skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • A sensor array for the discrimination of polycyclic aromatic hydrocarbons using conjugated polymers and the inner filter effect
Title: A sensor array for the discrimination of polycyclic aromatic hydrocarbons using conjugated polymers and the inner filter effect
Natural and anthropogenic activities result in the production of polycyclic aromatic hydrocarbons (PAHs), persistent pollutants that negatively impact the environment and human health. Rapid and reliable methods for the detection and discrimination of these compounds remains a technological challenge owing to their relatively featureless properties, structural similarities, and existence as complex mixtures. Here, we demonstrate that the inner filter effect (IFE), in combination with conjugated polymer (CP) array-based sensing, offers a straightforward approach for the quantitative and qualitative profiling of PAHs. The sensor array was constructed from six fluorescent fluorene-based copolymers, which incorporate side chains with peripheral 2-phenylbenzimidazole substituents that provide spectral overlap with PAHs and give rise to a pronounced IFE. Subtle structural differences in copolymer structure result in distinct spectral signatures, which provide a unique “chemical fingerprint” for each PAH. The discriminatory power of the array was evaluated using linear discriminant analysis (LDA) and principal component analysis (PCA) in order to discriminate between 16 PAH compounds identified as priority pollutants by the US Environmental Protection Agency (EPA). This array is the first multivariate system reliant on the modulation of the spectral signatures of CPs through the IFE for the detection and discrimination of closely related polynuclear aromatic species.  more » « less
Award ID(s):
1632825
PAR ID:
10147607
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Science
Volume:
10
Issue:
44
ISSN:
2041-6520
Page Range / eLocation ID:
10247 to 10255
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; (, Journal of Mass Spectrometry)
    Abstract Polycyclic aromatic hydrocarbons (PAHs) are common pollutants present in atmospheric aerosols and other environmental mixtures. They are of particular air quality and human health concerns as many of them are carcinogenic toxins. They also affect absorption of solar radiation by aerosols, therefore contributing to the radiative forcing of climate. For environmental chemistry studies, it is advantageous to quantify PAH components using the same analytical technics that are commonly applied to characterize a broad range of polar analytes present in the same environmental mixtures. Liquid chromatography coupled with photodiode array and high‐resolution mass spectrometric detection (LC‐PDA‐HRMS) is a method of choice for comprehensive characterization of chemical composition and quantification of light absorption properties of individual organic compounds present in the environmental samples. However, quantification of non‐polar PAHs by this method is poorly established because of their imperfect ionization in electrospray ionization (ESI) technique. This tutorial article provides a comprehensive evaluation of the quantitative analysis of 16 priority pollutant PAHs in a standard reference material using the LC–MS platform coupled with the ESI source. Results are further corroborated by the quantitation experiments using an atmospheric pressure photoionization (APPI) method, which is more sensitive for the PAH detection. The basic concepts and step‐by‐step practical guidance for the PAHs quantitative characterization are offered based on the systematic experiments, which include (1) Evaluation effects of different acidification levels by formic acid on the (+)ESI‐MS detection of PAHs. (2) Comparison of detection limits in ESI+ versus APPI+ experiments. (3) Investigation of the PAH fragmentation patterns in MS2experiments at different collision energies. (4) Calculation of wavelength dependent mass absorption coefficient (MACλ) of the standard mixture and its individual PAHs using LC‐PDA data. (5) Assessment of the minimal injected mass required for accurate quantification ofMACλof the standard mixture and of a multi‐component environmental sample. 
    more » « less
  2. ; (, Microbiology Spectrum)
    Steven, Blaire (Ed.)
    ABSTRACT Polycyclic aromatic hydrocarbons (PAHs) are common toxic and carcinogenic pollutants in marine ecosystems. Despite their prevalence in these habitats, relatively little is known about the natural microflora and biochemical pathways that contribute to their degradation. Approaches to investigate marine microbial PAH degraders often heavily rely on genetic biomarkers, which requires prior knowledge of specific degradative enzymes and genes encoding them. As such, these biomarker-reliant approaches cannot efficiently identify novel degradation pathways or degraders. Here, we screen 18 marine bacterial strains representing the Pseudomonadota, Bacillota, and Bacteroidota phyla for degradation of two model PAHs, pyrene (high molecular weight) and phenanthrene (low molecular weight). Using a qualitative PAH plate screening assay, we determined that 16 of 18 strains show some ability to degrade either or both compounds. Degradative ability was subsequently confirmed with a quantitative high-performance liquid chromatography approach, where an additional strain showed some degradation in liquid culture. Several members of the prominent marineRoseobacteraceaefamily degraded pyrene and phenanthrene with varying efficiency (1.2%–29.6% and 5.2%–52.2%, respectively) over 26 days. Described PAH genetic biomarkers were absent in all PAH degrading strains for which genome sequences are available, suggesting that these strains harbor novel transformation pathways. These results demonstrate the utility of culture-based approaches in expanding the knowledge landscape concerning PAH degradation in marine systems. IMPORTANCEPolycyclic aromatic hydrocarbon (PAH) pollution is widespread throughout marine environments and significantly affects native flora and fauna. Investigating microbes responsible for degrading PAHs in these environments provides a greater understanding of natural attenuation in these systems. In addition, the use of culture-based approaches to inform bioinformatic and omics-based approaches is useful in identifying novel mechanisms of PAH degradation that elude genetic biomarker-based investigations. Furthermore, culture-based approaches allow for the study of PAH co-metabolism, which increasingly appears to be a prominent mechanism for PAH degradation in marine microbes. 
    more » « less
  3. ; ; ; ; ; (, PLOS ONE)
    Cao, Yi (Ed.)
    Polycyclic aromatic hydrocarbons (PAHs) are among the most widespread natural and anthropogenic pollutants, and some PAHs are proven developmental toxicants. We chemically characterized clean and heavily polluted sites and exposed fish embryos to PAH polluted sediment extracts during four critical developmental stages. Embryos were collected from Fundulus heteroclitus populations inhabiting the clean and heavily polluted Superfund estuary. Embryos of parents from the clean sites are sensitive to PAH pollutants while those of parents from the heavily polluted site are resistant. Chemical analysis of embryos suggests PAH accumulation and pollution-induced toxicity among sensitive embryos during development that ultimately kills all sensitive embryos before hatching, while remarkably, the resistant embryos develop normally. The adverse effects on sensitive embryos are manifested as developmental delays, reduced heart rates, and severe heart, liver, and kidney morphological abnormalities. Gene expression analysis of early somitogenesis, heartbeat initiation, late organogenesis, and pre-hatching developmental stages reveals genes whose expression significantly differs between sensitive and resistant embryo populations and helps to explain mechanisms of sensitivity and resistance to polluted environments during vertebrate animal development. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, The Astrophysical Journal)
    Abstract We report the detection of near- and mid-infrared emission from polycyclic aromatic hydrocarbons (PAHs) out to ∼35 kpc in the Makani Galaxy, a compact massive galaxy with a record-breaking 100 kpc scale starburst-driven wind at redshiftz= 0.459. The NIRCam and MIRI observations with JWST take advantage of a coincidental match between the PAH spectral features at 3.3, 7.7, and (11.3 + 12.2)μm in Makani and the bandpasses of the MIRI and NIRCam filters. The warm dust is not only detected in the cool-gas tracers of the galactic wind associated with the more recent (7 Myr) starburst episode, but also in the outer warm ionized gas wind produced by the older (0.4 Gyr) episode. The presence of PAHs in the outer wind indicates that the PAHs have survived the long (R/v∼ 108yr) journey to the halo despite the harsh environment of the galactic wind. The measured F1800W/F1130W flux ratios in the unresolved nucleus, inner halo (R= 10–20 kpc), and outer halo (R= 20–35 kpc), tracers of the PAH (11.3 + 12.2)/7.7 ratios, indicate decreasing starlight intensity incident on the PAHs, decreasing PAH sizes, and increasing PAH ionization fractions with increasing distance from the nucleus. These data provide the strongest evidence to date that the ejected dust of galactic winds survives the long journey to the circumgalactic medium, but is eroded along the way. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; ; et al (, American Geophysical Union)
    Pyrogenic compounds, such as polycyclic aromatic hydrocarbons (PAHs), can track the type and intensity of fires and are preserved in many environmental matrices including speleothems. We recently reported on a stalagmite record of PAH abundance distributions from cave KNI-51, located among the eucalypt savanna in the Ningbing range of tropical Western Australia. In order to better understand the manner by which PAHs from local bushfires are deposited on the land surface and transported into caves, we performed a controlled burn and irrigation experiment at cave KNI-140, located near to and in the same bedrock as cave KNI-51. Samples of soil, vegetation, ash, and air were collected prior to and immediately succeeding the prescribed burn. The fire, which burned predominantly grasses, was ignited by matches (no accelerants were used) and covered approximately 30,000 square meters upwind from the cave. The land surface above the cave was irrigated prior to and immediately succeeding the burn with resulting dripwater collected for analysis. Next, ash samples were deposited directly above the cave and then similarly irrigated, with the drip water also collected. The PAHs present in these samples were measured via gas chromatography-mass spectrometry at Ca’ Foscari University, Venice. Our results reveal that low molecular weight PAHs were the most abundant species of PAH in the drip water and heavier PAHs were substantially less abundant. This result is likely due to the low combustion temperature of the burn, with abundances increasing through each of the three stages of sample collection, demonstrating that deposition from smoke and cinders produces identifiable signals in dripwater (and thus stalagmite) PAHs, supporting the contention that KNI-51 stalagmites record fire activity occurring not just above the cave but within km of the cave. On-going analyses of soil, vegetation, and ash samples will further clarify the role of fire on production and transmission of PAHs at this site, and thus how these organic compounds preserved in speleothems can help delineate the fire history in the region. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email