of goodness-of-fit metrics in top-down modeling reveals the importance of considering the range of allowable mixtures over any single best-fit mixture calculation. Bottom-up modeling of 12 daughter samples from beaches and submarine canyons yields modeled parent distributions that are remarkably similar to those expected from the geologic context of the sediment-routing system. In general, mixture modeling has potential to supplement more widely applied approaches in comparing detrital geochronologic data by casting differences between samples as differing proportions of geologically meaningful end-member provenance categories.

Pesticide Toxicity Index: a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms

USGS Publications Warehouse

Nowell, Lisa H.; Norman, Julia E.; Moran, Patrick W.; Martin, Jeffrey D.; Stone, Wesley W.

2014-01-01

Pesticide mixtures are common in streams with agricultural or urban influence in the watershed. The Pesticide Toxicity Index (PTI) is a screening tool to assess potential aquatic toxicity of complex pesticide mixtures by combining measures of pesticide exposure and acute toxicity in an additive toxic-unit model. The PTI is determined separately for fish, cladocerans, and benthic invertebrates. This study expands the number of pesticides and degradates included in previous editions of the PTI from 124 to 492 pesticides and degradates, and includes two types of PTI for use in different applications, depending on study objectives. The Median-PTI was calculated from median toxicity values for individual pesticides, so is robust to outliers and is appropriate for comparing relative potential toxicity among samples, sites, or pesticides. The Sensitive-PTI uses the 5th percentile of available toxicity values, so is a more sensitive screening-level indicator of potential toxicity. PTI predictions of toxicity in environmental samples were tested using data aggregated from published field studies that measured pesticide concentrations and toxicity to Ceriodaphnia dubia in ambient stream water. C. dubia survival was reduced to ≤ 50% of controls in 44% of samples with Median-PTI values of 0.1–1, and to 0% in 96% of samples with Median-PTI values > 1. The PTI is a relative, but quantitative, indicator of potential toxicity that can be used to evaluate relationships between pesticide exposure and biological condition.

Identifying Complex Mixtures in the Environment with Cheminformatics and Non-targeted High Resolution Mass Spectrometry (SETAC NA Focused Topic Meeting : Risk Assessment of Chemical Mixtures)

EPA Science Inventory

Non-target high resolution mass spectrometry techniques combined with advanced cheminformatics offer huge potential for exploring complex mixtures in our environment – yet also offers plenty of challenges. Peak inventories of several non-target studies from within Europe reveal t...

75 FR 73080 - Science Advisory Board Staff Office; Request for Nominations of Experts for the SAB...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-29

... are IRIS reference doses (RfDs) for two commercial PCB mixtures: Aroclor 1016 and Aroclor 1254 that... developing a draft assessment of the potential noncancer health hazards of complex PCB mixtures for inclusion... with the goal of establishing an RfD for application to complex PCB mixtures. The EPA's National Center...

Chemical mixtures in untreated water from public-supply wells in the U.S. — Occurrence, composition, and potential toxicity

USGS Publications Warehouse

Toccalino, Patricia L.; Norman, Julia E.; Scott, Jonathon C.

2012-01-01

Chemical mixtures are prevalent in groundwater used for public water supply, but little is known about their potential health effects. As part of a large-scale ambient groundwater study, we evaluated chemical mixtures across multiple chemical classes, and included more chemical contaminants than in previous studies of mixtures in public-supply wells. We (1) assessed the occurrence of chemical mixtures in untreated source-water samples from public-supply wells, (2) determined the composition of the most frequently occurring mixtures, and (3) characterized the potential toxicity of mixtures using a new screening approach. The U.S. Geological Survey collected one untreated water sample from each of 383 public wells distributed across 35 states, and analyzed the samples for as many as 91 chemical contaminants. Concentrations of mixture components were compared to individual human-health benchmarks; the potential toxicity of mixtures was characterized by addition of benchmark-normalized component concentrations. Most samples (84%) contained mixtures of two or more contaminants, each at concentrations greater than one-tenth of individual benchmarks. The chemical mixtures that most frequently occurred and had the greatest potential toxicity primarily were composed of trace elements (including arsenic, strontium, or uranium), radon, or nitrate. Herbicides, disinfection by-products, and solvents were the most common organic contaminants in mixtures. The sum of benchmark-normalized concentrations was greater than 1 for 58% of samples, suggesting that there could be potential for mixtures toxicity in more than half of the public-well samples. Our findings can be used to help set priorities for groundwater monitoring and suggest future research directions for drinking-water treatment studies and for toxicity assessments of chemical mixtures in water resources.

Analytical Chemical Sensing in the Submillimeter/terahertz Spectral Range

NASA Astrophysics Data System (ADS)

Moran, Benjamin L.; Fosnight, Alyssa M.; Medvedev, Ivan R.; Neese, Christopher F.

2012-06-01

Highly sensitive and selective Terahertz sensor utilized to quantitatively analyze a complex mixture of Volatile Organic Compounds is reported. To best demonstrate analytical capabilities of THz chemical sensors we chose to perform analytical quantitative analysis of a certified gas mixture using a novel prototype chemical sensor that couples a commercial preconcentration system (Entech 7100A) to a high resolution THz spectrometer. We selected Method TO-14A certified mixture of 39 volatile organic compounds (VOCs) diluted to 1 part per million (ppm) in nitrogen. 26 of the 39 chemicals were identified by us as suitable for THz spectroscopic detection. Entech 7100A system is designed and marketed as an inlet system for Gas Chromatography-Mass Spectrometry (GC-MS) instruments with a specific focus on TO-14 and TO-15 EPA sampling methods. Its preconcentration efficiency is high for the 39 chemicals in the mixture used for this study and our preliminary results confirm this. Here we present the results of this study which serves as basis for our ongoing research in environmental sensing and analysis of exhaled human breath.

UP-HILIC-MS/MS to Determine the Action Pattern of Penicillium sp. Dextranase.

PubMed

Yi, Lin; Sun, Xue; Du, Kenze; Ouyang, Yilan; Wu, Chengling; Xu, Naiyu; Linhardt, Robert J; Zhang, Zhenqing

2015-07-01

Investigation of the action pattern of enzymes acting on carbohydrates is challenging, as both the substrate and the digestion products are complex mixtures. Dextran and its enzyme-derived oligosaccharides are widely used for many industrial applications. In this work, a new method relying on ultra-performance hydrophilic interaction liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UP-HILIC-Q/TOF-MS/MS) was developed to analyze a complex mixture of dextran oligosaccharide products to determine the action pattern of dextranase. No derivatization of oligosaccharides was required and the impact of the α- and β-configurations of the native oligosaccharides on the chromatographic separation was eliminated. The 1→6, 1→3, 1→4 backbone linkages and the branch linkages of these oligosaccharides were all distinguished from diagnostic ions in their MS/MS spectra, including fragments corresponding to (0,2)A, (0,3)A, (0,4)A, B-H2O, (2,5)A, and (3,5)A. The sequences of the oligosaccharide products were similarly established. Thus, the complex oligosaccharide mixtures in dextran digestion products were profiled and identified using this method. The more enzyme-resistant structures in dextran were established using much less sample, labor, time, and uncertainty than in previous studies. This method provides an efficient, sensitive, and straightforward way to monitor the entire process of digestion, establish the action pattern of the dextranase from Penicillium sp., and to support the proper industrial application of dextranase.

UP-HILIC-MS/MS to Determine the Action Pattern of Penicillium sp. Dextranase

NASA Astrophysics Data System (ADS)

Yi, Lin; Sun, Xue; Du, Kenze; Ouyang, Yilan; Wu, Chengling; Xu, Naiyu; Linhardt, Robert J.; Zhang, Zhenqing

2015-07-01

Investigation of the action pattern of enzymes acting on carbohydrates is challenging, as both the substrate and the digestion products are complex mixtures. Dextran and its enzyme-derived oligosaccharides are widely used for many industrial applications. In this work, a new method relying on ultra-performance hydrophilic interaction liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UP-HILIC- Q/TOF-MS/MS) was developed to analyze a complex mixture of dextran oligosaccharide products to determine the action pattern of dextranase. No derivatization of oligosaccharides was required and the impact of the α- and β-configurations of the native oligosaccharides on the chromatographic separation was eliminated. The 1→6, 1→3, 1→4 backbone linkages and the branch linkages of these oligosaccharides were all distinguished from diagnostic ions in their MS/MS spectra, including fragments corresponding to 0,2A, 0,3A, 0,4A, B-H2O, 2,5A, and 3,5A. The sequences of the oligosaccharide products were similarly established. Thus, the complex oligosaccharide mixtures in dextran digestion products were profiled and identified using this method. The more enzyme-resistant structures in dextran were established using much less sample, labor, time, and uncertainty than in previous studies. This method provides an efficient, sensitive, and straightforward way to monitor the entire process of digestion, establish the action pattern of the dextranase from Penicillium sp., and to support the proper industrial application of dextranase.

STRATEGIES TO IDENTIFY BIOACTIVE SUBSTANCES IN COMPLEX AIR POLLUTANT MIXTURES

EPA Science Inventory

Both indoor and outdoor air contains a very complex mixture of gas and particulate matter (PM) pollutants. The assessment of the role of each pollutant in the complex atmosphere in the induction of an associated health effect or a response can be difficult due to many factors, i...

Protein and gene model inference based on statistical modeling in k-partite graphs.

PubMed

Gerster, Sarah; Qeli, Ermir; Ahrens, Christian H; Bühlmann, Peter

2010-07-06

One of the major goals of proteomics is the comprehensive and accurate description of a proteome. Shotgun proteomics, the method of choice for the analysis of complex protein mixtures, requires that experimentally observed peptides are mapped back to the proteins they were derived from. This process is also known as protein inference. We present Markovian Inference of Proteins and Gene Models (MIPGEM), a statistical model based on clearly stated assumptions to address the problem of protein and gene model inference for shotgun proteomics data. In particular, we are dealing with dependencies among peptides and proteins using a Markovian assumption on k-partite graphs. We are also addressing the problems of shared peptides and ambiguous proteins by scoring the encoding gene models. Empirical results on two control datasets with synthetic mixtures of proteins and on complex protein samples of Saccharomyces cerevisiae, Drosophila melanogaster, and Arabidopsis thaliana suggest that the results with MIPGEM are competitive with existing tools for protein inference.

Ligand Fishing: A Remarkable Strategy for Discovering Bioactive Compounds from Complex Mixture of Natural Products.

PubMed

Zhuo, Rongjie; Liu, Hao; Liu, Ningning; Wang, Yi

2016-11-11

Identification of active compounds from natural products is a critical and challenging task in drug discovery pipelines. Besides commonly used bio-guided screening approaches, affinity selection strategy coupled with liquid chromatography or mass spectrometry, known as ligand fishing, has been gaining increasing interest from researchers. In this review, we summarized this emerging strategy and categorized those methods as off-line or on-line mode according to their features. The separation principles of ligand fishing were introduced based on distinct analytical techniques, including biochromatography, capillary electrophoresis, ultrafiltration, equilibrium dialysis, microdialysis, and magnetic beads. The applications of ligand fishing approaches in the discovery of lead compounds were reviewed. Most of ligand fishing methods display specificity, high efficiency, and require less sample pretreatment, which makes them especially suitable for screening active compounds from complex mixtures of natural products. We also summarized the applications of ligand fishing in the modernization of Traditional Chinese Medicine (TCM), and propose some perspectives of this remarkable technique.

Associations between complex OHC mixtures and thyroid and cortisol hormone levels in East Greenland polar bears

PubMed Central

TØ, Bechshøft; Sonne, C; Dietz, R; Born, EW; Muir, DCG; Letcher, RJ; Novak, MA; Henchey, E; Meyer, JS; Jenssen, BM; Villanger, GD

2012-01-01

The multivariate relationship between hair cortisol, whole blood thyroid hormones, and the complex mixtures of organohalogen contaminant (OHC) levels measured in subcutaneous adipose of 23 East Greenland polar bears (eight males and 15 females, all sampled between the years 1999 and 2001) was analyzed using projection to latent structure (PLS) regression modeling. In the resulting PLS model, most important variables with a negative influence on cortisol levels were particularly BDE-99, but also CB-180, -201, BDE-153, and CB-170/190. The most important variables with a positive influence on cortisol were CB-66/95, α-HCH, TT3, as well as heptachlor epoxide, dieldrin, BDE-47, p,p′-DDD. Although statistical modeling does not necessarily fully explain biological cause-effect relationships, relationships indicate that (1) the hypothalamic-pituitary-adrenal (HPA) axis in East Greenland polar bears is likely to be affected by OHC-contaminants and (2) the association between OHCs and cortisol may be linked with the hypothalamus-pituitary-thyroid (HPT) axis. PMID:22575327

Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment

ERIC Educational Resources Information Center

Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin

2011-01-01

A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the…

Analyte quantification with comprehensive two-dimensional gas chromatography: assessment of methods for baseline correction, peak delineation, and matrix effect elimination for real samples.

PubMed

Samanipour, Saer; Dimitriou-Christidis, Petros; Gros, Jonas; Grange, Aureline; Samuel Arey, J

2015-01-02

Comprehensive two-dimensional gas chromatography (GC×GC) is used widely to separate and measure organic chemicals in complex mixtures. However, approaches to quantify analytes in real, complex samples have not been critically assessed. We quantified 7 PAHs in a certified diesel fuel using GC×GC coupled to flame ionization detector (FID), and we quantified 11 target chlorinated hydrocarbons in a lake water extract using GC×GC with electron capture detector (μECD), further confirmed qualitatively by GC×GC with electron capture negative chemical ionization time-of-flight mass spectrometer (ENCI-TOFMS). Target analyte peak volumes were determined using several existing baseline correction algorithms and peak delineation algorithms. Analyte quantifications were conducted using external standards and also using standard additions, enabling us to diagnose matrix effects. We then applied several chemometric tests to these data. We find that the choice of baseline correction algorithm and peak delineation algorithm strongly influence the reproducibility of analyte signal, error of the calibration offset, proportionality of integrated signal response, and accuracy of quantifications. Additionally, the choice of baseline correction and the peak delineation algorithm are essential for correctly discriminating analyte signal from unresolved complex mixture signal, and this is the chief consideration for controlling matrix effects during quantification. The diagnostic approaches presented here provide guidance for analyte quantification using GC×GC. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

PubMed

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution 'Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10(-9) M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

Modeling the chemistry of complex petroleum mixtures.

PubMed Central

Quann, R J

1998-01-01

Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the astronomical number of molecular components. Modeling the composition and behavior of such complex mixtures in refinery processes has accordingly evolved along a simplifying concept called lumping. Lumping reduces the complexity of the problem to a manageable form by grouping the entire set of molecular components into a handful of lumps. This traditional approach does not have a molecular basis and therefore excludes important aspects of process chemistry and molecular property fundamentals from the model's formulation. A new approach called structure-oriented lumping has been developed to model the composition and chemistry of complex mixtures at a molecular level. The central concept is to represent an individual molecular or a set of closely related isomers as a mathematical construct of certain specific and repeating structural groups. A complex mixture such as petroleum can then be represented as thousands of distinct molecular components, each having a mathematical identity. This enables the automated construction of large complex reaction networks with tens of thousands of specific reactions for simulating the chemistry of complex mixtures. Further, the method provides a convenient framework for incorporating molecular physical property correlations, existing group contribution methods, molecular thermodynamic properties, and the structure--activity relationships of chemical kinetics in the development of models. PMID:9860903

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique.

PubMed

Kassem, Mohammed A; Amin, Alaa S

2015-02-05

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4'-nitro-2',6'-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50°C, the surfactant-rich phase was heated again at 100°C to remove water after decantation and the remaining phase was dissolved using 0.5mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75ngmL(-1) and the detection limit was 0.15ngmL(-1) of the original solution. The enhancement factor of 500 was achieved for 250mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Comprehensive evaluation of direct injection mass spectrometry for the quantitative profiling of volatiles in food samples

PubMed Central

2016-01-01

Although qualitative strategies based on direct injection mass spectrometry (DIMS) have recently emerged as an alternative for the rapid classification of food samples, the potential of these approaches in quantitative tasks has scarcely been addressed to date. In this paper, the applicability of different multivariate regression procedures to data collected by DIMS from simulated mixtures has been evaluated. The most relevant factors affecting quantitation, such as random noise, the number of calibration samples, type of validation, mixture complexity and similarity of mass spectra, were also considered and comprehensively discussed. Based on the conclusions drawn from simulated data, and as an example of application, experimental mass spectral fingerprints collected by direct thermal desorption coupled to mass spectrometry were used for the quantitation of major volatiles in Thymus zygis subsp. zygis chemotypes. The results obtained, validated with the direct thermal desorption coupled to gas chromatography–mass spectrometry method here used as a reference, show the potential of DIMS approaches for the fast and precise quantitative profiling of volatiles in foods. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644978

Search for Chemical Biomarkers on Mars Using the Sample Analysis at Mars Instrument Suite on the Mars Science Laboratory

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Conrad, P.; Dworkin, J. P.; Eigenbrode, J.; Mahaffy, P. R.

2011-01-01

One key goal for the future exploration of Mars is the search for chemical biomarkers including complex organic compounds important in life on Earth. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) will provide the most sensitive measurements of the organic composition of rocks and regolith samples ever carried out in situ on Mars. SAM consists of a gas chromatograph (GC), quadrupole mass spectrometer (QMS), and tunable laser spectrometer to measure volatiles in the atmosphere and released from rock powders heated up to 1000 C. The measurement of organics in solid samples will be accomplished by three experiments: (1) pyrolysis QMS to identify alkane fragments and simple aromatic compounds; pyrolysis GCMS to separate and identify complex mixtures of larger hydrocarbons; and (3) chemical derivatization and GCMS extract less volatile compounds including amino and carboxylic acids that are not detectable by the other two experiments.

THE DETERMINATION OF BORON IN ZIRCALOY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freegarde, M.; Cartwright, J.

1962-03-01

An account is given of the development of a simple and reliable procedure for determining boron in Zircaloy at the parts per million level. The sample is dissolved in a mixture of bromine and methanol, and the boron is separated by distillation and determined as its rosocyanin complex with curcumin. The reproducibility of the method is characterized by a standard deviation of 0.03 ppm at the 0.3 ppm level. (auth)

OVERVIEW OF AN INTEGRATIVE SAMPLER FOR ...

EPA Pesticide Factsheets

Anthropogenic pollution is recognized as a global problem contributing to degradation of ecosystem quality, to loss of numerous plant and animal species, and to adverse impacts on human health. There is an increasing realization that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants as well. An approach to provide a time-weighted average (TWA) assessment is critical in understanding organism exposure to the complex mixture of pollutants present in the environment. A recently developed device, the polar organic chemical integrative sampler (POCIS), is designed to integratively sample the more polar waterborne organic chemicals. Laboratory trials and field deployments have demonstrated that the POCIS is very effective for sequestering hydrophilic chemicals such as antibiotics, hormones, other pharmaceutically derived chemicals, polar pesticides, surfactants, etc. Environmentally derived sample extracts from the integrative samplers are readily amenable for assays utilizing bio-indicator tests. An overview of the POCIS and selected environmental applications will be presented. The research focused on in the subtasks is the development and application of state-of the-art technologies to meet the needs of the public, Office of Water, and ORD in the area of Water Quality. Located In the subtasks are the various research projects being performed in support of this Task and

MULTISUBSTRATE BIODEGRADATION KINETICS FOR BINARY AND COMPLEX MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Biodegradation kinetics were studied for binary and complex mixtures of nine polycyclic aromatic hydrocarbons (PAHs): naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-ethylnaphthalene, phenanthrene, anthracene, pyrene, fluorene and fluoranthene. Discrepancies between the ...

Phenol removal pretreatment process

DOEpatents

Hames, Bonnie R.

2004-04-13

A process for removing phenols from an aqueous solution is provided, which comprises the steps of contacting a mixture comprising the solution and a metal oxide, forming a phenol metal oxide complex, and removing the complex from the mixture.

Supercritical separation process for complex organic mixtures

DOEpatents

Chum, Helena L.; Filardo, Giuseppe

1990-01-01

A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70.degree. C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool.

PubMed

Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

2018-03-01

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H] - . Nevertheless, NH 3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous C x H y O z bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. Graphical Abstract ᅟ.

Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool

NASA Astrophysics Data System (ADS)

Hertzog, Jasmine; Carré, Vincent; Dufour, Anthony; Aubriet, Frédéric

2018-03-01

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M - H]-. Nevertheless, NH3 may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous CxHyOz bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. [Figure not available: see fulltext.

BiomeNet: A Bayesian Model for Inference of Metabolic Divergence among Microbial Communities

PubMed Central

Chipman, Hugh; Gu, Hong; Bielawski, Joseph P.

2014-01-01

Metagenomics yields enormous numbers of microbial sequences that can be assigned a metabolic function. Using such data to infer community-level metabolic divergence is hindered by the lack of a suitable statistical framework. Here, we describe a novel hierarchical Bayesian model, called BiomeNet (Bayesian inference of metabolic networks), for inferring differential prevalence of metabolic subnetworks among microbial communities. To infer the structure of community-level metabolic interactions, BiomeNet applies a mixed-membership modelling framework to enzyme abundance information. The basic idea is that the mixture components of the model (metabolic reactions, subnetworks, and networks) are shared across all groups (microbiome samples), but the mixture proportions vary from group to group. Through this framework, the model can capture nested structures within the data. BiomeNet is unique in modeling each metagenome sample as a mixture of complex metabolic systems (metabosystems). The metabosystems are composed of mixtures of tightly connected metabolic subnetworks. BiomeNet differs from other unsupervised methods by allowing researchers to discriminate groups of samples through the metabolic patterns it discovers in the data, and by providing a framework for interpreting them. We describe a collapsed Gibbs sampler for inference of the mixture weights under BiomeNet, and we use simulation to validate the inference algorithm. Application of BiomeNet to human gut metagenomes revealed a metabosystem with greater prevalence among inflammatory bowel disease (IBD) patients. Based on the discriminatory subnetworks for this metabosystem, we inferred that the community is likely to be closely associated with the human gut epithelium, resistant to dietary interventions, and interfere with human uptake of an antioxidant connected to IBD. Because this metabosystem has a greater capacity to exploit host-associated glycans, we speculate that IBD-associated communities might arise from opportunist growth of bacteria that can circumvent the host's nutrient-based mechanism for bacterial partner selection. PMID:25412107

Rabbit Neonates and Human Adults Perceive a Blending 6-Component Odor Mixture in a Comparable Manner

PubMed Central

Sinding, Charlotte; Thomas-Danguin, Thierry; Chambault, Adeline; Béno, Noelle; Dosne, Thibaut; Chabanet, Claire; Schaal, Benoist; Coureaud, Gérard

2013-01-01

Young and adult mammals are constantly exposed to chemically complex stimuli. The olfactory system allows for a dual processing of relevant information from the environment either as single odorants in mixtures (elemental perception) or as mixtures of odorants as a whole (configural perception). However, it seems that human adults have certain limits in elemental perception of odor mixtures, as suggested by their inability to identify each odorant in mixtures of more than 4 components. Here, we explored some of these limits by evaluating the perception of three 6-odorant mixtures in human adults and newborn rabbits. Using free-sorting tasks in humans, we investigated the configural or elemental perception of these mixtures, or of 5-component sub-mixtures, or of the 6-odorant mixtures with modified odorants' proportion. In rabbit pups, the perception of the same mixtures was evaluated by measuring the orocephalic sucking response to the mixtures or their components after conditioning to one of these stimuli. The results revealed that one mixture, previously shown to carry the specific odor of red cordial in humans, was indeed configurally processed in humans and in rabbits while the two other 6-component mixtures were not. Moreover, in both species, such configural perception was specific not only to the 6 odorants included in the mixture but also to their respective proportion. Interestingly, rabbit neonates also responded to each odorant after conditioning to the red cordial mixture, which demonstrates their ability to perceive elements in addition to configuration in this complex mixture. Taken together, the results provide new insights related to the processing of relatively complex odor mixtures in mammals and the inter-species conservation of certain perceptual mechanisms; the results also revealed some differences in the expression of these capacities between species putatively linked to developmental and ecological constraints. PMID:23341948

Two-dimensional fingerprinting approach for comparison of complex substances analysed by HPLC-UV and fluorescence detection.

PubMed

Ni, Yongnian; Liu, Ying; Kokot, Serge

2011-02-07

This work is concerned with the research and development of methodology for analysis of complex mixtures such as pharmaceutical or food samples, which contain many analytes. Variously treated samples (swill washed, fried and scorched) of the Rhizoma atractylodis macrocephalae (RAM) traditional Chinese medicine (TCM) as well as the common substitute, Rhizoma atractylodis (RA) TCM were chosen as examples for analysis. A combined data matrix of chromatographic 2-D HPLC-DAD-FLD (two-dimensional high performance liquid chromatography with diode array and fluorescence detectors) fingerprint profiles was constructed with the use of the HPLC-DAD and HPLC-FLD individual data matrices; the purpose was to collect maximum information and to interpret this complex data with the use of various chemometrics methods e.g. the rank-ordering multi-criteria decision making (MCDM) PROMETHEE and GAIA, K-nearest neighbours (KNN), partial least squares (PLS), back propagation-artificial neural networks (BP-ANN) methods. The chemometrics analysis demonstrated that the combined 2-D HPLC-DAD-FLD data matrix does indeed provide more information and facilitates better performing classification/prediction models for the analysis of such complex samples as the RAM and RA ones noted above. It is suggested that this fingerprint approach is suitable for analysis of other complex, multi-analyte substances.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Distler, T. M.; Wong, C. M.

Runoff-water samples for the first, third, and fourth quarters of 1975 were analyzed for pesticide residues at LLL and independently by the LFE Environmental Analysis Laboratories. For the compounds analyzed, upper limits to possible contamination were placed conservatively at the low parts-per-billion level. In addition, soil samples were also analyzed. Future work will continue to include quarterly sampling and will be broadened in scope to include quantitative analysis of a larger number of compounds. A study of recovery efficiency is planned. Because of the high backgrounds on soil samples together with the uncertainties introduced by the cleanup procedures, there ismore » little hope of evaluating the distribution of a complex mixture of pesticides among the aqueous and solid phases in a drainage sample. No further sampling of soil from the streambed is therefore contemplated.« less

Measuring pair-wise molecular interactions in a complex mixture

NASA Astrophysics Data System (ADS)

Chakraborty, Krishnendu; Varma, Manoj M.; Venkatapathi, Murugesan

2016-03-01

Complex biological samples such as serum contain thousands of proteins and other molecules spanning up to 13 orders of magnitude in concentration. Present measurement techniques do not permit the analysis of all pair-wise interactions between the components of such a complex mixture to a given target molecule. In this work we explore the use of nanoparticle tags which encode the identity of the molecule to obtain the statistical distribution of pair-wise interactions using their Localized Surface Plasmon Resonance (LSPR) signals. The nanoparticle tags are chosen such that the binding between two molecules conjugated to the respective nanoparticle tags can be recognized by the coupling of their LSPR signals. This numerical simulation is done by DDA to investigate this approach using a reduced system consisting of three nanoparticles (a gold ellipsoid with aspect ratio 2.5 and short axis 16 nm, and two silver ellipsoids with aspect ratios 3 and 2 and short axes 8 nm and 10 nm respectively) and the set of all possible dimers formed between them. Incident light was circularly polarized and all possible particle and dimer orientations were considered. We observed that minimum peak separation between two spectra is 5 nm while maximum is 184nm.

Using Big Data Analytics to Address Mixtures Exposure

EPA Science Inventory

The assessment of chemical mixtures is a complex issue for regulators and health scientists. We propose that assessing chemical co-occurrence patterns and prevalence rates is a relatively simple yet powerful approach in characterizing environmental mixtures and mixtures exposure...

Ground-Based Aerosol Measurements

EPA Science Inventory

Atmospheric particulate matter (PM) is a complex chemical mixture of liquid and solid particles suspended in air (Seinfeld and Pandis 2016). Measurements of this complex mixture form the basis of our knowledge regarding particle formation, source-receptor relationships, data to ...

Indoor air-assessment: Indoor concentrations of environmental carcinogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gold, K.W.; Naugle, D.F.; Berry, M.A.

1991-01-01

In the report, indoor concentration data are presented for the following general categories of air pollutants: radon-222, environmental tobacco smoke (ETS), asbestos, gas phase organic compounds, formaldehyde, polycyclic aromatic hydrocarbons (PAH), pesticides, and inorganic compounds. These pollutants are either known or suspect carcinogens (i.e., radon-222, asbestos) or more complex mixtures or classes of compounds which contain known or suspect carcinogens. Concentration data for individual carcinogenic compounds in complex mixtures are usually far from complete. The data presented for complex mixtures often include compounds which are not carcinogenic or for which data are insufficient to evaluate carcinogenicity. Their inclusion is justified,more » however, by the possibility that further work may show them to be carcinogens, cocarcinogens, initiators or promotors, or that they may be employed as markers (e.g., nicotine, acrolein) for the estimation of exposure to complex mixtures.« less

Measurement of complex permittivities of biological materials and human skin in vivo in the frequency band

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghodgaonkar, D.K.

1987-01-01

A new method, namely, modified infinite sample method, has been developed which is particularly suitable for millimeter-wave dielectric measurements of biological materials. In this method, an impedance transformer is used which reduces the reflectivity of the biological sample. Because of the effect of introducing impendance transformer, the measured reflection coefficients are more sensitive to the complex permittivities of biological samples. For accurate measurement of reflection coefficients, two automated measurment systems were developed which cover the frequencies range of 26.5-60 GHz. An uncertainty analysis was performed to get an estimate of the errors in the measured complex permittivities. The dielectric propertiesmore » were measured for 10% saline solution, whole human blood, 200 mg/ml bovine serum albumin (BSA) solution and suspension of Saccharomyces cerevisiae cells. The Maxwell-Fricke equation, which is derived from dielectric mixture theory, was used for determination bound water in BSA solution. The results of all biological samples were interpreted by fitting Debye relaxation and Cole-Cole model. It is observed that the dielectric data for the biological materials can be explained on the basis of Debye relaxation of water molecule.« less

Simple hollow fiber renewal liquid membrane extraction method for pre-concentration of Cd(II) in environmental samples and detection by flame atomic absorption spectrometry.

PubMed

Carletto, Jeferson Schneider; Luciano, Raquel Medeiros; Bedendo, Gizelle Cristina; Carasek, Eduardo

2009-04-06

A hollow fiber renewal liquid membrane (HFRLM) extraction method to determine cadmium (II) in water samples using Flame Atomic Absorption Spectrometry (FAAS) was developed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex (ML(2)). The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the poly(dimethylsiloxane) (PDMS) membrane, that had their walls previously filled with the same organic solvent. The organic solvent is solubilized inside the PDMS membrane, leading to a homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and cadmium (II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. A multivariate procedure was used to optimize the studied variables. The optimized variables were: sample (donor phase) pH 3.25, DDTP concentration 0.05% (m/v), stripping (acceptor phase) pH 8.75, EDTA concentration 1.5x10(-2) mol L(-1), extraction temperature 40 degrees C, extraction time 40 min, a solvent mixture N-butyl acetate and hexane (60/40%, v/v) with a volume of 100 microL, and addition of ammonium sulfate to saturate the sample. The sample volume used was 20 mL and the stripping volume was 165 microL. The analyte enrichment factor was 120, limit of detection (LOD) 1.3 microg L(-1), relative standard deviation (RSD) 5.5% and the working linear range 2-30 microg L(-1).

MixGF: spectral probabilities for mixture spectra from more than one peptide.

PubMed

Wang, Jian; Bourne, Philip E; Bandeira, Nuno

2014-12-01

In large-scale proteomic experiments, multiple peptide precursors are often cofragmented simultaneously in the same mixture tandem mass (MS/MS) spectrum. These spectra tend to elude current computational tools because of the ubiquitous assumption that each spectrum is generated from only one peptide. Therefore, tools that consider multiple peptide matches to each MS/MS spectrum can potentially improve the relatively low spectrum identification rate often observed in proteomics experiments. More importantly, data independent acquisition protocols promoting the cofragmentation of multiple precursors are emerging as alternative methods that can greatly improve the throughput of peptide identifications but their success also depends on the availability of algorithms to identify multiple peptides from each MS/MS spectrum. Here we address a fundamental question in the identification of mixture MS/MS spectra: determining the statistical significance of multiple peptides matched to a given MS/MS spectrum. We propose the MixGF generating function model to rigorously compute the statistical significance of peptide identifications for mixture spectra and show that this approach improves the sensitivity of current mixture spectra database search tools by a ≈30-390%. Analysis of multiple data sets with MixGF reveals that in complex biological samples the number of identified mixture spectra can be as high as 20% of all the identified spectra and the number of unique peptides identified only in mixture spectra can be up to 35.4% of those identified in single-peptide spectra. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

MixGF: Spectral Probabilities for Mixture Spectra from more than One Peptide*

PubMed Central

Wang, Jian; Bourne, Philip E.; Bandeira, Nuno

2014-01-01

In large-scale proteomic experiments, multiple peptide precursors are often cofragmented simultaneously in the same mixture tandem mass (MS/MS) spectrum. These spectra tend to elude current computational tools because of the ubiquitous assumption that each spectrum is generated from only one peptide. Therefore, tools that consider multiple peptide matches to each MS/MS spectrum can potentially improve the relatively low spectrum identification rate often observed in proteomics experiments. More importantly, data independent acquisition protocols promoting the cofragmentation of multiple precursors are emerging as alternative methods that can greatly improve the throughput of peptide identifications but their success also depends on the availability of algorithms to identify multiple peptides from each MS/MS spectrum. Here we address a fundamental question in the identification of mixture MS/MS spectra: determining the statistical significance of multiple peptides matched to a given MS/MS spectrum. We propose the MixGF generating function model to rigorously compute the statistical significance of peptide identifications for mixture spectra and show that this approach improves the sensitivity of current mixture spectra database search tools by a ≈30–390%. Analysis of multiple data sets with MixGF reveals that in complex biological samples the number of identified mixture spectra can be as high as 20% of all the identified spectra and the number of unique peptides identified only in mixture spectra can be up to 35.4% of those identified in single-peptide spectra. PMID:25225354

Combining TXRF, FT-IR and GC-MS information for identification of inorganic and organic components in black pigments of rock art from Alero Hornillos 2 (Jujuy, Argentina).

PubMed

Vázquez, Cristina; Maier, Marta S; Parera, Sara D; Yacobaccio, Hugo; Solá, Patricia

2008-06-01

Archaeological samples are complex in composition since they generally comprise a mixture of materials submitted to deterioration factors largely dependent on the environmental conditions. Therefore, the integration of analytical tools such as TXRF, FT-IR and GC-MS can maximize the amount of information provided by the sample. Recently, two black rock art samples of camelid figures at Alero Hornillos 2, an archaeological site located near the town of Susques (Jujuy Province, Argentina), were investigated. TXRF, selected for inorganic information, showed the presence of manganese and iron among other elements, consistent with an iron and manganese oxide as the black pigment. Aiming at the detection of any residual organic compounds, the samples were extracted with a chloroform-methanol mixture and the extracts were analyzed by FT-IR, showing the presence of bands attributable to lipids. Analysis by GC-MS of the carboxylic acid methyl esters prepared from the sample extracts, indicated that the main organic constituents were saturated (C(16:0) and C(18:0)) fatty acids in relative abundance characteristic of degraded animal fat. The presence of minor C(15:0) and C(17:0) fatty acids and branched-chain iso-C(16:0) pointed to a ruminant animal source.

Method for the determination of chromium in feed matrix by HPLC.

PubMed

Umesh, Balakrishnan; Rajendran, Rajendra Moorthy; Manoharan, Muthu Tamizh

2015-11-01

An improved method for the chromatographic separation and determination of chromium (III) and (VI) [ CRIII AND CRVI: ] in mineral mixtures and feed samples has been developed. The method uses precolumn derivatization using ammonium pyrrolidinedithiocarbamate ( APD: ) followed by reversed-phase liquid chromatography to separate the chromium ions. Both Cr(III) and Cr(VI) species are chelated with ammonium pyrrolidinedithiocarbamate prior to separation by mixing with acetonitrile and 0.5 mmol acetate buffer (pH 4.5). Optimum chromatographic separations were obtained with a polymer-based reversed-phase column (Kinetex, 5 μ, 250 × 4.5 mm, Phenomenex, Torrance, CA) and a mobile phase containing acetonitrile and water (7:3). Both Cr(III) and Cr(VI) ion concentrations were directly determined from the corresponding areas in the chromatogram. The effect of analytical parameters, including pH, concentration of ligand, incubation temperature, and mobile phase, was optimized for both chromium complexes. The range of the procedure was found to be linear for Cr(III) and Cr(VI) concentrations between 0.125 and 4 μg/mL (r² = 0.9926) and 0.1 and 3.0 μg/mL (r² = 0.9983), respectively. Precision was evaluated by replicate analysis in which the percentage relative standard deviation values for chromium complex were found to be below 4.0. The recoveries obtained (85-115%) for both Cr(III) and Cr(VI) complexes indicated the accuracy of the developed method. The degradation products, as well as the excipients, were well resolved from the chromium complex peak in the chromatogram. Finally, the new method proved to be suitable for routine analysis of Cr(III) and Cr(VI) species in raw materials, mineral mixtures, and feed samples. © 2015 Poultry Science Association Inc.

Glass polymorphism in glycerol–water mixtures: II. Experimental studies

PubMed Central

Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolas

2016-01-01

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s–1–10 K h–1) and for the whole range of glycerol mole fractions, χ g. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χ g ≥ 0.20), ice (χ g ≤ 0.32), and/or “distorted ice” (0 < χ g ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χ g ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol–water mixtures is shown to be possible only up to χ g ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χ g < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χ g ≈ 0.38. Accordingly, in the range 0.32 < χ g < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χ g ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 < χ g ≤ 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (χ g ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex “phase” behavior of glassy binary mixtures due to phase-separation (ice formation) and polyamorphism, and the relevance of sample preparation, concentration as well as cooling rates. The presence of the distorted ice (called “interphase” by us) also explains the debated “drift anomaly” upon melting. These results are compatible with the high-pressure study by Suzuki and Mishima indicating disappearance of polyamorphism at P ≈ 0.03–0.05 GPa at χ g ≈ 0.12–0.15 [J. Chem. Phys., 2014, 141, 094505]. PMID:27044677

Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches

USGS Publications Warehouse

Schoenfuss, Heiko L.; Furlong, Edward T.; Phillips, Patrick J.; Scott, Tia-Marie; Kolpin, Dana W.; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E.; Rearick, Daniel C.

2016-01-01

Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning levels of biological organization and life stages when assessing contaminant interactions.

Transcriptional responses to complex mixtures - A review

EPA Science Inventory

Exposure of people to hazardous compounds is primarily through complex environmental mixtures, those that occur through media such as air, soil, water, food, cigarette smoke, and combustion emissions. Microarray technology offers the ability to query the entire genome after expos...

Using partially labeled data for normal mixture identification with application to class definition

NASA Technical Reports Server (NTRS)

Shahshahani, Behzad M.; Landgrebe, David A.

1992-01-01

The problem of estimating the parameters of a normal mixture density when, in addition to the unlabeled samples, sets of partially labeled samples are available is addressed. The density of the multidimensional feature space is modeled with a normal mixture. It is assumed that the set of components of the mixture can be partitioned into several classes and that training samples are available from each class. Since for any training sample the class of origin is known but the exact component of origin within the corresponding class is unknown, the training samples as considered to be partially labeled. The EM iterative equations are derived for estimating the parameters of the normal mixture in the presence of partially labeled samples. These equations can be used to combine the supervised and nonsupervised learning processes.

Fact or artifact: the representativeness of ESI-MS for complex natural organic mixtures.

PubMed

Novotny, Nicole R; Capley, Erin N; Stenson, Alexandra C

2014-04-01

Because mass spectrometers provide their own dispersion and resolution of analytes, electrospray ionization mass spectrometry (ESI-MS) has become a workhorse for the characterization of complex mixtures from aerosols to crude oil. Unfortunately, ESI mass spectra commonly contain multimers, adducts and fragments. For the characterization of complex mixtures of unknown initial composition, this presents a significant concern. Mixed-multimer formation could potentially lead to results that bare no resemblance to the original mixture. Conversely, ESI-MS has continually reflected subtle differences between natural organic matter mixtures that are in agreement with prediction or theory. Knowing the real limitations of the technique is therefore critical to avoiding both over-interpretation and unwarranted skepticism. Here, data were collected on four mass spectrometers under a battery of conditions. Results indicate that formation of unrepresentative ions cannot entirely be ruled out, but non-covalent multimers do not appear to make a major contribution to typical natural organic matter spectra based on collision-induced dissociation results. Multimers also appear notably reduced when a cooling gas is present in the accumulation region of the mass spectrometer. For less complex mixtures, the choice of spray solvent can make a difference, but generally spectrum cleanliness (i.e. representativeness) comes at the price of increased selectivity. Copyright © 2014 John Wiley & Sons, Ltd.

MALDI-MS SCREENING FOR PSEUDOURIDINE IN MIXTURES OF SMALL RNAS BY CHEMICAL DERIVATIZATION, RNASE DIGESTION AND SIGNATURE PRODUCTS

PubMed Central

Durairaj, Anita; Limbach, Patrick A.

2010-01-01

We have developed a method to screen for pseudouridines in complex mixtures of small RNAs using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS). First, the unfractionated crude mixture of tRNAs is digested to completion with an endoribonuclease, such as RNase T1, and the digestion products are examined using MALDI-MS. Individual RNAs are identified by their signature digestion products, which arise through the detection of unique mass values after nuclease digestion. Next, the endonuclease digest is derivatized using N-cyclohexyl-N’-(2-morpholinoethyl)-carbodiimide metho-p-toluenesulfonate (CMCT), which selectively modifies all pseudouridine, thiouridine and 2-methylthio-6-isopentenyladenosine nucleosides. MALDI-MS determination of the CMCT-derivatized endonuclease digest reveals the presence of pseudouridine through a 252 Da mass increase over the underivatized digest. Proof-of-concept experiments were conducted using a mixture of Escherichia coli transfer RNAs and endoribonucleases T1 and A. More than 80% of the expected pseudouridines from this mixture were detected using this screening approach, even on a unfractionated sample of tRNAs. This approach should be particularly useful in the identification of putative pseudouridine synthases through detection of their target RNAs and can provide insight into specific small RNAs that may contain pseudouridine. PMID:18973194

Evaluation of sample recovery of malodorous livestock gases from air sampling bags, solid-phase microextraction fibers, Tenax TA sorbent tubes, and sampling canisters.

PubMed

Koziel, Jacek A; Spinhirne, Jarett P; Lloyd, Jenny D; Parker, David B; Wright, Donald W; Kuhrt, Fred W

2005-08-01

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75-microm solid-phase microextraction fibers, polyvinyl fluoride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b-diphenylene-oxide polymer resin (Tenax TA) tubes, and standard 6-L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p-cresol, indole, 4-ethylphenol, and 2'-aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5- and 24-hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in-house-made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N-dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.

Supercritical separation process for complex organic mixtures

DOEpatents

Chum, H.L.; Filardo, G.

1990-10-23

A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70 C and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution. 1 fig.

Toward the Rational Use of Exposure Information in Mixtures Toxicology

EPA Science Inventory

Of all the disciplines of toxicology, perhaps none is as dependent on exposure information as Mixtures Toxicology. Identifying real world mixtures and replicating them in the laboratory (or in silico) is critical to understanding their risks. Complex mixtures such as cigarett...

Estimating mineral abundances of clay and gypsum mixtures using radiative transfer models applied to visible-near infrared reflectance spectra

NASA Astrophysics Data System (ADS)

Robertson, K. M.; Milliken, R. E.; Li, S.

2016-10-01

Quantitative mineral abundances of lab derived clay-gypsum mixtures were estimated using a revised Hapke VIS-NIR and Shkuratov radiative transfer model. Montmorillonite-gypsum mixtures were used to test the effectiveness of the model in distinguishing between subtle differences in minor absorption features that are diagnostic of mineralogy in the presence of strong H2O absorptions that are not always diagnostic of distinct phases or mineral abundance. The optical constants (k-values) for both endmembers were determined from bi-directional reflectance spectra measured in RELAB as well as on an ASD FieldSpec3 in a controlled laboratory setting. Multiple size fractions were measured in order to derive a single k-value from optimization of the optical path length in the radiative transfer models. It is shown that with careful experimental conditions, optical constants can be accurately determined from powdered samples using a field spectrometer, consistent with previous studies. Variability in the montmorillonite hydration level increased the uncertainties in the derived k-values, but estimated modal abundances for the mixtures were still within 5% of the measured values. Results suggest that the Hapke model works well in distinguishing between hydrated phases that have overlapping H2O absorptions and it is able to detect gypsum and montmorillonite in these simple mixtures where they are present at levels of ∼10%. Care must be taken however to derive k-values from a sample with appropriate H2O content relative to the modeled spectra. These initial results are promising for the potential quantitative analysis of orbital remote sensing data of hydrated minerals, including more complex clay and sulfate assemblages such as mudstones examined by the Curiosity rover in Gale crater.

Highly-Complex Environmentally-Realistic Mixtures: Challenges and Advances

EPA Science Inventory

The difficulties involved in design, conduct, analysis and interpretation of defmed mixtures experiments and use of the resulting data in risk assessment are now wellknown to the toxicology, risk assessment and risk management communities. The arena of highly-complex environment...

Multicomponent quantitative spectroscopic analysis without reference substances based on ICA modelling.

PubMed

Monakhova, Yulia B; Mushtakova, Svetlana P

2017-05-01

A fast and reliable spectroscopic method for multicomponent quantitative analysis of targeted compounds with overlapping signals in complex mixtures has been established. The innovative analytical approach is based on the preliminary chemometric extraction of qualitative and quantitative information from UV-vis and IR spectral profiles of a calibration system using independent component analysis (ICA). Using this quantitative model and ICA resolution results of spectral profiling of "unknown" model mixtures, the absolute analyte concentrations in multicomponent mixtures and authentic samples were then calculated without reference solutions. Good recoveries generally between 95% and 105% were obtained. The method can be applied to any spectroscopic data that obey the Beer-Lambert-Bouguer law. The proposed method was tested on analysis of vitamins and caffeine in energy drinks and aromatic hydrocarbons in motor fuel with 10% error. The results demonstrated that the proposed method is a promising tool for rapid simultaneous multicomponent analysis in the case of spectral overlap and the absence/inaccessibility of reference materials.

Single-Scan Multidimensional NMR Analysis of Mixtures at Sub-Millimolar Concentrations by using SABRE Hyperpolarization.

PubMed

Daniele, Valeria; Legrand, François-Xavier; Berthault, Patrick; Dumez, Jean-Nicolas; Huber, Gaspard

2015-11-16

Signal amplification by reversible exchange (SABRE) is a promising method to increase the sensitivity of nuclear magnetic resonance (NMR) experiments. However, SABRE-enhanced (1)H NMR signals are short lived, and SABRE is often used to record 1D NMR spectra only. When the sample of interest is a complex mixture, this results in severe overlaps for (1)H spectra. In addition, the use of a co-substrate, whose signals may obscure the (1) H spectra, is currently the most efficient way to lower the detection limit of SABRE experiments. Here, we describe an approach to obtain clean, SABRE-hyperpolarized 2D (1)H NMR spectra of mixtures of small molecules at sub-millimolar concentrations in a single scan. The method relies on the use of para-hydrogen together with a deuterated co-substrate for hyperpolarization and ultrafast 2D NMR for acquisition. It is applicable to all substrates that can be polarized with SABRE. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: complexation versus mixture.

PubMed

Zhang, Yu; Cai, Xiyun; Lang, Xianming; Qiao, Xianliang; Li, Xuehua; Chen, Jingwen

2012-07-01

Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC(50) values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. Copyright © 2012 Elsevier Ltd. All rights reserved.

A novel particle engineering technology to enhance dissolution of poorly water soluble drugs: spray-freezing into liquid.

PubMed

Rogers, True L; Nelsen, Andrew C; Hu, Jiahui; Brown, Judith N; Sarkari, Marazban; Young, Timothy J; Johnston, Keith P; Williams, Robert O

2002-11-01

A novel cryogenic spray-freezing into liquid (SFL) process was developed to produce microparticulate powders consisting of an active pharmaceutical ingredient (API) molecularly embedded within a pharmaceutical excipient matrix. In the SFL process, a feed solution containing the API was atomized beneath the surface of a cryogenic liquid such that the liquid-liquid impingement between the feed and cryogenic liquids resulted in intense atomization into microdroplets, which were frozen instantaneously into microparticles. The SFL micronized powder was obtained following lyophilization of the frozen microparticles. The objective of this study was to develop a particle engineering technology to produce micronized powders of the hydrophobic drug, danazol, complexed with hydroxypropyl-beta-cyclodextrin (HPbetaCD) and to compare these SFL micronized powders to inclusion complex powders produced from other techniques, such as co-grinding of dry powder mixtures and lyophilization of bulk solutions. Danazol and HPbetaCD were dissolved in a water/tetrahydrofuran cosolvent mixture prior to SFL processing or slow freezing. Identical quantities of the API and HPbetaCD used in the solutions were co-ground in a mortar and pestle and blended to produce a co-ground physical mixture for comparison. The powder samples were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), scanning electron microscopy, surface area analysis, and dissolution testing. The results provided by DSC, XRD, and FTIR suggested the formation of inclusion complexes by both slow-freezing and SFL. However, the specific surface area was significantly higher for the latter. Dissolution results suggested that equilibration of the danazol/HPbetaCD solution prior to SFL processing was required to produce the most soluble conformation of the resulting inclusion complex following SFL. SFL micronized powders exhibited better dissolution profiles than the slowly frozen aggregate powder. Results indicated that micronized SFL inclusion complex powders dissolved faster in aqueous dissolution media than inclusion complexes formed by conventional techniques due to higher surface areas and stabilized inclusion complexes obtained by ultra-rapid freezing.

Identification of PAH Isomeric Structure in Cosmic Dust Analogs: The AROMA Setup

NASA Astrophysics Data System (ADS)

Sabbah, Hassan; Bonnamy, Anthony; Papanastasiou, Dimitris; Cernicharo, Jose; Martín-Gago, Jose-Angel; Joblin, Christine

2017-07-01

We developed a new analytical experimental setup called AROMA (Astrochemistry Research of Organics with Molecular Analyzer) that combines laser desorption/ionization techniques with ion trap mass spectrometry. We report here on the ability of the apparatus to detect aromatic species in complex materials of astrophysical interest and characterize their structures. A limit of detection of 100 femto-grams has been achieved using pure polycyclic aromatic hydrocarbon (PAH) samples, which corresponds to 2 × 108 molecules in the case of coronene (C24H12). We detected the PAH distribution in the Murchison meteorite, which is made of a complex mixture of extraterrestrial organic compounds. In addition, collision induced dissociation experiments were performed on selected species detected in Murchison, which led to the first firm identification of pyrene and its methylated derivatives in this sample.

Capillary electrophoresis for aluminum ion speciation: Optimized separation conditions for complex polycation mixtures.

PubMed

Ouadah, Nesrine; Moire, Claudine; Brothier, Fabien; Kuntz, Jean-François; Deschaume, Olivier; Bartic, Carmen; Cottet, Hervé

2018-06-01

Aluminum chlorohydrates (ACH) are used in numerous applications and commercial products on a global scale including water treatment, catalysis or antiperspirants. They are complex mixtures of water soluble aluminum polycations of different degrees of polymerization, that are difficult to separate and quantify due to their susceptibility to depolymerize in solution when placed out of equilibrium, which is inherent to any separation process. We recently achieved the first capillary electrophoresis separation and characterization of ACH oligomers using 4-morpholineethanesulfonic acid (MES) as background electrolyte counter-ion. MES stabilizes the separated ACH oligomers during the electrophoretic process leading to highly repeatable and fast separations. In this work, the separation of ACH oligomers was further studied and perfected by varying the ionic strength, MES concentration and pH of the background electrolyte. Complex electrophoretic behavior is reported for the separation of Al 13 , Al 30 and Na + ions according to these experimental parameters. The transformation of the electropherograms in effective mobility scale and the use of the slope-plot approach are used to better understand the observed changes in selectivity/resolution. Optimal conditions (700 mM MES at 25 mM ionic strength containing 0.1 mM didodecyldimethylammonium bromide for dynamic capillary coating, pH 4.8) obtained for the separation of ACH oligomers are used for the baseline separation of samples difficult to analyze with other methods, including different molecular, aggregated and colloidal forms of aluminum from the Al 13 , Al 30 and Na + mixture, validating the rationale of the approach. Copyright © 2018. Published by Elsevier B.V.

Understanding the human health effects of chemical mixtures.

PubMed Central

Carpenter, David O; Arcaro, Kathleen; Spink, David C

2002-01-01

Most research on the effects of chemicals on biologic systems is conducted on one chemical at a time. However, in the real world people are exposed to mixtures, not single chemicals. Although various substances may have totally independent actions, in many cases two substances may act at the same site in ways that can be either additive or nonadditive. Many even more complex interactions may occur if two chemicals act at different but related targets. In the extreme case there may be synergistic effects, in which case the effects of two substances together are greater than the sum of either effect alone. In reality, most persons are exposed to many chemicals, not just one or two, and therefore the effects of a chemical mixture are extremely complex and may differ for each mixture depending on the chemical composition. This complexity is a major reason why mixtures have not been well studied. In this review we attempt to illustrate some of the principles and approaches that can be used to study effects of mixtures. By the nature of the state of the science, this discussion is more a presentation of what we do not know than of what we do know about mixtures. We approach the study of mixtures at three levels, using specific examples. First, we discuss several human diseases in relation to a variety of environmental agents believed to influence the development and progression of the disease. We present results of selected cellular and animal studies in which simple mixtures have been investigated. Finally, we discuss some of the effects of mixtures at a molecular level. PMID:11834461

Evaluation of forensic DNA mixture evidence: protocol for evaluation, interpretation, and statistical calculations using the combined probability of inclusion.

PubMed

Bieber, Frederick R; Buckleton, John S; Budowle, Bruce; Butler, John M; Coble, Michael D

2016-08-31

The evaluation and interpretation of forensic DNA mixture evidence faces greater interpretational challenges due to increasingly complex mixture evidence. Such challenges include: casework involving low quantity or degraded evidence leading to allele and locus dropout; allele sharing of contributors leading to allele stacking; and differentiation of PCR stutter artifacts from true alleles. There is variation in statistical approaches used to evaluate the strength of the evidence when inclusion of a specific known individual(s) is determined, and the approaches used must be supportable. There are concerns that methods utilized for interpretation of complex forensic DNA mixtures may not be implemented properly in some casework. Similar questions are being raised in a number of U.S. jurisdictions, leading to some confusion about mixture interpretation for current and previous casework. Key elements necessary for the interpretation and statistical evaluation of forensic DNA mixtures are described. Given the most common method for statistical evaluation of DNA mixtures in many parts of the world, including the USA, is the Combined Probability of Inclusion/Exclusion (CPI/CPE). Exposition and elucidation of this method and a protocol for use is the focus of this article. Formulae and other supporting materials are provided. Guidance and details of a DNA mixture interpretation protocol is provided for application of the CPI/CPE method in the analysis of more complex forensic DNA mixtures. This description, in turn, should help reduce the variability of interpretation with application of this methodology and thereby improve the quality of DNA mixture interpretation throughout the forensic community.

A Multiplex PCR for the Simultaneous Detection and Genotyping of the Echinococcus granulosus Complex

PubMed Central

Boubaker, Ghalia; Macchiaroli, Natalia; Prada, Laura; Cucher, Marcela A.; Rosenzvit, Mara C.; Ziadinov, Iskender; Deplazes, Peter; Saarma, Urmas; Babba, Hamouda; Gottstein, Bruno; Spiliotis, Markus

2013-01-01

Echinococcus granulosus is characterized by high intra-specific variability (genotypes G1–G10) and according to the new molecular phylogeny of the genus Echinococcus, the E. granulosus complex has been divided into E. granulosus sensu stricto (G1–G3), E. equinus (G4), E. ortleppi (G5), and E. canadensis (G6–G10). The molecular characterization of E. granulosus isolates is fundamental to understand the spatio-temporal epidemiology of this complex in many endemic areas with the simultaneous occurrence of different Echinococcus species and genotypes. To simplify the genotyping of the E. granulosus complex we developed a single-tube multiplex PCR (mPCR) allowing three levels of discrimination: (i) Echinococcus genus, (ii) E. granulosus complex in common, and (iii) the specific genotype within the E. granulosus complex. The methodology was established with known DNA samples of the different strains/genotypes, confirmed on 42 already genotyped samples (Spain: 22 and Bulgaria: 20) and then successfully applied on 153 unknown samples (Tunisia: 114, Algeria: 26 and Argentina: 13). The sensitivity threshold of the mPCR was found to be 5 ng Echinoccoccus DNA in a mixture of up to 1 µg of foreign DNA and the specificity was 100% when template DNA from closely related members of the genus Taenia was used. Additionally to DNA samples, the mPCR can be carried out directly on boiled hydatid fluid or on alkaline-lysed frozen or fixed protoscoleces, thus avoiding classical DNA extractions. However, when using Echinococcus eggs obtained from fecal samples of infected dogs, the sensitivity of the mPCR was low (<40%). Thus, except for copro analysis, the mPCR described here has a high potential for a worldwide application in large-scale molecular epidemiological studies on the Echinococcus genus. PMID:23350011

A multiplex PCR for the simultaneous detection and genotyping of the Echinococcus granulosus complex.

PubMed

Boubaker, Ghalia; Macchiaroli, Natalia; Prada, Laura; Cucher, Marcela A; Rosenzvit, Mara C; Ziadinov, Iskender; Deplazes, Peter; Saarma, Urmas; Babba, Hamouda; Gottstein, Bruno; Spiliotis, Markus

2013-01-01

Echinococcus granulosus is characterized by high intra-specific variability (genotypes G1-G10) and according to the new molecular phylogeny of the genus Echinococcus, the E. granulosus complex has been divided into E. granulosus sensu stricto (G1-G3), E. equinus (G4), E. ortleppi (G5), and E. canadensis (G6-G10). The molecular characterization of E. granulosus isolates is fundamental to understand the spatio-temporal epidemiology of this complex in many endemic areas with the simultaneous occurrence of different Echinococcus species and genotypes. To simplify the genotyping of the E. granulosus complex we developed a single-tube multiplex PCR (mPCR) allowing three levels of discrimination: (i) Echinococcus genus, (ii) E. granulosus complex in common, and (iii) the specific genotype within the E. granulosus complex. The methodology was established with known DNA samples of the different strains/genotypes, confirmed on 42 already genotyped samples (Spain: 22 and Bulgaria: 20) and then successfully applied on 153 unknown samples (Tunisia: 114, Algeria: 26 and Argentina: 13). The sensitivity threshold of the mPCR was found to be 5 ng Echinoccoccus DNA in a mixture of up to 1 µg of foreign DNA and the specificity was 100% when template DNA from closely related members of the genus Taenia was used. Additionally to DNA samples, the mPCR can be carried out directly on boiled hydatid fluid or on alkaline-lysed frozen or fixed protoscoleces, thus avoiding classical DNA extractions. However, when using Echinococcus eggs obtained from fecal samples of infected dogs, the sensitivity of the mPCR was low (<40%). Thus, except for copro analysis, the mPCR described here has a high potential for a worldwide application in large-scale molecular epidemiological studies on the Echinococcus genus.

PACE: Probabilistic Assessment for Contributor Estimation- A machine learning-based assessment of the number of contributors in DNA mixtures.

PubMed

Marciano, Michael A; Adelman, Jonathan D

2017-03-01

The deconvolution of DNA mixtures remains one of the most critical challenges in the field of forensic DNA analysis. In addition, of all the data features required to perform such deconvolution, the number of contributors in the sample is widely considered the most important, and, if incorrectly chosen, the most likely to negatively influence the mixture interpretation of a DNA profile. Unfortunately, most current approaches to mixture deconvolution require the assumption that the number of contributors is known by the analyst, an assumption that can prove to be especially faulty when faced with increasingly complex mixtures of 3 or more contributors. In this study, we propose a probabilistic approach for estimating the number of contributors in a DNA mixture that leverages the strengths of machine learning. To assess this approach, we compare classification performances of six machine learning algorithms and evaluate the model from the top-performing algorithm against the current state of the art in the field of contributor number classification. Overall results show over 98% accuracy in identifying the number of contributors in a DNA mixture of up to 4 contributors. Comparative results showed 3-person mixtures had a classification accuracy improvement of over 6% compared to the current best-in-field methodology, and that 4-person mixtures had a classification accuracy improvement of over 20%. The Probabilistic Assessment for Contributor Estimation (PACE) also accomplishes classification of mixtures of up to 4 contributors in less than 1s using a standard laptop or desktop computer. Considering the high classification accuracy rates, as well as the significant time commitment required by the current state of the art model versus seconds required by a machine learning-derived model, the approach described herein provides a promising means of estimating the number of contributors and, subsequently, will lead to improved DNA mixture interpretation. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Characterization of the Androgen-sensitive MDA-kb2 Cell Line for Assessing Complex Environmental Mixtures

EPA Science Inventory

Complex mixtures of synthetic and natural androgens and estrogens, and many other non-steroidal components are commonly released to the aquatic environment from anthropogenic sources. It is important to understand the potential interactive (i.e., additive, synergistic, antagonist...

Diagnostic Assessment of the Ecological Risk of EDCs in Complex Mixtures

EPA Science Inventory

Although it is important to be able to forecast the potential endocrine toxicity of chemical mixtures that could enter aquatic environments, in many instances there is a need to determine possible effects of endocrine-active chemicals already present in complex environmental mixt...

SOLUBILITY, SORPTION AND TRANSPORT OF HYDROPHOBIC ORGANIC CHEMICALS IN COMPLEX MIXTURES

EPA Science Inventory

The research summarized in this report focuses on the effects which organic cosolvents have on the sorption and mobility of organic contaminants. This work was initiated In an effort to improve our understanding of the environmental consequences associated with complex mixtur...

Assessing chemical exposure and ecological impacts of environmental surface waters using cell culture-based metabolomic

EPA Science Inventory

Waste water treatment plants (WWTPs), as well as industrial and agricultural operations release complex mixtures of anthropogenic chemicals that negatively affect surface water quality. Previous studies have shown that exposure to such complex chemical mixtures can produce adver...

DIRECT AND PHOTOACTIVATED TOXICITY OF A COMPLEX PETROLEUM MIXTURE: A COMPARISON OF SOLUBILIZATION METHODS

EPA Science Inventory

This work addresses several issues associated with the toxicity of a complex petroleum mixture (combined kerosene/diesel and crude oil), including developmental effects and early lifestage mortality, method of solubilization, and potential photo-activated and photo-modified toxic...

Evaluation of "shotgun" proteomics for identification of biological threat agents in complex environmental matrixes: experimental simulations.

PubMed

Verberkmoes, Nathan C; Hervey, W Judson; Shah, Manesh; Land, Miriam; Hauser, Loren; Larimer, Frank W; Van Berkel, Gary J; Goeringer, Douglas E

2005-02-01

There is currently a great need for rapid detection and positive identification of biological threat agents, as well as microbial species in general, directly from complex environmental samples. This need is most urgent in the area of homeland security, but also extends into medical, environmental, and agricultural sciences. Mass-spectrometry-based analysis is one of the leading technologies in the field with a diversity of different methodologies for biothreat detection. Over the past few years, "shotgun"proteomics has become one method of choice for the rapid analysis of complex protein mixtures by mass spectrometry. Recently, it was demonstrated that this methodology is capable of distinguishing a target species against a large database of background species from a single-component sample or dual-component mixtures with relatively the same concentration. Here, we examine the potential of shotgun proteomics to analyze a target species in a background of four contaminant species. We tested the capability of a common commercial mass-spectrometry-based shotgun proteomics platform for the detection of the target species (Escherichia coli) at four different concentrations and four different time points of analysis. We also tested the effect of database size on positive identification of the four microbes used in this study by testing a small (13-species) database and a large (261-species) database. The results clearly indicated that this technology could easily identify the target species at 20% in the background mixture at a 60, 120, 180, or 240 min analysis time with the small database. The results also indicated that the target species could easily be identified at 20% or 6% but could not be identified at 0.6% or 0.06% in either a 240 min analysis or a 30 h analysis with the small database. The effects of the large database were severe on the target species where detection above the background at any concentration used in this study was impossible, though the three other microbes used in this study were clearly identified above the background when analyzed with the large database. This study points to the potential application of this technology for biological threat agent detection but highlights many areas of needed research before the technology will be useful in real world samples.

Comparison of various types of stationary phases in non-aqueous reversed-phase high-performance liquid chromatography-mass spectrometry of glycerolipids in blackcurrant oil and its enzymatic hydrolysis mixture.

PubMed

Lísa, Miroslav; Holcapek, Michal; Sovová, Helena

2009-11-20

The selection of column packing during the development of high-performance liquid chromatography method is a crucial step to achieve sufficient chromatographic resolution of analyzed species in complex mixtures. Various stationary phases are tested in this paper for the analysis of complex mixture of triacylglycerols (TGs) in blackcurrant oil using non-aqueous reversed-phase (NARP) system with acetonitrile-2-propanol mobile phase. Conventional C(18) column in the total length of 45 cm is used for the separation of TGs according to their equivalent carbon number, the number and positions of double bonds and acyl chain lengths. The separation of TGs and their more polar hydrolysis products after the partial enzymatic hydrolysis of blackcurrant oil in one chromatographic run is achieved using conventional C(18) column. Retention times of TGs are reduced almost 10 times without the loss of the chromatographic resolution using ultra high-performance liquid chromatography with 1.7 microm C(18) particles. The separation in NARP system on C(30) column shows an unusual phenomenon, because the retention order of TGs changes depending on the column temperature, which is reported for the first time. The commercial monolithic column modified with C(18) is used for the fast analysis of TGs to increase the sample throughput but at cost of low resolution.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

DART - LTQ ORBITRAP as an expedient tool for the identification of synthetic cannabinoids.

PubMed

Habala, Ladislav; Valentová, Jindra; Pechová, Iveta; Fuknová, Mária; Devínsky, Ferdinand

2016-05-01

Synthetic cannabinoids as designer drugs constitute a major problem due to their rapid increase in number and the difficulties connected with their identification in complex mixtures. DART (Direct Analysis in Real Time) has emerged as an advantageous tool for the direct and rapid analysis of complex samples by mass spectrometry. Here we report on the identification of six synthetic cannabinoids originating from seized material in various matrices, employing the combination of ambient pressure ion source DART and hybrid ion trap - LTQ ORBITRAP mass spectrometer. This report also describes the sampling techniques for the provided herbal material containing the cannabinoids, either directly as plant parts or as an extract in methanol and their influence on the outcome of the analysis. The high resolution mass spectra supplied by the LTQ ORBITRAP instrument allowed for an unambiguous assignment of target compounds. The utilized instrumental coupling proved to be a convenient way for the identification of synthetic cannabinoids in real-world samples. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Associations between complex OHC mixtures and thyroid and cortisol hormone levels in East Greenland polar bears.

PubMed

Bechshøft, T Ø; Sonne, C; Dietz, R; Born, E W; Muir, D C G; Letcher, R J; Novak, M A; Henchey, E; Meyer, J S; Jenssen, B M; Villanger, G D

2012-07-01

The multivariate relationship between hair cortisol, whole blood thyroid hormones, and the complex mixtures of organohalogen contaminant (OHC) levels measured in subcutaneous adipose of 23 East Greenland polar bears (eight males and 15 females, all sampled between the years 1999 and 2001) was analyzed using projection to latent structure (PLS) regression modeling. In the resulting PLS model, most important variables with a negative influence on cortisol levels were particularly BDE-99, but also CB-180, -201, BDE-153, and CB-170/190. The most important variables with a positive influence on cortisol were CB-66/95, α-HCH, TT3, as well as heptachlor epoxide, dieldrin, BDE-47, p,p'-DDD. Although statistical modeling does not necessarily fully explain biological cause-effect relationships, relationships indicate that (1) the hypothalamic-pituitary-adrenal (HPA) axis in East Greenland polar bears is likely to be affected by OHC-contaminants and (2) the association between OHCs and cortisol may be linked with the hypothalamus-pituitary-thyroid (HPT) axis. Copyright © 2012 Elsevier Inc. All rights reserved.

Monitoring of protease catalyzed reactions by quantitative MALDI MS using metal labeling.

PubMed

Gregorius, Barbara; Jakoby, Thomas; Schaumlöffel, Dirk; Tholey, Andreas

2013-05-21

Quantitative mass spectrometry is a powerful tool for the determination of enzyme activities as it does not require labeled substrates and simultaneously allows for the identification of reaction products. However, major restrictions are the limited number of samples which can be measured in parallel due to the need for isotope labeled internal standards. Here we describe the use of metal labeling of peptides for the setup of multiplexed enzyme activity assays. After proteolytic reaction, using the protease trypsin, remaining substrates and peptide products formed in the reaction were labeled with metal chelators complexing rare earth metal ions. Labeled peptides were quantified with high accuracy and over a wide dynamic range (at least 2 orders of magnitude) using MALDI MS in case of simple peptide mixtures or by LC-MALDI MS for complex substrate mixtures and used for the monitoring of time-dependent product formation and substrate consumption. Due to multiplexing capabilities and accuracy, the presented approach will be useful for the determination of enzyme activities with a wide range of biochemical and biotechnological applications.

Determining the Partial Pressure of Volatile Components via Substrate-Integrated Hollow Waveguide Infrared Spectroscopy with Integrated Microfluidics.

PubMed

Kokoric, Vjekoslav; Theisen, Johannes; Wilk, Andreas; Penisson, Christophe; Bernard, Gabriel; Mizaikoff, Boris; Gabriel, Jean-Christophe P

2018-04-03

A microfluidic system combined with substrate-integrated hollow waveguide (iHWG) vapor phase infrared spectroscopy has been developed for evaluating the chemical activity of volatile compounds dissolved in complex fluids. Chemical activity is an important yet rarely exploited parameter in process analysis and control. Access to chemical activity parameters enables systematic studies on phase diagrams of complex fluids, the detection of aggregation processes, etc. The instrumental approach developed herein uniquely enables controlled evaporation/permeation from a sample solution into a hollow waveguide structure and the analysis of the partial pressures of volatile constituents. For the example of a binary system, it was shown that the chemical activity may be deduced from partial pressure measurements at thermodynamic equilibrium conditions. The combined microfluidic-iHWG midinfrared sensor system (μFLUID-IR) allows the realization of such studies in the absence of any perturbations provoked by sampling operations, which is unavoidable using state-of-the-art analytical techniques such as headspace gas chromatography. For demonstration purposes, a water/ethanol mixture was investigated, and the derived data was cross-validated with established literature values at different mixture ratios. Next to perturbation-free measurements, a response time of the sensor <150 s ( t 90 ) at a recovery time <300 s ( t recovery ) has been achieved, which substantiates the utility of μFLUID-IR for future process analysis-and-control applications.

Detection of potential genetic hazards in complex environmental mixtures using plant cytogenetics and microbial mutagenesis assays. [Arsenic-contaminated groundwater and power plant fly ash extract

DOE Office of Scientific and Technical Information (OSTI.GOV)

Constantin, M J; Lowe, K; Rao, T K

1980-01-01

Solid wastes have been characterized to determine their potential hazards to humans and the environment. An arsenic-contaminated ground water sample increased the frequency of histidine revertants in Salmonella typhimurium (TA-98) at 0.025 to 5.000 ..mu..l per plate with Aroclor-induced S-9 liver microsomes. When 2.5 to 75 ..mu..l of the XAD-2 concentrate (12.5-fold, v:v) were used, the mutant frequency was increased in strains TA-98, TA-100, and TA-1537; metabolic activation was not required. Only the XAD-2 concentrate was mutagenic in the Saccharomyces cerevisiae haploid strain XL-7-10B; metabolic activation was not required. The mutagenic principal, which is not known, appears to be atmore » the limit of resolution; hence, the XAD-2 concentration is necessary to demonstrate mutagenic activity. The arsenic-contaminated ground water (0.0625 and 0.125 dilutions) and the power plant fly ash extract (undiluted) increased the frequency of bridges and fragements at anaphase in root tip cells of Hordeum. The fly ash sample was negative in the microbial assays. Results emphasize (1) the need for a battery of assays with different organisms and (2) the potential of a simple assay using plant root tip cells to detect mutagenic activity in complex environmental mixtures.« less

Toxicity assessment of heavy metal mixtures by Lemna minor L.

PubMed

Horvat, Tea; Vidaković-Cifrek, Zeljka; Orescanin, Visnja; Tkalec, Mirta; Pevalek-Kozlina, Branka

2007-10-01

The discharge of untreated electroplating wastewaters directly into the environment is a certain source of heavy metals in surface waters. Even though heavy metal discharge is regulated by environmental laws many small-scale electroplating facilities do not apply adequate protective measures. Electroplating wastewaters contain large amounts of various heavy metals (the composition depending on the facility) and the pH value often bellow 2. Such pollution diminishes the biodiversity of aquatic ecosystems and also endangers human health. The aim of our study was to observe/measure the toxic effects induced by a mixture of seven heavy metals on a bioindicator species Lemna minor L. Since artificial laboratory metal mixtures cannot entirely predict behaviour of metal mixtures nor provide us with informations relating to the specific conditions in the realistic environment we have used an actual electroplating wastewater sample discharged from a small electroplating facility. In order to obtain three more samples with the same composition of heavy metals but at different concentrations, the original electroplating wastewater sample has undergone a purification process. The purification process used was developed by Orescanin et al. [Orescanin V, Mikelić L, Lulić S, Nad K, Rubcić M, Pavlović G. Purification of electroplating wastewaters utilizing waste by-product ferrous sulphate and wood fly ash. J Environ Sci Health A 2004; 39 (9): 2437-2446.] in order to remove the heavy metals and adjust the pH value to acceptable values for discharge into the environment. Studies involving plants and multielemental waters are very rare because of the difficulty in explaining interactions of the combined toxicities. Regardless of the complexity in interpretation, Lemna bioassay can be efficiently used to assess combined effects of multimetal samples. Such realistic samples should not be avoided because they can provide us with a wide range of information which can help explain many different interactions of metals on plant growth and metabolism. In this study we have primarily evaluated classical toxicity endpoints (relative growth rate, Nfronds/Ncolonies ratio, dry to fresh weight ratio and frond area) and measured guaiacol peroxidase (GPX) activity as early indicator of oxidative stress. Also, we have measured metal accumulation in plants treated with waste ash water sample with EDXRF analysis and have used toxic unit (TU) approach to predict which metal will contribute the most to the general toxicity of the tested samples.

Sand effects on thermal barrier coatings for gas turbine engines

NASA Astrophysics Data System (ADS)

Walock, Michael; Barnett, Blake; Ghoshal, Anindya; Murugan, Muthuvel; Swab, Jeffrey; Pepi, Marc; Hopkins, David; Gazonas, George; Kerner, Kevin

Accumulation and infiltration of molten/ semi-molten sand and subsequent formation of calcia-magnesia-alumina-silicate (CMAS) deposits in gas turbine engines continues to be a significant problem for aviation assets. This complex problem is compounded by the large variations in the composition, size, and topology of natural sands, gas generator turbine temperatures, thermal barrier coating properties, and the incoming particulate's momentum. In order to simplify the materials testing process, significant time and resources have been spent in the development of synthetic sand mixtures. However, there is debate whether these mixtures accurately mimic the damage observed in field-returned engines. With this study, we provide a direct comparison of CMAS deposits from both natural and synthetic sands. Using spray deposition techniques, 7% yttria-stabilized zirconia coatings are deposited onto bond-coated, Ni-superalloy discs. Each sample is coated with a sand slurry, either natural or synthetic, and exposed to a high temperature flame for 1 hour. Test samples are characterized before and after flame exposure. In addition, the test samples will be compared to field-returned equipment. This research was sponsored by the US Army Research Laboratory, and was accomplished under Cooperative Agreement # W911NF-12-2-0019.

The Precise Measurement of Vapor-Liquid Equilibrium Properties of the CO2/Isopentane Binary Mixture, and Fitted Parameters for a Helmholtz Energy Mixture Model

NASA Astrophysics Data System (ADS)

Miyamoto, H.; Shoji, Y.; Akasaka, R.; Lemmon, E. W.

2017-10-01

Natural working fluid mixtures, including combinations of CO2, hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor-liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm3 equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO2/ethanol and CO2/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.

Matrix-assisted laser desorption/ionization-mass spectrometry of hydrophobic proteins in mixtures using formic acid, perfluorooctanoic acid, and sorbitol.

PubMed

Loo, Rachel R Ogorzalek; Loo, Joseph A

2007-02-01

Three MALDI-MS sample/matrix preparation approaches were evaluated for their ability to enhance hydrophobic protein detection from complex mixtures: (1) formic acid-based formulations, (2) perfluorooctanoic acid (PFOA) surfactant addition, and (3) sorbitol addition. While MALDI-MS of Escherichia coli cells desorbed from a standard sinapinic acid matrix displayed 94 (M + H)+ ions, 119 were observed from a formic acid-based matrix with no more than 10 common to both. Formic acid matrix revealed many lipoproteins and an 8282 m/z ion proposed to be the abundant, water-insoluble ATPase proteolipid. Among the formic acid-based cocktails examined, the slowest rate of serine/threonine formylation was found for 50% H2O/33% 2-propanol/17% formic acid. Faster formylation was observed from cocktails containing more formic acid and from mixtures including CH3CN. Sinapinic, ferulic, DHB, 4-hydroxybenzylidene malononitrile, and 2-mercaptobenzothiazole matrixes performed well in formic acid formulations. Dramatic differences in mixture spectra were also observed from PFOA/sinapinic acid, at detergent concentrations exceeding the critical micelle concentration, although these matrix cocktails proved difficult to crystallize. E. coli ions observed from these matrix conditions are listed in Tables S-1 and S-3 (Supporting Information). Similar complementarity was observed for M. acetivorans whole-cell mixtures. Including sorbitol in the sinapinic acid matrix was found to promote homogeneous crystallization and to enhance medium and higher m/z ion detection from dilute E. coli cellular mixtures.

Microbial soil community analyses for forensic science: Application to a blind test.

PubMed

Demanèche, Sandrine; Schauser, Leif; Dawson, Lorna; Franqueville, Laure; Simonet, Pascal

2017-01-01

Soil complexity, heterogeneity and transferability make it valuable in forensic investigations to help obtain clues as to the origin of an unknown sample, or to compare samples from a suspect or object with samples collected at a crime scene. In a few countries, soil analysis is used in matters from site verification to estimates of time after death. However, up to date the application or use of soil information in criminal investigations has been limited. In particular, comparing bacterial communities in soil samples could be a useful tool for forensic science. To evaluate the relevance of this approach, a blind test was performed to determine the origin of two questioned samples (one from the mock crime scene and the other from a 50:50 mixture of the crime scene and the alibi site) compared to three control samples (soil samples from the crime scene, from a context site 25m away from the crime scene and from the alibi site which was the suspect's home). Two biological methods were used, Ribosomal Intergenic Spacer Analysis (RISA), and 16S rRNA gene sequencing with Illumina Miseq, to evaluate the discriminating power of soil bacterial communities. Both techniques discriminated well between soils from a single source, but a combination of both techniques was necessary to show that the origin was a mixture of soils. This study illustrates the potential of applying microbial ecology methodologies in soil as an evaluative forensic tool. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Evaluating the Similarity of Complex Drinking-Water Disinfection By-Product Mixtures: Overview of the Issues

EPA Science Inventory

The Presentation describes the advantages and challenges of working with Whole Mixtures, discusses an exploratory approach for evaluating sufficient similarity, and challenges of applying such approaches to other environmental mixtures.

Differential effects of a complex organochlorine mixture on the proliferation of breast cancer cell lines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aube, Michel, E-mail: 4aubem@videotron.ca; Larochelle, Christian, E-mail: christian.larochelle@inspq.qc.ca; Ayotte, Pierre, E-mail: pierre.ayotte@inspq.qc.ca

2011-04-15

Organochlorine compounds (OCs) are a group of persistent chemicals that accumulate in fatty tissues with age. Although OCs has been tested individually for their capacity to induce breast cancer cell proliferation, few studies examined the effect of complex mixtures that comprise compounds frequently detected in the serum of women. We constituted such an OC mixture containing 15 different components in environmentally relevant proportions and assessed its proliferative effects in four breast cancer cell lines (MCF-7, T47D, CAMA-1, MDAMB231) and in non-cancerous CV-1 cells. We also determined the capacity of the mixture to modulate cell cycle stage of breast cancer cellsmore » and to induce estrogenic and antiandrogenic effects using gene reporter assays. We observed that low concentrations of the mixture (100x10{sup 3} and 50x10{sup 3} dilutions) stimulated the proliferation of MCF-7 cells while higher concentrations (10x10{sup 3} and 5x10{sup 3} dilutions) had the opposite effect. In contrast, the mixture inhibited the proliferation of non-hormone-dependent cell lines. The mixture significantly increased the number of MCF-7 cells entering the S phase, an effect that was blocked by the antiestrogen ICI 182,780. Low concentrations of the mixture also caused an increase in CAMA-1 cell proliferation but only in the presence estradiol and dihydrotestosterone (p<0.05 at the 50x10{sup 3} dilution). DDT analogs and polychlorinated biphenyls all had the capacity to stimulate the proliferation of CAMA-1 cells in the presence of sex steroids. Reporter gene assays further revealed that the mixture and several of its constituents (DDT analogs, aldrin, dieldrin, {beta}-hexachlorocyclohexane, toxaphene) induced estrogenic effects, whereas the mixture and several components (DDT analogs, aldrin, dieldrin and PCBs) inhibited the androgen signaling pathway. Our results indicate that the complex OC mixture increases the proliferation of MCF-7 cells due to its estrogenic potential. The proliferative effect of the mixture on CAMA-1 cells in the presence of sex steroids appears mostly due to the antiandrogenic properties of p,p'-DDE, a major constituent of the mixture. Other mixtures of contaminants that include emerging compounds of interest such as brominated flame retardants and perfluoroalkyl compounds should be tested for their capacity to induce breast cancer cell proliferation. - Research highlights: {yields} We studied effects of a complex organochlorine mixture on breast cancer cell growth. {yields} Weak xenoestrogens in the mixture stimulated the proliferation of MCF-7 cells. {yields} Antiandrogens increased the proliferation CAMA-1 cells grown with sex steroids. {yields} High concentrations of the mixture decreased the proliferation of all cell lines.« less

Isolation and genetic analysis of pure cells from forensic biological mixtures: The precision of a digital approach.

PubMed

Fontana, F; Rapone, C; Bregola, G; Aversa, R; de Meo, A; Signorini, G; Sergio, M; Ferrarini, A; Lanzellotto, R; Medoro, G; Giorgini, G; Manaresi, N; Berti, A

2017-07-01

Latest genotyping technologies allow to achieve a reliable genetic profile for the offender identification even from extremely minute biological evidence. The ultimate challenge occurs when genetic profiles need to be retrieved from a mixture, which is composed of biological material from two or more individuals. In this case, DNA profiling will often result in a complex genetic profile, which is then subject matter for statistical analysis. In principle, when more individuals contribute to a mixture with different biological fluids, their single genetic profiles can be obtained by separating the distinct cell types (e.g. epithelial cells, blood cells, sperm), prior to genotyping. Different approaches have been investigated for this purpose, such as fluorescent-activated cell sorting (FACS) or laser capture microdissection (LCM), but currently none of these methods can guarantee the complete separation of different type of cells present in a mixture. In other fields of application, such as oncology, DEPArray™ technology, an image-based, microfluidic digital sorter, has been widely proven to enable the separation of pure cells, with single-cell precision. This study investigates the applicability of DEPArray™ technology to forensic samples analysis, focusing on the resolution of the forensic mixture problem. For the first time, we report here the development of an application-specific DEPArray™ workflow enabling the detection and recovery of pure homogeneous cell pools from simulated blood/saliva and semen/saliva mixtures, providing full genetic match with genetic profiles of corresponding donors. In addition, we assess the performance of standard forensic methods for DNA quantitation and genotyping on low-count, DEPArray™-isolated cells, showing that pure, almost complete profiles can be obtained from as few as ten haploid cells. Finally, we explore the applicability in real casework samples, demonstrating that the described approach provides complete separation of cells with outstanding precision. In all examined cases, DEPArray™ technology proves to be a groundbreaking technology for the resolution of forensic biological mixtures, through the precise isolation of pure cells for an incontrovertible attribution of the obtained genetic profiles. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Improvement of the relaxation time and the order parameter of nematic liquid crystal using a hybrid alignment mixture of carbon nanotube and polyimide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hyojin; Yang, Seungbin; Lee, Ji-Hoon, E-mail: jihoonlee@jbnu.ac.kr

2014-05-12

We examined the electrooptical properties of a nematic liquid crystal (LC) sample whose substrates were coated with a mixture of carbon nanotube (CNT) and polyimide (PI). The relaxation time of the sample coated with 1.5 wt. % CNT mixture was about 35% reduced compared to the pure polyimide sample. The elastic constant and the order parameter of the CNT-mixture sample were increased and the fast relaxation of LC could be approximated to the mean-field theory. We found the CNT-mixed polyimide formed more smooth surface than the pure PI from atomic force microscopy images, indicating the increased order parameter is related to themore » smooth surface topology of the CNT-polyimide mixture.« less

Intermolecular forces in acetonitrile + ethanol binary liquid mixtures

NASA Astrophysics Data System (ADS)

Elangovan, A.; Shanmugam, R.; Arivazhagan, G.; Mahendraprabu, A.; Karthick, N. K.

2015-10-01

FTIR spectral measurements have been carried out on the binary mixtures of acetonitrile with ethanol at 1:0 (acetonitrile:ethanol), 1:1, 1:2, 1:3 and 0:1 at room temperature. DFT and isosurface calculations have been performed. The acetonitrile + ethanol binary mixtures consist of 1:1, 1:2, 1:3 and 1:4 complexes formed through both the red and blue shifting H-bonds. Inter as well as intra molecular forces are found to exist in 1:3 and 1:4 complexes.

Characterisation of metals in the electronic waste of complex mixtures of end-of-life ICT products for development of cleaner recovery technology.

PubMed

Sun, Z H I; Xiao, Y; Sietsma, J; Agterhuis, H; Visser, G; Yang, Y

2015-01-01

Recycling of valuable metals from electronic waste, especially complex mixtures of end-of-life information and communication technology (ICT) products, is of great difficulty due to their complexity and heterogeneity. One of the important reasons is the lack of comprehensive characterisation on such materials, i.e. accurate compositions, physical/chemical properties. In the present research, we focus on developing methodologies for the characterisation of metals in an industrially processed ICT waste. The morphology, particle size distribution, compositional distribution, occurrence, liberation as well as the thermo-chemical properties of the ICT waste were investigated with various characterisation techniques, including X-ray Fluorescence Spectrometry (XRF), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) with energy dispersed spectroscopy (EDS). Due to the high heterogeneity of the material, special sample preparation procedures were introduced to minimise the discrepancies during compositional analyses. As a result, a clearer overview of the ICT waste has been reached. This research provides better understanding of the extractability of each metal and improves the awareness of potential obstacles for extraction. It will lead to smarter decisions during further development of a clean and effective recovery process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Analytical Application of Flow Immunosensor in Detection of Thyroxine and Triiodothyronine in Serum.

PubMed

Wani, Tanveer A; Zargar, Seema; Majid, Salma; Darwish, Ibrahim A

2016-11-01

In this study, an immunosensor based on kinetic exclusion analysis (KinExA) was used for thyroxine (T4) and triiodothyronine (T3) estimation. A KinExA™ 3200 instrument was used for this analysis, which is an automated flow fluorimeter designed to separate free unbound antibody binding sites in reaction mixtures of antibody, antigen, and antibody-antigen complex. A T3-BSA- and T4-BSA-coated polymethyl methacrylate (PMMA) bead microcolumn is generated inside the flow cell of the instrument. A sample mixture containing T3 and T4 with their respective monoclonal antibodies and their complexes are drawn past the microbead column. The unbound T3 or T4 monoclonal antibody binding sites are captured by their respective T3 and T4 antigens coated on the PMMA beads as bovine serum albumin conjugates. Fluorescently labeled secondary antibodies bind to the T3 or T4 antigen-antibody complex to generate fluorescence intensity for analysis. The limit of detection for the T3 and T4 assays was found to be 0.06 and 1.9 ng mL -1 with acceptable precision values. The convenience of the automated KinExA format may be valuable in medical diagnostic laboratories.

Combining Toxicological and Chemical Characterization of Complex Mixtures to Understand the Impact of the Unknown Fraction

EPA Science Inventory

Toxicological assessment of adverse health outcomes associated with exposure to complex mixtures provides an integrated response of the organism (or in vitro test system) that accounts for additivity among the components (both dose and response) as well as any greater than or les...

Integrating multiple lines of evidence to assess biological hazards of complex mixtures: A case study in the Maumee River

EPA Science Inventory

Product Description:Due to technological improvements, increasing numbers of chemical contaminants are being detected in surface waters nation-wide, including the Great Lakes. Methods are needed to understand what impact these complex mixtures of contaminants can have on aquatic ...

The Developmental Effects Of A Municipal Wastewater Effluent On The Northern Leopard Frog, Rana pipiens

EPA Science Inventory

Wastewater effluents are complex mixtures containing a variety of anthropogenic compounds, many of which are known endocrine disruptors. In order to characterize the development and behavorial effects of such a complex mixture, northern leopard frogs, Rana pipiens, were e...

Experimental design-based strategy for the simulation of complex gaseous mixture spectra to detect drug precursors

NASA Astrophysics Data System (ADS)

Calderisi, Marco; Ulrici, Alessandro; Pigani, Laura; Secchi, Alberto; Seeber, Renato

2012-09-01

The EU FP7 project CUSTOM (Drugs and Precursor Sensing by Complementing Low Cost Multiple Techniques) aims at developing a new sensing system for the detection of drug precursors in gaseous samples, which includes an External Cavity-Quantum Cascade Laser Photo-Acoustic Sensor (EC-QCLPAS) that is in the final step of realisation. Thus, a simulation based on FT-IR literature spectra has been accomplished, where the development of a proper strategy for the design of the composition of the environment, as much as possible realistic and representative of different scenarios, is of key importance. To this aim, an approach based on the combination of signal processing and experimental design techniques has been developed. The gaseous mixtures were built by adding the considered 4 drug precursor (target) species to the gases typically found in atmosphere, taking also into account possible interfering species. These last chemicals were selected considering custom environments (20 interfering chemical species), whose concentrations have been inferred from literature data. The spectra were first denoised by means of a Fast Wavelet Transform-based algorithm; then, a procedure based on a sigmoidal transfer function was developed to multiply the pure components spectra by the respective concentration values, in a way to correctly preserve background intensity and shape, and to operate only on the absorption bands. The noise structure of the EC-QCLPAS was studied using sample spectra measured with a prototype instrument, and added to the simulated mixtures. Finally a matrix containing 5000 simulated spectra of gaseous mixtures was built up.

Using machine learning tools to model complex toxic interactions with limited sampling regimes.

PubMed

Bertin, Matthew J; Moeller, Peter; Guillette, Louis J; Chapman, Robert W

2013-03-19

A major impediment to understanding the impact of environmental stress, including toxins and other pollutants, on organisms, is that organisms are rarely challenged by one or a few stressors in natural systems. Thus, linking laboratory experiments that are limited by practical considerations to a few stressors and a few levels of these stressors to real world conditions is constrained. In addition, while the existence of complex interactions among stressors can be identified by current statistical methods, these methods do not provide a means to construct mathematical models of these interactions. In this paper, we offer a two-step process by which complex interactions of stressors on biological systems can be modeled in an experimental design that is within the limits of practicality. We begin with the notion that environment conditions circumscribe an n-dimensional hyperspace within which biological processes or end points are embedded. We then randomly sample this hyperspace to establish experimental conditions that span the range of the relevant parameters and conduct the experiment(s) based upon these selected conditions. Models of the complex interactions of the parameters are then extracted using machine learning tools, specifically artificial neural networks. This approach can rapidly generate highly accurate models of biological responses to complex interactions among environmentally relevant toxins, identify critical subspaces where nonlinear responses exist, and provide an expedient means of designing traditional experiments to test the impact of complex mixtures on biological responses. Further, this can be accomplished with an astonishingly small sample size.

Zur chemie der marsoberfläche

USGS Publications Warehouse

Keil, Klaus; Clark, Benton C.; Baird, A.K.; Toulmin, Priestley; Rose, Harry J.

1978-01-01

Analyses of 13 samples of Martian surface materials with the Viking X-ray fluorescence spectrometers show SiO2 similar to that of terrestrial mafic rocks, whereas Fe2O3, Cl, and S are higher and Al2O3, K2O, Rb, Sr, Y, and Zr are lower. Low totals suggest presence of CO2, H2O, and Na2O. Duricrust fragments are higher in S than fines, but samples from both landing sites are surprisingly similar. We suggest that Martian surface materials are aeolian deposits of complex mixtures of weathering products of maficultramafic rocks, possibly consisting of iron-rich clays, sulfates, iron oxides, carbonates, and chlorides.

Accurate Identification of Unknown and Known Metabolic Mixture Components by Combining 3D NMR with Fourier Transform Ion Cyclotron Resonance Tandem Mass Spectrometry.

PubMed

Wang, Cheng; He, Lidong; Li, Da-Wei; Bruschweiler-Li, Lei; Marshall, Alan G; Brüschweiler, Rafael

2017-10-06

Metabolite identification in metabolomics samples is a key step that critically impacts downstream analysis. We recently introduced the SUMMIT NMR/mass spectrometry (MS) hybrid approach for the identification of the molecular structure of unknown metabolites based on the combination of NMR, MS, and combinatorial cheminformatics. Here, we demonstrate the feasibility of the approach for an untargeted analysis of both a model mixture and E. coli cell lysate based on 2D/3D NMR experiments in combination with Fourier transform ion cyclotron resonance MS and MS/MS data. For 19 of the 25 model metabolites, SUMMIT yielded complete structures that matched those in the mixture independent of database information. Of those, seven top-ranked structures matched those in the mixture, and four of those were further validated by positive ion MS/MS. For five metabolites, not part of the 19 metabolites, correct molecular structural motifs could be identified. For E. coli, SUMMIT MS/NMR identified 20 previously known metabolites with three or more 1 H spins independent of database information. Moreover, for 15 unknown metabolites, molecular structural fragments were determined consistent with their spin systems and chemical shifts. By providing structural information for entire metabolites or molecular fragments, SUMMIT MS/NMR greatly assists the targeted or untargeted analysis of complex mixtures of unknown compounds.

Near-infrared reflectance spectra of mixtures of kaolin-group minerals: Use in clay mineral studies

USGS Publications Warehouse

Crowley, James K.; Vergo, Norma

1988-01-01

Near-infrared (NIR) reflectance spectra for mixtures of ordered kaolinite and ordered dickite have been found to simulate the spectral response of disordered kaolinite. The amount of octahedral vacancy disorder in nine disordered kaolinite samples was estimated by comparing the sample spectra to the spectra of reference mixtures. The resulting estimates are consistent with previously published estimates of vacancy disorder for similar kaolin minerals that were modeled from calculated X-ray diffraction patterns. The ordered kaolinite and dickite samples used in the reference mixtures were carefully selected to avoid undesirable particle size effects that could bias the spectral results.NIR spectra were also recorded for laboratory mixtures of ordered kaolinite and halloysite to assess whether the spectra could be potentially useful for determining mineral proportions in natural physical mixtures of these two clays. Although the kaolinite-halloysite proportions could only be roughly estimated from the mixture spectra, the halloysite component was evident even when halloysite was present in only minor amounts. A similar approach using NIR spectra for laboratory mixtures may have applications in other studies of natural clay mixtures.

Identification of PAH Isomeric Structure in Cosmic Dust Analogs: The AROMA Setup

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sabbah, Hassan; Bonnamy, Anthony; Joblin, Christine

We developed a new analytical experimental setup called AROMA (Astrochemistry Research of Organics with Molecular Analyzer) that combines laser desorption/ionization techniques with ion trap mass spectrometry. We report here on the ability of the apparatus to detect aromatic species in complex materials of astrophysical interest and characterize their structures. A limit of detection of 100 femto-grams has been achieved using pure polycyclic aromatic hydrocarbon (PAH) samples, which corresponds to 2 × 10{sup 8} molecules in the case of coronene (C{sub 24}H{sub 12}). We detected the PAH distribution in the Murchison meteorite, which is made of a complex mixture of extraterrestrialmore » organic compounds. In addition, collision induced dissociation experiments were performed on selected species detected in Murchison, which led to the first firm identification of pyrene and its methylated derivatives in this sample.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xing; Ibrahim, Yehia M.; Chen, Tsung-Chi

We report the first evaluation of a platform coupling a high speed field asymmetric ion mobility spectrometry microchip (µFAIMS) with drift tube ion mobility and mass spectrometry (IMS-MS). The µFAIMS/IMS-MS platform was used to analyze biological samples and simultaneously acquire multidimensional information of detected features from the measured FAIMS compensation fields and IMS drift times, while also obtaining accurate ion masses. These separations thereby increase the overall separation power, resulting increased information content, and provide more complete characterization of more complex samples. The separation conditions were optimized for sensitivity and resolving power by the selection of gas compositions and pressuresmore » in the FAIMS and IMS separation stages. The resulting performance provided three dimensional separations, benefitting both broad complex mixture studies and targeted analyses by e.g. improving isomeric separations and allowing detection of species obscured by “chemical noise” and other interfering peaks.« less

A competitive binding model predicts the response of mammalian olfactory receptors to mixtures

NASA Astrophysics Data System (ADS)

Singh, Vijay; Murphy, Nicolle; Mainland, Joel; Balasubramanian, Vijay

Most natural odors are complex mixtures of many odorants, but due to the large number of possible mixtures only a small fraction can be studied experimentally. To get a realistic understanding of the olfactory system we need methods to predict responses to complex mixtures from single odorant responses. Focusing on mammalian olfactory receptors (ORs in mouse and human), we propose a simple biophysical model for odor-receptor interactions where only one odor molecule can bind to a receptor at a time. The resulting competition for occupancy of the receptor accounts for the experimentally observed nonlinear mixture responses. We first fit a dose-response relationship to individual odor responses and then use those parameters in a competitive binding model to predict mixture responses. With no additional parameters, the model predicts responses of 15 (of 18 tested) receptors to within 10 - 30 % of the observed values, for mixtures with 2, 3 and 12 odorants chosen from a panel of 30. Extensions of our basic model with odorant interactions lead to additional nonlinearities observed in mixture response like suppression, cooperativity, and overshadowing. Our model provides a systematic framework for characterizing and parameterizing such mixing nonlinearities from mixture response data.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

The Blue-Shift of Photoluminescence Spectra of Zinc Complexes of 8-Hydroxyquinoline by Addition of ZnO Nanoparticles

NASA Astrophysics Data System (ADS)

Keshmiri, Laleh; Elahi, Seyed Mohammad; Jafari, Mohammad Reza; Jafari, Fatemeh; Parhizgar, Sara Sadat

2018-02-01

In this research, an organo-metallic complex based on zinc ions (Znq2), which can be used in organic light-emitting diodes, was investigated. Nanoparticles of ZnO were produced and added to the Znq2 complex. By means of x-ray diffraction, the structure of Znq2 complex and ZnO nanoparticles and the energy levels of them were determined from cyclic-voltammetry analysis. From thermal gravimetric studies, it was found that the complexes have a high thermal stability in the air atmosphere. The purity of samples was confirmed by Fourier transform infrared spectroscopy. The maximum intensity of the photoluminescence spectrum of Znq2 occurred at 565 nm and showed a blue shift to 511 nm by adding ZnO nanoparticles to the Znq2 complex. The optical and electrical properties of the Znq2 and the mixture of Znq2 and ZnO nano powders were studied in order to find any possible applications in organic light emitting devices.

Inhibition of cholinesterase activity by extracts, fractions and compounds from Calceolaria talcana and C. integrifolia (Calceolariaceae: Scrophulariaceae).

PubMed

Cespedes, Carlos L; Muñoz, Evelyn; Salazar, Juan R; Yamaguchi, Lydia; Werner, Enrique; Alarcon, Julio; Kubo, Isao

2013-12-01

Extracts, fractions and compounds from Calceolaria talcana and C. integrifolia exhibited strong inhibitory effects of the activity of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes using the in vitro Ellman's method. The most active samples were from the ethyl acetate extract, which caused a mixed-type inhibition against AChE (69.8% and 79.5% at 100 and 200 μg/ml, respectively) and against BChE (98.5% and 99.8% at 100 and 200 μg/ml, respectively) and its major components verbascoside 8 (50.9% and 70.0% at 200 μg/ml, against AChE and BChE, respectively), martynoside 9, and fraction F-7 (which corresponds to a mixture of 8, 9, and other phenylethanoids and phenolics that remain unidentified) (80.2% and 85.3% at 100 and 200 μg/ml, against AChE, respectively and 99.1% and 99.7% at 100 and 200 μg/ml, against BChE, respectively) inhibited the acetylcholinesterase enzyme competitively. The most polar fraction F-5 from n-hexane extract (a mixture of naphthoquinones: 2-hydroxy-3-(1,1-dimethylallyl-1,4-naphthoquinone) 6, α-dunnione 7 and other polar compounds that remain unidentified) showed a mixed-type inhibition (71.5% and 72.1% against AChE and BChE at 200 μg/ml, respectively). Finally, the methanol-soluble residue presented a complex, mixed-type inhibition (39.9% and 67.9% against AChE and BChE at 200 μg/ml, respectively). The mixture F-3 with diterpenes was obtained from the n-hexane extract: (1,10-cyclopropyl-9-epi-ent-isopimarol) 1, 19-α-hydroxy-abietatriene 2, and F-4 a mixture of triterpenes α-lupeol 3, β-sitosterol 4, ursolic acid 5 together with a complex mixture of terpenes that did not show activity. In summary, extracts and natural compounds from C. talcana and C. integrifolia were isolated, identified and characterized as cholinesterase inhibitors.

Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.

PubMed

Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana

2016-12-01

Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

Proteomics-based compositional analysis of complex cellulase-hemicellulase mixtures.

PubMed

Chundawat, Shishir P S; Lipton, Mary S; Purvine, Samuel O; Uppugundla, Nirmal; Gao, Dahai; Balan, Venkatesh; Dale, Bruce E

2011-10-07

Efficient deconstruction of cellulosic biomass to fermentable sugars for fuel and chemical production is accomplished by a complex mixture of cellulases, hemicellulases, and accessory enzymes (e.g., >50 extracellular proteins). Cellulolytic enzyme mixtures, produced industrially mostly using fungi like Trichoderma reesei, are poorly characterized in terms of their protein composition and its correlation to hydrolytic activity on cellulosic biomass. The secretomes of commercial glycosyl hydrolase-producing microbes was explored using a proteomics approach with high-throughput quantification using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Here, we show that proteomics-based spectral counting approach is a reasonably accurate and rapid analytical technique that can be used to determine protein composition of complex glycosyl hydrolase mixtures that also correlates with the specific activity of individual enzymes present within the mixture. For example, a strong linear correlation was seen between Avicelase activity and total cellobiohydrolase content. Reliable, quantitative and cheaper analytical methods that provide insight into the cellulosic biomass degrading fungal and bacterial secretomes would lead to further improvements toward commercialization of plant biomass-derived fuels and chemicals.

Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures

NASA Technical Reports Server (NTRS)

Smith, Karen E.; Callahan, Michael P.; Cleaves, Henderson J.; Dworkin, Jason P.; House, Christopher H.

2011-01-01

A long standing question in the field of prebiotic chemistry is the origin of the genetic macromolecules DNA and RNA. DNA and RNA have very complex structures with repeating subunits of nucleotides, which are composed of nucleobases (nitrogen heterocycles) connected to sugar-phosphate. Due to the instability of some nucleobases (e.g. cytosine), difficulty of synthesis and instability of D-ribose, and the likely scarcity of polyphosphates necessary for the modern nucleotides, alternative nucleotides have been proposed for constructing the first genetic material. Thus, we have begun to investigate the chemistry of nitrogen heterocycles in plausible, complex prebiotic mixtures in an effort to identify robust reactions and potential alternative nucleotides. We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2, and reacted it with four nitrogen heterocycles: uracil, 5-hydroxymethyluracil, guanine, and isoxanthopterin (2-amino-4,7-dihydroxypteridine). The products of the reaction between the spark mixture and each nitrogen heterocycle were characterized by liquid chromatography coupled to UV spectroscopy and Orbitrap mass spectrometry. We found that the reaction between the spark mixtUl'e and isoxanthopterin formed one major product, which was a cyanide adduct. 5-hydroxymethyluracil also reacted with the spark mixture to form a cyanide adduct, uracil-5-acetonitrile, which has been synthesized previously by reacting HCN with S-hydroxymethyluracil. Unlike isoxanthopterin, the chromatogram of the 5-hydroxymethyluracil reaction was much more complex with multiple products including spark-modified dimers. Additionally, we observed that HMU readily self-polymerizes in solution to a variety of oligomers consistent with those suggested by Cleaves. Guanine and uracil, the biological nucleobases, did not react with the spark mixture, even at high temperature (100 C). This suggests that there are alternative nucleobases which are more reactive under prebiotic conditions and may have been involved in producing precursor nucleotides.

Analysis of Proteins, Protein Complexes, and Organellar Proteomes Using Sheathless Capillary Zone Electrophoresis - Native Mass Spectrometry

NASA Astrophysics Data System (ADS)

Belov, Arseniy M.; Viner, Rosa; Santos, Marcia R.; Horn, David M.; Bern, Marshall; Karger, Barry L.; Ivanov, Alexander R.

2017-12-01

Native mass spectrometry (MS) is a rapidly advancing field in the analysis of proteins, protein complexes, and macromolecular species of various types. The majority of native MS experiments reported to-date has been conducted using direct infusion of purified analytes into a mass spectrometer. In this study, capillary zone electrophoresis (CZE) was coupled online to Orbitrap mass spectrometers using a commercial sheathless interface to enable high-performance separation, identification, and structural characterization of limited amounts of purified proteins and protein complexes, the latter with preserved non-covalent associations under native conditions. The performance of both bare-fused silica and polyacrylamide-coated capillaries was assessed using mixtures of protein standards known to form non-covalent protein-protein and protein-ligand complexes. High-efficiency separation of native complexes is demonstrated using both capillary types, while the polyacrylamide neutral-coated capillary showed better reproducibility and higher efficiency for more complex samples. The platform was then evaluated for the determination of monoclonal antibody aggregation and for analysis of proteomes of limited complexity using a ribosomal isolate from E. coli. Native CZE-MS, using accurate single stage and tandem-MS measurements, enabled identification of proteoforms and non-covalent complexes at femtomole levels. This study demonstrates that native CZE-MS can serve as an orthogonal and complementary technique to conventional native MS methodologies with the advantages of low sample consumption, minimal sample processing and losses, and high throughput and sensitivity. This study presents a novel platform for analysis of ribosomes and other macromolecular complexes and organelles, with the potential for discovery of novel structural features defining cellular phenotypes (e.g., specialized ribosomes). [Figure not available: see fulltext.

Mixture and method for simulating soiling and weathering of surfaces

DOEpatents

Sleiman, Mohamad; Kirchstetter, Thomas; Destaillats, Hugo; Levinson, Ronnen; Berdahl, Paul; Akbari, Hashem

2018-01-02

This disclosure provides systems, methods, and apparatus related to simulated soiling and weathering of materials. In one aspect, a soiling mixture may include an aqueous suspension of various amounts of salt, soot, dust, and humic acid. In another aspect, a method may include weathering a sample of material in a first exposure of the sample to ultraviolet light, water vapor, and elevated temperatures, depositing a soiling mixture on the sample, and weathering the sample in a second exposure of the sample to ultraviolet light, water vapor, and elevated temperatures.

ANALYTICAL METHOD FOR THE ABSORPTIOMETRIC DETERMINATION OF BORON IN AMMONIA SOLUTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1962-01-01

ABS>A weighed sample is evaporated to dryness with caustic soda solution on a water bath. The residue is dissolved by addlng a solution of curcumin in acetic acid. After adding a mixture of H/sub 2/SO/sub 4/ and acetic acid, the solution is allowed to stand at room temperature for 15 minutes. The solution is then diluted to 100 ml with ethanol, and a portion is filtered and measured absorptiometrically on the residue as the curcumin complex. (P.C.H.)

ORD'S FOUR LAB STUDY: TOXICOLOGICAL AND CHEMICAL EVALUATION OF COMPLEX MIXTURES OF DRINKING WATER DISINFECTION BY-PRODUCTS

EPA Science Inventory

Disinfectants used in the production of drinking water react with naturally occurring organic and inorganic material in the source water to produce disinfection by-products (DBPs). Humans are exposed daily to a complex mixture of DBPs via oral, dermal, and inhalation routes. To ...

ION COMPOSITION ELUCIDATION (ICE): A HIGH RESOLUTION MASS SPECTROMETRIC TECHNIQUE FOR IDENTIFYING COMPOUNDS IN COMPLEX MIXTURES

EPA Science Inventory

When tentatively identifying compounds in complex mixtures using mass spectral libraries, multiple matches or no plausible matches due to a high level of chemical noise or interferences can occur. Worse yet, most analytes are not in the libraries. In each case, Ion Composition El...

On-line preconcentration of fluorescent derivatives of catecholamines in cerebrospinal fluid using flow-gated capillary electrophoresis.

PubMed

Zhang, Qiyang; Gong, Maojun

2016-06-10

Flow-gated capillary electrophoresis (CE) coupled with microdialysis has become an important tool for in vivo bioanalytical measurements because it is capable of performing rapid and efficient separations of complex biological mixtures thus enabling high temporal resolution in chemical monitoring. However, the limit of detection (LOD) is often limited to a micro- or nano-molar range while many important target analytes have picomolar or sub-nanomolar levels in brain and other tissues. To enhance the capability of flow-gated CE for catecholamine detection, a novel and simple on-line sample preconcentration method was developed exclusively for fluorescent derivatives of catecholamines that were fluorogenically derivatized with naphthalene-2,3-dicarboxaldehyde (NDA) in the presence of cyanide. The effective preconcentration coupled with the sensitive laser-induced fluorescence (LIF) detection lowered the LOD down to 20pM for norepinephrine (NE) and 50pM for dopamine (DA) at 3-fold of S/N ratio, and the signal enhancement was estimated to be over 100-fold relative to normal injection when standard analytes were dissolved in artificial cerebrospinal fluid (aCSF). The basic focusing principle is novel since the sample plug contains borate while the background electrolyte (BGE) is void of borate. This strategy took advantage of the complexation between diols and borate, through which one negative charge was added to the complex entity. The sample derivatization mixture was electrokinetically injected into a capillary via the flow-gated injection, and then NE and DA derivatives were selectively focused to a narrow zone by the reversible complexation. Separation of NE and DA derivatives was executed by incoming surfactants of cholate and deoxycholate mixed in the front BGE plug. This on-line preconcentration method was finally applied to the detection of DA in rat cerebrospinal fluid (CSF) via microdialysis and on-line derivatization. It is anticipated that the method would be valuable for in vivo monitoring of DA and NE in various brain regions of live animals on flow-gated CE or microchip platforms. Published by Elsevier B.V.

Enabling the identification, quantification, and characterization of organics in complex mixtures to understand atmospheric aerosols

NASA Astrophysics Data System (ADS)

Isaacman, Gabriel Avram

Particles in the atmosphere are known to have negative health effects and important but highly uncertain impacts on global and regional climate. A majority of this particulate matter is formed through atmospheric oxidation of naturally and anthropogenically emitted gases to yield highly oxygenated secondary organic aerosol (SOA), an amalgamation of thousands of individual chemical compounds. However, comprehensive analysis of SOA composition has been stymied by its complexity and lack of available measurement techniques. In this work, novel instrumentation, analysis methods, and conceptual frameworks are introduced for chemically characterizing atmospherically relevant mixtures and ambient aerosols, providing a fundamentally new level of detailed knowledge on their structures, chemical properties, and identification of their components. This chemical information is used to gain insights into the formation, transformation and oxidation of organic aerosols. Biogenic and anthropogenic mixtures are observed in this work to yield incredible complexity upon oxidation, producing over 100 separable compounds from a single precursor. As a first step toward unraveling this complexity, a method was developed for measuring the polarity and volatility of individual compounds in a complex mixture using two-dimensional gas chromatography, which is demonstrated in Chapter 2 for describing the oxidation of SOA formed from a biogenic compound (longifolene: C15H24). Several major products and tens of substantial minor products were produced, but none could be identified by traditional methods or have ever been isolated and studied in the laboratory. A major realization of this work was that soft ionization mass spectrometry could be used to identify the molecular mass and formula of these unidentified compounds, a major step toward a comprehensive description of complex mixtures. This was achieved by coupling gas chromatography to high resolution time-of-flight mass spectrometry with vacuum ultraviolet (VUV) photo-ionization. Chapters 3 and 4 describe this new analytical technique and its initial application to determine the structures of unknown compounds and formerly unresolvable mixtures, including a complete description of the chemical composition of two common petroleum products related to anthropogenic emissions: diesel fuel and motor oil. The distribution of hydrocarbon isomers in these mixtures - found to be mostly of branched, cyclic, and saturated -- is described with unprecedented detail. Instead of measuring average bulk aerosol properties, the methods developed and applied in this work directly measure the polarity, volatility, and structure of individual components to allow a mechanistic understanding of oxidation processes. Novel characterizations of these complex mixtures are used to elucidate the role of structure and functionality in particle-phase oxidation, including in Chapter 4 the first measurements of relative reaction rates in a complex hydrocarbon particle. Molecular structure is observed to influence particle-phase oxidation in unexpected and important ways, with cyclization decreasing reaction rates by ~30% and branching increasing reaction rates by ~20-50%. The observed structural dependence is proposed to result in compositional changes in anthropogenic organic aerosol downwind of urban areas, which has been confirmed in subsequent work by applying the techniques described here. Measurement of organic aerosol components is extended to ambient environments through the development of instrumentation with the unprecedented capability to measure hourly concentrations and gas/particle partitioning of individual highly oxygenated organic compounds in the atmosphere. Chapters 5 and 6 describe development of new procedures and hardware for the calibration and analysis of oxygenates using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG), a custom instrument for in situ quantification of gas- and particle-phase organic compounds in the atmosphere. High time resolution measurement of oxygenated compounds is achieved through a reproducible and quantitative methodology for in situ "derivatization" -- replacing highly polar functional groups that cannot be analyzed by traditional gas chromatography with less polar groups. Implementation of a two-channel sampling system for the simultaneous collection of particle-phase and total gas-plus-particle phase samples allows for the first direct measurements of gas/particle partitioning in the atmosphere, significantly advancing the study of atmospheric composition and variability, as well as the processes governing condensation and re-volatilization. This work presents the first in situ measurements of a large suite of highly oxygenated biogenic oxidation products in both the gas- and particle-phase. Isoprene, the most ubiquitous biogenic emission, oxidizes to form 2-methyltetrols and C5 alkene triols, while α-pinene, the most common monoterpene, forms pinic, pinonic, hydroxyglutaric, and other acids. These compounds are reported in Chapter 7 with unprecedented time resolution and are shown for the first time to have a large gas-phase component, contrary to typical assumptions. Hourly comparisons of these products with anthropogenic aerosol components elucidate the interaction of human and natural emissions at two rural sites: the southeastern, U.S. and Amazonia, Brazil. Anthropogenic influence on SOA formation is proposed to occur through the increase in liquid water caused by anthropogenic sulfate. Furthermore, these unparalleled observations of gas/particle partitioning of biogenic oxidation products demonstrate that partitioning of oxygenates is unexpectedly independent of volatility: many volatile, highly oxygenated compounds have a large particle-phase component that is poorly described by traditional models. These novel conclusions are reached in part by applying the new frameworks developed in previous chapters to understand the properties of unidentified compounds, demonstrating the importance of detailed characterization of atmospheric organic mixtures. Comprehensive analysis of anthropogenic and biogenic emissions and oxidation product mixtures is coupled in this work with high time-resolution measurement of individual organic components to yield significant insights into the transformations of organic aerosols. Oxidation chemistry is observed in both laboratory and field settings to depend on molecular properties, volatility, and atmospheric composition. However, this work demonstrates that these complex processes can be understood through the quantification of individual known and unidentified compounds, combined with their classification into descriptive frameworks.

Tailoring of the titanium surface by immobilization of heparin/fibronectin complexes for improving blood compatibility and endothelialization: an in vitro study.

PubMed

Li, Guicai; Yang, Ping; Liao, Yuzhen; Huang, Nan

2011-04-11

To improve the blood compatibility and endothelialization simultaneously and to ensure the long-term effectiveness of the cardiovascular implants, we developed a surface modification method, enabling the coimmobilization of biomolecules to metal surfaces. In the present study, a heparin and fibronectin mixture (Hep/Fn) covalently immobilized on a titanium (Ti) substrate for biocompatibility was investigated. Different systems [N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide and N-hydroxysuccinimide, electrostatic] were used for the formation of Hep/Fn layers. Atomic force microscopy (AFM) showed that the roughness of the silanized Ti surface decreased after the immobilization of Hep/Fn. Fourier transform infrared spectroscopy (FTIR), Toluidine Blue O (TBO) test, and immunochemistry assay showed that Hep/Fn mixture was successfully immobilized on Ti surface. Blood compatibility tests (hemolysis rate, APTT, platelet adhesion, fibrinogen conformational change) showed that the coimmobilized films of Hep/Fn mixture reduced blood hemolysis rate, prolonged blood coagulation time, reduced platelets activation and aggregation, and induced less fibrinogen conformational change compared with a bare Ti surface. Endothelial cell (EC) seeding showed more EC with better morphology on pH 4 samples than on pH 7 and EDC/NHS samples, which showed rounded and aggregated cells. Systematic evaluation showed that the pH 4 samples also had much better blood compatibility. All results suggest that the coimmobilized films of Hep/Fn can confer excellent antithrombotic properties and with good endothelialization. We envisage that this method will provide a potential and effective solution for the surface modification of cardiovascular implant materials.

Distribution, fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes.

PubMed

Riefer, Patrick; Klausmeyer, Timm; Schäffer, Andreas; Schwarzbauer, Jan; Schmidt, Burkhard

2011-01-01

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.

Phase modulated 2D HSQC-TOCSY for unambiguous assignment of overlapping spin systems

NASA Astrophysics Data System (ADS)

Singh, Amrinder; Dubey, Abhinav; Adiga, Satish K.; Atreya, Hanudatta S.

2018-01-01

We present a new method that allows one to unambiguously resolve overlapping spin systems often encountered in biomolecular systems such as peptides and proteins or in samples containing a mixture of different molecules such as in metabolomics. We address this problem using the recently proposed phase modulation approach. By evolving the 1H chemical shifts in a conventional two dimensional (2D) HSQC-TOCSY experiment for a fixed delay period, the phase/intensity of set of cross peaks belonging to one spin system are modulated differentially relative to those of its overlapping counterpart, resulting in their discrimination and recognition. The method thus accelerates the process of identification and resonance assignment of individual compounds in complex mixtures. This approach facilitated the assignment of molecules in the embryo culture medium used in human assisted reproductive technology.

Photoacoustic study on the possible components of total suspended particles

NASA Astrophysics Data System (ADS)

Wang, Xidong; Huang, Zuohua; Tang, Zhilie

2006-02-01

Total suspended particles (TSP) are one of the main atmospheric pollutants. The ingredients are very complex, mainly including black carbon (C),organic compound, inorganic compound and biologic component, which will do great harm to human's health. During environmental monitoring, the airborne suspended particle always is an index for evaluating the quality of atmosphere. In this article, possible mixture of TSP is proposed to determine its ingredients and content by photoacoustic spectroscopy. The normalized photoacoustic (PA) signal of the sulfur powder, mixtures of sulfur and black carbon in different proportions are obtained respectively. Simulation with linear equation says that the PA signal has a certain relationship with the content of sample. The normalized PA spectroscopy of various materials is acquired via examining the sample of the powder of cupric sulfate mixed with nitro compound (2, 5 -methoxybenzoic-4nitro-dehyde), Portland cement, residual particles of automobile exhaust pipe, ash of power plant's stocks. The experimental results have important reference value to the practical analysis of TSP, it also provides new possible methodology to the environmental monitoring.

Environmental tobacco smoke aerosol in non-smoking households of patients with chronic respiratory diseases

NASA Astrophysics Data System (ADS)

Chalbot, Marie-Cecile; Vei, Ino-Christina; Lianou, Maria; Kotronarou, Anastasia; Karakatsani, Anna; Katsouyanni, Klea; Hoek, Gerard; Kavouras, Ilias G.

2012-12-01

Fine particulate matter samples were collected in an urban ambient fixed site and, outside and inside residencies in Athens greater area, Greece. n-Alkanes, iso/anteiso-alkanes and polycyclic aromatic hydrocarbons (PAHs) were identified by gas chromatography and mass spectrometry. The values of concentration diagnostic ratios indicated a mixture of vehicular emissions, fuel evaporation, oil residues and environmental tobacco smoke (ETS) in outdoor and indoor samples. Particulate iso/anteiso-alkanes, specific tracers of ETS, were detected in both non-smoking and smoking households. The indoor-to-outdoor ratios of particulate iso/anteiso-alkanes and unresolved complex mixture (a tracer of outdoor air pollution) in non-smoking households were comparable to the measured air exchange rate. This suggested that penetration of outdoor air was solely responsible for the detection of tobacco smoke particulate tracers in indoor non-smoking environments. Overall, residential outdoor concentrations accounted for a large fraction (from 25 up to 79%) of indoor aliphatic and polyaromatic hydrocarbons. Open windows/doors and the operation of an air condition unit yielded also in higher indoor concentrations than those measured outdoors.

Occurrence and sources of natural and anthropogenic lipid tracers in surface soils from arid urban areas of Saudi Arabia.

PubMed

Rushdi, Ahmed I; Al-Mutlaq, Khalid F; El-Mubarak, Aarif H; Al-Saleh, Mohammed A; El-Otaibi, Mubarak T; Ibrahim, Sami M M; Simoneit, Bernd R T

2016-01-01

Soil particles contain a variety of natural and anthropogenic organic components, and in urban areas can be considered as local collectors of pollutants. Surface soil samples were taken from ten urban areas in Riyadh during early winter of 2007. They were extracted with dichloromethane-methanol mixture and the extracts were analyzed by gas chromatography-mass spectrometry. The major compounds were unresolved complex mixture (UCM), plasticizers, n-alkanes, carbohydrates, n-alkanoic acids, hopanes, n-alkanols, and sterols. Vegetation detritus was the major natural source of organic compounds (24.0 ± 15.7%) in samples from areas with less human activities and included n-alkanes, n-alkanoic acids, n-alkanols, sterols and carbohydrates. Vehicular emission products and discarded plastics were the major anthropogenic sources in the soil particles (53.3 ± 21.3% and 22.7 ± 10.7%, respectively). The anthropogenic tracers were UCM, plasticizers, n-alkanes, hopanes and traces of steranes. Vegetation and human activities control the occurrence and distribution of natural and anthropogenic extractable organic matter in this arid urban area. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method for Hot Real-Time Sampling of Gasification Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pomeroy, Marc D

The Thermochemical Process Development Unit (TCPDU) at the National Renewable Energy Laboratory (NREL) is a highly instrumented half-ton/day pilot scale plant capable of demonstrating industrially relevant thermochemical technologies from lignocellulosic biomass conversion, including gasification. Gasification creates primarily Syngas (a mixture of Hydrogen and Carbon Monoxide) that can be utilized with synthesis catalysts to form transportation fuels and other valuable chemicals. Biomass derived gasification products are a very complex mixture of chemical components that typically contain Sulfur and Nitrogen species that can act as catalysis poisons for tar reforming and synthesis catalysts. Real-time hot online sampling techniques, such as Molecular Beammore » Mass Spectrometry (MBMS), and Gas Chromatographs with Sulfur and Nitrogen specific detectors can provide real-time analysis providing operational indicators for performance. Sampling typically requires coated sampling lines to minimize trace sulfur interactions with steel surfaces. Other materials used inline have also shown conversion of sulfur species into new components and must be minimized. Sample line Residence time within the sampling lines must also be kept to a minimum to reduce further reaction chemistries. Solids from ash and char contribute to plugging and must be filtered at temperature. Experience at NREL has shown several key factors to consider when designing and installing an analytical sampling system for biomass gasification products. They include minimizing sampling distance, effective filtering as close to source as possible, proper line sizing, proper line materials or coatings, even heating of all components, minimizing pressure drops, and additional filtering or traps after pressure drops.« less

X-Ray Fluorescence Determination of Sulphur in Oils by a Thin Film Method.

DTIC Science & Technology

1983-09-01

thickness. The procedure utilises a mixture of samp and an alkyd resin to improve adhesion to a Mylar substrate and to reduce sample flow during...thickness. The procedure utilises a mixture of sample and an alkyd resin to improve adhesion to a Mylar substrate and to reduce sample flow during...film. By incorporating an alkyd resin into the sample mixture the adhesion of the oil film to the Mylar sheet substrate is improved to the extent that

Lifetimes and stabilities of familiar explosives molecular adduct complexes during ion mobility measurements

PubMed Central

McKenzie, Alan; DeBord, John Daniel; Ridgeway, Mark; Park, Melvin; Eiceman, Gary; Fernandez-Lima, Francisco

2015-01-01

Trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) was utilized for the separation and identification of familiar explosives in complex mixtures. For the first time, molecular adduct complex lifetimes, relative stability, binding energies and candidate structures are reported for familiar explosives. Experimental and theoretical results showed that the adduct size and reactivity, complex binding energy and the explosive structure tailors the stability of the molecular adduct complex. TIMS flexibility to adapt the mobility separation as a function of the molecular adduct complex stability (i.e., short or long IMS experiments / low or high IMS resolution) permits targeted measurements of explosives in complex mixtures with higher confidence levels. PMID:26153567

In vitro screening for population variability in toxicity of pesticide-containing mixtures

PubMed Central

Abdo, Nour; Wetmore, Barbara A.; Chappell, Grace A.; Shea, Damian; Wright, Fred A.; Rusyna, Ivan

2016-01-01

Population-based human in vitro models offer exceptional opportunities for evaluating the potential hazard and mode of action of chemicals, as well as variability in responses to toxic insults among individuals. This study was designed to test the hypothesis that comparative population genomics with efficient in vitro experimental design can be used for evaluation of the potential for hazard, mode of action, and the extent of population variability in responses to chemical mixtures. We selected 146 lymphoblast cell lines from 4 ancestrally and geographically diverse human populations based on the availability of genome sequence and basal RNA-seq data. Cells were exposed to two pesticide mixtures – an environmental surface water sample comprised primarily of organochlorine pesticides and a laboratory-prepared mixture of 36 currently used pesticides – in concentration response and evaluated for cytotoxicity. On average, the two mixtures exhibited a similar range of in vitro cytotoxicity and showed considerable inter-individual variability across screened cell lines. However, when in vitroto-in vivo extrapolation (IVIVE) coupled with reverse dosimetry was employed to convert the in vitro cytotoxic concentrations to oral equivalent doses and compared to the upper bound of predicted human exposure, we found that a nominally more cytotoxic chlorinated pesticide mixture is expected to have greater margin of safety (more than 5 orders of magnitude) as compared to the current use pesticide mixture (less than 2 orders of magnitude) due primarily to differences in exposure predictions. Multivariate genome-wide association mapping revealed an association between the toxicity of current use pesticide mixture and a polymorphism in rs1947825 in C17orf54. We conclude that a combination of in vitro human population-based cytotoxicity screening followed by dosimetric adjustment and comparative population genomics analyses enables quantitative evaluation of human health hazard from complex environmental mixtures. Additionally, such an approach yields testable hypotheses regarding potential toxicity mechanisms. PMID:26386728

Increasing arsenic sorption on red mud by phosphogypsum addition.

PubMed

Lopes, G; Guilherme, L R G; Costa, E T S; Curi, N; Penha, H G V

2013-11-15

Mining by-products have been tested as adsorbents for arsenic in order to reduce As bioavailability. This study evaluated a red mud (RM) treated with or without phosphogypsum (G) in order to improve its As retention. Red mud and G samples and their mixtures were chemically and mineralogically characterized to gather information concerning their composition, which is key for a better understanding of the adsorbent properties. Phosphogypsum was added to RM in the following proportions: 0, 1, 2, 5, 10, and 25% by weight. These mixtures were subjected to As adsorption and desorption and tested for their maximum adsorption capacity of As (AsMAC). Arsenic adsorption increased upon increasing the proportion of G added to RM. The AsMAC at pure RM reached 909 mg kg(-1), whereas the 75%-RM+25%-G mixture sorbed up to 3333 mg kg(-1) of As, i.e., a 3.5-fold increase in AsMAC. Using G in mixtures with RM increases the efficiency of As adsorption due to the presence of Ca(2+), which alters the charge balance of the adsorbent, leading to the formation of ternary complexes. Addition of G to RM is thus a promising technique to improve As retention, while providing additional value to both by-products, G and RM. Copyright © 2012 Elsevier B.V. All rights reserved.

Toxicity of natural mixtures of organic pollutants in temperate and polar marine phytoplankton.

PubMed

Echeveste, Pedro; Galbán-Malagón, Cristóbal; Dachs, Jordi; Berrojalbiz, Naiara; Agustí, Susana

2016-11-15

Semivolatile and persistent organic pollutants (POPs) undergo atmospheric transport before being deposited to the oceans, where they partition to phytoplankton organic matter. The goal of this study was to determine the toxicity of naturally occurring complex mixtures of organic pollutants to temperate and polar phytoplankton communities from the Mediterranean Sea, the North East (NE) Atlantic, and Southern Oceans. The cell abundance of the different phytoplankton groups, chlorophyll a concentrations, viability of the cells, and growth and decay constants were monitored in response to addition of a range of concentrations of mixtures of organic pollutants obtained from seawater extracts. Almost all of the phytoplankton groups were significantly affected by the complex mixtures of non-polar and polar organic pollutants, with toxicity being greater for these mixtures than for single POPs or simple POP mixtures. Cocktails' toxicity arose at concentrations as low as tenfold the field oceanic levels, probably due to a higher chemical activity of the mixture than of simple POPs mixtures. Overall, smaller cells were the most affected, although Mediterranean picophytoplankton was significantly more tolerant to non-polar POPs than picophytoplankton from the Atlantic Ocean or the Bellingshausen Sea microphytoplankton. Copyright © 2016 Elsevier B.V. All rights reserved.

Combining measurements to estimate properties and characterization extent of complex biochemical mixtures; applications to Heparan Sulfate

PubMed Central

Pradines, Joël R.; Beccati, Daniela; Lech, Miroslaw; Ozug, Jennifer; Farutin, Victor; Huang, Yongqing; Gunay, Nur Sibel; Capila, Ishan

2016-01-01

Complex mixtures of molecular species, such as glycoproteins and glycosaminoglycans, have important biological and therapeutic functions. Characterization of these mixtures with analytical chemistry measurements is an important step when developing generic drugs such as biosimilars. Recent developments have focused on analytical methods and statistical approaches to test similarity between mixtures. The question of how much uncertainty on mixture composition is reduced by combining several measurements still remains mostly unexplored. Mathematical frameworks to combine measurements, estimate mixture properties, and quantify remaining uncertainty, i.e. a characterization extent, are introduced here. Constrained optimization and mathematical modeling are applied to a set of twenty-three experimental measurements on heparan sulfate, a mixture of linear chains of disaccharides having different levels of sulfation. While this mixture has potentially over two million molecular species, mathematical modeling and the small set of measurements establish the existence of nonhomogeneity of sulfate level along chains and the presence of abundant sulfate repeats. Constrained optimization yields not only estimations of sulfate repeats and sulfate level at each position in the chains but also bounds on these levels, thereby estimating the extent of characterization of the sulfation pattern which is achieved by the set of measurements. PMID:27112127

Combining measurements to estimate properties and characterization extent of complex biochemical mixtures; applications to Heparan Sulfate.

PubMed

Pradines, Joël R; Beccati, Daniela; Lech, Miroslaw; Ozug, Jennifer; Farutin, Victor; Huang, Yongqing; Gunay, Nur Sibel; Capila, Ishan

2016-04-26

Complex mixtures of molecular species, such as glycoproteins and glycosaminoglycans, have important biological and therapeutic functions. Characterization of these mixtures with analytical chemistry measurements is an important step when developing generic drugs such as biosimilars. Recent developments have focused on analytical methods and statistical approaches to test similarity between mixtures. The question of how much uncertainty on mixture composition is reduced by combining several measurements still remains mostly unexplored. Mathematical frameworks to combine measurements, estimate mixture properties, and quantify remaining uncertainty, i.e. a characterization extent, are introduced here. Constrained optimization and mathematical modeling are applied to a set of twenty-three experimental measurements on heparan sulfate, a mixture of linear chains of disaccharides having different levels of sulfation. While this mixture has potentially over two million molecular species, mathematical modeling and the small set of measurements establish the existence of nonhomogeneity of sulfate level along chains and the presence of abundant sulfate repeats. Constrained optimization yields not only estimations of sulfate repeats and sulfate level at each position in the chains but also bounds on these levels, thereby estimating the extent of characterization of the sulfation pattern which is achieved by the set of measurements.

Combining measurements to estimate properties and characterization extent of complex biochemical mixtures; applications to Heparan Sulfate

NASA Astrophysics Data System (ADS)

Pradines, Joël R.; Beccati, Daniela; Lech, Miroslaw; Ozug, Jennifer; Farutin, Victor; Huang, Yongqing; Gunay, Nur Sibel; Capila, Ishan

2016-04-01

Complex mixtures of molecular species, such as glycoproteins and glycosaminoglycans, have important biological and therapeutic functions. Characterization of these mixtures with analytical chemistry measurements is an important step when developing generic drugs such as biosimilars. Recent developments have focused on analytical methods and statistical approaches to test similarity between mixtures. The question of how much uncertainty on mixture composition is reduced by combining several measurements still remains mostly unexplored. Mathematical frameworks to combine measurements, estimate mixture properties, and quantify remaining uncertainty, i.e. a characterization extent, are introduced here. Constrained optimization and mathematical modeling are applied to a set of twenty-three experimental measurements on heparan sulfate, a mixture of linear chains of disaccharides having different levels of sulfation. While this mixture has potentially over two million molecular species, mathematical modeling and the small set of measurements establish the existence of nonhomogeneity of sulfate level along chains and the presence of abundant sulfate repeats. Constrained optimization yields not only estimations of sulfate repeats and sulfate level at each position in the chains but also bounds on these levels, thereby estimating the extent of characterization of the sulfation pattern which is achieved by the set of measurements.

Evaluate the contribution of the mixture components on the longevity and performance of FC-5 : [summary].

DOT National Transportation Integrated Search

2014-05-01

At its most basic, an asphalt mixture is asphalt : binder and crushed stone aggregate. This : seemingly simple mixture is very complex; method : of preparation and application, additives, and : aggregate type all influence the quality and : durabilit...

SELECTIVE CHANGES IN BRAIN PROTEIN KINASE C ISOFORMS FOLLOWING DEVELOPMENTAL EXPOSURE TO A PCB MIXTURE.

EPA Science Inventory

Introduction
Polychlorinated biphenyls (PCBs) offer a unique model to understand the major issues related to complex environmental mixtures. These environmental pollutants are ubiquitous, persistent, bioaccumulate in human body through the food chain, and exist as mixtures of ...

NATURE OF UNRESOLVED COMPLEX MIXTURE IN SIZE-DISTRIBUTED EMISSIONS FROM RESIDENTIAL WOOD COMBUSTION AS MEASURED BY THERMAL DESORPTION-GAS CHROMATOGRAPHY-MASS SPECTROMETRY

EPA Science Inventory

In this study, the unresolved complex mixture (UCM) in size resolved fine aerosol emissions from residential wood combustion (RWC) is examined. The aerosols are sorted by size in an electrical low-pressure impactor (ELPI) and subsequently analyzed by thermal desorbtion/gas chroma...

Behavior of complex mixtures in aquatic environments: a synthesis of PNL ecological research

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fickeisen, D.H.; Vaughan, B.E.

1984-06-01

The term complex mixture has been recently applied to energy-related process streams, products and wastes that typically contain hundreds or thousands of individual organic compounds, like petroleum or synthetic fuel oils; but it is more generally applicable. A six-year program of ecological research has focused on four areas important to understanding the environmental behavior of complex mixtures: physicochemical variables, individual organism responses, ecosystems-level determinations, and metabolism. Of these areas, physicochemical variables and organism responses were intensively studied; system-level determinations and metabolism represent more recent directions. Chemical characterization was integrated throughout all areas of the program, and state-of-the-art methods were applied.more » 155 references, 35 figures, 4 tables.« less

Enrichment of Cross-Linked Peptides Using Charge-Based Fractional Diagonal Chromatography (ChaFRADIC).

PubMed

Tinnefeld, Verena; Venne, A Saskia; Sickmann, Albert; Zahedi, René P

2017-02-03

Chemical cross-linking of proteins is an emerging field with huge potential for the structural investigation of proteins and protein complexes. Owing to the often relatively low yield of cross-linking products, their identification in complex samples benefits from enrichment procedures prior to mass spectrometry analysis. So far, this is mainly accomplished by using biotin moieties in specific cross-linkers or by applying strong cation exchange chromatography (SCX) for a relatively crude enrichment. We present a novel workflow to enrich cross-linked peptides by utilizing charge-based fractional diagonal chromatography (ChaFRADIC). On the basis of two-dimensional diagonal SCX separation, we could increase the number of identified cross-linked peptides for samples of different complexity: pure cross-linked BSA, cross-linked BSA spiked into a simple protein mixture, and cross-linked BSA spiked into a HeLa lysate. We also compared XL-ChaFRADIC with size exclusion chromatography-based enrichment of cross-linked peptides. The XL-ChaFRADIC approach is straightforward, reproducible, and independent of the cross-linking chemistry and cross-linker properties.

Complex mixture analysis by photoionization mass spectrometry with a VUV hydrogen laser source

NASA Astrophysics Data System (ADS)

Huth, T. C.; Denton, M. B.

1985-12-01

Trace organic analysis in complex matrix presents one of the most challenging problems in analytical mass spectrometry. When ionization is accomplished non-selectively using electron impact, extensive sample clean-up is often necessary in order to isolate the analyte from the matrix. Sample preparation can be greatly reduced when the VUV H2 laser is used to selectively photoionize only a small fraction of compounds introduced into the ion source. This device produces parent ions only for all compounds whose ionization potentials lie below a threshold value determined by the photon energy of 7.8 eV. The only observed interference arises from electron impact ionization, when scattered laser radiation interacts with metal surfaces, producing electrons which are then accelerated by potential fields inside the source. These can be suppressed to levels acceptable for practical analysis through proper instrumental design. Results are presented which indicate the ability of this ion source to discriminate against interfering matrix components, in simple extracts from a variety of complex real world matrices, such as brewed coffee, beer, and urine.

Spectrophotometric Determination of Cr(III) and Pb(II) Using Their Complexes with 5,11,17,23-Tetra[(2-ethyl acetoethoxyphenyl)(azo)phenyl]calix[4]arene

PubMed Central

Van Tan, Le; Quang Hieu, Tran; Van Cuong, Nguyen

2015-01-01

New complexes of 5,11,17,23-tetra[(2-ethyl acetoethoxyphenyl)(azo)phenyl]calix[4]arene (TEAC) with Pb(II) and Cr(III) were prepared in basic solution with a mixture of MeOH and H2O as solvent. The ratio of TEAC and metal ion in complexes was found to be 1 : 1 under investigated condition. The complex formation constants (based on Benesi-Hildebrand method) for TEAC-Pb(II) and TEAC-Cr(III) were 4.03 × 104 and 1.2 × 104, respectively. Additionally, the molar extinction coefficients were 5 × 104 and 1.42 × 104 for TEAC-Pb(II) and TEAC-Cr(III), respectively. The H-Point Standard Addition Method (HPSAM) has been applied for simultaneous determination of complexes formation of Cr(III)/Pb(II) and TEAC with concentration from 2 : 1 to 1 : 20 (w/w). The proposed method was successfully utilized to invest lead and chromium contents in plating wastewater samples. The results for several analyzed samples were found to be in satisfied agreement with those acquired by using the inductively coupled plasma mass spectrometry (ICP-MS) technique. PMID:25984379

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This purpose of this report is to summarize the activities of the Analytical Chemistry Laboratory (ACL) at Argonne National Laboratory (ANL) for Fiscal Year 1990. The ACL has four technical groups -- Chemical Analysis, Instrumental Analysis, Organic Analysis, and Environmental Analysis. The Chemical Analysis Group uses wet-chemical and instrumental methods for elemental, compositional, and isotopic analyses of solid, liquid, and gaseous samples and provides specialized analytical services. The Instrumental Analysis Group uses nuclear counting techniques in radiochemical analyses over a wide range of sample types from low-level environmental samples to samples of high radioactivity. The Organic Analysis Group uses amore » number of complementary techniques to separate and to quantitatively and qualitatively analyze complex organic mixtures and compounds at the trace level, including synthetic fuels, toxic substances, fossil-fuel residues and emissions, pollutants, biologically active compounds, pesticides, and drugs. The Environmental Analysis Group performs analyses of inorganic environmental and hazardous waste and coal samples.« less

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1995-04-11

A process is described for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal. 2 figures.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1994-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to exposure additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, James W.

1995-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Fast identification of microplastics in complex environmental samples by a thermal degradation method.

PubMed

Dümichen, Erik; Eisentraut, Paul; Bannick, Claus Gerhard; Barthel, Anne-Kathrin; Senz, Rainer; Braun, Ulrike

2017-05-01

In order to determine the relevance of microplastic particles in various environmental media, comprehensive investigations are needed. However, no analytical method exists for fast identification and quantification. At present, optical spectroscopy methods like IR and RAMAN imaging are used. Due to their time consuming procedures and uncertain extrapolation, reliable monitoring is difficult. For analyzing polymers Py-GC-MS is a standard method. However, due to a limited sample amount of about 0.5 mg it is not suited for analysis of complex sample mixtures like environmental samples. Therefore, we developed a new thermoanalytical method as a first step for identifying microplastics in environmental samples. A sample amount of about 20 mg, which assures the homogeneity of the sample, is subjected to complete thermal decomposition. The specific degradation products of the respective polymer are adsorbed on a solid-phase adsorber and subsequently analyzed by thermal desorption gas chromatography mass spectrometry. For certain identification, the specific degradation products for the respective polymer were selected first. Afterwards real environmental samples from the aquatic (three different rivers) and the terrestrial (bio gas plant) systems were screened for microplastics. Mainly polypropylene (PP), polyethylene (PE) and polystyrene (PS) were identified for the samples from the bio gas plant and PE and PS from the rivers. However, this was only the first step and quantification measurements will follow. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of DNA damage in ceramic workers.

PubMed

Anlar, Hatice Gul; Taner, Gokce; Bacanli, Merve; Iritas, Servet; Kurt, Turker; Tutkun, Engin; Yilmaz, Omer Hinc; Basaran, Nursen

2018-02-24

It is known that ceramic workers are potentially exposed to complex mixture of chemicals such as silica, inorganic lead, lime, beryllium and aluminum that can be associated with an increased risk of several diseases. All operations in the ceramic industries such as mixing, moulding, casting, shaking out and finishing jobs, have been associated with the higher exposure levels and in most of the silica-related industries, average overall exposure exceeded permissible exposure levels for respirable crystalline silica. The aim of this study was to evaluate the possible genotoxic damage in ceramic workers exposed to complex mixture of chemicals mainly crystalline silica. For this purpose, the blood and buccal epithelial cell samples were taken from the ceramic workers (n = 99) and their controls (n = 81). The genotoxicity was assessed by the alkaline comet assay in isolated lymphocytes and whole blood. Micronucleus (MN), binucleated (BN), pyknotic (PYC), condensed chromatin (CC), karyolytic (KYL), karyorrhectic (KHC) and nuclear bud (NBUD) frequencies in buccal epithelial cells and plasma 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) levels were also evaluated. In the study, 38 workers were diagnosed with silicosis, 9 workers were suspected to have silicosis, whereas 52 workers were found to be healthy. DNA damage in blood and lymphocytes; MN, CC + KHC, PYC frequencies in buccal epithelial cells and 8-oxodG levels in plasma were increased in workers compared to their controls. These results showed that occupational chemical mixture exposure in ceramic industry may cause genotoxic damage that can lead to important health problems in the workers.

Automated tandem mass spectrometry by orthogonal acceleration TOF data acquisition and simultaneous magnet scanning for the characterization of petroleum mixtures.

PubMed

Roussis, S G

2001-08-01

The automated acquisition of the product ion spectra of all precursor ions in a selected mass range by using a magnetic sector/orthogonal acceleration time-of-flight (oa-TOF) tandem mass spectrometer for the characterization of complex petroleum mixtures is reported. Product ion spectra are obtained by rapid oa-TOF data acquisition and simultaneous scanning of the magnet. An analog signal generator is used for the scanning of the magnet. Slow magnet scanning rates permit the accurate profiling of precursor ion peaks and the acquisition of product ion spectra for all isobaric ion species. The ability of the instrument to perform both high- and low-energy collisional activation experiments provides access to a large number of dissociation pathways useful for the characterization of precursor ions. Examples are given that illustrate the capability of the method for the characterization of representative petroleum mixtures. The structural information obtained by the automated MS/MS experiment is used in combination with high-resolution accurate mass measurement results to characterize unknown components in a polar extract of a refinery product. The exhaustive mapping of all precursor ions in representative naphtha and middle-distillate fractions is presented. Sets of isobaric ion species are separated and their structures are identified by interpretation from first principles or by comparison with standard 70-eV EI libraries of spectra. The utility of the method increases with the complexity of the samples.

Improving the Stability and the Pharmaceutical Properties of Norfloxacin Form C Through Binary Complexes with β-Cyclodextrin.

PubMed

Garnero, Claudia; Chattah, Ana Karina; Aloisio, Carolina; Fabietti, Luis; Longhi, Marcela

2018-05-10

Norfloxacin, an antibiotic that exists in different solid forms, has very unfavorable properties in terms of solubility and stability. Binary complexes of norfloxacin, in the solid form C, and β-cyclodextrin were procured by the kneading method and physical mixture. Their effect on the solubility, the dissolution rate, and the chemical and physical stability of norfloxacin was evaluated. To perform stability studies, the solid samples were stored under accelerated storage conditions, for a period of 6 months. Physical stability was monitored through powder X-ray diffraction, high-resolution 13 C solid-state nuclear magnetic resonance, and scanning electron microscopy. The results showed evidence that the kneaded complex increased and modulated the dissolution rate of norfloxacin C. Furthermore, it was demonstrated that the photochemical stability was increased in the complex, without affecting its physical stability. The results point to the conclusion that the new kneading complex of norfloxacin constitutes an alternative tool to formulate a potential oral drug delivery system with improve oral bioavailability.

Molecular investigation on the binding of Cd(II) by the binary mixtures of montmorillonite with two bacterial species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Huihui; Qu, ChenChen; Liu, Jing

Bacteria and phyllosilicate commonly coexist in the natural environment, producing various bacteria–clay complexes that are capable of immobilizing heavy metals, such as cadmium, via adsorption. However, the molecular binding mechanisms of heavy metals on these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive B. subtilis, Gram-negative P. putida and their binary mixtures with montmorillonite (Mont) using the Cd K-edge x-ray absorption spectroscopy (XAS) and isothermal titration calorimetry (ITC). We observed a lower adsorptive capacity for P. putida than B. subtilis, whereas P. putida–Mont and B. subtilis–Mont mixtures showed nearly identical Cd adsorption behaviors. EXAFS fitsmore » and ITC measurements demonstrated more phosphoryl binding of Cd in P. putida. The decreased coordination of C atoms around Cd and the reduced adsorption enthalpies and entropies for the binary mixtures compared to that for individual bacteria suggested that the bidentate Cd-carboxyl complexes in pure bacteria systems were probably transformed into monodentate complexes that acted as ionic bridging structure between bacteria and motmorillonite. This study clarified the binding mechanism of Cd at the bacteria–phyllosilicate interfaces from a molecular and thermodynamic view, which has an environmental significance for predicting the chemical behavior of trace elements in complex mineral–organic systems.« less

Toxicokinetics and oral bioavailability of halogenated acetic acids mixtures in naïve and GSTzeta-depleted rats.

PubMed

Saghir, Shakil A; Schultz, Irvin R

2005-04-01

Disinfection of drinking water typically produces a mixture of mono-, di-, and tri-halogenated acetic acids (HAAs). In this study, we investigated the toxicokinetics of HAA mixtures in naive and glutathione transferase zeta 1 (GSTzeta)-depleted male F344 rats administered orally or iv to Mixture-1 (monobromo [MBAA]- dichloro- [DCAA], chlorodibromo- [CDBAA], tribromo- [TBAA] acetic acids) or Mixture-2 (bromochloro- [BCAA], dibromo- [DBAA], trichloro- [TCAA] bromodichloro- [BDCAA] acetic acids) at a dose of 25 micromol/kg HAA. Serial blood samples were collected at various times up to 36 h, and the plasma concentrations of each HAA quantified by GC-ECD. Rats were pretreated for 7 d with drinking water containing 0.2 g/l DCAA to deplete the GSTzeta (GSTZ1-1) activity in the liver. An additional group of GSTzeta-depleted rats were orally dosed with each mixture and euthanized at 0.25, 0.5, 1, 2, and 4 h to determine tissue distribution of mixture components. In both mixtures, GSTzeta depletion primarily affected the toxicokinetics of di-HAAs (DCAA, BCAA, and DBAA), with the total body clearance (Cl b) decreasing 3- to 10-fold. Interestingly, DCAA pretreatment appeared to increase the elimination of Mixture-2 tri-HAAs (TCAA and BDCAA). After oral administration, DCAA exhibited a complex time-course plasma profile with secondary peaks appearing long after completion of the initial absorption phase. This phenomenon coincided with elevated DCA levels in the lower portion of the GI tract compared to CDBAA and TBAA. Comparison of the results with previous studies employing similar or higher doses of individual HAAs indicated the primary difference in HAA toxicokinetics when administered as mixture was a reduction in Cl b. These results suggest competitive interactions between tri- and di-HAAs beyond what would be predicted from individual HAA studies. For di-HAAs, the total dose is important, as clearance is dose dependent due to competition for GSTzeta. When considering HAA dosimetry, importance should be placed on both the components of the mixture and prior exposure history to di-HAAs.

Hidden drivers of low-dose pharmaceutical pollutant mixtures revealed by the novel GSA-QHTS screening method

PubMed Central

Rodea-Palomares, Ismael; Gonzalez-Pleiter, Miguel; Gonzalo, Soledad; Rosal, Roberto; Leganes, Francisco; Sabater, Sergi; Casellas, Maria; Muñoz-Carpena, Rafael; Fernández-Piñas, Francisca

2016-01-01

The ecological impacts of emerging pollutants such as pharmaceuticals are not well understood. The lack of experimental approaches for the identification of pollutant effects in realistic settings (that is, low doses, complex mixtures, and variable environmental conditions) supports the widespread perception that these effects are often unpredictable. To address this, we developed a novel screening method (GSA-QHTS) that couples the computational power of global sensitivity analysis (GSA) with the experimental efficiency of quantitative high-throughput screening (QHTS). We present a case study where GSA-QHTS allowed for the identification of the main pharmaceutical pollutants (and their interactions), driving biological effects of low-dose complex mixtures at the microbial population level. The QHTS experiments involved the integrated analysis of nearly 2700 observations from an array of 180 unique low-dose mixtures, representing the most complex and data-rich experimental mixture effect assessment of main pharmaceutical pollutants to date. An ecological scaling-up experiment confirmed that this subset of pollutants also affects typical freshwater microbial community assemblages. Contrary to our expectations and challenging established scientific opinion, the bioactivity of the mixtures was not predicted by the null mixture models, and the main drivers that were identified by GSA-QHTS were overlooked by the current effect assessment scheme. Our results suggest that current chemical effect assessment methods overlook a substantial number of ecologically dangerous chemical pollutants and introduce a new operational framework for their systematic identification. PMID:27617294

Short-term bioassay of complex organic mixtures. Part II. Mutagenicity testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Epler, J.L.; Clark, B.R.; Ho, C.

1978-01-01

The feasibility of using short-term mutagenicity assays to predict the potential biohazard of various crude and complex test materials has been examined in a coupled chemical and biological approach. The principal focus of the research has involved the preliminary chemical characterizatiion and preparation for bioassay, followed by testing in the Salmonella histidine reversion assay system. The mutagenicity tests are intended to act as predictors of profound long-range health effects such as mutagenesis and/or carcinogenesis; act as a mechanism to rapidly isolate and identify a hazardous agent in a complex mixture; and function as a measure of biological activity correlating baselinemore » data with changes in process conditions. Since complex mixtures can be fractionated and approached in these short-term assays, information reflecting on the actual compounds responsible for the biological effect may be accumulated.« less

Investigating the discrimination potential of linear and nonlinear spectral multivariate calibrations for analysis of phenolic compounds in their binary and ternary mixtures and calculation pKa values.

PubMed

Rasouli, Zolaikha; Ghavami, Raouf

2016-08-05

Vanillin (VA), vanillic acid (VAI) and syringaldehyde (SIA) are important food additives as flavor enhancers. The current study for the first time is devote to the application of partial least square (PLS-1), partial robust M-regression (PRM) and feed forward neural networks (FFNNs) as linear and nonlinear chemometric methods for the simultaneous detection of binary and ternary mixtures of VA, VAI and SIA using data extracted directly from UV-spectra with overlapped peaks of individual analytes. Under the optimum experimental conditions, for each compound a linear calibration was obtained in the concentration range of 0.61-20.99 [LOD=0.12], 0.67-23.19 [LOD=0.13] and 0.73-25.12 [LOD=0.15] μgmL(-1) for VA, VAI and SIA, respectively. Four calibration sets of standard samples were designed by combination of a full and fractional factorial designs with the use of the seven and three levels for each factor for binary and ternary mixtures, respectively. The results of this study reveal that both the methods of PLS-1 and PRM are similar in terms of predict ability each binary mixtures. The resolution of ternary mixture has been accomplished by FFNNs. Multivariate curve resolution-alternating least squares (MCR-ALS) was applied for the description of spectra from the acid-base titration systems each individual compound, i.e. the resolution of the complex overlapping spectra as well as to interpret the extracted spectral and concentration profiles of any pure chemical species identified. Evolving factor analysis (EFA) and singular value decomposition (SVD) were used to distinguish the number of chemical species. Subsequently, their corresponding dissociation constants were derived. Finally, FFNNs has been used to detection active compounds in real and spiked water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigating the discrimination potential of linear and nonlinear spectral multivariate calibrations for analysis of phenolic compounds in their binary and ternary mixtures and calculation pKa values

NASA Astrophysics Data System (ADS)

Rasouli, Zolaikha; Ghavami, Raouf

2016-08-01

Vanillin (VA), vanillic acid (VAI) and syringaldehyde (SIA) are important food additives as flavor enhancers. The current study for the first time is devote to the application of partial least square (PLS-1), partial robust M-regression (PRM) and feed forward neural networks (FFNNs) as linear and nonlinear chemometric methods for the simultaneous detection of binary and ternary mixtures of VA, VAI and SIA using data extracted directly from UV-spectra with overlapped peaks of individual analytes. Under the optimum experimental conditions, for each compound a linear calibration was obtained in the concentration range of 0.61-20.99 [LOD = 0.12], 0.67-23.19 [LOD = 0.13] and 0.73-25.12 [LOD = 0.15] μg mL- 1 for VA, VAI and SIA, respectively. Four calibration sets of standard samples were designed by combination of a full and fractional factorial designs with the use of the seven and three levels for each factor for binary and ternary mixtures, respectively. The results of this study reveal that both the methods of PLS-1 and PRM are similar in terms of predict ability each binary mixtures. The resolution of ternary mixture has been accomplished by FFNNs. Multivariate curve resolution-alternating least squares (MCR-ALS) was applied for the description of spectra from the acid-base titration systems each individual compound, i.e. the resolution of the complex overlapping spectra as well as to interpret the extracted spectral and concentration profiles of any pure chemical species identified. Evolving factor analysis (EFA) and singular value decomposition (SVD) were used to distinguish the number of chemical species. Subsequently, their corresponding dissociation constants were derived. Finally, FFNNs has been used to detection active compounds in real and spiked water samples.

ANALYSIS OF FUNCTIONAL EFFECTS OF A MIXTURE OF FIVE PESTICIDES USING A RAY DESIGN

EPA Science Inventory

Abstract
The protection of human health from the adverse effects of cumulative environmental exposure to chemical mixtures is an important issue. Of particular interest is the potential detection and characterization of interaction among chemicals in complex mixtures. R...

Prototype of an Interface for Hyphenating Distillation with Gas Chromatography and Mass Spectrometry

PubMed Central

Tang, Ya-Ru; Yang, Hui-Hsien; Urban, Pawel L.

2017-01-01

Chemical analysis of complex matrices—containing hundreds of compounds—is challenging. Two-dimensional separation techniques provide an efficient way to reduce complexity of mixtures analyzed by mass spectrometry (MS). For example, gasoline is a mixture of numerous compounds, which can be fractionated by distillation techniques. However, coupling conventional distillation with other separations as well as MS is not straightforward. We have established an automatic system for online coupling of simple microscale distillation with gas chromatography (GC) and electron ionization MS. The developed system incorporates an interface between the distillation condenser and the injector of a fused silica capillary GC column. Development of this multidimensional separation (distillation-GC-MS) was preceded by a series of preliminary off-line experiments. In the developed technique, the components with different boiling points are fractionated and instantly analyzed by GC-MS. The obtained data sets illustrate dynamics of the distillation process. An important advantage of the distillation-GC-MS technique is that raw samples can directly be analyzed without removal of the non-volatile matrix residues that could contaminate the GC injection port and the column. Distilling the samples immediately before the injection to the GC column may reduce possible matrix effects—especially in the early phase of separation, when molecules with different volatilities co-migrate. It can also reduce losses of highly volatile components (during fraction collection and transfer). The two separation steps are partly orthogonal, what can slightly increase selectivity of the entire analysis. PMID:28337400

Inconsistent magnetic polarities in magnetite- and greigite-bearing sediments: Understanding complex magnetizations in the late Messinian in the Adana Basin (southern Turkey)

NASA Astrophysics Data System (ADS)

Lucifora, Stella; Cifelli, Francesca; Mattei, Massimo; Sagnotti, Leonardo; Cosentino, Domenico; Roberts, Andrew P.

2012-10-01

We present paleomagnetic, rock magnetic and scanning electron microscope data from three upper Messinian stratigraphic sections from the Adana Basin (southern Turkey). The collected samples are from fine-grained units, which were deposited during the Messinian Salinity Crisis (within subchron C3r). Paleomagnetic results reveal an inconsistent polarity record, related to a mixture of magnetite and greigite that hinders determination of a reliable magnetostratigraphy. Three classes of samples are recognized on the basis of paleomagnetic results. The first is characterized by a single magnetization component, with normal polarity, that is stable up to 530-580°C and is carried by magnetite. The second is characterized by a single magnetization component, with reversed polarity, that is stable up to 330-420°C. This magnetization is due to greigite, which developed after formation of slumps and before tectonic tilting of the studied successions. The third is characterized by reversed polarity, which is stable up to 530-580°C. We interpret this component as a primary magnetization carried by fine-grained and magnetically stable detrital magnetite. Results indicate that in the Adana Basin the assumption that a primary magnetization is carried by magnetite, and a magnetic overprint carried by greigite, does not hold because a late magnetic overprint has also been found for magnetite-bearing samples. Our data illustrate the complexity of magnetostratigraphic reconstructions in successions characterized by variable mixtures of magnetic minerals with different magnetic stability that formed at different stages. We demonstrate the need to perform detailed magnetic mineralogy analyses when conducting magnetostratigraphic studies of clay-rich sediments from marine or lacustrine environments.

SPR imaging based electronic tongue via landscape images for complex mixture analysis.

PubMed

Genua, Maria; Garçon, Laurie-Amandine; Mounier, Violette; Wehry, Hillary; Buhot, Arnaud; Billon, Martial; Calemczuk, Roberto; Bonnaffé, David; Hou, Yanxia; Livache, Thierry

2014-12-01

Electronic noses/tongues (eN/eT) have emerged as promising alternatives for analysis of complex mixtures in the domain of food and beverage quality control. We have recently developed an electronic tongue by combining surface plasmon resonance imaging (SPRi) with an array of non-specific and cross-reactive receptors prepared by simply mixing two small molecules in varying and controlled proportions and allowing the mixtures to self-assemble on the SPRi prism surface. The obtained eT generated novel and unique 2D continuous evolution profiles (CEPs) and 3D continuous evolution landscapes (CELs) based on which the differentiation of complex mixtures such as red wine, beer and milk were successful. The preliminary experiments performed for monitoring the deterioration of UHT milk demonstrated its potential for quality control applications. Furthermore, the eT exhibited good repeatability and stability, capable of operating after a minimum storage period of 5 months. Copyright © 2014 Elsevier B.V. All rights reserved.

Equilibration of a polycation - anionic surfactant mixture at the water/vapor interface.

PubMed

Akanno, Andrew; Guzmán, Eduardo; Fernández-Peña, Laura; Llamas, Sara; Ortega, Francisco; Rubio, Ramon Gonzalez

2018-06-01

The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC) - sodium lauryl ether sulfate (SLES) mixtures at the water / vapor interface has been studied by different surface tension techniques and dilational visco-elasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte - surfactant complexes in the bulk affects to the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC - SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work helps on the understanding of the most fundamental bases of the physico-chemical behavior of concentrated polyelectrolyte - surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

Development of a NIST standard reference material containing thirty volatile organic compounds at 5 nmol/mol in nitrogen.

PubMed

Rhoderick, George C; Yen, James H

2006-05-01

Primary gravimetric gas cylinder standards containing 30 volatile organic compounds (VOCs) in nitrogen were prepared using a procedure previously developed to prepare gas mixture cylinder standards of VOCs at the 5 nmol/mol level. This set of primary standards was intercompared to existing gas cylinder standards, containing as many as 19 of the 30 volatile organics present in these new primaries, using gas chromatography with a hydrogen flame ionization detector coupled with cryogenic preconcentration. The linear regression analysis showed excellent agreement among the standards for each compound. Similar mixtures containing many of these compounds in treated aluminum gas cylinders have been evaluated over time and have shown stability for as much as 10 years. The development of these 30-component primary standards led to the preparation and certification of a reissue of Standard Reference Material (SRM) 1804 at the nominal amount-of-substance fraction of 5 nmol/mol for each analyte. A lot of 20 cylinders containing the mixture was prepared at NIST following previously demonstrated protocols for preparation of the cylinders. Each cylinder was analyzed against one cylinder from the lot, designated as the "lot standard," for each of the 30 compounds. As a result of the uncertainty analysis, the data showed that rather than declaring the lot homogeneous with a much higher uncertainty, each cylinder could be individually certified. The expanded uncertainty limits ranged from 1.5 to 10% for 28 of the 30 analytes, with two of the analytes having uncertainties as high as 19% in those SRM cylinders certified. Due to stability issues and some high uncertainties for a few analytes in 2 of the samples, 18 of the 20 candidate SRM samples were certified. These volatile organic gas mixtures represent the most complex gas SRMs developed at NIST.

Water-quality assessment of the largely urban blue river basin, Metropolitan Kansas City, USA, 1998 to 2007

USGS Publications Warehouse

Wilkison, D.H.; Armstrong, D.J.; Hampton, S.A.

2009-01-01

From 1998 through 2007, over 750 surface-water or bed-sediment samples in the Blue River Basin - a largely urban basin in metropolitan Kansas City - were analyzed for more than 100 anthropogenic compounds. Compounds analyzed included nutrients, fecal-indicator bacteria, suspended sediment, pharmaceuticals and personal care products. Non-point source runoff, hydrologic alterations, and numerous waste-water discharge points resulted in the routine detection of complex mixtures of anthropogenic compounds in samples from basin stream sites. Temporal and spatial variations in concentrations and loads of nutrients, pharmaceuticals, and organic wastewater compounds were observed, primarily related to a site's proximity to point-source discharges and stream-flow dynamics. ?? 2009 ASCE.

Sampling Error in a Particulate Mixture: An Analytical Chemistry Experiment.

ERIC Educational Resources Information Center

Kratochvil, Byron

1980-01-01

Presents an undergraduate experiment demonstrating sampling error. Selected as the sampling system is a mixture of potassium hydrogen phthalate and sucrose; using a self-zeroing, automatically refillable buret to minimize titration time of multiple samples and employing a dilute back-titrant to obtain high end-point precision. (CS)

Cytotoxic and Inflammatory Potential of Air Samples from Occupational Settings with Exposure to Organic Dust

PubMed Central

Viegas, Susana; Caetano, Liliana Aranha; Korkalainen, Merja; Faria, Tiago; Pacífico, Cátia; Carolino, Elisabete; Quintal Gomes, Anita; Viegas, Carla

2017-01-01

Organic dust and related microbial exposures are the main inducers of several respiratory symptoms. Occupational exposure to organic dust is very common and has been reported in diverse settings. In vitro tests using relevant cell cultures can be very useful for characterizing the toxicity of complex mixtures present in the air of occupational environments such as organic dust. In this study, the cell viability and the inflammatory response, as measured by the production of pro-inflammatory cytokines tumor necrosis factor-α (TNFα) and interleukin-1 β (IL-1β), were determined in human macrophages derived from THP-1 monocytic cells. These cells were exposed to air samples from five occupational settings known to possess high levels of contamination of organic dust: poultry and swine feed industries, waste sorting, poultry production and slaughterhouses. Additionally, fungi and particle contamination of those settings was studied to better characterize the organic dust composition. All air samples collected from the assessed workplaces caused both cytotoxic and pro-inflammatory effects. The highest responses were observed in the feed industry, particularly in swine feed production. This study emphasizes the importance of measuring the organic dust/mixture effects in occupational settings and suggests that differences in the organic dust content may result in differences in health effects for exposed workers. PMID:29051440

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source

NASA Astrophysics Data System (ADS)

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H]+ was observed in the case of individual alkanes (C5-C19) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. [Figure not available: see fulltext.

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source.

PubMed

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H] + was observed in the case of individual alkanes (C 5 -C 19 ) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. Graphical Abstract ᅟ.

CHANGES IN NUCLEAR TRANSCRIPTION FACTORS IN RAT HIPPOCAMPUS AND CEREBELLUM FOLLOWING DEVELOPMENTAL EXPOSURE TO A COMMERCIAL PCB MIXTURE.

EPA Science Inventory

Polychlorinated biphenyls (PCBs) offer a unique model to understand the major issues related to complex environmental mixtures. These pollutants are ubiquitous and exist as mixtures of several congeners in the environment. Human exposures to PCBs are associated with a variety of ...

CHANGES IN HIPPOCAMPAL SPINE DENSITY AND PROTEIN KINASE C ISOFORMS FOLLOWING DEVELOPMENTAL EXPOSURE TO A MIXTURE OF PERSISTENT CHEMICALS.

EPA Science Inventory

Polychlorinated biphenyls (PCBs) offer a unique model to understand the major issues related to complex environmental mixtures of persistent chemicals. These pollutants are ubiquitous, persistent, bioaccumulate in human body through the food chain, and exist as mixtures of severa...

The Design of a Quantitative Western Blot Experiment

PubMed Central

Taylor, Sean C.; Posch, Anton

2014-01-01

Western blotting is a technique that has been in practice for more than three decades that began as a means of detecting a protein target in a complex sample. Although there have been significant advances in both the imaging and reagent technologies to improve sensitivity, dynamic range of detection, and the applicability of multiplexed target detection, the basic technique has remained essentially unchanged. In the past, western blotting was used simply to detect a specific target protein in a complex mixture, but now journal editors and reviewers are requesting the quantitative interpretation of western blot data in terms of fold changes in protein expression between samples. The calculations are based on the differential densitometry of the associated chemiluminescent and/or fluorescent signals from the blots and this now requires a fundamental shift in the experimental methodology, acquisition, and interpretation of the data. We have recently published an updated approach to produce quantitative densitometric data from western blots (Taylor et al., 2013) and here we summarize the complete western blot workflow with a focus on sample preparation and data analysis for quantitative western blotting. PMID:24738055

Population transcriptomics with single-cell resolution: a new field made possible by microfluidics: a technology for high throughput transcript counting and data-driven definition of cell types.

PubMed

Plessy, Charles; Desbois, Linda; Fujii, Teruo; Carninci, Piero

2013-02-01

Tissues contain complex populations of cells. Like countries, which are comprised of mixed populations of people, tissues are not homogeneous. Gene expression studies that analyze entire populations of cells from tissues as a mixture are blind to this diversity. Thus, critical information is lost when studying samples rich in specialized but diverse cells such as tumors, iPS colonies, or brain tissue. High throughput methods are needed to address, model and understand the constitutive and stochastic differences between individual cells. Here, we describe microfluidics technologies that utilize a combination of molecular biology and miniaturized labs on chips to study gene expression at the single cell level. We discuss how the characterization of the transcriptome of each cell in a sample will open a new field in gene expression analysis, population transcriptomics, that will change the academic and biomedical analysis of complex samples by defining them as quantified populations of single cells. Copyright © 2013 WILEY Periodicals, Inc.

Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures

PubMed Central

Bogart, Justin A.; Cole, Bren E.; Boreen, Michael A.; Lippincott, Connor A.; Manor, Brian C.; Carroll, Patrick J.; Schelter, Eric J.

2016-01-01

Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx3–, featured a size-sensitive aperture formed of its three η2-(N,O) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)]2 species. Differences in the equilibrium constants Kdimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La–Sm and RE2 = Gd–Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early–late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation. PMID:27956636

Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures.

PubMed

Bogart, Justin A; Cole, Bren E; Boreen, Michael A; Lippincott, Connor A; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

2016-12-27

Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx 3- , featured a size-sensitive aperture formed of its three η 2 -(N,O) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)] 2 species. Differences in the equilibrium constants K dimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La-Sm and RE2 = Gd-Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early-late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation.

Development of a highly sensitive and selective method for extractive spectrophotometric determination of aluminum(III) from environmental matrices, synthetic mixtures, and alloys using orthohydroxypropiophenoneisonicotinoylhydrazone.

PubMed

Ramachandraiah, C; Rajesh Kumar, J; Adinarayana Reddy, S; Lee, Jin-Young; Varada Reddy, A

2010-01-01

Orthohydroxypropiophenoneisonicotinoylhydrazone (OHPINH) is proposed as a new sensitive reagent for the spectrophotometric determination of aluminum(III). OHPINH formed a greenish-yellow colored complex with aluminum(III) in buffer solutions of pH 1 to 3. The color in pH 2 was stable for more than 48 h. The complex solution has given maximum absorbance at 390 nm when the reagent was chosen as blank and the absorbance of the reagent at this wavelength is negligible; the molar absorptivity and Sandell's sensitivity being 0.6371x10(4) L mol(-1) cm(-1) and 4.234x10(-3) microg cm(-2), respectively. The system obeys Beer's law in the range of 0.5-3.5 microg mL(-1) with excellent linearity in terms of the correlation coefficient value of 0.999. Most of the common metal ions generally found associated with aluminum(III) do not interfere. The repeatability of the method was checked by finding the relative standard deviation. The developed method has been successfully employed for the determination of aluminum(III) environmental matrices like medicinal and leafy samples, alloys, and synthetic mixtures.

Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

PubMed Central

Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

2016-01-01

NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

Mapping the Gulf of Maine with side-scan sonar: A new bottom-type classification for complex seafloors

USGS Publications Warehouse

Barnhardt, W.A.; Kelley, J.T.; Dickson, S.M.; Belknap, D.F.

1998-01-01

The bedrock-framed seafloor in the northwestern Gulf of Maine is characterized by extreme changes in bathymetric relief and covered with a wide variety of surficial materials. Traditional methods of mapping cannot accurately represent the great heterogeneity of such a glaciated region. A new mapping scheme for complex seafloors, based primarily on the interpretation of side-scan sonar imagery, utilizes four easily recognized units: rock, gravel, sand and mud. In many places, however, the seafloor exhibits a complicated mixture or extremely 'patchy' distribution of the four basic units, which are too small to map individually. Twelve composite units, each a two-component mixture of the basic units, were established to represent this patchiness at a small scale (1:100,000). Using a geographic information system, these and all other available data (seismic profiles, grab samples, submersible dives and cores) were referenced to a common geographic base, superimposed on bathymetric contours and then integrated into surficial geologic maps of the regional inner continental shelf. This digital representation of the seafloor comprises a multidimensional, interactive model complete with explicit attributes (depth, bottom type) that allow for detailed analysis of marine environments.

Method for milling and drilling glass

NASA Technical Reports Server (NTRS)

Rice, S. H. (Inventor)

1980-01-01

A process for machining glass by placing a rotating carbide working surface under minimum pressure against an area of glass to be worked is described. Concurrently the region between the working surface and the area of glass is wet with a lubricant consisting essentially of a petroleum carrier, a complex mixture of esters and a complex mixture of naturally occurring aromatic oils.

Discrimination of complex mixtures by a colorimetric sensor array: coffee aromas.

PubMed

Suslick, Benjamin A; Feng, Liang; Suslick, Kenneth S

2010-03-01

The analysis of complex mixtures presents a difficult challenge even for modern analytical techniques, and the ability to discriminate among closely similar such mixtures often remains problematic. Coffee provides a readily available archetype of such highly multicomponent systems. The use of a low-cost, sensitive colorimetric sensor array for the detection and identification of coffee aromas is reported. The color changes of the sensor array were used as a digital representation of the array response and analyzed with standard statistical methods, including principal component analysis (PCA) and hierarchical clustering analysis (HCA). PCA revealed that the sensor array has exceptionally high dimensionality with 18 dimensions required to define 90% of the total variance. In quintuplicate runs of 10 commercial coffees and controls, no confusions or errors in classification by HCA were observed in 55 trials. In addition, the effects of temperature and time in the roasting of green coffee beans were readily observed and distinguishable with a resolution better than 10 degrees C and 5 min, respectively. Colorimetric sensor arrays demonstrate excellent potential for complex systems analysis in real-world applications and provide a novel method for discrimination among closely similar complex mixtures.

Discrimination of Complex Mixtures by a Colorimetric Sensor Array: Coffee Aromas

PubMed Central

Suslick, Benjamin A.; Feng, Liang; Suslick, Kenneth S.

2010-01-01

The analysis of complex mixtures presents a difficult challenge even for modern analytical techniques, and the ability to discriminate among closely similar such mixtures often remains problematic. Coffee provides a readily available archetype of such highly multicomponent systems. The use of a low-cost, sensitive colorimetric sensor array for the detection and identification of coffee aromas is reported. The color changes of the sensor array were used as a digital representation of the array response and analyzed with standard statistical methods, including principal component analysis (PCA) and hierarchical clustering analysis (HCA). PCA revealed that the sensor array has exceptionally high dimensionality with 18 dimensions required to define 90% of the total variance. In quintuplicate runs of 10 commercial coffees and controls, no confusions or errors in classification by HCA were observed in 55 trials. In addition, the effects of temperature and time in the roasting of green coffee beans were readily observed and distinguishable with a resolution better than 10 °C and 5 min, respectively. Colorimetric sensor arrays demonstrate excellent potential for complex systems analysis in real-world applications and provide a novel method for discrimination among closely similar complex mixtures. PMID:20143838

Bayesian spatiotemporal crash frequency models with mixture components for space-time interactions.

PubMed

Cheng, Wen; Gill, Gurdiljot Singh; Zhang, Yongping; Cao, Zhong

2018-03-01

The traffic safety research has developed spatiotemporal models to explore the variations in the spatial pattern of crash risk over time. Many studies observed notable benefits associated with the inclusion of spatial and temporal correlation and their interactions. However, the safety literature lacks sufficient research for the comparison of different temporal treatments and their interaction with spatial component. This study developed four spatiotemporal models with varying complexity due to the different temporal treatments such as (I) linear time trend; (II) quadratic time trend; (III) Autoregressive-1 (AR-1); and (IV) time adjacency. Moreover, the study introduced a flexible two-component mixture for the space-time interaction which allows greater flexibility compared to the traditional linear space-time interaction. The mixture component allows the accommodation of global space-time interaction as well as the departures from the overall spatial and temporal risk patterns. This study performed a comprehensive assessment of mixture models based on the diverse criteria pertaining to goodness-of-fit, cross-validation and evaluation based on in-sample data for predictive accuracy of crash estimates. The assessment of model performance in terms of goodness-of-fit clearly established the superiority of the time-adjacency specification which was evidently more complex due to the addition of information borrowed from neighboring years, but this addition of parameters allowed significant advantage at posterior deviance which subsequently benefited overall fit to crash data. The Base models were also developed to study the comparison between the proposed mixture and traditional space-time components for each temporal model. The mixture models consistently outperformed the corresponding Base models due to the advantages of much lower deviance. For cross-validation comparison of predictive accuracy, linear time trend model was adjudged the best as it recorded the highest value of log pseudo marginal likelihood (LPML). Four other evaluation criteria were considered for typical validation using the same data for model development. Under each criterion, observed crash counts were compared with three types of data containing Bayesian estimated, normal predicted, and model replicated ones. The linear model again performed the best in most scenarios except one case of using model replicated data and two cases involving prediction without including random effects. These phenomena indicated the mediocre performance of linear trend when random effects were excluded for evaluation. This might be due to the flexible mixture space-time interaction which can efficiently absorb the residual variability escaping from the predictable part of the model. The comparison of Base and mixture models in terms of prediction accuracy further bolstered the superiority of the mixture models as the mixture ones generated more precise estimated crash counts across all four models, suggesting that the advantages associated with mixture component at model fit were transferable to prediction accuracy. Finally, the residual analysis demonstrated the consistently superior performance of random effect models which validates the importance of incorporating the correlation structures to account for unobserved heterogeneity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pacific Northwest Laboratory annual report for 1984 to the DOE Office of Energy Research. Part 1. Biomedical sciences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Felton, D.L.

1985-02-01

Research progress is reported in the following areas: (1) evaluation of possible health effects among nuclear workers; (2) dose-effect relationship studies of carcinogenesis from both nuclear materials and complex mixtures; (3) microbial mutagenesis studies with 6-aminochrysene and benzo(a)pyrene in coal-derived complex mixtures; and (4) a variety of studies relating to noncarcinogenic and nonmutagenic endpoints, including teratology, perinatal studies and studies to determine absorption, metabolism, and doses to critical tissues and organs of coal-derived mixtures and radionuclides. Items have been individually abstracted for the data base. (ACR)

Investigation of solvent-free MALDI-TOFMS sample preparation methods for the analysis of organometallic and coordination compounds.

PubMed

Hughes, Laura; Wyatt, Mark F; Stein, Bridget K; Brenton, A Gareth

2009-01-15

An investigation of various solvent-free matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample preparation methods for the characterization of organometallic and coordination compounds is described. Such methods are desirable for insoluble materials, compounds that are only soluble in disadvantageous solvents, or complexes that dissociate in solution, all of which present a major "difficulty" to most mass spectrometry techniques. First-row transition metal acetylacetonate complexes, which have been characterized previously by solution preparation MALDI-TOFMS, were used to evaluate the various solvent-free procedures. These procedures comprise two distinct steps: the first being the efficient "solids mixing" (the mixing of sample and matrix), and the second being the effective transfer of the sample/matrix mixture to the MALDI target plate. This investigation shows that vortex mixing is the most efficient first step and that smearing using a microspatula is the most effective second step. In addition, the second step is shown to be much more critical than the first step in obtaining high-quality data. Case studies of truly insoluble materials highlight the importance of these techniques for the wider chemistry community.

Effect of CMC addition on steady and dynamic shear rheological properties of binary systems of xanthan gum and guar gum.

PubMed

Bak, J H; Yoo, B

2018-04-12

The effect of CMC on the steady and dynamic shear rheological properties of binary mixtures of XG and GG was examined at different mixing ratios. All XG-GG-CMC ternary mixtures had high shear-thinning behavior and the n value of the sample with 5% CMC was the smallest compared with those of other samples. A marked increase in K and η a,50 values was observed for ternary mixtures at a lower content (5%) of CMC, indicating that the synergistic interactions of the XG-GG binary mixture were affected by the content of CMC. The effect of temperature on the η a,50 was well described by the Arrhenius equation for all samples. The activation energy values of all ternary gum mixtures are higher than that of binary gum mixture, and these values also decreased with an increase in CMC content from 5 to 15%. The dynamic moduli of ternary gum mixtures decreased with an increase in CMC content. The tan δ value of the ternary gum mixture with 5% CMC was much lower than those of other ternary mixtures. In general, these results suggest that the flow and dynamic shear rheological properties of XG-GG binary mixtures are strongly influenced by a small addition of CMC. Copyright © 2018. Published by Elsevier B.V.

Electrophoresis-mass spectrometry probe

DOEpatents

Andresen, Brian D.; Fought, Eric R.

1987-01-01

The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface.

Quantitative carbon detector for enhanced detection of molecules in foods, pharmaceuticals, cosmetics, flavors, and fuels.

PubMed

Beach, Connor A; Krumm, Christoph; Spanjers, Charles S; Maduskar, Saurabh; Jones, Andrew J; Dauenhauer, Paul J

2016-03-07

Analysis of trace compounds, such as pesticides and other contaminants, within consumer products, fuels, and the environment requires quantification of increasingly complex mixtures of difficult-to-quantify compounds. Many compounds of interest are non-volatile and exhibit poor response in current gas chromatography and flame ionization systems. Here we show the reaction of trimethylsilylated chemical analytes to methane using a quantitative carbon detector (QCD; the Polyarc™ reactor) within a gas chromatograph (GC), thereby enabling enhanced detection (up to 10×) of highly functionalized compounds including carbohydrates, acids, drugs, flavorants, and pesticides. Analysis of a complex mixture of compounds shows that the GC-QCD method exhibits faster and more accurate analysis of complex mixtures commonly encountered in everyday products and the environment.

Lagged kernel machine regression for identifying time windows of susceptibility to exposures of complex mixtures.

PubMed

Liu, Shelley H; Bobb, Jennifer F; Lee, Kyu Ha; Gennings, Chris; Claus Henn, Birgit; Bellinger, David; Austin, Christine; Schnaas, Lourdes; Tellez-Rojo, Martha M; Hu, Howard; Wright, Robert O; Arora, Manish; Coull, Brent A

2018-07-01

The impact of neurotoxic chemical mixtures on children's health is a critical public health concern. It is well known that during early life, toxic exposures may impact cognitive function during critical time intervals of increased vulnerability, known as windows of susceptibility. Knowledge on time windows of susceptibility can help inform treatment and prevention strategies, as chemical mixtures may affect a developmental process that is operating at a specific life phase. There are several statistical challenges in estimating the health effects of time-varying exposures to multi-pollutant mixtures, such as: multi-collinearity among the exposures both within time points and across time points, and complex exposure-response relationships. To address these concerns, we develop a flexible statistical method, called lagged kernel machine regression (LKMR). LKMR identifies critical exposure windows of chemical mixtures, and accounts for complex non-linear and non-additive effects of the mixture at any given exposure window. Specifically, LKMR estimates how the effects of a mixture of exposures change with the exposure time window using a Bayesian formulation of a grouped, fused lasso penalty within a kernel machine regression (KMR) framework. A simulation study demonstrates the performance of LKMR under realistic exposure-response scenarios, and demonstrates large gains over approaches that consider each time window separately, particularly when serial correlation among the time-varying exposures is high. Furthermore, LKMR demonstrates gains over another approach that inputs all time-specific chemical concentrations together into a single KMR. We apply LKMR to estimate associations between neurodevelopment and metal mixtures in Early Life Exposures in Mexico and Neurotoxicology, a prospective cohort study of child health in Mexico City.

Development of a 45kpsi ultrahigh pressure liquid chromatography instrument for gradient separations of peptides using long microcapillary columns and sub-2μm particles.

PubMed

Grinias, Kaitlin M; Godinho, Justin M; Franklin, Edward G; Stobaugh, Jordan T; Jorgenson, James W

2016-10-21

Commercial chromatographic instrumentation for bottom-up proteomics is often inadequate to resolve the number of peptides in many samples. This has inspired a number of complex approaches to increase peak capacity, including various multidimensional approaches, and reliance on advancements in mass spectrometry. One-dimensional reversed phase separations are limited by the pressure capabilities of commercial instruments and prevent the realization of greater separation power in terms of speed and resolution inherent to smaller sorbents and ultrahigh pressure liquid chromatography. Many applications with complex samples could benefit from the increased separation performance of long capillary columns packed with sub-2μm sorbents. Here, we introduce a system that operates at a constant pressure and is capable of separations at pressures up to 45kpsi. The system consists of a commercially available capillary liquid chromatography instrument, for sample management and gradient creation, and is modified with a storage loop and isolated pneumatic amplifier pump for elevated separation pressure. The system's performance is assessed with a complex peptide mixture and a range of microcapillary columns packed with sub-2μm C18 particles. Copyright © 2016 Elsevier B.V. All rights reserved.

A fractal approach to dynamic inference and distribution analysis

PubMed Central

van Rooij, Marieke M. J. W.; Nash, Bertha A.; Rajaraman, Srinivasan; Holden, John G.

2013-01-01

Event-distributions inform scientists about the variability and dispersion of repeated measurements. This dispersion can be understood from a complex systems perspective, and quantified in terms of fractal geometry. The key premise is that a distribution's shape reveals information about the governing dynamics of the system that gave rise to the distribution. Two categories of characteristic dynamics are distinguished: additive systems governed by component-dominant dynamics and multiplicative or interdependent systems governed by interaction-dominant dynamics. A logic by which systems governed by interaction-dominant dynamics are expected to yield mixtures of lognormal and inverse power-law samples is discussed. These mixtures are described by a so-called cocktail model of response times derived from human cognitive performances. The overarching goals of this article are twofold: First, to offer readers an introduction to this theoretical perspective and second, to offer an overview of the related statistical methods. PMID:23372552

Estimation of yohimbine base in complex mixtures by quantitative HPTLC application.

PubMed

Adel-Kader, Maged Saad; Alwahebi, Naif Wahebi Hamadan; Alam, Prawez

2017-01-01

The indole alkaloid Yohimbine has been used for over two centuries in the treatment of erectly dysfunction. Several formulations containing yohimbine salts, yohimbe bark power or extract are marketed worldwide. Determination of the amount of yohimbine in such formulation is a challenging task due to their complex nature. Extraction followed by acid-base purification resulted in a relatively pure alkaloids containing fractions. The exact amounts of yohimbine free base in different formulations were determined by densitometric HPTLC validated methods using silica gel TLC plates. Standard curve for yohimbine was generated using yohimbine hydrochloride subjected to the same acid-base treatment as the used samples. All formulations found to contain yohimbine though some with less concentration than the labeled amount.

Isolating cells from female/male blood mixtures using florescence in situ hybridization combined with low volume PCR and its application in forensic science.

PubMed

Feng, Lei; Li, Cai-Xia; Han, Jun-Ping; Xu, Cheng; Hu, Lan

2015-11-01

To obtain single-source short tandem repeat (STR) profiles in trace female/male blood mixture samples, we combined florescence in situ hybridization (FISH), laser microdissection, and low volume PCR (LV-PCR) to isolate male/female cells and improve sensitivity. The results showed that isolation of as few as 10 leukocytes was sufficient to yield full STR profiles in fresh female or male blood samples for 32 independent tests with a low additional alleles rate (3.91%) and drop-out alleles rate (5.01%). Moreover, this procedure was tested in two fresh blood mixture series at three ratios (1:5, 1:10, and 1:20), two mock female/male blood mixture casework samples, and one practical casework sample. Male and female STR profiles were successfully detected in all of these samples, showing that this procedure could be used in forensic casework in the future.

Dielectric constant of liquid alkanes and hydrocarbon mixtures

NASA Technical Reports Server (NTRS)

Sen, A. D.; Anicich, V. G.; Arakelian, T.

1992-01-01

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

Dielectric properties of benzylamine in 1,2,6-hexanetriol mixture using time domain reflectometry technique

NASA Astrophysics Data System (ADS)

Swami, M. B.; Hudge, P. G.; Pawar, V. P.

The dielectric properties of binary mixtures of benzylamine-1,2,6-hexantriol mixtures at different volume fractions of 1,2,6-hexanetriol have been measured using Time Domain Reflectometry (TDR) technique in the frequency range of 10 MHz to 30 GHz. Complex permittivity spectra were fitted using Havriliak-Negami equation. By using least square fit method the dielectric parameters such as static dielectric constant (ɛ0), dielectric constant at high frequency (ɛ∞), relaxation time τ (ps) and relaxation distribution parameter (β) were extracted from complex permittivity spectra at 25∘C. The intramolecular interaction of different molecules has been discussed using the Kirkwood correlation factor, Bruggeman factor. The Kirkwood correlation factor (gf) and effective Kirkwood correlation factor (geff) indicate the dipole ordering of the binary mixtures.

Bayesian kernel machine regression for estimating the health effects of multi-pollutant mixtures.

PubMed

Bobb, Jennifer F; Valeri, Linda; Claus Henn, Birgit; Christiani, David C; Wright, Robert O; Mazumdar, Maitreyi; Godleski, John J; Coull, Brent A

2015-07-01

Because humans are invariably exposed to complex chemical mixtures, estimating the health effects of multi-pollutant exposures is of critical concern in environmental epidemiology, and to regulatory agencies such as the U.S. Environmental Protection Agency. However, most health effects studies focus on single agents or consider simple two-way interaction models, in part because we lack the statistical methodology to more realistically capture the complexity of mixed exposures. We introduce Bayesian kernel machine regression (BKMR) as a new approach to study mixtures, in which the health outcome is regressed on a flexible function of the mixture (e.g. air pollution or toxic waste) components that is specified using a kernel function. In high-dimensional settings, a novel hierarchical variable selection approach is incorporated to identify important mixture components and account for the correlated structure of the mixture. Simulation studies demonstrate the success of BKMR in estimating the exposure-response function and in identifying the individual components of the mixture responsible for health effects. We demonstrate the features of the method through epidemiology and toxicology applications. © The Author 2014. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Phase behaviour of oat β-glucan/sodium caseinate mixtures varying in molecular weight.

PubMed

Agbenorhevi, Jacob K; Kontogiorgos, Vassilis; Kasapis, Stefan

2013-05-01

The isothermal phase behaviour at 5 °C of mixtures of sodium caseinate and oat β-glucan isolates varying in molecular weight (MW) was investigated by means of phase diagram construction, rheometry, fluorescence microscopy and electrophoresis. Phase diagrams indicated that the compatibility of the β-glucan/sodium caseinate system increases as β-glucan MW decreases. Images of mixtures taken at various biopolymer concentrations revealed phase separated domains. Results also revealed that at the state of thermodynamic equilibrium, lower MW samples yielded considerable viscosity in the mixture. At equivalent hydrodynamic volume of β-glucan in the mixtures, samples varying in molecular weight exhibited similar flow behaviour. A deviation dependent on the protein concentration was observed for the high MW sample in the concentrated regime due to the size of β-glucan aggregates formed. Results demonstrate that by controlling the structural features of β-glucan in mixtures with sodium caseinate, informed manipulation of rheological properties in these systems can be achieved. Copyright © 2012 Elsevier Ltd. All rights reserved.

A comparison of complexation of Li+ ion with macrocyclic ligands 15-crown-5 and 12-crown-4 in binary nitromethane-acetonitrile mixtures by using lithium-7 NMR technique and ab initio calculation.

PubMed

Alizadeh, Nina

2011-01-01

Lithium-7 NMR measurements were used to investigate the stoichiometry and stability of Li+ complexes with 15-crown-5 (15C5), benzo-15-crown-5 (B15C5), dibenzo-15-crown-5 (DB15C5) and 12-crown-4 (12C4) in a number of nitromethane (NM)-acetonitrile (AN) binary mixtures. In all cases, the exchange between the free and complexed lithium ion was fast on the NMR time scale and a single population average resonance was observed. While all crown ethers form 1:1 complexes with Li+ ion in the binary mixtures used, both 1:1 and 2:1 (sandwich) complexes were observed between lithium ion and 12C4 in pure nitromethane solution. Stepwise formation constants of the 1:1 and 2:1 (ligand/metal) complexes were evaluated from computer fitting of the NMR-mole ratio data to equations which relate the observed metal ion chemical shifts to formation constants. There is an inverse linear relationship between the logarithms of the stability constants and the mole fraction of acetonitrile in the solvent mixtures. The stability order of the 1:1 complexes was found to be 15C5·Li+>B15C5·Li+>DB15C5·Li+>12C4·Li+. The optimized structures of the free ligands and their 1:1 and 2:1 complexes with Li+ ion were predicted by ab initio theoretical calculations using the Gaussian 98 software, and the results are discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

High-performance liquid chromatography/high-resolution multiple stage tandem mass spectrometry using negative-ion-mode hydroxide-doped electrospray ionization for the characterization of lignin degradation products.

PubMed

Owen, Benjamin C; Haupert, Laura J; Jarrell, Tiffany M; Marcum, Christopher L; Parsell, Trenton H; Abu-Omar, Mahdi M; Bozell, Joseph J; Black, Stuart K; Kenttämaa, Hilkka I

2012-07-17

In the search for a replacement for fossil fuel and the valuable chemicals currently obtained from crude oil, lignocellulosic biomass has become a promising candidate as an alternative biorenewable source for crude oil. Hence, many research efforts focus on the extraction, degradation, and catalytic transformation of lignin, hemicellulose, and cellulose. Unfortunately, these processes result in the production of very complex mixtures. Further, while methods have been developed for the analysis of mixtures of oligosaccharides, this is not true for the complex mixtures generated upon degradation of lignin. For example, high-performance liquid chromatography/multiple stage tandem mass spectrometry (HPLC/MS(n)), a tool proven to be invaluable in the analysis of complex mixtures derived from many other biopolymers, such as proteins and DNA, has not been implemented for lignin degradation products. In this study, we have developed an HPLC separation method for lignin degradation products that is amenable to negative-ion-mode electrospray ionization (ESI doped with NaOH), the best method identified thus far for ionization of lignin-related model compounds without fragmentation. The separated and ionized compounds are then analyzed by MS(3) experiments to obtain detailed structural information while simultaneously performing high-resolution measurements to determine their elemental compositions in the two parts of a commercial linear quadrupole ion trap/Fourier-transform ion cyclotron resonance mass spectrometer. A lignin degradation product mixture was analyzed using this method, and molecular structures were proposed for some components. This methodology significantly improves the ability to analyze complex product mixtures that result from degraded lignin.

Trace level detection of compounds related to the chemical weapons convention by 1H-detected 13C NMR spectroscopy executed with a sensitivity-enhanced, cryogenic probehead.

PubMed

Cullinan, David B; Hondrogiannis, George; Henderson, Terry J

2008-04-15

Two-dimensional 1H-13C HSQC (heteronuclear single quantum correlation) and fast-HMQC (heteronuclear multiple quantum correlation) pulse sequences were implemented using a sensitivity-enhanced, cryogenic probehead for detecting compounds relevant to the Chemical Weapons Convention present in complex mixtures. The resulting methods demonstrated exceptional sensitivity for detecting the analytes at trace level concentrations. 1H-13C correlations of target analytes at < or = 25 microg/mL were easily detected in a sample where the 1H solvent signal was approximately 58,000-fold more intense than the analyte 1H signals. The problem of overlapping signals typically observed in conventional 1H spectroscopy was essentially eliminated, while 1H and 13C chemical shift information could be derived quickly and simultaneously from the resulting spectra. The fast-HMQC pulse sequences generated magnitude mode spectra suitable for detailed analysis in approximately 4.5 h and can be used in experiments to efficiently screen a large number of samples. The HSQC pulse sequences, on the other hand, required roughly twice the data acquisition time to produce suitable spectra. These spectra, however, were phase-sensitive, contained considerably more resolution in both dimensions, and proved to be superior for detecting analyte 1H-13C correlations. Furthermore, a HSQC spectrum collected with a multiplicity-edited pulse sequence provided additional structural information valuable for identifying target analytes. The HSQC pulse sequences are ideal for collecting high-quality data sets with overnight acquisitions and logically follow the use of fast-HMQC pulse sequences to rapidly screen samples for potential target analytes. Use of the pulse sequences considerably improves the performance of NMR spectroscopy as a complimentary technique for the screening, identification, and validation of chemical warfare agents and other small-molecule analytes present in complex mixtures and environmental samples.

Next generation offline approaches to trace organic compound speciation: Approaching comprehensive speciation with soft ionization and very high resolution tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Khare, P.; Marcotte, A.; Sheu, R.; Ditto, J.; Gentner, D. R.

2017-12-01

Intermediate- and semi-volatile organic compounds (IVOCs and SVOCs) have high secondary organic aerosol (SOA) yields, as well as significant ozone formation potentials. Yet, their emission sources and oxidation pathways remain largely understudied due to limitations in current analytical capabilities. Online mass spectrometers are able to collect real time data but their limited mass resolving power renders molecular level characterization of IVOCs and SVOCs from the unresolved complex mixture unfeasible. With proper sampling techniques and powerful analytical instrumentation, our offline tandem mass spectrometry (i.e. MS×MS) techniques provide molecular-level and structural identification over wide polarity and volatility ranges. We have designed a novel analytical system for offline analysis of gas-phase SOA precursors collected on custom-made multi-bed adsorbent tubes. Samples are desorbed into helium via a gradual temperature ramp and sample flow is split equally for direct-MS×MS analysis and separation via gas chromatography (GC). The effluent from GC separation is split again for analysis via atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-Q×TOF) and traditional electron ionization mass spectrometry (EI-MS). The compounds for direct-MS×MS analysis are delivered via a transfer line maintained at 70ºC directly to APCI-Q×TOF, thus preserving the molecular integrity of thermally-labile, or other highly-reactive, organic compounds. Both our GC-MS×MS and direct-MS×MS analyses report high accuracy parent ion masses as well as information on molecular structure via MS×MS, which together increase the resolution of unidentified complex mixtures. We demonstrate instrument performance and present preliminary results from urban atmospheric samples collected from New York City with a wide range of compounds including highly-functionalized organic compounds previously understudied in outdoor air. Our work offers new insights into emerging emission sources in urban environments that can have a major impact on public health and also improves understanding of anthropogenic SOA precursor emissions.

ChromAlign: A two-step algorithmic procedure for time alignment of three-dimensional LC-MS chromatographic surfaces.

PubMed

Sadygov, Rovshan G; Maroto, Fernando Martin; Hühmer, Andreas F R

2006-12-15

We present an algorithmic approach to align three-dimensional chromatographic surfaces of LC-MS data of complex mixture samples. The approach consists of two steps. In the first step, we prealign chromatographic profiles: two-dimensional projections of chromatographic surfaces. This is accomplished by correlation analysis using fast Fourier transforms. In this step, a temporal offset that maximizes the overlap and dot product between two chromatographic profiles is determined. In the second step, the algorithm generates correlation matrix elements between full mass scans of the reference and sample chromatographic surfaces. The temporal offset from the first step indicates a range of the mass scans that are possibly correlated, then the correlation matrix is calculated only for these mass scans. The correlation matrix carries information on highly correlated scans, but it does not itself determine the scan or time alignment. Alignment is determined as a path in the correlation matrix that maximizes the sum of the correlation matrix elements. The computational complexity of the optimal path generation problem is reduced by the use of dynamic programming. The program produces time-aligned surfaces. The use of the temporal offset from the first step in the second step reduces the computation time for generating the correlation matrix and speeds up the process. The algorithm has been implemented in a program, ChromAlign, developed in C++ language for the .NET2 environment in WINDOWS XP. In this work, we demonstrate the applications of ChromAlign to alignment of LC-MS surfaces of several datasets: a mixture of known proteins, samples from digests of surface proteins of T-cells, and samples prepared from digests of cerebrospinal fluid. ChromAlign accurately aligns the LC-MS surfaces we studied. In these examples, we discuss various aspects of the alignment by ChromAlign, such as constant time axis shifts and warping of chromatographic surfaces.

Introducing Students to Gas Chromatography-Mass Spectrometry Analysis and Determination of Kerosene Components in a Complex Mixture

ERIC Educational Resources Information Center

Pacot, Giselle Mae M.; Lee, Lyn May; Chin, Sung-Tong; Marriott, Philip J.

2016-01-01

Gas chromatography-mass spectrometry (GC-MS) and GC-tandem MS (GC-MS/MS) are useful in many separation and characterization procedures. GC-MS is now a common tool in industry and research, and increasingly, GC-MS/MS is applied to the measurement of trace components in complex mixtures. This report describes an upper-level undergraduate experiment…

Modeling of Complex Mixtures: JP-8 Toxicokinetics

DTIC Science & Technology

2008-10-01

generic tissue compartments in which we have combined diffusion limitation and deep tissue (global tissue model). We also applied a QSAR approach for...SUBJECT TERMS jet fuel, JP-8, PBPK modeling, complex mixtures, nonane, decane, naphthalene, QSAR , alternative fuels 16. SECURITY CLASSIFICATION OF...necessary, to apply to the interaction of specific compounds with specific tissues. We have also applied a QSAR approach for estimating blood and tissue

The Control of Orbital Mixing in Ruthenium Complexes Containing Quinone Related Ligands

DTIC Science & Technology

1991-04-04

and sodium, respectively. Tetrabutylammonium perchlorate (TBAP) and tetrabutylammonium hexafluorophosphate (Kodak; TBAH) were recrystallized from...solution. Lithium perchlorate trihydrate (0.036 g; 0.23 mmol) in methanol (2 mL) was added to the hot reaction mixture. The mixture was cooled to room...and lithium aluminum hydride suspension in THF (this required the use of the 4,5-dimethylated orthophenylenediamine complex for solubility reasons

OFFICE OF RESEARCH AND DEVELOPMENT'S FOUR LAB STUDY: TOXICOLOGICCAL AND CHEMICAL EVALUATION OF COMPLEX MIXTURES OF DISINFECTION BY-PRODUCTS (DBPS) AND QUALITY ASSURANCE ACTIVITIES FOR A LARGE U. S. EPA MULTILABORATORY STUDY

EPA Science Inventory

Office of Research and Development's Four Lab Study: Toxicological and Chemical Evaluation of Complex Mixtures of Disinfection By-Products (DBPs), and Quality Assurance Activities for a Large U.S. EPA Multilaboratoty Study

Thomas J. Hughes, Project and QA Manager, Expe...

Pharmacokinetic Modeling of JP-8 Jet Fuel Components: II. A Conceptual Framework

DTIC Science & Technology

2003-12-01

example, a single type of (simple) binary interaction between 300 components would require the specification of some 105 interaction coefficients . One...individual substances, via binary mechanisms, is enough to predict the interactions present in the mixture. Secondly, complex mixtures can often be...approximated as pseudo- binary systems, consisting of the compound of interest plus a single interacting complex vehicle with well-defined, composite

Development of Composite Spectrophotometric Procedures for the Analysis of Low-Alloy Steels and of Aluminum and Its Alloys

DTIC Science & Technology

1952-11-01

COPPER lb Although copper can be determined by measurement of the blue cupric ammonia complex, the reaction is not very sensitive and is subject to...alkaline solution of the sample con- taining tartrate , provided a means of separation of copper by extraction of WADO TR 52-246 1 the copper bensoinoximate...potassium tartrate ), and sodium hydroxide solution added to ad- just the pH within the range ll3 to 12-3. After adding alpha-benzoinoxime the mixture was

Aspects of High-Resolution Gas Chromatography as Applied to the Analysis of Hydrocarbon Fuels and Other Complex Organic Mixtures. Volume 2. Survey of Sample Insertion Techniques.

DTIC Science & Technology

1985-06-01

packed column, with low liquid loading (2. 0 mm ID, 4% liquid phase loading on diatomaceous earth *) 0.3 Medium bore analytical packed column, with...moderate liquid loading (4. 5 mm ID, 8%16 liquid phase loading on diatomaceous earth *) 3.0 -3 * diatomaceous earth density 0.24 gm cm 12 associated with the...hydrocarbon fuels. Certain injector inserts have contained packed chromatographic media, e.g., stationary phases coated onto diatomaceous earth . This type

Crater Morphology in the Phoenix Landing Ellipse: Insights Into Net Erosion and Ice Table Depth

NASA Technical Reports Server (NTRS)

Noe Dobrea, E. Z.; Stoker, C. R.; McKay, C. P.; Davila, A. F.; Krco, M.

2015-01-01

Icebreaker [1] is a Discovery class mission being developed for future flight opportunities. Under this mission concept, the Icebreaker payload is carried on a stationary lander, and lands in the same landing ellipse as Phoenix. Samples are acquired from the subsurface using a drilling system that penetrates into materials which may include loose or cemented soil, icy soil, pure ice, rocks, or mixtures of these. To avoid the complexity of mating additional strings, the drill is single-string, limiting it to a total length of 1 m.

Protein-Mediated Precipitation of Calcium Carbonate

PubMed Central

Polowczyk, Izabela; Bastrzyk, Anna; Fiedot, Marta

2016-01-01

Calcium carbonate is an important component in exoskeletons of many organisms. The synthesis of calcium carbonate was performed by mixing dimethyl carbonate and an aqueous solution of calcium chloride dihydrate. The precipitation product was characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) measurements. In addition, the turbidity of the reaction solution was acquired to monitor the kinetics of the calcium carbonate structure’s growth in the investigated system. In this study, samples of CaCO3 particles obtained with individual proteins, such as ovalbumin, lysozyme, and a mixture of the proteins, were characterized and compared with a control sample, i.e., synthesized without proteins. The obtained data indicated that the addition of ovalbumin to the reaction changed the morphology of crystals from rhombohedral to ‘stack-like’ structures. Lysozyme, however, did not affect the morphology of calcium carbonate, yet the presence of the protein mixture led to the creation of more complex composites in which the calcium carbonate crystals were constructed in protein matrices formed by the ovalbumin-lysozyme interaction. It was also observed that in the protein mixture, ovalbumin has a major influence on the CaCO3 formation through a strong interaction with calcium ions, which leads to the coalescence and creation of a steric barrier reducing particle growth. The authors proposed a mechanism of calcium carbonate grain growth in the presence of both proteins, taking into account the interaction of calcium ions with the protein. PMID:28774065

Use of genetic data to infer population-specific ecological and phenotypic traits from mixed aggregations

USGS Publications Warehouse

Moran, Paul; Bromaghin, Jeffrey F.; Masuda, Michele

2014-01-01

Many applications in ecological genetics involve sampling individuals from a mixture of multiple biological populations and subsequently associating those individuals with the populations from which they arose. Analytical methods that assign individuals to their putative population of origin have utility in both basic and applied research, providing information about population-specific life history and habitat use, ecotoxins, pathogen and parasite loads, and many other non-genetic ecological, or phenotypic traits. Although the question is initially directed at the origin of individuals, in most cases the ultimate desire is to investigate the distribution of some trait among populations. Current practice is to assign individuals to a population of origin and study properties of the trait among individuals within population strata as if they constituted independent samples. It seemed that approach might bias population-specific trait inference. In this study we made trait inferences directly through modeling, bypassing individual assignment. We extended a Bayesian model for population mixture analysis to incorporate parameters for the phenotypic trait and compared its performance to that of individual assignment with a minimum probability threshold for assignment. The Bayesian mixture model outperformed individual assignment under some trait inference conditions. However, by discarding individuals whose origins are most uncertain, the individual assignment method provided a less complex analytical technique whose performance may be adequate for some common trait inference problems. Our results provide specific guidance for method selection under various genetic relationships among populations with different trait distributions.

Rheological behavior of water-ash mixtures from Sakurajima and Ontake volcanoes: implications for lahar flow dynamics

NASA Astrophysics Data System (ADS)

Kurokawa, Aika K.; Ishibashi, Hidemi; Miwa, Takahiro; Nanayama, Futoshi

2018-06-01

Lahars represent one of the most serious volcanic hazards, potentially causing severe damage to the surrounding environment, not only immediately after eruption but also later due to rainfall or snowfall. The flow of a lahar is governed by volcanic topography and its rheological behavior, which is controlled by its volume, microscale properties, and the concentration of particles. However, the effects of particle properties on the rheology of lahars are poorly understood. In this study, viscosity measurements were performed on water-ash mixtures from Sakurajima and Ontake volcanoes. Samples from Sakurajima show strong and simple shear thinning, whereas those from Ontake show viscosity fluctuations and a transition between shear thinning and shear thickening. Particle analysis of the volcanic ash together with a theoretical analysis suggests that the rheological difference between the two types of suspension can be explained by variations in particle size distribution and shape. In particular, to induce the complex rheology of the Ontake samples, coexistence of two particle size groups may be required since two independent behaviors, one of which follows the streamline (Stokes number St << 1, inertial number I < 0.001) and the other shows a complicated motion ( St 1, I 0.001), compete against each other. The variations in the spatial distribution of polydisperse particles, and the time dependence of this feature which generates apparent rheological changes, indicate that processes related to microscale particle heterogeneities are important in understanding the flow dynamics of lahars and natural polydisperse granular-fluid mixtures in general.

Use of Genetic Data to Infer Population-Specific Ecological and Phenotypic Traits from Mixed Aggregations

PubMed Central

Moran, Paul; Bromaghin, Jeffrey F.; Masuda, Michele

2014-01-01

Many applications in ecological genetics involve sampling individuals from a mixture of multiple biological populations and subsequently associating those individuals with the populations from which they arose. Analytical methods that assign individuals to their putative population of origin have utility in both basic and applied research, providing information about population-specific life history and habitat use, ecotoxins, pathogen and parasite loads, and many other non-genetic ecological, or phenotypic traits. Although the question is initially directed at the origin of individuals, in most cases the ultimate desire is to investigate the distribution of some trait among populations. Current practice is to assign individuals to a population of origin and study properties of the trait among individuals within population strata as if they constituted independent samples. It seemed that approach might bias population-specific trait inference. In this study we made trait inferences directly through modeling, bypassing individual assignment. We extended a Bayesian model for population mixture analysis to incorporate parameters for the phenotypic trait and compared its performance to that of individual assignment with a minimum probability threshold for assignment. The Bayesian mixture model outperformed individual assignment under some trait inference conditions. However, by discarding individuals whose origins are most uncertain, the individual assignment method provided a less complex analytical technique whose performance may be adequate for some common trait inference problems. Our results provide specific guidance for method selection under various genetic relationships among populations with different trait distributions. PMID:24905464

Identification and quantification of homologous series of compound in complex mixtures: autocovariance study of GC/MS chromatograms.

PubMed

Pietrogrande, Maria Chiara; Zampolli, Maria Grazia; Dondi, Francesco

2006-04-15

The paper describes a method for determining homologous classes of compounds in a multicomponent complex chromatogram obtained under programming elution conditions. The method is based on the computation of the autocovariance function of the experimental chromatogram (EACVF). The EACVF plot, if properly interpreted, can be regarded as a "class chromatogram" i.e., a virtual chromatogram formed by peaks whose positions and heights allow identification and quantification of the different homologous series, even if they are embedded in a random complex chromatogram. Theoretical models were developed to describe complex chromatograms displaying random retention pattern, ordered sequences or a combination of them. On the basis of theoretical autocovariance function, the properties of the chromatogram can be experimentally evaluated, under well-defined conditions: in particular, the two components of the chromatogram, ordered and random, can be identified. Moreover, the total number of single components (SCs) and the separated number of the SCs belonging to the random and ordered components can be determined, when the two components display the same concentration. If the mixture contains several homologous series with common frequency and different phase values, the number and identity of the different homologous series as well as the number of SCs belonging to each of them can be evaluated. Moreover, the power of the EACVF method can be magnified by applying it to the single ion monitoring (SIM) signals to selectively detect specific compound classes in order to identify the different homologous series. By this way, a full "decoding" of the complex multicomponent chromatogram is achieved. The method was validated on synthetic mixtures containing known amount of SCs belonging to homologous series of hydrocarbon, alcohols, ketones, and aromatic compounds in addition to other not structurally related SCs. The method was applied to both the total ion monitoring (TIC) and the SIM signals, to describe step by step the essence of the procedure. Moreover, the systematic use of both SIM and TIC can simplify the decoding procedure of complex chromatograms by singling out only specific compound classes or by confirming the identification of the different homologous series. The method was further applied to a sample containing unknown number of compounds and homologous series (a petroleum benzin, bp 140-160 degrees C): the results obtained were meaningful in terms of both the identified number of components and identified homologous series.

Simulation of Particle Size Effect on Dynamic Properties and Fracture of PTFE-W-Al Composites

NASA Astrophysics Data System (ADS)

Herbold, Eric; Cai, Jing; Benson, David; Nesterenko, Vitali

2007-06-01

Recent investigations of the dynamic compressive strength of cold isostatically pressed (CIP) composites of polytetrafluoroethylene (PTFE), tungsten and aluminum powders show significant differences depending on the size of metallic particles. PTFE and aluminum mixtures are known to be energetic under dynamic and thermal loading. The addition of tungsten increases density and overall strength of the sample. Multi-material Eulerian and arbitrary Lagrangian-Eulerian methods were used for the investigation due to the complexity of the microstructure, relatively large deformations and the ability to handle the formation of free surfaces in a natural manner. The calculations indicate that the observed dependence of sample strength on particle size is due to the formation of force chains under dynamic loading in samples with small particle sizes even at larger porosity in comparison with samples with large grain size and larger density.

Validation of molecularly imprinted polymers for side chain selective phosphopeptide enrichment.

PubMed

Chen, Jing; Shinde, Sudhirkumar; Subedi, Prabal; Wierzbicka, Celina; Sellergren, Börje; Helling, Stefan; Marcus, Katrin

2016-11-04

Selective enrichment techniques are essential for mapping of protein posttranslational modifications (PTMs). Phosphorylation is one of the PTMs which continues to be associated with significant analytical challenges. Particularly problematic are tyrosine-phosphorylated peptides (pY-peptides) resulting from tryptic digestion which commonly escape current chemo- or immuno- affinity enrichments and hence remain undetected. We here report on significant improvements in this regard using pY selective molecularly imprinted polymers (pY-MIPs). The pY-MIP was compared with titanium dioxide (TiO 2 ) affinity based enrichment and immunoprecipitation (IP) with respect to selective enrichment from a mixture of 13 standard peptides at different sample loads. At a low sample load (1pmol of each peptide), IP resulted in enrichment of only a triply phosphorylated peptide whereas TiO 2 enriched phosphopeptides irrespective of the amino acid side chain. However, with increased sample complexity, TiO 2 failed to enrich the doubly phosphorylated peptides. This contrasted with the pY-MIP showing enrichment of all four tyrosine phosphorylated peptides at 1pmol sample load of each peptide with a few other peptides binding unselectively. At an increased sample complexity consisting of the standard peptides spiked into mouse brain digest, the MIP showed clear enrichment of all four pY- peptides. Copyright © 2016 Elsevier B.V. All rights reserved.

Matrix-assisted laser desorption-ionization time-of-flight mass spectrometry in the subunit stoichiometry study of high-mass non-covalent complexes

NASA Astrophysics Data System (ADS)

Moniatte, M.; Lesieur, C.; Vecsey-Semjen, B.; Buckley, J. T.; Pattus, F.; van der Goot, F. G.; van Dorsselaer, A.

1997-12-01

This study explores the potential of MALDI-TOF MS for the mass measurement of large non-covalent protein complexes. The following non-covalent complexes have been investigated: aerolysin from Aeromonas hydrophila (335 kDa) and [alpha]-haemolysin from Staphylococcus aureus (233 kDa) which are both cytolytic toxins, three enzymes known to be homotetramers in solution: bovine liver catalase (235 kDa), rabbit muscle pyruvate kinase (232 kDa), yeast alcohol dehydrogenase (147 kDa) and finally a lectin, concanavalin A (102 kDa). Three different matrix preparations were systematically tested under various conditions: ferulic acid dissolved in THF, 2,6-dihydroxyacetophenone in 20 mM aqueous ammonium citrate and a two-step sample preparation with sinapinic acid. It was possible to find a suitable combination of matrix and preparation type which allowed the molecularity of all complexes tested to be deduced from the MALDI mass spectrum. Trimeric and tetrameric intermediates accumulating during the formation of the active heptameric aerolysin complex were also identified, this allowing a formation mechanism to be proposed. The observation of large specific non-covalent complexes has been found to be dependent on the choice of matrix, the type of sample preparation used, the solvent evaporation speed, the pH of the resulting matrix-sample mixture and the number of shots acquired on a given area. From this set of experiments, some useful guidelines for the observation of large complexes by MALDI could therefore be deduced. Fast evaporation of the solvent is particularly necessary in the case of pH sensitive complexes. An ESMS study on the same non-covalent complexes indicated that, rather surprisingly, reliable results could be obtained by MALDI-TOF MS on several very large complexes (above 200 kDa) for which ESMS yielded no clear spectra.

General baseline toxicity QSAR for nonpolar, polar and ionisable chemicals and their mixtures in the bioluminescence inhibition assay with Aliivibrio fischeri.

PubMed

Escher, Beate I; Baumer, Andreas; Bittermann, Kai; Henneberger, Luise; König, Maria; Kühnert, Christin; Klüver, Nils

2017-03-22

The Microtox assay, a bioluminescence inhibition assay with the marine bacterium Aliivibrio fischeri, is one of the most popular bioassays for assessing the cytotoxicity of organic chemicals, mixtures and environmental samples. Most environmental chemicals act as baseline toxicants in this short-term screening assay, which is typically run with only 30 min of exposure duration. Numerous Quantitative Structure-Activity Relationships (QSARs) exist for the Microtox assay for nonpolar and polar narcosis. However, typical water pollutants, which have highly diverse structures covering a wide range of hydrophobicity and speciation from neutral to anionic and cationic, are often outside the applicability domain of these QSARs. To include all types of environmentally relevant organic pollutants we developed a general baseline toxicity QSAR using liposome-water distribution ratios as descriptors. Previous limitations in availability of experimental liposome-water partition constants were overcome by reliable prediction models based on polyparameter linear free energy relationships for neutral chemicals and the COSMOmic model for charged chemicals. With this QSAR and targeted mixture experiments we could demonstrate that ionisable chemicals fall in the applicability domain. Most investigated water pollutants acted as baseline toxicants in this bioassay, with the few outliers identified as uncouplers or reactive toxicants. The main limitation of the Microtox assay is that chemicals with a high melting point and/or high hydrophobicity were outside of the applicability domain because of their low water solubility. We quantitatively derived a solubility cut-off but also demonstrated with mixture experiments that chemicals inactive on their own can contribute to mixture toxicity, which is highly relevant for complex environmental mixtures, where these chemicals may be present at concentrations below the solubility cut-off.

Microfluidic-based mini-metagenomics enables discovery of novel microbial lineages from complex environmental samples.

PubMed

Yu, Feiqiao Brian; Blainey, Paul C; Schulz, Frederik; Woyke, Tanja; Horowitz, Mark A; Quake, Stephen R

2017-07-05

Metagenomics and single-cell genomics have enabled genome discovery from unknown branches of life. However, extracting novel genomes from complex mixtures of metagenomic data can still be challenging and represents an ill-posed problem which is generally approached with ad hoc methods. Here we present a microfluidic-based mini-metagenomic method which offers a statistically rigorous approach to extract novel microbial genomes while preserving single-cell resolution. We used this approach to analyze two hot spring samples from Yellowstone National Park and extracted 29 new genomes, including three deeply branching lineages. The single-cell resolution enabled accurate quantification of genome function and abundance, down to 1% in relative abundance. Our analyses of genome level SNP distributions also revealed low to moderate environmental selection. The scale, resolution, and statistical power of microfluidic-based mini-metagenomics make it a powerful tool to dissect the genomic structure of microbial communities while effectively preserving the fundamental unit of biology, the single cell.

Analysis of Graphite Reinforced Cementitious Composites

NASA Technical Reports Server (NTRS)

Vaughan, Robert E.; Gilbert, John A.; Spanyer, Karen (Technical Monitor)

2001-01-01

This paper describes analytical methods that can be used to determine the deflections and stresses in highly compliant graphite-reinforced cementitious composites. It is demonstrated that the standard transform section fails to provide accurate results when the elastic modulus ratio exceeds 20. So an alternate approach is formulated by using the rule of mixtures to determine a set of effective material properties for the composite. Tensile tests are conducted on composite samples to verify this approach; and, when the effective material properties are used to characterize the deflections of composite beams subject to pure bending, an excellent agreement is obtained. Laminated composite plate theory is also investigated as a means for analyzing even more complex composites, consisting of multiple graphite layers oriented in different directions. In this case, composite beams are analyzed by incorporating material properties established from tensile tests. Finite element modeling is used to verity the results and, considering the complexity of the samples, a very good agreement is obtained.

DTWscore: differential expression and cell clustering analysis for time-series single-cell RNA-seq data.

PubMed

Wang, Zhuo; Jin, Shuilin; Liu, Guiyou; Zhang, Xiurui; Wang, Nan; Wu, Deliang; Hu, Yang; Zhang, Chiping; Jiang, Qinghua; Xu, Li; Wang, Yadong

2017-05-23

The development of single-cell RNA sequencing has enabled profound discoveries in biology, ranging from the dissection of the composition of complex tissues to the identification of novel cell types and dynamics in some specialized cellular environments. However, the large-scale generation of single-cell RNA-seq (scRNA-seq) data collected at multiple time points remains a challenge to effective measurement gene expression patterns in transcriptome analysis. We present an algorithm based on the Dynamic Time Warping score (DTWscore) combined with time-series data, that enables the detection of gene expression changes across scRNA-seq samples and recovery of potential cell types from complex mixtures of multiple cell types. The DTWscore successfully classify cells of different types with the most highly variable genes from time-series scRNA-seq data. The study was confined to methods that are implemented and available within the R framework. Sample datasets and R packages are available at https://github.com/xiaoxiaoxier/DTWscore .

Determinants of Whether or not Mixtures of Disinfection By-products are Similar

EPA Science Inventory

This project summary and its related publications provide information on the development of chemical, toxicological and statistical criteria for determining the sufficient similarity of complex chemical mixtures.

Synthesis and Evaluation of a Novel Adenosine-Ribose Probe for Global-Scale Profiling of Nucleoside and Nucleotide-Binding Proteins

PubMed Central

Mahajan, Shikha; Manetsch, Roman; Merkler, David J.; Stevens Jr., Stanley M.

2015-01-01

Proteomics is a powerful approach used for investigating the complex molecular mechanisms of disease pathogenesis and progression. An important challenge in modern protein profiling approaches involves targeting of specific protein activities in order to identify altered molecular processes associated with disease pathophysiology. Adenosine-binding proteins represent an important subset of the proteome where aberrant expression or activity changes of these proteins have been implicated in numerous human diseases. Herein, we describe an affinity-based approach for the enrichment of adenosine-binding proteins from a complex cell proteome. A novel N 6-biotinylated-8-azido-adenosine probe (AdoR probe) was synthesized, which contains a reactive group that forms a covalent bond with the target proteins, as well as a biotin tag for affinity enrichment using avidin chromatography. Probe specificity was confirmed with protein standards prior to further evaluation in a complex protein mixture consisting of a lysate derived from mouse neuroblastoma N18TG2 cells. Protein identification and relative quantitation using mass spectrometry allowed for the identification of small variations in abundance of nucleoside- and nucleotide-binding proteins in these samples where a significant enrichment of AdoR-binding proteins in the labeled proteome from the neuroblastoma cells was observed. The results from this study demonstrate the utility of this method to enrich for nucleoside- and nucleotide-binding proteins in a complex protein mixture, pointing towards a unique set of proteins that can be examined in the context of further understanding mechanisms of disease, or fundamental biological processes in general. PMID:25671571

High-performance liquid chromatography coupled with post-column dual-bioactivity assay for simultaneous screening of xanthine oxidase inhibitors and free radical scavengers from complex mixture.

PubMed

Li, D Q; Zhao, J; Li, S P

2014-06-06

Xanthine oxidase (XO) can catalyze hypoxanthine and xanthine to generate uric acid and reactive oxygen species (ROS), including superoxide anion radical (O₂(•-)) and hydrogen peroxide. XO inhibitors and free radical scavengers are beneficial to the treatment of gout and many related diseases. In the present study, an on-line high-performance liquid chromatography (HPLC) coupled with post-column dual-bioactivity assay was established and successfully applied to simultaneously screening of XO inhibitors and free radical scavengers from a complex mixture, Oroxylum indicum extract. The integrated system of HPLC separation, bioactivity screening and mass spectrometry identification was proved to be simple and effective for rapid and sensitive screening of individual bioactive compounds in complex mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrophoresis-mass spectrometry probe

DOEpatents

Andresen, B.D.; Fought, E.R.

1987-11-10

The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface. 8 figs.

Advanced instrumental methods for analyzing organics in solid waste: The use of gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR) and supercritical fluid chromatography (SFC) for waste characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raphaelian, L.A.; Boparai, A.S.; Schneider, J.F.

1987-01-01

Objectives of this research project were: (1) to enhance the capabilities of analyzing the complex mixtures found in coal wastes by using gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR); (2) to separate, by supercritical fluid chromatography (SFC), the complex mixtures found in coal wastes into a few, less-complex mixtures so that analysis by gas chromatography (GC/MS) and GC/MIIR would be simplified. Preliminary results are presented for the mass spectra and infrared spectra of xylene isomers, gas chromatogram of 12 C/sub 2/-Napthalenes, averaged IR spectrum and a comparison of matrix isolation with light-pipe infrared spectra. A SFC chromatogram of polynuclear aromatic hydrocarbonsmore » is also presented. 2 refs., 5 figs.« less

Differential gene expression patterns in developing sexually dimorphic rat brain regions exposed to antiandrogenic, estrogenic, or complex endocrine disruptor mixtures: glutamatergic synapses as target.

PubMed

Lichtensteiger, Walter; Bassetti-Gaille, Catherine; Faass, Oliver; Axelstad, Marta; Boberg, Julie; Christiansen, Sofie; Rehrauer, Hubert; Georgijevic, Jelena Kühn; Hass, Ulla; Kortenkamp, Andreas; Schlumpf, Margret

2015-04-01

The study addressed the question whether gene expression patterns induced by different mixtures of endocrine disrupting chemicals (EDCs) administered in a higher dose range, corresponding to 450×, 200×, and 100× high-end human exposure levels, could be characterized in developing brain with respect to endocrine activity of mixture components, and which developmental processes were preferentially targeted. Three EDC mixtures, A-Mix (anti-androgenic mixture) with 8 antiandrogenic chemicals (di-n-butylphthalate, diethylhexylphthalate, vinclozolin, prochloraz, procymidone, linuron, epoxiconazole, and DDE), E-Mix (estrogenic mixture) with 4 estrogenic chemicals (bisphenol A, 4-methylbenzylidene camphor, 2-ethylhexyl 4-methoxycinnamate, and butylparaben), a complex mixture, AEP-Mix, containing the components of A-Mix and E-Mix plus paracetamol, and paracetamol alone, were administered by oral gavage to rat dams from gestation day 7 until weaning. General developmental endpoints were not affected by EDC mixtures or paracetamol. Gene expression was analyzed on postnatal day 6, during sexual brain differentiation, by exon microarray in medial preoptic area in the high-dose group, and by real-time RT-PCR in medial preoptic area and ventromedial hypothalamus in all dose groups. Expression patterns were mixture, sex, and region specific. Effects of the analgesic drug paracetamol, which exhibits antiandrogenic activity in peripheral systems, differed from those of A-Mix. All mixtures had a strong, mixture-specific impact on genes encoding for components of excitatory glutamatergic synapses and genes controlling migration and pathfinding of glutamatergic and GABAergic neurons, as well as genes linked with increased risk of autism spectrum disorders. Because development of glutamatergic synapses is regulated by sex steroids also in hippocampus, this may represent a general target of ECD mixtures.

Toxicity interactions between manganese (Mn) and lead (Pb) or cadmium (Cd) in a model organism the nematode C. elegans.

PubMed

Lu, Cailing; Svoboda, Kurt R; Lenz, Kade A; Pattison, Claire; Ma, Hongbo

2018-06-01

Manganese (Mn) is considered as an emerging metal contaminant in the environment. However, its potential interactions with companying toxic metals and the associated mixture effects are largely unknown. Here, we investigated the toxicity interactions between Mn and two commonly seen co-occurring toxic metals, Pb and Cd, in a model organism the nematode Caenorhabditis elegans. The acute lethal toxicity of mixtures of Mn+Pb and Mn+Cd were first assessed using a toxic unit model. Multiple toxicity endpoints including reproduction, lifespan, stress response, and neurotoxicity were then examined to evaluate the mixture effects at sublethal concentrations. Stress response was assessed using a daf-16::GFP transgenic strain that expresses GFP under the control of DAF-16 promotor. Neurotoxicity was assessed using a dat-1::GFP transgenic strain that expresses GFP in dopaminergic neurons. The mixture of Mn+Pb induced a more-than-additive (synergistic) lethal toxicity in the worm whereas the mixture of Mn+Cd induced a less-than-additive (antagonistic) toxicity. Mixture effects on sublethal toxicity showed more complex patterns and were dependent on the toxicity endpoints as well as the modes of toxic action of the metals. The mixture of Mn+Pb induced additive effects on both reproduction and lifespan, whereas the mixture of Mn+Cd induced additive effects on lifespan but not reproduction. Both mixtures seemed to induce additive effects on stress response and neurotoxicity, although a quantitative assessment was not possible due to the single concentrations used in mixture tests. Our findings demonstrate the complexity of metal interactions and the associated mixture effects. Assessment of metal mixture toxicity should take into consideration the unique property of individual metals, their potential toxicity mechanisms, and the toxicity endpoints examined.

TomoMiner and TomoMinerCloud: A software platform for large-scale subtomogram structural analysis

PubMed Central

Frazier, Zachary; Xu, Min; Alber, Frank

2017-01-01

SUMMARY Cryo-electron tomography (cryoET) captures the 3D electron density distribution of macromolecular complexes in close to native state. With the rapid advance of cryoET acquisition technologies, it is possible to generate large numbers (>100,000) of subtomograms, each containing a macromolecular complex. Often, these subtomograms represent a heterogeneous sample due to variations in structure and composition of a complex in situ form or because particles are a mixture of different complexes. In this case subtomograms must be classified. However, classification of large numbers of subtomograms is a time-intensive task and often a limiting bottleneck. This paper introduces an open source software platform, TomoMiner, for large-scale subtomogram classification, template matching, subtomogram averaging, and alignment. Its scalable and robust parallel processing allows efficient classification of tens to hundreds of thousands of subtomograms. Additionally, TomoMiner provides a pre-configured TomoMinerCloud computing service permitting users without sufficient computing resources instant access to TomoMiners high-performance features. PMID:28552576

Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

PubMed

Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A; Alsberg, Tomas; de Wit, Cynthia A

2017-09-19

Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a "congener group" C n Cl m . Recently, we resolved individual C n Cl m by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying C n Cl m by introducing C n Cl m specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each C n Cl m are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. C n Cl m concentrations determined with the three instruments were highly correlated (R 2 > 0.90) with each other.

Binary Mixtures of Permanganate and Chlorinated Volatile Organic Compounds in Groundwater Samples: Sample Preservation and Analysis

EPA Science Inventory

Ground water samples collected at sites where in-situ chemical oxidation (ISCO) has been deployed may contain binary mixtures of ground water contaminants and permanganate (MnO4-), an oxidant injected into the subsurface to destroy the contaminant. Commingling of the oxidant and ...

Gradient elution moving boundary electrophoresis enables rapid analysis of acids in complex biomass-derived streams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munson, Matthew S.; Karp, Eric M.; Nimlos, Claire T.

Biomass conversion processes such as pretreatment, liquefaction, and pyrolysis often produce complex mixtures of intermediates that are a substantial challenge to analyze rapidly and reliably. To characterize these streams more comprehensively and efficiently, new techniques are needed to track species through biomass deconstruction and conversion processes. Here, we present the application of an emerging analytical method, gradient elution moving boundary electrophoresis (GEMBE), to quantify a suite of acids in a complex, biomass-derived streams from alkaline pretreatment of corn stover. GEMBE offers distinct advantages over common chromatography-spectrometry analytical approaches in terms of analysis time, sample preparation requirements, and cost of equipment.more » As demonstrated here, GEMBE is able to track 17 distinct compounds (oxalate, formate, succinate, malate, acetate, glycolate, protocatechuate, 3-hydroxypropanoate, lactate, glycerate, 2-hydroxybutanoate, 4-hydroxybenzoate, vanillate, p-coumarate, ferulate, sinapate, and acetovanillone). The lower limit of detection was compound dependent and ranged between 0.9 and 3.5 umol/L. Results from GEMBE were similar to recent results from an orthogonal method based on GCxGC-TOF/MS. Altogether, GEMBE offers a rapid, robust approach to analyze complex biomass-derived samples, and given the ease and convenience of deployment, may offer an analytical solution for online tracking of multiple types of biomass streams.« less

Gradient elution moving boundary electrophoresis enables rapid analysis of acids in complex biomass-derived streams

DOE PAGES

Munson, Matthew S.; Karp, Eric M.; Nimlos, Claire T.; ...

2016-09-27

Biomass conversion processes such as pretreatment, liquefaction, and pyrolysis often produce complex mixtures of intermediates that are a substantial challenge to analyze rapidly and reliably. To characterize these streams more comprehensively and efficiently, new techniques are needed to track species through biomass deconstruction and conversion processes. Here, we present the application of an emerging analytical method, gradient elution moving boundary electrophoresis (GEMBE), to quantify a suite of acids in a complex, biomass-derived streams from alkaline pretreatment of corn stover. GEMBE offers distinct advantages over common chromatography-spectrometry analytical approaches in terms of analysis time, sample preparation requirements, and cost of equipment.more » As demonstrated here, GEMBE is able to track 17 distinct compounds (oxalate, formate, succinate, malate, acetate, glycolate, protocatechuate, 3-hydroxypropanoate, lactate, glycerate, 2-hydroxybutanoate, 4-hydroxybenzoate, vanillate, p-coumarate, ferulate, sinapate, and acetovanillone). The lower limit of detection was compound dependent and ranged between 0.9 and 3.5 umol/L. Results from GEMBE were similar to recent results from an orthogonal method based on GCxGC-TOF/MS. Altogether, GEMBE offers a rapid, robust approach to analyze complex biomass-derived samples, and given the ease and convenience of deployment, may offer an analytical solution for online tracking of multiple types of biomass streams.« less

High-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe

USGS Publications Warehouse

Chou, I.-Ming; Pasteris, J.D.; Seitz, J.C.

1990-01-01

Three methods have been used to produce high-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe (LRM): synthetic fluid-inclusion, sealed fused-quartz-tube, and high-pressure-cell methods. Because quantitative interpretation of a Raman spectrum of mixed-volatile fluid inclusions requires accurate knowledge of pressure- and composition-sensitive Raman scattering efficiencies or quantification factors for each species, calibrations of these parameters for mixtures of volatiles of known composition and pressure are necessary. Two advantages of the synthetic fluid-inclusion method are that the inclusions can be used readily in complementary microthermometry (MT) studies and that they have sizes and optical properties like those in natural samples. Some disadvantages are that producing H2O-free volatile mixtures is difficult, the composition may vary from one inclusion to another, the exact composition and density of the inclusions are difficult to obtain, and the experimental procedures are complicated. The primary advantage of the method using sealed fused-quartz tubes is its simplicity. Some disadvantages are that exact compositions for complex volatile mixtures are difficult to predict, densities can be approximated only, and complementary MT studies on the tubes are difficult to conduct. The advantages of the high-pressure-cell method are that specific, known compositions of volatile mixtures can be produced and that their pressures can be varied easily and are monitored during calibration. Some disadvantages are that complementary MT analysis is impossible, and the setup is bulky. Among the three methods for the calibration of an LRM, the high-pressure-cell method is the most reliable and convenient for control of composition and total pressure. We have used the high-pressure cell to obtain preliminary data on 1. (1) the ratio of the Raman quantification factors for CH4 and N2 in an equimolar CH4N2 mixture and 2. (2) the spectral peak position of ??1 of CH4 in that mixture, as well as in pure CH4, at pressures up to 690 bars. These data were successfully applied to natural inclusions from the Duluth Complex in order to derive their compositions and total pressures. ?? 1990.

Determination of delorazepam in urine by solid-phase microextraction coupled to high performance liquid chromatography.

PubMed

Aresta, Antonella; Monaci, Linda; Zambonin, Carlo Giorgio

2002-06-01

An SPME-HPLC-UV method for the determination of delorazepam, a representative benzodiazepine, in spiked human urine samples was developed for the first time. The performances of two commercially available fibers, a carbowax/templated resin (Carbowax/TPR-100) and a polydimethylsiloxane/divinylbenzene (PDMS/DVB), were compared, indicating the latter as the most suitable for urine samples analysis. All the aspects influencing adsorption (extraction time, pH, temperature, salt addition) and desorption (desorption and injection time, desorption solvent mixture composition) of the analyte on the fiber have been investigated. In particular, short extraction times were necessary to reach the equilibrium and very short desorption times were employed. The procedure required simple sample pre-treatment and was able to detect 5 ng/ml in spiked urine, regardless of the complexity of the matrix.

A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.

1985-01-01

A valence-specific analytical method for determining V3+ in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V3+/Vtot ratio, followed by determination of V3+ in the presence of V4+. The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100?? in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V3+-thiocyanate complex in aqueous-acetone medium. Fe3+ is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mo??ssbauer spectroscopy. ?? 1985.

Solution of rocks and refractory minerals by acids at high temperatures and pressures. Determination of silica after decomposition with hydrofluoric acid

USGS Publications Warehouse

May, I.; Rowe, J.J.

1965-01-01

A modified Morey bomb was designed which contains a removable nichromecased 3.5-ml platinium crucible. This bomb is particularly useful for decompositions of refractory samples for micro- and semimicro-analysis. Temperatures of 400-450?? and pressures estimated as great as 6000 p.s.i. were maintained in the bomb for periods as long as 24 h. Complete decompositions of rocks, garnet, beryl, chrysoberyl, phenacite, sapphirine, and kyanite were obtained with hydrofluoric acid or a mixture of hydrofluoric and sulfuric acids; the decomposition of chrome refractory was made with hydrochloric acid. Aluminum-rich samples formed difficultly soluble aluminum fluoride precipitates. Because no volatilization losses occur, silica can be determined on sample solutions by a molybdenum-blue procedure using aluminum(III) to complex interfering fluoride. ?? 1965.

Tracermodel1- Excel workbook for calculation and presentation of environmental tracer data for simple groundwater mixtures: Use of chlorofluorocarbons in hydrology - a guidebook; Section III.10.3

USGS Publications Warehouse

Böhlke, John Karl

2006-01-01

Atmospheric environmental tracers commonly used to date groundwater on timescales of years to decades include CFC-11, CFC-12, CFC-113, SF6, 85Kr, 3 H and 3 H/3 H0 , where 3 H0 refers to initial tritium (3 H + tritiogenic 3 He) (Cook and Herczeg, 2000). Interpretation of age from environmental tracer data may be relatively simple for a water sample with a single age, but the interpretation is more complex for a sample that is a mixture of waters of varying ages. A mixture can be a natural result of convergence of flow lines to a discharge area such as a spring or stream, or it can be an artefact of sampling a long-screen well. TRACERMODEL1 contains a worksheet that can be used to determine hypothetical concentrations of atmospheric environmental tracers in water samples with several different age distributions. It is designed to permit plotting of ages and tracer concentrations in a variety of different combinations to facilitate interpretation of measurements. TRACERMODEL1 includes several different types of graphs that are linked to the calculations. The spreadsheet and accompanying graphs can be modified for specific applications. For example, the selection of atmospheric environmental tracers can be changed to reflect analytes of interest, the input tracer data can be modified to reflect local conditions or different timescales, and the analytes of interest can include other types of non-point-source contaminants, such as nitrate (Böhlke, 2002). Previous versions of this workbook have been used to evaluate field data in studies of groundwater residence time and agricultural contamination (Böhlke and Denver, 1995; Focazio et al., 1998; Katz et al., 1999; Katz et al., 2001; Plummer et al., 2001; Böhlke and Krantz, 2003; Lindsey et al., 2003).

Validated univariate and multivariate spectrophotometric methods for the determination of pharmaceuticals mixture in complex wastewater

NASA Astrophysics Data System (ADS)

Riad, Safaa M.; Salem, Hesham; Elbalkiny, Heba T.; Khattab, Fatma I.

2015-04-01

Five, accurate, precise, and sensitive univariate and multivariate spectrophotometric methods were developed for the simultaneous determination of a ternary mixture containing Trimethoprim (TMP), Sulphamethoxazole (SMZ) and Oxytetracycline (OTC) in waste water samples collected from different cites either production wastewater or livestock wastewater after their solid phase extraction using OASIS HLB cartridges. In univariate methods OTC was determined at its λmax 355.7 nm (0D), while (TMP) and (SMZ) were determined by three different univariate methods. Method (A) is based on successive spectrophotometric resolution technique (SSRT). The technique starts with the ratio subtraction method followed by ratio difference method for determination of TMP and SMZ. Method (B) is successive derivative ratio technique (SDR). Method (C) is mean centering of the ratio spectra (MCR). The developed multivariate methods are principle component regression (PCR) and partial least squares (PLS). The specificity of the developed methods is investigated by analyzing laboratory prepared mixtures containing different ratios of the three drugs. The obtained results are statistically compared with those obtained by the official methods, showing no significant difference with respect to accuracy and precision at p = 0.05.

Validated univariate and multivariate spectrophotometric methods for the determination of pharmaceuticals mixture in complex wastewater.

PubMed

Riad, Safaa M; Salem, Hesham; Elbalkiny, Heba T; Khattab, Fatma I

2015-04-05

Five, accurate, precise, and sensitive univariate and multivariate spectrophotometric methods were developed for the simultaneous determination of a ternary mixture containing Trimethoprim (TMP), Sulphamethoxazole (SMZ) and Oxytetracycline (OTC) in waste water samples collected from different cites either production wastewater or livestock wastewater after their solid phase extraction using OASIS HLB cartridges. In univariate methods OTC was determined at its λmax 355.7 nm (0D), while (TMP) and (SMZ) were determined by three different univariate methods. Method (A) is based on successive spectrophotometric resolution technique (SSRT). The technique starts with the ratio subtraction method followed by ratio difference method for determination of TMP and SMZ. Method (B) is successive derivative ratio technique (SDR). Method (C) is mean centering of the ratio spectra (MCR). The developed multivariate methods are principle component regression (PCR) and partial least squares (PLS). The specificity of the developed methods is investigated by analyzing laboratory prepared mixtures containing different ratios of the three drugs. The obtained results are statistically compared with those obtained by the official methods, showing no significant difference with respect to accuracy and precision at p=0.05. Copyright © 2015 Elsevier B.V. All rights reserved.

UNiquant, a program for quantitative proteomics analysis using stable isotope labeling.

PubMed

Huang, Xin; Tolmachev, Aleksey V; Shen, Yulei; Liu, Miao; Huang, Lin; Zhang, Zhixin; Anderson, Gordon A; Smith, Richard D; Chan, Wing C; Hinrichs, Steven H; Fu, Kai; Ding, Shi-Jian

2011-03-04

Stable isotope labeling (SIL) methods coupled with nanoscale liquid chromatography and high resolution tandem mass spectrometry are increasingly useful for elucidation of the proteome-wide differences between multiple biological samples. Development of more effective programs for the sensitive identification of peptide pairs and accurate measurement of the relative peptide/protein abundance are essential for quantitative proteomic analysis. We developed and evaluated the performance of a new program, termed UNiquant, for analyzing quantitative proteomics data using stable isotope labeling. UNiquant was compared with two other programs, MaxQuant and Mascot Distiller, using SILAC-labeled complex proteome mixtures having either known or unknown heavy/light ratios. For the SILAC-labeled Jeko-1 cell proteome digests with known heavy/light ratios (H/L = 1:1, 1:5, and 1:10), UNiquant quantified a similar number of peptide pairs as MaxQuant for the H/L = 1:1 and 1:5 mixtures. In addition, UNiquant quantified significantly more peptides than MaxQuant and Mascot Distiller in the H/L = 1:10 mixtures. UNiquant accurately measured relative peptide/protein abundance without the need for postmeasurement normalization of peptide ratios, which is required by the other programs.

UNiquant, a Program for Quantitative Proteomics Analysis Using Stable Isotope Labeling

PubMed Central

Huang, Xin; Tolmachev, Aleksey V.; Shen, Yulei; Liu, Miao; Huang, Lin; Zhang, Zhixin; Anderson, Gordon A.; Smith, Richard D.; Chan, Wing C.; Hinrichs, Steven H.; Fu, Kai; Ding, Shi-Jian

2011-01-01

Stable isotope labeling (SIL) methods coupled with nanoscale liquid chromatography and high resolution tandem mass spectrometry are increasingly useful for elucidation of the proteome-wide differences between multiple biological samples. Development of more effective programs for the sensitive identification of peptide pairs and accurate measurement of the relative peptide/protein abundance are essential for quantitative proteomic analysis. We developed and evaluated the performance of a new program, termed UNiquant, for analyzing quantitative proteomics data using stable isotope labeling. UNiquant was compared with two other programs, MaxQuant and Mascot Distiller, using SILAC-labeled complex proteome mixtures having either known or unknown heavy/light ratios. For the SILAC-labeled Jeko-1 cell proteome digests with known heavy/light ratios (H/L = 1:1, 1:5, and 1:10), UNiquant quantified a similar number of peptide pairs as MaxQuant for the H/L = 1:1 and 1:5 mixtures. In addition, UNiquant quantified significantly more peptides than MaxQuant and Mascot Distiller in the H/L = 1:10 mixtures. UNiquant accurately measured relative peptide/protein abundance without the need for post-measurement normalization of peptide ratios, which is required by the other programs. PMID:21158445

Bayesian parameter estimation for the Wnt pathway: an infinite mixture models approach.

PubMed

Koutroumpas, Konstantinos; Ballarini, Paolo; Votsi, Irene; Cournède, Paul-Henry

2016-09-01

Likelihood-free methods, like Approximate Bayesian Computation (ABC), have been extensively used in model-based statistical inference with intractable likelihood functions. When combined with Sequential Monte Carlo (SMC) algorithms they constitute a powerful approach for parameter estimation and model selection of mathematical models of complex biological systems. A crucial step in the ABC-SMC algorithms, significantly affecting their performance, is the propagation of a set of parameter vectors through a sequence of intermediate distributions using Markov kernels. In this article, we employ Dirichlet process mixtures (DPMs) to design optimal transition kernels and we present an ABC-SMC algorithm with DPM kernels. We illustrate the use of the proposed methodology using real data for the canonical Wnt signaling pathway. A multi-compartment model of the pathway is developed and it is compared to an existing model. The results indicate that DPMs are more efficient in the exploration of the parameter space and can significantly improve ABC-SMC performance. In comparison to alternative sampling schemes that are commonly used, the proposed approach can bring potential benefits in the estimation of complex multimodal distributions. The method is used to estimate the parameters and the initial state of two models of the Wnt pathway and it is shown that the multi-compartment model fits better the experimental data. Python scripts for the Dirichlet Process Gaussian Mixture model and the Gibbs sampler are available at https://sites.google.com/site/kkoutroumpas/software konstantinos.koutroumpas@ecp.fr. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Characterization of the pharmacokinetics of gasoline using PBPK modeling with a complex mixtures chemical lumping approach.

PubMed

Dennison, James E; Andersen, Melvin E; Yang, Raymond S H

2003-09-01

Gasoline consists of a few toxicologically significant components and a large number of other hydrocarbons in a complex mixture. By using an integrated, physiologically based pharmacokinetic (PBPK) modeling and lumping approach, we have developed a method for characterizing the pharmacokinetics (PKs) of gasoline in rats. The PBPK model tracks selected target components (benzene, toluene, ethylbenzene, o-xylene [BTEX], and n-hexane) and a lumped chemical group representing all nontarget components, with competitive metabolic inhibition between all target compounds and the lumped chemical. PK data was acquired by performing gas uptake PK studies with male F344 rats in a closed chamber. Chamber air samples were analyzed every 10-20 min by gas chromatography/flame ionization detection and all nontarget chemicals were co-integrated. A four-compartment PBPK model with metabolic interactions was constructed using the BTEX, n-hexane, and lumped chemical data. Target chemical kinetic parameters were refined by studies with either the single chemical alone or with all five chemicals together. o-Xylene, at high concentrations, decreased alveolar ventilation, consistent with respiratory irritation. A six-chemical interaction model with the lumped chemical group was used to estimate lumped chemical partitioning and metabolic parameters for a winter blend of gasoline with methyl t-butyl ether and a summer blend without any oxygenate. Computer simulation results from this model matched well with experimental data from single chemical, five-chemical mixture, and the two blends of gasoline. The PBPK model analysis indicated that metabolism of individual components was inhibited up to 27% during the 6-h gas uptake experiments of gasoline exposures.

OXIDATIVE DNA DAMAGE FROM POTASSIUM BROMATE EXPOSURE IN LONG-EVANS RATS IS NOT ENHANCED BY A MIXTURE OF DRINKING WATER DISINFECTION BY-PRODUCTS

EPA Science Inventory

Public drinking water treated with chemical disinfectants contains a complex mixture of disinfection by-products (DBPs) for which the relative toxicity of the mixtures needs to be characterized to accurately assess risk. Potassium bromate (KBrO3) is a by-product from ozonation of...

Quantification of Complex Polycyclic Aromatic Hydrocarbon Mixtures in Standard Reference Materials Using GC×GC/ToF-MS

PubMed Central

Manzano, Carlos; Hoh, Eunha; Massey Simonich, Staci L.

2014-01-01

This research is the first to quantify complex PAH mixtures in NIST SRMs using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/ToF-MS), with and without extract cleanup, and reports previously unidentified PAH isomers in the NIST SRMs. We tested a novel, high orthogonality GC column combination (LC-50×NSP-35), as well as with a commonly used column combination (Rtx-5ms×Rxi-17) for the quantification of a complex mixture of 85 different PAHs, including parent (PAHs), alkyl- (MPAHs), nitro- (NPAHs), oxy- (OPAHs), thio- (SPAHs), bromo- (BrPAHs), and chloro-PAHs (ClPAHs) in extracts from two standard reference materials: NIST SRM1650b (diesel particulate matter), with cleanup and NIST SRM1975 (diesel particulate extract), with and without extract cleanup. The LC-50×NSP-35 column combination resulted in an average absolute percent difference of 33.8%, 62.2% and 30.8% compared to the NIST certified PAH concentrations for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, while the Rtx-5ms×Rxi-17 resulted in an absolute percent difference of 38.6%, 67.2% and 79.6% for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, respectively. This GC×GC/ToF-MS method increases the number of PAHs detected and quantified in complex environmental extracts using a single chromatographic run. Without clean-up, 7 additional compounds were detected and quantified in NIST SRM1975 using the LC-50×NSP-35 column combination. These results suggest that the use of the LC-50×NSP-35 column combination in GC×GC/ToF-MS not only results in better chromatographic resolution and greater orthogonality for the separation of complex PAH mixtures, but can also be used for the accurate quantification of complex PAH mixtures in environmental extracts without cleanup. PMID:23932031

The influence of water-ethanol mixture on the thermodynamics of complex formation between 18-crown-6 ether and L-phenylalanine

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Sharnin, V. A.; Chernov, I. V.; Matteoli, E.; Terekhova, I. V.; Kumeev, R. S.

2012-08-01

The influence of water-ethanol mixture composition on the complex formation between 18-crown-6 ether and L-phenylalanine was studied by titration calorimetry at Т = 298.15 K. The standard thermodynamic parameters (ΔrGо, ΔrHо, ТΔrSо) of formation of [Phe18C6] molecular complex were calculated from data obtained by means of the microcalorimetric system TAM III (TA Instruments, USA) at X(EtOH) = 0.0/0.6 mol fraction. The stability of [Phe18C6] and the mechanism of complexation in water were investigated using the 1Н and 13С NMR spectroscopy. The increase of EtOH concentration results in an increase of the complex stability and of the exothermicity of complexation.

Inert gases in Sea of Fertility regolith

NASA Technical Reports Server (NTRS)

Vinogradov, A. P.; Zadorozhnyy, I. K.

1974-01-01

The content and isotopic composition were studied of inert gases -- He, Ne, Ar, Kr, and Xe -- in samples of lunar regolith returned by the Luna 16 automatic station. The samples were taken from depths of about 12 and 30 cm. The high concentrations of inert gases exceed by several orders their concentrations observed in ordinary stony meteorites. The gases in lunar regolith were a complex mixture of gases of different origins: Solar, cosmogenic, radiogenic, and so on. Solar wind gases predominated, distributed in the thin surficial layer of the regolith grains. The concentrations of these gases in the surficial layer is several cubic centimeters per gram. The isotopic composition of the inert gases of solar origin approaches their composition measured in gas-rich meteorites.

Distribution of rhodopin and spirilloxanthin between LH1 and LH2 complexes when incorporating carotenoid mixture into the membrane of purple sulfur bacterium Allochromatium minutissimum in vitro.

PubMed

Bolshakov, M A; Ashikhmin, A A; Makhneva, Z K; Moskalenko, A A

2016-11-01

Carotenoid mixture enriched by rhodopin and spirilloxanthin was incorporated in LH2 and LH1 complexes from Allochromatium (Alc.) minutissimum in vitro. The maximum incorporating level was ~95%. Rhodopin (56.4%) and spirilloxanthin (13.8%) were incorporated into the LH1 complex, in contrast to the control complex, which contained primarily spirilloxanthin (66.8%). After incorporating, the LH2 complex contained rhodopin (66.7%) and didehydrorhodopin (14.6%), which was close to their content in the control (67.4 and 20.5%, respectively). Thus, it was shown that carotenoids from the total pool are not selectively incorporated into LH2 and LH1 complexes in vitro in the proportion corresponding to the carotenoid content in the complexes in vivo.

Application of high performance liquid chromatography for the profiling of complex chemical mixtures with the aid of chemometrics.

PubMed

Ni, Yongnian; Zhang, Liangsheng; Churchill, Jane; Kokot, Serge

2007-06-15

In this paper, chemometrics methods were applied to resolve the high performance liquid chromatography (HPLC) fingerprints of complex, many-component substances to compare samples from a batch from a given manufacturer, or from those of different producers. As an example of such complex substances, we used a common Chinese traditional medicine, Huoxiang Zhengqi Tincture (HZT) for this research. Twenty-one samples, each representing a separate HZT production batch from one of three manufacturers were analyzed by HPLC with the aid of a diode array detector (DAD). An Agilent Zorbax Eclipse XDB-C18 column with an Agilent Zorbax high pressure reliance cartridge guard-column were used. The mobile phase consisted of water (A) and methanol (B) with a gradient program of 25-65% (v/v, B) during 0-30min, 65-55% (v/v, B) during 30-35min and 55-100% (v/v, B) during 35-60min (flow rate, 1.0mlmin(-1); injection volume, 20mul; and column temperature-ambient). The detection wavelength was adjusted for maximum sensitivity at different time periods. A peak area matrix with 21objectsx14HPLC variables was obtained by sampling each chromatogram at 14 common retention times. Similarities were then calculated to discriminate the batch-to-batch samples and also, a more informative multi-criteria decision making methodology (MCDM), PROMETHEE and GAIA, was applied to obtain more information from the chromatograms in order to rank and compare the complex HZT profiles. The results showed that with the MCDM analysis, it was possible to match and discriminate correctly the batch samples from the three different manufacturers. Fourier transform infrared (FT-IR) spectra taken from samples from several batches were compared by the common similarity method with the HPLC results. It was found that the FT-IR spectra did not discriminate the samples from the different batches.

Intestinal Permeability of β-Lapachone and Its Cyclodextrin Complexes and Physical Mixtures.

PubMed

Mangas-Sanjuan, Victor; Gutiérrez-Nieto, Jorge; Echezarreta-López, Magdalena; González-Álvarez, Isabel; González-Álvarez, Marta; Casabó, Vicente-Germán; Bermejo, Marival; Landin, Mariana

2016-12-01

β-Lapachone (βLAP) is a promising, poorly soluble, antitumoral drug. βLAP combination with cyclodextrins (CDs) improves its solubility and dissolution but there is not enough information about the impact of cyclodextrins on βLAP intestinal permeability. The objectives of this work were to characterize βLAP intestinal permeability and to elucidate cyclodextrins effect on the dissolution properties and on the intestinal permeability. The final goal was to evaluate CDs influence on the oral absorption of βLAP. Binary systems (physical mixtures and inclusion complexes) including βLAP and CDs (β-cyclodextrin: βCD, random-methyl-β-cyclodextrin: RMβCD and sulfobutylether-β-cyclodextrin: SBEβCD) have been prepared and analysed by differential scanning calorimetry. βLAP (and its combinations with CDs) absorption rate coefficients and effective permeability values have been determined in vitro in MDCK or MDCK-Mdr1 monolayers and in situ in rat by a closed loop perfusion technique. DSC results confirmed the formation of the inclusion complexes. βLAP-CDs inclusion complexes improve drug solubility and dissolution rate in comparison with physical mixtures. βLAP presented a high permeability value which can provide complete oral absorption. Its oral absorption is limited by its low solubility and dissolution rate. Cyclodextrin (both as physical mixtures and inclusion complexes) showed a positive effect on the intestinal permeability of βLAP. Complexation with CDs does not reduce βLAP intestinal permeability in spite of the potential negative effect of the reduction in free fraction of the drug. The use of RMβCD or SBEβCD inclusion complexes could benefit βLAP oral absorption by enhancing its solubility, dissolution rate and permeability.

Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions.

PubMed

Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan

2014-06-10

The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

Sediment unmixing using detrital geochronology

NASA Astrophysics Data System (ADS)

Sharman, Glenn R.; Johnstone, Samuel A.

2017-11-01

Sediment mixing within sediment routing systems can exert a strong influence on the preservation of provenance signals that yield insight into the effect of environmental forcing (e.g., tectonism, climate) on the Earth's surface. Here, we discuss two approaches to unmixing detrital geochronologic data in an effort to characterize complex changes in the sedimentary record. First, we summarize 'top-down' mixing, which has been successfully employed in the past to characterize the different fractions of prescribed source distributions ('parents') that characterize a derived sample or set of samples ('daughters'). Second, we propose the use of 'bottom-up' methods, previously used primarily for grain size distributions, to model parent distributions and the abundances of these parents within a set of daughters. We demonstrate the utility of both top-down and bottom-up approaches to unmixing detrital geochronologic data within a well-constrained sediment routing system in central California. Use of a variety of goodness-of-fit metrics in top-down modeling reveals the importance of considering the range of allowable that is well mixed over any single best-fit mixture calculation. Bottom-up modeling of 12 daughter samples from beaches and submarine canyons yields modeled parent distributions that are remarkably similar to those expected from the geologic context of the sediment-routing system. In general, mixture modeling has the potential to supplement more widely applied approaches in comparing detrital geochronologic data by casting differences between samples as differing proportions of geologically meaningful end-member provenance categories.

[The lysate and recombinant antigens in ELISA-test-systems for diagnostic of herpes simplex].

PubMed

Ganova, L A; Kovtoniuk, G V; Korshun, L N; Kiseleva, E K; Tereshchenko, M I; Vudmaska, M I; Moĭsa, L N; Shevchuk, V A; Spivak, N Ia

2014-08-01

The lysate and recombinant antigens of various production included informula of ELISA-test-systems were analyzed. The ELISA-test-systems are used for detection of IgG to Herpes simplex virus type I and II. For testing the panel of serums PTH 201 (BBI Inc.) were used. The samples of this panel contain antibodies to Herpes simplex virus type I and II in mixed titers. The 69 serums of donors were used too (17 samples had IgG to Herpes simplex virus type I, 23 samples to Herpes simplex virus type II and 29 samples had no antibodies to Herpes simplex virus). The diagnostic capacity of mixture of recombinant antigens gG1 Herpes simplex virus type I and gG2 Herpes simplex virus type II (The research-and-production complex "DiaprofMed") was comparable with mixture of lysate antigen Herpes simplex virus type I and II (Membrane) EIE Antigen ("Virion Ltd."). In the test-systems for differentiation of IgG to Herpes simplex virus type I the recombinant antigen gG1 Herpes simplex virus type I proved to be comparable with commercial analogue Herpes simplex virus-1 gG1M ("Viral Therapeutics Inc."'). At the same time, capacity to detect IgG to Herpes simplex virus type II in recombinant protein gG2 Herpes simplex virus type II is significantly higher than in its analogue Herpes simplex virus-2 gG2c ("Viral Therapeutics Inc.").

Top-down and middle-down approach by fraction collection enrichment using off-line capillary electrophoresis - mass spectrometry coupling: Application to monoclonal antibody Fc/2 charge variants.

PubMed

Biacchi, Michael; Said, Nassur; Beck, Alain; Leize-Wagner, Emmanuelle; François, Yannis-Nicolas

2017-05-19

The characterization of complex protein mixtures represents one of the biggest challenge in many research fields such as biological or biopharmaceutical sciences. Out of all categories, monoclonal antibodies (mAbs) and related products drawn the most interest due to their strong therapeutic potency and specificity. Because of their intrinsic complexity due to a large number of micro-heterogeneities, there is a crucial need for analytical methods to provide comprehensive in-depth characterization of these proteins. In this work, we developed a methodology using CE-UV/MALDI-MS to perform top-down or middle-down characterization after fraction collection enrichment applied to intact protein and mAbs samples. The performance of the method was evaluated with the rapid separation of three intact protein mixture. Good robustness of CZE separation and quality of MALDI-MS spectra and MALDI-ISD spectra of each protein confirms the usefulness of sample enrichment to obtain adequate quantity of deposed protein for top-down analysis and the proof of principle of the method. In a second step, the method was applied to the middle-down characterization of Fc/2 cetuximab variants. Identification of around 9% sequence coverage of Fc/2 cetuximab fragments allows to conclude on the feasibility of the strategy for middle-down characterization of Fc/2 cetuximab variants using CE-UV/MALDI-MS. Moreover, MALDI-ISD fragmentation of Fc/2 cetuximab variants confirm separation phenomenon based on the formation of Fc/2 dimers with and without C-terminal truncation. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermally oxidized titania nanotubes enhance the corrosion resistance of Ti6Al4V.

PubMed

Grotberg, John; Hamlekhan, Azhang; Butt, Arman; Patel, Sweetu; Royhman, Dmitry; Shokuhfar, Tolou; Sukotjo, Cortino; Takoudis, Christos; Mathew, Mathew T

2016-02-01

The negative impact of in vivo corrosion of metallic biomedical implants remains a complex problem in the medical field. We aimed to determine the effects of electrochemical anodization (60V, 2h) and thermal oxidation (600°C) on the corrosive behavior of Ti-6Al-4V, with serum proteins, at physiological temperature. Anodization produced a mixture of anatase and amorphous TiO2 nanopores and nanotubes, while the annealing process yielded an anatase/rutile mixture of TiO2 nanopores and nanotubes. The surface area was analyzed by the Brunauer-Emmett-Teller method and was estimated to be 3 orders of magnitude higher than that of polished control samples. Corrosion resistance was evaluated on the parameters of open circuit potential, corrosion potential, corrosion current density, passivation current density, polarization resistance and equivalent circuit modeling. Samples both anodized and thermally oxidized exhibited shifts of open circuit potential and corrosion potential in the noble direction, indicating a more stable nanoporous/nanotube layer, as well as lower corrosion current densities and passivation current densities than the smooth control. They also showed increased polarization resistance and diffusion limited charge transfer within the bulk oxide layer. The treatment groups studied can be ordered from greatest corrosion resistance to least as Anodized+Thermally Oxidized > Anodized > Smooth > Thermally Oxidized for the conditions investigated. This study concludes that anodized surface has a potential to prevent long term implant failure due to corrosion in a complex in-vivo environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Chemical transformations of complex mixtures relevant to atmospheric processes: Laboratory and ambient studies

NASA Astrophysics Data System (ADS)

Samy, Shahryar (Shar)

The study of atmospheric chemistry and chemical transformations, which are relevant to conditions in the ambient atmosphere require the investigation of complex mixtures. In the atmosphere, complex mixtures (e.g. diesel emissions) are continually evolving as a result of physical and chemical transformations. This dissertation examines the transformations of modern diesel emissions (DE) in a series of experiments conducted at the European Outdoor Simulation Chamber (EUPHORE) in Valencia, Spain. Experimental design challenges are addressed, and the development of a NOx removal technology (denuder) is described with results from the application of the newly developed NOx denuder in the most recent EUPHORE campaign (2006). In addition, the data from an ambient aerosol study that examines atmospheric transformation products is presented and discussed. Atmospheric transformations of DE and associated secondary organic aerosol (SOA) production, along with chemical characterization of polar organic compounds (POC) in the EUPHORE experiments, provides a valuable insight on the tranformations of modern DE in environmentally relevant atmospheres. The greatest SOA production occurred in DE with toluene addition experiments (>40%), followed by DE with HCHO (for OH radical generation) experiments. A small amount of SOA (3%) was observed for DE in dark with N2O5 (for NO3 radical production) experiments. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The production of diacids (as a compound group) demonstrates a consistent indicator for photochemical transformation in relation to studies in the ambient atmosphere. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA %yield (in relation to toluene) of 5.3+/-1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NO x]o on SOA production in more simplified mixtures. Characterization of nitrated polycyclic aromatic hydrocarbons (NPAH, nitroarenes), which have been shown to be mutagenic and/or carcinogenic, was performed on time-intergrated samples from the EUPHORE experiments. NPAH concentrations indicated significant formation and/or degradation was taking place. An inter-experimental comparison showed that distinct gas (2-nitronaphthalene) and particle (2-nitrofluoranthene, 4-nitropyrene) phase NPAH production resulted in light versus dark experiments, and degradation most likely due to photolysis was observed for one of the most abundant NPAH (1-nitropyrene) in the ambient atmosphere. The evaluation of dark experiments in high and low NOx conditions, revealed a significantly higher concentration of gas phase NPAH (mostly due to 1-nitronaphthalene) in high NOx experiments. Electrophilic nitration on chamber surfaces or sampling media can not be ruled out as a possible mechanism for the elevated NPAH concentrations. Chapter 5 presents results from an aerosol sampling study at the Storm Peak Laboratory (SPL) (3210 MSL, 40.45° N, 106.74° W) in the winter of 2007. The unique geographical character of SPL allows for extended observations/sampling of the free tropospheric interface. Of 84 analytes included in the GC-MS method, over 50 individual water extractable POC were present at concentrations greater than 0.1 ngm-3. Diurnal averages over the sampling period revealed a higher total concentration of POC at night, 211 ngm-3 (105-265 ngm-3), versus day, 160 ngm-3 (137-205 ngm -3), which suggests a more aged nighttime aerosol character. During a snow event (Jan. 11-13, 2007), the concentrations of daytime dicarboxylic acids, which may be considered as atmospheric transformation products, were reduced. Lower actinic flux, reduced transport distance, and ice crystal scavenging may explain this variability. Further evaluation of compound ratios (e.g. diacids to monoacids/levoglucosan) and the sampling period dynamics was performed to delineate diurnal aerosol character.

Bioanalytical Methods for Food Contaminant Analysis

EPA Science Inventory

Foods are complex mixtures of lipids, carbohydrates, proteins, vitamins, organic compounds and other naturally occurring compounds. Sometimes added to this mixture are residues of pesticides, veterinary and human drugs, microbial toxins, preservatives, contaminants from food proc...

Euroforgen-NoE collaborative exercise on LRmix to demonstrate standardization of the interpretation of complex DNA profiles.

PubMed

Prieto, L; Haned, H; Mosquera, A; Crespillo, M; Alemañ, M; Aler, M; Alvarez, F; Baeza-Richer, C; Dominguez, A; Doutremepuich, C; Farfán, M J; Fenger-Grøn, M; García-Ganivet, J M; González-Moya, E; Hombreiro, L; Lareu, M V; Martínez-Jarreta, B; Merigioli, S; Milans Del Bosch, P; Morling, N; Muñoz-Nieto, M; Ortega-González, E; Pedrosa, S; Pérez, R; Solís, C; Yurrebaso, I; Gill, P

2014-03-01

There has been very little work published on the variation of reporting practices of mixtures between laboratories, but it has been previously demonstrated that there is little consistency. This is because there is no current uniformity of practice, so different laboratories will operate using different rules. The interpretation of mixtures is not solely a matter of using some software to provide 'an answer'. An assessment of a case will usually begin with a consideration of the circumstances of a crime. Assumptions made about the numbers of contributors follow from an examination of the electropherogram(s)--and these may differ between the prosecution and the defence hypotheses. There may be a necessity to evaluate several sets of hypotheses for any given case if the circumstances are uncertain. Once the hypotheses are formulated, the mathematical analysis is complex and can only be accomplished by the use of specialist software. In order to obtain meaningful results, it is essential that scientists are trained, not only in the use of the software, but also in the methodology to understand the likelihood ratio concept that is used. The Euroforgen-NoE initiative has developed a training course that utilizes the LRmix program to carry out the calculations. This software encompasses the recommendations of the ISFG DNA commissions on mixture interpretation and is able to interpret samples that may come from two or more contributors and may also be partial profiles. Recently, eighteen different laboratories were trained in the methodology. Afterwards they were asked to independently analyze two different cases with partial mixture DNA evidence and to write a statement court-report. We show that by introducing a structured training programme, it is possible to demonstrate, for the first time, that a high degree of standardization, leading to uniformity of results can be achieved by participating laboratories. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Tandem mass spectrometry in combination with product ion mobility for the identification of phospholipids

DOE PAGES

Berry, Karin A. Zemski; Barkley, Robert M.; Berry, Joseph J.; ...

2016-11-29

Concerted tandem and traveling wave ion mobility mass spectrometry (CTS analysis) is a unique method that results in a four-dimensional data set including nominal precursor ion mass, product ion mobility, accurate mass of product ion, and ion abundance. This nontargeted lipidomics CTS approach was applied in both positive- and negative-ion mode to phospholipids present in human serum, and the data set was used to evaluate the value of product ion mobility in identifying lipids in a complex mixture. As a result, it was determined that the combination of diagnostic product ions and unique collisional cross-section values of product ions ismore » a powerful tool in the structural identification of lipids in a complex biological sample.« less

Tandem mass spectrometry in combination with product ion mobility for the identification of phospholipids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, Karin A. Zemski; Barkley, Robert M.; Berry, Joseph J.

Concerted tandem and traveling wave ion mobility mass spectrometry (CTS analysis) is a unique method that results in a four-dimensional data set including nominal precursor ion mass, product ion mobility, accurate mass of product ion, and ion abundance. This nontargeted lipidomics CTS approach was applied in both positive- and negative-ion mode to phospholipids present in human serum, and the data set was used to evaluate the value of product ion mobility in identifying lipids in a complex mixture. As a result, it was determined that the combination of diagnostic product ions and unique collisional cross-section values of product ions ismore » a powerful tool in the structural identification of lipids in a complex biological sample.« less

Proof of concept of a "greener" protein purification/enrichment method based on carboxylate-terminated carbosilane dendrimer-protein interactions.

PubMed

González-García, Estefanía; Maly, Marek; de la Mata, Francisco Javier; Gómez, Rafael; Marina, María Luisa; García, María Concepción

2016-11-01

Protein sample preparation is a critical and an unsustainable step since it involves the use of tedious methods that usually require high amount of solvents. The development of new materials offers additional opportunities in protein sample preparation. This work explores, for the first time, the potential application of carboxylate-terminated carbosilane dendrimers to the purification/enrichment of proteins. Studies on dendrimer binding to proteins, based on protein fluorescence intensity and emission wavelengths measurements, demonstrated the interaction between carboxylate-terminated carbosilane dendrimers and proteins at all tested pH levels. Interactions were greatly affected by the protein itself, pH, and dendrimer concentration and generation. Especially interesting was the interaction at acidic pH since it resulted in a significant protein precipitation. Dendrimer-protein interactions were modeled observing stable complexes for all proteins. Carboxylate-terminated carbosilane dendrimers at acidic pH were successfully used in the purification/enrichment of proteins extracted from a complex sample. Graphical Abstract Images showing the growing turbidity of solutions containing a mixture of proteins (lysozyme, myoglobin, and BSA) at different protein:dendrimer ratios (1:0, 1:1, 1:8, and 1:20) at acidic pH and SDS-PAGE profiles of the corresponsing supernatants. Comparison of SDS-PAGE profiles for the pellets obtained during the purification of proteins present in a complex sample using a conventional "no-clean" method based on acetone precipitation and the proposed "greener" method using carboxylate-terminated carbosilane dendrimer at a 1:20 protein:dendrimer ratio.

Effects of Polar Bear and Killer Whale Derived Contaminant Cocktails on Marine Mammal Immunity.

PubMed

Desforges, Jean-Pierre; Levin, Milton; Jasperse, Lindsay; De Guise, Sylvain; Eulaers, Igor; Letcher, Robert J; Acquarone, Mario; Nordøy, Erling; Folkow, Lars P; Hammer Jensen, Trine; Grøndahl, Carsten; Bertelsen, Mads F; St Leger, Judy; Almunia, Javier; Sonne, Christian; Dietz, Rune

2017-10-03

Most controlled toxicity studies use single chemical exposures that do not represent the real world situation of complex mixtures of known and unknown natural and anthropogenic substances. In the present study, complex contaminant cocktails derived from the blubber of polar bears (PB; Ursus maritimus) and killer whales (KW; Orcinus orca) were used for in vitro concentration-response experiments with PB, cetacean and seal spp. immune cells to evaluate the effect of realistic contaminant mixtures on various immune functions. Cytotoxic effects of the PB cocktail occurred at lower concentrations than the KW cocktail (1 vs 16 μg/mL), likely due to differences in contaminant profiles in the mixtures derived from the adipose of each species. Similarly, significant reduction of lymphocyte proliferation occurred at much lower exposures in the PB cocktail (EC 50 : 0.94 vs 6.06 μg/mL; P < 0.01), whereas the KW cocktail caused a much faster decline in proliferation (slope: 2.9 vs 1.7; P = 0.04). Only the KW cocktail modulated natural killer (NK) cell activity and neutrophil and monocyte phagocytosis in a concentration- and species-dependent manner. No clear sensitivity differences emerged when comparing cetaceans, seals and PB. Our results showing lower effect levels for complex mixtures relative to single compounds suggest that previous risk assessments underestimate the effects of real world contaminant exposure on immunity. Our results using blubber-derived contaminant cocktails add realism to in vitro exposure experiments and confirm the immunotoxic risk marine mammals face from exposure to complex mixtures of environmental contaminants.

Sound stream segregation: a neuromorphic approach to solve the “cocktail party problem” in real-time

PubMed Central

Thakur, Chetan Singh; Wang, Runchun M.; Afshar, Saeed; Hamilton, Tara J.; Tapson, Jonathan C.; Shamma, Shihab A.; van Schaik, André

2015-01-01

The human auditory system has the ability to segregate complex auditory scenes into a foreground component and a background, allowing us to listen to specific speech sounds from a mixture of sounds. Selective attention plays a crucial role in this process, colloquially known as the “cocktail party effect.” It has not been possible to build a machine that can emulate this human ability in real-time. Here, we have developed a framework for the implementation of a neuromorphic sound segregation algorithm in a Field Programmable Gate Array (FPGA). This algorithm is based on the principles of temporal coherence and uses an attention signal to separate a target sound stream from background noise. Temporal coherence implies that auditory features belonging to the same sound source are coherently modulated and evoke highly correlated neural response patterns. The basis for this form of sound segregation is that responses from pairs of channels that are strongly positively correlated belong to the same stream, while channels that are uncorrelated or anti-correlated belong to different streams. In our framework, we have used a neuromorphic cochlea as a frontend sound analyser to extract spatial information of the sound input, which then passes through band pass filters that extract the sound envelope at various modulation rates. Further stages include feature extraction and mask generation, which is finally used to reconstruct the targeted sound. Using sample tonal and speech mixtures, we show that our FPGA architecture is able to segregate sound sources in real-time. The accuracy of segregation is indicated by the high signal-to-noise ratio (SNR) of the segregated stream (90, 77, and 55 dB for simple tone, complex tone, and speech, respectively) as compared to the SNR of the mixture waveform (0 dB). This system may be easily extended for the segregation of complex speech signals, and may thus find various applications in electronic devices such as for sound segregation and speech recognition. PMID:26388721

Sound stream segregation: a neuromorphic approach to solve the "cocktail party problem" in real-time.

PubMed

Thakur, Chetan Singh; Wang, Runchun M; Afshar, Saeed; Hamilton, Tara J; Tapson, Jonathan C; Shamma, Shihab A; van Schaik, André

2015-01-01

The human auditory system has the ability to segregate complex auditory scenes into a foreground component and a background, allowing us to listen to specific speech sounds from a mixture of sounds. Selective attention plays a crucial role in this process, colloquially known as the "cocktail party effect." It has not been possible to build a machine that can emulate this human ability in real-time. Here, we have developed a framework for the implementation of a neuromorphic sound segregation algorithm in a Field Programmable Gate Array (FPGA). This algorithm is based on the principles of temporal coherence and uses an attention signal to separate a target sound stream from background noise. Temporal coherence implies that auditory features belonging to the same sound source are coherently modulated and evoke highly correlated neural response patterns. The basis for this form of sound segregation is that responses from pairs of channels that are strongly positively correlated belong to the same stream, while channels that are uncorrelated or anti-correlated belong to different streams. In our framework, we have used a neuromorphic cochlea as a frontend sound analyser to extract spatial information of the sound input, which then passes through band pass filters that extract the sound envelope at various modulation rates. Further stages include feature extraction and mask generation, which is finally used to reconstruct the targeted sound. Using sample tonal and speech mixtures, we show that our FPGA architecture is able to segregate sound sources in real-time. The accuracy of segregation is indicated by the high signal-to-noise ratio (SNR) of the segregated stream (90, 77, and 55 dB for simple tone, complex tone, and speech, respectively) as compared to the SNR of the mixture waveform (0 dB). This system may be easily extended for the segregation of complex speech signals, and may thus find various applications in electronic devices such as for sound segregation and speech recognition.

Considerations for potency equivalent calculations in the Ah receptor-based CALUX bioassay: Normalization of superinduction results for improved sample potency estimation

PubMed Central

Baston, David S.; Denison, Michael S.

2011-01-01

The chemically activated luciferase expression (CALUX) system is a mechanistically based recombinant luciferase reporter gene cell bioassay used in combination with chemical extraction and clean-up methods for the detection and relative quantitation of 2,3,7,8-tetrachlorodibenzo-p-dioxin and related dioxin-like halogenated aromatic hydrocarbons in a wide variety of sample matrices. While sample extracts containing complex mixtures of chemicals can produce a variety of distinct concentration-dependent luciferase induction responses in CALUX cells, these effects are produced through a common mechanism of action (i.e. the Ah receptor (AhR)) allowing normalization of results and sample potency determination. Here we describe the diversity in CALUX response to PCDD/Fs from sediment and soil extracts and not only report the occurrence of superinduction of the CALUX bioassay, but we describe a mechanistically based approach for normalization of superinduction data that results in a more accurate estimation of the relative potency of such sample extracts. PMID:21238730

The equilibrium constant of complex formation in solution: A study utilizing a dielectric constant method

NASA Astrophysics Data System (ADS)

Loh, C. W.

1980-03-01

A method was developed for determining equilibrium constants, heat of reaction, and change in free energy and entropy during a 1:1 complex formation in solutions. The measurements were carried out on ternary systems containing two interacting solutes in an inert solvent. The procedures was applied to the investigation of hydrogen bond complex formations in two mixtures systems, phenol and pyridine in carbon tetrachloride, and 4, 5, 6, 7-tetrachloro-2-trifluoromethylbenzimidazole (TTFB) and alkyl acetate in styrene. The first mixture system was studied in order to compare the results with those obtained by other methods. Results for the second mixture system indicated strong association between molecules of TTFB and alkyl acetate and suggested that the blocking of valinomycin-mediated bilayer membrane conductance by substituted benzimidazoles was due to competition for a limited number of adsorption sites on the membrane surface.

Study of complex permittivity spectra of binary mixtures of 2-chloroaniline and methanol in frequency range 10 KHz to 2 MHz at different temperatures

NASA Astrophysics Data System (ADS)

Shah, N. S.; Vankar, H. P.; Rana, V. A.

2017-05-01

The complex relative dielectric function ɛ*(ω)=ɛ'-jɛ″ of the binary mixture of 2-chloroaniline(2-CA) and methanol (MeOH) were measured using precision LCR meter in the frequency range of 10 KHz to 2 MHz The measurements were carried out at eight different temperatures and five different concentrations of 2-CA and MeOH. The loss tangent peaks were observed in the studied frequency range for all the binary mixtures. From the loss tangent peaks electrode polarization relaxation time were evaluated. In the plot of real part of complex permittivity against frequency, at different temperatures for 2-CA (54.54%) + MeOH (45.45%) and 2-CA (27.27%) + MeOH (72.72%)and 100% MeOH systems permittivity inversion effect was observed.

State of research: environmental pathways and food chain transfer.

PubMed Central

Vaughan, B E

1984-01-01

Data on the chemistry of biologically active components of petroleum, synthetic fuel oils, certain metal elements and pesticides provide valuable generic information needed for predicting the long-term fate of buried waste constituents and their likelihood of entering food chains. Components of such complex mixtures partition between solid and solution phases, influencing their mobility, volatility and susceptibility to microbial transformation. Estimating health hazards from indirect exposures to organic chemicals involves an ecosystem's approach to understanding the unique behavior of complex mixtures. Metabolism by microbial organisms fundamentally alters these complex mixtures as they move through food chains. Pathway modeling of organic chemicals must consider the nature and magnitude of food chain transfers to predict biological risk where metabolites may become more toxic than the parent compound. To obtain predictions, major areas are identified where data acquisition is essential to extend our radiological modeling experience to the field of organic chemical contamination. PMID:6428875

Sol-gel derived sorbents

DOEpatents

Sigman, Michael E.; Dindal, Amy B.

2003-11-11

Described is a method for producing copolymerized sol-gel derived sorbent particles for the production of copolymerized sol-gel derived sorbent material. The method for producing copolymerized sol-gel derived sorbent particles comprises adding a basic solution to an aqueous metal alkoxide mixture for a pH.ltoreq.8 to hydrolyze the metal alkoxides. Then, allowing the mixture to react at room temperature for a precalculated period of time for the mixture to undergo an increased in viscosity to obtain a desired pore size and surface area. The copolymerized mixture is then added to an immiscible, nonpolar solvent that has been heated to a sufficient temperature wherein the copolymerized mixture forms a solid upon the addition. The solid is recovered from the mixture, and is ready for use in an active sampling trap or activated for use in a passive sampling trap.

EDCs Mixtures: A Stealthy Hazard for Human Health?

PubMed

Ribeiro, Edna; Ladeira, Carina; Viegas, Susana

2017-02-07

Endocrine disrupting chemicals (EDCs) are exogenous chemicals that may occur naturally (e.g., phytoestrogens), while others are industrial substances and plasticizers commonly utilized worldwide to which human exposure, particularly at low-doses, is omnipresent, persistent and occurs in complex mixtures. EDCs can interfere with/or mimic estrogenic hormones and, consequently, can simultaneously trigger diverse signaling pathways which result in diverse and divergent biological responses. Additionally, EDCs can also bioaccumulate in lipid compartments of the organism forming a mixed "body burden" of contaminants. Although the independent action of chemicals has been considered the main principle in EDCs mixture toxicity, recent studies have demonstrated that numerous effects cannot be predicted when analyzing single compounds independently. Co-exposure to these agents, particularly in critical windows of exposure, may induce hazardous health effects potentially associated with a complex "body burden" of different origins. Here, we performed an exhaustive review of the available literature regarding EDCs mixtures exposure, toxicity mechanisms and effects, particularly at the most vulnerable human life stages. Although the assessment of potential risks to human health due to exposure to EDCs mixtures is a major topic for consumer safety, information regarding effective mixtures effects is still scarce.

EDCs Mixtures: A Stealthy Hazard for Human Health?

PubMed Central

Ribeiro, Edna; Ladeira, Carina; Viegas, Susana

2017-01-01

Endocrine disrupting chemicals (EDCs) are exogenous chemicals that may occur naturally (e.g., phytoestrogens), while others are industrial substances and plasticizers commonly utilized worldwide to which human exposure, particularly at low-doses, is omnipresent, persistent and occurs in complex mixtures. EDCs can interfere with/or mimic estrogenic hormones and, consequently, can simultaneously trigger diverse signaling pathways which result in diverse and divergent biological responses. Additionally, EDCs can also bioaccumulate in lipid compartments of the organism forming a mixed “body burden” of contaminants. Although the independent action of chemicals has been considered the main principle in EDCs mixture toxicity, recent studies have demonstrated that numerous effects cannot be predicted when analyzing single compounds independently. Co-exposure to these agents, particularly in critical windows of exposure, may induce hazardous health effects potentially associated with a complex “body burden” of different origins. Here, we performed an exhaustive review of the available literature regarding EDCs mixtures exposure, toxicity mechanisms and effects, particularly at the most vulnerable human life stages. Although the assessment of potential risks to human health due to exposure to EDCs mixtures is a major topic for consumer safety, information regarding effective mixtures effects is still scarce. PMID:29051438

Characterisation of metals in the electronic waste of complex mixtures of end-of-life ICT products for development of cleaner recovery technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Z.H.I.; Xiao, Y.; Sietsma, J.

2015-01-15

Highlights: • New characterisation methodology has been established to understand an industrially processed ICT waste. • Particle size distribution, composition, thermal–chemical behaviour and occurrence of metals were considered. • The characterisation provides direct guidelines for values recovery from the waste. - Abstract: Recycling of valuable metals from electronic waste, especially complex mixtures of end-of-life information and communication technology (ICT) products, is of great difficulty due to their complexity and heterogeneity. One of the important reasons is the lack of comprehensive characterisation on such materials, i.e. accurate compositions, physical/chemical properties. In the present research, we focus on developing methodologies for themore » characterisation of metals in an industrially processed ICT waste. The morphology, particle size distribution, compositional distribution, occurrence, liberation as well as the thermo-chemical properties of the ICT waste were investigated with various characterisation techniques, including X-ray Fluorescence Spectrometry (XRF), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) with energy dispersed spectroscopy (EDS). Due to the high heterogeneity of the material, special sample preparation procedures were introduced to minimise the discrepancies during compositional analyses. As a result, a clearer overview of the ICT waste has been reached. This research provides better understanding of the extractability of each metal and improves the awareness of potential obstacles for extraction. It will lead to smarter decisions during further development of a clean and effective recovery process.« less

Use of Activity-Based Probes to Develop High Throughput Screening Assays That Can Be Performed in Complex Cell Extracts

PubMed Central

Deu, Edgar; Yang, Zhimou; Wang, Flora; Klemba, Michael; Bogyo, Matthew

2010-01-01

Background High throughput screening (HTS) is one of the primary tools used to identify novel enzyme inhibitors. However, its applicability is generally restricted to targets that can either be expressed recombinantly or purified in large quantities. Methodology and Principal Findings Here, we described a method to use activity-based probes (ABPs) to identify substrates that are sufficiently selective to allow HTS in complex biological samples. Because ABPs label their target enzymes through the formation of a permanent covalent bond, we can correlate labeling of target enzymes in a complex mixture with inhibition of turnover of a substrate in that same mixture. Thus, substrate specificity can be determined and substrates with sufficiently high selectivity for HTS can be identified. In this study, we demonstrate this method by using an ABP for dipeptidyl aminopeptidases to identify (Pro-Arg)2-Rhodamine as a specific substrate for DPAP1 in Plasmodium falciparum lysates and Cathepsin C in rat liver extracts. We then used this substrate to develop highly sensitive HTS assays (Z’>0.8) that are suitable for use in screening large collections of small molecules (i.e >300,000) for inhibitors of these proteases. Finally, we demonstrate that it is possible to use broad-spectrum ABPs to identify target-specific substrates. Conclusions We believe that this approach will have value for many enzymatic systems where access to large amounts of active enzyme is problematic. PMID:20700487

Spectroscopic Case-Based Studies in a Flipped Quantum Mechanics Course

NASA Astrophysics Data System (ADS)

Shipman, Steven

2015-06-01

Students in a flipped Quantum Mechanics course were expected to apply their knowledge of spectroscopy to a variety of case studies involving complex mixtures of chemicals. They used simulated data, prepared in advance by the instructor, to determine the major chemical constituents of complex mixtures. Students were required to request the appropriate data in order to ultimately make plausible guesses about the composition of the mixtures, allowing them ownership over the discovery process. This talk will describe how these activities worked in practice, give caveats for instructors who wish to adopt them in the future, and discuss how the results of these exercises can be used for both formative and summative assessment.

Formation of hydrogen peroxide from illuminated polar snows and frozen solutions of model compounds

NASA Astrophysics Data System (ADS)

Hullar, Ted; Patten, Kelley; Anastasio, Cort

2012-08-01

Hydrogen peroxide (HOOH) is an important trace constituent in snow and ice, including in Arctic and Antarctic ice cores. To better understand the budget of snowpack HOOH, here we examine its production in illuminated snow and ice. To evaluate what types of compounds might be important photochemical sources of HOOH, we first illuminated laboratory ice samples containing 10 different model organic compounds: guaiacol, phenol, syringol, benzoate, formate, octanal, octanoic acid, octanedioic acid, phenylalanine, and mixtures of oxalate with iron (III). Half of these compounds produced little or no HOOH during illumination, but two classes of compounds were very reactive: phenolic compounds (with rates of HOOH of 6-62 nM-HOOH h-1 μM-1-phenolic) and mixtures of Fe(III) with a stoichiometric excess of oxalate (with rates of HOOH production as high as 2,000,000 nM h-1 per μM iron). To quantify rates of HOOH production in the environment we also illuminated snow samples collected from the Arctic and Antarctic. The average (±1σ) HOOH production rate in these samples was low, 5.3 ± 5.0 nM h-1 and replicate measurements showed high variability. In some natural samples there was an initial burst of HOOH production (with a rate approximately 10 times higher than the average production rate), followed by reduced rates at subsequent time points. Although our laboratory ice samples reveal that illuminated organics and metal-organic complexes can form HOOH, the low rates of HOOH formation in the Arctic and Antarctic snow samples suggest this process has only a modest impact on the HOOH budget in the snowpack.

Evaluation of laboratory powder X-ray micro-diffraction for applications in the fields of cultural heritage and forensic science.

PubMed

Svarcová, Silvie; Kocí, Eva; Bezdicka, Petr; Hradil, David; Hradilová, Janka

2010-09-01

The uniqueness and limited amounts of forensic samples and samples from objects of cultural heritage together with the complexity of their composition requires the application of a wide range of micro-analytical methods, which are non-destructive to the samples, because these must be preserved for potential late revision. Laboratory powder X-ray micro-diffraction (micro-XRD) is a very effective non-destructive technique for direct phase analysis of samples smaller than 1 mm containing crystal constituents. It compliments optical and electron microscopy with elemental micro-analysis, especially in cases of complicated mixtures containing phases with similar chemical composition. However, modification of X-ray diffraction to the micro-scale together with its application for very heterogeneous real samples leads to deviations from the standard procedure. Knowledge of both the limits and the phenomena which can arise during the analysis is crucial for the meaningful and proper application of the method. We evaluated basic limits of micro-XRD equipped with a mono-capillary with an exit diameter of 0.1 mm, for example the size of irradiated area, appropriate grain size, and detection limits allowing identification of given phases. We tested the reliability and accuracy of quantitative phase analysis based on micro-XRD data in comparison with conventional XRD (reflection and transmission), carrying out experiments with two-phase model mixtures simulating historic colour layers. Furthermore, we demonstrate the wide use of micro-XRD for investigation of various types of micro-samples (contact traces, powder traps, colour layers) and we show how to enhance data quality by proper choice of experiment geometry and conditions.

Application of a multivariate analysis method for non-target screening detection of persistent transformation products during the cork boiling wastewater treatment.

PubMed

Ponce-Robles, L; Oller, I; Agüera, A; Trinidad-Lozano, M J; Yuste, F J; Malato, S; Perez-Estrada, L A

2018-08-15

Cork boiling wastewater is a very complex mixture of naturally occurring compounds leached and partially oxidized during the boiling cycles. The effluent generated is recalcitrant and could cause a significant environmental impact. Moreover, if this untreated industrial wastewater enters a municipal wastewater treatment plant it could hamper or reduce the efficiency of most activated sludge degradation processes. Despite the efforts to treat the cork boiling wastewater for reusing purposes, is still not well-known how safe these compounds (original compounds and oxidation by-products) will be. The purpose of this work was to apply an HPLC-high resolution mass spectrometry method and subsequent non-target screening using a multivariate analysis method (PCA), to explore relationships between samples (treatments) and spectral features (masses or compounds) that could indicate changes in formation, degradation or polarity, during coagulation/flocculation (C/F) and photo-Fenton (PhF). Although, most of the signal intensities were reduced after the treatment line, 16 and 4 new peaks were detected to be formed after C/F and PhF processes respectively. The use of this non-target approach showed to be an effective strategy to explore, classify and detect transformation products during the treatment of an unknown complex mixture. Copyright © 2018 Elsevier B.V. All rights reserved.

High resolution separations of charge variants and disulfide isomers of monoclonal antibodies and antibody drug conjugates using ultra-high voltage capillary electrophoresis with high electric field strength.

PubMed

Henley, W Hampton; He, Yan; Mellors, J Scott; Batz, Nicholas G; Ramsey, J Michael; Jorgenson, James W

2017-11-10

Ultra-high voltage capillary electrophoresis with high electric field strength has been applied to the separation of the charge variants, drug conjugates, and disulfide isomers of monoclonal antibodies. Samples composed of many closely related species are difficult to resolve and quantify using traditional analytical instrumentation. High performance instrumentation can often save considerable time and effort otherwise spent on extensive method development. Ideally, the resolution obtained for a given CE buffer system scales with the square root of the applied voltage. Currently available commercial CE instrumentation is limited to an applied voltage of approximately 30kV and a maximum electric field strength of 1kV/cm due to design limitations. The instrumentation described here is capable of safely applying potentials of at least 120kV with electric field strengths over 2000V/cm, potentially doubling the resolution of the best conventional CE buffer/capillary systems while decreasing analysis time in some applications. Separations of these complex mixtures using this new instrumentation demonstrate the potential of ultra-high voltage CE to identify the presence of previously unresolved components and to reduce analysis time for complex mixtures of antibody variants and drug conjugates. Copyright © 2017 Elsevier B.V. All rights reserved.

Gene expression profiling to characterize sediment toxicity – a pilot study using Caenorhabditis elegans whole genome microarrays

PubMed Central

Menzel, Ralph; Swain, Suresh C; Hoess, Sebastian; Claus, Evelyn; Menzel, Stefanie; Steinberg, Christian EW; Reifferscheid, Georg; Stürzenbaum, Stephen R

2009-01-01

Background Traditionally, toxicity of river sediments is assessed using whole sediment tests with benthic organisms. The challenge, however, is the differentiation between multiple effects caused by complex contaminant mixtures and the unspecific toxicity endpoints such as survival, growth or reproduction. The use of gene expression profiling facilitates the identification of transcriptional changes at the molecular level that are specific to the bio-available fraction of pollutants. Results In this pilot study, we exposed the nematode Caenorhabditis elegans to three sediments of German rivers with varying (low, medium and high) levels of heavy metal and organic contamination. Beside chemical analysis, three standard bioassays were performed: reproduction of C. elegans, genotoxicity (Comet assay) and endocrine disruption (YES test). Gene expression was profiled using a whole genome DNA-microarray approach to identify overrepresented functional gene categories and derived cellular processes. Disaccharide and glycogen metabolism were found to be affected, whereas further functional pathways, such as oxidative phosphorylation, ribosome biogenesis, metabolism of xenobiotics, aging and several developmental processes were found to be differentially regulated only in response to the most contaminated sediment. Conclusion This study demonstrates how ecotoxicogenomics can identify transcriptional responses in complex mixture scenarios to distinguish different samples of river sediments. PMID:19366437

Design and Construction of a Single-Tube, LATE-PCR, Multiplex Endpoint Assay with Lights-On/Lights-Off Probes for the Detection of Pathogens Associated with Sepsis

PubMed Central

Carver-Brown, Rachel K.; Reis, Arthur H.; Rice, Lisa M.; Czajka, John W.; Wangh, Lawrence J.

2012-01-01

Aims. The goal of this study was to construct a single tube molecular diagnostic multiplex assay for the detection of microbial pathogens commonly associated with septicemia, using LATE-PCR and Lights-On/Lights-Off probe technology. Methods and Results. The assay described here identified pathogens associated with sepsis by amplification and analysis of the 16S ribosomal DNA gene sequence for bacteria and specific gene sequences for fungi. A sequence from an unidentified gene in Lactococcus lactis subsp. cremoris served as a positive control for assay function. LATE-PCR was used to generate single-stranded amplicons that were then analyzed at endpoint over a wide temperature range in a specific fluorescent color. Each bacterial target was identified by its pattern of hybridization to Lights-On/Lights-Off probes derived from molecular beacons. Complex mixtures of targets were also detected. Conclusions. All microbial targets were identified in samples containing low starting copy numbers of pathogen genomic DNA, both as individual targets and in complex mixtures. Significance and Impact of the Study. This assay uses new technology to achieve an advance in the field of molecular diagnostics: a single-tube multiplex assay for identification of pathogens commonly associated with sepsis. PMID:23326668

Development of a Small, Inexpensive, and Field-deployable Gas Chromatograph for the Automated Collection, Separation, and Analysis of Gas-phase Organic Compounds

NASA Astrophysics Data System (ADS)

Skog, K.; Xiong, F.; Gentner, D. R.

2017-12-01

The identification and quantification of gas-phase organic compounds, like volatile organic compounds (VOCs), in the atmosphere relies on separation of complex mixtures and sensitive detection. Gas chromatography (GC) is widely applied, but relies on the need for high-purity compressed gases for separation and, often for detection. We have developed a low-cost, compact GC-based system for the collection and quantitative chemical speciation of complex mixtures of common atmospheric VOCs without the need for compressed high-purity gases or expensive detectors. We present results of lab and field testing against a commercially-available GC system. At optimized linear velocities challenging VOC pairs of similar volatility were resolved within 30 minutes, including n- and i-pentane; n-pentane and isoprene; and ethylbenzene and m/p-xylene. For 5-30 minute samples, we observe ppt-level detection limits for common VOCs such as benzene, toluene, ethylbenzene, xylenes, alpha-pinene, and limonene. We also present results of in-field use for VOC measurements. In all, this instrument is accurate, precise, small, and inexpensive (<$2500). Its lack of compressed gas cylinders make it ideal for field deployment and has been demonstrated to produce similar quality data to available GC technology.

Vaccine-driven pharmacodynamic dissection and mitigation of fenethylline psychoactivity

NASA Astrophysics Data System (ADS)

Wenthur, Cody J.; Zhou, Bin; Janda, Kim D.

2017-08-01

Fenethylline, also known by the trade name Captagon, is a synthetic psychoactive stimulant that has recently been linked to a substance-use disorder and ‘pharmacoterrorism’ in the Middle East. Although fenethylline shares a common phenethylamine core with other amphetamine-type stimulants, it also incorporates a covalently linked xanthine moiety into its parent structure. These independently active pharmacophores are liberated during metabolism, resulting in the release of a structurally diverse chemical mixture into the central nervous system. Although the psychoactive properties of fenethylline have been reported to differ from those of other synthetic stimulants, the in vivo chemical complexity it manifests upon ingestion has impeded efforts to unambiguously identify the specific species responsible for these effects. Here we develop a ‘dissection through vaccination’ approach, called DISSECTIV, to mitigate the psychoactive effects of fenethylline and show that its rapid-onset and distinct psychoactive properties are facilitated by functional synergy between theophylline and amphetamine. Our results demonstrate that incremental vaccination against a single chemical species within a multi-component mixture can be used to uncover emergent properties arising from polypharmacological activity. We anticipate that DISSECTIV will be used to expose unidentified active chemical species and resolve pharmacodynamic interactions within other chemically complex systems, such as those found in counterfeit or illegal drug preparations, post-metabolic tissue samples and natural product extracts.

Vaccine-driven pharmacodynamic dissection and mitigation of fenethylline psychoactivity.

PubMed

Wenthur, Cody J; Zhou, Bin; Janda, Kim D

2017-08-24

Fenethylline, also known by the trade name Captagon, is a synthetic psychoactive stimulant that has recently been linked to a substance-use disorder and 'pharmacoterrorism' in the Middle East. Although fenethylline shares a common phenethylamine core with other amphetamine-type stimulants, it also incorporates a covalently linked xanthine moiety into its parent structure. These independently active pharmacophores are liberated during metabolism, resulting in the release of a structurally diverse chemical mixture into the central nervous system. Although the psychoactive properties of fenethylline have been reported to differ from those of other synthetic stimulants, the in vivo chemical complexity it manifests upon ingestion has impeded efforts to unambiguously identify the specific species responsible for these effects. Here we develop a 'dissection through vaccination' approach, called DISSECTIV, to mitigate the psychoactive effects of fenethylline and show that its rapid-onset and distinct psychoactive properties are facilitated by functional synergy between theophylline and amphetamine. Our results demonstrate that incremental vaccination against a single chemical species within a multi-component mixture can be used to uncover emergent properties arising from polypharmacological activity. We anticipate that DISSECTIV will be used to expose unidentified active chemical species and resolve pharmacodynamic interactions within other chemically complex systems, such as those found in counterfeit or illegal drug preparations, post-metabolic tissue samples and natural product extracts.

Evaluation of capillary zone electrophoresis for the quality control of complex biologic samples: Application to snake venoms.

PubMed

Kpaibe, André P S; Ben-Ameur, Randa; Coussot, Gaëlle; Ladner, Yoann; Montels, Jérôme; Ake, Michèle; Perrin, Catherine

2017-08-01

Snake venoms constitute a very promising resource for the development of new medicines. They are mainly composed of very complex peptide and protein mixtures, which composition may vary significantly from batch to batch. This latter consideration is a challenge for routine quality control (QC) in the pharmaceutical industry. In this paper, we report the use of capillary zone electrophoresis for the development of an analytical fingerprint methodology to assess the quality of snake venoms. The analytical fingerprint concept is being widely used for the QC of herbal drugs but rarely for venoms QC so far. CZE was chosen for its intrinsic efficiency in the separation of protein and peptide mixtures. The analytical fingerprint methodology was first developed and evaluated for a particular snake venom, Lachesis muta. Optimal analysis conditions required the use of PDADMAC capillary coating to avoid protein and peptide adsorption. Same analytical conditions were then applied to other snake venom species. Different electrophoretic profiles were obtained for each venom. Excellent repeatability and intermediate precision was observed for each batch. Analysis of different batches of the same species revealed inherent qualitative and quantitative composition variations of the venoms between individuals. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MALDI Q-TOF CID MS for Diagnostic Ion Screening of Human Milk Oligosaccharide Samples

PubMed Central

Jovanović, Marko; Tyldesley-Worster, Richard; Pohlentz, Gottfried; Peter-Katalinić, Jasna

2014-01-01

Human milk oligosaccharides (HMO) represent the bioactive components of human milk, influencing the infant’s gastrointestinal microflora and immune system. Structurally, they represent a highly complex class of analyte, where the main core oligosaccharide structures are built from galactose and N-acetylglucosamine, linked by 1–3 or 1–4 glycosidic linkages and potentially modified with fucose and sialic acid residues. The core structures can be linear or branched. Additional structural complexity in samples can be induced by endogenous exoglycosidase activity or chemical procedures during the sample preparation. Here, we show that using matrix-assisted laser desorption/ionization (MALDI) quadrupole-time-of-flight (Q-TOF) collision-induced dissociation (CID) as a fast screening method, diagnostic structural information about single oligosaccharide components present in a complex mixture can be obtained. According to sequencing data on 14 out of 22 parent ions detected in a single high molecular weight oligosaccharide chromatographic fraction, 20 different oligosaccharide structure types, corresponding to over 30 isomeric oligosaccharide structures and over 100 possible HMO isomers when biosynthetic linkage variations were taken into account, were postulated. For MS/MS data analysis, we used the de novo sequencing approach using diagnostic ion analysis on reduced oligosaccharides by following known biosynthetic rules. Using this approach, de novo characterization has been achieved also for the structures, which could not have been predicted. PMID:24743894

Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, Patrick Allen

2005-12-17

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity ofmore » the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5%-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.« less

Temperature-controlled micro-TLC: a versatile green chemistry and fast analytical tool for separation and preliminary screening of steroids fraction from biological and environmental samples.

PubMed

Zarzycki, Paweł K; Slączka, Magdalena M; Zarzycka, Magdalena B; Bartoszuk, Małgorzata A; Włodarczyk, Elżbieta; Baran, Michał J

2011-11-01

This paper is a continuation of our previous research focusing on development of micro-TLC methodology under temperature-controlled conditions. The main goal of present paper is to demonstrate separation and detection capability of micro-TLC technique involving simple analytical protocols without multi-steps sample pre-purification. One of the advantages of planar chromatography over its column counterpart is that each TLC run can be performed using non-previously used stationary phase. Therefore, it is possible to fractionate or separate complex samples characterized by heavy biological matrix loading. In present studies components of interest, mainly steroids, were isolated from biological samples like fish bile using single pre-treatment steps involving direct organic liquid extraction and/or deproteinization by freeze-drying method. Low-molecular mass compounds with polarity ranging from estetrol to progesterone derived from the environmental samples (lake water, untreated and treated sewage waters) were concentrated using optimized solid-phase extraction (SPE). Specific bands patterns for samples derived from surface water of the Middle Pomerania in northern part of Poland can be easily observed on obtained micro-TLC chromatograms. This approach can be useful as simple and non-expensive complementary method for fast control and screening of treated sewage water discharged by the municipal wastewater treatment plants. Moreover, our experimental results show the potential of micro-TLC as an efficient tool for retention measurements of a wide range of steroids under reversed-phase (RP) chromatographic conditions. These data can be used for further optimalization of SPE or HPLC systems working under RP conditions. Furthermore, we also demonstrated that micro-TLC based analytical approach can be applied as an effective method for the internal standard (IS) substance search. Generally, described methodology can be applied for fast fractionation or screening of the whole range of target substances as well as chemo-taxonomic studies and fingerprinting of complex mixtures, which are present in biological or environmental samples. Due to low consumption of eluent (usually 0.3-1mL/run) mainly composed of water-alcohol binary mixtures, this method can be considered as environmentally friendly and green chemistry focused analytical tool, supplementary to analytical protocols involving column chromatography or planar micro-fluidic devices. Copyright © 2011 Elsevier Ltd. All rights reserved.

Development of size-selective sampling of Bacillus anthracis surrogate spores from simulated building air intake mixtures for analysis via laser-induced breakdown spectroscopy.

PubMed

Gibb-Snyder, Emily; Gullett, Brian; Ryan, Shawn; Oudejans, Lukas; Touati, Abderrahmane

2006-08-01

Size-selective sampling of Bacillus anthracis surrogate spores from realistic, common aerosol mixtures was developed for analysis by laser-induced breakdown spectroscopy (LIBS). A two-stage impactor was found to be the preferential sampling technique for LIBS analysis because it was able to concentrate the spores in the mixtures while decreasing the collection of potentially interfering aerosols. Three common spore/aerosol scenarios were evaluated, diesel truck exhaust (to simulate a truck running outside of a building air intake), urban outdoor aerosol (to simulate common building air), and finally a protein aerosol (to simulate either an agent mixture (ricin/anthrax) or a contaminated anthrax sample). Two statistical methods, linear correlation and principal component analysis, were assessed for differentiation of surrogate spore spectra from other common aerosols. Criteria for determining percentages of false positives and false negatives via correlation analysis were evaluated. A single laser shot analysis of approximately 4 percent of the spores in a mixture of 0.75 m(3) urban outdoor air doped with approximately 1.1 x 10(5) spores resulted in a 0.04 proportion of false negatives. For that same sample volume of urban air without spores, the proportion of false positives was 0.08.

Quantum-dot-based suspension microarray for multiplex detection of lung cancer markers: preclinical validation and comparison with the Luminex xMAP® system

NASA Astrophysics Data System (ADS)

Bilan, Regina; Ametzazurra, Amagoia; Brazhnik, Kristina; Escorza, Sergio; Fernández, David; Uríbarri, María; Nabiev, Igor; Sukhanova, Alyona

2017-03-01

A novel suspension multiplex immunoassay for the simultaneous specific detection of lung cancer markers in bronchoalveolar lavage fluid (BALF) clinical samples based on fluorescent microspheres having different size and spectrally encoded with quantum dots (QDEM) was developed. The designed suspension immunoassay was validated for the quantitative detection of three lung cancer markers in BALF samples from 42 lung cancer patients and 10 control subjects. Tumor markers were detected through simultaneous formation of specific immune complexes consisting of a capture molecule, the target antigen, and biotinylated recognition molecule on the surface of the different QDEM in a mixture. The immune complexes were visualized by fluorescently labeled streptavidin and simultaneously analyzed using a flow cytometer. Preclinical validation of the immunoassay was performed and results were compared with those obtained using an alternative 3-plex immunoassay based on Luminex xMAP® technology, developed on classical organic fluorophores. The comparison showed that the QDEM and xMAP® assays yielded almost identical results, with clear discrimination between control and clinical samples. Thus, developed QDEM technology can become a good alternative to xMAP® assays permitting analysis of multiple protein biomarkers using conventional flow cytometers.

Quantum-dot-based suspension microarray for multiplex detection of lung cancer markers: preclinical validation and comparison with the Luminex xMAP® system

PubMed Central

Bilan, Regina; Ametzazurra, Amagoia; Brazhnik, Kristina; Escorza, Sergio; Fernández, David; Uríbarri, María; Nabiev, Igor; Sukhanova, Alyona

2017-01-01

A novel suspension multiplex immunoassay for the simultaneous specific detection of lung cancer markers in bronchoalveolar lavage fluid (BALF) clinical samples based on fluorescent microspheres having different size and spectrally encoded with quantum dots (QDEM) was developed. The designed suspension immunoassay was validated for the quantitative detection of three lung cancer markers in BALF samples from 42 lung cancer patients and 10 control subjects. Tumor markers were detected through simultaneous formation of specific immune complexes consisting of a capture molecule, the target antigen, and biotinylated recognition molecule on the surface of the different QDEM in a mixture. The immune complexes were visualized by fluorescently labeled streptavidin and simultaneously analyzed using a flow cytometer. Preclinical validation of the immunoassay was performed and results were compared with those obtained using an alternative 3-plex immunoassay based on Luminex xMAP® technology, developed on classical organic fluorophores. The comparison showed that the QDEM and xMAP® assays yielded almost identical results, with clear discrimination between control and clinical samples. Thus, developed QDEM technology can become a good alternative to xMAP® assays permitting analysis of multiple protein biomarkers using conventional flow cytometers. PMID:28300171

High Degree of Interlaboratory Reproducibility of Human Immunodeficiency Virus Type 1 Protease and Reverse Transcriptase Sequencing of Plasma Samples from Heavily Treated Patients

PubMed Central

Shafer, Robert W.; Hertogs, Kurt; Zolopa, Andrew R.; Warford, Ann; Bloor, Stuart; Betts, Bradley J.; Merigan, Thomas C.; Harrigan, Richard; Larder, Brendon A.

2001-01-01

We assessed the reproducibility of human immunodeficiency virus type 1 (HIV-1) reverse transcriptase (RT) and protease sequencing using cryopreserved plasma aliquots obtained from 46 heavily treated HIV-1-infected individuals in two laboratories using dideoxynucleotide sequencing. The rates of complete sequence concordance between the two laboratories were 99.1% for the protease sequence and 99.0% for the RT sequence. Approximately 90% of the discordances were partial, defined as one laboratory detecting a mixture and the second laboratory detecting only one of the mixture's components. Only 0.1% of the nucleotides were completely discordant between the two laboratories, and these were significantly more likely to occur in plasma samples with lower plasma HIV-1 RNA levels. Nucleotide mixtures were detected at approximately 1% of the nucleotide positions, and in every case in which one laboratory detected a mixture, the second laboratory either detected the same mixture or detected one of the mixture's components. The high rate of concordance in detecting mixtures and the fact that most discordances between the two laboratories were partial suggest that most discordances were caused by variation in sampling of the HIV-1 quasispecies by PCR rather than by technical errors in the sequencing process itself. PMID:11283081

Different applications of isosbestic points, normalized spectra and dual wavelength as powerful tools for resolution of multicomponent mixtures with severely overlapping spectra.

PubMed

Mohamed, Ekram H; Lotfy, Hayam M; Hegazy, Maha A; Mowaka, Shereen

2017-05-25

Analysis of complex mixture containing three or more components represented a challenge for analysts. New smart spectrophotometric methods have been recently evolved with no limitation. A study of different novel and smart spectrophotometric techniques for resolution of severely overlapping spectra were presented in this work utilizing isosbestic points present in different absorption spectra, normalized spectra as a divisor and dual wavelengths. A quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PCT) and para-aminophenol (PAP) was taken as an example for application of the proposed techniques without any separation steps. The adopted techniques adopted of successive and progressive steps manipulating zero /or ratio /or derivative spectra. The proposed techniques includes eight novel and simple methods namely direct spectrophotometry after applying derivative transformation (DT) via multiplying by a decoding spectrum, spectrum subtraction (SS), advanced absorbance subtraction (AAS), advanced amplitude modulation (AAM), simultaneous derivative ratio (S 1 DD), advanced ratio difference (ARD), induced ratio difference (IRD) and finally double divisor-ratio difference-dual wavelength (DD-RD-DW) methods. The proposed methods were assessed by analyzing synthetic mixtures of the studied drugs. They were also successfully applied to commercial pharmaceutical formulations without interference from other dosage form additives. The methods were validated according to the ICH guidelines, accuracy, precision, repeatability, were found to be within the acceptable limits. The proposed procedures are accurate, simple and reproducible and yet economic. They are also sensitive and selective and could be used for routine analysis of complex most of the binary, ternary and quaternary mixtures and even more complex mixtures.

The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

NASA Astrophysics Data System (ADS)

Goenawan, Joshua; Trisanti, P. N.; Sumarno

2015-12-01

This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

In-Source Fragmentation and the Sources of Partially Tryptic Peptides in Shotgun Proteomics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jong-Seo; Monroe, Matthew E.; Camp, David G.

2013-02-01

Partially tryptic peptides are often identified in shotgun proteomics using trypsin as the proteolytic enzyme; however, it has been controversial regarding the sources of such partially tryptic peptides. Herein we investigate the impact of in-source fragmentation on shotgun proteomics using three biological samples, including a standard protein mixture, a mouse brain tissue homogenate, and a mouse plasma sample. Since the in-source fragments of a peptide retain the same elution time with its parent fully tryptic peptide, the partially tryptic peptides from in-source fragmentation can be distinguished from the other partially tryptic peptides by plotting the observed retention times against themore » computationally predicted retention times. Most partially tryptic in-source fragmentation artifacts were misaligned from the linear distribution of fully tryptic peptides. The impact of in-source fragmentation on peptide identifications was clearly significant in a less complex sample such as a standard protein digest, where ~60 % of unique peptides were observed as partially tryptic peptides from in-source fragmentation. In mouse brain or mouse plasma samples, in-source fragmentation contributed to 1-3 % of all identified peptides. The other major source of partially tryptic peptides in complex biological samples is presumably proteolytic processing by endogenous proteases in the samples. By filtering out the in-source fragmentation artifacts from the identified partially tryptic or non-tryptic peptides, it is possible to directly survey in-vivo proteolytic processing in biological samples such as blood plasma.« less

Real time viability detection of bacterial spores

DOEpatents

Vanderberg, Laura A.; Herdendorf, Timothy J.; Obiso, Richard J.

2003-07-29

This invention relates to a process for detecting the presence of viable bacterial spores in a sample and to a spore detection system, the process including placing a sample in a germination medium for a period of time sufficient for commitment of any present viable bacterial spores to occur, mixing the sample with a solution of a lanthanide capable of forming a fluorescent complex with dipicolinic acid, and, measuring the sample for the presence of dipicolinic acid, and the system including a germination chamber having inlets from a sample chamber, a germinant chamber and a bleach chamber, the germination chamber further including an outlet through a filtering means, the outlet connected to a detection chamber, the detection chamber having an inlet from a fluorescence promoting metal chamber and the detection chamber including a spectral excitation source and a means of measuring emission spectra from a sample, the detection chamber further connected to a waste chamber. A germination reaction mixture useful for promoting commitment of any viable bacterial spores in a sample including a combination of L-alanine, L-asparagine and D-glucose is also described.

Maximum likelihood estimation of finite mixture model for economic data

NASA Astrophysics Data System (ADS)

Phoong, Seuk-Yen; Ismail, Mohd Tahir

2014-06-01

Finite mixture model is a mixture model with finite-dimension. This models are provides a natural representation of heterogeneity in a finite number of latent classes. In addition, finite mixture models also known as latent class models or unsupervised learning models. Recently, maximum likelihood estimation fitted finite mixture models has greatly drawn statistician's attention. The main reason is because maximum likelihood estimation is a powerful statistical method which provides consistent findings as the sample sizes increases to infinity. Thus, the application of maximum likelihood estimation is used to fit finite mixture model in the present paper in order to explore the relationship between nonlinear economic data. In this paper, a two-component normal mixture model is fitted by maximum likelihood estimation in order to investigate the relationship among stock market price and rubber price for sampled countries. Results described that there is a negative effect among rubber price and stock market price for Malaysia, Thailand, Philippines and Indonesia.

Tandem mass spectrometry: analysis of complex mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singleton, K.E.

1985-01-01

Applications of tandem mass spectrometry (MS/MS) for the analysis of complex mixtures results in increased specificity and selectivity by using a variety of reagent gases in both negative and positive ion modes. Natural isotopic abundance ratios were examined in both simple and complex mixtures using parent, daughter and neutral loss scans. MS/MS was also used to discover new compounds. Daughter scans were used to identify seven new alkaloids in a cactus species. Three of these alkaloids were novel compounds, and included the first simple, fully aromatic isoquinoline alkaloids reported in Cactaceae. MS/MS was used to characterize the chemical reaction productsmore » of coal in studies designed to probe its macromolecular structure. Negative ion chemical ionization was utilized to study reaction products resulting from the oxidation of coal. Possible structural units in the precursor coal were predicted based on the reaction products identified, aliphatic and aromatic acids and their anhydrides. The MS/MS method was also used to characterize reaction products resulting from coal liquefaction and/or extraction. These studies illustrate the types of problems for which MS/MS is useful. Emphasis has been placed on characterization of complex mixtures by selecting experimental parameters which enhance the information obtained. The value of using MS/MS in conjunction with other analytical techniques as well as the chemical pretreatment is demonstrated.« less

Antioxidant capacity of pure compounds and complex mixtures evaluated by the ORAC-pyrogallol red assay in the presence of Triton X-100 micelles.

PubMed

Romero, Max; Rojano, Benjamin; Mella-Raipán, Jaime; Pessoa-Mahana, Carlos David; Lissi, Eduardo; López-Alarcón, Camilo

2010-09-01

The protective effect of different antioxidants and complex mixtures on the consumption of pyrogallol red (PGR) induced by peroxyl radicals was studied in the absence and presence of Triton X-100 micelles. The presence of micelles decreased significantly the protection of PGR afforded by lipophilic antioxidants (β-carotene, octyl gallate), while no effect of micelles was observed for hydrophilic antioxidants such as Trolox, caffeic acid, gallic acid, and ascorbic acid. In the presence of complex mixtures a clear effect of Triton X-100 micelles was also observed in the protection afforded by wines, tea infusions, and seed extracts of Eugenia jambolana and Myrciaria cauliflora. On the other hand, no effect of micelles was observed for orange juice and pulp fruit extracts. The ORAC (Oxygen Radical Absorbance Capacity) index was evaluated in the absence (ORAC-PGR) and presence of Triton X-100 micelles (ORAC-PGR(MIC)). Triton X-100 micelles affect ORAC-PGR values of antioxidants in a lipophilicity-dependent way. From the obtained results, we conclude that ORAC-PGR and ORAC-PGR(MIC) assays could be considered as an alternative to estimate the antioxidant ability (ORAC-PGR) and to infer the association to Triton X-100 micelles (ORAC-PGR/ORAC-PGR(MIC)) of pure antioxidants and their complex mixtures.

Dissolution of aerosol particles collected from nuclear facility plutonium production process

DOE PAGES

Xu, Ning; Martinez, Alexander; Schappert, Michael Francis; ...

2015-08-14

Here, a simple, robust analytical chemistry method has been developed to dissolve plutonium containing particles in a complex matrix. The aerosol particles collected on Marple cascade impactor substrates were shown to be dissolved completely with an acid mixture of 12 M HNO 3 and 0.1 M HF. A pressurized closed vessel acid digestion technique was utilized to heat the samples at 130 °C for 16 h to facilitate the digestion. The dissolution efficiency for plutonium particles was 99 %. The resulting particle digestate solution was suitable for trace elemental analysis and isotope composition determination, as well as radiochemistry measurements.

Evaluation of sample preparation methods for the detection of total metal content using inductively coupled plasma optical emission spectrometry (ICP-OES) in wastewater and sludge

NASA Astrophysics Data System (ADS)

Dimpe, K. M.; Ngila, J. C.; Mabuba, N.; Nomngongo, P. N.

Heavy metal contamination exists in aqueous wastes and sludge of many industrial discharges and domestic wastewater, among other sources. Determination of metals in the wastewater and sludge requires sample pre-treatment prior to analysis because of certain challenges such as the complexity of the physical state of the sample, which may lead to wrong readings in the measurement. This is particularly the case with low analyte concentration to be detected by the instrument. The purpose of this work was to assess and validate the different sample preparation methods namely, hot plate and microwave-assisted digestion procedures for extraction of metal ions in wastewater and sludge samples prior to their inductively coupled plasma optical emission spectrometric (ICP-OES) determination. For the extraction of As, Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn, three acid mixtures, that is, HNO3/H2O2, HNO3/HClO4/H2O2 and aqua regia + H2O2, were evaluated. Influent wastewater spiked with the SRM (CWW-TM-B) was used for the optimization of acid mixtures affecting the extraction procedure. After sample digestion, the filtration capabilities of cellulose-acetate filter paper and the acrodisc syringe filter with the pore size of 0.45 μm were compared. In terms of performance, acrodisc syringe filter in terms of the improved recoveries obtained, was found to be the best filtration method compared to the filter paper. Based on the analytical results obtained, microwave-assisted digestion (MAD) using aqua regia + H2O2 mixture was found to be the most suitable method for extraction of heavy metals and major elements in all the sample matrices. Therefore, MAD using aqua regia + H2O2 mixture was used for further investigations. The precision of the developed MAD method expressed in terms of relative standard deviations (% RSD) for different metals was found to be <5%. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.12% to 2.18 μg L-1 and 0.61% to 3.43 μg L-1, respectively. The accuracy of the developed method (MAD using aqua regia + H2O2) was verified by analyzing two SRMs (CWW-TM-A and CWW-TM-B) and the obtained results were in agreement with certified values with recoveries ranging from 80% to 104% for CWW-TM-A and 84% to 102% for CWW-TM-B. The accuracy of the developed method was verified also by the recovery test in the spiked sludge samples. The accuracy and spike recovery test for different metal ions were in the range 80-104% and 92-106%, respectively. The developed method was applied for extraction of the As, Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn in environmental samples, namely wastewater and sludge.

Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore

NASA Astrophysics Data System (ADS)

Biswas, Sujoy; Pathak, P. N.; Roy, S. B.

2012-06-01

An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λmax) for UO22+-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol-1 cm-1). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to >24 h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO22+-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is <2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ±2%. This method can be used to determine 2.5-250 μg mL-1 uranium in ore leach solutions with high accuracy and precision.

The Investigation of Chlorate and Perchlorate/Saponite Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

NASA Technical Reports Server (NTRS)

Clark, J.; Sutter, B.; Min, D. W.; Mahaffy, P.

2016-01-01

The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected O2 and HCl gas releases from all analyzed Gale Crater sediments, which are attributed to the presence of perchlorates and/or chlorates in martian sediment. Previous SAM analog laboratory analyses found that most pure perchlorates and chlorates release O2 and HCl at different temperatures than those observed in the SAM data. Subsequent studies examined the effects of perchlorate and chlorate mixtures with Gale Crater analog iron phases, which are known to catalyze oxychlorine decomposition. Several mixtures produced O2 releases at similar temperatures as Gale Crater materials, but most of these mixtures did not produce significant HCl releases comparable to those detected by the SAM instrument. In order to better explain the Gale Crater HCl releases, perchlorates and chlorates were mixed with Gale Crater analog saponite, which is found at abundances from 8 to 20 wt % in the John Klein and Cumberland drill samples. Mixtures of chlorates or perchlorates with calcium-saponite or ferrian-saponite were heated to 1000 deg C in a Labsys EVO differential scanning calorimeter/mass spectrometer configured to operate similarly to the SAM oven/quadrupole mass spectrometer system. Our results demonstrate that all chlorate and perchlorate mixtures produce significant HCl releases below 1000 deg C as well as depressed oxygen peak release temperatures when mixed with saponite. The type of saponite (calcium or ferrian saponite) did not affect the evolved gas results significantly. Saponite/Mg-perchlorate mixtures produced two HCl releases similar to the Cumberland drilled sample. Mg-chlorate mixed with saponite produced HCl releases similar to the Big Sky drilled sample in an eolian sandstone. A mixture of Ca-perchlorate and saponite produced HCl and oxygen releases similar to the Buckskin mudstone drilled sample and the Gobabeb 2 eolian dune material. Ca-chlorate mixed with saponite produced both HCl and oxygen releases within the same range as the Rock-nest windblown deposit, the Greenhorn eolian sandstone, and the John Klein drilled mudstone. Overall, mixtures of perchlorates or chlorates with saponite provide the first explanation for the high temperature HCl releases in addition to the oxygen releases observed in Gale Crater materials.

Generation of two-dimensional binary mixtures in complex plasmas

NASA Astrophysics Data System (ADS)

Wieben, Frank; Block, Dietmar

2016-10-01

Complex plasmas are an excellent model system for strong coupling phenomena. Under certain conditions the dust particles immersed into the plasma form crystals which can be analyzed in terms of structure and dynamics. Previous experiments focussed mostly on monodisperse particle systems whereas dusty plasmas in nature and technology are polydisperse. Thus, a first and important step towards experiments in polydisperse systems are binary mixtures. Recent experiments on binary mixtures under microgravity conditions observed a phase separation of particle species with different radii even for small size disparities. This contradicts several numerical studies of 2D binary mixtures. Therefore, dedicated experiments are required to gain more insight into the physics of polydisperse systems. In this contribution first ground based experiments on two-dimensional binary mixtures are presented. Particular attention is paid to the requirements for the generation of such systems which involve the consideration of the temporal evolution of the particle properties. Furthermore, the structure of these two-component crystals is analyzed and compared to simulations. This work was supported by the Deutsche Forschungsgemeinschaft DFG in the framework of the SFB TR24 Greifswald Kiel, Project A3b.

Solubility Limits in Lennard-Jones Mixtures: Effects of Disparate Molecule Geometries.

PubMed

Dyer, Kippi M; Perkyns, John S; Pettitt, B Montgomery

2015-07-23

In order to better understand general effects of the size and energy disparities between macromolecules and solvent molecules in solution, especially for macromolecular constructs self-assembled from smaller molecules, we use the first- and second-order exact bridge diagram extensions of the HNC integral equation theory to investigate single-component, binary, ternary, and quaternary mixtures of Lennard-Jones fluids. For pure fluids, we find that the HNCH3 bridge function integral equation (i.e., exact to third order in density) is necessary to quantitatively predict the pure gas and pure liquid sides of the coexistence region of the phase diagram of the Lennard-Jones fluid. For the mixtures, we find that the HNCH2 bridge function integral equation is sufficient to qualitatively predict solubility in the binary, ternary, and quaternary mixtures, up to the nominal solubility limit. The results, as limiting cases, should be useful to several problems, including accurate phase diagram predictions for complex mixtures, design of self-assembling nanostructures via solvent controls, and the solvent contributions to the conformational behavior of macromolecules in complex fluids.

INTEGRATED DISINFECTION BY-PRODUCTS (DBP) MIXTURES RESEARCH: GENE EXPRESSION ALTERATIONS IN PRIMARY RAT HEPATOCYTE CULTURES EXPOSED TO DBP MIXTURES FORMED BY CHLORINATION AND OZONATION/POSTCHLORINATION

EPA Science Inventory

What is the study?
This study was designed to provide data on the in vitro toxicity of water concentrates containing complex mixtures of DBPs. Rat hepatocytes in primary culture were exposed for 24 hr to full strength, 1:10 or 1:20 dilutions of chlorination or ozonation/chl...

Shock Reactivity of Non-Porous Mixtures of Manganese and Sulfur

NASA Astrophysics Data System (ADS)

Jetté, F. X.; Goroshin, S.; Higgins, A. J.

2007-12-01

Equimolar mixtures of manganese powder and sulfur were melt-cast into solid pellets in order to study the mechanism of shock-enhanced reactivity in non-porous heterogeneous mixtures. This mixture was selected due to the large exothermic heat release of the manganese-sulfur reaction (214 kJ/mol), which causes the reaction to be self-sustaining once initiated. The test samples were placed in planar recovery ampoules and a strong shock was delivered via the detonation of a charge of amine-sensitized nitromethane. Various shock strengths were achieved by placing different thicknesses of PMMA attenuator discs between the explosive charge and the ampoule. The results confirmed that shock-induced reactions can be produced in highly non-porous mixtures. Indeed, the critical shock pressure that caused ignition of the mixture in the ampoule was found to be in the range 2.2-3.0 GPa (pressures were estimated using LS-DYNA simulations of samples with 100% TMD).

Multivariate analysis of standoff laser-induced breakdown spectroscopy spectra for classification of explosive-containing residues

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Lucia, Frank C. Jr.; Gottfried, Jennifer L.; Munson, Chase A.

2008-11-01

A technique being evaluated for standoff explosives detection is laser-induced breakdown spectroscopy (LIBS). LIBS is a real-time sensor technology that uses components that can be configured into a ruggedized standoff instrument. The U.S. Army Research Laboratory has been coupling standoff LIBS spectra with chemometrics for several years now in order to discriminate between explosives and nonexplosives. We have investigated the use of partial least squares discriminant analysis (PLS-DA) for explosives detection. We have extended our study of PLS-DA to more complex sample types, including binary mixtures, different types of explosives, and samples not included in the model. We demonstrate themore » importance of building the PLS-DA model by iteratively testing it against sample test sets. Independent test sets are used to test the robustness of the final model.« less

Challenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and off-line GC-FID

NASA Astrophysics Data System (ADS)

Perraud, V.; Meinardi, S.; Blake, D. R.; Finlayson-Pitts, B. J.

2015-12-01

Organosulfur compounds (OSC) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to have negative effects on visibility, climate and human health. In order to predict particle formation events, accurate measurements of the OSC precursors are essential. Here, two different approaches, proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and canister sampling coupled with GC-FID are compared for both laboratory standards [dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and methanethiol (MTO)] and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air.

Headspace versus direct immersion solid phase microextraction in complex matrixes: investigation of analyte behavior in multicomponent mixtures.

PubMed

Gionfriddo, Emanuela; Souza-Silva, Érica A; Pawliszyn, Janusz

2015-08-18

This work aims to investigate the behavior of analytes in complex mixtures and matrixes with the use of solid-phase microextraction (SPME). Various factors that influence analyte uptake such as coating chemistry, extraction mode, the physicochemical properties of analytes, and matrix complexity were considered. At first, an aqueous system containing analytes bearing different hydrophobicities, molecular weights, and chemical functionalities was investigated by using commercially available liquid and solid porous coatings. The differences in the mass transfer mechanisms resulted in a more pronounced occurrence of coating saturation in headspace mode. Contrariwise, direct immersion extraction minimizes the occurrence of artifacts related to coating saturation and provides enhanced extraction of polar compounds. In addition, matrix-compatible PDMS-modified solid coatings, characterized by a new morphology that avoids coating fouling, were compared to their nonmodified analogues. The obtained results indicate that PDMS-modified coatings reduce artifacts associated with coating saturation, even in headspace mode. This factor, coupled to their matrix compatibility, make the use of direct SPME very practical as a quantification approach and the best choice for metabolomics studies where wide coverage is intended. To further understand the influence on analyte uptake on a system where additional interactions occur due to matrix components, ex vivo and in vivo sampling conditions were simulated using a starch matrix model, with the aim of mimicking plant-derived materials. Our results corroborate the fact that matrix handling can affect analyte/matrix equilibria, with consequent release of high concentrations of previously bound hydrophobic compounds, potentially leading to coating saturation. Direct immersion SPME limited the occurrence of the artifacts, which confirms the suitability of SPME for in vivo applications. These findings shed light into the implementation of in vivo SPME strategies in quantitative metabolomics studies of complex plant-based systems.

Continuous flow immobilized enzyme reactor-tandem mass spectrometry for screening of AChE inhibitors in complex mixtures.

PubMed

Forsberg, Erica M; Green, James R A; Brennan, John D

2011-07-01

A method is described for identifying bioactive compounds in complex mixtures based on the use of capillary-scale monolithic enzyme-reactor columns for rapid screening of enzyme activity. A two-channel nanoLC system was used to continuously infuse substrate coupled with automated injections of substrate/small molecule mixtures, optionally containing the chromogenic Ellman reagent, through sol-gel derived acetylcholinesterase (AChE) doped monolithic columns. This is the first report of AChE encapsulated in monolithic silica for use as an immobilized enzyme reactor (IMER), and the first use of such IMERs for mixture screening. AChE IMER columns were optimized to allow rapid functional screening of compound mixtures based on changes in the product absorbance or the ratio of mass spectrometric peaks for product and substrate ions in the eluent. The assay had robust performance and produced a Z' factor of 0.77 in the presence of 2% (v/v) DMSO. A series of 52 mixtures consisting of 1040 compounds from the Canadian Compound Collection of bioactives was screened and two known inhibitors, physostigmine and 9-aminoacridine, were identified from active mixtures by manual deconvolution. The activity of the compounds was confirmed using the enzyme reactor format, which allowed determination of both IC(50) and K(I) values. Screening results were found to correlate well with a recently published fluorescence-based microarray screening assay for AChE inhibitors.

Monte Carlo simulations of mixtures involving ketones and aldehydes by a direct bubble pressure calculation.

PubMed

Ferrando, Nicolas; Lachet, Véronique; Boutin, Anne

2010-07-08

Ketone and aldehyde molecules are involved in a large variety of industrial applications. Because they are mainly present mixed with other compounds, the prediction of phase equilibrium of mixtures involving these classes of molecules is of first interest particularly to design and optimize separation processes. The main goal of this work is to propose a transferable force field for ketones and aldehydes that allows accurate molecular simulations of not only pure compounds but also complex mixtures. The proposed force field is based on the anisotropic united-atoms AUA4 potential developed for hydrocarbons, and it introduces only one new atom, the carbonyl oxygen. The Lennard-Jones parameters of this oxygen atom have been adjusted on saturated thermodynamic properties of both acetone and acetaldehyde. To simulate mixtures, Monte Carlo simulations are carried out in a specific pseudoensemble which allows a direct calculation of the bubble pressure. For polar mixtures involved in this study, we show that this approach is an interesting alternative to classical calculations in the isothermal-isobaric Gibbs ensemble. The pressure-composition diagrams of polar + polar and polar + nonpolar binary mixtures are well reproduced. Mutual solubilities as well as azeotrope location, if present, are accurately predicted without any empirical binary interaction parameters or readjustment. Such result highlights the transferability of the proposed force field, which is an essential feature toward the simulation of complex oxygenated mixtures of industrial interest.

Comparative Chemistry and Toxicity of Diesel and Biomass Combustion Emissions

EPA Science Inventory

Air pollution includes a complex mixture of carbonaceous gases and particles emitted from multiple anthropogenic, biogenic, and biomass burning sources, and also includes secondary organic components that form during atmospheric aging of these emissions. Exposure to these mixture...

EXPERIMENTS AT THE INTERFACE OF CARBON PARTICLE CHEMISTRY AND TOXCIOLOGY

EPA Science Inventory

Air pollution includes a complex mixture of carbonaceous gases and particles emitted from multiple anthropogenic, biogenic, and biomass burning sources, and also includes secondary organic components that form during atmospheric aging of these emissions. Exposure to these mixture...