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Uranyl Speciation on the Surface of Amidoximated Polyacrylonitrile Mats.

ABSTRACT: Naturally occurring uranium is a widespread contaminant present in the water resources around the abandoned uranium mines in the southwest United States. A novel method for rapid uranium detection has been recently developed that relies on the sequestering of uranium by amidoximated polyacrylonitrile (AO-PAN) polymer mats and uses the Raman-active (ν₁) symmetric stretch as the signal. The Raman signals obtained from uranium bearing AO-PAN were challenging to interpret due to an unknown uranyl speciation on the surface of the mats. Herein, we provide the synthesis and structural characterization of six model coordination compounds that contain acetamidoxime/benzamidoxime (AAO/BAO) coordinated to the uranyl cation: [UO₂(η¹-AAO)(NO₃)₂(H₂O)] (1), [UO₂(η¹-AAO)₂(NO₃)₂] (2), [UO₂(η²-BAO)₂(CH₃OH)₂] (3), [(UO₂)₃(η²-BAO)₃(μ₂-NO₃)₃] (4), [(UO₂)₄(μ₃-O)₂(μ₂-BAO)₄(η¹-BAO)₄(H₂O)₂](NO₃)₄ (5), and [(UO₂)₄(μ₃-O)₂(μ₂-BAO)₄(η¹-BAO)₆Na(NO₃)₂](NO₃)₃ (6). Solid-state Raman spectra of 1-6 showed dramatic differences in the uranyl ν₁ symmetric stretch depending on the coordination of the amidoxime functional group. The assignments made from the solid-state Raman spectra were used to deconvolute the solution-state Raman spectra of uranyl-acetamidoxime/benzamidoxime methanol solutions at different metal to ligand molar ratios. At low molar ratios (1 U:1 AAO/BAO and 1 U:2 AAO/BAO) the dominant species is the uranyl coordinated via the η¹-oxygen atom of the oxime group, while at high molar ratios (1 U:3 AAO/BAO and 1 U:4 AAO/BAO) the dominant species are a tetrameric uranyl-μ₃-O-η¹-amidoxime complex similar to compounds 5 and 6 and a uranyl-η²-amidoxime complex similar to compounds 3 and 4. Solid-state Raman spectra showed good agreement with Raman signals obtained from the uranyl-AO-PAN mats, demonstrating that binding motifs between uranyl and amidoxime in compounds 5 and 6 are the most representative of the uranyl species on the surface of the AO-PAN mats.

SUBMITTER: Kravchuk DV

PROVIDER: S-EPMC7718723 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The plasmonic properties of carboxylated gold nanostars distributed on amidoximated polyacrylonitrile (AO PAN) electrospun polymer films scale with surface-enhanced Raman scattering (SERS) intensities for coordinated uranium(VI) oxide (uranyl) species. This two-step plasmonic sensor first isolates uranyl from solution using functionalized polymers; then carboxylated gold nanostars are subsequently deposited for SERS. Spatially resolved localized surface plasmon resonance (LSPR) and SERS facilitate correlated nanostar optical density and uranyl quantification. To reduce sampling bias, gold nanostars are deposited in an inverted drop-coating geometry and measurements are conducted inside resulting nanoparticle coffee rings that form on the polymer substrates. This approach naturally preserves the plasmonic properties of gold nanostars while reducing the deposition of nanoparticle aggregates in active sensing regions, thereby maximizing both the accuracy and the precision of SERS measurements. Several advances are made. First, second-derivative analysis of LSPR spectra facilitates the quantification of local nanostar density across large regions of the sensor substrate by reducing background variations caused by the polymeric and gold materials. Second, local nanostar densities ranging from 140 to 200 pM·cm are shown to result in uranyl signals that are independent of nanostar concentration. Third, the Gibbs free energy of uranyl adsorption to carboxylated nanostars is estimated at 8.4 ± 0.2 kcal/mol. Finally, a linear dynamic range from ∼0.3 to 3.4 μg U/mg polymer is demonstrated. Signals vary by 10% or less. As such, the uniformity of the plasmonic activity of distributed gold nanostars and the employment of spatially resolved spectroscopic measurements on the composite nanomaterial sensor interface facilitate the quantitative detection of uranyl while also reducing the dependence on user expertise and the selected sampling region. These important advances are critical for the development of a user-friendly SERS-based sensor for uranyl.

Project description:Phenolic compound even at low concentrations, are considered to be priority pollutants due to their significant toxicity. Electrospinning was used to create a polyacrylonitril (PAN) nanofiber, which was then impregnated with graphene oxide (GO). After a preliminary investigation into the electrospinning parameters (e.g., using various voltages and polymer concentrations), the electrospun nanofibres were tuned, this study evaluated the effectiveness of these materials in removing phenolic compounds from wastewater through adsorption. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the synthesized nanofiber mats. The scanning electron microscopy (SEM) analysis revealed that the structure of nanofiber mats was altered by the addition of graphene oxide (GO) in different ratios. Specifically, the surface of the fibres exhibited increased roughness, and the diameter of the fibres also experienced an increase. The average diameter of the fibres was measured to be (134.9 ± 21.43 nm) for the PAN/2.5% GO composite and (198 ± 33.94 nm) for the PAN/5% GO composite. FTIR spectra of the PAN/GO nanocomposites nanofiber displayed distinct peaks associated with graphene oxide (GO). These included a wide peak at 3400 cm-1, related to the presence of hydroxyl (O-H) groups, as well as peaks on 1600 as well as 1000 cm-1, which indicated the existence of epoxy groups. In this study response surface methodology (RSM) was implemented. To enhance the efficiency of removing substances, it is necessary to optimise parameters such as pH, contact time, and dosage of the adsorbent. The optimum pH for removing phenol via all nanofiber mats was determined to be 7, while at a dose of 2 mg dose adsorbents maximum removals for pure PAN, PAN/2.5 GO, and PAN/5 GO were 61.3941, 77.2118, and 92.76139%, respectively. All the adsorbents obey Langmuir isotherm model, and the empirical adsorption findings were fitted with the second-order model kinetically, also non-linear Elovich model. The maximal monolayer adsorption capacities for PAN, PAN/2.5 GO, and PAN/5 GO were found to be 57.4, 66.18, and 69.7 mg/g, respectively. Thermodynamic studies discovered that the adsorption of phenol on all adsorbents nanofiber mats was exothermic, the adsorption of phenol on nanofiber mats decreases as the temperature increases. All the adsorbents exhibit negative enthalpy and entropy. The PAN/GO composite's superior phenol removal suggested that it could be used as a latent adsorbent for efficient phenol removal from water and wastewater streams.

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Project description:Background: The Dobzhansky-Muller (D-M) model of speciation by genic incompatibility is widely accepted as the primary cause of interspecific postzygotic isolation. Since the introduction of this model, there have been theoretical and experimental data supporting the existence of such incompatibilities. However, speciation genes have been largely elusive, with only a handful of candidate genes identified in a few organisms. The Saccharomyces sensu stricto yeasts have small genomes, can be easily cultured, and can mate interspecifically to produce sterile hybrids, are thus an ideal model for studying postzygotic isolation. Among them, only a single D-M pair has been found, between S. bayanus and S. cerevisiae, comprising the mitochondrially targeted product of a nuclear gene, AEP2, and a mitochondrially encoded locus, OLI1, the 5' region of whose transcript is bound by Aep2. Thus far, no D-M pair of nuclear genes has been identified between any sensu stricto yeasts. Methods: We report here the first detailed genome-wide analysis of rare F2 progeny from an otherwise sterile hybrid, and show that no classic D-M pairs of speciation genes exist between the nuclear genomes of the closely related yeasts S. cerevisiae and S. paradoxus. Instead, our analyses suggest that more complex interactions may be responsible for their post-zygotic separation. These interactions most likely involve multiple loci having weak effects, as there were multiple significant pairwise combinations of loci, with no single combination being completely excluded from the viable F2s. Conclusions: The lack of a nuclear encoded classic D-M pair between these two yeasts, yet the existence of multiple loci that may each exert a small effect through complex interactions, suggests that initial speciation events might not always be mediated by D-M pairs. An alternative explanation may be that "death by a thousand cuts" leads to speciation, whereby an accumulation of polymorphisms can lead to an incompatibility between the species "transcriptional and metabolic networks, with no single pair at least initially being responsible for the incompatibility. After such a speciation event, it is possible that one or more D-M pairs might subsequently arise following isolation. Genotypes for hybrids between S. cerevisiae and S. paradoxus. A genotyping experiment design type classifies an individual or group of individuals on the basis of alleles, haplotypes, SNP's.

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Uranyl Speciation on the Surface of Amidoximated Polyacrylonitrile Mats.

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